WO2019069960A1 - Compound, latent ultraviolet light absorber, composition, cured product, and cured product production method - Google Patents
Compound, latent ultraviolet light absorber, composition, cured product, and cured product production method Download PDFInfo
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- WO2019069960A1 WO2019069960A1 PCT/JP2018/036958 JP2018036958W WO2019069960A1 WO 2019069960 A1 WO2019069960 A1 WO 2019069960A1 JP 2018036958 W JP2018036958 W JP 2018036958W WO 2019069960 A1 WO2019069960 A1 WO 2019069960A1
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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Definitions
- the present invention relates to a compound which is less likely to inhibit curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
- Patent Documents 1 to 3 In order to improve the ultraviolet ray absorbing ability and heat resistance of the curable composition, methods of stabilizing by adding an ultraviolet light absorber and an antioxidant to the curable composition are known (Patent Documents 1 to 3) .
- latent additives which can be activated after curing are inactivated in the above-mentioned light absorbing action in the polymerization system.
- activation of the latent additive that can be activated after curing may require heating or the like, but may require easier activation.
- the present invention has been made in view of the above problems, and has as its main object to provide a compound which is less in inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
- the present inventors used a photoleaving group as a protecting group to protect the phenolic hydroxyl group contained in the ultraviolet absorber with the photoleaving group. It has been found that the adjustment of the time to develop the ultraviolet light absorbing ability is easy and the above-mentioned problems can be solved, and the present invention has been completed.
- the present invention provides a compound represented by the following general formula (I-1).
- A represents an atomic group capable of absorbing ultraviolet light
- B represents a photoleaving group
- k represents an integer of 1 to 10
- the present invention also provides a latent UV absorber comprising the compound represented by the above general formula (I-1).
- the present invention also provides a composition comprising the compound represented by the above general formula (I-1).
- the present invention also provides a cured product of a composition comprising a compound represented by the above general formula (I-1) and a polymerizable compound.
- a composition containing the compound represented by the general formula (I-1) and a polymerizable compound is cured to form a cured product, and the cured product is irradiated with light. And a step of removing the photoleaving group contained in the compound represented by the general formula (I-1).
- the present invention also relates to a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound And B) (hereinafter, may be referred to as “second composition”).
- compound I-2 a compound represented by the following general formula (I-2)
- compound And B a leaving substance derived from a photoleaving group
- A represents an atomic group having an ultraviolet absorbing ability
- k represents an integer of 1 to 10.
- the present invention relates to a compound and a UV absorber using the same, a composition, a cured product thereof, a method for producing a cured product, and a second composition. These will be described in detail below.
- the compound of the present invention is represented by the following general formula (I-1) (hereinafter, the compound of the present invention is also referred to as compound I-1).
- A is an atomic group having an ultraviolet absorbing ability
- B is a photoleaving group
- k is an integer of 1 to 10
- the atomic group A has an ultraviolet absorbing ability.
- the compound I-1 of the present invention has a low ultraviolet absorbing ability before the elimination of the photoleaving group B, but exhibits an excellent ultraviolet absorbing ability based on the atomic group A after the elimination of the photoleaving group B. Therefore, when the compound I-1 before elimination of the photoleaving group B is added, for example, into the polymerization system, the compound I-1 has a low ability to absorb ultraviolet light, so absorption of light irradiated for polymerization is caused. Performance is low and it is difficult to inhibit the curing of the polymerization system.
- the compound I-1 of the present invention when the compound I-1 of the present invention is irradiated with light, the photoleaving group is released and exhibits excellent ultraviolet absorbing ability. Therefore, by irradiating the cured product containing compound I-1 with light, the cured product can be easily imparted with ultraviolet absorbing ability.
- the compound I-1 has the advantage of being less likely to cause damage to the cured product and its peripheral members such as the base material, since the compound I-1 does not need to be heat-treated to develop its ultraviolet absorbing ability. For the above reasons, the compound I-1 has, for example, little inhibition of curing, and can easily impart ultraviolet light absorbing ability and the like to a cured product.
- the compound I-1 of the present invention has a low ability to absorb light irradiated for the development of photosensitivity before desorption of the photoleaving group B. Therefore, when the compound I-1 is added to a photosensitive composition whose solubility in an alkali developer changes by light irradiation, it is possible to stably exhibit photosensitivity.
- the compound I-1 can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition by carrying out light irradiation capable of releasing the light leaving group. As described above, the compound I-1 has less inhibition of expression of photosensitivity with respect to the photosensitive composition, and can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition.
- the compound I-1 of the present invention can easily adjust, for example, the dispersion or dissolution stability in the composition by having a photoleaving group B.
- the compound I-1 can impart excellent dispersibility in the composition by selecting the photoleaving group B such that the affinity with other components contained in the composition is improved. Therefore, the compound I-1 can impart excellent ultraviolet light absorbing ability to the composition, and can also impart excellent dispersion stability during storage before use.
- the compound I-1 of the present invention has a photoleaving group B.
- the photoleaving group in the present invention can be a group which can be eliminated from compound I-1 by being irradiated with light of a specific wavelength.
- the photoleaving group B is eliminated from compound I-1, and an atomic group having a hydroxyl group and an ultraviolet light absorbing ability, represented by the following general formula (I-2) A compound having A is formed.
- A represents an atomic group capable of absorbing ultraviolet light
- k represents an integer of 1 to 10
- the wavelength of the light from which the photoleaving group B leaves the compound I-1 is, for example, the wavelength range of ultraviolet light or visible light. Specifically, the wavelength of 365 nm can be included, more specifically, the light of wavelength of 250 nm or more and 450 nm or less can be included, and preferably, the light of wavelength of 280 nm or more and 380 nm or less can be included. Can.
- Integrated light quantity of the light irradiated to detach the light leaving group B from above Compound I-1 for example, be a 1000 mJ / cm 2 or more 10000 mJ / cm 2 or less, 1000 mJ / cm 2 or more 5000mJ / Cm 2 or less is preferable, and 2000 mJ / cm 2 or more and 4000 mJ / cm 2 or less is more preferable.
- the integrated light quantity of the light irradiated for curing the composition containing the polymerizable compound etc. can be usually less than 1000 mJ / cm 2 . Therefore, when the integrated light amount is in the above-mentioned range, for example, application to a photocurable composition becomes easy.
- the elimination of the photoleaving group B may be any one capable of imparting a desired ultraviolet absorbing ability, and for example, the elimination rate of the photoleaving group can be 50% or more, Especially, it is preferable that it becomes 80% or more. It is because application to a photocurable composition becomes easy.
- the compound I-1 may have an integrated light quantity that suppresses photodetachment as long as a desired curing inhibition suppressing effect can be obtained, and can be less than 1000 mJ / cm 2 . It is because application to a photocurable composition becomes easy. Further, to suppress photodetachment may be any as long as a desired curing inhibition inhibitory effect can be obtained.
- the desorption rate of the photoleaving group B can be less than 50%. Especially, it is preferable that it becomes 20% or less. It is because application to a photocurable composition becomes easy.
- the integrated light quantity can be measured by preparing a 0.01% by mass acetonitrile solution of compound I-1 and using the same method as the method of measuring the desorption rate described in the examples.
- the photoleaving group B satisfying the above requirements is represented by the following general formulas (B-1), (B-2), (B-3), (B-4), (B-5) And groups represented by (B-6), (B-7) and (B-8).
- the following general formulas (B-1-a), (B-2-a), (B-3-a), (B-4), (B-5), (B-6), (B) -7-a), (B-7-b) and (B-8-a) are preferable, and a group represented by the following general formula (B-1-a) Is preferred.
- the compound I-1 can be easily released and the cured product can be easily imparted with ultraviolet light absorbing ability and the like.
- groups represented by the following general formulas (B-9) and (B-10) can also be mentioned.
- R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group
- R 12, R 14, R 17 , R 21, R 22, R 24, R 25, R 27, R 29 and R 30 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl A group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-
- each of R 31 and R 40 independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon Represents an arylalkyl group having 7 to 20 atoms or a heterocycle-containing group having 2 to 20 carbon atoms
- R 32 , R 33 , R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
- alkyl group having 1 to 40 carbon atoms represented by (C) there are methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, iso-butyl group.
- amyl group iso-amyl group, tert-amyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, 4-methylcyclohexyl group, heptyl group, 2 Heptyl, 3-heptyl group, iso- heptyl, tert- heptyl, 1-octyl group, iso- octyl group, and a tert- octyl group and adamantyl group.
- Examples of the aryl group having 6 to 20 carbon atoms represented by R 11 and the like include a phenyl group, a naphthyl group and an anthracenyl group.
- Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 11 and the like include a benzyl group, a fluorenyl group, an indenyl group and a 9-fluorenylmethyl group.
- heterocycle-containing group having 2 to 20 carbon atoms represented by R 11 and the like described above examples include, for example, pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group , Isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group , Isothiazolyl group, isoxazolyl group, indolyl group, 2-pyrrolidinone-1-yl group, 2-piperidone-1-yl group, 2,4-di
- Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ include those exemplified for the alkyl group represented by R 11 and the like, and those having 1 to 8 carbon atoms.
- the alkyl group, the aryl group, the arylalkyl group and the heterocyclic group may have a substituent.
- the compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.
- Examples of the substituent which may substitute a hydrogen atom such as an alkyl group, an aryl group, an arylalkyl group and a heterocycle-containing group include, for example, ethylenic unsaturated groups such as a vinyl group, an allyl group, an acryl group and a methacryl group; Halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl group, 2-chloroacetyl group, propionyl group, octanoyl group, acryloyl group, methacryloyl group, phenylcarbonyl (benzoyl) group, phthaloyl group, 4-trifluoromethylbenzoyl group
- acyl groups such as pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadec
- the number of carbon atoms of the group defines the number of carbon atoms of the group after the substitution.
- the term "C1 to 40 carbon atoms” refers to the number of carbon atoms after the hydrogen atom has been substituted, and the hydrogen atom is substituted Does not refer to the number of carbon atoms before the
- the number of carbon atoms of the group defines the number of carbon atoms of the group after the replacement.
- the “1 to 40 carbon atoms” means a group after a methylene group is replaced. It does not refer to the number of carbon atoms before the methylene group is replaced.
- “—CO—O—C 39 H 79 ” corresponds to “an alkyl group having 40 carbon atoms in which the terminal methylene group is replaced by —CO—O—”.
- the combination which substitutes the said methylene group can be made into the combination on the conditions which oxygen atom does not adjoin.
- the terminal methylene group on the proximal side may be replaced by -O- to form an alkoxy group.
- an alkoxy group for example, an alkoxy group having 1 to 10 carbon atoms can be mentioned.
- Each of R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a nitro group or a carboxyl group It is preferably an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or the like.
- the photoleaving group B is easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.
- R 11 and R 23 are particularly preferably an alkoxy group having 1 to 10 carbon atoms such as a nitro group or a methoxy group, an alkyl group having 1 to 40 carbon atoms such as a methyl group, a halogen atom or the like. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
- R 11 is preferably an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen atom, and an alkoxy group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms It is more preferably an alkyl group or a halogen atom, still more preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and it is an alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom Particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
- the R 13 , R 18 , R 19 , R 20 , R 26 and R 28 are preferably an alkyl group having 1 to 40 carbon atoms. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
- R 16 it is preferable that two adjacent R 16 's combine with each other to form a benzene ring. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
- R 31 and R 40 each is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, the number of carbon atoms
- the arylalkyl group is preferably 7 to 20, or a heterocycle-containing group having 2 to 20 carbon atoms.
- R 31 is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
- -O- replacing the methylene group is such that the alkyl group and the arylalkyl group are interrupted respectively In other words, it may be substituted by a methylene group other than the ends of the alkyl group and the arylalkyl group.
- R 12 is preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
- R 14 , R 17 , R 21 , R 24 , R 25 , R 27 , R 29 and R 30 are preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and a hydrogen atom Being particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
- R 15 and R 22 are preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
- Each of R 32 and R 33 independently is preferably a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
- R 41 to R 44 are preferably each independently a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and it is a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
- the above b 1, b 2, b 3, b 6, b 7, b 8 and b 9 can be each independently an integer of 0 to 4 but preferably an integer of 0 to 3 from the viewpoint of easiness of synthesis, It is more preferably an integer of 0 to 2, still more preferably 0 to 1, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
- the above b 4 and b 5 can be each independently an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3 and more preferably an integer of 0 to 2 Preferably, it is 0 to 1, more preferably 0.
- the above c1 can be an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 It is more preferable that it is an integer of, and it is particularly preferable that it is 1. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
- the above c 2 can be an integer of 0 to 4, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 More preferably, it is an integer of 0, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
- the type of photoleaving group B contained in compound I-1 of the present invention may be one type per compound I-1, and may be two or more types. From the viewpoint of facilitating the synthesis of the compound I-1, it is preferable to use one type, since curing inhibition is small, ultraviolet absorptivity and the like can be easily given to the cured product, and the compound I-1 can be easily synthesized.
- the content number k of the photoleaving group is an integer of 1 to 10, the curing inhibition is small, and the cured product can be easily imparted with ultraviolet light absorbing ability and the like, and from the viewpoint of easiness of synthesis, It is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.
- Atomic group A having ultraviolet absorbing ability The atomic group A is an atomic group having an ultraviolet absorbing ability.
- the compound I-1 of the present invention is irradiated with light of a specific wavelength, whereby the photoleaving group B is eliminated to produce a compound I-2 having a hydroxyl group. And, when the atomic group A has an ultraviolet absorbing ability, the compound I-2 exhibits an ultraviolet absorbing ability.
- the phrase "having ultraviolet absorbing ability" means, for example, a compound having ultraviolet absorbing ability, specifically, compound I-1 after elimination of photoleaving group B, ie, compound I-2, having a wavelength of 250 nm or more It can be capable of absorbing light in the range of 450 nm or less.
- the atomic group having ultraviolet absorbing ability can be a group of atoms having at least one group having ultraviolet absorbing ability or at least one group having ultraviolet absorbing ability. More specifically, the compound I-1 after elimination of the photoleaving group B, that is, the compound I-2, has a maximum absorption wavelength within the wavelength range of 250 nm to 600 nm.
- It is preferably capable of absorbing light having a wavelength of 250 nm to 400 nm and capable of absorbing light having a maximum absorption wavelength of 260 nm to 390 nm, and particularly preferably absorbing a light having a maximum absorption wavelength of 280 nm to 380 nm. .
- the maximum absorption wavelength of the compound I-1 after removal of the photoleaving group B, ie, the compound I-2 can be measured, for example, by the following measurement method.
- a compound I-1 after elimination of the photoleaving group B that is, a compound I-2 dissolved in a solvent (acetonitrile) to a concentration of 0.01% by mass
- a solvent acetonitrile
- the evaluation sample is filled in a quartz cell (optical path length 10 mm, thickness 1.25 mm), and obtained by measuring the absorbance using an absorptiometer (for example, U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.)) Can.
- the compound I-1 of the present invention is a compound I-1 (compound I-2) after the elimination of the photoleaving group B and the maximum absorption wavelength of the compound I-1 before the elimination of the photoleaving group B.
- the maximum absorption wavelength of compound I-1 before elimination of photoleaving group B is shorter than the maximum absorption wavelength of compound I-2 in the range of 250 nm to 600 nm when the maximum absorption wavelength of Is preferred. It is because application to a photocurable composition becomes easy.
- the difference in the maximum absorption wavelength of the compound I-1 with the compound I-2 after elimination of the photoleaving group B is preferably 1 nm or more, and more preferably 1 nm to 100 nm. It is particularly preferable to be 1 nm or more and 50 nm or less. It is because application to a photocurable composition becomes easy.
- Such atomic group A can be the same as the atomic group generally used for a UV absorber having a phenolic hydroxyl group. That is, the compound I-2 is generally used as a UV absorber having a phenolic hydroxyl group.
- the compound I-2 2-hydroxybenzophenones, 2- (2'-hydroxyphenyl) benzotriazoles, benzoates and triaryltriazines described in JP-A-2017-008221, etc.
- benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers described in JP-A-2002-97224 can be used.
- Examples of the atomic group A include a phenol structure in which a phenolic hydroxyl group is protected by a photoleaving group B, that is, one containing a benzene ring to which the B-O- is directly bonded.
- a photoleaving group B that is, one containing a benzene ring to which the B-O- is directly bonded.
- an atomic group containing a benzene ring and a benzotriazole ring to which B-O- is directly bonded an atomic group containing a benzophenone ring to which B-O- is directly bonded
- benzene to which B-O- is directly bonded Mention may be made of atomic groups comprising a ring and a triazine ring.
- At least one group of a benzotriazole group, a benzophenone group and a triazine group includes a structure directly bonded to a benzene ring contained in the above-mentioned phenol structure, and among them, a benzotriazole group, a benzophenone group and triazine group It is preferable that the bonding position of at least one group of the group to the benzene ring is ortho to the bonding position of B-O-. It is because it is easy to set it as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened
- Examples of the compound I-1 of the present invention include those represented by the following general formulas (A-1), (A-2) and (A-3).
- R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl having 6 to 20 carbon atoms A group, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or the above -O-B
- At least one of R 1 and R 2 is the above-mentioned -O-B
- R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, the number of carbon atoms
- n and m2 each independently represent an integer of 1 to 10, n represents an integer of 1 to 3; a1 represents an integer of 0 to 4; a2 represents an integer of 0 to 2; a3 represents an integer of 0 to 4; a4 represents an integer of 0 to 3; a5 represents an integer of 0 to 3; a6 represents an integer of 0 to 3-n, X 1 and X 2 each represent an m1 monovalent or m2 divalent linking group.
- Examples of the arylalkyl group having 7 to 20 carbons, a heterocycle-containing group having 2 to 20 carbons, and the alkyl group having 1 to 8 carbons represented by R ′ include the above-mentioned “1. And those exemplified as R 11 etc. and R ′ described in the above section can be mentioned.
- At least one of R 1 and R 2 is -O-B. From the viewpoint of easiness of synthesis, it is preferable that one of the R 1 and R 2 be the above-described —O—B. From the viewpoint of making the change of the ultraviolet ray absorbing ability large, in the above R 1 and R 2 , it is preferable that both R 1 and R 2 be the above-described —O—B.
- R 1 and R 2 each represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carbon atom, when only one is the above —O—B It is preferably an arylalkyl group having 7 to 20 atoms or a heterocyclic group having 2 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms.
- the compound I-1 has a large change in the ultraviolet light absorbing ability.
- the compound I-1 has a reduced inhibition of curing.
- the above-mentioned alkyl group and arylalkyl group for example, those in which a methylene group is interrupted by -O-, -CO- or the like can be preferably used.
- R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are preferably a cyano group, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms More preferably a cyano group, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms, and more preferably an alkyl group having 3 to 20 carbon atoms.
- the alkyl group is preferably an alkyl group having 3 to 10 carbon atoms. This is because the synthesis of the compound I-1 of the present invention is facilitated, and the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
- R 4 is preferably an alkyl group having a branched structure of 3 to 15 carbon atoms, An alkyl group having a branched structure of 5 to 12 is more preferable, an alkyl group having a branched structure of 6 to 11 carbon atoms is still more preferable, and an alkyl having a branched structure of 7 to 10 carbon atoms Particularly preferred is a group.
- the bonding site in the benzene ring of R 4 may be bonded to any bondable position, but is preferably para to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
- R 5 and R 6 each have 1 to 10 carbon atoms in which the methylene group at the benzene ring side terminal is replaced by -O- 20 alkyl groups, that is, alkoxy groups having 1 to 20 carbon atoms are preferable, and alkoxy groups having 3 to 15 carbon atoms are particularly preferable, and alkoxy groups having 5 to 12 carbon atoms are preferable. Being particularly preferred.
- the bonding site in the benzene ring of R 5 and R 6 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. . This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
- R 7 is an alkyl having 1 to 20 carbon atoms in which the methylene group at the terminal of the benzene ring is replaced by -O- Group, that is, an alkoxy group having 1 to 20 carbon atoms is preferable, and in particular, a methylene chain other than the benzene ring side terminal is substituted by -O- or -O-CO-, having 3 to carbon atoms 20 alkoxy groups are preferable, and particularly, an alkoxy group having 3 to 15 carbon atoms in which a methylene chain other than the benzene ring side terminal is replaced by -O- or -O-CO- is particularly preferable, in particular And an alkoxy group having 6 to 15 carbon atoms in which a methylene chain other than the benzene ring side end is replaced by -O- or -O-CO-, and in particular, a methylene chain other than
- the bonding site in the benzene ring of R 7 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
- R8 is preferably an aryl group having 6 to 20 carbon atoms from the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of the photoleaving group B, and in particular, it is possible to use 6 to 12 carbon atoms.
- the aryl group is preferably an aryl group, and particularly preferably a phenyl group which may have a substituent.
- any of those in which a methylene group is not interrupted, and those in which it is interrupted by -O-, -CO- or the like can be preferably used.
- m1 and m2 represent an integer of 1 to 10.
- m1 and m2 are preferably each independently an integer of 1 to 6, more preferably an integer of 1 to 4, and an integer of 1 to 3 It is particularly preferable, and in particular, an integer of 1 to 2 is particularly preferable. This is because the synthesis of the compound I-1 is facilitated, and the compound I-1 exhibits an excellent ultraviolet absorbing ability after the elimination of the photoleaving group B. Further, from the viewpoint of the compound I-1 exerting an excellent ultraviolet absorbing ability after elimination of the photoleaving group B, m2 is preferably an integer of 1.
- the above n represents an integer of 1 to 3.
- the above n is preferably an integer of 2 to 3, and particularly preferably 3, from the viewpoint that the compound I-1 has a large change in the ultraviolet light absorbing ability.
- the compound n is preferably an integer of 1 to 2, and particularly preferably 1.
- the above a1 and a3 each independently represent an integer of 0 to 4. From the viewpoint of easiness of synthesis, the above a1 and a3 are preferably each independently an integer of 0 to 3, more preferably an integer of 0 to 2, and an integer of 0 to 1 Particularly preferred. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
- the above a2 represents an integer of an integer of 0 to 2. From the viewpoint of solubility, the a2 is preferably an integer of 1 to 2. Further, from the viewpoint of exhibiting excellent ultraviolet absorbing ability after the compound I-1 exhibits the elimination of the photoleaving group B, the a2 is preferably 1.
- the above a4 and a5 each independently represent an integer of 0 to 3. From the viewpoint of easiness of synthesis, the above a4 and a5 are preferably an integer of 0 to 2, particularly preferably an integer of 1 to 2, and particularly preferably 1. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
- the above a6 represents an integer of 0 to 3-n.
- the above a6 is preferably an integer of 0 to 1, and is 0, from the viewpoint that compound I-1 exerts an excellent ultraviolet absorptivity after removal of photoleaving group B and easiness of synthesis. Is preferred.
- the compounds I-1 represented by the above general formulas (A-1) and (A-2) are each represented by X 1 and X 2 (hereinafter sometimes referred to as X) an m monovalent or m divalent
- X an m monovalent or m divalent
- m an m monovalent or m divalent
- m an m monovalent or m divalent
- m m1 or m2 (hereinafter sometimes referred to as m) specific groups are bonded to a specific atom or group which may be referred to as m-valent).
- the m specific groups may be identical to one another or may be different.
- the above X represents an m-valent bonding group.
- the bonding group X is a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following (II-a) or (II-b),> C OO,> NR 53 , -OR 53 , -SR 53 , -NR 53 R 54 or an aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same number of valences as m, an aromatic having 6 to 35 carbon atoms
- R 53 and R 54 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, or the number of carbon atoms.
- an aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic group having 2 to 35 carbon atoms wherein the aliphatic hydrocarbon group, the aromatic ring containing hydrocarbon group and the heterocyclic group are -O-,- S-, -CO-, -O-CO-, -CO-O-, -O-CO-O- -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH -CO-O -, - NH- CO-O -, - NR '-, - S-S -, - SO 2 -, nitrogen atom or may have been interrupted in these combinations, the aromatic or heterocyclic
- the ring may be fused to another ring.
- the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is, for example, a methyl group, an ethyl group or a propyl group, as m is a monovalent group.
- the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m which is represented by the above linking group X, is a methylene group, an ethylene group, a propylene group, a butylene group as the one where m is divalent And alkylene groups such as butyldiyl group; those in which the methylene chain of the above alkylene group is replaced with -O-, -S-, -CO-O-, -O-CO-; ethanediol, propanediol, butanediol, Residues of diol groups such as pentanediol and hexanediol; Residues of dithiol groups such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol and the like, and groups in which these groups are substitute
- the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the above linking group X, is, for example, a propyridine group and 1,1, Alkylidine groups such as 3-butylidine propyridine group; and groups in which these groups are substituted by a substituent described later.
- the aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the above linking group X, is, for example, a benzyl group, a phenethyl group or diphenylmethyl when m is monovalent
- Arylalkyl groups such as triphenylmethyl group, styryl group and cinnamyl group; aryl groups such as phenyl group and naphthyl group; aryloxy groups such as phenoxy group and naphthyloxy group; arylthio groups such as phenylthio group and naphthylthio group:
- the group etc. by which these groups were substituted by the substituent mentioned later are mentioned.
- the aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the bonding group X, is an arylene group such as a phenylene group and a naphthylene group when m is divalent.
- arylene group such as a phenylene group and a naphthylene group when m is divalent.
- residues of bifunctional phenol groups such as catechol groups and bisphenol groups
- 2,4,8,10-tetraoxaspiro [5,5] undecane groups and groups in which these groups are substituted by substituents described later Can be mentioned.
- the aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the above linking group X, is not particularly limited as m is trivalent: phenyl-1,3,5- A trimethylene group and a group in which this group is substituted by a substituent described later can be mentioned.
- the heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a pyridyl group, a pyrimidyl group, a pyridazyl group, a piperidyl group as the one in which m is monovalent , Pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group, isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group , Thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, isothiazolyl group, isoxazolyl group, indolyl group
- the heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring as the m is divalent And a divalent group having a triazine ring, a furan ring, a thiophene ring, an indole ring and the like, and a group in which these groups are substituted by a substituent described later.
- the hetero ring-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a trivalent group having an isocyanuric ring, a triazine ring, as m is trivalent. And groups in which these groups are substituted by the substituents described later.
- the aliphatic hydrocarbon group represented by said X or this aliphatic hydrocarbon group is substituted by the substituent mentioned later Among the above groups, those having 1 to 35 carbon atoms can be mentioned.
- the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by R 53 and R 54 has 6 to 35 carbon atoms represented by X above. Examples thereof include an aromatic ring-containing hydrocarbon group, a heterocyclic ring-containing group having 2 to 35 carbon atoms, or a group in which these groups are substituted by a substituent described later.
- Each functional group such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group-containing group may have a substituent.
- the compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.
- Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. It can be mentioned.
- X may represent a group represented by the following general formula (1).
- Y 1 represents a single bond, -CR 55 R 56 -, - NR 57 -, a divalent aliphatic hydrocarbon group having a carbon number of 1 to 35, divalent carbon atoms 6 to 35 aromatic ring-containing hydrocarbon group, divalent heterocyclic group having 2 to 35 carbon atoms, or any group represented by the following (1-1) to (1-3)
- the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms are -O-, -S-, -CO-, -COO- And -OCO- or -NH- or combinations thereof may be interrupted
- R 55 and R 56 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms
- Z 1 and Z 2 are each independently represent a
- R 59 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent
- R 60 represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or a halogen atom
- c1 represents an integer of 0 to 5
- the * means that at the * part, it bonds to an adjacent group.
- R 61 and R 62 each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or the like An arylthio group of 6 to 20, an arylalkenyl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heterocycle-containing group of 2 to 20 carbon atoms, or a halogen atom;
- the methylene group in the arylalkyl group may be replaced by an unsaturated bond, -O- or -S-, R 61 may form a ring between adjacent R 61 in some cases, c2 represents a number from 0 to 4; c3 represents a number from 0 to 8, c4 represents a number from 0 to 4; c5 represents a number from 0 to 4;
- the sum of the numbers of c4 and c5 is 2 to 4,
- Y 11 is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms Represents an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms
- Z 1 , Z 2 and Z 3 are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO 2- , -SS-,- SO—,> NR 62 , PR 62 , an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms
- R 62 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to
- Y 12 represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or Represents an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms;
- -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- may be interrupted, and Z 1 to Z 4 each independently represent the general formula (2) Represents a group in the same range as the group represented by Z 1 to Z 3 in
- Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent aromatic ring-containing hydrocarbon group having 6 to 30 carbon atoms, or pentavalent carbon And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms represented by the formula: -COO- And Z 1 to Z 5 may each independently be Z 1 to Z 1 in the above general formula (2), which may be interrupted by —O—, —OCO—, —NHCO—, —NH— or Represents the same group as the group represented by Z 3 )
- Y 14 is a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent aromatic ring containing hydrocarbon group having 6 to 35 carbon atoms, or And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, In some cases, it may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and each of Z 1 to Z 6 is independently represented by the above general formula (7) Represents the same group as the groups represented by Z 1 to Z 3 )
- Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 1 in the group represented by the above general formula (1) include methane, ethane, propane, iso-propane, butane, sec- Butane, tert-butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane And tert-octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like, and divalent groups substituted with Z 1 and Z 2 .
- These groups may be interrupted by —O—, —S
- Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y 1 in the group represented by the above general formula (1) include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, and hexa Hydrotriazines, furans, tetrahydrofurans, chromans, xanthenes, thiophenes, thiolanes and the like include divalent groups substituted by Z 1 and Z 2 .
- the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocycle-containing group represented by Y 1 in the group represented by the above general formula (1) have a halogen atom, a cyano group, a nitro group or one carbon atom It may be substituted with an alkoxy group of -8.
- Each functional group such as the above aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise specified, has a substituent. Not substituted or substituted.
- Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. .
- the alkyl group having 1 to 8 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s- group Butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl Groups, 3-heptyl group, isoheptyl group, t-heptyl group, 1-octyl group, isooctyl group, t-octyl group and the like.
- the aryl group having 6 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a phenyl group, a naphthyl group, a 2-methylphenyl group and a 3-methylphenyl group , 4-methylphenyl group, 4-vinylphenyl group, 3-iso-propylphenyl group, 4-iso-propylphenyl group, 4-butylphenyl group, 4-iso-butylphenyl group, 4-tert-butylphenyl group , 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethyl Phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-
- the arylalkyl group having 7 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, And diphenylmethyl group, triphenylmethyl group, styryl, cinnamyl and the like.
- Examples of the heterocycle-containing group of the formulas 2 to 35 may be the same as those exemplified as R 53 and R 54 .
- the cycloalkyl group having 3 to 10 carbon atoms represented by R 59 in the group represented by the above general formula (1-1) is a cyclopropyl group, cyclobutyl group, cyclopentyl group, cycloheptyl group, cyclo Examples thereof include an octyl group and the like, and a group in which these groups are substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
- Examples of the alkyl group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) include R 11 and the like in the above “1.
- Photoleaving group B” Among the exemplified alkyl groups, those having 1 to 10 carbon atoms can be mentioned.
- the alkoxy group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) is exemplified by R 11 and the like in the above “1.
- Photoleaving group B” Among the exemplified alkoxy groups, those having 1 to 10 carbon atoms can be mentioned.
- alkenyl group having 2 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, 2- Examples include butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-octenyl and the like.
- the alkyl group, alkoxy group and alkenyl group represented by R 60 may be substituted with a halogen atom, and the position of substitution is not limited.
- an alkyl group having 1 to 10 carbon atoms represented by R 61 and R 62 an alkyl group having 6 to 20 carbon atoms, and 7 to carbon atoms
- Examples of the arylalkyl group of 20 include those exemplified as R 11 and the like in the above-mentioned section “1.
- Photoleaving group B those having a predetermined number of carbon atoms.
- the arylalkenyl group having 8 to 20 carbon atoms represented by R 61 and R 62 in the group represented by the above general formula (1-3) is a carbon atom which may be substituted by the above halogen atom Groups in which the oxygen atom of the aryloxy group of formulas 6 to 20 is substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc. It can be mentioned.
- the heterocyclic group containing 2 to 20 carbon atoms represented by R 61 and R 62 in the group represented by the above general formula (1-3) includes a pyridine group, a pyrazine group, a piperidine group, a piperazine group, A pyrimidine group, a pyridazine group, a triazine group, a hexahydro triazine group, a furan group, a tetrahydrofuran group, a chromane group, a xanthene group, a thiophene group and a thiofuran group, and groups in which these groups are substituted with a halogen atom are listed.
- Each functional group in the group represented by the above general formula (1-3), such as aryloxy group, arylthio group, arylalkenyl group, heterocycle-containing group, represented by R 61 and R 62 has a substituent. And, unless otherwise specified, they are unsubstituted ones having no substituent or ones having a substituent.
- the substituent that substitutes a hydrogen atom such as an aryloxy group, an arylthio group, an arylalkenyl group, and a heterocycle-containing group has the same content as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. be able to.
- Examples of the trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms represented by Y 11 in the group represented by the above general formula (2) include the fats exemplified in the explanation of X in the above general formula (1)
- Group hydrocarbon group is substituted by Z 1 , Z 2 and Z 3 , and these groups include -O-, -S-, -CO-, -CO-O-,- O-CO-, -SO 2- , -NH- or a combination thereof may be substituted.
- the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 11 in the group represented by the general formula (2) is exemplified in the description of X in the general formula (1) Examples thereof include trivalent groups in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 and Z 3 .
- Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y 11 in the group represented by the above general formula (2) include the heterocycles exemplified in the description of X in the above general formula (1)
- Examples include trivalent groups in which the containing group is substituted with Z 1 , Z 2 and Z 3 .
- Examples of the hydrocarbon group or the heterocycle-containing group having 2 to 35 carbon atoms can include the same ones as those exemplified as R 53 and R 54 described above.
- Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms having a tetravalent carbon atom represented by Y 12 in the group represented by the general formula (3) include the fats exemplified in the description of X in the general formula (1)
- Group hydrocarbon group is substituted by Z 1 , Z 2 , Z 3 and Z 4 and examples thereof include -O-, -S-, -CO-, -COO-, -OCO-,- It may be interrupted by NH-or a combination of these.
- the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 12 in the group represented by the above general formula (3) is exemplified in the description of X in the above general formula (1)
- a tetravalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 , Z 3 and Z 4 can be mentioned.
- Examples of the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by Y 12 in the group represented by the general formula (3) include the heterocyclic rings exemplified in the description of X in the general formula (1). Examples include tetravalent groups in which the containing group is substituted by Z 1 , Z 2 , Z 3 and Z 4 .
- Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the group represented by the above general formula (4) include the fats exemplified in the explanation of X in the above general formula (1)
- Group hydrocarbon group is substituted by Z 1 , Z 2 , Z 3 , Z 4 and Z 5 and examples thereof include -O-, -S-, -CO-, -CO-O-, It may be replaced by a group of -O-CO-, -SO 2- , -NH- or a combination thereof.
- the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 13 in the group represented by the general formula (4) is exemplified in the description of X in the general formula (1)
- a pentavalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 can be mentioned.
- Examples of the pentavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 13 in the group represented by the general formula (4) include the heterocycles exemplified in the description of X in the general formula (1) containing groups include pentavalent group substituted with Z 1, Z 2, Z 3 , Z 4 and Z 5.
- Examples of the aliphatic hydrocarbon group having 2 to 35 carbon atoms which is represented by Y 14 in the general formula (5) include the aliphatic hydrocarbon groups exemplified in the description of X in the general formula (1). And a hexavalent group substituted by Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 , and the groups include -O-, -S-, -CO-, -COO-,- It may be interrupted by OCO-, -SO 2- , -NH- or a combination thereof.
- Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms having a hexavalent carbon atom represented by Y 14 in the general formula (5) include the aromatic ring-containing hydrocarbons exemplified in the description of X in the general formula (1)
- a hexavalent group in which a group is substituted by Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 can be mentioned.
- Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) include the heterocyclic groups exemplified in the description of X in the general formula (1) as Z And hexavalent groups substituted with 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
- the bonding group X is preferably an aliphatic hydrocarbon group having 1 to 120 carbon atoms, more preferably an alkylene group or a residue of a diol, and having 1 to 12 carbon atoms.
- an alkylene group of 10 or a diol residue of 1 to 10 carbon atoms is preferable, and an alkylene group of 1 to 5 carbon atoms or a diol residue of 1 to 5 carbon atoms is particularly preferable.
- an alkylene group having 1 to 3 carbon atoms is preferable. This is because the compound can be made to be a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product, and furthermore, the production of the compound I-1 is easy.
- the bonding position of the bonding group X to the benzene ring may be any position in the benzene ring that can be bonded, but for example, the ortho position or the meta position with respect to R 2 is preferable. It is because it can be set as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened
- the above atomic group A may be one containing a phenolic hydroxyl group, that is, one in which the compound I-1 contains a phenolic hydroxyl group not protected by the photoleaving group B, but the number of phenolic hydroxyl groups is 2 The number is preferably not more than one, more preferably zero. This is because the compound I-1 has less inhibition of curing.
- Compound The compound of the present invention may be any compound represented by the above general formula (I-1), but is represented by the above general formula (A-1), (A-2) or (A-3) It is preferably a compound, and as the photoleaving group B, one represented by the above general formula (B-1-a) is preferable. It is because synthesis is easy, and furthermore, photodetachment is easy. Moreover, it is because an ultraviolet absorptivity etc. can be easily provided with respect to hardened
- the molecular weight of the compound I-1 can be set according to the use of the compound I-1.
- the molecular weight of the compound I-1 is, for example, preferably 250 or more and 5000 or less, more preferably 300 or more and 2500 or less, and particularly preferably 350 or more and 1500 or less. It is because it can be set as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened
- the molecular weight of the compound I-1 is represented by weight average molecular weight (Mw) when the compound I-1 is a polymer having a repeating structure as its structure.
- the weight average molecular weight (Mw) can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
- the weight average molecular weight Mw is, for example, HLC-8120 GPC manufactured by Tosoh Corp., and the elution solvent is N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide is added, and the polystyrene standard for calibration curve is Mw 377400 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh Corp.), and the measurement column is TSK-GEL ALPHA- It can be obtained by measurement as M ⁇ 2 (made by Tosoh Corp.). Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.
- the method for producing the compound I-1 is not particularly limited as long as it can obtain a desired structure, and, for example, JP-A-57-111375, JP-A-3-173843 and JP-A-6- It is obtained by reacting an alkyl halide compound with a phenolic compound produced by the method described in Japanese Patent Application Laid-Open No. 128195, Japanese Patent Application Laid-Open No. 7-206771, Japanese Patent Application Laid-Open No. 7-252191 or Japanese Patent Application Laid-Open No. Can.
- the compound I-1 is inactive before light irradiation, and the light leaving group is eliminated by light irradiation to generate a compound I-2 having a phenolic hydroxyl group. Further, the compound I-2 exhibits ultraviolet absorbing ability.
- the application of the compound I-1 is preferably an application that is required to exhibit an ultraviolet absorptivity by light irradiation. Can.
- the latent ultraviolet light absorber of the present invention comprises the compound I-1 of the present invention.
- the latent UV absorber of the present invention has less inhibition of curing and can easily impart ultraviolet absorptivity and the like to a cured product.
- the content of the compound I-1 in the latent ultraviolet absorber of the present invention is not particularly limited, and can be appropriately set according to the application of the latent ultraviolet absorber and the like.
- the latent ultraviolet absorber of the present invention comprises 100 parts by mass of the compound I-1 in 100 parts by mass of the latent ultraviolet absorber, that is, the latent ultraviolet absorber comprises only the compound I-1 It can be done.
- the latent ultraviolet absorber of the present invention may contain other components.
- the content of the compound I-1 may be, for example, more than 20 parts by mass and 99 parts by mass or less in 100 parts by mass of the latent ultraviolet absorber.
- the latent ultraviolet absorber has a small amount of inhibition of curing, and can effectively exhibit the effect of easily imparting ultraviolet absorptivity and the like to a cured product.
- the type of the compound I-1 contained in the latent ultraviolet absorber may be only one type or two or more types.
- the number of types can be, for example, 2 or more and 5 or less.
- the compound I-1 described above can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.
- the latent ultraviolet absorber preferably contains, as another component, a resin component such as a polymer having no polymerizable group. This is because the compound I-1 can be stably held.
- the shape of the latent ultraviolet absorber may be powdery, and may be pelletized.
- a method for producing the latent ultraviolet absorber for example, a method may be used in which the compound I-1 and the resin component are mixed using an extruder etc. it can.
- composition of the present invention comprises the compound I-1.
- composition of the present invention it is possible to provide, for example, a composition which has less inhibition of curing and which can provide an excellent cured product of ultraviolet absorption ability.
- each component of the said composition is demonstrated.
- the content of the compound I-1 in the composition of the present invention is not particularly limited as long as it is an amount capable of imparting a desired ultraviolet absorbing ability and the like to the composition.
- the content of the compound I-1 in the composition of the present invention can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the solid content of the composition, and 0.005 parts by mass or more and 10 parts by mass It is preferable that it is less than part. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened
- solid content contains all the components other than a solvent.
- the content is on a mass basis unless otherwise noted.
- the content of the compound I-1 varies depending on the content of the solvent and the like, and can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. And 0.005 parts by mass or more and 10 parts by mass or less. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened
- the type of the compound I-1 contained in the composition may be only one type or two or more types.
- the type can be, for example, two or more and five or less.
- the compound I-1 described above can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.
- the above composition may contain other components other than the above compound I-1 depending on its use and the like.
- the resin component is mentioned, for example. This is because, for example, when the composition of the present invention contains a resin component in addition to the compound I-1, curability and the like can be easily imparted to the above composition, for example.
- the composition of this invention contains a polymerization initiator with the said resin component as another component. By containing the resin component and the polymerization initiator as other components, the composition of the present invention can easily impart curability and the like to the composition.
- Resin component examples include those capable of holding the above-mentioned compound I-1, which may be appropriately set depending on the application etc. of the composition, for example, polymerizing having a polymerizable group The compound etc. and the polymer which does not have a polymeric group etc. can be mentioned.
- a polymerizable compound as the resin component, the composition can be used, for example, as a photocurable composition or a thermosetting composition.
- the polymerizable compound varies depending on the type of the polymerizable group, that is, the type of the polymerization reaction, and may be, for example, a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, etc. it can. It is preferable that the said polymeric compound contains a radically polymerizable compound from a viewpoint of demonstrating the effect that hardening inhibition decreases effectively.
- the radically polymerizable compound may have one or more radically polymerizable group and may contain two or more radically polymerizable group.
- the above-mentioned radical polymerizable compound is usually used together with a radical polymerization initiator.
- a radically polymerizable polymerizable group ethylenic unsaturated double bond groups, such as a (meth) acryl group and a vinyl group, can be mentioned, for example.
- (meth) acryl is used by the meaning containing an acryl and methacryl.
- (meth) acrylate is used in the meaning including acrylate and methacrylate.
- the radically polymerizable compound may be a compound having an acid value, or may be a compound having no acid value.
- a compound which has an acid value the compound etc. which have a carboxyl group can be mentioned, for example.
- the composition can be used, for example, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the above-mentioned composition can be used as a negative working composition by including a compound having an acid value.
- an alkali developing solution what is generally used as alkali developing solutions, such as tetramethyl ammonium hydroxide (TMAH) aqueous solution and potassium hydroxide aqueous solution, can be used.
- TMAH tetramethyl ammonium hydroxide
- the radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having an acid value, (meth) acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid 1) Mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends such as acryloyloxyethyl] and ⁇ -carboxypolycaprolactone mono (meth) acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth)
- X 41 represents a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO 2- , -SS- Or —SO—, —CO—, —OCO— or a substituent represented by (1-1) to (1-3) above, R 41 , R 42 , R 44 and R 44 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or Represents a halogen atom, d is an integer of 0 to 10; )
- Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms and the alkenyl group having 2 to 5 carbon atoms represented by R 41 , R 42 , R 44 and R 44 include the above-mentioned “A Among those exemplified as R 11 and the like in the item of “compound”, those satisfying a predetermined number of carbon atoms can be mentioned.
- Examples of the C 1-4 alkylidene group represented by X 41 include methylidene group, ethylidene group, propylidene group and butylidene group.
- Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by X 41 include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group and a cycloheptylene group.
- the above-mentioned alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group may have a substituent, and unless otherwise specified, it is an unsubstituted group having no substituent. Or a substituent.
- Examples of the substituent that substitutes a hydrogen atom of the alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group are the same as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. It can be content.
- the above-mentioned radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having no acid value, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl, glycidyl (meth) acrylate, the following compound No. 1 A1 to No.
- A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxye
- the said radically polymerizable compound can be used individually or in mixture of 2 or more types.
- the radically polymerizable compound has an ethylenically unsaturated double bond group, and uses a compound having an acid value and a compound having an ethylenically unsaturated double bond group and not having an acid value in combination.
- a radically polymerizable compound is used in mixture of 2 or more types, they may be copolymerized beforehand and it may be used as a copolymer.
- the content of the radically polymerizable compound can be appropriately set according to the application etc.
- the composition can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts It is preferable that it is a part or more and 90 mass parts or less, Especially, it is preferable that it is 40 mass parts or more and 80 mass parts or less.
- the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
- the content of the polymerizable compound may be any one as long as the composition can be used as a curable composition, but 1 part by mass or more to 99 parts in total of 100 parts by mass of the compound I-1 and the polymerizable compound. It can be made into parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and 90 parts by mass or more and 98 parts by mass or less Is preferred. When the content is in the above-mentioned range, the composition can provide a composition which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product.
- the content of the compound I-1 and the radically polymerizable compound can be appropriately set according to the application of the composition and the like, and for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition.
- the amount is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less.
- the composition can be used as a negative composition excellent in sensitivity.
- a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
- the cationic polymerizable compound may be one having one or more cationically polymerizable groups.
- the cationically polymerizable compound is usually used together with a cationic polymerization initiator.
- the cationically polymerizable polymerizable group include cyclic ether groups such as an epoxy group and an oxetane group, and a vinyl ether group. That is, as a cationically polymerizable compound, cyclic ether compounds, such as an epoxy compound and an oxetane compound, a vinyl ether compound, etc. are mentioned.
- Examples of the above epoxy compounds include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, phenyl 2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl Glycidyl
- an epoxidized polyolefin can also be used as said epoxy compound.
- the epoxidized polyolefin is a polyolefin in which an epoxy group is introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer, by any of a copolymerization method and a graft method. Ethylene or an ⁇ -olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer and another monomer may be polymerized alone or in combination with other monomers.
- the double bond of a non-conjugated polybutadiene having a hydroxyl group at the end can be obtained by epoxidation by the peracetic acid method, and one having a hydroxyl group in the molecule may be used.
- a hydroxyl group can be urethane-ized with isocyanate, and a primary hydroxyl group-containing epoxy compound can be made to react here, and an epoxy group can be introduce
- ethylene or ⁇ -olefins of 3 to 20 carbon atoms examples include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3 -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like can be mentioned.
- Examples of the epoxy group-containing monomer include glycidyl esters of ⁇ , ⁇ -unsaturated acids, vinyl benzyl glycidyl ether and allyl glycidyl ether.
- Specific examples of glycidyl esters of ⁇ , ⁇ -unsaturated acids include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid, with glycidyl methacrylate being particularly preferred.
- Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid ) Acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono (meth) acrylate, etc.
- unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene
- a commercial item can also be used as said epoxidized polyolefin,
- Epolide PB3600, Epolide PB4700 made by Daicel
- BF-1000, FC-3000 made by ADEKA
- Bond first 2C bond first E
- JP-100, JP-200 (Nippon Soda Co., Ltd.)
- Poly bd R And -45 HT Poly bd R-15 HT
- Ricon 657 manufactured by Arkema
- oxetane compounds examples include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1 , 6-Bis (3-ethyl-3-oxet
- vinyl ether compounds examples include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether and 1,6-cyclohexane dimethanol divinyl ether.
- anionically polymerizable compound those having one or more polymerizable groups capable of anionic polymerization may be used.
- the above-mentioned anionically polymerizable compound is usually used together with an anionic polymerization initiator.
- an anionizable polymerizable group an epoxy group, a lactone group, a (meth) acryl group etc. can be mentioned, for example. That is, as the above-mentioned anion polymerization compound, an epoxy compound, a lactone compound, a compound which has a (meth) acryl group, etc. are mentioned. Examples of the lactone compound include ⁇ -propiolactone and ⁇ -caprolactone.
- an epoxy compound the epoxy compound illustrated as said cationically polymerizable compound can be used.
- a compound which has a (meth) acryl group what was illustrated as said radically polymerizable compound can be used.
- the said cationically polymerizable compound and anionically polymerizable compound can be used individually or in mixture of 2 or more types, respectively.
- (B) Polymer Having No Polymerizable Group As a resin that can be used for the composition of the present invention, as described above, a polymer having no polymerizable group can be used.
- the weight average molecular weight (Mw) of the polymer having no polymerizable group is appropriately set according to the application etc. of the composition, but can be, for example, 1500 or more, and 1500 or more and 300000 or less can do.
- Mw weight average molecular weight of the polymer having no polymerizable group
- the composition of the present invention can be used as a photosensitive composition, for example, by including a photosensitive resin as a resin component.
- Photosensitive resin has photosensitivity, and is used together with an acid generator, for example, it dissolves in a developer such as cleavage of chemical bond such as ester group or acetal group by action of acid Mention may be made of positive resins which change in the direction in which the properties increase.
- the composition described above contains a positive resin as a resin component, whereby the solubility of the light-irradiated portion in the alkali developer is increased. Therefore, the composition can be used, for example, as a positive type composition, more specifically, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation.
- polystyrene and derivatives thereof polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof and two or more formed Copolymer: two or more copolymers selected from hydroxystyrene, styrene and their derivatives, cycloolefin and its derivatives, maleic anhydride, and three or more copolymers selected from acrylic acid and its derivatives Combined; cycloolefin and derivatives thereof, maleimide, and three or more copolymers selected from acrylic acid and derivatives thereof; polynorbornene; at least one polymer selected from the group consisting of metathesis ring-opening polymers Etc.
- the acid labile group to be introduced into the above-mentioned polymer includes heteroalicyclic groups such as tertiary alkyl group, trialkylsilyl group, oxoalkyl group, aryl group substituted alkyl group, tetrahydropyran-2-yl group, etc.
- heteroalicyclic groups such as tertiary alkyl group, trialkylsilyl group, oxoalkyl group, aryl group substituted alkyl group, tetrahydropyran-2-yl group, etc.
- Tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyl groups, alkyloxycarbonyl groups and the like can be mentioned.
- positive resin Detailed examples of the positive resin are the same as the contents described in, for example, JP-A-2003-192665, JP-A-2004-323704, claim 3, JP-A-10-10733, etc. Can.
- a well-known acid generator can be used as an acid generator used with said positive resin.
- the photocationic polymerization initiator mentioned later, a thermal cationic polymerization initiator, etc. can be mentioned.
- Non-Photosensitive resin may be any one not having photosensitivity, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene -(Meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66 Nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin and the like.
- the non-photosensitive resin for example, a polymer of the above-mentioned polymerizable compound can also be used.
- (C) Resin component The content of the above resin component in the composition of the present invention can be appropriately determined according to the application etc. of the composition, and for example, 1 part by mass in 100 parts by mass of the solid content of the composition
- the content is preferably 99 parts by mass or less, more preferably 20 parts by mass or more and 95 parts by mass or less, and particularly preferably 30 parts by mass or more and 90 parts by mass or less. It is because the said composition can hold
- the content of the resin component can be appropriately set according to the application etc.
- the composition can be, for example, 1 part by mass or more and 99 parts by mass or less, and 10 parts by mass or more in 100 parts by mass of the composition.
- the content is preferably 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less.
- the composition can be used as a negative composition excellent in sensitivity.
- the content of the above resin component varies depending on the application etc.
- the composition can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass in total of the compound I-1 and the resin component.
- the content is preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and preferably 90 parts by mass or more and 98 parts by mass or less. It is because the said composition can provide the composition which can easily provide an ultraviolet absorptivity etc. easily with respect to hardened
- the composition is 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less.
- the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
- the type of the resin component contained in the composition of the present invention may be only one type or a combination of two or more types.
- the resin component may contain, for example, only one or both of the polymerizable compound and the polymer.
- the content of the polymerizable compound can be appropriately set according to the application of the composition, etc. It can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the polymerizable compound and the polymer.
- the above-mentioned polymerization initiator is contained as a curable component, and is usually used together with a polymerizable compound or the like.
- the above-mentioned polymerization initiator may be any one capable of polymerizing a polymerizable compound, for example, a photopolymerization initiator capable of polymerizing a polymerizable compound by receiving light irradiation, and can polymerize a polymerizable compound by heating And thermal polymerization initiators.
- the above-mentioned polymerization initiator is preferably a photopolymerization initiator from the viewpoint of effectively exerting the effect that the above-mentioned compound I-1 functions as an ultraviolet absorber.
- photopolymerization initiator may be any one capable of polymerizing the polymerizable compound by receiving light irradiation, for example, photo radical polymerization initiator, photo cationic polymerization initiator, photo anion A polymerization initiator etc. can be mentioned.
- the photo radical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used.
- an acetophenone type compound, a benzyl type compound, a benzophenone series compound, a thioxanthone type compound, an oxime ester type compound etc. can be illustrated as a preferable thing, for example.
- acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl- 2-Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiary butyl dichloroacetophenone, p-tertiary butyl trichloroacetophenone, p-azidoben Salacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butanone-1, b Zoin, benzoin methyl ether, benzoin ethyl-N-phenyl
- benzyl compound examples include benzyl and the like.
- benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide.
- thioxanthone compound examples include thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone and the like.
- R 71 and R 72 each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms
- R 73 and R 74 each independently represent a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 75 , OR 76 , SR 77 , NR 78 R 79 , COR 80 , SOR 81 , SO 2 R 82 or It represents CONR 83 R 84, R 73 and R 74 are, sometimes are bonded to each other to form a ring, R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 and R 84 are each
- Examples of the oxime-based compound include: ethanone-1- [9-ethyl-6- (2-methylbenzoyl-9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl -6-Benzoyl-9H-carbazol-3-yl-octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane- 1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime),
- an indole oxime ester compound having an indole structure can also be used.
- an indole type oxime ester compound the oxime ester compound etc. which are represented by the following general formula (V) described in international publication 2017/051680 can be mentioned, for example.
- R 201 and R 202 each independently represent R 211 , OR 211 , COR 211 , SR 211 , CONR 212 R 213 or CN
- R 211 , R 212 and R 213 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom
- the hydrogen atoms of the groups represented by R 211 , R 212 and R 213 are further R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR
- the hydrogen atom of the group represented by R 203 further includes R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , It may be substituted by OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 221 , R 204 , R 205 , R 206 and R 207 are each independently R 211 , OR 211 , SR 211 , COR 214 , CONR 215 R 216 , NR 212 COR 211 , OCOR 211 , COOR 214 , SCOR 211 , OCSR 211 , CO
- the hydrogen atoms of the groups represented by R 204 , R 205 , R 206 and R 207 are further selected from R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , and may be substituted with a hydroxyl group, a nitro group, CN, a halogen atom or COOR 221 , R 214 , R 215 and R 216 each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, The alkyl part of the group represented by R 214 , R 215 and R 216 may be branched side chain or cyclic alkyl; R 208 represents R 211
- Examples of the alkyl group, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include the items of the above-mentioned “1. Among the contents exemplified as R 11 and the like, those having a predetermined number of carbon atoms can be mentioned.
- radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1) -Yl)] Titanocene compounds such as titanium etc. may be mentioned.
- radical polymerization initiators include Adeka optomer N-1414, N-1717, N-1919, Adeka Arkles NCI-831, NCI-930 (manufactured by ADEKA Corporation), IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE 784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314 (manufactured by Tronly) and the like. Be
- photo radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.
- the content of the photo radical polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, 0.001 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the polymerizable compound The amount may be as follows, preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
- the photocationic polymerization initiator is not particularly limited as long as it is a compound capable of releasing a substance that causes cationic polymerization to be initiated by light irradiation, and it is possible to use an existing compound, and preferably an energy ray.
- the compound is a double salt which is an onium salt that releases a Lewis acid upon irradiation with or a derivative thereof.
- Representative examples of such compounds include the following general formula: [A1] r + [B1] r- And salts of cations and anions represented by
- the cation [A1] r + is preferably onium, and the structure thereof can be represented by, for example, the following general formula. [(R 101 ) f 1 Q] r +
- R 101 is an organic group having 1 to 60 carbon atoms and which may contain several atoms other than carbon atoms.
- f1 is an integer of 1 to 5;
- Each of e R 58 is independent of each other and may be the same or different.
- at least one of R 101 is preferably an organic group as described above having an aromatic ring. For example, even when substituted by an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkoxy group, a halogen atom, a benzyl group, a thiophenoxy group, a 4-benzoylphenylthio group, a 2-chloro-4-benzoylphenylthio group, etc. A certain phenyl group is mentioned.
- the anion [B1] r- is preferably a halide complex, and its structure can be represented, for example, by the following general formula, [LX f2 ] r- .
- L is a metal or metalloid (Metalloid) which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
- anion [LX f2 ] r- of the above general formula examples include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4 ) ⁇ , Hexafluorophosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroarsenate (AsF 6 ) ⁇ and hexachloroantimonate (SbCl 6 ) ⁇ can be mentioned.
- the anion [B1] r- has the following general formula, [LX f2-1 (OH)] r-
- L, X and f2 are the same as above.
- Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethyl sulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , toluene sulfonate anion And trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraaryl borate and tetrakis (pentafluorophenyl) borate.
- 1 type can be used individually or in mixture of 2 or more types.
- aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate.
- Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate and tolycamyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt.
- Sulfonium salts represented by the following Group I or Group II: sulfonium salts such as hexafluoroantimony ion, tetrakis (pentafluorophenyl) borate ion and the like.
- other preferable ones are ( ⁇ 5-2, 4-cyclopentadien-1-yl) [(1, 2, 3, 4, 5, 6 ⁇ )-(1-methylethyl) benzene] -iron- Iron-arene complexes such as hexafluorophosphate; aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum; mixtures with silanols such as triphenylsilanol : Etc. can also be mentioned.
- a commercial item can also be used as said photocationic polymerization initiator, For example, IRUGACURE 261 (made by BASF Corporation), Adeka optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP -172 (made by Adeka), UVE-1014 (made by General Electronics), CD-1012 (made by Sartmar), CI-2064, CI-2481 (made by Nippon Soda Co., Ltd.), Uvacure 1590, 1591 (Daicel UCB), CYRACURE UVI-6990 (manufactured by Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103 and NDS-103 (manufactured by Midori Chemical Co., Ltd.), and the like.
- aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferably used from the viewpoint of practical use and light sensitivity.
- photoanion polymerization initiator what generate
- the photoanion polymerization initiator include acetophenone O-aroyloxime (acetophenone O-aroyloxime), nifedipine and the like.
- thermal polymerization initiator any one capable of polymerizing a polymerizable compound by heating may be used, and a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, etc. may be mentioned. Can.
- thermal radical polymerization initiator what generate
- a thermal radical polymerization initiator an azo compound, a peroxide, a persulfate, etc. can be illustrated as a preferable thing, for example.
- azo compounds examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1 ' And -azobis (1-acetoxy-1-phenylethane) and the like.
- peroxides examples include benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxy dicarbonate.
- persulfate examples include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
- thermal cationic polymerization initiator what generate
- Specific examples of the thermal cationic polymerization initiator include salts such as sulfonium salts, thiophenium salts, thiolanium salts, benzyl ammonium, pyridinium salts and hydrazinium salts; and polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine.
- Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophorone diamine; Aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenyl sulfone Glycidyl ethers such as the above polyamines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether Or a polyepoxy adduct modified product produced by reaction with various epoxy resins such as glycidyl esters of carboxylic acid according to a conventional method; the above organic polyamines and carboxylic acids such as phthalic acid, isophthalic acid and dimer acid Amidated modified products produced by reaction according to a conventional method; the above-mentioned polyamines
- a commercial item can also be used as said thermal cationic polymerization initiator,
- Adeka opton CP-77 Adeka opton CP-66 (made by ADEKA), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun Aid SI -60 L, San Aid SI-80 L, San Aid SI-100 L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.
- thermal anion polymerization initiator what generate
- Specific examples of the anionic polymerization initiator include aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, and boron trifluoride-amine complex. , Dicyandiamide, organic acid hydrazide and the like can be used.
- the content of the polymerization initiator may be any as long as it can impart desired curability and the like, and for example, 0.1 parts by mass or more and 30 parts by mass in 100 parts by mass of solid content. It can be made into parts by mass or less and preferably 0.5 parts by mass or more and 10 parts by mass or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
- the content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity, and for example, 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound It is preferable that it is 0.1 mass part or more and 30 mass parts or less, and it is preferable that it is 0.5 mass part or more and 10 mass parts or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
- the other components may be, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol or phenothiazine; plasticizer; adhesion promoter; filler; Foaming agents; leveling agents; surface conditioners; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants, etc .; UV absorbers other than the compounds represented by the above compound I-1; Dispersion aids; aggregation inhibitors; catalysts; effects accelerators; crosslinkers; additives such as thickeners etc. can be included.
- a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol or phenothiazine
- plasticizer adhesion promoter
- filler Filler
- Foaming agents leveling agents
- surface conditioners such as phenolic antioxidants, phosphite antioxidants, thioether
- a dye or a pigment may be mentioned as long as it can impart a desired color to a composition or a cured product thereof or the like.
- a compound having absorption at 380 to 1200 nm can be used, and for example, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazole compound, naphthol Compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound, perylene compound, polyene naphtholactam compound, coumarin compound, squalilium compound, squarylium compound, Spiropyran compounds, s
- an inorganic pigment or an organic pigment can be used.
- pigments can also be used as the above-mentioned inorganic pigment or organic pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 22, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment oranges 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 126, 127, 129, 137, 138, 139
- the coloring agent As content of the said coloring agent, it can be referred to as 0.01 mass part or more and 50 mass parts or less with respect to 100 mass parts of solid content of a composition.
- the content of the coloring agent can be 0.01 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.
- the solvent may be any solvent as long as it can dissolve or disperse the above-mentioned components.
- BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine oil, D-limonene, Terpene-based hydrocarbon oils such as Nene; paraffin spirits such as Mineral Spirit, Swazor # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethyl
- the content of the solvent varies depending on the application of the composition, etc., and can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass or more and 70 parts by mass It is preferable that it is less than part. It is because it is easy to make it excellent in coating property etc.
- (C) Chain Transfer Agent and Sensitizer As the chain transfer agent and the sensitizer, the sensitivity of the composition can be adjusted, and a sulfur atom-containing compound is generally used.
- a sulfur atom-containing compound is generally used.
- C1 aliphatic polyfunctional thiol compounds, such as tri-mercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, manufactured by Showa Denko KK Karenz MT BD1, PE1, NR 1, and the like.
- (D) Surfactant As said surfactant, what can improve the dispersion stability of a composition, coating property, etc. can be used, Fluorine, such as perfluoro alkyl phosphate ester and perfluoro alkyl carboxylic acid salt Surfactants, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, cationic surfactants such as higher amine halides and quaternary ammonium salts, polyethylene glycol alkyl ether, polyethylene Nonionic surfactants such as glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, surfactants such as amphoteric surfactants and silicone surfactants can be used, and these may be used in combination.
- Fluorine such as perfluoro alkyl phosphate ester and perfluoro alkyl carboxylic acid salt
- Surfactants anionic surfactants such as higher fatty acid
- the above silane coupling agent is a silane compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material such as a synthetic resin, What can improve the adhesiveness etc. of a thing or its hardened
- cured material can be used.
- a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
- (F) Melamine compound As the above-mentioned melamine compound, those which can improve the curability can be used, for example, (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, (poly) methylolurea and the like of active methylol groups of the nitrogen compound (CH 2 OH groups) of all or part (at least two) can be exemplified compounds alkyl etherified.
- an alkyl group which comprises an alkyl ether a methyl group, an ethyl group, or a butyl group is mentioned, It may mutually be same or different.
- the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
- hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
- alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.
- the viscosity of the composition may be, for example, 200 mPa ⁇ s or less, and 1 mPa ⁇ s or more and 200 mPa ⁇ s or less from the viewpoint of having coatability. It is because the said composition is excellent in coatability.
- the method for producing the above composition may be any method as long as the above-mentioned components can be blended at a desired content, and may be a method in which the above-mentioned components are simultaneously added and mixed. It may be a method of mixing.
- thermosetting coatings thermosetting coatings, photocurable coatings or varnishes, thermosetting adhesives, photocurable adhesives, printed circuit boards, or color televisions such as color televisions, PC monitors, personal digital assistants, digital cameras, etc.
- Color filters for liquid crystal display panels for display color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, for dental use
- Composition resin for photolithography, gel coat, photoresist for electronics, electroplating resist, etching resist, both liquid and dry film, solder resist, for manufacturing color filters for various display applications or plasma display
- Resists for forming optical structures compositions for encapsulating electric and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass Fiber cable coatings, stencils for screen printing, materials
- the application is not limited to the application in which the durability to ultraviolet light is required at the time of use as a product etc.
- it can be suitably used also for a member which receives ultraviolet irradiation or the like in the manufacturing process.
- a member which receives ultraviolet irradiation etc. in a manufacturing process in order to aim at surface modification of surface wettability improvement, adhesion improvement, etc., a member which receives irradiation, such as ultraviolet light, can be mentioned, for example.
- the members required to have the above-mentioned wettability improvement and adhesion improvement include members laminated with other members.
- various members such as a plasma display panel, an organic electroluminescence display, a liquid crystal display, etc.
- Image display various sensors such as touch panels, color filters, photo spacers, brightness enhancement plates, light guide plates, light guide plates, TFT substrates, alignment films, liquid crystal layers, insulating films, acoustic elements such as speakers, members for constituting circuit boards etc.
- a member include a surface modification in the manufacturing process of a lens, a keypad, a magnetic head for an HDD, and the like, and the prevention of deterioration of the member.
- members required to prevent surface modification and deterioration of members in the above-mentioned manufacturing process members to be laminated with other members via an adhesive, members to be covered with other members by paints, etc. should also be mentioned.
- the base material may be irradiated with ultraviolet light or the like together with the base material for surface modification of the exposed base material.
- required in such a manufacturing process for example, members used together with members that require surface cleaning or surface modification such as plastic film, glass, silicon wafer, various engineering plastics, optical lenses, metal surfaces, plating, ceramics, dies etc. It can be mentioned.
- the cured product of the present invention is a cured product of a composition containing the compound I-1 of the present invention and a polymerizable compound.
- composition of the present invention uses the above-mentioned composition, it has a good ultraviolet absorbing ability and the like.
- the cured product of the present invention uses the composition described above. Hereinafter, the cured product of the present invention will be described in detail.
- the composition contains the compound I-1 and a polymerizable compound.
- the composition may also contain components other than the compound I-1 and the polymerizable compound.
- About the content of each component of such a composition it can be made to be the same as the content as described in the term of "2. other components" of the above-mentioned "C. composition”.
- the compound I-1 contained in the composition may be before or after elimination of the photoleaving group B in the cured product, but is preferably after elimination . It is because the said hardened
- the above-mentioned cured product usually contains a polymer of a polymerizable compound.
- the remaining amount of the polymerizable compound contained in the cured product is appropriately set according to the application of the cured product and the like, and is, for example, 10 parts by mass or less in 100 parts by mass of the cured product, and 1 part It is preferable that it is less than part.
- the cured product may be substantially free of a solvent.
- cured material it can be 1 mass part or less in 100 mass parts of hardened
- the elastic modulus of the cured product is usually higher than that of the composition, and can be, for example, 10 -3 M or more, and can be 10 MPa or more. With the elastic modulus, the cured product can stably hold the compound I-1 and the like. About the upper limit of the above-mentioned elastic modulus, although it can set suitably according to the use etc. of hardened material, it can be made into 10 6 MPa or less, for example.
- the elastic modulus refers to the compressive elastic modulus and can be measured at 23 ° C. in accordance with JIS K7181. For the measurement sample, for example, a cube-shaped test piece having a side length of 6 mm can be prepared or cut out, and measurement can be performed at a test speed of 1 ⁇ 0.2 mm / min according to JIS K7181.
- the method for producing the above-mentioned cured product may be any method as long as the above-mentioned composition can be cured, for example, it may be the same as the method described in “F. Method for producing a cured product” described later. it can.
- the second composition of the present invention comprises a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound I-2”) , And may be referred to as "compound B '").
- A represents an atomic group having an ultraviolet absorbing ability
- k represents an integer of 1 to 10.
- the second composition can be easily formed, for example, using the composition described above.
- the second composition can easily impart ultraviolet absorbing ability and the like.
- the second composition of the present invention comprises the compound I-2 and the compound B ′.
- the second composition of the present invention will be described in detail.
- Compound I-2 The compound I-2 exhibits ultraviolet absorbing ability.
- the compound I-2 is a compound in which the B-O- in the compound I-1 is substituted with an -OH group.
- the contents of such compound I-1 can be the same as the contents described in the section “A. Compound” above, so the description thereof is omitted here.
- the content of the compound I-2 in the composition may be any as long as it can impart a desired ultraviolet absorbing ability and the like.
- the total of the compound I-2 and the compound B ′ corresponds to the “C. It can be made the same as the content in the solid content of the above-mentioned compound I-1 described in the item of Article].
- the compound B ′ is a leaving substance derived from a photoleaving group.
- the photoleaving group may be any group capable of binding to the phenolic hydroxyl group as a protecting group, and the same as the contents described in “1.
- Photoleaving group B” of the above “A. Compound”. be able to.
- any compound can be used as long as it can be taken after the photoleaving group is eliminated from the phenolic hydroxyl group.
- the photoleaving group B after leaving the phenolic hydroxyl group is usually highly reactive and can have various structures.
- the photoleaving group B is preferably a compound represented by the general formulas (B-1-a), (B-2), (B-3), (B-4), (B-5), When it is represented by B-6), (B-7), etc., for example, the following general formulas (B-111-a), (B-112), (B-113), (B) -114), (B-115), (B-116), (B-117) and the like can be included.
- R 11 contained in the compound B', R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25 , R 26 and R 27 and b 1, b 2, b 3, b 4, b 5, b 6, b 7 and b 8 are the same as the contents described in the section “A. I omit it.
- the type of the compound B ′ may be only one type or a combination of two or more types.
- the above-mentioned second composition comprises the compound I-2 and the compound B ′, and usually comprises other components.
- other components include the contents described in the section "2.
- the other components preferably include a resin component, and particularly preferably include a polymer having no polymerizable group such as a polymer of a polymerizable compound. This is because, for example, the second composition can effectively exert the effect of being able to easily impart the ultraviolet absorptivity and the like to a cured product and the like.
- the number of kinds of resin components may be one, or two or more kinds may be used in combination.
- the second composition contains a solvent, a polymerizable compound, etc., and may have a coating property, and the viscosity in that case is the same as the content described in the above-mentioned "C. composition”. It can be done.
- the second composition is a cured product containing a polymer of a polymerizable compound
- the elastic modulus of the second composition is the same as the content described in the section "D. cured product”. can do.
- the method for producing a cured product of the present invention comprises the steps of curing the composition containing the compound I-1 and the polymerizable compound described above to form a cured product, and irradiating the cured product with light. And d) removing the photoleaving group B contained in the compound.
- the above-mentioned production method can be easily cured and can easily impart ultraviolet absorbing ability and the like.
- the production method of the present invention includes the steps of forming a cured product and removing it.
- each process of the manufacturing method of this invention is demonstrated in detail.
- Step of forming a cured product is a step of forming a cured product of the composition described above.
- the curing method uses a method of irradiating the composition with light to polymerize the polymerizable compounds.
- the light irradiated to the composition may include light with a wavelength of 300 nm to 450 nm.
- an ultra-high pressure mercury, a mercury vapor arc, a carbon arc, a xenon arc etc. can be mentioned, for example.
- Laser light may be used as the light to be irradiated.
- the laser light one containing light with a wavelength of 340 to 430 nm can be used.
- those emitting light in the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser can also be used.
- the said composition can contain the sensitizing dye which absorbs the said area
- the total light quantity of the irradiated light is preferably one that can suppress the detachment of the photoleaving group B, and can be, for example, less than 1000 mJ / cm 2 and not more than 800 mJ / cm 2. And can be 500 mJ / cm 2 or less.
- the above curing method uses a method of subjecting the composition to a heat treatment to polymerize the polymerizable compounds.
- the heating temperature may be any temperature as long as the composition can be cured stably, and can be 60 ° C. or more, preferably 100 ° C. or more and 300 ° C. or less.
- heating temperature can be made into the temperature of the coating-film surface of a composition.
- the heating time can be about 10 seconds to 3 hours.
- the type of the curing method may include only one type, or may include two or more types.
- the composition used in this step contains the compound I-1 and a polymerizable compound.
- the composition may include other components other than the compound I-1 and the polymerizable compound.
- About the content of each component of such a composition since it can be made to be the same as the content as described in the item of "2. other components" of the above-mentioned “C. composition", explanation here is omitted. .
- Step of leaving is a step of leaving the photoleaving group B contained in the compound I-1.
- any method may be used as long as the cured product is irradiated with light.
- the light irradiated to the cured product and the total light amount thereof are not particularly limited as long as the light leaving group B can be eliminated, but the light of “1. light of the above-mentioned“ A.
- the same contents as those described in the section of "Leaving group B" can be adopted.
- a light source of light irradiation although it is suitably selected according to the wavelength of the light irradiated, it shall be the same as the content as described in the term of said "1.
- Process of forming hardened material for example. be able to.
- the temperature of the cured product in this step can be appropriately set according to the heat resistance and the like of the cured product and the substrate supporting the cured product, but can be, for example, 200 ° C. or less, 0 ° C. or more, The temperature is preferably 150 ° C. or less, and more preferably 0 ° C. or more and 100 ° C. or less. It is because detachment
- the temperature of the cured product is the temperature of the surface of the cured product.
- the above-mentioned production method includes the step of forming a cured product and the step of desorbing, but may include other steps as required.
- coating the said composition on a base material etc. can be mentioned, for example.
- known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like can be used.
- the substrate can be appropriately set depending on the application of the cured product and the like, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics and the like.
- the cured product after the cured product is formed on a substrate, it may be used after being peeled off from the substrate or may be transferred from the substrate to another adherend.
- the present invention is not limited to the above embodiment.
- the above embodiment is an exemplification, has substantially the same configuration as the technical idea described in the present invention, and exhibits the same operation and effect as that of the technical scope of the present invention. Is included in
- Example 1 0.005 mol of the phenol compound (compound I-2) in scheme 1 below, 0.005 mol of potassium carbonate and 12 g of DMF are mixed, and 0.0075 mol of o-nitrobenzyl chloride is added dropwise at room temperature under a nitrogen atmosphere, and at 80 ° C. The mixture was stirred for 2 hours, and the following reaction gave compound I-1-2 corresponding to compound I-1.
- Oil-water separation was performed by adding 50 g of ethyl acetate and 50 g of ion-exchanged water to the reaction solution. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and crystallization was performed with methanol. The obtained white solid was dried under reduced pressure at 45 ° C. for 2 hours to obtain the desired product (Compound I-1-2). It was confirmed by H-NMR and IR that the obtained white solid was the desired product.
- Example 2 The following compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28, in the same manner as in Example 1, except that o-nitrobenzyl chloride was changed Obtained I-1-34. Specifically, compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28 and 1-34 of Examples 2-7 are prepared by the following method. Manufactured. In addition, it was confirmed by H-NMR that the white solid obtained in Examples 2 to 7 was the desired product. Example 2 The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN with respect to 2-ethylnitrobenzene.
- Example 4 Compound I-1-32 was obtained in the same manner as in Example 1 except that 4'-methoxyphenacyl bromide was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Example 5 Compound I-1-35 was obtained in the same manner as in Example 1 except that 2-bromo-2-phenylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Example 6 Compound I-1-28 was obtained in the same manner as in Example 1 except that 2-bromo-2'-nitroacetophenone was used instead of o-nitrobenzyl chloride.
- Example 7 Compound I-1-34 was obtained in the same manner as in Example 1 except that 4-bromomethyl-7-methoxycoumarin was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Example 8 The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN based on 4-methoxy-2-nitrotoluene. After oil-water separation with ethyl acetate and washing with water, purification with a silica column gave the corresponding benzyl bromide compound.
- Compound I-1-4 was obtained in the same manner as in Example 1 except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Example 9 Compound I-1-41 was obtained in the same manner as in Example 8 except that 3-chloro-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Compound I-1-42 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Example 11 Compound I-1-43 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitro-6-bromotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Example 12 Compound I-1-44 was obtained in the same manner as in Example 1 except that 2-bromo-2′-methylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
- Example 13 An intermediate compound was obtained in the same manner as in Example 1 except that 4- (2-bromoacetyl) phenyl t-butyl carbonate was used instead of o-nitrobenzyl chloride.
- Example 14 Dissolve 0.004 mol of a phenol compound (phenol compound in scheme 1) in 40 mL of pyridine, add 0.006 mol of NPPOC-Cl (2- (2-nitrophenyl) propyl chloroformate) dropwise, and stir for 6 hours at room temperature It stirred. 200 g of ethyl acetate and 50 g of ion-exchanged water were added to the reaction solution to conduct oil-water separation.
- Table 5 The components shown in Table 5 below were mixed in the proportions shown in Table 5 to obtain the compositions of Examples 18 to 20 and Comparative Examples 1 and 2.
- the symbols in Table 5 indicate the following compounds.
- the numerical value in a table represents a mass part.
- A-1 Polymerizable compound (NK Oligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.)
- A-2 Radically polymerizable compound (Kayarad DPHA (a mixture of dipentaerythritol penta and hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)
- B-1 IRGACURE 907 manufactured by BASF (radical polymerization initiator)
- C-1 Shine Chemical Industry Co., Ltd. silane coupling agent KBE-403
- D-1 2-butanone
- E-1 compound represented by the following formula (1) (ultraviolet absorber)
- F-1 Compound I-1-3
- F-2 Compound I-1-35
- F-3 Compound I-1-47
- compositions of Examples 18 to 20 and Comparative Examples 1 and 2 were each applied to a glass substrate by a spin coater, prebaked at 80 ° C. for 3 minutes, and then exposed using a super high pressure mercury lamp (UL 750) as a light source. (20 mW / cm 2 ). The exposure was performed so that the exposure light amount was 100 mJ / cm 2 . Thereafter, the sample was further irradiated with 3000 mJ / cm 2 to prepare a sample for light resistance evaluation. A 24-hour light resistance test was performed on the sample for evaluation using a Suga Test Instruments Xenon Light Resistance Tester Table Sun XT-1500L.
- the difference in transmittance (%) at a wavelength of 470 nm before and after the light resistance test of the sample for evaluation was measured.
- the light resistance was evaluated on the basis of the standard.
- Good The difference in transmittance (%) is less than 5% relative to the transmittance before the light resistance test.
- X The difference in transmittance (%) is 5% or more with respect to the transmittance before the light resistance test. It shows that a cured
- compositions of Examples 18 to 20 containing the compound I-1 have better light resistance as compared with the composition of Comparative Example 1 which does not contain a UV absorber. Further, the compositions of Examples 18 to 20 have better curability as compared with the composition of Comparative Example 2 containing a known ultraviolet absorber. From this, it can be seen that according to the present invention, a composition having less curing inhibition and having excellent light resistance can be obtained.
- the compound of the present invention it is possible to provide a compound which is less in inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
- the latent ultraviolet absorber of the present invention has little inhibition of curing and can easily impart ultraviolet absorptivity and the like to a cured product.
- the composition of the present invention it is possible to provide a composition capable of obtaining a cured product having excellent curing performance and having excellent ultraviolet absorptivity.
- cured material of this invention the hardened
- a cured product having excellent ultraviolet absorptivity and the like can be produced without causing inhibition of curing.
- the second composition of the present invention it is possible to provide a composition capable of obtaining a cured product having excellent ultraviolet absorption ability without causing inhibition of curing.
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Abstract
A compound shown in general formula (I-1). (In the formula, A represents an atom group having ultraviolet light absorption capacity, B represents a photoelimination group, and k represents an integer from 1 to 10). A composition containing a compound shown in general formula (I-2) and an elimination product derived from the photoelimination group. (In the formula, A represents the atom group having ultraviolet light absorption capacity, and k represents an integer from 1 to 10).
Description
本発明は、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物に関するものである。
The present invention relates to a compound which is less likely to inhibit curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
硬化性組成物の紫外線吸収能や耐熱性を向上させるために、硬化性組成物中に紫外線吸収剤や酸化防止剤を添加して安定化させる方法が知られている(特許文献1~3)。
In order to improve the ultraviolet ray absorbing ability and heat resistance of the curable composition, methods of stabilizing by adding an ultraviolet light absorber and an antioxidant to the curable composition are known (Patent Documents 1 to 3) .
しかしながら、特許文献1~3に記載の紫外線吸収剤は硬化性組成物の硬化を阻害する場合があるという課題があった。
このような課題に対して、本発明者等は、紫外線吸収剤が硬化性組成物を硬化させるために照射される光を吸収する作用があること、及び、このような作用を有するために、紫外線吸収剤を重合系内に添加すると、硬化阻害を生じる場合があることを見出した。 However, there has been a problem that the UV absorbers described in Patent Documents 1 to 3 may inhibit the curing of the curable composition.
With respect to such problems, the present inventors have found that the ultraviolet absorber has an action of absorbing the light irradiated for curing the curable composition, and because such an action It has been found that the addition of a UV absorber into the polymerization system may result in cure inhibition.
このような課題に対して、本発明者等は、紫外線吸収剤が硬化性組成物を硬化させるために照射される光を吸収する作用があること、及び、このような作用を有するために、紫外線吸収剤を重合系内に添加すると、硬化阻害を生じる場合があることを見出した。 However, there has been a problem that the UV absorbers described in Patent Documents 1 to 3 may inhibit the curing of the curable composition.
With respect to such problems, the present inventors have found that the ultraviolet absorber has an action of absorbing the light irradiated for curing the curable composition, and because such an action It has been found that the addition of a UV absorber into the polymerization system may result in cure inhibition.
上記課題の解決手段として、重合系内では上述の光を吸収する作用が不活性化され、硬化後に活性化可能な潜在性添加剤が知られている。
しかしながら、硬化後に活性化可能な潜在性添加剤の活性化には、加熱等が必要な場合があるところ、より容易な活性化が要求される場合があった。 As means for solving the above-mentioned problems, latent additives which can be activated after curing are inactivated in the above-mentioned light absorbing action in the polymerization system.
However, activation of the latent additive that can be activated after curing may require heating or the like, but may require easier activation.
しかしながら、硬化後に活性化可能な潜在性添加剤の活性化には、加熱等が必要な場合があるところ、より容易な活性化が要求される場合があった。 As means for solving the above-mentioned problems, latent additives which can be activated after curing are inactivated in the above-mentioned light absorbing action in the polymerization system.
However, activation of the latent additive that can be activated after curing may require heating or the like, but may require easier activation.
本発明は、上記課題に鑑みてなされたものであり、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することを主目的とする。
The present invention has been made in view of the above problems, and has as its main object to provide a compound which is less in inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
本発明者らは上記課題を解決するために鋭意検討を行った結果、保護基として光脱離基を用いて、該光脱離基で紫外線吸収剤に含まれるフェノール性水酸基を保護することで、紫外線吸収能を発現させる時期の調整が容易となり、上記課題を解決できることを見出し、本発明を完成させるに至った。
As a result of intensive studies to solve the above problems, the present inventors used a photoleaving group as a protecting group to protect the phenolic hydroxyl group contained in the ultraviolet absorber with the photoleaving group. It has been found that the adjustment of the time to develop the ultraviolet light absorbing ability is easy and the above-mentioned problems can be solved, and the present invention has been completed.
すなわち、本発明は、下記一般式(I-1)で表される化合物を提供する。
That is, the present invention provides a compound represented by the following general formula (I-1).
(式中、Aは紫外線吸収能を有する原子団を表し、Bは光脱離基を表し、kは1~10の整数を表す。)
(Wherein, A represents an atomic group capable of absorbing ultraviolet light, B represents a photoleaving group, and k represents an integer of 1 to 10).
また、本発明は、上記一般式(I-1)で表される化合物を含む潜在性紫外線吸収剤を提供する。
The present invention also provides a latent UV absorber comprising the compound represented by the above general formula (I-1).
また、本発明は、上記一般式(I-1)で表される化合物を含む組成物を提供する。
The present invention also provides a composition comprising the compound represented by the above general formula (I-1).
また、本発明は、上記一般式(I-1)で表される化合物と、重合性化合物とを含む組成物の硬化物を提供する。
The present invention also provides a cured product of a composition comprising a compound represented by the above general formula (I-1) and a polymerizable compound.
また、本発明は、前記一般式(I-1)で表される化合物と重合性化合物とを含む組成物を硬化させて硬化物を形成する工程と、前記硬化物に対して光を照射して、前記一般式(I-1)で表される化合物に含まれる光脱離基を脱離する工程とを有する硬化物の製造方法を提供する。
In the present invention, a composition containing the compound represented by the general formula (I-1) and a polymerizable compound is cured to form a cured product, and the cured product is irradiated with light. And a step of removing the photoleaving group contained in the compound represented by the general formula (I-1).
また、本発明は、下記一般式(I-2)で表される化合物(以下、「化合物I-2と称する場合がある。)と、光脱離基由来の脱離物(以下、「化合物B´」と称する場合がある。)とを含む組成物(以下、「第2組成物」と称する場合がある。)を提供する。
The present invention also relates to a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound And B) (hereinafter, may be referred to as “second composition”).
(式中、Aは、紫外線吸収能を有する原子団であり、kは1~10の整数を表す。)
(In the formula, A represents an atomic group having an ultraviolet absorbing ability, and k represents an integer of 1 to 10)
本発明は、化合物並びにそれを用いた紫外線吸収剤、組成物、その硬化物、硬化物の製造方法及び第2組成物に関するものである。以下、これらについて詳細に説明する。
The present invention relates to a compound and a UV absorber using the same, a composition, a cured product thereof, a method for producing a cured product, and a second composition. These will be described in detail below.
A.化合物
まず、本発明の化合物について説明する。
本発明の化合物は下記一般式(I-1)で表される(以下、本発明の化合物を化合物I-1ともいう)。 A. Compounds First, the compounds of the present invention will be described.
The compound of the present invention is represented by the following general formula (I-1) (hereinafter, the compound of the present invention is also referred to as compound I-1).
まず、本発明の化合物について説明する。
本発明の化合物は下記一般式(I-1)で表される(以下、本発明の化合物を化合物I-1ともいう)。 A. Compounds First, the compounds of the present invention will be described.
The compound of the present invention is represented by the following general formula (I-1) (hereinafter, the compound of the present invention is also referred to as compound I-1).
(式中、Aは、紫外線吸収能を有する原子団であり、Bは光脱離基であり、kは1~10の整数を表す。)
(Wherein, A is an atomic group having an ultraviolet absorbing ability, B is a photoleaving group, and k is an integer of 1 to 10).
本発明の化合物I-1は、原子団Aが紫外線吸収能を有するものである。本発明の化合物I-1は、光脱離基Bの脱離前は紫外線吸収能が低いが、光脱離基Bの脱離後は、原子団Aに基づき優れた紫外線吸収能を示す。
よって、光脱離基Bが脱離前の化合物I-1を、例えば、重合系内に添加した場合、化合物I-1は紫外線吸収能が低いため、重合のために照射される光の吸収能が低く、重合系の硬化を阻害しづらい。
一方、本発明の化合物I-1は、光を照射することで、光脱離基が離脱し、優れた紫外線吸収能を発現する。よって、化合物I-1を含む硬化物に対して光照射することで、該硬化物に容易に紫外線吸収能を付与できる。化合物I-1はその紫外線吸収能を発現させるために加熱処理する必要がないことから、硬化物及び基材等のその周辺部材に対する加熱によるダメージを与えづらいという利点を有する。
以上の理由により、上記化合物I-1は、例えば、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できるのである。 In the compound I-1 of the present invention, the atomic group A has an ultraviolet absorbing ability. The compound I-1 of the present invention has a low ultraviolet absorbing ability before the elimination of the photoleaving group B, but exhibits an excellent ultraviolet absorbing ability based on the atomic group A after the elimination of the photoleaving group B.
Therefore, when the compound I-1 before elimination of the photoleaving group B is added, for example, into the polymerization system, the compound I-1 has a low ability to absorb ultraviolet light, so absorption of light irradiated for polymerization is caused. Performance is low and it is difficult to inhibit the curing of the polymerization system.
On the other hand, when the compound I-1 of the present invention is irradiated with light, the photoleaving group is released and exhibits excellent ultraviolet absorbing ability. Therefore, by irradiating the cured product containing compound I-1 with light, the cured product can be easily imparted with ultraviolet absorbing ability. The compound I-1 has the advantage of being less likely to cause damage to the cured product and its peripheral members such as the base material, since the compound I-1 does not need to be heat-treated to develop its ultraviolet absorbing ability.
For the above reasons, the compound I-1 has, for example, little inhibition of curing, and can easily impart ultraviolet light absorbing ability and the like to a cured product.
よって、光脱離基Bが脱離前の化合物I-1を、例えば、重合系内に添加した場合、化合物I-1は紫外線吸収能が低いため、重合のために照射される光の吸収能が低く、重合系の硬化を阻害しづらい。
一方、本発明の化合物I-1は、光を照射することで、光脱離基が離脱し、優れた紫外線吸収能を発現する。よって、化合物I-1を含む硬化物に対して光照射することで、該硬化物に容易に紫外線吸収能を付与できる。化合物I-1はその紫外線吸収能を発現させるために加熱処理する必要がないことから、硬化物及び基材等のその周辺部材に対する加熱によるダメージを与えづらいという利点を有する。
以上の理由により、上記化合物I-1は、例えば、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できるのである。 In the compound I-1 of the present invention, the atomic group A has an ultraviolet absorbing ability. The compound I-1 of the present invention has a low ultraviolet absorbing ability before the elimination of the photoleaving group B, but exhibits an excellent ultraviolet absorbing ability based on the atomic group A after the elimination of the photoleaving group B.
Therefore, when the compound I-1 before elimination of the photoleaving group B is added, for example, into the polymerization system, the compound I-1 has a low ability to absorb ultraviolet light, so absorption of light irradiated for polymerization is caused. Performance is low and it is difficult to inhibit the curing of the polymerization system.
On the other hand, when the compound I-1 of the present invention is irradiated with light, the photoleaving group is released and exhibits excellent ultraviolet absorbing ability. Therefore, by irradiating the cured product containing compound I-1 with light, the cured product can be easily imparted with ultraviolet absorbing ability. The compound I-1 has the advantage of being less likely to cause damage to the cured product and its peripheral members such as the base material, since the compound I-1 does not need to be heat-treated to develop its ultraviolet absorbing ability.
For the above reasons, the compound I-1 has, for example, little inhibition of curing, and can easily impart ultraviolet light absorbing ability and the like to a cured product.
また、本発明の化合物I-1は、光脱離基Bの脱離前は、感光性発現のために照射される光の吸収能が低い。そのため、化合物I-1を、光照射によりアルカリ現像液に対する溶解性が変化する感光性組成物に添加した場合、感光性を安定的に発現可能となる。また、上記化合物I-1は、感光性組成物に対して、光脱離基が脱離可能な光照射を実施することで、紫外線吸収能等を容易に付与できる。
このように、上記化合物I-1は、感光性組成物に対して、感光性の発現阻害が少なく、感光性組成物に対して容易に紫外線吸収能等を付与できるのである。 In addition, the compound I-1 of the present invention has a low ability to absorb light irradiated for the development of photosensitivity before desorption of the photoleaving group B. Therefore, when the compound I-1 is added to a photosensitive composition whose solubility in an alkali developer changes by light irradiation, it is possible to stably exhibit photosensitivity. In addition, the compound I-1 can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition by carrying out light irradiation capable of releasing the light leaving group.
As described above, the compound I-1 has less inhibition of expression of photosensitivity with respect to the photosensitive composition, and can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition.
このように、上記化合物I-1は、感光性組成物に対して、感光性の発現阻害が少なく、感光性組成物に対して容易に紫外線吸収能等を付与できるのである。 In addition, the compound I-1 of the present invention has a low ability to absorb light irradiated for the development of photosensitivity before desorption of the photoleaving group B. Therefore, when the compound I-1 is added to a photosensitive composition whose solubility in an alkali developer changes by light irradiation, it is possible to stably exhibit photosensitivity. In addition, the compound I-1 can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition by carrying out light irradiation capable of releasing the light leaving group.
As described above, the compound I-1 has less inhibition of expression of photosensitivity with respect to the photosensitive composition, and can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition.
更に、本発明の化合物I-1は、光脱離基Bを有することにより、例えば、組成物中での分散又は溶解安定性を容易に調整できる。
化合物I-1は、組成物に含まれる他の成分との親和性が向上するように、光脱離基Bを選択することで、組成物中での優れた分散性を付与できる。
したがって、上記化合物I-1は、組成物に対して優れた紫外線吸収能を付与できるとともに、使用前の保存時等における優れた分散安定性も付与できる。 Furthermore, the compound I-1 of the present invention can easily adjust, for example, the dispersion or dissolution stability in the composition by having a photoleaving group B.
The compound I-1 can impart excellent dispersibility in the composition by selecting the photoleaving group B such that the affinity with other components contained in the composition is improved.
Therefore, the compound I-1 can impart excellent ultraviolet light absorbing ability to the composition, and can also impart excellent dispersion stability during storage before use.
化合物I-1は、組成物に含まれる他の成分との親和性が向上するように、光脱離基Bを選択することで、組成物中での優れた分散性を付与できる。
したがって、上記化合物I-1は、組成物に対して優れた紫外線吸収能を付与できるとともに、使用前の保存時等における優れた分散安定性も付与できる。 Furthermore, the compound I-1 of the present invention can easily adjust, for example, the dispersion or dissolution stability in the composition by having a photoleaving group B.
The compound I-1 can impart excellent dispersibility in the composition by selecting the photoleaving group B such that the affinity with other components contained in the composition is improved.
Therefore, the compound I-1 can impart excellent ultraviolet light absorbing ability to the composition, and can also impart excellent dispersion stability during storage before use.
以下、本発明の化合物I-1について詳細に説明する。
Hereinafter, the compound I-1 of the present invention will be described in detail.
1.光脱離基B
本発明の化合物I-1は、光脱離基Bを有する。
本発明における光脱離基は、特定の波長の光が照射されることより化合物I-1から脱離可能な基とすることができる。化合物I-1に特定の波長の光を照射すると、化合物I-1から光脱離基Bが脱離し、下記一般式(I-2)で表される、水酸基と紫外線吸収能を有する原子団Aとを有する化合物が生成する。 1. Photo leaving group B
The compound I-1 of the present invention has a photoleaving group B.
The photoleaving group in the present invention can be a group which can be eliminated from compound I-1 by being irradiated with light of a specific wavelength. When compound I-1 is irradiated with light of a specific wavelength, the photoleaving group B is eliminated from compound I-1, and an atomic group having a hydroxyl group and an ultraviolet light absorbing ability, represented by the following general formula (I-2) A compound having A is formed.
本発明の化合物I-1は、光脱離基Bを有する。
本発明における光脱離基は、特定の波長の光が照射されることより化合物I-1から脱離可能な基とすることができる。化合物I-1に特定の波長の光を照射すると、化合物I-1から光脱離基Bが脱離し、下記一般式(I-2)で表される、水酸基と紫外線吸収能を有する原子団Aとを有する化合物が生成する。 1. Photo leaving group B
The compound I-1 of the present invention has a photoleaving group B.
The photoleaving group in the present invention can be a group which can be eliminated from compound I-1 by being irradiated with light of a specific wavelength. When compound I-1 is irradiated with light of a specific wavelength, the photoleaving group B is eliminated from compound I-1, and an atomic group having a hydroxyl group and an ultraviolet light absorbing ability, represented by the following general formula (I-2) A compound having A is formed.
(式中、Aは、紫外線吸収能を有する原子団を表し、kは1~10の整数を表す。)
(Wherein, A represents an atomic group capable of absorbing ultraviolet light, and k represents an integer of 1 to 10).
光脱離基Bが化合物I-1から脱離する光の波長は、例えば、紫外線又は可視光線の波長域である。具体的には、365nmの波長を含むものとすることができ、より具体的には、250nm以上450nm以下の波長の光を含むものとすることができ、好ましくは280nm以上380nm以下の波長の光を含むものとすることができる。
上記化合物I-1から光脱離基Bを脱離するために照射される光の積算光量は、例えば、1000mJ/cm2以上10000mJ/cm2以下とすることができ、1000mJ/cm2以上5000mJ/cm2以下であることが好ましく、2000mJ/cm2以上4000mJ/cm2以下であることがより好ましい。重合性化合物等を含む組成物の硬化のために照射される光の積算光量としては、通常、1000mJ/cm2未満とすることができる。したがって、積算光量が上述の範囲であることで、例えば、光硬化性組成物への適用が容易となるからである。
なお、光脱離基Bが脱離するとは、所望の紫外線吸収能を付与できるものであればよく、例えば、光脱離基の脱離率が50%以上となることとすることができ、なかでも、80%以上となることが好ましい。光硬化性組成物への適用が容易となるからである。
一方、上記化合物I-1は、光脱離が抑制される積算光量としては、所望の硬化阻害抑制効果が得られるものであればよく、1000mJ/cm2未満とすることができる。光硬化性組成物への適用が容易となるからである。
また、光脱離が抑制されるとは、所望の硬化阻害抑制効果が得られるものであればよく、例えば、光脱離基Bの脱離率が50%未満となることとすることができ、なかでも、20%以下となることが好ましい。光硬化性組成物への適用が容易となるからである。
上記積算光量は、化合物I-1の0.01質量%アセトニトリル溶液を調製し、実施例に記載の脱離率の測定方法と同様の方法を用いて測定することができる。 The wavelength of the light from which the photoleaving group B leaves the compound I-1 is, for example, the wavelength range of ultraviolet light or visible light. Specifically, the wavelength of 365 nm can be included, more specifically, the light of wavelength of 250 nm or more and 450 nm or less can be included, and preferably, the light of wavelength of 280 nm or more and 380 nm or less can be included. Can.
Integrated light quantity of the light irradiated to detach the light leaving group B from above Compound I-1, for example, be a 1000 mJ / cm 2 or more 10000 mJ / cm 2 or less, 1000 mJ / cm 2 or more 5000mJ / Cm 2 or less is preferable, and 2000 mJ / cm 2 or more and 4000 mJ / cm 2 or less is more preferable. The integrated light quantity of the light irradiated for curing the composition containing the polymerizable compound etc. can be usually less than 1000 mJ / cm 2 . Therefore, when the integrated light amount is in the above-mentioned range, for example, application to a photocurable composition becomes easy.
The elimination of the photoleaving group B may be any one capable of imparting a desired ultraviolet absorbing ability, and for example, the elimination rate of the photoleaving group can be 50% or more, Especially, it is preferable that it becomes 80% or more. It is because application to a photocurable composition becomes easy.
On the other hand, the compound I-1 may have an integrated light quantity that suppresses photodetachment as long as a desired curing inhibition suppressing effect can be obtained, and can be less than 1000 mJ / cm 2 . It is because application to a photocurable composition becomes easy.
Further, to suppress photodetachment may be any as long as a desired curing inhibition inhibitory effect can be obtained. For example, the desorption rate of the photoleaving group B can be less than 50%. Especially, it is preferable that it becomes 20% or less. It is because application to a photocurable composition becomes easy.
The integrated light quantity can be measured by preparing a 0.01% by mass acetonitrile solution of compound I-1 and using the same method as the method of measuring the desorption rate described in the examples.
上記化合物I-1から光脱離基Bを脱離するために照射される光の積算光量は、例えば、1000mJ/cm2以上10000mJ/cm2以下とすることができ、1000mJ/cm2以上5000mJ/cm2以下であることが好ましく、2000mJ/cm2以上4000mJ/cm2以下であることがより好ましい。重合性化合物等を含む組成物の硬化のために照射される光の積算光量としては、通常、1000mJ/cm2未満とすることができる。したがって、積算光量が上述の範囲であることで、例えば、光硬化性組成物への適用が容易となるからである。
なお、光脱離基Bが脱離するとは、所望の紫外線吸収能を付与できるものであればよく、例えば、光脱離基の脱離率が50%以上となることとすることができ、なかでも、80%以上となることが好ましい。光硬化性組成物への適用が容易となるからである。
一方、上記化合物I-1は、光脱離が抑制される積算光量としては、所望の硬化阻害抑制効果が得られるものであればよく、1000mJ/cm2未満とすることができる。光硬化性組成物への適用が容易となるからである。
また、光脱離が抑制されるとは、所望の硬化阻害抑制効果が得られるものであればよく、例えば、光脱離基Bの脱離率が50%未満となることとすることができ、なかでも、20%以下となることが好ましい。光硬化性組成物への適用が容易となるからである。
上記積算光量は、化合物I-1の0.01質量%アセトニトリル溶液を調製し、実施例に記載の脱離率の測定方法と同様の方法を用いて測定することができる。 The wavelength of the light from which the photoleaving group B leaves the compound I-1 is, for example, the wavelength range of ultraviolet light or visible light. Specifically, the wavelength of 365 nm can be included, more specifically, the light of wavelength of 250 nm or more and 450 nm or less can be included, and preferably, the light of wavelength of 280 nm or more and 380 nm or less can be included. Can.
Integrated light quantity of the light irradiated to detach the light leaving group B from above Compound I-1, for example, be a 1000 mJ / cm 2 or more 10000 mJ / cm 2 or less, 1000 mJ / cm 2 or more 5000mJ / Cm 2 or less is preferable, and 2000 mJ / cm 2 or more and 4000 mJ / cm 2 or less is more preferable. The integrated light quantity of the light irradiated for curing the composition containing the polymerizable compound etc. can be usually less than 1000 mJ / cm 2 . Therefore, when the integrated light amount is in the above-mentioned range, for example, application to a photocurable composition becomes easy.
The elimination of the photoleaving group B may be any one capable of imparting a desired ultraviolet absorbing ability, and for example, the elimination rate of the photoleaving group can be 50% or more, Especially, it is preferable that it becomes 80% or more. It is because application to a photocurable composition becomes easy.
On the other hand, the compound I-1 may have an integrated light quantity that suppresses photodetachment as long as a desired curing inhibition suppressing effect can be obtained, and can be less than 1000 mJ / cm 2 . It is because application to a photocurable composition becomes easy.
Further, to suppress photodetachment may be any as long as a desired curing inhibition inhibitory effect can be obtained. For example, the desorption rate of the photoleaving group B can be less than 50%. Especially, it is preferable that it becomes 20% or less. It is because application to a photocurable composition becomes easy.
The integrated light quantity can be measured by preparing a 0.01% by mass acetonitrile solution of compound I-1 and using the same method as the method of measuring the desorption rate described in the examples.
上述の要件を満たす光脱離基Bとしては、具体的には、下記一般式(B-1)、(B-2)、(B-3)、(B-4)、(B-5)、(B-6)(B-7)及び(B-8)で表される基を挙げることができる。なかでも、下記一般式(B-1-a)、(B-2-a)、(B-3-a)、(B-4)、(B-5)、(B-6)、(B-7-a)、(B-7―b)及び(B-8-a)で表される基であることが好ましく、下記一般式(B-1-a)で表される基であることが好ましい。これらの光脱離基を採用することにより、化合物I-1から容易に脱離し、硬化物に対して容易に紫外線吸収能等を付与できるからである。また、上述の要件を満たす光脱離基Bとしては、具体的には、下記一般式(B-9)及び(B-10)で表される基も挙げることができる。
Specifically, the photoleaving group B satisfying the above requirements is represented by the following general formulas (B-1), (B-2), (B-3), (B-4), (B-5) And groups represented by (B-6), (B-7) and (B-8). Among them, the following general formulas (B-1-a), (B-2-a), (B-3-a), (B-4), (B-5), (B-6), (B) -7-a), (B-7-b) and (B-8-a) are preferable, and a group represented by the following general formula (B-1-a) Is preferred. By employing these photoleaving groups, the compound I-1 can be easily released and the cured product can be easily imparted with ultraviolet light absorbing ability and the like. Further, as the photoleaving group B satisfying the above-mentioned requirements, specifically, groups represented by the following general formulas (B-9) and (B-10) can also be mentioned.
(式中、R11、R13、R16、R18、R19、R20、R23、R26及びR28は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R12、R14、R17、R21、R22、R24、R25、R27、R29及びR30は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R15は、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29及びR30で表されるアルキル基及びアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があり、
R’は、水素原子又は炭素原子数1~8のアルキル基を表し、
複数のR11同士、複数のR13同士、複数のR16同士、複数のR18同士、複数のR19同士、複数のR20同士、複数のR23同士、複数のR26同士及び複数のR28同士は、それぞれ結合してベンゼン環又はナフタレン環を形成している場合があり、
複数のR11、R12、R13、R14、R16、R17、R18、R19、R20、R23、R25、R26、R27、R28、R29及びR30は、それぞれ同じである場合があり、異なる場合があり、
b1、b2、b3、b6、b7、b8及びb9は、それぞれ独立に0~4の整数を表し、
b4及びb5は、それぞれ独立に0~5の整数を表し、
**は、前記A-O-との結合位置を表す。) (Wherein, R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
R 12, R 14, R 17 , R 21, R 22, R 24, R 25, R 27, R 29 and R 30 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl A group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 15 represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 11, R 12, R 13 , R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27 And the methylene group in the alkyl group and arylalkyl group represented by R 28 , R 29 and R 30 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof, Yes,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Multiple R 11 each other, multiple R 13 each other, multiple R 16 each other, multiple R 18 each other, multiple R 19 each other, multiple R 20 each other, multiple R 23 each other, multiple R 26 each other and multiple R 28 may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 , Each may be the same, may be different,
b1, b2, b3, b6, b7, b8 and b9 each independently represent an integer of 0 to 4;
b4 and b5 each independently represent an integer of 0 to 5;
** represents the bonding position with the AO-. )
R12、R14、R17、R21、R22、R24、R25、R27、R29及びR30は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R15は、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29及びR30で表されるアルキル基及びアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があり、
R’は、水素原子又は炭素原子数1~8のアルキル基を表し、
複数のR11同士、複数のR13同士、複数のR16同士、複数のR18同士、複数のR19同士、複数のR20同士、複数のR23同士、複数のR26同士及び複数のR28同士は、それぞれ結合してベンゼン環又はナフタレン環を形成している場合があり、
複数のR11、R12、R13、R14、R16、R17、R18、R19、R20、R23、R25、R26、R27、R28、R29及びR30は、それぞれ同じである場合があり、異なる場合があり、
b1、b2、b3、b6、b7、b8及びb9は、それぞれ独立に0~4の整数を表し、
b4及びb5は、それぞれ独立に0~5の整数を表し、
**は、前記A-O-との結合位置を表す。) (Wherein, R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
R 12, R 14, R 17 , R 21, R 22, R 24, R 25, R 27, R 29 and R 30 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl A group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 15 represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 11, R 12, R 13 , R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27 And the methylene group in the alkyl group and arylalkyl group represented by R 28 , R 29 and R 30 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof, Yes,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Multiple R 11 each other, multiple R 13 each other, multiple R 16 each other, multiple R 18 each other, multiple R 19 each other, multiple R 20 each other, multiple R 23 each other, multiple R 26 each other and multiple R 28 may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 , Each may be the same, may be different,
b1, b2, b3, b6, b7, b8 and b9 each independently represent an integer of 0 to 4;
b4 and b5 each independently represent an integer of 0 to 5;
** represents the bonding position with the AO-. )
(式中、R31及びR40は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R32、R33、R41、R42、R43、R44は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R31、R32、R33、R40、R41、R42、R43及びR44で表されるアルキル基及びアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR’-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があり、
前記アルキル基、アリール基、アリールアルキル基及び複素環含有基は、置換基を有している場合があり、
c1は0~5の整数を表し、
c2は0~4の整数を表し、
**は、前記A-O-との結合位置を表す。) (Wherein, each of R 31 and R 40 independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon Represents an arylalkyl group having 7 to 20 atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 32 , R 33 , R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
The methylene group in the alkyl group and arylalkyl group represented by R 31 , R 32 , R 33 , R 40 , R 41 , R 42 , R 43 and R 44 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO 2 -or a combination of these may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
c1 represents an integer of 0 to 5;
c2 represents an integer of 0 to 4;
** represents the bonding position with the AO-. )
R32、R33、R41、R42、R43、R44は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R31、R32、R33、R40、R41、R42、R43及びR44で表されるアルキル基及びアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR’-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があり、
前記アルキル基、アリール基、アリールアルキル基及び複素環含有基は、置換基を有している場合があり、
c1は0~5の整数を表し、
c2は0~4の整数を表し、
**は、前記A-O-との結合位置を表す。) (Wherein, each of R 31 and R 40 independently represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon Represents an arylalkyl group having 7 to 20 atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 32 , R 33 , R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
The methylene group in the alkyl group and arylalkyl group represented by R 31 , R 32 , R 33 , R 40 , R 41 , R 42 , R 43 and R 44 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO 2 -or a combination of these may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
c1 represents an integer of 0 to 5;
c2 represents an integer of 0 to 4;
** represents the bonding position with the AO-. )
上記R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R40、R41、R42、R43及びR44(以下、これらの官能基をまとめてR11等と称する場合がある。)で表される炭素原子数1~40のアルキル基としては、メチル基、エチル基、プロピル基、iso-プロピル基、ブチル基、sec-ブチル基、tert-ブチル基、iso-ブチル基、アミル基、iso-アミル基、tert-アミル基、シクロペンチル基、ヘキシル基、2-ヘキシル基、3-ヘキシル基、シクロヘキシル基、4-メチルシクロヘキシル基、ヘプチル基、2-ヘプチル基、3-ヘプチル基、iso-ヘプチル基、tert-ヘプチル基、1-オクチル基、iso-オクチル基、tert-オクチル基及びアダマンチル基等を挙げることができる。
R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 40 , R 41 , R 42 , R 43 and R 44 (hereinafter, these functional groups are collectively referred to as R 11 etc. As the alkyl group having 1 to 40 carbon atoms represented by (C), there are methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, iso-butyl group. Group, amyl group, iso-amyl group, tert-amyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, 4-methylcyclohexyl group, heptyl group, 2 Heptyl, 3-heptyl group, iso- heptyl, tert- heptyl, 1-octyl group, iso- octyl group, and a tert- octyl group and adamantyl group.
上記R11等で表される炭素原子数6~20のアリール基としては、例えば、フェニル基、ナフチル基及びアントラセニル基等を挙げることができる。
Examples of the aryl group having 6 to 20 carbon atoms represented by R 11 and the like include a phenyl group, a naphthyl group and an anthracenyl group.
上記R11等で表される炭素原子数7~20のアリールアルキル基としては、例えば、ベンジル基、フルオレニル基、インデニル基及び9-フルオレニルメチル基等を挙げることができる。
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 11 and the like include a benzyl group, a fluorenyl group, an indenyl group and a 9-fluorenylmethyl group.
上記R11等で表される炭素原子数2~20の複素環含有基としては、例えば、ピリジル基、ピリミジル基、ピリダジル基、ピペリジル基、ピラニル基、ピラゾリル基、トリアジル基、ピロリル基、キノリル基、イソキノリル基、イミダゾリル基、ベンゾイミダゾリル基、トリアゾリル基、フリル基、フラニル基、ベンゾフラニル基、チエニル基、チオフェニル基、ベンゾチオフェニル基、チアジアゾリル基、チアゾリル基、ベンゾチアゾリル基、オキサゾリル基、ベンゾオキサゾリル基、イソチアゾリル基、イソオキサゾリル基、インドリル基、2-ピロリジノン-1-イル基、2-ピペリドン-1-イル基、2,4-ジオキシイミダゾリジン-3-イル基及び2,4-ジオキシオキサゾリジン-3-イル基等を挙げることができる。
Examples of the heterocycle-containing group having 2 to 20 carbon atoms represented by R 11 and the like described above include, for example, pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group , Isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group , Isothiazolyl group, isoxazolyl group, indolyl group, 2-pyrrolidinone-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazolidin-3-yl group and 2,4-dioxyoxazolidine- A 3-yl group etc. can be mentioned.
上記R’で表される炭素原子数1~8のアルキル基としては、R11等で表されるアルキル基として例示したものうち、炭素原子数が1~8であるものを挙げることができる。
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ include those exemplified for the alkyl group represented by R 11 and the like, and those having 1 to 8 carbon atoms.
上記アルキル基、アリール基、アリールアルキル基及び複素環含有基は、置換基を有している場合がある。本発明の化合物I-1は、特に断りがない限り、置換基を有していないもの及び置換基を有しているものを含む。
The alkyl group, the aryl group, the arylalkyl group and the heterocyclic group may have a substituent. The compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.
アルキル基、アリール基、アリールアルキル基及び複素環含有基等の水素原子を置換する場合がある置換基としては、例えば、ビニル基、アリル基、アクリル基及びメタクリル基等のエチレン性不飽和基;フッ素、塩素、臭素及びヨウ素等のハロゲン原子;アセチル基、2-クロロアセチル基、プロピオニル基、オクタノイル基、アクリロイル基、メタクリロイル基、フェニルカルボニル(ベンゾイル)基、フタロイル基、4-トリフルオロメチルベンゾイル基、ピバロイル基、サリチロイル基、オキザロイル基、ステアロイル基、メトキシカルボニル基、エトキシカルボニル基、t-ブトキシカルボニル基、n-オクタデシルオキシカルボニル基及びカルバモイル基等のアシル基;アセチルオキシ基及びベンゾイルオキシ基等のアシルオキシ基;アミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ブチルアミノ基、シクロペンチルアミノ基、2-エチルヘキシルアミノ基、ドデシルアミノ基、アニリノ基、クロロフェニルアミノ基、トルイジノ基、アニシジノ基、N-メチル-アニリノ基、ジフェニルアミノ基,ナフチルアミノ基、2-ピリジルアミノ基、メトキシカルボニルアミノ基、フェノキシカルボニルアミノ基、アセチルアミノ基、ベンゾイルアミノ基、ホルミルアミノ基、ピバロイルアミノ基、ラウロイルアミノ基、カルバモイルアミノ基、N,N-ジメチルアミノカルボニルアミノ基、N,N-ジエチルアミノカルボニルアミノ基、モルホリノカルボニルアミノ基、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、t-ブトキシカルボニルアミノ基、n-オクタデシルオキシカルボニルアミノ基、N-メチル-メトキシカルボニルアミノ基、フェノキシカルボニルアミノ基、スルファモイルアミノ基、N,N-ジメチルアミノスルホニルアミノ基、メチルスルホニルアミノ基、ブチルスルホニルアミノ基及びフェニルスルホニルアミノ基等の置換アミノ基;スルホンアミド基、スルホニル基、カルボキシル基、シアノ基、スルホ基、水酸基、ニトロ基、メルカプト基、イミド基、カルバモイル基、スルホンアミド基、ホスホン酸基、リン酸基又はカルボキシル基、スルホ基、ホスホン酸基、リン酸基の塩等を挙げることができる。
Examples of the substituent which may substitute a hydrogen atom such as an alkyl group, an aryl group, an arylalkyl group and a heterocycle-containing group include, for example, ethylenic unsaturated groups such as a vinyl group, an allyl group, an acryl group and a methacryl group; Halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl group, 2-chloroacetyl group, propionyl group, octanoyl group, acryloyl group, methacryloyl group, phenylcarbonyl (benzoyl) group, phthaloyl group, 4-trifluoromethylbenzoyl group And acyl groups such as pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and carbamoyl; acetyloxy and benzoyloxy Aclio Amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, chlorophenylamino group, toluidino group, anisidino group, N- Methyl-anilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, methoxycarbonylamino group, phenoxycarbonylamino group, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, carbamoylamino group , N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholino carbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycal Nylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, phenoxycarbonylamino group, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, methylsulfonylamino group, butylsulfonylamino group And substituted amino groups such as phenylsulfonylamino group; sulfonamide group, sulfonyl group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphorus Examples thereof include salts of acid groups or carboxyl groups, sulfo groups, phosphonic acid groups and phosphoric acid groups.
本発明において、基の炭素原子数は、基中の水素原子が置換基で置換されている場合、その置換後の基の炭素原子数を規定する。例えば、上記炭素原子数1~40のアルキル基の水素原子が置換されている場合、炭素原子数1~40とは、水素原子が置換された後の炭素原子数を指し、水素原子が置換される前の炭素原子数を指すのではない。
In the present invention, when the hydrogen atom in the group is substituted by a substituent, the number of carbon atoms of the group defines the number of carbon atoms of the group after the substitution. For example, when the hydrogen atom of the alkyl group having 1 to 40 carbon atoms is substituted, the term "C1 to 40 carbon atoms" refers to the number of carbon atoms after the hydrogen atom has been substituted, and the hydrogen atom is substituted Does not refer to the number of carbon atoms before the
本発明において、基の炭素原子数は、基中のメチレン基が上記2価の基で置き換わっている場合、その置換後の基の炭素原子数を規定する。例えば、本明細書中、炭素原子数1~40のアルキル基中のメチレン基が上記2価の基で置き換わっている場合、該「炭素原子数1~40」とは、メチレン基が置き換わった後の炭素原子数を指し、メチレン基が置き換わる前の炭素原子数を指すのではない。従って、「-O-C40H81」は、「末端のメチレン基が-O-で置き換えられている、炭素原子数40のアルキル基(=炭素原子数40のアルコキシ基)」に該当するものである。同様に、「-CO-O-C39H79」は、「末端のメチレン基が-CO-O-で置き換えられている、炭素原子数40のアルキル基」に該当するものである。
In the present invention, when the methylene group in the group is replaced by the above divalent group, the number of carbon atoms of the group defines the number of carbon atoms of the group after the replacement. For example, in the present specification, when a methylene group in an alkyl group having 1 to 40 carbon atoms is replaced by the above divalent group, the “1 to 40 carbon atoms” means a group after a methylene group is replaced. It does not refer to the number of carbon atoms before the methylene group is replaced. Accordingly, “—O—C 40 H 81 ” corresponds to “an alkyl group having 40 carbon atoms (= an alkoxy group having 40 carbon atoms) in which the terminal methylene group is replaced by —O— It is. Similarly, “—CO—O—C 39 H 79 ” corresponds to “an alkyl group having 40 carbon atoms in which the terminal methylene group is replaced by —CO—O—”.
R11等に用いられるアルキル基及びアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があるものである。
なお、上記メチレン基を置換する組み合わせは、酸素原子が隣り合わない条件での組み合わせとすることができる。 The methylene group in the alkyl group and arylalkyl group used for R 11 and the like is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-,- O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- NH—CO—, —NH—CO—O—, —NR′—,> P = O, —S—S—, —SO 2 — or a combination thereof may be substituted.
In addition, the combination which substitutes the said methylene group can be made into the combination on the conditions which oxygen atom does not adjoin.
なお、上記メチレン基を置換する組み合わせは、酸素原子が隣り合わない条件での組み合わせとすることができる。 The methylene group in the alkyl group and arylalkyl group used for R 11 and the like is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-,- O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-,- NH—CO—, —NH—CO—O—, —NR′—,> P = O, —S—S—, —SO 2 — or a combination thereof may be substituted.
In addition, the combination which substitutes the said methylene group can be made into the combination on the conditions which oxygen atom does not adjoin.
R11等で表される炭素原子数1~40のアルキル基は、基端側の末端のメチレン基が-O-で置き換えられ、アルコキシ基が形成される場合がある。そのようなアルコキシ基としては、例えば、炭素原子数1~10のアルコキシ基が挙げられる。具体的には、メチルオキシ基、エチルオキシ基、iso-プロピルオキシ基、ブチルオキシ基、sec-ブチルオキシ基、tert-ブチルオキシ基、iso-ブチルオキシ基、アミルオキシ基、iso-アミルオキシ基、tert-アミルオキシ基、ヘキシルオキシ基、2-ヘキシルオキシ基、3-ヘキシルオキシ基、シクロヘキシルオキシ基、4-メチルシクロヘキシルオキシ基、ヘプチルオキシ基、2-ヘプチルオキシ基、3-ヘプチルオキシ基、iso-ヘプチルオキシ基、tert-ヘプチルオキシ基、1-オクチルオキシ基、iso-オクチルオキシ基及びtert-オクチルオキシ基等が挙げられる。
In the alkyl group having 1 to 40 carbon atoms represented by R 11 or the like, the terminal methylene group on the proximal side may be replaced by -O- to form an alkoxy group. As such an alkoxy group, for example, an alkoxy group having 1 to 10 carbon atoms can be mentioned. Specifically, methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyl Oxy group, 2-hexyloxy group, 3-hexyloxy group, cyclohexyloxy group, 4-methylcyclohexyloxy group, heptyloxy group, 2-heptyloxy group, 3-heptyloxy group, iso-heptyloxy group, tert- A heptyloxy group, 1-octyloxy group, iso-octyloxy group, tert-octyloxy group and the like can be mentioned.
上記R11、R13、R16、R18、R19、R20、R23、R26及びR28は、水酸基以外の基であることが好ましく、ハロゲン原子、シアノ基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基等であることが好ましい。水酸基以外の基とすることで、光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R11及びR23は、ニトロ基、メトキシ基等の炭素原子数1~10のアルコキシ基、メチル基等の炭素原子数1~40のアルキル基、ハロゲン原子等であることが特に好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R11は、炭素原子数1~10のアルコキシ基、炭素原子数1~10のアルキル基又はハロゲン原子であることが好ましく、炭素原子数1~5のアルコキシ基、炭素原子数1~5のアルキル基又はハロゲン原子であることがより好ましく、炭素原子数1~5のアルコキシ基又はハロゲン原子であることが更に好ましく、炭素原子数1~3のアルコキシ基、塩素原子又は臭素原子であることが特に好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R13、R18、R19、R20、R26及びR28は、炭素原子数1~40のアルキル基であることが好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R16は、隣接する2つのR16同士が結合してベンゼン環を形成することが好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R31及びR40は、水酸基以外の基であることが好ましく、ハロゲン原子、シアノ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基等であることが好ましい。水酸基以外の基とすることで、光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R31は、炭素原子数1~40のアルキル基であることが好ましく、炭素原子数1~10のアルキル基であることがより好ましく、炭素原子数1~5のアルキル基であることが更に好ましく、炭素原子数1~3のアルキル基であることが特に好ましい。 Each of R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a nitro group or a carboxyl group It is preferably an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or the like. By using a group other than a hydroxyl group, the photoleaving group B is easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.
The above R 11 and R 23 are particularly preferably an alkoxy group having 1 to 10 carbon atoms such as a nitro group or a methoxy group, an alkyl group having 1 to 40 carbon atoms such as a methyl group, a halogen atom or the like. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
R 11 is preferably an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen atom, and an alkoxy group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms It is more preferably an alkyl group or a halogen atom, still more preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and it is an alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom Particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
The R 13 , R 18 , R 19 , R 20 , R 26 and R 28 are preferably an alkyl group having 1 to 40 carbon atoms. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
In the above R 16 , it is preferable that two adjacent R 16 's combine with each other to form a benzene ring. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
R 31 and R 40 each is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, the number of carbon atoms The arylalkyl group is preferably 7 to 20, or a heterocycle-containing group having 2 to 20 carbon atoms. By using a group other than a hydroxyl group, the photoleaving group B is easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.
R 31 is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
上記R11及びR23は、ニトロ基、メトキシ基等の炭素原子数1~10のアルコキシ基、メチル基等の炭素原子数1~40のアルキル基、ハロゲン原子等であることが特に好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R11は、炭素原子数1~10のアルコキシ基、炭素原子数1~10のアルキル基又はハロゲン原子であることが好ましく、炭素原子数1~5のアルコキシ基、炭素原子数1~5のアルキル基又はハロゲン原子であることがより好ましく、炭素原子数1~5のアルコキシ基又はハロゲン原子であることが更に好ましく、炭素原子数1~3のアルコキシ基、塩素原子又は臭素原子であることが特に好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R13、R18、R19、R20、R26及びR28は、炭素原子数1~40のアルキル基であることが好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R16は、隣接する2つのR16同士が結合してベンゼン環を形成することが好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R31及びR40は、水酸基以外の基であることが好ましく、ハロゲン原子、シアノ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基等であることが好ましい。水酸基以外の基とすることで、光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R31は、炭素原子数1~40のアルキル基であることが好ましく、炭素原子数1~10のアルキル基であることがより好ましく、炭素原子数1~5のアルキル基であることが更に好ましく、炭素原子数1~3のアルキル基であることが特に好ましい。 Each of R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a nitro group or a carboxyl group It is preferably an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or the like. By using a group other than a hydroxyl group, the photoleaving group B is easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.
The above R 11 and R 23 are particularly preferably an alkoxy group having 1 to 10 carbon atoms such as a nitro group or a methoxy group, an alkyl group having 1 to 40 carbon atoms such as a methyl group, a halogen atom or the like. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
R 11 is preferably an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen atom, and an alkoxy group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms It is more preferably an alkyl group or a halogen atom, still more preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and it is an alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom Particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
The R 13 , R 18 , R 19 , R 20 , R 26 and R 28 are preferably an alkyl group having 1 to 40 carbon atoms. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
In the above R 16 , it is preferable that two adjacent R 16 's combine with each other to form a benzene ring. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
R 31 and R 40 each is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, the number of carbon atoms The arylalkyl group is preferably 7 to 20, or a heterocycle-containing group having 2 to 20 carbon atoms. By using a group other than a hydroxyl group, the photoleaving group B is easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.
R 31 is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
上記R18及びR19で表されるアルキル基及びアリールアルキル基中のメチレン基が-O-置き換わっている場合、上記メチレン基を置き換わる-O-は、アルキル基及びアリールアルキル基をそれぞれ中断するように含まれる場合、すなわち、アルキル基及びアリールアルキル基の端部以外のメチレン基に置き換わっている場合がある。
When the methylene group in the alkyl group and the arylalkyl group represented by R 18 and R 19 is -O-substituted, -O- replacing the methylene group is such that the alkyl group and the arylalkyl group are interrupted respectively In other words, it may be substituted by a methylene group other than the ends of the alkyl group and the arylalkyl group.
上記R12は、水素原子、カルボキシル基、炭素原子数1~5のアルキル基であることが好ましく、水素原子、メチル基であることが特に好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R14、R17、R21、R24、R25、R27、R29及びR30は、なかでも、水素原子、炭素原子数1~40のアルキル基であることが好ましく、水素原子であることが特に好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R15及びR22は、炭素原子数1~5のアルキル基であることが好ましく、メチル基であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記R32及びR33は、それぞれ独立に、水素原子、カルボキシル基又は炭素原子数1~5のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましく、水素原子であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記R41~R44は、それぞれ独立に、水素原子、カルボキシル基又は炭素原子数1~5のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましく、水素原子であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。 R 12 is preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
Among the above, R 14 , R 17 , R 21 , R 24 , R 25 , R 27 , R 29 and R 30 are preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and a hydrogen atom Being particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
The above R 15 and R 22 are preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
Each of R 32 and R 33 independently is preferably a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above R 41 to R 44 are preferably each independently a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and it is a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
上記R14、R17、R21、R24、R25、R27、R29及びR30は、なかでも、水素原子、炭素原子数1~40のアルキル基であることが好ましく、水素原子であることが特に好ましい。光脱離基Bが化合物I-1から容易に脱離するものとなり、且つ化合物I-1の合成が容易となるからである。
上記R15及びR22は、炭素原子数1~5のアルキル基であることが好ましく、メチル基であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記R32及びR33は、それぞれ独立に、水素原子、カルボキシル基又は炭素原子数1~5のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましく、水素原子であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記R41~R44は、それぞれ独立に、水素原子、カルボキシル基又は炭素原子数1~5のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましく、水素原子であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。 R 12 is preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
Among the above, R 14 , R 17 , R 21 , R 24 , R 25 , R 27 , R 29 and R 30 are preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and a hydrogen atom Being particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
The above R 15 and R 22 are preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
Each of R 32 and R 33 independently is preferably a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above R 41 to R 44 are preferably each independently a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and it is a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
上記b1、b2、b3、b6、b7、b8及びb9は、それぞれ独立に0~4の整数とすることができるが、合成の容易さの観点から、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1であることが更に好ましく、0であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記b4及びb5は、それぞれ独立に0~5の整数とすることができるが、合成の容易さの観点から、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1であることが更に好ましく、0であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記c1は、0~5の整数とすることができるが、合成の容易さの観点から、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1の整数であることが更に好ましく、1であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記c2は、0~4の整数とすることができるが、合成の容易さの観点から、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1の整数であることが更に好ましく、0であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。 The above b 1, b 2, b 3, b 6, b 7, b 8 and b 9 can be each independently an integer of 0 to 4 but preferably an integer of 0 to 3 from the viewpoint of easiness of synthesis, It is more preferably an integer of 0 to 2, still more preferably 0 to 1, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above b 4 and b 5 can be each independently an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3 and more preferably an integer of 0 to 2 Preferably, it is 0 to 1, more preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above c1 can be an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 It is more preferable that it is an integer of, and it is particularly preferable that it is 1. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above c 2 can be an integer of 0 to 4, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 More preferably, it is an integer of 0, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
上記b4及びb5は、それぞれ独立に0~5の整数とすることができるが、合成の容易さの観点から、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1であることが更に好ましく、0であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記c1は、0~5の整数とすることができるが、合成の容易さの観点から、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1の整数であることが更に好ましく、1であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
上記c2は、0~4の整数とすることができるが、合成の容易さの観点から、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1の整数であることが更に好ましく、0であることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。 The above b 1, b 2, b 3, b 6, b 7, b 8 and b 9 can be each independently an integer of 0 to 4 but preferably an integer of 0 to 3 from the viewpoint of easiness of synthesis, It is more preferably an integer of 0 to 2, still more preferably 0 to 1, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above b 4 and b 5 can be each independently an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3 and more preferably an integer of 0 to 2 Preferably, it is 0 to 1, more preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above c1 can be an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 It is more preferable that it is an integer of, and it is particularly preferable that it is 1. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The above c 2 can be an integer of 0 to 4, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 More preferably, it is an integer of 0, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
本発明の化合物I-1に含まれる光脱離基Bの種類は、kが2以上である場合、化合物I-1当たり1種類である場合があり、2種類以上である場合があるが、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与でき、且つ、化合物I-1の合成を容易にする観点から、1種類であることが好ましい。
When k is 2 or more, the type of photoleaving group B contained in compound I-1 of the present invention may be one type per compound I-1, and may be two or more types. From the viewpoint of facilitating the synthesis of the compound I-1, it is preferable to use one type, since curing inhibition is small, ultraviolet absorptivity and the like can be easily given to the cured product, and the compound I-1 can be easily synthesized.
上記光脱離基の含有数kは、1~10の整数であるが、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与でき、且つ、合成の容易さの観点から、1~5の整数であることが好ましく、1~4の整数であることがより好ましく、1~3の整数であることが特に好ましい。
Although the content number k of the photoleaving group is an integer of 1 to 10, the curing inhibition is small, and the cured product can be easily imparted with ultraviolet light absorbing ability and the like, and from the viewpoint of easiness of synthesis, It is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.
2.紫外線吸収能を有する原子団A
原子団Aは、紫外線吸収能を有する原子団である。
本発明の化合物I-1は特定の波長の光が照射されることで、光脱離基Bが脱離し、水酸基を有する化合物I-2が生成される。そして、原子団Aが紫外線吸収能を有することにより、化合物I-2が紫外線吸収能を発揮する。 2. Atomic group A having ultraviolet absorbing ability
The atomic group A is an atomic group having an ultraviolet absorbing ability.
The compound I-1 of the present invention is irradiated with light of a specific wavelength, whereby the photoleaving group B is eliminated to produce a compound I-2 having a hydroxyl group. And, when the atomic group A has an ultraviolet absorbing ability, the compound I-2 exhibits an ultraviolet absorbing ability.
原子団Aは、紫外線吸収能を有する原子団である。
本発明の化合物I-1は特定の波長の光が照射されることで、光脱離基Bが脱離し、水酸基を有する化合物I-2が生成される。そして、原子団Aが紫外線吸収能を有することにより、化合物I-2が紫外線吸収能を発揮する。 2. Atomic group A having ultraviolet absorbing ability
The atomic group A is an atomic group having an ultraviolet absorbing ability.
The compound I-1 of the present invention is irradiated with light of a specific wavelength, whereby the photoleaving group B is eliminated to produce a compound I-2 having a hydroxyl group. And, when the atomic group A has an ultraviolet absorbing ability, the compound I-2 exhibits an ultraviolet absorbing ability.
「紫外線吸収能を有する」とは、例えば、紫外線吸収能を有する化合物、具体的には光脱離基Bの脱離後の化合物I-1、即ち、化合物I-2が、波長が250nm以上450nm以下の範囲の光を吸収できるものとすることができる。本発明において紫外線吸収能を有する原子団は、紫外線吸収能を有する基又は紫外線吸収能を有する基を少なくとも一つ有する原子の集合体とすることができる。
紫外線吸収能を有するとは、より具体的には、光脱離基Bの脱離後の化合物I-1、即ち、化合物I-2が、波長250nm以上600nm以内の範囲で、最大吸収波長が250nm以上400nm以下である光を吸収することができ、最大吸収波長が260nm以上390nm以下の光を吸収することができることが好ましく、最大吸収波長が280nm以上380nm以下の光を吸収することが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
光脱離基Bの脱離後の化合物I-1、即ち、化合物I-2の最大吸収波長は、例えば、以下の測定方法で測定することができる。
評価用サンプルとして、例えば、光脱離基Bの脱離後の化合物I-1、即ち、化合物I-2を溶媒(アセトニトリル)中に0.01質量%の濃度となるように溶解したものを用いる。そして、評価用サンプルを、石英セル(光路長10mm、厚み1.25mm)に充填し、吸光光度計(例えば、U-3900(日立ハイテクサイエンス社製)を用いて吸光度を測定することで得ることができる。 The phrase "having ultraviolet absorbing ability" means, for example, a compound having ultraviolet absorbing ability, specifically, compound I-1 after elimination of photoleaving group B, ie, compound I-2, having a wavelength of 250 nm or more It can be capable of absorbing light in the range of 450 nm or less. In the present invention, the atomic group having ultraviolet absorbing ability can be a group of atoms having at least one group having ultraviolet absorbing ability or at least one group having ultraviolet absorbing ability.
More specifically, the compound I-1 after elimination of the photoleaving group B, that is, the compound I-2, has a maximum absorption wavelength within the wavelength range of 250 nm to 600 nm. It is preferably capable of absorbing light having a wavelength of 250 nm to 400 nm and capable of absorbing light having a maximum absorption wavelength of 260 nm to 390 nm, and particularly preferably absorbing a light having a maximum absorption wavelength of 280 nm to 380 nm. . This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The maximum absorption wavelength of the compound I-1 after removal of the photoleaving group B, ie, the compound I-2, can be measured, for example, by the following measurement method.
As a sample for evaluation, for example, a compound I-1 after elimination of the photoleaving group B, that is, a compound I-2 dissolved in a solvent (acetonitrile) to a concentration of 0.01% by mass, is used. Use. Then, the evaluation sample is filled in a quartz cell (optical path length 10 mm, thickness 1.25 mm), and obtained by measuring the absorbance using an absorptiometer (for example, U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.)) Can.
紫外線吸収能を有するとは、より具体的には、光脱離基Bの脱離後の化合物I-1、即ち、化合物I-2が、波長250nm以上600nm以内の範囲で、最大吸収波長が250nm以上400nm以下である光を吸収することができ、最大吸収波長が260nm以上390nm以下の光を吸収することができることが好ましく、最大吸収波長が280nm以上380nm以下の光を吸収することが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができるからである。
光脱離基Bの脱離後の化合物I-1、即ち、化合物I-2の最大吸収波長は、例えば、以下の測定方法で測定することができる。
評価用サンプルとして、例えば、光脱離基Bの脱離後の化合物I-1、即ち、化合物I-2を溶媒(アセトニトリル)中に0.01質量%の濃度となるように溶解したものを用いる。そして、評価用サンプルを、石英セル(光路長10mm、厚み1.25mm)に充填し、吸光光度計(例えば、U-3900(日立ハイテクサイエンス社製)を用いて吸光度を測定することで得ることができる。 The phrase "having ultraviolet absorbing ability" means, for example, a compound having ultraviolet absorbing ability, specifically, compound I-1 after elimination of photoleaving group B, ie, compound I-2, having a wavelength of 250 nm or more It can be capable of absorbing light in the range of 450 nm or less. In the present invention, the atomic group having ultraviolet absorbing ability can be a group of atoms having at least one group having ultraviolet absorbing ability or at least one group having ultraviolet absorbing ability.
More specifically, the compound I-1 after elimination of the photoleaving group B, that is, the compound I-2, has a maximum absorption wavelength within the wavelength range of 250 nm to 600 nm. It is preferably capable of absorbing light having a wavelength of 250 nm to 400 nm and capable of absorbing light having a maximum absorption wavelength of 260 nm to 390 nm, and particularly preferably absorbing a light having a maximum absorption wavelength of 280 nm to 380 nm. . This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
The maximum absorption wavelength of the compound I-1 after removal of the photoleaving group B, ie, the compound I-2, can be measured, for example, by the following measurement method.
As a sample for evaluation, for example, a compound I-1 after elimination of the photoleaving group B, that is, a compound I-2 dissolved in a solvent (acetonitrile) to a concentration of 0.01% by mass, is used. Use. Then, the evaluation sample is filled in a quartz cell (optical path length 10 mm, thickness 1.25 mm), and obtained by measuring the absorbance using an absorptiometer (for example, U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.)) Can.
また、本発明の化合物I-1は、光脱離基Bの脱離前の化合物I-1の最大吸収波長と光脱離基Bの脱離後の化合物I-1(化合物I-2)の最大吸収波長を比較したときに、250nm以上600nm以内の範囲で、光脱離基Bの脱離前の化合物I-1の最大吸収波長が、化合物I-2の最大吸収波長よりも短波長であることが好ましい。光硬化性組成物への適用が容易となるからである。
上記化合物I-1の、上記光脱離基Bの脱離後の化合物I-2との最大吸収波長の差は、1nm以上であることが好ましく、1nm以上100nm以下であることがより好ましく、1nm以上50nm以下であることが特に好ましい。光硬化性組成物への適用が容易となるからである。 The compound I-1 of the present invention is a compound I-1 (compound I-2) after the elimination of the photoleaving group B and the maximum absorption wavelength of the compound I-1 before the elimination of the photoleaving group B. The maximum absorption wavelength of compound I-1 before elimination of photoleaving group B is shorter than the maximum absorption wavelength of compound I-2 in the range of 250 nm to 600 nm when the maximum absorption wavelength of Is preferred. It is because application to a photocurable composition becomes easy.
The difference in the maximum absorption wavelength of the compound I-1 with the compound I-2 after elimination of the photoleaving group B is preferably 1 nm or more, and more preferably 1 nm to 100 nm. It is particularly preferable to be 1 nm or more and 50 nm or less. It is because application to a photocurable composition becomes easy.
上記化合物I-1の、上記光脱離基Bの脱離後の化合物I-2との最大吸収波長の差は、1nm以上であることが好ましく、1nm以上100nm以下であることがより好ましく、1nm以上50nm以下であることが特に好ましい。光硬化性組成物への適用が容易となるからである。 The compound I-1 of the present invention is a compound I-1 (compound I-2) after the elimination of the photoleaving group B and the maximum absorption wavelength of the compound I-1 before the elimination of the photoleaving group B. The maximum absorption wavelength of compound I-1 before elimination of photoleaving group B is shorter than the maximum absorption wavelength of compound I-2 in the range of 250 nm to 600 nm when the maximum absorption wavelength of Is preferred. It is because application to a photocurable composition becomes easy.
The difference in the maximum absorption wavelength of the compound I-1 with the compound I-2 after elimination of the photoleaving group B is preferably 1 nm or more, and more preferably 1 nm to 100 nm. It is particularly preferable to be 1 nm or more and 50 nm or less. It is because application to a photocurable composition becomes easy.
このような原子団Aとしては、フェノール性水酸基を有する紫外線吸収剤に一般的に用いられる原子団と同様とすることができる。すなわち、上記化合物I-2は、フェノール性水酸基を有する紫外線吸収剤として一般的に用いられるものである。
具体的には、上記化合物I-2として、特開2017-008221号公報に記載の2-ヒドロキシベンゾフェノン類、2-(2'-ヒドロキシフェニル)ベンゾトリアゾール類、ベンゾエート類及びトリアリールトリアジン類等や、特開2002-97224号公報に記載のベンゾトリアゾール系紫外線吸収剤及びベンゾフェノン系紫外線吸収剤等を用いることができる。 Such atomic group A can be the same as the atomic group generally used for a UV absorber having a phenolic hydroxyl group. That is, the compound I-2 is generally used as a UV absorber having a phenolic hydroxyl group.
Specifically, as the compound I-2, 2-hydroxybenzophenones, 2- (2'-hydroxyphenyl) benzotriazoles, benzoates and triaryltriazines described in JP-A-2017-008221, etc. For example, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers described in JP-A-2002-97224 can be used.
具体的には、上記化合物I-2として、特開2017-008221号公報に記載の2-ヒドロキシベンゾフェノン類、2-(2'-ヒドロキシフェニル)ベンゾトリアゾール類、ベンゾエート類及びトリアリールトリアジン類等や、特開2002-97224号公報に記載のベンゾトリアゾール系紫外線吸収剤及びベンゾフェノン系紫外線吸収剤等を用いることができる。 Such atomic group A can be the same as the atomic group generally used for a UV absorber having a phenolic hydroxyl group. That is, the compound I-2 is generally used as a UV absorber having a phenolic hydroxyl group.
Specifically, as the compound I-2, 2-hydroxybenzophenones, 2- (2'-hydroxyphenyl) benzotriazoles, benzoates and triaryltriazines described in JP-A-2017-008221, etc. For example, benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers described in JP-A-2002-97224 can be used.
上記原子団Aとしては、例えば、光脱離基Bによりフェノール性水酸基が保護されているフェノール構造、すなわち、上記B-O-が直接結合しているベンゼン環を含むものが挙げられる。具体的には、B-O-が直接結合するベンゼン環とベンゾトリアゾール環とを含む原子団;B-O-が直接結合するベンゾフェノン環を含む原子団;及びB-O-が直接結合するベンゼン環とトリアジン環を含む原子団を挙げることができる。ベンゾトリアゾール基、ベンゾフェノン基及びトリアジン基の少なくとも1種の基が、上記フェノール構造に含まれるベンゼン環に直接結合している構造を含むものであることが好ましく、なかでも、ベンゾトリアゾール基、ベンゾフェノン基及びトリアジン基の少なくとも1種の基のベンゼン環への結合位置が、上記B-O-の結合位置に対して、オルト位であるものであることが好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物とすることが容易だからである。
Examples of the atomic group A include a phenol structure in which a phenolic hydroxyl group is protected by a photoleaving group B, that is, one containing a benzene ring to which the B-O- is directly bonded. Specifically, an atomic group containing a benzene ring and a benzotriazole ring to which B-O- is directly bonded; an atomic group containing a benzophenone ring to which B-O- is directly bonded; and benzene to which B-O- is directly bonded Mention may be made of atomic groups comprising a ring and a triazine ring. It is preferable that at least one group of a benzotriazole group, a benzophenone group and a triazine group includes a structure directly bonded to a benzene ring contained in the above-mentioned phenol structure, and among them, a benzotriazole group, a benzophenone group and triazine group It is preferable that the bonding position of at least one group of the group to the benzene ring is ortho to the bonding position of B-O-. It is because it is easy to set it as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
本願発明の化合物I-1としては、例えば、下記一般式(A-1)、(A-2)及び(A-3)で表されるものを挙げることができる。
Examples of the compound I-1 of the present invention include those represented by the following general formulas (A-1), (A-2) and (A-3).
(式中、R1及びR2は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基、炭素原子数2~20の複素環含有基又は前記-O-Bを表し、
R1及びR2の少なくとも一方は、前記-O-Bであり、
R3、R4、R5、R6、R7及びR8は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R1、R2、R3、R4、R5、R6、R7及びR8で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合もあり、
R’は、水素原子又は炭素原子数1~8のアルキル基を表し、
複数のR3同士、複数のR4同士、複数のR5同士、複数のR6同士及び複数のR7同士は、それぞれ結合してベンゼン環又はナフタレン環を形成している場合があり、
複数のR3、R4、R5、R6、R7及びR8は、それぞれ同じ場合があり、異なる場合があり、
m1及びm2は、それぞれ独立に、1~10の整数を表し、
nは、1~3の整数を表し、
a1は、0~4の整数を表し、
a2は、0~2の整数を表し、
a3は、0~4の整数を表し、
a4は、0~3の整数を表し、
a5は、0~3の整数を表し、
a6は、0~3-nの整数を表し、
X1及びX2は、それぞれm1価及びm2価の結合基を表す。) (Wherein, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl having 6 to 20 carbon atoms A group, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or the above -O-B,
At least one of R 1 and R 2 is the above-mentioned -O-B
R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, the number of carbon atoms An aryl group of 6 to 20, an arylalkyl group of 7 to 20 carbon atoms, or a heterocycle-containing group of 2 to 20 carbon atoms,
The methylene group in the alkyl group or arylalkyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO 2 -or a combination of these may be substituted,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R 3 's , a plurality of R 4' s , a plurality of R 5 's , a plurality of R 6' s and a plurality of R 7 's may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be the same or different.
m1 and m2 each independently represent an integer of 1 to 10,
n represents an integer of 1 to 3;
a1 represents an integer of 0 to 4;
a2 represents an integer of 0 to 2;
a3 represents an integer of 0 to 4;
a4 represents an integer of 0 to 3;
a5 represents an integer of 0 to 3;
a6 represents an integer of 0 to 3-n,
X 1 and X 2 each represent an m1 monovalent or m2 divalent linking group. )
R1及びR2の少なくとも一方は、前記-O-Bであり、
R3、R4、R5、R6、R7及びR8は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R1、R2、R3、R4、R5、R6、R7及びR8で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合もあり、
R’は、水素原子又は炭素原子数1~8のアルキル基を表し、
複数のR3同士、複数のR4同士、複数のR5同士、複数のR6同士及び複数のR7同士は、それぞれ結合してベンゼン環又はナフタレン環を形成している場合があり、
複数のR3、R4、R5、R6、R7及びR8は、それぞれ同じ場合があり、異なる場合があり、
m1及びm2は、それぞれ独立に、1~10の整数を表し、
nは、1~3の整数を表し、
a1は、0~4の整数を表し、
a2は、0~2の整数を表し、
a3は、0~4の整数を表し、
a4は、0~3の整数を表し、
a5は、0~3の整数を表し、
a6は、0~3-nの整数を表し、
X1及びX2は、それぞれm1価及びm2価の結合基を表す。) (Wherein, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl having 6 to 20 carbon atoms A group, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or the above -O-B,
At least one of R 1 and R 2 is the above-mentioned -O-B
R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, the number of carbon atoms An aryl group of 6 to 20, an arylalkyl group of 7 to 20 carbon atoms, or a heterocycle-containing group of 2 to 20 carbon atoms,
The methylene group in the alkyl group or arylalkyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO 2 -or a combination of these may be substituted,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R 3 's , a plurality of R 4' s , a plurality of R 5 's , a plurality of R 6' s and a plurality of R 7 's may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be the same or different.
m1 and m2 each independently represent an integer of 1 to 10,
n represents an integer of 1 to 3;
a1 represents an integer of 0 to 4;
a2 represents an integer of 0 to 2;
a3 represents an integer of 0 to 4;
a4 represents an integer of 0 to 3;
a5 represents an integer of 0 to 3;
a6 represents an integer of 0 to 3-n,
X 1 and X 2 each represent an m1 monovalent or m2 divalent linking group. )
上記R1、R2、R3、R4、R5、R6、R7及びR8で表される炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基、炭素原子数2~20の複素環含有基、及びR’で表される炭素原子数1~8のアルキル基としては、上記「1.光脱離基B」の項に記載のR11等及びR’として例示したものを挙げることができる。
An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carbon atom represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Examples of the arylalkyl group having 7 to 20 carbons, a heterocycle-containing group having 2 to 20 carbons, and the alkyl group having 1 to 8 carbons represented by R ′ include the above-mentioned “1. And those exemplified as R 11 etc. and R ′ described in the above section can be mentioned.
上記R1及びR2は、少なくとも一方が、上記-O-Bである。
上記R1及びR2は、合成容易の観点からは、一方が上記-O-Bであることが好ましい。
上記R1及びR2は、紫外線吸収能の変化を大きいものとする観点からは、R1及びR2の両者が上記-O-Bであることが好ましい。
上記R1及びR2は、一方のみが上記-O-Bである場合、他方は、水素原子、水酸基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基であることが好ましく、水素原子又は炭素原子数1~40のアルキル基であることがより好ましい。上記R1及びR2の他方が、上記官能基であることで、上記化合物I-1は、紫外線吸収能の変化が大きいものとなるからである。また、上記化合物I-1は、硬化阻害が少ないものとなるからである。
また、上記アルキル基及びアリールアルキル基等としては、例えば、メチレン基が-O-、-CO-等により中断されているもの等も好ましく用いることができる。 At least one of R 1 and R 2 is -O-B.
From the viewpoint of easiness of synthesis, it is preferable that one of the R 1 and R 2 be the above-described —O—B.
From the viewpoint of making the change of the ultraviolet ray absorbing ability large, in the above R 1 and R 2 , it is preferable that both R 1 and R 2 be the above-described —O—B.
R 1 and R 2 each represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carbon atom, when only one is the above —O—B It is preferably an arylalkyl group having 7 to 20 atoms or a heterocyclic group having 2 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms. When the other of R 1 and R 2 is the above functional group, the compound I-1 has a large change in the ultraviolet light absorbing ability. In addition, the compound I-1 has a reduced inhibition of curing.
Further, as the above-mentioned alkyl group and arylalkyl group, for example, those in which a methylene group is interrupted by -O-, -CO- or the like can be preferably used.
上記R1及びR2は、合成容易の観点からは、一方が上記-O-Bであることが好ましい。
上記R1及びR2は、紫外線吸収能の変化を大きいものとする観点からは、R1及びR2の両者が上記-O-Bであることが好ましい。
上記R1及びR2は、一方のみが上記-O-Bである場合、他方は、水素原子、水酸基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基であることが好ましく、水素原子又は炭素原子数1~40のアルキル基であることがより好ましい。上記R1及びR2の他方が、上記官能基であることで、上記化合物I-1は、紫外線吸収能の変化が大きいものとなるからである。また、上記化合物I-1は、硬化阻害が少ないものとなるからである。
また、上記アルキル基及びアリールアルキル基等としては、例えば、メチレン基が-O-、-CO-等により中断されているもの等も好ましく用いることができる。 At least one of R 1 and R 2 is -O-B.
From the viewpoint of easiness of synthesis, it is preferable that one of the R 1 and R 2 be the above-described —O—B.
From the viewpoint of making the change of the ultraviolet ray absorbing ability large, in the above R 1 and R 2 , it is preferable that both R 1 and R 2 be the above-described —O—B.
R 1 and R 2 each represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carbon atom, when only one is the above —O—B It is preferably an arylalkyl group having 7 to 20 atoms or a heterocyclic group having 2 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms. When the other of R 1 and R 2 is the above functional group, the compound I-1 has a large change in the ultraviolet light absorbing ability. In addition, the compound I-1 has a reduced inhibition of curing.
Further, as the above-mentioned alkyl group and arylalkyl group, for example, those in which a methylene group is interrupted by -O-, -CO- or the like can be preferably used.
上記R3、R4、R5、R6、R7及びR8は、シアノ基、水酸基、炭素原子数1~40のアルキル基、炭素原子数7~20のアリールアルキル基であることが好ましく、シアノ基、水酸基、炭素原子数1~20のアルキル基、炭素原子数7~10のアリールアルキル基であることがより好ましく、なかでも、炭素原子数3~20のアルキル基であることがより好ましく、炭素原子数3~10のアルキル基であることがより好ましい。本発明の化合物I-1の合成が容易となり、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。
R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are preferably a cyano group, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms More preferably a cyano group, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms, and more preferably an alkyl group having 3 to 20 carbon atoms. The alkyl group is preferably an alkyl group having 3 to 10 carbon atoms. This is because the synthesis of the compound I-1 of the present invention is facilitated, and the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
また、光脱離基Bの脱離後に優れた紫外線吸収能を発揮可能とする観点からは、R4は、炭素原子数3~15の分岐構造を有するアルキル基であることが好ましく、炭素原子数5~12の分岐構造を有するアルキル基であることがより好ましく、炭素原子数6~11の分岐構造を有するアルキル基であることが更に好ましく、炭素原子数7~10の分岐構造を有するアルキル基であることが特に好ましい。
R4のベンゼン環中の結合箇所としては、結合可能ないずれの位置に結合するものであってもよいが、-O-Bの結合箇所に対して、パラ位であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。 Further, from the viewpoint of being able to exhibit excellent ultraviolet light absorbing ability after elimination of the photoleaving group B, R 4 is preferably an alkyl group having a branched structure of 3 to 15 carbon atoms, An alkyl group having a branched structure of 5 to 12 is more preferable, an alkyl group having a branched structure of 6 to 11 carbon atoms is still more preferable, and an alkyl having a branched structure of 7 to 10 carbon atoms Particularly preferred is a group.
The bonding site in the benzene ring of R 4 may be bonded to any bondable position, but is preferably para to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
R4のベンゼン環中の結合箇所としては、結合可能ないずれの位置に結合するものであってもよいが、-O-Bの結合箇所に対して、パラ位であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。 Further, from the viewpoint of being able to exhibit excellent ultraviolet light absorbing ability after elimination of the photoleaving group B, R 4 is preferably an alkyl group having a branched structure of 3 to 15 carbon atoms, An alkyl group having a branched structure of 5 to 12 is more preferable, an alkyl group having a branched structure of 6 to 11 carbon atoms is still more preferable, and an alkyl having a branched structure of 7 to 10 carbon atoms Particularly preferred is a group.
The bonding site in the benzene ring of R 4 may be bonded to any bondable position, but is preferably para to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
光脱離基Bの脱離後に優れた紫外線吸収能を発揮可能とする観点からは、R5及びR6は、ベンゼン環側末端のメチレン基が-O-で置き換わっている炭素原子数1~20のアルキル基、すなわち、炭素原子数1~20のアルコキシ基であることが好ましく、なかでも、炭素原子数3~15のアルコキシ基であることが好ましく、炭素原子数5~12のアルコキシ基であることが特に好ましい。
R5及びR6のベンゼン環中の結合箇所としては、結合可能ないずれの位置に結合するものであってもよいが、-O-Bの結合箇所に対して、メタ位であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。 From the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of the photoleaving group B, R 5 and R 6 each have 1 to 10 carbon atoms in which the methylene group at the benzene ring side terminal is replaced by -O- 20 alkyl groups, that is, alkoxy groups having 1 to 20 carbon atoms are preferable, and alkoxy groups having 3 to 15 carbon atoms are particularly preferable, and alkoxy groups having 5 to 12 carbon atoms are preferable. Being particularly preferred.
The bonding site in the benzene ring of R 5 and R 6 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. . This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
R5及びR6のベンゼン環中の結合箇所としては、結合可能ないずれの位置に結合するものであってもよいが、-O-Bの結合箇所に対して、メタ位であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。 From the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of the photoleaving group B, R 5 and R 6 each have 1 to 10 carbon atoms in which the methylene group at the benzene ring side terminal is replaced by -O- 20 alkyl groups, that is, alkoxy groups having 1 to 20 carbon atoms are preferable, and alkoxy groups having 3 to 15 carbon atoms are particularly preferable, and alkoxy groups having 5 to 12 carbon atoms are preferable. Being particularly preferred.
The bonding site in the benzene ring of R 5 and R 6 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. . This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
光脱離基Bの脱離後に優れた紫外線吸収能を発揮可能とする観点からは、R7は、ベンゼン環側末端のメチレン基が-O-で置き換わっている炭素原子数1~20のアルキル基、すなわち、炭素原子数1~20のアルコキシ基であることが好ましく、なかでも、ベンゼン環側末端以外のメチレン鎖が、-O-、-O-CO-で置き換えられた炭素原子数3~20のアルコキシ基であることが好ましく、特に、ベンゼン環側末端以外のメチレン鎖が-O-、-O-CO-で置き換えられた炭素原子数3~15のアルコキシ基であることが好ましく、特に、ベンゼン環側末端以外のメチレン鎖が-O-、-O-CO-で置き換えられた炭素原子数6~15のアルコキシ基であることが好ましく、なかでも特に、ベンゼン環側末端以外のメチレン鎖が-O-、-O-CO-で置き換えられた炭素原子数8~13のアルコキシ基であることが好ましい。
R7のベンゼン環中の結合箇所としては、結合可能ないずれの位置に結合するものであってもよいが、-O-Bの結合箇所に対して、メタ位であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。
光脱離基Bの脱離後に優れた紫外線吸収能を発揮可能とする観点からは、R8は、炭素原子数6~20のアリール基であることが好ましく、なかでも、炭素原子数6~12のアリール基であることが好ましく、特に、置換基を有している場合があるフェニル基であることが好ましい。 From the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of photoleaving group B, R 7 is an alkyl having 1 to 20 carbon atoms in which the methylene group at the terminal of the benzene ring is replaced by -O- Group, that is, an alkoxy group having 1 to 20 carbon atoms is preferable, and in particular, a methylene chain other than the benzene ring side terminal is substituted by -O- or -O-CO-, having 3 to carbon atoms 20 alkoxy groups are preferable, and particularly, an alkoxy group having 3 to 15 carbon atoms in which a methylene chain other than the benzene ring side terminal is replaced by -O- or -O-CO- is particularly preferable, in particular And an alkoxy group having 6 to 15 carbon atoms in which a methylene chain other than the benzene ring side end is replaced by -O- or -O-CO-, and in particular, a methylene chain other than the benzene ring side end Is preferably an alkoxy group having 8 to 13 carbon atoms substituted with -O- or -O-CO-.
The bonding site in the benzene ring of R 7 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
R8 is preferably an aryl group having 6 to 20 carbon atoms from the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of the photoleaving group B, and in particular, it is possible to use 6 to 12 carbon atoms. The aryl group is preferably an aryl group, and particularly preferably a phenyl group which may have a substituent.
R7のベンゼン環中の結合箇所としては、結合可能ないずれの位置に結合するものであってもよいが、-O-Bの結合箇所に対して、メタ位であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。
光脱離基Bの脱離後に優れた紫外線吸収能を発揮可能とする観点からは、R8は、炭素原子数6~20のアリール基であることが好ましく、なかでも、炭素原子数6~12のアリール基であることが好ましく、特に、置換基を有している場合があるフェニル基であることが好ましい。 From the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of photoleaving group B, R 7 is an alkyl having 1 to 20 carbon atoms in which the methylene group at the terminal of the benzene ring is replaced by -O- Group, that is, an alkoxy group having 1 to 20 carbon atoms is preferable, and in particular, a methylene chain other than the benzene ring side terminal is substituted by -O- or -O-CO-, having 3 to carbon atoms 20 alkoxy groups are preferable, and particularly, an alkoxy group having 3 to 15 carbon atoms in which a methylene chain other than the benzene ring side terminal is replaced by -O- or -O-CO- is particularly preferable, in particular And an alkoxy group having 6 to 15 carbon atoms in which a methylene chain other than the benzene ring side end is replaced by -O- or -O-CO-, and in particular, a methylene chain other than the benzene ring side end Is preferably an alkoxy group having 8 to 13 carbon atoms substituted with -O- or -O-CO-.
The bonding site in the benzene ring of R 7 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
R8 is preferably an aryl group having 6 to 20 carbon atoms from the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of the photoleaving group B, and in particular, it is possible to use 6 to 12 carbon atoms. The aryl group is preferably an aryl group, and particularly preferably a phenyl group which may have a substituent.
また、上記アルキル基及び上記アリールアルキル基としては、メチレン基が中断されていないもの、及び-O-、-CO-等により中断されているものいずれも好ましく用いることができる。
In addition, as the above-mentioned alkyl group and the above-mentioned arylalkyl group, any of those in which a methylene group is not interrupted, and those in which it is interrupted by -O-, -CO- or the like can be preferably used.
上記m1及びm2は、1~10の整数を表す。合成の容易さの観点から、上記m1及びm2は、それぞれ独立に、1~6の整数であることが好ましく、1~4の整数であることがより好ましく、1~3の整数であることが特に好ましく、なかでも特に、1~2の整数であることが好ましい。上記化合物I-1の合成が容易となり、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮するからである。
また、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する観点からは、m2は、1の整数であることが好ましい。 The above m1 and m2 represent an integer of 1 to 10. From the viewpoint of easiness of synthesis, m1 and m2 are preferably each independently an integer of 1 to 6, more preferably an integer of 1 to 4, and an integer of 1 to 3 It is particularly preferable, and in particular, an integer of 1 to 2 is particularly preferable. This is because the synthesis of the compound I-1 is facilitated, and the compound I-1 exhibits an excellent ultraviolet absorbing ability after the elimination of the photoleaving group B.
Further, from the viewpoint of the compound I-1 exerting an excellent ultraviolet absorbing ability after elimination of the photoleaving group B, m2 is preferably an integer of 1.
また、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する観点からは、m2は、1の整数であることが好ましい。 The above m1 and m2 represent an integer of 1 to 10. From the viewpoint of easiness of synthesis, m1 and m2 are preferably each independently an integer of 1 to 6, more preferably an integer of 1 to 4, and an integer of 1 to 3 It is particularly preferable, and in particular, an integer of 1 to 2 is particularly preferable. This is because the synthesis of the compound I-1 is facilitated, and the compound I-1 exhibits an excellent ultraviolet absorbing ability after the elimination of the photoleaving group B.
Further, from the viewpoint of the compound I-1 exerting an excellent ultraviolet absorbing ability after elimination of the photoleaving group B, m2 is preferably an integer of 1.
上記nは、1~3の整数を表す。化合物I-1が紫外線吸収能の変化が大きいものとなる観点から、上記nは2~3の整数であることが好ましく、3であることが特に好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する観点からは、上記nは、1~2の整数であることが好ましく、1であることが特に好ましい。
The above n represents an integer of 1 to 3. The above n is preferably an integer of 2 to 3, and particularly preferably 3, from the viewpoint that the compound I-1 has a large change in the ultraviolet light absorbing ability. From the viewpoint of exhibiting excellent ultraviolet absorbing ability after removal of the photoleaving group B, the compound n is preferably an integer of 1 to 2, and particularly preferably 1.
上記a1及びa3は、それぞれ独立に、0~4の整数を表す。合成の容易さの観点から、上記a1及びa3は、それぞれ独立に、0~3の整数であることが好ましく、0~2の整数であることがより好ましく、0~1の整数であることが特に好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する化合物とすることができるからである。
上記a2は、0~2の整数の整数を表す。溶解性の観点から、上記a2は1~2の整数であることが好ましい。また、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する観点からは、上記a2は、1であることが好ましい。
上記a4及びa5は、それぞれ独立に、0~3の整数を表す。合成の容易さの観点から、上記a4及びa5は0~2の整数であることが好ましく、1~2の整数であることが特に好ましく、特に1であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する化合物とすることができるからである。
上記a6は、0~3-nの整数を表す。上記a6は、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する観点、合成の容易さの観点から、0~1の整数であることが好ましく、0であることが好ましい。 The above a1 and a3 each independently represent an integer of 0 to 4. From the viewpoint of easiness of synthesis, the above a1 and a3 are preferably each independently an integer of 0 to 3, more preferably an integer of 0 to 2, and an integer of 0 to 1 Particularly preferred. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
The above a2 represents an integer of an integer of 0 to 2. From the viewpoint of solubility, the a2 is preferably an integer of 1 to 2. Further, from the viewpoint of exhibiting excellent ultraviolet absorbing ability after the compound I-1 exhibits the elimination of the photoleaving group B, the a2 is preferably 1.
The above a4 and a5 each independently represent an integer of 0 to 3. From the viewpoint of easiness of synthesis, the above a4 and a5 are preferably an integer of 0 to 2, particularly preferably an integer of 1 to 2, and particularly preferably 1. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
The above a6 represents an integer of 0 to 3-n. The above a6 is preferably an integer of 0 to 1, and is 0, from the viewpoint that compound I-1 exerts an excellent ultraviolet absorptivity after removal of photoleaving group B and easiness of synthesis. Is preferred.
上記a2は、0~2の整数の整数を表す。溶解性の観点から、上記a2は1~2の整数であることが好ましい。また、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する観点からは、上記a2は、1であることが好ましい。
上記a4及びa5は、それぞれ独立に、0~3の整数を表す。合成の容易さの観点から、上記a4及びa5は0~2の整数であることが好ましく、1~2の整数であることが特に好ましく、特に1であることが好ましい。化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する化合物とすることができるからである。
上記a6は、0~3-nの整数を表す。上記a6は、化合物I-1が光脱離基Bの脱離後に優れた紫外線吸収能を発揮する観点、合成の容易さの観点から、0~1の整数であることが好ましく、0であることが好ましい。 The above a1 and a3 each independently represent an integer of 0 to 4. From the viewpoint of easiness of synthesis, the above a1 and a3 are preferably each independently an integer of 0 to 3, more preferably an integer of 0 to 2, and an integer of 0 to 1 Particularly preferred. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
The above a2 represents an integer of an integer of 0 to 2. From the viewpoint of solubility, the a2 is preferably an integer of 1 to 2. Further, from the viewpoint of exhibiting excellent ultraviolet absorbing ability after the compound I-1 exhibits the elimination of the photoleaving group B, the a2 is preferably 1.
The above a4 and a5 each independently represent an integer of 0 to 3. From the viewpoint of easiness of synthesis, the above a4 and a5 are preferably an integer of 0 to 2, particularly preferably an integer of 1 to 2, and particularly preferably 1. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
The above a6 represents an integer of 0 to 3-n. The above a6 is preferably an integer of 0 to 1, and is 0, from the viewpoint that compound I-1 exerts an excellent ultraviolet absorptivity after removal of photoleaving group B and easiness of synthesis. Is preferred.
上記一般式(A-1)及び(A-2)で表される化合物I-1は、X1及びX2(以下、Xと称する場合がある。)で表されるm1価又はm2価(以下、m価と称する場合がある。)の特定の原子又は基に、m1個又はm2個(以下、m個と称する場合がある。)の特定の基が結合した構造を有する。このm個の特定の基は、互いに同じである場合があり、異なる場合がある。
The compounds I-1 represented by the above general formulas (A-1) and (A-2) are each represented by X 1 and X 2 (hereinafter sometimes referred to as X) an m monovalent or m divalent Hereinafter, it has a structure in which m1 or m2 (hereinafter sometimes referred to as m) specific groups are bonded to a specific atom or group which may be referred to as m-valent). The m specific groups may be identical to one another or may be different.
上記Xは、m価の結合基を表すものである。
上記結合基Xとしては、具体的には、直接結合、水素原子、窒素原子、酸素原子、硫黄原子、リン原子、下記(II-a)若しくは(II-b)で表される基、>C=O、>NR53、-OR53、-SR53、-NR53R54又はmと同数の価数を有する炭素原子数1~120の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基若しくは炭素原子数2~35の複素環含有基を表し、R53及びR54は、それぞれ独立に、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NH-CO-O-、-NR’-、-S-S-、-SO2-、窒素原子又はこれらの組み合わせで中断されている場合もあり、上記芳香環又は複素環は、他の環と縮合されている場合もある。
但し、Xが窒素原子、リン原子又は下記(II-a)又は(II-b)で表される結合基の場合、mは3であり、Xが酸素原子又は硫黄原子、>C=O、-NH-CO-、-CO-NH-又は>NR53の場合、mは2であり、Xが-OR53、-SR53又は-NR53R54の場合、mは1であり、Xは、ベンゼン環と一緒になって環を形成している場合もある。 The above X represents an m-valent bonding group.
Specifically, the bonding group X is a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following (II-a) or (II-b),> C OO,> NR 53 , -OR 53 , -SR 53 , -NR 53 R 54 or an aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same number of valences as m, an aromatic having 6 to 35 carbon atoms And R 53 and R 54 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, or the number of carbon atoms. And an aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic group having 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the aromatic ring containing hydrocarbon group and the heterocyclic group are -O-,- S-, -CO-, -O-CO-, -CO-O-, -O-CO-O- -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH -CO-O -, - NH- CO-O -, - NR '-, - S-S -, - SO 2 -, nitrogen atom or may have been interrupted in these combinations, the aromatic or heterocyclic The ring may be fused to another ring.
However, in the case where X is a nitrogen atom, a phosphorus atom or a bonding group represented by (II-a) or (II-b) below, m is 3, and X is an oxygen atom or a sulfur atom,> C = O, In the case of -NH-CO-, -CO-NH- or> NR 53 , m is 2 and when X is -OR 53 , -SR 53 or -NR 53 R 54 , m is 1 and X is And may form a ring together with a benzene ring.
上記結合基Xとしては、具体的には、直接結合、水素原子、窒素原子、酸素原子、硫黄原子、リン原子、下記(II-a)若しくは(II-b)で表される基、>C=O、>NR53、-OR53、-SR53、-NR53R54又はmと同数の価数を有する炭素原子数1~120の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基若しくは炭素原子数2~35の複素環含有基を表し、R53及びR54は、それぞれ独立に、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NH-CO-O-、-NR’-、-S-S-、-SO2-、窒素原子又はこれらの組み合わせで中断されている場合もあり、上記芳香環又は複素環は、他の環と縮合されている場合もある。
但し、Xが窒素原子、リン原子又は下記(II-a)又は(II-b)で表される結合基の場合、mは3であり、Xが酸素原子又は硫黄原子、>C=O、-NH-CO-、-CO-NH-又は>NR53の場合、mは2であり、Xが-OR53、-SR53又は-NR53R54の場合、mは1であり、Xは、ベンゼン環と一緒になって環を形成している場合もある。 The above X represents an m-valent bonding group.
Specifically, the bonding group X is a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following (II-a) or (II-b),> C OO,> NR 53 , -OR 53 , -SR 53 , -NR 53 R 54 or an aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same number of valences as m, an aromatic having 6 to 35 carbon atoms And R 53 and R 54 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, or the number of carbon atoms. And an aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic group having 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the aromatic ring containing hydrocarbon group and the heterocyclic group are -O-,- S-, -CO-, -O-CO-, -CO-O-, -O-CO-O- -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH -CO-O -, - NH- CO-O -, - NR '-, - S-S -, - SO 2 -, nitrogen atom or may have been interrupted in these combinations, the aromatic or heterocyclic The ring may be fused to another ring.
However, in the case where X is a nitrogen atom, a phosphorus atom or a bonding group represented by (II-a) or (II-b) below, m is 3, and X is an oxygen atom or a sulfur atom,> C = O, In the case of -NH-CO-, -CO-NH- or> NR 53 , m is 2 and when X is -OR 53 , -SR 53 or -NR 53 R 54 , m is 1 and X is And may form a ring together with a benzene ring.
(*は、*部分で隣接する基と結合することを意味する。)
(* Means that it bonds to an adjacent group in the * part.)
上記結合基Xで表される、mと同数の価数を有する炭素原子数1~120の脂肪族炭化水素基は、mが1価のものとしては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、第二ブチル基、第三ブチル基、イソブチル基、アミル基、イソアミル基、第三アミル基、シクロペンチル基、ヘキシル基、2-ヘキシル基、3-ヘキシル基、シクロヘキシル基、ビシクロヘキシル基、1-メチルシクロヘキシル基、ヘプチル基、2-ヘプチル基、3-ヘプチル基、イソヘプチル基、第三ヘプチル基、n-オクチル基、イソオクチル基、第三オクチル基、2-エチルヘキシル基、ノニル基、イソノニル基及びデシル基等のアルキル基;メチルオキシ基、エチルオキシ基、プロピルオキシ基、イソプロピルオキシ基、ブチルオキシ基、第二ブチルオキシ基、第三ブチルオキシ基、イソブチルオキシ基、アミルオキシ基、イソアミルオキシ基、第三アミルオキシ基、ヘキシルオキシ基、シクロヘキシルオキシ基、ヘプチルオキシ基、イソヘプチルオキシ基、第三ヘプチルオキシ基、n-オクチルオキシ基、イソオクチルオキシ基、第三オクチルオキシ基、2-エチルヘキシルオキシ基、ノニルオキシ基及びデシルオキシ基等のアルコキシ基;メチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ブチルチオ基、第二ブチルチオ基、第三ブチルチオ基、イソブチルチオ基、アミルチオ基、イソアミルチオ基、第三アミルチオ基、ヘキシルチオ基、シクロヘキシルチオ基、ヘプチルチオ基、イソヘプチルチオ基、第三ヘプチルチオ基、n-オクチルチオ基、イソオクチルチオ基、第三オクチルチオ基及び2-エチルヘキシルチオ基等のアルキルチオ基;ビニル基、1-メチルエテニル基、2-メチルエテニル基、2-プロペニル基、1-メチル-3-プロペニル基、3-ブテニル基、1-メチル-3-ブテニル基、イソブテニル基、3-ペンテニル基、4-ヘキセニル基、シクロヘキセニル基、ビシクロヘキセニル基、ヘプテニル基、オクテニル基、デセニル基、ぺンタデセニル基、エイコセニル基及びトリコセニル基等のアルケニル基;並びにこれらの基が後述する置換基により置換された基等が挙げられる。
The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is, for example, a methyl group, an ethyl group or a propyl group, as m is a monovalent group. , Isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl , Cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2- Alkyl groups such as ethylhexyl, nonyl, isononyl and decyl; methyloxy, ethyloxy, propyloxy, isopropyl Cyclic, butyloxy, secondary butyloxy, tertiary butyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, Alkoxy groups such as triheptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy and decyloxy; methylthio, ethylthio, propylthio, isopropylthio , Butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n Alkylthio groups such as octylthio, isooctylthio, tertiary octylthio and 2-ethylhexylthio; vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl group, 1-methyl-3-butenyl group, isobutenyl group, 3-pentenyl group, 4-hexenyl group, cyclohexenyl group, bicyclohexenyl group, heptenyl group, octenyl group, decenyl group, pentadecenyl group, eicosenyl group And alkenyl groups such as tricocenyl group; and groups in which these groups are substituted by a substituent described later.
上記結合基Xで表される、mと同数の価数を有する炭素原子数1~120の脂肪族炭化水素基は、mが2価のものとしては、メチレン基、エチレン基、プロピレン基、ブチレン基及びブチルジイル基等のアルキレン基;上記アルキレン基のメチレン鎖が-O-、-S-、-CO-O-、-O-CO-で置き換えられたもの;エタンジオール、プロパンジオール、ブタンジオール、ペンタンジオール、ヘキサンジオール等のジオール基の残基;エタンジチオール、プロパンジチオール、ブタンジチオール、ペンタンジチオール、ヘキサンジチオール等のジチオール基の残基及びこれらの基が後述する置換基により置換された基等が挙げられる。
The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the above linking group X, is a methylene group, an ethylene group, a propylene group, a butylene group as the one where m is divalent And alkylene groups such as butyldiyl group; those in which the methylene chain of the above alkylene group is replaced with -O-, -S-, -CO-O-, -O-CO-; ethanediol, propanediol, butanediol, Residues of diol groups such as pentanediol and hexanediol; Residues of dithiol groups such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol and the like, and groups in which these groups are substituted by a substituent described later It can be mentioned.
上記結合基Xで表される、mと同数の価数を有する炭素原子数1~120の脂肪族炭化水素基は、mが3価のものとしては、例えば、プロピリジン基及び1,1,3-ブチリジンプロピリジン基等のアルキリジン基;並びにこれらの基が後述する置換基により置換された基が挙げられる。
The aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the above linking group X, is, for example, a propyridine group and 1,1, Alkylidine groups such as 3-butylidine propyridine group; and groups in which these groups are substituted by a substituent described later.
上記結合基Xで表される、mと同数の価数を有する、炭素原子数6~35の芳香環含有炭化水素基は、mが1価のものとしては、ベンジル基、フェネチル基、ジフェニルメチル基、トリフェニルメチル基、スチリル基及びシンナミル基等のアリールアルキル基;フェニル基及びナフチル基等のアリール基;フェノキシ基及びナフチルオキシ基等のアリールオキシ基;フェニルチオ基及びナフチルチオ基等のアリールチオ基:並びに、これらの基が後述する置換基により置換された基等が挙げられる。
The aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the above linking group X, is, for example, a benzyl group, a phenethyl group or diphenylmethyl when m is monovalent Arylalkyl groups such as triphenylmethyl group, styryl group and cinnamyl group; aryl groups such as phenyl group and naphthyl group; aryloxy groups such as phenoxy group and naphthyloxy group; arylthio groups such as phenylthio group and naphthylthio group: Moreover, the group etc. by which these groups were substituted by the substituent mentioned later are mentioned.
上記結合基Xで表される、mと同数の価数を有する、炭素原子数6~35の芳香環含有炭化水素基は、mが2価のものとしては、フェニレン基及びナフチレン基等のアリーレン基;カテコール基、ビスフェノール基等の二官能フェノール基の残基;2,4,8,10-テトラオキサスピロ[5,5]ウンデカン基;並びにこれらの基が後述する置換基により置換された基が挙げられる。
The aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the bonding group X, is an arylene group such as a phenylene group and a naphthylene group when m is divalent. Groups; residues of bifunctional phenol groups such as catechol groups and bisphenol groups; 2,4,8,10-tetraoxaspiro [5,5] undecane groups; and groups in which these groups are substituted by substituents described later Can be mentioned.
上記結合基Xで表される、mと同数の価数を有する、炭素原子数6~35の芳香環含有炭化水素基は、mが3価のものとしては、フェニル-1,3,5-トリメチレン基及びこの基が後述する置換基により置換された基が挙げられる。
The aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the above linking group X, is not particularly limited as m is trivalent: phenyl-1,3,5- A trimethylene group and a group in which this group is substituted by a substituent described later can be mentioned.
上記結合基Xで表される、mと同数の価数を有する炭素原子数2~35の複素環含有基は、mが1価のものとしては、ピリジル基、ピリミジル基、ピリダジル基、ピペリジル基、ピラニル基、ピラゾリル基、トリアジル基、ピロリル基、キノリル基、イソキノリル基、イミダゾリル基、ベンゾイミダゾリル基、トリアゾリル基、フリル基、フラニル基、ベンゾフラニル基、チエニル基、チオフェニル基、ベンゾチオフェニル基、チアジアゾリル基、チアゾリル基、ベンゾチアゾリル基、オキサゾリル基、ベンゾオキサゾリル基、イソチアゾリル基、イソオキサゾリル基、インドリル基、2-ピロリジノン-1-イル基、2-ピペリドン-1-イル基、2,4-ジオキシイミダゾリジン-3-イル基、2,4-ジオキシオキサゾリジン-3-イル基及びベンゾトリアゾイル基等、並びにこれらの基が後述する置換基により置換された基等が挙げられる。
The heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a pyridyl group, a pyrimidyl group, a pyridazyl group, a piperidyl group as the one in which m is monovalent , Pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group, isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group , Thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, isothiazolyl group, isoxazolyl group, indolyl group, 2-pyrrolidin-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazo Lysin-3-yl group, 2,4-dioxazolidine-3- Le group and benzotriazoyl group, as well as groups substituted by a substituent which these groups will be described later and the like.
上記結合基Xで表される、mと同数の価数を有する炭素原子数2~35の複素環含有基は、mが2価のものとしては、ピリジン環、ピリミジン環、ピペリジン環、ピペラジン環、トリアジン環、フラン環、チオフェン環及びインドール環等を有する2価の基、並びにこれらの基が後述する置換基により置換された基が挙げられる。
The heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring as the m is divalent And a divalent group having a triazine ring, a furan ring, a thiophene ring, an indole ring and the like, and a group in which these groups are substituted by a substituent described later.
上記結合基Xで表される、mと同数の価数を有する炭素原子数2~35の複素環含有基は、mが3価のものとしては、イソシアヌル環を有する3価の基、トリアジン環を有する3価の基及びこれらの基が後述する置換基により置換された基が挙げられる。
The hetero ring-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a trivalent group having an isocyanuric ring, a triazine ring, as m is trivalent. And groups in which these groups are substituted by the substituents described later.
R53及びR54で表される炭素原子数1~35の脂肪族炭化水素基としては、上記Xで表される脂肪族炭化水素基又は該脂肪族炭化水素基が後述する置換基により置換された基のうち、炭素原子数が1~35のものが挙げられる。
R53及びR54で表される炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基としては、上記Xで表される炭素原子数6~35の芳香環含有炭化水素基若しくは炭素原子数2~35の複素環含有基又はこれらの基が後述する置換基により置換された基が挙げられる。 As a C1-C35 aliphatic hydrocarbon group represented by R53 and R54 , the aliphatic hydrocarbon group represented by said X or this aliphatic hydrocarbon group is substituted by the substituent mentioned later Among the above groups, those having 1 to 35 carbon atoms can be mentioned.
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by R 53 and R 54 has 6 to 35 carbon atoms represented by X above. Examples thereof include an aromatic ring-containing hydrocarbon group, a heterocyclic ring-containing group having 2 to 35 carbon atoms, or a group in which these groups are substituted by a substituent described later.
R53及びR54で表される炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基としては、上記Xで表される炭素原子数6~35の芳香環含有炭化水素基若しくは炭素原子数2~35の複素環含有基又はこれらの基が後述する置換基により置換された基が挙げられる。 As a C1-C35 aliphatic hydrocarbon group represented by R53 and R54 , the aliphatic hydrocarbon group represented by said X or this aliphatic hydrocarbon group is substituted by the substituent mentioned later Among the above groups, those having 1 to 35 carbon atoms can be mentioned.
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by R 53 and R 54 has 6 to 35 carbon atoms represented by X above. Examples thereof include an aromatic ring-containing hydrocarbon group, a heterocyclic ring-containing group having 2 to 35 carbon atoms, or a group in which these groups are substituted by a substituent described later.
上記脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基等の各官能基は、置換基を有している場合がある。本発明の化合物I-1は、特に断りがない限り、置換基を有していないもの及び置換基を有しているものを含む。
このような脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基等の置換基としては、例えば、R11等に用いられるアルキル基等の水素原子を置換する置換基と同じものを挙げることができる。 Each functional group such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group-containing group may have a substituent. The compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.
Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. It can be mentioned.
このような脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基等の置換基としては、例えば、R11等に用いられるアルキル基等の水素原子を置換する置換基と同じものを挙げることができる。 Each functional group such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group-containing group may have a substituent. The compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.
Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. It can be mentioned.
上記一般式(A-1)及び(A-2)において、mが2であるとき、Xは、下記一般式(1)で表される基を表す場合がある。
In the general formulas (A-1) and (A-2), when m is 2, X may represent a group represented by the following general formula (1).
(上記一般式(1)中、Y1は、単結合、-CR55R56-、-NR57-、二価の炭素原子数1~35の脂肪族炭化水素基、二価の炭素原子数6~35の芳香環含有炭化水素基、二価の炭素原子数2~35の複素環含有基、又は、下記(1-1)~(1-3)で表されるいずれかの基を表し、該脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基及び炭素原子数2~35の複素環含有基は、-O-、-S-、-CO-、-COO-、-OCO-若しくは-NH-又はこれらの組み合わせの基で中断されている場合もあり、
R55及びR56は、それぞれ独立に、水素原子、炭素原子数1~8のアルキル基、炭素原子数6~20のアリール基又は炭素原子数7~20のアリールアルキル基を表し、
Z1及びZ2は、それぞれ独立に、直接結合、-O-、-S-、>CO、-CO-O-、-O-CO-、-SO2-、-SS-、-SO-、>NR57又は>PR58を表し、
R57及びR58は、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、
*は、*部分で、隣接する基と結合することを意味する。) (In the general formula (1), Y 1 represents a single bond, -CR 55 R 56 -, - NR 57 -, a divalent aliphatic hydrocarbon group having a carbon number of 1 to 35, divalent carbon atoms 6 to 35 aromatic ring-containing hydrocarbon group, divalent heterocyclic group having 2 to 35 carbon atoms, or any group represented by the following (1-1) to (1-3) And the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms are -O-, -S-, -CO-, -COO- And -OCO- or -NH- or combinations thereof may be interrupted,
R 55 and R 56 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
Z 1 and Z 2 are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO 2- , -SS-, -SO-, Represents> NR 57 or> PR 58 ,
R 57 and R 58 each represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocycle containing group having 2 to 35 carbon atoms ,
The * means that at the * part, it bonds to an adjacent group. )
R55及びR56は、それぞれ独立に、水素原子、炭素原子数1~8のアルキル基、炭素原子数6~20のアリール基又は炭素原子数7~20のアリールアルキル基を表し、
Z1及びZ2は、それぞれ独立に、直接結合、-O-、-S-、>CO、-CO-O-、-O-CO-、-SO2-、-SS-、-SO-、>NR57又は>PR58を表し、
R57及びR58は、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、
*は、*部分で、隣接する基と結合することを意味する。) (In the general formula (1), Y 1 represents a single bond, -CR 55 R 56 -, - NR 57 -, a divalent aliphatic hydrocarbon group having a carbon number of 1 to 35, divalent carbon atoms 6 to 35 aromatic ring-containing hydrocarbon group, divalent heterocyclic group having 2 to 35 carbon atoms, or any group represented by the following (1-1) to (1-3) And the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms are -O-, -S-, -CO-, -COO- And -OCO- or -NH- or combinations thereof may be interrupted,
R 55 and R 56 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
Z 1 and Z 2 are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO 2- , -SS-, -SO-, Represents> NR 57 or> PR 58 ,
R 57 and R 58 each represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocycle containing group having 2 to 35 carbon atoms ,
The * means that at the * part, it bonds to an adjacent group. )
(上記式中、R59は水素原子、置換基を有している場合もあるフェニル基、又は置換基を有している場合もある炭素原子数3~10のシクロアルキル基を表し、
R60は炭素原子数1~10のアルキル基、炭素原子数1~10のアルコキシ基、炭素原子数2~10のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有している場合もあり、
c1は0~5の整数を表す、
*は、*部分で、隣接する基と結合することを意味する。) (Wherein, R 59 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent,
R 60 represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or a halogen atom In some cases,
c1 represents an integer of 0 to 5,
The * means that at the * part, it bonds to an adjacent group. )
R60は炭素原子数1~10のアルキル基、炭素原子数1~10のアルコキシ基、炭素原子数2~10のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有している場合もあり、
c1は0~5の整数を表す、
*は、*部分で、隣接する基と結合することを意味する。) (Wherein, R 59 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent,
R 60 represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or a halogen atom In some cases,
c1 represents an integer of 0 to 5,
The * means that at the * part, it bonds to an adjacent group. )
(*は、*部分で、隣接する基と結合することを意味する。)
(* Indicates that it is a bond to an adjacent group in the * part.)
(上記式中、R61及びR62は、それぞれ独立に、炭素原子数1~10のアルキル基、炭素原子数6~20のアリール基、炭素原子数6~20のアリールオキシ基、炭素原子数6~20のアリールチオ基、炭素原子数6~20のアリールアルケニル基、炭素原子数7~20のアリールアルキル基、炭素原子数2~20の複素環含有基又はハロゲン原子を表し、該アルキル基及びアリールアルキル基中のメチレン基は不飽和結合、-O-又は-S-で置き換わっている場合もあり、
R61は、隣接するR61同士で環を形成している場合もあり、
c2は0~4の数を表し、
c3は0~8の数を表し、
c4は0~4の数を表し、
c5は0~4の数を表し、
c4とc5の数の合計は2~4であり、
*は、*部分で、隣接する基と結合することを意味する。) (In the above formula, R 61 and R 62 each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or the like An arylthio group of 6 to 20, an arylalkenyl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heterocycle-containing group of 2 to 20 carbon atoms, or a halogen atom; The methylene group in the arylalkyl group may be replaced by an unsaturated bond, -O- or -S-,
R 61 may form a ring between adjacent R 61 in some cases,
c2 represents a number from 0 to 4;
c3 represents a number from 0 to 8,
c4 represents a number from 0 to 4;
c5 represents a number from 0 to 4;
The sum of the numbers of c4 and c5 is 2 to 4,
The * means that at the * part, it bonds to an adjacent group. )
R61は、隣接するR61同士で環を形成している場合もあり、
c2は0~4の数を表し、
c3は0~8の数を表し、
c4は0~4の数を表し、
c5は0~4の数を表し、
c4とc5の数の合計は2~4であり、
*は、*部分で、隣接する基と結合することを意味する。) (In the above formula, R 61 and R 62 each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or the like An arylthio group of 6 to 20, an arylalkenyl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heterocycle-containing group of 2 to 20 carbon atoms, or a halogen atom; The methylene group in the arylalkyl group may be replaced by an unsaturated bond, -O- or -S-,
R 61 may form a ring between adjacent R 61 in some cases,
c2 represents a number from 0 to 4;
c3 represents a number from 0 to 8,
c4 represents a number from 0 to 4;
c5 represents a number from 0 to 4;
The sum of the numbers of c4 and c5 is 2 to 4,
The * means that at the * part, it bonds to an adjacent group. )
(上記一般式(2)中、Y11は、三価の炭素原子数3~35の脂肪族炭化水素基、炭素原子数3~35の脂環族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、
Z1、Z2及びZ3は、それぞれ独立に、直接結合、-O-、-S-、>CO、-CO-O-、-O-CO-、-SO2-、-SS-、-SO-、>NR62、PR62、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、
R62は、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、
該脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基及び炭素原子数2~35の複素環含有基は、炭素-炭素二重結合、-O-、-CO-、-O-CO-、-CO-O-又は-SO2-で中断されている場合がある。) (In the above general formula (2), Y 11 is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms Represents an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms,
Z 1 , Z 2 and Z 3 are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO 2- , -SS-,- SO—,> NR 62 , PR 62 , an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms ,
R 62 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a heterocycle containing group having 2 to 35 carbon atoms,
The aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic group having 2 to 35 carbon atoms have a carbon-carbon double bond, -O-, -CO-,- It may be interrupted by O-CO-, -CO-O- or -SO 2- . )
Z1、Z2及びZ3は、それぞれ独立に、直接結合、-O-、-S-、>CO、-CO-O-、-O-CO-、-SO2-、-SS-、-SO-、>NR62、PR62、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、
R62は、水素原子、炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基を表し、
該脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基及び炭素原子数2~35の複素環含有基は、炭素-炭素二重結合、-O-、-CO-、-O-CO-、-CO-O-又は-SO2-で中断されている場合がある。) (In the above general formula (2), Y 11 is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms Represents an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms,
Z 1 , Z 2 and Z 3 are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO 2- , -SS-,- SO—,> NR 62 , PR 62 , an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms ,
R 62 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or a heterocycle containing group having 2 to 35 carbon atoms,
The aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic group having 2 to 35 carbon atoms have a carbon-carbon double bond, -O-, -CO-,- It may be interrupted by O-CO-, -CO-O- or -SO 2- . )
(上記一般式(3)中、Y12は、炭素原子、四価の炭素原子数1~35の脂肪族炭化水素基、四価の炭素原子数6~35の芳香環含有炭化水素基、又は四価の炭素原子数2~35の複素環含有基を表し、該脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基は、-COO-、-O-、-OCO-、-NHCO-、-NH-又は-CONH-で中断されている場合があり、Z1~Z4は、それぞれ独立に、上記一般式(2)におけるZ1~Z3で表される基と同じ範囲の基を表す。)
(In the above general formula (3), Y 12 represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or Represents an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms; And -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- may be interrupted, and Z 1 to Z 4 each independently represent the general formula (2) Represents a group in the same range as the group represented by Z 1 to Z 3 in
(上記一般式(4)中、Y13は、五価の炭素原子数2~35の脂肪族炭化水素基、五価の炭素原子数6~30の芳香環含有炭化水素基又は五価の炭素原子数2~30の複素環含有基を表し、該脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基若しくは炭素原子数2~35の複素環含有基は、-COO-、-O-、-OCO-、-NHCO-、-NH-又は-CONH-で中断されている場合もあり、Z1~Z5は、それぞれ独立に、上記一般式(2)におけるZ1~Z3で表される基と同じ基を表す。)
(In the above general formula (4), Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent aromatic ring-containing hydrocarbon group having 6 to 30 carbon atoms, or pentavalent carbon And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms represented by the formula: -COO- And Z 1 to Z 5 may each independently be Z 1 to Z 1 in the above general formula (2), which may be interrupted by —O—, —OCO—, —NHCO—, —NH— or Represents the same group as the group represented by Z 3 )
(上記一般式(5)中、Y14は、単結合、六価の炭素原子数2~35の脂肪族炭化水素基、六価の炭素原子数6~35の芳香環含有炭化水素基又は六価の炭素原子数2~35の複素環含有基を表し、該脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基若しくは炭素原子数2~35の複素環含有基は、-COO-、-O-、-OCO-、-NHCO-、-NH-又は-CONH-で中断されている場合があり、Z1~Z6は、それぞれ独立に、上記一般式(7)におけるZ1~Z3で表される基と同じ基を表す。)
(In the above general formula (5), Y 14 is a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent aromatic ring containing hydrocarbon group having 6 to 35 carbon atoms, or And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, In some cases, it may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and each of Z 1 to Z 6 is independently represented by the above general formula (7) Represents the same group as the groups represented by Z 1 to Z 3 )
上記一般式(1)で表される基におけるY1で表される二価の炭素原子数1~35の脂肪族炭化水素基としては、メタン、エタン、プロパン、iso-プロパン、ブタン、sec-ブタン、tert-ブタン、iso-ブタン、ヘキサン、2-メチルヘキサン、3-メチルヘキサン、ヘプタン、2-メチルヘプタン、3-メチルヘプタン、iso-ヘプタン、tert-ヘプタン、1-メチルオクタン、iso-オクタン、tert-オクタン、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、2,4-ジメチルシクロブタン、4-メチルシクロヘキサン等が、Z1及びZ2で置換された二価の基が挙げられる。これらの基は、-O-、-S-、-CO-、-COO-、-OCO-、-NH-又はこれらを組み合わせた基で中断されている場合がある。
Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 1 in the group represented by the above general formula (1) include methane, ethane, propane, iso-propane, butane, sec- Butane, tert-butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane And tert-octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like, and divalent groups substituted with Z 1 and Z 2 . These groups may be interrupted by —O—, —S—, —CO—, —COO—, —OCO—, —NH— or a combination thereof.
上記一般式(1)で表される基におけるY1で表される二価の炭素原子数6~35の芳香環含有炭化水素基としては、フェニレン、ナフチレン、ビフェニル等の基が、Z1及びZ2で置換された二価の基等が挙げられる。
The divalent aromatic ring-containing hydrocarbon group having a carbon number of 6-35 represented by Y 1 in the group represented by the general formula (1), phenylene, naphthylene, a group of biphenyl, Z 1 and Examples thereof include divalent groups substituted by Z 2 and the like.
上記一般式(1)で表される基におけるY1で表される二価の炭素原子数2~35の複素環含有基としては、ピリジン、ピラジン、ピペリジン、ピペラジン、ピリミジン、ピリダジン、トリアジン、ヘキサヒドロトリアジン、フラン、テトラヒドロフラン、クロマン、キサンテン、チオフェン、チオラン等が、Z1及びZ2で置換された二価の基が挙げられる。
Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y 1 in the group represented by the above general formula (1) include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, and hexa Hydrotriazines, furans, tetrahydrofurans, chromans, xanthenes, thiophenes, thiolanes and the like include divalent groups substituted by Z 1 and Z 2 .
上記一般式(1)で表される基におけるY1で表される脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、ハロゲン原子、シアノ基、ニトロ基又は炭素原子数1~8のアルコキシ基で置換されている場合がある。
上記脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基等の各官能基は、置換基を有している場合があるものであり、特に断りがない限り、置換基を有していない無置換である又は置換基を有しているものである。
このような脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基等の置換基としては、R11等に用いられるアルキル基等の水素原子を置換する置換基と同じものが挙げられる。 The aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocycle-containing group represented by Y 1 in the group represented by the above general formula (1) have a halogen atom, a cyano group, a nitro group or one carbon atom It may be substituted with an alkoxy group of -8.
Each functional group such as the above aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise specified, has a substituent. Not substituted or substituted.
Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. .
上記脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基等の各官能基は、置換基を有している場合があるものであり、特に断りがない限り、置換基を有していない無置換である又は置換基を有しているものである。
このような脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基等の置換基としては、R11等に用いられるアルキル基等の水素原子を置換する置換基と同じものが挙げられる。 The aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocycle-containing group represented by Y 1 in the group represented by the above general formula (1) have a halogen atom, a cyano group, a nitro group or one carbon atom It may be substituted with an alkoxy group of -8.
Each functional group such as the above aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise specified, has a substituent. Not substituted or substituted.
Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. .
上記一般式(1)で表される基におけるR55及びR56で表される炭素原子数1~8のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、s-ブチル基、t-ブチル基、イソブチル基、アミル基、イソアミル基、t-アミル基、ヘキシル基、2-ヘキシル基、3-ヘキシル基、シクロヘキシル基、4-メチルシクロヘキシル基、ヘプチル基、2-ヘプチル基、3-ヘプチル基、イソヘプチル基、t-ヘプチル基、1-オクチル基、イソオクチル基及びt-オクチル基等が挙げられる。
The alkyl group having 1 to 8 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s- group Butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl Groups, 3-heptyl group, isoheptyl group, t-heptyl group, 1-octyl group, isooctyl group, t-octyl group and the like.
上記一般式(1)で表される基におけるR55及びR56で表される炭素原子数6~20のアリール基としては、フェニル基、ナフチル基、2-メチルフェニル基、3-メチルフェニル基、4-メチルフェニル基、4-ビニルフェニル基、3-iso-プロピルフェニル基、4-iso-プロピルフェニル基、4-ブチルフェニル基、4-iso-ブチルフェニル基、4-tert-ブチルフェニル基、4-ヘキシルフェニル基、4-シクロヘキシルフェニル基、4-オクチルフェニル基、4-(2-エチルヘキシル)フェニル基、2,3-ジメチルフェニル基、2,4-ジメチルフェニル基、2,5-ジメチルフェニル基、2,6-ジメチルフェニル基、3,4-ジメチルフェニル基、3,5-ジメチルフェニル基、2,4-ジ-tert-ブチルフェニル基、2,5-ジ-tert-ブチルフェニル基、2,6-ジ-tert-ブチルフェニル基、2,4-ジ-tert-ペンチルフェニル基、2,5-ジ-tert-アミルフェニル基及び2,4,5-トリメチルフェニル基等が挙げられる。
上記一般式(1)で表される基におけるR55及びR56で表される炭素原子数7~20のアリールアルキル基としては、ベンジル基、フェネチル基、2-フェニルプロパン-2-イル基、ジフェニルメチル基、トリフェニルメチル基、スチリル、シンナミル等が挙げられる。 The aryl group having 6 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a phenyl group, a naphthyl group, a 2-methylphenyl group and a 3-methylphenyl group , 4-methylphenyl group, 4-vinylphenyl group, 3-iso-propylphenyl group, 4-iso-propylphenyl group, 4-butylphenyl group, 4-iso-butylphenyl group, 4-tert-butylphenyl group , 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethyl Phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-ter -Butylphenyl group, 2,5-di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-di-tert-pentylphenyl group, 2,5-di-tert-amyl group Examples include phenyl and 2,4,5-trimethylphenyl.
The arylalkyl group having 7 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, And diphenylmethyl group, triphenylmethyl group, styryl, cinnamyl and the like.
上記一般式(1)で表される基におけるR55及びR56で表される炭素原子数7~20のアリールアルキル基としては、ベンジル基、フェネチル基、2-フェニルプロパン-2-イル基、ジフェニルメチル基、トリフェニルメチル基、スチリル、シンナミル等が挙げられる。 The aryl group having 6 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a phenyl group, a naphthyl group, a 2-methylphenyl group and a 3-methylphenyl group , 4-methylphenyl group, 4-vinylphenyl group, 3-iso-propylphenyl group, 4-iso-propylphenyl group, 4-butylphenyl group, 4-iso-butylphenyl group, 4-tert-butylphenyl group , 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethyl Phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-ter -Butylphenyl group, 2,5-di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-di-tert-pentylphenyl group, 2,5-di-tert-amyl group Examples include phenyl and 2,4,5-trimethylphenyl.
The arylalkyl group having 7 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, And diphenylmethyl group, triphenylmethyl group, styryl, cinnamyl and the like.
上記一般式(1)で表される基におけるR57及びR58で表される炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基は、R53及びR54として例示したものと同じものを挙げることができる。
An aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a carbon atom represented by R 57 and R 58 in a group represented by the above general formula (1) Examples of the heterocycle-containing group of the formulas 2 to 35 may be the same as those exemplified as R 53 and R 54 .
上記一般式(1-1)で表される基における、R59で表される炭素原子数3~10のシクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへブチル基、シクロオクチル基等及びこれらの基が炭素原子数1~10のアルキル基若しくは炭素原子数1~10のアルコキシ基で置換された基等が挙げられる。
The cycloalkyl group having 3 to 10 carbon atoms represented by R 59 in the group represented by the above general formula (1-1) is a cyclopropyl group, cyclobutyl group, cyclopentyl group, cycloheptyl group, cyclo Examples thereof include an octyl group and the like, and a group in which these groups are substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
上記一般式(1-1)で表される基における、R60で表される炭素原子数1~10のアルキル基としては、上記「1.光脱離基B」の項においてR11等で表されるアルキル基として例示したもののうち、炭素原子数が1~10であるものが挙げられる。
上記一般式(1-1)で表される基における、R60で表される炭素原子数1~10のアルコキシ基としては、上記「1.光脱離基B」の項においてR11等で表されるアルコキシ基として例示したもののうち、炭素原子数が1~10のものが挙げられる。
上記一般式(1-1)で表される基における、R60で表される炭素原子数2~10のアルケニル基としては、ビニル基、アリル基、1-プロペニル基、イソプロペニル基、2-ブテニル基、1,3-ブタジエニル基、2-ペンテニル基及び2-オクテニル等が挙げられる。
上記R60で表されるアルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されている場合もあり、その置換位置は制限されない。 Examples of the alkyl group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) include R 11 and the like in the above “1. Photoleaving group B” Among the exemplified alkyl groups, those having 1 to 10 carbon atoms can be mentioned.
The alkoxy group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) is exemplified by R 11 and the like in the above “1. Photoleaving group B” Among the exemplified alkoxy groups, those having 1 to 10 carbon atoms can be mentioned.
As the alkenyl group having 2 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1), a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, 2- Examples include butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-octenyl and the like.
The alkyl group, alkoxy group and alkenyl group represented by R 60 may be substituted with a halogen atom, and the position of substitution is not limited.
上記一般式(1-1)で表される基における、R60で表される炭素原子数1~10のアルコキシ基としては、上記「1.光脱離基B」の項においてR11等で表されるアルコキシ基として例示したもののうち、炭素原子数が1~10のものが挙げられる。
上記一般式(1-1)で表される基における、R60で表される炭素原子数2~10のアルケニル基としては、ビニル基、アリル基、1-プロペニル基、イソプロペニル基、2-ブテニル基、1,3-ブタジエニル基、2-ペンテニル基及び2-オクテニル等が挙げられる。
上記R60で表されるアルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されている場合もあり、その置換位置は制限されない。 Examples of the alkyl group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) include R 11 and the like in the above “1. Photoleaving group B” Among the exemplified alkyl groups, those having 1 to 10 carbon atoms can be mentioned.
The alkoxy group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) is exemplified by R 11 and the like in the above “1. Photoleaving group B” Among the exemplified alkoxy groups, those having 1 to 10 carbon atoms can be mentioned.
As the alkenyl group having 2 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1), a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, 2- Examples include butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-octenyl and the like.
The alkyl group, alkoxy group and alkenyl group represented by R 60 may be substituted with a halogen atom, and the position of substitution is not limited.
上記一般式(1-3)で表される基における、R61及びR62で表される炭素原子数1~10のアルキル基、炭索原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基としては、上記「1.光脱離基B」の項にR11等として例示したものうち、所定の炭素原子数を満たすものが挙げられる。
In the group represented by the above general formula (1-3), an alkyl group having 1 to 10 carbon atoms represented by R 61 and R 62 , an aryl group having 6 to 20 carbon atoms, and 7 to carbon atoms Examples of the arylalkyl group of 20 include those exemplified as R 11 and the like in the above-mentioned section “1. Photoleaving group B”, those having a predetermined number of carbon atoms.
上記一般式(1-3)で表される基における、R61及びR62で表される炭素原子数6~20のアリールオキシ基としては、フェニルオキシ基、ナフチルオキシ基、2-メチルフェニルオキシ基、3-メチルフェニルオキシ基、4-メチルフェニルオキシ基、4-ビニルフェニル二オキシ基、3-iso-プロピルフェニルオキシ基、4-iso-プロピルフェニルオキシ基、4-ブチルフェニルオキシ基、4-tert-ブチルフェニルオキシ基、4-へキシルフェニルオキシ基、4-シクロヘキシルフェニルオキシ基、4-オクチルフェニルオキシ基、4-(2-エチルヘキシル)フェニルオキシ基、2,3-ジメチルフェニルオキシ基、2,4-ジメチルフェニルオキシ基、2,5-ジメチルフェニルオキシ基、2,6-ジメチルフェニルオキシ基、3,4-ジメチルフェニルオキシ基、3,5-ジメチルフェニルオキシ基、2,4-ジーtert-ブチルフェニルオキシ基、2,5-ジーtert-ブチルフェニルオキシ基、2,6-ジーtert-ブチルフェニルオキシ基、2,4-ジーtert-ペンチルフェニルオキシ基、2,5-tert-アミルフェニルオキシ基、4-シクロへキシルフェニルオキシ基、2,4,5-トリメチルフェニルオキシ基及びフェロセニルオキシ基及びこれらの基がハロゲン原子で置換された基が挙げられる。
As a C6-C20 aryloxy group represented by R 61 and R 62 in the group represented by the above general formula (1-3), a phenyloxy group, a naphthyloxy group, 2-methylphenyloxy Group, 3-methylphenyloxy group, 4-methylphenyloxy group, 4-vinylphenyldioxy group, 3-iso-propylphenyloxy group, 4-iso-propylphenyloxy group, 4-butylphenyloxy group, 4 -Tert-butylphenyloxy group, 4-hexylphenyloxy group, 4-cyclohexylphenyloxy group, 4-octylphenyloxy group, 4- (2-ethylhexyl) phenyloxy group, 2,3-dimethylphenyloxy group, 2,4-Dimethylphenyloxy, 2,5-dimethylphenyloxy, 2,6-dimethyl Phenyloxy, 3,4-dimethylphenyloxy, 3,5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di tert-Butylphenyloxy, 2,4-di-tert-pentylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy and A ferrocenyl oxy group and the group by which these groups were substituted by the halogen atom are mentioned.
上記一般式(1-3)で表される基における、R61及びR62で表される炭素原子数6~20のアリールチオ基としては、上記ハロゲン原子で置換されている場合がある炭素原子数6~20のアリールオキシ基の酸素原子を硫黄原子に置換したものが挙げられる。
As a C6-C20 arylthio group represented by R 61 and R 62 in the group represented by the above general formula (1-3), the number of carbon atoms which may be substituted by the above halogen atom What substituted the oxygen atom of the 6-20 aryloxy group by the sulfur atom is mentioned.
上記一般式(1-3)で表される基における、R61及びR62で表される炭素原子数8~20のアリールアルケニル基としては、上記ハロゲン原子で置換されている場合もある炭素原子数6-20のアリールオキシ基の酸素原子をビニル、アリル、1-プロペニル、イソプロペニル、2-ブテニル、1,3-ブタジエニル、2-ペンテニル、2-オクテニル等のアルケニル基で置換した基等が挙げられる。
The arylalkenyl group having 8 to 20 carbon atoms represented by R 61 and R 62 in the group represented by the above general formula (1-3) is a carbon atom which may be substituted by the above halogen atom Groups in which the oxygen atom of the aryloxy group of formulas 6 to 20 is substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc. It can be mentioned.
上記一般式(1-3)で表される基における、R61及びR62で表される炭素原子数2~20の複素環含有基としては、ピリジン基、ピラジン基、ピペリジン基、ピペラジン基、ピリミジン基、ピリダジン基、トリアジン基、ヘキサヒドロトリアジン基、フラン基、テトラヒドロフラン基、クロマン基、キサンテン基、チオフェン基及びチオフラン基並びにこれらの基がハロゲン原子で置換された基等が挙げられる。
The heterocyclic group containing 2 to 20 carbon atoms represented by R 61 and R 62 in the group represented by the above general formula (1-3) includes a pyridine group, a pyrazine group, a piperidine group, a piperazine group, A pyrimidine group, a pyridazine group, a triazine group, a hexahydro triazine group, a furan group, a tetrahydrofuran group, a chromane group, a xanthene group, a thiophene group and a thiofuran group, and groups in which these groups are substituted with a halogen atom are listed.
上記一般式(1-3)で表される基における、R61及びR62で表されるアリールオキシ基、アリールチオ基、アリールアルケニル基、複素環含有基等の各官能基は、置換基を有している場合があるものであり、特に断りがない限り、置換基を有していない無置換なものであるか又は置換基を有しているものである。
アリールオキシ基、アリールチオ基、アリールアルケニル基、複素環含有基等の水素原子を置換する置換基としては、R11等に用いられるアルキル基等の水素原子を置換する置換基と同様の内容とすることができる。 Each functional group in the group represented by the above general formula (1-3), such as aryloxy group, arylthio group, arylalkenyl group, heterocycle-containing group, represented by R 61 and R 62 has a substituent. And, unless otherwise specified, they are unsubstituted ones having no substituent or ones having a substituent.
The substituent that substitutes a hydrogen atom such as an aryloxy group, an arylthio group, an arylalkenyl group, and a heterocycle-containing group has the same content as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. be able to.
アリールオキシ基、アリールチオ基、アリールアルケニル基、複素環含有基等の水素原子を置換する置換基としては、R11等に用いられるアルキル基等の水素原子を置換する置換基と同様の内容とすることができる。 Each functional group in the group represented by the above general formula (1-3), such as aryloxy group, arylthio group, arylalkenyl group, heterocycle-containing group, represented by R 61 and R 62 has a substituent. And, unless otherwise specified, they are unsubstituted ones having no substituent or ones having a substituent.
The substituent that substitutes a hydrogen atom such as an aryloxy group, an arylthio group, an arylalkenyl group, and a heterocycle-containing group has the same content as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. be able to.
上記一般式(2)で表される基におけるY11で表される三価の炭素原子数3~35の脂肪族炭化水素基としては、上記一般式(1)におけるXの説明で例示した脂肪族炭化水素基が、Z1、Z2及びZ3で置換された三価の基が挙げられ、これらの基は、-O-、-S-、-CO-、-CO-O-、-O-CO-、-SO2-、-NH-又はこれらを組み合わせた基で置き換えられている場合がある。
Examples of the trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms represented by Y 11 in the group represented by the above general formula (2) include the fats exemplified in the explanation of X in the above general formula (1) Group hydrocarbon group is substituted by Z 1 , Z 2 and Z 3 , and these groups include -O-, -S-, -CO-, -CO-O-,- O-CO-, -SO 2- , -NH- or a combination thereof may be substituted.
上記一般式(2)で表される基におけるY11で表される三価の炭素原子数6~35の芳香環含有炭化水素基としては、上記一般式(1)におけるXの説明で例示した芳香環含有炭化水素基が、Z1、Z2及びZ3で置換された三価の基が挙げられる。
The trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 11 in the group represented by the general formula (2) is exemplified in the description of X in the general formula (1) Examples thereof include trivalent groups in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 and Z 3 .
上記一般式(2)で表される基におけるY11で表される三価の炭素原子数2~35の複素環含有基としては、上記一般式(1)におけるXの説明で例示した複素環含有基が、Z1、Z2及びZ3で置換された三価の基が挙げられる。
Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y 11 in the group represented by the above general formula (2) include the heterocycles exemplified in the description of X in the above general formula (1) Examples include trivalent groups in which the containing group is substituted with Z 1 , Z 2 and Z 3 .
上記一般式(2)で表される基におけるZ1、Z2及びZ3並びにR62で表される炭素原子数1~35の脂肪族炭化水素基、炭素原子数6~35の芳香環含有炭化水素基又は炭素原子数2~35の複素環含有基としては、上述したR53及びR54として例示したものと同じものを挙げることができる。
The aliphatic hydrocarbon group having 1 to 35 carbon atoms and the aromatic ring having 6 to 35 carbon atoms represented by Z 1 , Z 2 and Z 3 and R 62 in the group represented by the above general formula (2) Examples of the hydrocarbon group or the heterocycle-containing group having 2 to 35 carbon atoms can include the same ones as those exemplified as R 53 and R 54 described above.
上記一般式(3)で表される基におけるY12で表される四価の炭素原子数1~35の脂肪族炭化水素基としては、上記一般式(1)におけるXの説明で例示した脂肪族炭化水素基が、Z1、Z2、Z3及びZ4で置換された四価の基が挙げられ、-O-、-S-、-CO-、-COO-、-OCO-、-NH-又はこれらを組み合わせた基で中断されている場合がある。
Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms having a tetravalent carbon atom represented by Y 12 in the group represented by the general formula (3) include the fats exemplified in the description of X in the general formula (1) Group hydrocarbon group is substituted by Z 1 , Z 2 , Z 3 and Z 4 and examples thereof include -O-, -S-, -CO-, -COO-, -OCO-,- It may be interrupted by NH-or a combination of these.
上記一般式(3)で表される基におけるY12で表される四価の炭素原子数6~35の芳香環含有炭化水素基としては、上記一般式(1)におけるXの説明で例示した芳香環含有炭化水素基が、Z1、Z2、Z3及びZ4で置換された四価の基が挙げられる。
The tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 12 in the group represented by the above general formula (3) is exemplified in the description of X in the above general formula (1) A tetravalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 , Z 3 and Z 4 can be mentioned.
上記一般式(3)で表される基におけるY12で表される四価の炭素原子数2~35の複素環含有基としては、上記一般式(1)におけるXの説明で例示した複素環含有基が、Z1、Z2、Z3及びZ4で置換された四価の基が挙げられる。
Examples of the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by Y 12 in the group represented by the general formula (3) include the heterocyclic rings exemplified in the description of X in the general formula (1). Examples include tetravalent groups in which the containing group is substituted by Z 1 , Z 2 , Z 3 and Z 4 .
上記一般式(4)で表される基におけるY13で表される五価の炭素原子数2~35の脂肪族炭化水素基としては、上記一般式(1)におけるXの説明で例示した脂肪族炭化水素基が、Z1、Z2、Z3、Z4及びZ5で置換された五価の基が挙げられ、-O-、-S-、-CO-、-CO-O-、-O-CO-、-SO2-、-NH-又はこれらを組み合わせた基で置き換えられている場合がある。
Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the group represented by the above general formula (4) include the fats exemplified in the explanation of X in the above general formula (1) Group hydrocarbon group is substituted by Z 1 , Z 2 , Z 3 , Z 4 and Z 5 and examples thereof include -O-, -S-, -CO-, -CO-O-, It may be replaced by a group of -O-CO-, -SO 2- , -NH- or a combination thereof.
上記一般式(4)で表される基におけるY13で表される五価の炭素原子数6~35の芳香環含有炭化水素基としては、上記一般式(1)におけるXの説明で例示した芳香環含有炭化水素基が、Z1、Z2、Z3、Z4及びZ5で置換された五価の基が挙げられる。
The pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 13 in the group represented by the general formula (4) is exemplified in the description of X in the general formula (1) A pentavalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 can be mentioned.
上記一般式(4)で表される基におけるY13で表される五価の炭素原子数2~35の複素環含有基としては、上記一般式(1)におけるXの説明で例示した複素環含有基が、Z1、Z2、Z3、Z4及びZ5で置換された五価の基が挙げられる。
Examples of the pentavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 13 in the group represented by the general formula (4) include the heterocycles exemplified in the description of X in the general formula (1) containing groups include pentavalent group substituted with Z 1, Z 2, Z 3 , Z 4 and Z 5.
上記一般式(5)におけるY14で表される六価の炭素原子数2~35の脂肪族炭化水素基としては、上記一般式(1)におけるXの説明で例示した脂肪族炭化水素基が、Z1、Z2、Z3、Z4、Z5及びZ6で置換された六価の基が挙げられ、該基は-O-、-S-、-CO-、-COO-、-OCO-、-SO2-、-NH-又はこれらを組み合わせた基で中断されている場合がある。
Examples of the aliphatic hydrocarbon group having 2 to 35 carbon atoms which is represented by Y 14 in the general formula (5) include the aliphatic hydrocarbon groups exemplified in the description of X in the general formula (1). And a hexavalent group substituted by Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 , and the groups include -O-, -S-, -CO-, -COO-,- It may be interrupted by OCO-, -SO 2- , -NH- or a combination thereof.
上記一般式(5)におけるY14で表される六価の炭素原子数6~35の芳香環含有炭化水素基としては、上記一般式(1)におけるXの説明で例示した芳香環含有炭化水素基が、Z1、Z2、Z3、Z4、Z5及びZ6で置換された六価の基が挙げられる。
Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms having a hexavalent carbon atom represented by Y 14 in the general formula (5) include the aromatic ring-containing hydrocarbons exemplified in the description of X in the general formula (1) A hexavalent group in which a group is substituted by Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 can be mentioned.
上記一般式(5)におけるY14で表される六価の炭素原子数2~35の複素環含有基としては、上記一般式(1)におけるXの説明で例示した複素環含有基が、Z1、Z2、Z3、Z4、Z5及びZ6で置換された六価の基が挙げられる。
Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) include the heterocyclic groups exemplified in the description of X in the general formula (1) as Z And hexavalent groups substituted with 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
上記結合基Xは、mが2である場合、炭素原子数1~120の脂肪族炭化水素基であることが好ましく、アルキレン基又はジオールの残基であることがより好ましく、炭素原子数1~10のアルキレン基又は炭素原子数1~10のジオール残基であることが好ましく、なかでも、炭素原子数1~5のアルキレン基又は炭素原子数1~5のジオール残基であることが好ましく、特に、炭素原子数1~3のアルキレン基であることが好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物とすることができ、更に、化合物I-1の製造が容易だからである。
When m is 2, the bonding group X is preferably an aliphatic hydrocarbon group having 1 to 120 carbon atoms, more preferably an alkylene group or a residue of a diol, and having 1 to 12 carbon atoms. Among them, an alkylene group of 10 or a diol residue of 1 to 10 carbon atoms is preferable, and an alkylene group of 1 to 5 carbon atoms or a diol residue of 1 to 5 carbon atoms is particularly preferable. In particular, an alkylene group having 1 to 3 carbon atoms is preferable. This is because the compound can be made to be a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product, and furthermore, the production of the compound I-1 is easy.
上記結合基Xのベンゼン環との結合位置としては、ベンゼン環内の結合し得るいずれの位置であってもよいが、例えば、R2に対して、オルト位又はメタ位であることが好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物とすることができるからである。
The bonding position of the bonding group X to the benzene ring may be any position in the benzene ring that can be bonded, but for example, the ortho position or the meta position with respect to R 2 is preferable. It is because it can be set as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
上記Xは、m=1のとき、水素原子又はR2と同様の基であることが好ましい。
The above X is preferably a hydrogen atom or a group similar to R 2 when m = 1.
上記原子団Aは、フェノール性水酸基を含むもの、すなわち、化合物I-1が光脱離基Bにより保護されていないフェノール性水酸基を含むものであってもよいが、フェノール性水酸基の数は2個以下であることが好ましく、0個であることがより好ましい。上記化合物I-1は、硬化阻害が少ないものとなるからである。
The above atomic group A may be one containing a phenolic hydroxyl group, that is, one in which the compound I-1 contains a phenolic hydroxyl group not protected by the photoleaving group B, but the number of phenolic hydroxyl groups is 2 The number is preferably not more than one, more preferably zero. This is because the compound I-1 has less inhibition of curing.
3.化合物
本発明の化合物は、上記一般式(I-1)で表されるものであればよいが、上記一般式(A-1)、(A-2)又は(A-3)で表される化合物であり、光脱離基Bとして、上記一般式(B-1-a)で表されるものを含むことが好ましい。合成が容易であり、更に、光脱離が容易だからである。また、硬化物に対して容易に紫外線吸収能等を付与できるからである。また、化合物I-1が、一般式(A-1)、(A-2)又は(A-3)で表される化合物であるため、光脱離基Bの脱離により紫外線領域の光を安定的に吸収する化合物を生成可能だからである。 3. Compound The compound of the present invention may be any compound represented by the above general formula (I-1), but is represented by the above general formula (A-1), (A-2) or (A-3) It is preferably a compound, and as the photoleaving group B, one represented by the above general formula (B-1-a) is preferable. It is because synthesis is easy, and furthermore, photodetachment is easy. Moreover, it is because an ultraviolet absorptivity etc. can be easily provided with respect to hardened | cured material. Further, since the compound I-1 is a compound represented by the general formula (A-1), (A-2) or (A-3), the light in the ultraviolet region is released by the elimination of the photoleaving group B. This is because it is possible to produce a compound that absorbs stably.
本発明の化合物は、上記一般式(I-1)で表されるものであればよいが、上記一般式(A-1)、(A-2)又は(A-3)で表される化合物であり、光脱離基Bとして、上記一般式(B-1-a)で表されるものを含むことが好ましい。合成が容易であり、更に、光脱離が容易だからである。また、硬化物に対して容易に紫外線吸収能等を付与できるからである。また、化合物I-1が、一般式(A-1)、(A-2)又は(A-3)で表される化合物であるため、光脱離基Bの脱離により紫外線領域の光を安定的に吸収する化合物を生成可能だからである。 3. Compound The compound of the present invention may be any compound represented by the above general formula (I-1), but is represented by the above general formula (A-1), (A-2) or (A-3) It is preferably a compound, and as the photoleaving group B, one represented by the above general formula (B-1-a) is preferable. It is because synthesis is easy, and furthermore, photodetachment is easy. Moreover, it is because an ultraviolet absorptivity etc. can be easily provided with respect to hardened | cured material. Further, since the compound I-1 is a compound represented by the general formula (A-1), (A-2) or (A-3), the light in the ultraviolet region is released by the elimination of the photoleaving group B. This is because it is possible to produce a compound that absorbs stably.
上記化合物I-1の具体例としては、例えば、下記に表される化合物が挙げられる。
Specific examples of the compound I-1 include the compounds shown below.
上記化合物I-1の分子量は、化合物I-1の用途等に応じて設定することができる。上記化合物I-1の分子量は、例えば、250以上5000以下が好ましく、300以上2500以下がより好ましく、350以上1500以下とすることが特に好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物とすることができるからである。
なお、上記化合物I-1の分子量は、化合物I-1がその構造として繰り返し構造を含む重合体である場合には、重量平均分子量(Mw)で表すものとする。重量平均分子量(Mw)は、ゲル・パーミエーション・クロマトグラフィー(GPC)により、標準ポリスチレン換算値として求めることができる。 The molecular weight of the compound I-1 can be set according to the use of the compound I-1. The molecular weight of the compound I-1 is, for example, preferably 250 or more and 5000 or less, more preferably 300 or more and 2500 or less, and particularly preferably 350 or more and 1500 or less. It is because it can be set as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
The molecular weight of the compound I-1 is represented by weight average molecular weight (Mw) when the compound I-1 is a polymer having a repeating structure as its structure. The weight average molecular weight (Mw) can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
なお、上記化合物I-1の分子量は、化合物I-1がその構造として繰り返し構造を含む重合体である場合には、重量平均分子量(Mw)で表すものとする。重量平均分子量(Mw)は、ゲル・パーミエーション・クロマトグラフィー(GPC)により、標準ポリスチレン換算値として求めることができる。 The molecular weight of the compound I-1 can be set according to the use of the compound I-1. The molecular weight of the compound I-1 is, for example, preferably 250 or more and 5000 or less, more preferably 300 or more and 2500 or less, and particularly preferably 350 or more and 1500 or less. It is because it can be set as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
The molecular weight of the compound I-1 is represented by weight average molecular weight (Mw) when the compound I-1 is a polymer having a repeating structure as its structure. The weight average molecular weight (Mw) can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
上記重量平均分子量Mwは、例えば、東ソー(株)製のHLC-8120GPCを用い、溶出溶剤を0.01モル/リットルの臭化リチウムを添加したN-メチルピロリドンとし、校正曲線用ポリスチレンスタンダードをMw377400、210500、96000、50400、20650、10850、5460、2930、1300、580(以上、Polymer Laboratories社製 Easi PS-2シリーズ)及びMw1090000(東ソー(株)製)とし、測定カラムをTSK-GEL ALPHA-M×2本(東ソー(株)製)として測定して得ることができる。また、測定温度は40℃とすることができ、流速は1.0mL/分とすることができる。
The weight average molecular weight Mw is, for example, HLC-8120 GPC manufactured by Tosoh Corp., and the elution solvent is N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide is added, and the polystyrene standard for calibration curve is Mw 377400 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh Corp.), and the measurement column is TSK-GEL ALPHA- It can be obtained by measurement as M × 2 (made by Tosoh Corp.). Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.
上記化合物I-1の製造方法は、所望の構造を得ることができる方法であれば特に限定されないが、例えば、特開昭57-111375号公報、特開平3-173843号公報、特開平6-128195号公報、特開平7-206771号公報、特開平7-252191号公報又は特表2004-501128号公報に記載された方法により製造されたフェノール系化合物と、アルキルハライド化合物を反応させて得ることができる。
The method for producing the compound I-1 is not particularly limited as long as it can obtain a desired structure, and, for example, JP-A-57-111375, JP-A-3-173843 and JP-A-6- It is obtained by reacting an alkyl halide compound with a phenolic compound produced by the method described in Japanese Patent Application Laid-Open No. 128195, Japanese Patent Application Laid-Open No. 7-206771, Japanese Patent Application Laid-Open No. 7-252191 or Japanese Patent Application Laid-Open No. Can.
上記化合物I-1は、光照射前は不活性であり、光照射することで光脱離基が脱離し、フェノール性水酸基を有する化合物I-2を生成するものである。
また、上記化合物I-2は、紫外線吸収能を発揮するものである。
このような化合物I-1の用途としては、光照射により紫外線吸収能を発揮することが要求される用途であることが好ましく、例えば、組成物に添加して用いられる紫外線吸収剤等を挙げることができる。 The compound I-1 is inactive before light irradiation, and the light leaving group is eliminated by light irradiation to generate a compound I-2 having a phenolic hydroxyl group.
Further, the compound I-2 exhibits ultraviolet absorbing ability.
The application of the compound I-1 is preferably an application that is required to exhibit an ultraviolet absorptivity by light irradiation. Can.
また、上記化合物I-2は、紫外線吸収能を発揮するものである。
このような化合物I-1の用途としては、光照射により紫外線吸収能を発揮することが要求される用途であることが好ましく、例えば、組成物に添加して用いられる紫外線吸収剤等を挙げることができる。 The compound I-1 is inactive before light irradiation, and the light leaving group is eliminated by light irradiation to generate a compound I-2 having a phenolic hydroxyl group.
Further, the compound I-2 exhibits ultraviolet absorbing ability.
The application of the compound I-1 is preferably an application that is required to exhibit an ultraviolet absorptivity by light irradiation. Can.
B.潜在性紫外線吸収剤
次に、本発明の潜在性紫外線吸収剤について説明する。
本発明の潜在性紫外線吸収剤は、本発明の化合物I-1を含む。 B. Next, the latent ultraviolet absorber of the present invention will be described.
The latent ultraviolet light absorber of the present invention comprises the compound I-1 of the present invention.
次に、本発明の潜在性紫外線吸収剤について説明する。
本発明の潜在性紫外線吸収剤は、本発明の化合物I-1を含む。 B. Next, the latent ultraviolet absorber of the present invention will be described.
The latent ultraviolet light absorber of the present invention comprises the compound I-1 of the present invention.
本発明の潜在性紫外線吸収剤は、本発明の化合物I-1を含むことで、例えば、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる。
By including the compound I-1 of the present invention, the latent UV absorber of the present invention, for example, has less inhibition of curing and can easily impart ultraviolet absorptivity and the like to a cured product.
本発明の潜在性紫外線吸収剤における化合物I-1の含有量は、特に制限はなく、潜在性紫外線吸収剤の用途等に応じて適宜設定することができる。
本発明の潜在性紫外線吸収剤は、潜在性紫外線吸収剤100質量部中、化合物I-1が100質量部含まれるもの、すなわち、上記潜在性紫外線吸収剤が上記化合物I-1のみからなるものとすることができる。
また、本発明の潜在性紫外線吸収剤は、化合物I-1に加え、その他の成分を含有する場合がある。本発明の潜在性紫外線吸収剤がその他の成分を含有する場合、化合物I-1の含有量は、潜在性紫外線吸収剤100質量部中、例えば、20質量部超99質量部以下とすることができ、25質量部以上99質量部以下であることが好ましく、50質量部以上99質量部以下であることがより好ましく、80質量部以上99質量部以下であることが特に好ましい。上記潜在性紫外線吸収剤は、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できるとの効果を効果的に発揮できるからである。 The content of the compound I-1 in the latent ultraviolet absorber of the present invention is not particularly limited, and can be appropriately set according to the application of the latent ultraviolet absorber and the like.
The latent ultraviolet absorber of the present invention comprises 100 parts by mass of the compound I-1 in 100 parts by mass of the latent ultraviolet absorber, that is, the latent ultraviolet absorber comprises only the compound I-1 It can be done.
In addition to the compound I-1, the latent ultraviolet absorber of the present invention may contain other components. When the latent ultraviolet absorber of the present invention contains other components, the content of the compound I-1 may be, for example, more than 20 parts by mass and 99 parts by mass or less in 100 parts by mass of the latent ultraviolet absorber. It is preferably 25 parts by mass or more and 99 parts by mass or less, more preferably 50 parts by mass or more and 99 parts by mass or less, and particularly preferably 80 parts by mass or more and 99 parts by mass or less. The latent ultraviolet absorber has a small amount of inhibition of curing, and can effectively exhibit the effect of easily imparting ultraviolet absorptivity and the like to a cured product.
本発明の潜在性紫外線吸収剤は、潜在性紫外線吸収剤100質量部中、化合物I-1が100質量部含まれるもの、すなわち、上記潜在性紫外線吸収剤が上記化合物I-1のみからなるものとすることができる。
また、本発明の潜在性紫外線吸収剤は、化合物I-1に加え、その他の成分を含有する場合がある。本発明の潜在性紫外線吸収剤がその他の成分を含有する場合、化合物I-1の含有量は、潜在性紫外線吸収剤100質量部中、例えば、20質量部超99質量部以下とすることができ、25質量部以上99質量部以下であることが好ましく、50質量部以上99質量部以下であることがより好ましく、80質量部以上99質量部以下であることが特に好ましい。上記潜在性紫外線吸収剤は、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できるとの効果を効果的に発揮できるからである。 The content of the compound I-1 in the latent ultraviolet absorber of the present invention is not particularly limited, and can be appropriately set according to the application of the latent ultraviolet absorber and the like.
The latent ultraviolet absorber of the present invention comprises 100 parts by mass of the compound I-1 in 100 parts by mass of the latent ultraviolet absorber, that is, the latent ultraviolet absorber comprises only the compound I-1 It can be done.
In addition to the compound I-1, the latent ultraviolet absorber of the present invention may contain other components. When the latent ultraviolet absorber of the present invention contains other components, the content of the compound I-1 may be, for example, more than 20 parts by mass and 99 parts by mass or less in 100 parts by mass of the latent ultraviolet absorber. It is preferably 25 parts by mass or more and 99 parts by mass or less, more preferably 50 parts by mass or more and 99 parts by mass or less, and particularly preferably 80 parts by mass or more and 99 parts by mass or less. The latent ultraviolet absorber has a small amount of inhibition of curing, and can effectively exhibit the effect of easily imparting ultraviolet absorptivity and the like to a cured product.
上記潜在性紫外線吸収剤に含まれる上記化合物I-1の種類は、1種類のみである場合があり、2種類以上である場合がある。上記潜在性紫外線吸収剤が数種類の化合物I-1を含有する場合、種類数は、例えば、2種類以上5種類以下とすることができる。
The type of the compound I-1 contained in the latent ultraviolet absorber may be only one type or two or more types. When the latent ultraviolet absorber contains several types of compound I-1, the number of types can be, for example, 2 or more and 5 or less.
なお、上述の化合物I-1については、「A.化合物」の項に記載の内容と同様とすることができるので、ここでの説明は省略する。
The compound I-1 described above can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.
上記潜在性紫外線吸収剤に含まれる上記その他の成分としては、例えば、後述する「C.組成物」の「2.その他の成分」の項に記載のものと同一のものを用いることができる。
上記潜在性紫外線吸収剤は、その他の成分として、重合性基を有しない重合体等の樹脂成分を含有することが好ましい。上記化合物I-1を安定的に保持可能となるからである。 As said other components contained in the said latent ultraviolet absorber, the same thing as what is described in the term of "2. other components" of "C. composition" mentioned later can be used, for example.
The latent ultraviolet absorber preferably contains, as another component, a resin component such as a polymer having no polymerizable group. This is because the compound I-1 can be stably held.
上記潜在性紫外線吸収剤は、その他の成分として、重合性基を有しない重合体等の樹脂成分を含有することが好ましい。上記化合物I-1を安定的に保持可能となるからである。 As said other components contained in the said latent ultraviolet absorber, the same thing as what is described in the term of "2. other components" of "C. composition" mentioned later can be used, for example.
The latent ultraviolet absorber preferably contains, as another component, a resin component such as a polymer having no polymerizable group. This is because the compound I-1 can be stably held.
上記潜在性紫外線吸収剤の形状は、粉末状である場合があり、ペレット状である場合がある。
ペレット状である場合、上記潜在性紫外線吸収剤の製造方法としては、例えば、押出機等を用いて、上記化合物I-1及び樹脂成分を混合した後、ペレット状に成型する方法を用いることができる。 The shape of the latent ultraviolet absorber may be powdery, and may be pelletized.
When it is in the form of a pellet, as the method for producing the latent ultraviolet absorber, for example, a method may be used in which the compound I-1 and the resin component are mixed using an extruder etc. it can.
ペレット状である場合、上記潜在性紫外線吸収剤の製造方法としては、例えば、押出機等を用いて、上記化合物I-1及び樹脂成分を混合した後、ペレット状に成型する方法を用いることができる。 The shape of the latent ultraviolet absorber may be powdery, and may be pelletized.
When it is in the form of a pellet, as the method for producing the latent ultraviolet absorber, for example, a method may be used in which the compound I-1 and the resin component are mixed using an extruder etc. it can.
C.組成物
次に、本発明の組成物について説明する。
本発明の組成物は、化合物I-1を含むものである。 C. Composition Next, the composition of the present invention will be described.
The composition of the present invention comprises the compound I-1.
次に、本発明の組成物について説明する。
本発明の組成物は、化合物I-1を含むものである。 C. Composition Next, the composition of the present invention will be described.
The composition of the present invention comprises the compound I-1.
本発明の組成物によれば、例えば、硬化阻害が少なく、優れた紫外線吸収能硬化物が得られる組成物を提供することができる。以下、上記組成物の各成分について説明する。
According to the composition of the present invention, it is possible to provide, for example, a composition which has less inhibition of curing and which can provide an excellent cured product of ultraviolet absorption ability. Hereinafter, each component of the said composition is demonstrated.
1.化合物
本発明の組成物における化合物I-1の含有量は、組成物に対して所望の紫外線吸収能等を付与できる量であれば特に限定されるものではない。本発明の組成物における化合物I-1の含有量は、例えば、組成物の固形分100質量中、0.001質量部以上20質量部以下とすることができ、0.005質量部以上10質量部以下であることが好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物とすることが容易だからである。
なお、固形分とは、溶剤以外の全ての成分を含むものである。
また、本明細書において特に断りがない場合には、含有量は質量基準である。
上記化合物I-1の含有量は、溶剤等の含有量によって異なるものであるが、例えば、組成物100質量部中に、0.001質量部以上20質量部以下とすることができ、なかでも、0.005質量部以上10質量部以下であることが好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物とすることが容易だからである。 1. Compound The content of the compound I-1 in the composition of the present invention is not particularly limited as long as it is an amount capable of imparting a desired ultraviolet absorbing ability and the like to the composition. The content of the compound I-1 in the composition of the present invention can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the solid content of the composition, and 0.005 parts by mass or more and 10 parts by mass It is preferable that it is less than part. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
In addition, solid content contains all the components other than a solvent.
Further, in the present specification, the content is on a mass basis unless otherwise noted.
The content of the compound I-1 varies depending on the content of the solvent and the like, and can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. And 0.005 parts by mass or more and 10 parts by mass or less. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
本発明の組成物における化合物I-1の含有量は、組成物に対して所望の紫外線吸収能等を付与できる量であれば特に限定されるものではない。本発明の組成物における化合物I-1の含有量は、例えば、組成物の固形分100質量中、0.001質量部以上20質量部以下とすることができ、0.005質量部以上10質量部以下であることが好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物とすることが容易だからである。
なお、固形分とは、溶剤以外の全ての成分を含むものである。
また、本明細書において特に断りがない場合には、含有量は質量基準である。
上記化合物I-1の含有量は、溶剤等の含有量によって異なるものであるが、例えば、組成物100質量部中に、0.001質量部以上20質量部以下とすることができ、なかでも、0.005質量部以上10質量部以下であることが好ましい。硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物とすることが容易だからである。 1. Compound The content of the compound I-1 in the composition of the present invention is not particularly limited as long as it is an amount capable of imparting a desired ultraviolet absorbing ability and the like to the composition. The content of the compound I-1 in the composition of the present invention can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the solid content of the composition, and 0.005 parts by mass or more and 10 parts by mass It is preferable that it is less than part. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
In addition, solid content contains all the components other than a solvent.
Further, in the present specification, the content is on a mass basis unless otherwise noted.
The content of the compound I-1 varies depending on the content of the solvent and the like, and can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. And 0.005 parts by mass or more and 10 parts by mass or less. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened | cured material.
上記組成物に含まれる上記化合物I-1の種類は、1種類のみであってもよく、2種類以上であってもよい。上記種類は、例えば、2種類以上5種類以下とすることができる。
The type of the compound I-1 contained in the composition may be only one type or two or more types. The type can be, for example, two or more and five or less.
なお、上述の化合物I-1については、「A.化合物」の項に記載の内容と同様とすることができるので、ここでの説明は省略する。
The compound I-1 described above can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.
2.その他の成分
上記組成物は、その用途等に応じて、上記化合物I-1以外の他の成分を含む場合がある。
上記他の成分としては、例えば、樹脂成分が挙げられる。本発明の組成物が、化合物I-1に加え、樹脂成分を含むことで、例えば、上記組成物に硬化性等を容易に付与できるからである。
また、本発明の組成物は、他の成分としては、上記樹脂成分と共に重合開始剤を含むことが好ましい。本発明の組成物が、他の成分として樹脂成分及び重合開始剤を含むことにより、組成物に硬化性等を容易に付与できるからである。 2. Other Components The above composition may contain other components other than the above compound I-1 depending on its use and the like.
As said other component, the resin component is mentioned, for example. This is because, for example, when the composition of the present invention contains a resin component in addition to the compound I-1, curability and the like can be easily imparted to the above composition, for example.
Moreover, it is preferable that the composition of this invention contains a polymerization initiator with the said resin component as another component. By containing the resin component and the polymerization initiator as other components, the composition of the present invention can easily impart curability and the like to the composition.
上記組成物は、その用途等に応じて、上記化合物I-1以外の他の成分を含む場合がある。
上記他の成分としては、例えば、樹脂成分が挙げられる。本発明の組成物が、化合物I-1に加え、樹脂成分を含むことで、例えば、上記組成物に硬化性等を容易に付与できるからである。
また、本発明の組成物は、他の成分としては、上記樹脂成分と共に重合開始剤を含むことが好ましい。本発明の組成物が、他の成分として樹脂成分及び重合開始剤を含むことにより、組成物に硬化性等を容易に付与できるからである。 2. Other Components The above composition may contain other components other than the above compound I-1 depending on its use and the like.
As said other component, the resin component is mentioned, for example. This is because, for example, when the composition of the present invention contains a resin component in addition to the compound I-1, curability and the like can be easily imparted to the above composition, for example.
Moreover, it is preferable that the composition of this invention contains a polymerization initiator with the said resin component as another component. By containing the resin component and the polymerization initiator as other components, the composition of the present invention can easily impart curability and the like to the composition.
(1)樹脂成分
上記樹脂成分としては、上記化合物I-1を保持できるものが挙げられ、組成物の用途等に応じて適宜設定されるものであるが、例えば、重合性基を有する重合性化合物及び重合性基を有しない重合体等を挙げることができる。
上記樹脂成分として重合性化合物を含むことにより、上記組成物は、例えば、光硬化性組成物又は熱硬化性組成物として用いることができる。 (1) Resin component Examples of the above-mentioned resin component include those capable of holding the above-mentioned compound I-1, which may be appropriately set depending on the application etc. of the composition, for example, polymerizing having a polymerizable group The compound etc. and the polymer which does not have a polymeric group etc. can be mentioned.
By including a polymerizable compound as the resin component, the composition can be used, for example, as a photocurable composition or a thermosetting composition.
上記樹脂成分としては、上記化合物I-1を保持できるものが挙げられ、組成物の用途等に応じて適宜設定されるものであるが、例えば、重合性基を有する重合性化合物及び重合性基を有しない重合体等を挙げることができる。
上記樹脂成分として重合性化合物を含むことにより、上記組成物は、例えば、光硬化性組成物又は熱硬化性組成物として用いることができる。 (1) Resin component Examples of the above-mentioned resin component include those capable of holding the above-mentioned compound I-1, which may be appropriately set depending on the application etc. of the composition, for example, polymerizing having a polymerizable group The compound etc. and the polymer which does not have a polymeric group etc. can be mentioned.
By including a polymerizable compound as the resin component, the composition can be used, for example, as a photocurable composition or a thermosetting composition.
(a)重合性化合物
重合性化合物は、重合性基の種類、すなわち、重合反応の種類により異なるものであり、例えば、ラジカル重合性化合物、カチオン重合性化合物、アニオン重合性化合物等を挙げることができる。
上記重合性化合物は、硬化阻害が少なくなるとの効果を効果的に発揮する観点からはラジカル重合性化合物を含むことが好ましい。 (A) Polymerizable Compound The polymerizable compound varies depending on the type of the polymerizable group, that is, the type of the polymerization reaction, and may be, for example, a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, etc. it can.
It is preferable that the said polymeric compound contains a radically polymerizable compound from a viewpoint of demonstrating the effect that hardening inhibition decreases effectively.
重合性化合物は、重合性基の種類、すなわち、重合反応の種類により異なるものであり、例えば、ラジカル重合性化合物、カチオン重合性化合物、アニオン重合性化合物等を挙げることができる。
上記重合性化合物は、硬化阻害が少なくなるとの効果を効果的に発揮する観点からはラジカル重合性化合物を含むことが好ましい。 (A) Polymerizable Compound The polymerizable compound varies depending on the type of the polymerizable group, that is, the type of the polymerization reaction, and may be, for example, a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, etc. it can.
It is preferable that the said polymeric compound contains a radically polymerizable compound from a viewpoint of demonstrating the effect that hardening inhibition decreases effectively.
(i)ラジカル重合性化合物
上記ラジカル重合性化合物は、ラジカル重合可能な重合性基を1以上有するものであればよく、2以上含むものであってもよい。
上記ラジカル重合性化合物は、通常、ラジカル重合開始剤と共に用いられるものである。
ラジカル重合可能な重合性基としては、例えば、(メタ)アクリル基、ビニル基等のエチレン性不飽和二重結合基を挙げることができる。
なお、(メタ)アクリルは、アクリル及びメタクリルを含む意味で用いるものである。また、(メタ)アクリレートは、アクリレート及びメタクリレートを含む意味で用いるものである。 (I) Radically Polymerizable Compound The radically polymerizable compound may have one or more radically polymerizable group and may contain two or more radically polymerizable group.
The above-mentioned radical polymerizable compound is usually used together with a radical polymerization initiator.
As a radically polymerizable polymerizable group, ethylenic unsaturated double bond groups, such as a (meth) acryl group and a vinyl group, can be mentioned, for example.
In addition, (meth) acryl is used by the meaning containing an acryl and methacryl. Also, (meth) acrylate is used in the meaning including acrylate and methacrylate.
上記ラジカル重合性化合物は、ラジカル重合可能な重合性基を1以上有するものであればよく、2以上含むものであってもよい。
上記ラジカル重合性化合物は、通常、ラジカル重合開始剤と共に用いられるものである。
ラジカル重合可能な重合性基としては、例えば、(メタ)アクリル基、ビニル基等のエチレン性不飽和二重結合基を挙げることができる。
なお、(メタ)アクリルは、アクリル及びメタクリルを含む意味で用いるものである。また、(メタ)アクリレートは、アクリレート及びメタクリレートを含む意味で用いるものである。 (I) Radically Polymerizable Compound The radically polymerizable compound may have one or more radically polymerizable group and may contain two or more radically polymerizable group.
The above-mentioned radical polymerizable compound is usually used together with a radical polymerization initiator.
As a radically polymerizable polymerizable group, ethylenic unsaturated double bond groups, such as a (meth) acryl group and a vinyl group, can be mentioned, for example.
In addition, (meth) acryl is used by the meaning containing an acryl and methacryl. Also, (meth) acrylate is used in the meaning including acrylate and methacrylate.
また、ラジカル重合性化合物としては、酸価を有する化合物であってもよく、酸価を有しない化合物であってもよい。
酸価を有する化合物としては、例えば、カルボキシル基を有する化合物等を挙げることができる。
上記組成物は、ラジカル重合性化合物として酸価を有する化合物を含むことにより、光照射部位のアルカリ現像液への溶解性が低下する。このため、上記組成物は、例えば、アルカリ現像液等の溶媒への溶解性が光照射前後で変化する感光性組成物として用いることができる。より具体的には、上記組成物は、酸価を有する化合物を含むことで、ネガ型組成物として用いることができる。
アルカリ現像液としては、テトラメチルアンモニウムヒドロキシド(TMAH)水溶液や、水酸化カリウム水溶液等のアルカリ現像液として一般的に使用されているものを用いることができる。 The radically polymerizable compound may be a compound having an acid value, or may be a compound having no acid value.
As a compound which has an acid value, the compound etc. which have a carboxyl group can be mentioned, for example.
By containing the compound which has an acid value as a radically polymerizable compound, the said composition reduces the solubility to the alkali developing solution of a light irradiation site | part. Therefore, the composition can be used, for example, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the above-mentioned composition can be used as a negative working composition by including a compound having an acid value.
As an alkali developing solution, what is generally used as alkali developing solutions, such as tetramethyl ammonium hydroxide (TMAH) aqueous solution and potassium hydroxide aqueous solution, can be used.
酸価を有する化合物としては、例えば、カルボキシル基を有する化合物等を挙げることができる。
上記組成物は、ラジカル重合性化合物として酸価を有する化合物を含むことにより、光照射部位のアルカリ現像液への溶解性が低下する。このため、上記組成物は、例えば、アルカリ現像液等の溶媒への溶解性が光照射前後で変化する感光性組成物として用いることができる。より具体的には、上記組成物は、酸価を有する化合物を含むことで、ネガ型組成物として用いることができる。
アルカリ現像液としては、テトラメチルアンモニウムヒドロキシド(TMAH)水溶液や、水酸化カリウム水溶液等のアルカリ現像液として一般的に使用されているものを用いることができる。 The radically polymerizable compound may be a compound having an acid value, or may be a compound having no acid value.
As a compound which has an acid value, the compound etc. which have a carboxyl group can be mentioned, for example.
By containing the compound which has an acid value as a radically polymerizable compound, the said composition reduces the solubility to the alkali developing solution of a light irradiation site | part. Therefore, the composition can be used, for example, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the above-mentioned composition can be used as a negative working composition by including a compound having an acid value.
As an alkali developing solution, what is generally used as alkali developing solutions, such as tetramethyl ammonium hydroxide (TMAH) aqueous solution and potassium hydroxide aqueous solution, can be used.
上記ラジカル重合性化合物は、例えば、エチレン性不飽和二重結合基を有し、酸価を有する化合物としては、(メタ)アクリル酸、α―クロルアクリル酸、イタコン酸、マレイン酸、シトラコン酸、フマル酸、ハイミック酸、クロトン酸、イソクロトン酸、ビニル酢酸、アリル酢酸、桂皮酸、ソルビン酸、メサコン酸、コハク酸モノ[2-(メタ)アクリロイロキシエチル]、フタル酸モノ[2-(メタ)アクリロイロキシエチル]及びω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ(メタ)アクリレート;ヒドロキシエチル(メタ)アクリレート・マレート、ヒドロキシプロピル(メタ)アクリレート・マレート、ジシクロペンタジエン・マレート或いは1個のカルボキシル基と2個以上の(メタ)アクリロイル基とを有する多官能(メタ)アクリレート等の不飽和一塩基酸;フェノール及び/又はクレゾールノボラックエポキシ樹脂、ビフェニル骨格、ナフタレン骨格を有するノボラックエポキシ樹脂、ビスフェノールAノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物、多官能エポキシ基を有するポリフェニルメタン型エポキシ樹脂、下記一般式(III)で表されるエポキシ化合物等のエポキシ樹脂のエポキシ基に不飽和一塩基酸を作用させた樹脂、下記一般式(III)で表されるエポキシ化合物等のエポキシ樹脂のエポキシ基に不飽和一塩基酸を作用させ、更に多塩基酸無水物を作用させて得られた樹脂、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレートと無水コハク酸、無水フタル酸、テトラヒドロ無水フタル酸等の二塩基酸無水物の反応物である酸価を有する多官能アクリレート等が挙げられる。
The radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having an acid value, (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid 1) Mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends such as acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Acrylate malate, dicyclopentadiene malate or a single powder Unsaturated monobasic acids such as polyfunctional (meth) acrylates having a voxyl group and two or more (meth) acryloyl groups; phenol and / or cresol novolac epoxy resin, novolac epoxy resin having a biphenyl skeleton and a naphthalene skeleton, bisphenol Anovolak type epoxy compounds, novolac type epoxy compounds such as dicyclopentadiene novolac type epoxy compounds, polyphenylmethane type epoxy resins having a multifunctional epoxy group, epoxy resins such as epoxy compounds represented by the following general formula (III) An epoxy group of an epoxy resin such as a resin obtained by reacting an unsaturated monobasic acid with an epoxy group or an epoxy compound represented by the following general formula (III) is reacted with an unsaturated monobasic acid, and a polybasic acid anhydride is further Resin obtained by reaction, pentaerythritol Examples include polyfunctional acrylates having an acid value, which are reaction products of hydroxyl group-containing polyfunctional acrylates such as diacrylates and dipentaerythritol pentaacrylates and dibasic acid anhydrides such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride. Be
(式中、X41は直接結合、炭素原子数1~4のアルキリデン基、炭素原子数3~20の脂環式炭化水素基、-O-、-S-、-SO2-、-SS-、-SO-、-CO-、-OCO-又は上記(1-1)~(1-3)で表される置換基を表し、
R41、R42、R44及びR44は、それぞれ独立に、水素原子、炭素原子数1~5のアルキル基、炭素原子数1~8のアルコキシ基、炭素原子数2~5のアルケニル基又はハロゲン原子を表し、
dは0~10の整数である。) (Wherein, X 41 represents a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO 2- , -SS- Or —SO—, —CO—, —OCO— or a substituent represented by (1-1) to (1-3) above,
R 41 , R 42 , R 44 and R 44 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or Represents a halogen atom,
d is an integer of 0 to 10; )
R41、R42、R44及びR44は、それぞれ独立に、水素原子、炭素原子数1~5のアルキル基、炭素原子数1~8のアルコキシ基、炭素原子数2~5のアルケニル基又はハロゲン原子を表し、
dは0~10の整数である。) (Wherein, X 41 represents a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO 2- , -SS- Or —SO—, —CO—, —OCO— or a substituent represented by (1-1) to (1-3) above,
R 41 , R 42 , R 44 and R 44 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or Represents a halogen atom,
d is an integer of 0 to 10; )
R41、R42、R44及びR44で表される炭素原子数1~5のアルキル基、炭素原子数1~8のアルコキシ基及び炭素原子数2~5のアルケニル基としては、上記「A.化合物」の項にR11等として例示したもののうち、所定の炭素原子数を満たすものを挙げることができる。
X41で表される炭素原子数1~4のアルキリデン基としては、例えば、メチリデン基、エチリデン基、プロピリデン基及びブチリデン基等を挙げることができる。
X41で表される炭素原子数3~20の脂環式炭化水素基としては、シクロプロピレン基、シクロペンチレン基、シクロヘキシレン基及びシクロヘプチレン基等が挙げられる。
上記アルキル基、アルコキシ基、アルケニル基、アルキリデン基及び脂環式炭化水素基は、置換基を有している場合があるものであり、特に断りがない限り、置換基を有していない無置換である又は置換基を有しているものである。該アルキル基、アルコキシ基、アルケニル基、アルキリデン基及び脂環式炭化水素基の水素原子を置換する置換基としては、R11等に用いられるアルキル基等の水素原子を置換する置換基と同様の内容とすることができる。 Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms and the alkenyl group having 2 to 5 carbon atoms represented by R 41 , R 42 , R 44 and R 44 include the above-mentioned “A Among those exemplified as R 11 and the like in the item of “compound”, those satisfying a predetermined number of carbon atoms can be mentioned.
Examples of the C 1-4 alkylidene group represented by X 41 include methylidene group, ethylidene group, propylidene group and butylidene group.
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by X 41 include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group and a cycloheptylene group.
The above-mentioned alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group may have a substituent, and unless otherwise specified, it is an unsubstituted group having no substituent. Or a substituent. Examples of the substituent that substitutes a hydrogen atom of the alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group are the same as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. It can be content.
X41で表される炭素原子数1~4のアルキリデン基としては、例えば、メチリデン基、エチリデン基、プロピリデン基及びブチリデン基等を挙げることができる。
X41で表される炭素原子数3~20の脂環式炭化水素基としては、シクロプロピレン基、シクロペンチレン基、シクロヘキシレン基及びシクロヘプチレン基等が挙げられる。
上記アルキル基、アルコキシ基、アルケニル基、アルキリデン基及び脂環式炭化水素基は、置換基を有している場合があるものであり、特に断りがない限り、置換基を有していない無置換である又は置換基を有しているものである。該アルキル基、アルコキシ基、アルケニル基、アルキリデン基及び脂環式炭化水素基の水素原子を置換する置換基としては、R11等に用いられるアルキル基等の水素原子を置換する置換基と同様の内容とすることができる。 Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms and the alkenyl group having 2 to 5 carbon atoms represented by R 41 , R 42 , R 44 and R 44 include the above-mentioned “A Among those exemplified as R 11 and the like in the item of “compound”, those satisfying a predetermined number of carbon atoms can be mentioned.
Examples of the C 1-4 alkylidene group represented by X 41 include methylidene group, ethylidene group, propylidene group and butylidene group.
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by X 41 include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group and a cycloheptylene group.
The above-mentioned alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group may have a substituent, and unless otherwise specified, it is an unsubstituted group having no substituent. Or a substituent. Examples of the substituent that substitutes a hydrogen atom of the alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group are the same as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. It can be content.
上記ラジカル重合性化合物は、例えば、エチレン性不飽和二重結合基を有し、酸価を有しない化合物としては、(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、(メタ)アクリル酸グリシジル、下記化合物No.A1~No.A4、(メタ)アクリル酸メチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸-t-ブチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸ジメチルアミノメチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸アミノプロピル、(メタ)アクリル酸ジメチルアミノプロピル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸ポリ(エトキシ)エチル、(メタ)アクリル酸ブトキシエトキシエチル、(メタ)アクリル酸エチルヘキシル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸テトラヒドロフリル、(メタ)アクリル酸ビニル、(メタ)アクリル酸アリル、(メタ)アクリル酸ベンジル、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリシクロデカンジメチロールジ(メタ)アクリレート、トリ[(メタ)アクリロイルエチル]イソシアヌレート、ポリエステル(メタ)アクリレートオリゴマー等の不飽和一塩基酸及び多価アルコール又は多価フェノールのエステル;(メタ)アクリル酸亜鉛、(メタ)アクリル酸マグネシウム等の不飽和多塩基酸の金属塩;マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸-無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等の不飽和多塩基酸の酸無水物;(メタ)アクリルアミド、メチレンビス-(メタ)アクリルアミド、ジエチレントリアミントリス(メタ)アクリルアミド、キシリレンビス(メタ)アクリルアミド、α-クロロアクリルアミド、N-2-ヒドロキシエチル(メタ)アクリルアミド等の不飽和一塩基酸及び多価アミンのアミド;アクロレイン等の不飽和アルデヒド;(メタ)アクリロニトリル、α-クロロアクリロニトリル、シアン化ビニリデン、シアン化アリル等の不飽和ニトリル;スチレン、4-メチルスチレン、4-エチルスチレン、4-メトキシスチレン、4-ヒドロキシスチレン、4-クロロスチレン、ジビニルベンゼン、ビニルトルエン、ビニル安息香酸、ビニルフェノール、ビニルスルホン酸、4-ビニルベンゼンスルホン酸、ビニルベンジルメチルエーテル、ビニルベンジルグリシジルエーテル等の不飽和芳香族化合物;メチルビニルケトン等の不飽和ケトン;ビニルアミン、アリルアミン、N-ビニルピロリドン、ビニルピペリジン等の不飽和アミン化合物;ビニルメチルエーテル、ビニルエチルエーテル、n-ブチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル等のビニルエーテル;マレイミド、N-フェニルマレイミド、N-シクロヘキシルマレイミド等の不飽和イミド類;インデン、1-メチルインデン等のインデン類;1,3-ブタジエン、イソプレン、クロロプレン等の脂肪族共役ジエン類;ポリスチレン、ポリメチル(メタ)アクリレート、ポリ-n-ブチル(メタ)アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ(メタ)アクリロイル基を有するマクロモノマー類;(メタ)アクリロニトリル、エチレン、プロピレン、ブチレン、塩化ビニル、酢酸ビニル等のその他のビニル化合物、及びポリメチルメタクリレートマクロモノマー、ポリスチレンマクロモノマー等のマクロモノマー類、トリシクロデカン骨格のモノメタクリレート、N-フェニルマレイミド、メタクリロイルオキシメチル-3-エチルオキセタン等と、(メタ)アクリル酸との共重合体及びこれらに昭和電工(株)社製カレンズMOI、AOIのような不飽和結合を有するイソシアネート化合物を反応させた(メタ)アクリル酸の共重合体や、ビニルクロリド、ビニリデンクロリド、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート、ビニルチオエーテル、ビニルイミダゾール、ビニルオキサゾリン、ビニルカルバゾール、ビニルピロリドン、ビニルピリジン、水酸基含有ビニルモノマー及びポリイソシアネート化合物のビニルウレタン化合物、水酸基含有ビニルモノマー及びポリエポキシ化合物のビニルエポキシ化合物、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレートとトリレンジイソシアネート、ヘキサメチレンジイソシアネート等の多官能イソシアネートの反応物等が挙げられる。
The above-mentioned radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having no acid value, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl, glycidyl (meth) acrylate, the following compound No. 1 A1 to No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meth ) Ethyl hexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuran Phthalic anhydride-anhydrous Acid anhydride of unsaturated polybasic acid such as leic acid adduct, dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylene Unsaturated aromatic compounds such as 2-phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide; And indenes such as 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- Macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chain such as chill (meth) acrylate and polysiloxane; (meth) acrylonitrile, other vinyl such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate Compounds, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyl oxetane, etc., and (meth) acrylic acid Polymers and copolymers of (meth) acrylic acid obtained by reacting an isocyanate compound having an unsaturated bond such as Karenz MOI manufactured by Showa Denko KK and AOI with these, vinyl chloride, vinylidene chloride, divinyl succ Nath, Allyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group-containing vinyl monomer And vinyl epoxy compounds of polyepoxy compounds, and reaction products of hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.
上記ラジカル重合性化合物は、単独で又は2種以上を混合して使用することができる。また、ラジカル重合性化合物は、エチレン性不飽和二重結合基を有し、酸価を有する化合物及びエチレン性不飽和二重結合基を有し、酸価を有しない化合物を組み合わせて使用することができる。
ラジカル重合性化合物は、2種以上を混合して使用する場合には、それらを予め共重合して共重合体として使用してもよい。
上記ラジカル重合性化合物の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
上記重合性化合物の含有量は、上記組成物を硬化性組成物として使用可能となるものであればよいが、化合物I-1及び重合性化合物の合計100質量部中に、1質量部以上99質量部以下とすることができ、50質量部以上99質量部以下であることが好ましく、なかでも、80質量部以上99質量部以下であることが好ましく、90質量部以上98質量部以下であることが好ましい。上記含有量が上述の範囲であることにより、上記組成物は、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
また、上記化合物I-1及びラジカル重合性化合物の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。 The said radically polymerizable compound can be used individually or in mixture of 2 or more types. In addition, the radically polymerizable compound has an ethylenically unsaturated double bond group, and uses a compound having an acid value and a compound having an ethylenically unsaturated double bond group and not having an acid value in combination. Can.
When a radically polymerizable compound is used in mixture of 2 or more types, they may be copolymerized beforehand and it may be used as a copolymer.
The content of the radically polymerizable compound can be appropriately set according to the application etc. of the composition, but for example, it can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts It is preferable that it is a part or more and 90 mass parts or less, Especially, it is preferable that it is 40 mass parts or more and 80 mass parts or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
The content of the polymerizable compound may be any one as long as the composition can be used as a curable composition, but 1 part by mass or more to 99 parts in total of 100 parts by mass of the compound I-1 and the polymerizable compound. It can be made into parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and 90 parts by mass or more and 98 parts by mass or less Is preferred. When the content is in the above-mentioned range, the composition can provide a composition which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product.
The content of the compound I-1 and the radically polymerizable compound can be appropriately set according to the application of the composition and the like, and for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. The amount is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
ラジカル重合性化合物は、2種以上を混合して使用する場合には、それらを予め共重合して共重合体として使用してもよい。
上記ラジカル重合性化合物の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
上記重合性化合物の含有量は、上記組成物を硬化性組成物として使用可能となるものであればよいが、化合物I-1及び重合性化合物の合計100質量部中に、1質量部以上99質量部以下とすることができ、50質量部以上99質量部以下であることが好ましく、なかでも、80質量部以上99質量部以下であることが好ましく、90質量部以上98質量部以下であることが好ましい。上記含有量が上述の範囲であることにより、上記組成物は、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
また、上記化合物I-1及びラジカル重合性化合物の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。 The said radically polymerizable compound can be used individually or in mixture of 2 or more types. In addition, the radically polymerizable compound has an ethylenically unsaturated double bond group, and uses a compound having an acid value and a compound having an ethylenically unsaturated double bond group and not having an acid value in combination. Can.
When a radically polymerizable compound is used in mixture of 2 or more types, they may be copolymerized beforehand and it may be used as a copolymer.
The content of the radically polymerizable compound can be appropriately set according to the application etc. of the composition, but for example, it can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts It is preferable that it is a part or more and 90 mass parts or less, Especially, it is preferable that it is 40 mass parts or more and 80 mass parts or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
The content of the polymerizable compound may be any one as long as the composition can be used as a curable composition, but 1 part by mass or more to 99 parts in total of 100 parts by mass of the compound I-1 and the polymerizable compound. It can be made into parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and 90 parts by mass or more and 98 parts by mass or less Is preferred. When the content is in the above-mentioned range, the composition can provide a composition which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product.
The content of the compound I-1 and the radically polymerizable compound can be appropriately set according to the application of the composition and the like, and for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. The amount is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
(ii)カチオン重合性化合物及びアニオン重合性化合物
上記カチオン重合性化合物は、カチオン重合可能な重合性基を1以上有するものであればよい。
上記カチオン重合性化合物は、通常、カチオン重合開始剤と共に用いられるものである。
カチオン重合可能な重合性基としては、例えば、エポキシ基及びオキセタン基等の環状エーテル基並びにビニルエーテル基等を挙げることができる。
すなわち、カチオン重合性化合物としては、エポキシ化合物及びオキセタン化合物等の環状エーテル化合物並びにビニルエーテル化合物等が挙げられる。 (Ii) Cationic Polymerizable Compound and Anionic Polymerizable Compound The cationic polymerizable compound may be one having one or more cationically polymerizable groups.
The cationically polymerizable compound is usually used together with a cationic polymerization initiator.
Examples of the cationically polymerizable polymerizable group include cyclic ether groups such as an epoxy group and an oxetane group, and a vinyl ether group.
That is, as a cationically polymerizable compound, cyclic ether compounds, such as an epoxy compound and an oxetane compound, a vinyl ether compound, etc. are mentioned.
上記カチオン重合性化合物は、カチオン重合可能な重合性基を1以上有するものであればよい。
上記カチオン重合性化合物は、通常、カチオン重合開始剤と共に用いられるものである。
カチオン重合可能な重合性基としては、例えば、エポキシ基及びオキセタン基等の環状エーテル基並びにビニルエーテル基等を挙げることができる。
すなわち、カチオン重合性化合物としては、エポキシ化合物及びオキセタン化合物等の環状エーテル化合物並びにビニルエーテル化合物等が挙げられる。 (Ii) Cationic Polymerizable Compound and Anionic Polymerizable Compound The cationic polymerizable compound may be one having one or more cationically polymerizable groups.
The cationically polymerizable compound is usually used together with a cationic polymerization initiator.
Examples of the cationically polymerizable polymerizable group include cyclic ether groups such as an epoxy group and an oxetane group, and a vinyl ether group.
That is, as a cationically polymerizable compound, cyclic ether compounds, such as an epoxy compound and an oxetane compound, a vinyl ether compound, etc. are mentioned.
上記エポキシ化合物としては、例えば、メチルグリシジルエーテル、2-エチルヘキシルグリシジルエーテル、ブチルグリシジルエーテル、デシルグリシジルエーテル、C12~13混合アルキルグリシジルエーテル、フェニル-2-メチルグリシジルエーテル、セチルグリシジルエーテル、ステアリルグリシジルエーテル、p-sec-ブチルフェニルグリシジルエーテル、p-tert-ブチルフェニルグリシジルエーテル、グリシジルメタクリレート、イソプロピルグリシジルエーテル、アリルグリシジルエーテル、エチルグリシジルエーテル、2-メチルオクチルグリシジルエーテル、フェニルグリシジルエーテル、4-n-ブチルフェニルグリシジルエーテル、4-フェニルフェノールグリシジルエーテル、クレジルグリシジルエーテル、ジブロモクレジルグリシジルエーテル、デシルグリシジルエーテル、メトキシポリエチレングリコールモノグリシジルエーテル、エトキシポリエチレングリコールモノグリシジルエーテル、ブトキシポリエチレングリコールモノグリシジルエーテル、フェノキシポリエチレングリコールモノグリシジルエーテル、ジブロモフェニルグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、1,5-ペンタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,1,2,2-テトラキス(グリシジルオキシフェニル)エタン及びペンタエリスリトールテトラグリシジルエーテル等のグリシジルエーテル化物;グリシジルアセテート、グリシジルステアレート等のグリシジルエステル類;2-(3,4-エポキシシクロヘキシル-5,5-スピロ-3,4-エポキシ)シクロヘキサン-メタジオキサン、メチレンビス(3,4-エポキシシクロヘキサン)、プロパン-2,2-ジイル-ビス(3,4-エポキシシクロヘキサン)、2,2-ビス(3,4-エポキシシクロヘキシル)プロパン、エチレンビス(3,4-エポキシシクロヘキサンカルボキシレート)、ビス(3,4-エポキシシクロヘキシルメチル)アジペート、3,4-エポキシシクロヘキシルメチル 3,4-エポキシシクロヘキサンカルボキシレート、3,4-エポキシ-1-メチルシクロヘキシル 3,4-エポキシ-1-メチルヘキサンカルボキシレート、6-メチル-3,4-エポキシシクロヘキシルメチル 6-メチル-3,4-エポキシシクロヘキサンカルボキシレート、3,4-エポキシ-3-メチルシクロヘキシルメチル 3,4-エポキシ-3-メチルシクロヘキサンカルボキシレート、3,4-エポキシ-5-メチルシクロヘキシルメチル 3,4-エポキシ-5-メチルシクロヘキサンカルボキシレート、1-エポキシエチル-3,4-エポキシシクロヘキサン、1,2-エポキシ-2-エポキシエチルシクロヘキサン、ジシクロペンタジエンジエポキサイド、3,4-エポキシ-6-メチルシクロヘキシルカルボキシレート、α-ピネンオキシド、スチレンオキシド、シクロヘキセンオキサイド及びシクロペンテンオキサイド等のエポキシシクロアルキル型化合物及びN-グリシジルフタルイミド等が挙げられる。
Examples of the above epoxy compounds include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, phenyl 2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl Glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl Ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butane Diol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol Glycidyl ether compounds such as tetraglycidyl ether; glycidyl acetate, Glycidyl esters such as sidyl stearate; 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, methylene bis (3,4-epoxycyclohexane), propane-2, 2-Diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, ethylene bis (3,4-epoxycyclohexane carboxylate), bis (3,4-epoxycyclohexyl) Methyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxycyclohexyl 6-Methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl , 4-Epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6- Examples thereof include epoxy cycloalkyl type compounds such as methyl cyclohexyl carboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide and cyclopentene oxide, and N-glycidyl phthalimide.
また上記エポキシ化合物としては、エポキシ化ポリオレフィンを用いることもできる。エポキシ化ポリオレフィンとは、ポリオレフィンをエポキシ基含有単量体で変性して、エポキシ基を導入したポリオレフィンである。エチレン又は炭素数3~20のα-オレフィン、エポキシ基含有単量体、及び必要に応じて他のモノマーを、共重合法及びグラフト法のいずれかにより共重合させることによって製造することができる。エチレン又は炭素数3~20のα-オレフィン、エポキシ基含有単量体及び他のモノマーは、それぞれ単独で重合させてもよく、他の単量体と複数で重合させてもよい。また、末端に水酸基を有する非共役のポリブタジエンの二重結合を、過酢酸法によりエポキシ化して得ることもでき、分子内に水酸基を持つものを使用してもよい。また、水酸基をイソシアネートでウレタン化し、ここに1級水酸基含有エポキシ化合物を反応させてエポキシ基を導入することもできる。
Moreover, an epoxidized polyolefin can also be used as said epoxy compound. The epoxidized polyolefin is a polyolefin in which an epoxy group is introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer, by any of a copolymerization method and a graft method. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer and another monomer may be polymerized alone or in combination with other monomers. Also, the double bond of a non-conjugated polybutadiene having a hydroxyl group at the end can be obtained by epoxidation by the peracetic acid method, and one having a hydroxyl group in the molecule may be used. Moreover, a hydroxyl group can be urethane-ized with isocyanate, and a primary hydroxyl group-containing epoxy compound can be made to react here, and an epoxy group can be introduce | transduced.
上記エチレン又は炭素数3~20のα-オレフィンとしては、エチレン、プロピレン、ブチレン、イソブチレン、1,3-ブタジエン、1,4-ブタジエン、1,3-ペンタジエン、2,3-ジメチル-1,3-ブタジエン、ピペリレン、3-ブチル-1,3-オクタジエン及びイソプレン等が挙げられる。
Examples of ethylene or α-olefins of 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3 -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like can be mentioned.
上記エポキシ基含有単量体としては、例えばα,β-不飽和酸のグリシジルエステル、ビニルベンジルグリシジルエーテル及びアリルグリシジルエーテル等が挙げられる。α,β-不飽和酸のグリシジルエステルとしては、具体的にはアクリル酸グリシジル、メタクリル酸グリシジル及びエタクリル酸グリシジル等が挙げられ、特にメタクリル酸グリシジルが好ましい。
Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids, vinyl benzyl glycidyl ether and allyl glycidyl ether. Specific examples of glycidyl esters of α, β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid, with glycidyl methacrylate being particularly preferred.
上記他のモノマーとしては、塩化ビニル、塩化ビニリデン、フッ化ビニリデン及びテトラフルオロエチレン等の不飽和脂肪族炭化水素;(メタ)アクリル酸、α―クロルアクリル酸、イタコン酸、マレイン酸、シトラコン酸、フマル酸、ハイミック酸、クロトン酸、イソクロトン酸、ビニル酢酸、アリル酢酸、桂皮酸、ソルビン酸、メサコン酸、コハク酸モノ[2-(メタ)アクリロイロキシエチル]、フタル酸モノ[2-(メタ)アクリロイロキシエチル]、ω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート・マレート、ヒドロキシプロピル(メタ)アクリレート・マレート、ジシクロペンタジエン・マレート及び1個のカルボキシル基と2個以上の(メタ)アクリロイル基とを有する多官能(メタ)アクリレート等の不飽和多塩基酸;(メタ)アクリル酸-2-ヒドロキシエチル、(メタ)アクリル酸-2-ヒドロキシプロピル、(メタ)アクリル酸メチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸-t-ブチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸ジメチルアミノメチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸アミノプロピル、(メタ)アクリル酸ジメチルアミノプロピル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸ポリ(エトキシ)エチル、(メタ)アクリル酸ブトキシエトキシエチル、(メタ)アクリル酸エチルヘキシル、(メタ)アクリル酸フェノキシエチル、(メタ)アクリル酸テトラヒドロフリル、(メタ)アクリル酸ビニル、(メタ)アクリル酸アリル、(メタ)アクリル酸ベンジル、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリシクロデカンジメチロールジ(メタ)アクリレート、トリ[(メタ)アクリロイルエチル]イソシアヌレート及びポリエステル(メタ)アクリレートオリゴマー等の不飽和一塩基酸及び多価アルコール又は多価フェノールのエステル;(メタ)アクリル酸亜鉛、(メタ)アクリル酸マグネシウム等の不飽和多塩基酸の金属塩;マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、5-(2,5-ジオキソテトラヒドロフリル)-3-メチル-3-シクロヘキセン-1,2-ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸-無水マレイン酸付加物、ドデセニル無水コハク酸及び無水メチルハイミック酸等の不飽和多塩基酸の酸無水物;(メタ)アクリルアミド、メチレンビス-(メタ)アクリルアミド、ジエチレントリアミントリス(メタ)アクリルアミド、キシリレンビス(メタ)アクリルアミド、α-クロロアクリルアミド、N-2-ヒドロキシエチル(メタ)アクリルアミド等の不飽和一塩基酸及び多価アミンのアミド;アクロレイン等の不飽和アルデヒド;(メタ)アクリロニトリル、α-クロロアクリロニトリル、シアン化ビニリデン、シアン化アリル等の不飽和ニトリル;スチレン、4-メチルスチレン、4-エチルスチレン、4-メトキシスチレン、4-ヒドロキシスチレン、4-クロロスチレン、ジビニルベンゼン、ビニルトルエン、ビニル安息香酸、ビニルフェノール、ビニルスルホン酸、4-ビニルベンゼンスルホン酸、ビニルベンジルメチルエーテル及びビニルナフタレン等の不飽和芳香族化合物;メチルビニルケトン等の不飽和ケトン;ビニルアミン、アリルアミン、N-ビニルピロリドン及びビニルピペリジン等の不飽和アミン化合物;アリルアルコール及びクロチルアルコール等のビニルアルコール;ビニルメチルエーテル、ビニルエチルエーテル、n-ブチルビニルエーテル及びイソブチルビニルエーテル等のビニルエーテル;マレイミド、N-フェニルマレイミド及びN-シクロヘキシルマレイミド等の不飽和イミド類;インデン及び1-メチルインデン等のインデン類;ポリスチレン、ポリメチル(メタ)アクリレート、ポリ-n-ブチル(メタ)アクリレート及びポリシロキサン等の重合体分子鎖の末端にモノ(メタ)アクリロイル基を有するマクロモノマー類;ビニルクロリド、ビニリデンクロリド、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート、ビニルチオエーテル、ビニルイミダゾール、ビニルオキサゾリン、ビニルカルバゾール、ビニルピロリドン、ビニルピリジン、水酸基含有ビニルモノマー及びポリイソシアネート化合物のビニルウレタン化合物、水酸基含有ビニルモノマー及びポリエポキシ化合物のビニルエポキシ化合物、ペンタエリスリトールトリアクリレート及びジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレート;トリレンジイソシアネート及びヘキサメチレンジイソシアネート等の多官能イソシアネートの反応物;ペンタエリスリトールトリアクリレート及びジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレートと無水コハク酸、無水フタル酸及びテトラヒドロ無水フタル酸等の二塩基酸無水物の反応物である酸価を有する多官能アクリレートが挙げられる。
Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid ) Acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Acrylate malate, dicyclopentadiene · And unsaturated polybasic acids such as polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acryloyl groups; 2-hydroxyethyl (meth) acrylate, (meth) acrylate -2-Hydroxypropyl, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n (meth) acrylate -Octyl, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, (meth ) Dimethylaminoethyl acrylate, aminopropyl (meth) acrylate, (meth) acrylic acid Dimethylaminopropyl, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) Tetrahydrofuryl acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol ethane Li (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tri Unsaturated monobasic acids such as cyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate and polyester (meth) acrylate oligomers and esters of polyhydric alcohols or polyhydric phenols; (meth) acrylic acid Zinc, metal salts of unsaturated polybasic acids such as magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydroanhydride Phthalic acid, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Adducts, acid anhydrides of unsaturated polybasic acids such as dodecenyl succinic anhydride and methyl hymic acid anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) acrylamide, Amides of unsaturated monobasic acids and polyvalent amines such as α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide, unsaturated aldehydes such as acrolein, (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, Shea Unsaturated nitriles such as allyl chloride; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfone Acids, unsaturated aromatic compounds such as 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether and vinyl naphthalene; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinyl amine, allylamine, N-vinyl pyrrolidone and vinyl piperidine Vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; maleimide, N-phenyl maleate Unsaturated imides such as nmid and N-cyclohexyl maleimide; indens such as indene and 1-methyl indene; polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane Macromonomers having a mono (meth) acryloyl group at the terminal of: vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, Vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, vinyl epoxy compound of hydroxyl group-containing vinyl monomer and polyepoxy compound Hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate; Reactant of polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate; Hydroxyl group-containing polyfunctional such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate A multifunctional acrylate having an acid value which is a reaction product of an acrylate and a dibasic acid anhydride such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride can be mentioned.
上記エポキシ化ポリオレフィンとしては、市販品を用いることもでき、例えば、エポリードPB3600、エポリードPB4700(ダイセル社製);BF-1000、FC-3000(ADEKA社製);ボンドファースト2C、ボンドファーストE、ボンドファーストCG5001、ボンドファーストCG5004、ボンドファースト2B、ボンドファースト7B、ボンドファースト7L、ボンドファースト7M、ボンドファーストVC40(住友化学社製);JP-100、JP-200(日本曹達社製);Poly bd R-45HT、Poly bd R-15HT(出光興産社製)及びRicon657(アルケマ社製)等が挙げられる。
A commercial item can also be used as said epoxidized polyolefin, For example, Epolide PB3600, Epolide PB4700 (made by Daicel); BF-1000, FC-3000 (made by ADEKA); Bond first 2C, bond first E, bond First CG 5001, Bond First CG 5004, Bond First 2 B, Bond First 7 B, Bond First 7 L, Bond First 7 M, Bond First VC 40 (Sumitomo Chemical Co., Ltd.); JP-100, JP-200 (Nippon Soda Co., Ltd.); Poly bd R And -45 HT, Poly bd R-15 HT (manufactured by Idemitsu Kosan Co., Ltd.) and Ricon 657 (manufactured by Arkema).
耐熱性が良好なことから、上記エポキシ化合物としては、上記一般式(II)で表されるカルド骨格を有する化合物を使用することがより好ましい。
From the viewpoint of good heat resistance, it is more preferable to use a compound having a cardo skeleton represented by the above general formula (II) as the above-mentioned epoxy compound.
上記オキセタン化合物としては、例えば、3,7-ビス(3-オキセタニル)-5-オキサ-ノナン、1,4-ビス[(3-エチル-3-オキセタニルメトキシ)メチル]ベンゼン、1,2-ビス[(3-エチル-3-オキセタニルメトキシ)メチル]エタン、1,3-ビス[(3-エチル-3-オキセタニルメトキシ)メチル]プロパン、エチレングリコールビス(3-エチル-3-オキセタニルメチル)エーテル、トリエチレングリコールビス(3-エチル-3-オキセタニルメチル)エーテル、テトラエチレングリコールビス(3-エチル-3-オキセタニルメチル)エーテル、1,4-ビス(3-エチル-3-オキセタニルメトキシ)ブタン、1,6-ビス(3-エチル-3-オキセタニルメトキシ)ヘキサン、3―エチル―3-[(フェノキシ)メチル]オキセタン、3―エチル―3-(ヘキシロキシメチル)オキセタン、3―エチル―3-(2-エチルヘキシロキシメチル)オキセタン、3―エチル―3-(ヒドロキシメチル)オキセタン及び3―エチル―3-(クロロメチル)オキセタン等が挙げられる。
Examples of the above-mentioned oxetane compounds include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1 , 6-Bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3- (Phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane and 3- Ethyl 3- (chloromethyl) oxetane and the like can be mentioned.
上記ビニルエーテル化合物としては、例えば、ジエチレングリコールモノビニルエーテル、トリエチレングリコールジビニルエーテル、n-ドデシルビニルエーテル、シクロヘキシルビニルエーテル、2-エチルヘキシルビニルエーテル、2-クロロエチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテル、トリエチレングリコールビニルエーテル、2-ヒドロキシエチルビニルエーテル、4-ヒドロキシブチルビニルエーテル、1,6-シクロヘキサンジメタノールモノビニルエーテル、エチレングリコールジビニルエーテル、1,4-ブタンジオールジビニルエーテル及び1,6-シクロヘキサンジメタノールジビニルエーテル等が挙げられる。
Examples of the vinyl ether compounds include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether and 1,6-cyclohexane dimethanol divinyl ether.
上記アニオン重合性化合物としては、アニオン重合可能な重合性基を1以上有するものであればよい。
上記アニオン重合性化合物は、通常、アニオン重合開始剤と共に用いられるものである。
上記アニオン重合可能な重合性基としては、例えば、エポキシ基、ラクトン基、(メタ)アクリル基等を挙げることができる。
すなわち、上記アニオン重合性化合物としては、エポキシ化合物、ラクトン化合物、(メタ)アクリル基を有する化合物等が挙げられる。
上記ラクトン化合物としては、β-プロピオラクトン、ε-カプロラクトン等を挙げることができる。
なお、エポキシ化合物については、上記カチオン重合性化合物として例示したエポキシ化合物を用いることができる。また、(メタ)アクリル基を有する化合物としては、上記ラジカル重合性化合物として例示したものを用いることができる。 As the above-mentioned anionically polymerizable compound, those having one or more polymerizable groups capable of anionic polymerization may be used.
The above-mentioned anionically polymerizable compound is usually used together with an anionic polymerization initiator.
As said anionizable polymerizable group, an epoxy group, a lactone group, a (meth) acryl group etc. can be mentioned, for example.
That is, as the above-mentioned anion polymerization compound, an epoxy compound, a lactone compound, a compound which has a (meth) acryl group, etc. are mentioned.
Examples of the lactone compound include β-propiolactone and ε-caprolactone.
In addition, as an epoxy compound, the epoxy compound illustrated as said cationically polymerizable compound can be used. Moreover, as a compound which has a (meth) acryl group, what was illustrated as said radically polymerizable compound can be used.
上記アニオン重合性化合物は、通常、アニオン重合開始剤と共に用いられるものである。
上記アニオン重合可能な重合性基としては、例えば、エポキシ基、ラクトン基、(メタ)アクリル基等を挙げることができる。
すなわち、上記アニオン重合性化合物としては、エポキシ化合物、ラクトン化合物、(メタ)アクリル基を有する化合物等が挙げられる。
上記ラクトン化合物としては、β-プロピオラクトン、ε-カプロラクトン等を挙げることができる。
なお、エポキシ化合物については、上記カチオン重合性化合物として例示したエポキシ化合物を用いることができる。また、(メタ)アクリル基を有する化合物としては、上記ラジカル重合性化合物として例示したものを用いることができる。 As the above-mentioned anionically polymerizable compound, those having one or more polymerizable groups capable of anionic polymerization may be used.
The above-mentioned anionically polymerizable compound is usually used together with an anionic polymerization initiator.
As said anionizable polymerizable group, an epoxy group, a lactone group, a (meth) acryl group etc. can be mentioned, for example.
That is, as the above-mentioned anion polymerization compound, an epoxy compound, a lactone compound, a compound which has a (meth) acryl group, etc. are mentioned.
Examples of the lactone compound include β-propiolactone and ε-caprolactone.
In addition, as an epoxy compound, the epoxy compound illustrated as said cationically polymerizable compound can be used. Moreover, as a compound which has a (meth) acryl group, what was illustrated as said radically polymerizable compound can be used.
上記カチオン重合性化合物及びアニオン重合性化合物は、それぞれ単独で又は2種以上を混合して使用することができる。
The said cationically polymerizable compound and anionically polymerizable compound can be used individually or in mixture of 2 or more types, respectively.
(b)重合性基を有しない重合体
本発明の組成物に用いることができる樹脂として、上述した通り、重合性基を有しない重合体を用いることができる。
上記重合性基を有しない重合体の重量平均分子量(Mw)は、組成物の用途等に応じて適宜設定されるものであるが、例えば、1500以上とすることができ、1500以上300000以下とすることができる。
このような重合体としては、繰り返し構造を含むものであればよく、感光性を有する感光性樹脂、感光性を有さない非感光性樹脂等を挙げることができる。
本発明の組成物は、例えば、樹脂成分として感光性樹脂を含むことにより、感光性組成物として用いることができる。 (B) Polymer Having No Polymerizable Group As a resin that can be used for the composition of the present invention, as described above, a polymer having no polymerizable group can be used.
The weight average molecular weight (Mw) of the polymer having no polymerizable group is appropriately set according to the application etc. of the composition, but can be, for example, 1500 or more, and 1500 or more and 300000 or less can do.
As such a polymer, what is necessary is just to include a repeating structure, and a photosensitive resin having photosensitivity, a non-photosensitive resin having no photosensitivity, and the like can be mentioned.
The composition of the present invention can be used as a photosensitive composition, for example, by including a photosensitive resin as a resin component.
本発明の組成物に用いることができる樹脂として、上述した通り、重合性基を有しない重合体を用いることができる。
上記重合性基を有しない重合体の重量平均分子量(Mw)は、組成物の用途等に応じて適宜設定されるものであるが、例えば、1500以上とすることができ、1500以上300000以下とすることができる。
このような重合体としては、繰り返し構造を含むものであればよく、感光性を有する感光性樹脂、感光性を有さない非感光性樹脂等を挙げることができる。
本発明の組成物は、例えば、樹脂成分として感光性樹脂を含むことにより、感光性組成物として用いることができる。 (B) Polymer Having No Polymerizable Group As a resin that can be used for the composition of the present invention, as described above, a polymer having no polymerizable group can be used.
The weight average molecular weight (Mw) of the polymer having no polymerizable group is appropriately set according to the application etc. of the composition, but can be, for example, 1500 or more, and 1500 or more and 300000 or less can do.
As such a polymer, what is necessary is just to include a repeating structure, and a photosensitive resin having photosensitivity, a non-photosensitive resin having no photosensitivity, and the like can be mentioned.
The composition of the present invention can be used as a photosensitive composition, for example, by including a photosensitive resin as a resin component.
(i)感光性樹脂
上記感光性樹脂は、感光性を有するものであり、例えば、酸発生剤と共に用いられ、酸の作用でエステル基又はアセタール基等の化学結合の切断等、現像液に対する溶解性が増加する方向に変化するポジ型樹脂を挙げることができる。
上記組成物は、樹脂成分としてポジ型樹脂を含むことにより、光照射部位のアルカリ現像液への溶解性が増加する。
このため、上記組成物は、例えば、アルカリ現像液等の溶媒への溶解性が光照射前後で変化する感光性組成物として、より具体的には、ポジ型組成物として用いることができる。 (I) Photosensitive resin The above-mentioned photosensitive resin has photosensitivity, and is used together with an acid generator, for example, it dissolves in a developer such as cleavage of chemical bond such as ester group or acetal group by action of acid Mention may be made of positive resins which change in the direction in which the properties increase.
The composition described above contains a positive resin as a resin component, whereby the solubility of the light-irradiated portion in the alkali developer is increased.
Therefore, the composition can be used, for example, as a positive type composition, more specifically, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation.
上記感光性樹脂は、感光性を有するものであり、例えば、酸発生剤と共に用いられ、酸の作用でエステル基又はアセタール基等の化学結合の切断等、現像液に対する溶解性が増加する方向に変化するポジ型樹脂を挙げることができる。
上記組成物は、樹脂成分としてポジ型樹脂を含むことにより、光照射部位のアルカリ現像液への溶解性が増加する。
このため、上記組成物は、例えば、アルカリ現像液等の溶媒への溶解性が光照射前後で変化する感光性組成物として、より具体的には、ポジ型組成物として用いることができる。 (I) Photosensitive resin The above-mentioned photosensitive resin has photosensitivity, and is used together with an acid generator, for example, it dissolves in a developer such as cleavage of chemical bond such as ester group or acetal group by action of acid Mention may be made of positive resins which change in the direction in which the properties increase.
The composition described above contains a positive resin as a resin component, whereby the solubility of the light-irradiated portion in the alkali developer is increased.
Therefore, the composition can be used, for example, as a positive type composition, more specifically, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation.
上記ポジ型樹脂としては、高分子重合体を、アルカリ溶解制御能を有する酸不安定基に部分的に置換したものを用いることができる。
上記高分子重合体としては、ポリヒドロキシスチレン及びその誘導体;ポリアクリル酸及びその誘導体;ポリメタクリル酸及びその誘導体;ヒドロキシスチレン、アクリル酸、メタクリル酸及びそれらの誘導体から選ばれ形成される2以上の共重合体;ヒドロキシスチレン、スチレン及びそれらの誘導体から選ばれ形成される2以上の共重合体;シクロオレフィン及びその誘導体、無水マレイン酸、並びに、アクリル酸及びその誘導体から選ばれる3以上の共重合体;シクロオレフィン及びその誘導体、マレイミド、並びに、アクリル酸及びその誘導体から選ばれる3以上の共重合体;ポリノルボルネン;メタセシス開環重合体からなる一群から選択される1種以上の高分子重合体等を挙げることができる。
上記高分子重合体に導入される酸不安定基としては、三級アルキル基、トリアルキルシリル基、オキソアルキル基、アリール基置換アルキル基、テトラヒドロピラン-2-イル基等の複素脂環基、三級アルキルカルボニル基、三級アルキルカルボニルアルキル基、アルキルオキシカルボニル基等が挙げられる。 As the positive resin, those obtained by partially replacing a high molecular weight polymer with an acid labile group having alkali solubility control ability can be used.
As the above-mentioned polymer, polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof and two or more formed Copolymer: two or more copolymers selected from hydroxystyrene, styrene and their derivatives, cycloolefin and its derivatives, maleic anhydride, and three or more copolymers selected from acrylic acid and its derivatives Combined; cycloolefin and derivatives thereof, maleimide, and three or more copolymers selected from acrylic acid and derivatives thereof; polynorbornene; at least one polymer selected from the group consisting of metathesis ring-opening polymers Etc. can be mentioned.
The acid labile group to be introduced into the above-mentioned polymer includes heteroalicyclic groups such as tertiary alkyl group, trialkylsilyl group, oxoalkyl group, aryl group substituted alkyl group, tetrahydropyran-2-yl group, etc. Tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyl groups, alkyloxycarbonyl groups and the like can be mentioned.
上記高分子重合体としては、ポリヒドロキシスチレン及びその誘導体;ポリアクリル酸及びその誘導体;ポリメタクリル酸及びその誘導体;ヒドロキシスチレン、アクリル酸、メタクリル酸及びそれらの誘導体から選ばれ形成される2以上の共重合体;ヒドロキシスチレン、スチレン及びそれらの誘導体から選ばれ形成される2以上の共重合体;シクロオレフィン及びその誘導体、無水マレイン酸、並びに、アクリル酸及びその誘導体から選ばれる3以上の共重合体;シクロオレフィン及びその誘導体、マレイミド、並びに、アクリル酸及びその誘導体から選ばれる3以上の共重合体;ポリノルボルネン;メタセシス開環重合体からなる一群から選択される1種以上の高分子重合体等を挙げることができる。
上記高分子重合体に導入される酸不安定基としては、三級アルキル基、トリアルキルシリル基、オキソアルキル基、アリール基置換アルキル基、テトラヒドロピラン-2-イル基等の複素脂環基、三級アルキルカルボニル基、三級アルキルカルボニルアルキル基、アルキルオキシカルボニル基等が挙げられる。 As the positive resin, those obtained by partially replacing a high molecular weight polymer with an acid labile group having alkali solubility control ability can be used.
As the above-mentioned polymer, polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof and two or more formed Copolymer: two or more copolymers selected from hydroxystyrene, styrene and their derivatives, cycloolefin and its derivatives, maleic anhydride, and three or more copolymers selected from acrylic acid and its derivatives Combined; cycloolefin and derivatives thereof, maleimide, and three or more copolymers selected from acrylic acid and derivatives thereof; polynorbornene; at least one polymer selected from the group consisting of metathesis ring-opening polymers Etc. can be mentioned.
The acid labile group to be introduced into the above-mentioned polymer includes heteroalicyclic groups such as tertiary alkyl group, trialkylsilyl group, oxoalkyl group, aryl group substituted alkyl group, tetrahydropyran-2-yl group, etc. Tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyl groups, alkyloxycarbonyl groups and the like can be mentioned.
上記ポジ型樹脂の詳細な具体例は、例えば、特開2003-192665号公報、特開2004-323704号公報の請求項3、特開平10-10733号公報等に記載の内容と同様とすることができる。
Detailed examples of the positive resin are the same as the contents described in, for example, JP-A-2003-192665, JP-A-2004-323704, claim 3, JP-A-10-10733, etc. Can.
上記ポジ型樹脂と共に用いられる酸発生剤としては、公知の酸発生剤を用いることができる。上記酸発生剤としては、具体的には、後述する光カチオン重合開始剤、熱カチオン重合開始剤等を挙げることができる。
A well-known acid generator can be used as an acid generator used with said positive resin. Specifically as said acid generator, the photocationic polymerization initiator mentioned later, a thermal cationic polymerization initiator, etc. can be mentioned.
(ii)非感光性樹脂
上記非感光性樹脂は、感光性を有しないものであればよく、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート-エチルアクリレート共重合体、ポリ(メタ)アクリル酸、スチレン-(メタ)アクリル酸共重合体、(メタ)アクリル酸-メチルメタクリレート共重合体、エチレン-塩化ビニル共重合体、エチレン-ビニル共重合体、ポリ塩化ビニル樹脂、ABS樹脂、ナイロン6、ナイロン66、ナイロン12、ウレタン樹脂、ポリカーボネートポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル、フェノール樹脂、フェノキシ樹脂、ポリアミドイミド樹脂、ポリアミック酸樹脂、エポキシ樹脂等が挙げられる。
上記非感光性樹脂は、例えば、上述の重合性化合物の重合物も用いることができる。 (Ii) Non-Photosensitive Resin The above-mentioned non-photosensitive resin may be any one not having photosensitivity, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene -(Meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66 Nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin and the like.
As the non-photosensitive resin, for example, a polymer of the above-mentioned polymerizable compound can also be used.
上記非感光性樹脂は、感光性を有しないものであればよく、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート-エチルアクリレート共重合体、ポリ(メタ)アクリル酸、スチレン-(メタ)アクリル酸共重合体、(メタ)アクリル酸-メチルメタクリレート共重合体、エチレン-塩化ビニル共重合体、エチレン-ビニル共重合体、ポリ塩化ビニル樹脂、ABS樹脂、ナイロン6、ナイロン66、ナイロン12、ウレタン樹脂、ポリカーボネートポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル、フェノール樹脂、フェノキシ樹脂、ポリアミドイミド樹脂、ポリアミック酸樹脂、エポキシ樹脂等が挙げられる。
上記非感光性樹脂は、例えば、上述の重合性化合物の重合物も用いることができる。 (Ii) Non-Photosensitive Resin The above-mentioned non-photosensitive resin may be any one not having photosensitivity, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene -(Meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66 Nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin and the like.
As the non-photosensitive resin, for example, a polymer of the above-mentioned polymerizable compound can also be used.
(c)樹脂成分
本発明の組成物における上記樹脂成分の含有量は、組成物の用途等に応じて適宜決定することができるが、例えば、組成物の固形分100質量部中、1質量部以上99質量部以下とすることが好ましく、20質量部以上95質量部以下であることがより好ましく、30質量部以上90質量部以下であることが特に好ましい。上記含有量が上述の範囲であることにより、上記組成物は、例えば、上記化合物I-1を安定的に保持可能だからである。
上記樹脂成分の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
上記樹脂成分の含有量は、組成物の用途等に応じて異なるものであるが、化合物I-1及び樹脂成分の合計100質量部中に、1質量部以上99質量部以下とすることができ、50質量部以上99質量部以下であることが好ましく、なかでも、80質量部以上99質量部以下であることが好ましく、90質量部以上98質量部以下であることが好ましい。上記含有量が上述の範囲であることにより、上記組成物は、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
また、上記化合物I-1及び樹脂成分の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。 (C) Resin component The content of the above resin component in the composition of the present invention can be appropriately determined according to the application etc. of the composition, and for example, 1 part by mass in 100 parts by mass of the solid content of the composition The content is preferably 99 parts by mass or less, more preferably 20 parts by mass or more and 95 parts by mass or less, and particularly preferably 30 parts by mass or more and 90 parts by mass or less. It is because the said composition can hold | maintain the said compound I-1 stably, for example, because the said content is the above-mentioned range.
The content of the resin component can be appropriately set according to the application etc. of the composition, but can be, for example, 1 part by mass or more and 99 parts by mass or less, and 10 parts by mass or more in 100 parts by mass of the composition. The content is preferably 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
The content of the above resin component varies depending on the application etc. of the composition, but can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass in total of the compound I-1 and the resin component. The content is preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and preferably 90 parts by mass or more and 98 parts by mass or less. It is because the said composition can provide the composition which can easily provide an ultraviolet absorptivity etc. easily with respect to hardened | cured material because the said content is the above-mentioned range.
Further, the content of the compound I-1 and the resin component can be appropriately set according to the application etc. of the composition, but for example, it is 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
本発明の組成物における上記樹脂成分の含有量は、組成物の用途等に応じて適宜決定することができるが、例えば、組成物の固形分100質量部中、1質量部以上99質量部以下とすることが好ましく、20質量部以上95質量部以下であることがより好ましく、30質量部以上90質量部以下であることが特に好ましい。上記含有量が上述の範囲であることにより、上記組成物は、例えば、上記化合物I-1を安定的に保持可能だからである。
上記樹脂成分の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
上記樹脂成分の含有量は、組成物の用途等に応じて異なるものであるが、化合物I-1及び樹脂成分の合計100質量部中に、1質量部以上99質量部以下とすることができ、50質量部以上99質量部以下であることが好ましく、なかでも、80質量部以上99質量部以下であることが好ましく、90質量部以上98質量部以下であることが好ましい。上記含有量が上述の範囲であることにより、上記組成物は、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。
また、上記化合物I-1及び樹脂成分の含有量としては、組成物の用途等に応じて適宜設定できるが、例えば、組成物100質量部中に、1質量部以上99質量部以下とすることができ、10質量部以上90質量部以下であることが好ましく、なかでも、40質量部以上80質量部以下であることが好ましい。上記含有量が上述の範囲であることで、例えば、上記組成物は、感度に優れたネガ型組成物として用いることができるからである。また、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を容易に付与できる組成物を提供することができるからである。 (C) Resin component The content of the above resin component in the composition of the present invention can be appropriately determined according to the application etc. of the composition, and for example, 1 part by mass in 100 parts by mass of the solid content of the composition The content is preferably 99 parts by mass or less, more preferably 20 parts by mass or more and 95 parts by mass or less, and particularly preferably 30 parts by mass or more and 90 parts by mass or less. It is because the said composition can hold | maintain the said compound I-1 stably, for example, because the said content is the above-mentioned range.
The content of the resin component can be appropriately set according to the application etc. of the composition, but can be, for example, 1 part by mass or more and 99 parts by mass or less, and 10 parts by mass or more in 100 parts by mass of the composition. The content is preferably 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
The content of the above resin component varies depending on the application etc. of the composition, but can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass in total of the compound I-1 and the resin component. The content is preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and preferably 90 parts by mass or more and 98 parts by mass or less. It is because the said composition can provide the composition which can easily provide an ultraviolet absorptivity etc. easily with respect to hardened | cured material because the said content is the above-mentioned range.
Further, the content of the compound I-1 and the resin component can be appropriately set according to the application etc. of the composition, but for example, it is 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
本発明の組成物に含まれる上記樹脂成分の種類は、1種類のみであってもよく、2種類以上の組み合わせであってもよい。
上記樹脂成分は、例えば、重合性化合物及び重合体のいずれか一方のみを含むもの又は両者を含むものとすることができる。
上記樹脂成分が重合性化合物及び重合性基を有しない重合体の両者を含む場合、上記重合性化合物の含有量としては、組成物の用途等に応じて適宜設定することができるが、例えば、重合性化合物及び重合体100質量部中、1質量部以上99質量部以下とすることができる。 The type of the resin component contained in the composition of the present invention may be only one type or a combination of two or more types.
The resin component may contain, for example, only one or both of the polymerizable compound and the polymer.
When the resin component contains both a polymerizable compound and a polymer not having a polymerizable group, the content of the polymerizable compound can be appropriately set according to the application of the composition, etc. It can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the polymerizable compound and the polymer.
上記樹脂成分は、例えば、重合性化合物及び重合体のいずれか一方のみを含むもの又は両者を含むものとすることができる。
上記樹脂成分が重合性化合物及び重合性基を有しない重合体の両者を含む場合、上記重合性化合物の含有量としては、組成物の用途等に応じて適宜設定することができるが、例えば、重合性化合物及び重合体100質量部中、1質量部以上99質量部以下とすることができる。 The type of the resin component contained in the composition of the present invention may be only one type or a combination of two or more types.
The resin component may contain, for example, only one or both of the polymerizable compound and the polymer.
When the resin component contains both a polymerizable compound and a polymer not having a polymerizable group, the content of the polymerizable compound can be appropriately set according to the application of the composition, etc. It can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the polymerizable compound and the polymer.
(2)重合開始剤
上記重合開始剤は、硬化性成分として含まれるものであり、通常、重合性化合物等と共に用いられるものである。
上記重合開始剤としては、重合性化合物を重合可能なものであればよく、例えば、光照射を受けることにより重合性化合物を重合可能な光重合開始剤、加熱することにより重合性化合物を重合可能な熱重合開始剤等を挙げることができる。
上記重合開始剤は、上記化合物I-1が、紫外線吸収剤として機能するとの効果を効果的に発揮する観点からは、光重合開始剤であることが好ましい。 (2) Polymerization initiator The above-mentioned polymerization initiator is contained as a curable component, and is usually used together with a polymerizable compound or the like.
The above-mentioned polymerization initiator may be any one capable of polymerizing a polymerizable compound, for example, a photopolymerization initiator capable of polymerizing a polymerizable compound by receiving light irradiation, and can polymerize a polymerizable compound by heating And thermal polymerization initiators.
The above-mentioned polymerization initiator is preferably a photopolymerization initiator from the viewpoint of effectively exerting the effect that the above-mentioned compound I-1 functions as an ultraviolet absorber.
上記重合開始剤は、硬化性成分として含まれるものであり、通常、重合性化合物等と共に用いられるものである。
上記重合開始剤としては、重合性化合物を重合可能なものであればよく、例えば、光照射を受けることにより重合性化合物を重合可能な光重合開始剤、加熱することにより重合性化合物を重合可能な熱重合開始剤等を挙げることができる。
上記重合開始剤は、上記化合物I-1が、紫外線吸収剤として機能するとの効果を効果的に発揮する観点からは、光重合開始剤であることが好ましい。 (2) Polymerization initiator The above-mentioned polymerization initiator is contained as a curable component, and is usually used together with a polymerizable compound or the like.
The above-mentioned polymerization initiator may be any one capable of polymerizing a polymerizable compound, for example, a photopolymerization initiator capable of polymerizing a polymerizable compound by receiving light irradiation, and can polymerize a polymerizable compound by heating And thermal polymerization initiators.
The above-mentioned polymerization initiator is preferably a photopolymerization initiator from the viewpoint of effectively exerting the effect that the above-mentioned compound I-1 functions as an ultraviolet absorber.
(a)光重合開始剤
上記光重合開始剤としては、光照射を受けることにより重合性化合物を重合可能なものであればよく、例えば、光ラジカル重合開始剤、光カチオン重合開始剤、光アニオン重合開始剤等を挙げることができる。 (A) Photopolymerization initiator The above-mentioned photopolymerization initiator may be any one capable of polymerizing the polymerizable compound by receiving light irradiation, for example, photo radical polymerization initiator, photo cationic polymerization initiator, photo anion A polymerization initiator etc. can be mentioned.
上記光重合開始剤としては、光照射を受けることにより重合性化合物を重合可能なものであればよく、例えば、光ラジカル重合開始剤、光カチオン重合開始剤、光アニオン重合開始剤等を挙げることができる。 (A) Photopolymerization initiator The above-mentioned photopolymerization initiator may be any one capable of polymerizing the polymerizable compound by receiving light irradiation, for example, photo radical polymerization initiator, photo cationic polymerization initiator, photo anion A polymerization initiator etc. can be mentioned.
上記光ラジカル重合開始剤としては、光照射によりラジカルを発生するものであれば特に制限されず従来既知の化合物を用いることができる。
上記光ラジカル重合開始剤としては、例えば、アセトフェノン系化合物、ベンジル系化合物、ベンゾフェノン系化合物、チオキサントン系化合物及びオキシムエステル系化合物等を好ましいものとして例示することができる。 The photo radical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used.
As said photo radical polymerization initiator, an acetophenone type compound, a benzyl type compound, a benzophenone series compound, a thioxanthone type compound, an oxime ester type compound etc. can be illustrated as a preferable thing, for example.
上記光ラジカル重合開始剤としては、例えば、アセトフェノン系化合物、ベンジル系化合物、ベンゾフェノン系化合物、チオキサントン系化合物及びオキシムエステル系化合物等を好ましいものとして例示することができる。 The photo radical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used.
As said photo radical polymerization initiator, an acetophenone type compound, a benzyl type compound, a benzophenone series compound, a thioxanthone type compound, an oxime ester type compound etc. can be illustrated as a preferable thing, for example.
上記アセトフェノン系化合物としては例えば、ジエトキシアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、4’-イソプロピル-2-ヒドロキシ-2-メチルプロピオフェノン、2-ヒドロキシメチル-2-メチルプロピオフェノン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、p-ジメチルアミノアセトフェノン、p-ターシャリブチルジクロロアセトフェノン、p-ターシャリブチルトリクロロアセトフェノン、p-アジドベンザルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパノン-1、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン-n-ブチルエーテル、ベンゾインイソブチルエーテル及び1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン等が挙げられる。
Examples of the above-mentioned acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl- 2-Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiary butyl dichloroacetophenone, p-tertiary butyl trichloroacetophenone, p-azidoben Salacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butanone-1, b Zoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1- on and the like.
上記ベンジル系化合物としては、ベンジル等が挙げられる。
Examples of the above-mentioned benzyl compound include benzyl and the like.
上記ベンゾフェノン系化合物としては、例えば、ベンゾフェノン、o-ベンゾイル安息香酸メチル、ミヒラーケトン、4,4’-ビスジエチルアミノベンゾフェノン、4,4’-ジクロロベンゾフェノン及び4-ベンゾイル-4’-メチルジフェニルスルフィド等が挙げられる。
Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. Be
上記チオキサントン系化合物としては、チオキサントン、2-メチルチオキサントン、2-エチルチオキサントン、2-クロロチオキサントン、2-イソプロピルチオキサントン、2,4-ジエチルチオキサントン等が挙げられる。
Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone and the like.
上記オキシム系化合物としては、例えば、下記一般式(IV)で表される化合物を挙げることができる。
As said oxime type compound, the compound represented by the following general formula (IV) can be mentioned, for example.
(式中、R71及びR72は、それぞれ独立に、水素原子、シアノ基、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R73及びR74は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、R75、OR76、SR77、NR78R79、COR80、SOR81、SO2R82又はCONR83R84を表し、R73及びR74は、互いに結合して環を形成している場合もあり、
R75、R76、R77、R78、R79、R80、R81、R82、R83及びR84は、それぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
X3は、酸素原子、硫黄原子、セレン原子、CR85R86、CO、NR87又はPR88を表し、
X4は、単結合又はCOを表し、
R85、R86、R87及びR88は、それぞれ独立に、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~20のアリール基又は炭素原子数7~20のアリールアルキル基を表し、該アルキル基又はアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環含有基で置換されている場合もあり、-O-で置き換えられている場合もあり、
R73及びR74は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成している場合もあり、
e1は、0~4の整数を表し、
e2は、0~5の整数を表す。) (Wherein, R 71 and R 72 each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms A group or a heterocycle-containing group having 2 to 20 carbon atoms,
R 73 and R 74 each independently represent a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 75 , OR 76 , SR 77 , NR 78 R 79 , COR 80 , SOR 81 , SO 2 R 82 or It represents CONR 83 R 84, R 73 and R 74 are, sometimes are bonded to each other to form a ring,
R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 and R 84 are each independently an alkyl group having 1 to 20 carbon atoms and 6 to 6 carbon atoms 30 aryl groups, arylalkyl groups having 7 to 30 carbon atoms, or heterocycle-containing groups having 2 to 20 carbon atoms,
X 3 represents an oxygen atom, a sulfur atom, a selenium atom, CR 85 R 86 , CO, NR 87 or PR 88 ,
X 4 represents a single bond or CO;
R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms And the methylene group in the alkyl group or the arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, and may be substituted with -O- May be
R 73 and R 74 may independently form a ring together with either of adjacent benzene rings,
e1 represents an integer of 0 to 4;
e2 represents an integer of 0 to 5; )
R73及びR74は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、R75、OR76、SR77、NR78R79、COR80、SOR81、SO2R82又はCONR83R84を表し、R73及びR74は、互いに結合して環を形成している場合もあり、
R75、R76、R77、R78、R79、R80、R81、R82、R83及びR84は、それぞれ独立に、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
X3は、酸素原子、硫黄原子、セレン原子、CR85R86、CO、NR87又はPR88を表し、
X4は、単結合又はCOを表し、
R85、R86、R87及びR88は、それぞれ独立に、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~20のアリール基又は炭素原子数7~20のアリールアルキル基を表し、該アルキル基又はアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環含有基で置換されている場合もあり、-O-で置き換えられている場合もあり、
R73及びR74は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成している場合もあり、
e1は、0~4の整数を表し、
e2は、0~5の整数を表す。) (Wherein, R 71 and R 72 each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms A group or a heterocycle-containing group having 2 to 20 carbon atoms,
R 73 and R 74 each independently represent a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 75 , OR 76 , SR 77 , NR 78 R 79 , COR 80 , SOR 81 , SO 2 R 82 or It represents CONR 83 R 84, R 73 and R 74 are, sometimes are bonded to each other to form a ring,
R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 and R 84 are each independently an alkyl group having 1 to 20 carbon atoms and 6 to 6 carbon atoms 30 aryl groups, arylalkyl groups having 7 to 30 carbon atoms, or heterocycle-containing groups having 2 to 20 carbon atoms,
X 3 represents an oxygen atom, a sulfur atom, a selenium atom, CR 85 R 86 , CO, NR 87 or PR 88 ,
X 4 represents a single bond or CO;
R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms And the methylene group in the alkyl group or the arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, and may be substituted with -O- May be
R 73 and R 74 may independently form a ring together with either of adjacent benzene rings,
e1 represents an integer of 0 to 4;
e2 represents an integer of 0 to 5; )
上記一般式(IV)中のR71、R72、R75、R76、R77、R78、R79、R80、R85、R86、R87及びR88に用いられる炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基並びにこれらの置換基としては、上記「1.光脱離基B」の項にR11等として例示した内容のうち、所定の炭素原子数を満たすものが挙げられる。
The carbon number of 1 used in R 71 , R 72 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 85 , R 86 , R 87 and R 88 in the above general formula (IV) As the alkyl group of to 20, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, and a substituent thereof, the above-mentioned "1. Among the contents exemplified as R 11 and the like in the section of “photoleaving group B”, those having a predetermined number of carbon atoms can be mentioned.
上記オキシム系化合物としては、例えば、エタノン-1-〔9-エチル-6-(2-メチルベンゾイル-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、1-〔9-エチル-6-ベンゾイル-9H-カルバゾール-3-イル-オクタン-1-オンオキシム-O-アセテート、1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-エタン-1-オンオキシム-O-ベンゾエート、1-〔9-n-ブチル-6-(2-エチルベンゾイル)-9H-カルバゾール-3-イル〕-エタン-1-オンオキシム-O-ベンゾエート、エタノン-1-〔9-エチル-6-(2-メチル-4-テトラヒドロフラニルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-( 2-メチル-4-テトラヒドロピラニルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-(2-メチル-5-テトラヒドロフラニルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-{2-メチル-4-(2,2-ジメチル-1,3-ジオキソラニル)メトキシベンゾイル}-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-(2-メチル-4-テトラヒドロフラニルメトキシベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)等のカルバゾール構造を有するカルバゾール系オキシムエステル化合物が挙げられる。
Examples of the oxime-based compound include: ethanone-1- [9-ethyl-6- (2-methylbenzoyl-9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl -6-Benzoyl-9H-carbazol-3-yl-octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane- 1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Non-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4 -(2,2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-) Carbazole-based ox having a carbazole structure such as methyl-4-tetrahydrofuranyl methoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) The simester compound is mentioned.
上記オキシム系化合物としては、例えば、インドール構造を有するインドール系オキシムエステル化合物も用いることができる。
インドール系オキシムエステル化合物としては、例えば、国際公開第2017/051680号に記載される下記一般式(V)で表されるオキシムエステル化合物等を挙げることができる。 As the oxime compound, for example, an indole oxime ester compound having an indole structure can also be used.
As an indole type oxime ester compound, the oxime ester compound etc. which are represented by the following general formula (V) described in international publication 2017/051680 can be mentioned, for example.
インドール系オキシムエステル化合物としては、例えば、国際公開第2017/051680号に記載される下記一般式(V)で表されるオキシムエステル化合物等を挙げることができる。 As the oxime compound, for example, an indole oxime ester compound having an indole structure can also be used.
As an indole type oxime ester compound, the oxime ester compound etc. which are represented by the following general formula (V) described in international publication 2017/051680 can be mentioned, for example.
(式中、R201及びR202は、それぞれ独立に、R211、OR211、COR211、SR211、CONR212R213又はCNを表し、
R211、R212及びR213は、それぞれ独立に、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R211、R212及びR213で表される基の水素原子は、更にR221、OR221、COR221、SR221、NR222R223、CONR222R223、NR222OR223、NCOR222OCOR223、NR222COR221、OCOR221、COOR221、SCOR221、OCSR221、COSR221、CSOR221、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR221で置換されている場合もあり、
R221、R222及びR223は、それぞれ独立に、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R221、R222及びR223で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、水酸基又はカルボキシル基で置換されている場合もあり、
R211、R212、R213、R221、R222及びR223で表される基のアルキレン部分のメチレン基は、-O-、-S-、-COO-、-OCO-、-OCOO-、-CONR224-、-NR224-、-NR224CO-、-NR224COO-、-OCONR224-、-SCO-、-COS-、-OCS-又は-SCOO-により置き換えられている場合もあり、
R224は、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R211、R212、R213、R221、R222、R223及びR224で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、
R203は、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、R203で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、また、R203とR207及びR203とR208はそれぞれ一緒になって環を形成している場合もあり、
R203で表される基の水素原子は、更にR221、OR221、COR221、SR221、NR222R223、CONR222R223、NR222OR223、NCOR222OCOR223、NR222COR221、OCOR221、COOR221、SCOR221、OCSR221、COSR221、CSOR221、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR221で置換されている場合もあり、
R204、R205、R206及びR207は、それぞれ独立に、R211、OR211、SR211、COR214、CONR215R216、NR212COR211、OCOR211、COOR214、SCOR211、OCSR211、COSR214、CSOR211、水酸基、CN又はハロゲン原子を表し、R204とR205、R205とR206及びR206とR207はそれぞれ一緒になって環を形成している場合もあり、
R204、R205、R206及びR207で表される基の水素原子は、更にR221、OR221、COR221、SR221、NR222R223、CONR222R223、NR222OR223、NCOR222OCOR223、NR222COR221、OCOR221、COOR221、SCOR221、OCSR221、COSR221、CSOR221、水酸基、ニトロ基、CN、ハロゲン原子又はCOOR221で置換されている場合もあり、
R214、R215及びR216は、水素原子又は炭素原子数1~20のアルキル基を表し、
R214、R215及びR216で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、
R208は、R211、OR211、SR211、COR211、CONR212R213、NR212COR211、OCOR211、COOR211、SCOR211、OCSR211、COSR211、CSOR211、水酸基、CN又はハロゲン原子を表し、
n1は、0又は1を表す。) (Wherein, R 201 and R 202 each independently represent R 211 , OR 211 , COR 211 , SR 211 , CONR 212 R 213 or CN,
R 211 , R 212 and R 213 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atoms of the groups represented by R 211 , R 212 and R 213 are further R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , hydroxyl group, nitro group, CN, halogen atom, or COOR 221 in some cases,
R 221 , R 222 and R 223 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atom of the group represented by R 221 , R 222 and R 223 may be further substituted by a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
Methylene groups in the alkylene portion of the group represented by R 211, R 212, R 213 , R 221, R 222 and R 223 is, -O -, - S -, - COO -, - OCO -, - OCOO-, -CONR 224 -, - NR 224 - , - NR 224 CO -, - NR 224 COO -, - OCONR 224 -, - SCO -, - COS -, - OCS- or -SCOO- by sometimes replaced ,
R 224 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms Represent
The alkyl part of the group represented by R 211 , R 212 , R 213 , R 221 , R 222 , R 223 and R 224 may have a branched side chain or may be a cyclic alkyl,
R 203 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms And the alkyl moiety of the group represented by R 203 may be branched side chain or cyclic alkyl, and R 203 and R 207 and R 203 and R 208 together respectively. May form a ring,
The hydrogen atom of the group represented by R 203 further includes R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , It may be substituted by OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 221 ,
R 204 , R 205 , R 206 and R 207 are each independently R 211 , OR 211 , SR 211 , COR 214 , CONR 215 R 216 , NR 212 COR 211 , OCOR 211 , COOR 214 , SCOR 211 , OCSR 211 , COSR 214 , CSOR 211 , a hydroxyl group, CN or a halogen atom, and R 204 and R 205 , R 205 and R 206, and R 206 and R 207 may together form a ring, respectively.
The hydrogen atoms of the groups represented by R 204 , R 205 , R 206 and R 207 are further selected from R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , and may be substituted with a hydroxyl group, a nitro group, CN, a halogen atom or COOR 221 ,
R 214 , R 215 and R 216 each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
The alkyl part of the group represented by R 214 , R 215 and R 216 may be branched side chain or cyclic alkyl;
R 208 represents R 211 , OR 211 , SR 211 , COR 211 , CONR 212 R 213 , NR 212 COR 211 , OCOR 211 , COOR 211 , SCOR 211 , OCSR 211 , COSR 211 , CSOR 211 , a hydroxyl group, CN or a halogen atom Represents
n1 represents 0 or 1; )
R211、R212及びR213は、それぞれ独立に、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R211、R212及びR213で表される基の水素原子は、更にR221、OR221、COR221、SR221、NR222R223、CONR222R223、NR222OR223、NCOR222OCOR223、NR222COR221、OCOR221、COOR221、SCOR221、OCSR221、COSR221、CSOR221、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR221で置換されている場合もあり、
R221、R222及びR223は、それぞれ独立に、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R221、R222及びR223で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、水酸基又はカルボキシル基で置換されている場合もあり、
R211、R212、R213、R221、R222及びR223で表される基のアルキレン部分のメチレン基は、-O-、-S-、-COO-、-OCO-、-OCOO-、-CONR224-、-NR224-、-NR224CO-、-NR224COO-、-OCONR224-、-SCO-、-COS-、-OCS-又は-SCOO-により置き換えられている場合もあり、
R224は、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R211、R212、R213、R221、R222、R223及びR224で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、
R203は、水素原子、炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、R203で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、また、R203とR207及びR203とR208はそれぞれ一緒になって環を形成している場合もあり、
R203で表される基の水素原子は、更にR221、OR221、COR221、SR221、NR222R223、CONR222R223、NR222OR223、NCOR222OCOR223、NR222COR221、OCOR221、COOR221、SCOR221、OCSR221、COSR221、CSOR221、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR221で置換されている場合もあり、
R204、R205、R206及びR207は、それぞれ独立に、R211、OR211、SR211、COR214、CONR215R216、NR212COR211、OCOR211、COOR214、SCOR211、OCSR211、COSR214、CSOR211、水酸基、CN又はハロゲン原子を表し、R204とR205、R205とR206及びR206とR207はそれぞれ一緒になって環を形成している場合もあり、
R204、R205、R206及びR207で表される基の水素原子は、更にR221、OR221、COR221、SR221、NR222R223、CONR222R223、NR222OR223、NCOR222OCOR223、NR222COR221、OCOR221、COOR221、SCOR221、OCSR221、COSR221、CSOR221、水酸基、ニトロ基、CN、ハロゲン原子又はCOOR221で置換されている場合もあり、
R214、R215及びR216は、水素原子又は炭素原子数1~20のアルキル基を表し、
R214、R215及びR216で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、
R208は、R211、OR211、SR211、COR211、CONR212R213、NR212COR211、OCOR211、COOR211、SCOR211、OCSR211、COSR211、CSOR211、水酸基、CN又はハロゲン原子を表し、
n1は、0又は1を表す。) (Wherein, R 201 and R 202 each independently represent R 211 , OR 211 , COR 211 , SR 211 , CONR 212 R 213 or CN,
R 211 , R 212 and R 213 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atoms of the groups represented by R 211 , R 212 and R 213 are further R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , hydroxyl group, nitro group, CN, halogen atom, or COOR 221 in some cases,
R 221 , R 222 and R 223 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atom of the group represented by R 221 , R 222 and R 223 may be further substituted by a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
Methylene groups in the alkylene portion of the group represented by R 211, R 212, R 213 , R 221, R 222 and R 223 is, -O -, - S -, - COO -, - OCO -, - OCOO-, -CONR 224 -, - NR 224 - , - NR 224 CO -, - NR 224 COO -, - OCONR 224 -, - SCO -, - COS -, - OCS- or -SCOO- by sometimes replaced ,
R 224 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms Represent
The alkyl part of the group represented by R 211 , R 212 , R 213 , R 221 , R 222 , R 223 and R 224 may have a branched side chain or may be a cyclic alkyl,
R 203 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms And the alkyl moiety of the group represented by R 203 may be branched side chain or cyclic alkyl, and R 203 and R 207 and R 203 and R 208 together respectively. May form a ring,
The hydrogen atom of the group represented by R 203 further includes R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , It may be substituted by OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 221 ,
R 204 , R 205 , R 206 and R 207 are each independently R 211 , OR 211 , SR 211 , COR 214 , CONR 215 R 216 , NR 212 COR 211 , OCOR 211 , COOR 214 , SCOR 211 , OCSR 211 , COSR 214 , CSOR 211 , a hydroxyl group, CN or a halogen atom, and R 204 and R 205 , R 205 and R 206, and R 206 and R 207 may together form a ring, respectively.
The hydrogen atoms of the groups represented by R 204 , R 205 , R 206 and R 207 are further selected from R 221 , OR 221 , COR 221 , SR 221 , NR 222 R 223 , CONR 222 R 223 , NR 222 OR 223 , NCOR 222 OCOR 223 , NR 222 COR 221 , OCOR 221 , COOR 221 , SCOR 221 , OCSR 221 , COSR 221 , CSOR 221 , and may be substituted with a hydroxyl group, a nitro group, CN, a halogen atom or COOR 221 ,
R 214 , R 215 and R 216 each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
The alkyl part of the group represented by R 214 , R 215 and R 216 may be branched side chain or cyclic alkyl;
R 208 represents R 211 , OR 211 , SR 211 , COR 211 , CONR 212 R 213 , NR 212 COR 211 , OCOR 211 , COOR 211 , SCOR 211 , OCSR 211 , COSR 211 , CSOR 211 , a hydroxyl group, CN or a halogen atom Represents
n1 represents 0 or 1; )
上記一般式(V)中のR203、R211、R212、R213、R214、R215、R216、R221、R222、R223及びR224に用いられる炭素原子数1~20のアルキル基、炭素原子数6~30のアリール基、炭素原子数7~30のアリールアルキル基又は炭素原子数2~20の複素環含有基としては、上記「1.光脱離基B」の項にR11等として例示した内容のうち、所定の炭素原子数を満たすものが挙げられる。
The number of carbon atoms used in R 203 , R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 221 , R 222 , R 223 and R 224 in the above general formula (V) Examples of the alkyl group, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include the items of the above-mentioned “1. Among the contents exemplified as R 11 and the like, those having a predetermined number of carbon atoms can be mentioned.
その他のラジカル重合開始剤としては、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド等のホスフィンオキサイド系化合物及びビス(シクロペンタジエニル)-ビス[2,6-ジフルオロ-3-(ピル-1-イル)]チタニウム等のチタノセン系化合物等が挙げられる。
Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1) -Yl)] Titanocene compounds such as titanium etc. may be mentioned.
市販のラジカル重合開始剤としては、アデカオプトマーN-1414、N-1717、N-1919、アデカアークルズNCI-831、NCI-930(ADEKA社製)、IRGACURE184、IRGACURE369、IRGACURE651、IRGACURE907、IRGACURE OXE 01、IRGACURE OXE 02、OXE 03、OXE 04、IRGACURE784(BASF社製)、TR-PBG-304、TR-PBG-305、TR-PBG-309及びTR-PBG-314(Tronly社製)等が挙げられる。
Commercially available radical polymerization initiators include Adeka optomer N-1414, N-1717, N-1919, Adeka Arkles NCI-831, NCI-930 (manufactured by ADEKA Corporation), IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE 784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314 (manufactured by Tronly) and the like. Be
これらの光ラジカル重合開始剤は1種或いは2種以上のものを所望の性能に応じて配合して使用することができる。
上記光ラジカル重合開始剤の含有量としては、所望の硬化性や感光性を付与できるものであればよいが、例えば、重合性化合物100質量部に対して、0.001質量部以上20質量部以下とすることができ、0.1質量部以上30質量部以下であることが好ましく、0.5質量部以上10質量部以下であることが好ましい。上記含有量であることで、組成物は、硬化性等に優れ、また、分散性等にも優れるからである。 These photo radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.
The content of the photo radical polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, 0.001 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the polymerizable compound The amount may be as follows, preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
上記光ラジカル重合開始剤の含有量としては、所望の硬化性や感光性を付与できるものであればよいが、例えば、重合性化合物100質量部に対して、0.001質量部以上20質量部以下とすることができ、0.1質量部以上30質量部以下であることが好ましく、0.5質量部以上10質量部以下であることが好ましい。上記含有量であることで、組成物は、硬化性等に優れ、また、分散性等にも優れるからである。 These photo radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.
The content of the photo radical polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, 0.001 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the polymerizable compound The amount may be as follows, preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
上記光カチオン重合開始剤としては、光照射によりカチオン重合を開始させる物質を放出させることが可能な化合物であれば特に制限されず、既存の化合物を用いることが可能であり、好ましくは、エネルギー線の照射によってルイス酸を放出するオニウム塩である複塩、又はその誘導体である。かかる化合物の代表的なものとしては、下記一般式、
[A1]r+[B1]r-
で表される陽イオンと陰イオンの塩を挙げることができる。 The photocationic polymerization initiator is not particularly limited as long as it is a compound capable of releasing a substance that causes cationic polymerization to be initiated by light irradiation, and it is possible to use an existing compound, and preferably an energy ray. The compound is a double salt which is an onium salt that releases a Lewis acid upon irradiation with or a derivative thereof. Representative examples of such compounds include the following general formula:
[A1] r + [B1] r-
And salts of cations and anions represented by
[A1]r+[B1]r-
で表される陽イオンと陰イオンの塩を挙げることができる。 The photocationic polymerization initiator is not particularly limited as long as it is a compound capable of releasing a substance that causes cationic polymerization to be initiated by light irradiation, and it is possible to use an existing compound, and preferably an energy ray. The compound is a double salt which is an onium salt that releases a Lewis acid upon irradiation with or a derivative thereof. Representative examples of such compounds include the following general formula:
[A1] r + [B1] r-
And salts of cations and anions represented by
上記陽イオン[A1]r+はオニウムであることが好ましく、その構造は、例えば、下記一般式で表すことができる。
[(R101)f1Q]r+ The cation [A1] r + is preferably onium, and the structure thereof can be represented by, for example, the following general formula.
[(R 101 ) f 1 Q] r +
[(R101)f1Q]r+ The cation [A1] r + is preferably onium, and the structure thereof can be represented by, for example, the following general formula.
[(R 101 ) f 1 Q] r +
更にここで、R101は炭素原子数が1~60であり、炭素原子以外の原子をいくつも含んでいる場合もある有機の基である。f1は1~5のいずれかの整数である。e個のR58は各々独立で、同一でも異なっている場合もある。また、R101の少なくとも1つは、芳香環を有する上記の如き有機の基であることが好ましい。例えば、アルキル基、アルコキシ基、ヒドロキシ基、ヒドロキシアルコキシ基、ハロゲン原子、ベンジル基、チオフェノキシ基、4-ベンゾイルフェニルチオ基、2-クロロ-4-ベンゾイルフェニルチオ基等で置換されている場合もあるフェニル基が挙げられる。QはS,N,Se,Te,P,As,Sb,Bi,O,I,Br,Cl,F,N=Nからなる群から選ばれる原子或いは原子団である。また、陽イオン[A1]r+中のQの原子価をqとしたとき、r=f1-qなる関係が成り立つことが必要である(但し、N=Nは原子価0として扱う)。
Furthermore, here, R 101 is an organic group having 1 to 60 carbon atoms and which may contain several atoms other than carbon atoms. f1 is an integer of 1 to 5; Each of e R 58 is independent of each other and may be the same or different. Further, at least one of R 101 is preferably an organic group as described above having an aromatic ring. For example, even when substituted by an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkoxy group, a halogen atom, a benzyl group, a thiophenoxy group, a 4-benzoylphenylthio group, a 2-chloro-4-benzoylphenylthio group, etc. A certain phenyl group is mentioned. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Also, when the valence of Q in the cation [A1] r + is q, it is necessary that the relationship r = f1-q holds (where N = N is treated as having a valence of 0).
また、陰イオン[B1]r-は、ハロゲン化物錯体であることが好ましく、その構造は、例えば、下記一般式、[LXf2]r-で表すことができる。
The anion [B1] r- is preferably a halide complex, and its structure can be represented, for example, by the following general formula, [LX f2 ] r- .
更にここで、Lはハロゲン化物錯体の中心原子である金属又は半金属(Metalloid)であり、B,P,As,Sb,Fe,Sn,Bi,Al,Ca,In,Ti,Zn,Sc,V,Cr,Mn及びCo等である。
Xf2は、ハロゲン原子、又は、ハロゲン原子やアルコキシ基等で置換されている場合もあるフェニル基である。f2は3~7なる整数である。
また、陰イオン[B1]r-中のLの原子価をpとしたとき、r=f2-pなる関係が成り立つことが必要である。 Furthermore, here, L is a metal or metalloid (Metalloid) which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
X f2 is a halogen atom or a phenyl group which may be substituted by a halogen atom, an alkoxy group or the like. f2 is an integer of 3 to 7;
Also, when the valence of L in the anion [B1] r -is p, it is necessary that the relationship r = f2-p holds.
Xf2は、ハロゲン原子、又は、ハロゲン原子やアルコキシ基等で置換されている場合もあるフェニル基である。f2は3~7なる整数である。
また、陰イオン[B1]r-中のLの原子価をpとしたとき、r=f2-pなる関係が成り立つことが必要である。 Furthermore, here, L is a metal or metalloid (Metalloid) which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
X f2 is a halogen atom or a phenyl group which may be substituted by a halogen atom, an alkoxy group or the like. f2 is an integer of 3 to 7;
Also, when the valence of L in the anion [B1] r -is p, it is necessary that the relationship r = f2-p holds.
上記一般式の陰イオン[LXf2]r-の具体例としては、テトラキス(ペンタフルオロフェニル)ボレート、テトラ(3,5-ジフルオロ-4-メトキシフェニル)ボレート、テトラフルオロボレート(BF4)-、ヘキサフルオロフォスフェート(PF6)-、ヘキサフルオロアンチモネート(SbF6)-、ヘキサフルオロアルセネート(AsF6)-及びヘキサクロロアンチモネート(SbCl6)-等を挙げることができる。
Specific examples of the anion [LX f2 ] r- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF 4 ) − , Hexafluorophosphate (PF 6 ) − , hexafluoroantimonate (SbF 6 ) − , hexafluoroarsenate (AsF 6 ) − and hexachloroantimonate (SbCl 6 ) − can be mentioned.
また、陰イオン[B1]r-は、下記一般式、
[LXf2-1(OH)]r-
で表される構造のものも好ましく用いることができる。L,X,f2は上記と同様である。また、その他用いることのできる陰イオンとしては、過塩素酸イオン(ClO4)-、トリフルオロメチル亜硫酸イオン(CF3SO3)-、フルオロスルホン酸イオン(FSO3)-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート及びテトラキス(ペンタフルオロフェニル)ボレート等を挙げることができる。 Further, the anion [B1] r- has the following general formula,
[LX f2-1 (OH)] r-
The thing of the structure represented by can also be used preferably. L, X and f2 are the same as above. Other anions that can be used include perchlorate ion (ClO 4 ) − , trifluoromethyl sulfite ion (CF 3 SO 3 ) − , fluorosulfonate ion (FSO 3 ) − , toluene sulfonate anion And trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraaryl borate and tetrakis (pentafluorophenyl) borate.
[LXf2-1(OH)]r-
で表される構造のものも好ましく用いることができる。L,X,f2は上記と同様である。また、その他用いることのできる陰イオンとしては、過塩素酸イオン(ClO4)-、トリフルオロメチル亜硫酸イオン(CF3SO3)-、フルオロスルホン酸イオン(FSO3)-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン、カンファースルフォネート、ノナフロロブタンスルフォネート、ヘキサデカフロロオクタンスルフォネート、テトラアリールボレート及びテトラキス(ペンタフルオロフェニル)ボレート等を挙げることができる。 Further, the anion [B1] r- has the following general formula,
[LX f2-1 (OH)] r-
The thing of the structure represented by can also be used preferably. L, X and f2 are the same as above. Other anions that can be used include perchlorate ion (ClO 4 ) − , trifluoromethyl sulfite ion (CF 3 SO 3 ) − , fluorosulfonate ion (FSO 3 ) − , toluene sulfonate anion And trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraaryl borate and tetrakis (pentafluorophenyl) borate.
本発明では、このようなオニウム塩の中でも、下記の(ホ)~(ト)の芳香族オニウム塩を使用することが特に有効であり、好ましい。これらの中から、その1種を単独で、又は2種以上を混合して使用することができる。
In the present invention, among such onium salts, it is particularly effective and preferable to use an aromatic onium salt of the following (e) to (t). Among these, 1 type can be used individually or in mixture of 2 or more types.
(ホ)フェニルジアゾニウムヘキサフルオロホスフェート、4-メトキシフェニルジアゾニウムヘキサフルオロアンチモネート及び4-メチルフェニルジアゾニウムヘキサフルオロホスフェート等のアリールジアゾニウム塩。
(E) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate.
(へ)ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ(4-メチルフェニル)ヨードニウムヘキサフルオロホスフェート、ジ(4-tert-ブチルフェニル)ヨードニウムヘキサフルオロホスフェート及びトリルクミルヨードニウムテトラキス(ペンタフルオロフェニル)ボレート等のジアリールヨードニウム塩。
(F) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate and tolycamyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt.
(ト)下記群I又は群IIで表されるスルホニウムカチオンとヘキサフルオロアンチモンイオン、テトラキス(ペンタフルオロフェニル)ボレートイオン等のスルホニウム塩。
(G) Sulfonium salts represented by the following Group I or Group II: sulfonium salts such as hexafluoroantimony ion, tetrakis (pentafluorophenyl) borate ion and the like.
また、その他好ましいものとしては、(η5-2,4-シクロペンタジエン-1-イル)〔(1,2,3,4,5,6-η)-(1-メチルエチル)ベンゼン〕-アイアン-ヘキサフルオロホスフェート等の鉄-アレーン錯体;トリス(アセチルアセトナト)アルミニウム、トリス(エチルアセトナトアセタト)アルミニウム、トリス(サリチルアルデヒダト)アルミニウム等のアルミニウム錯体;トリフェニルシラノール等のシラノール類との混合物:等も挙げることができる。
In addition, other preferable ones are (η5-2, 4-cyclopentadien-1-yl) [(1, 2, 3, 4, 5, 6 η)-(1-methylethyl) benzene] -iron- Iron-arene complexes such as hexafluorophosphate; aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum; mixtures with silanols such as triphenylsilanol : Etc. can also be mentioned.
上記光カチオン重合開始剤としては、市販品を用いることもでき、例えば、IRUGACURE261(BASF社製)、アデカオプトマーSP-150、SP-151、SP-152、SP-170、SP-171、SP-172(ADEKA社製)、UVE-1014(ゼネラルエレクトロニクス社製)、CD-1012(サートマー社製)、CI-2064、CI-2481(日本曹達社製)、Uvacure1590、1591(ダイセルUCB)、CYRACURE UVI-6990(ユニオンカーバイド社製)、BBI-103、MPI-103、TPS-103、MDS-103、DTS-103、NAT-103及びNDS-103(ミドリ化学社製)等が挙げられる。
A commercial item can also be used as said photocationic polymerization initiator, For example, IRUGACURE 261 (made by BASF Corporation), Adeka optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP -172 (made by Adeka), UVE-1014 (made by General Electronics), CD-1012 (made by Sartmar), CI-2064, CI-2481 (made by Nippon Soda Co., Ltd.), Uvacure 1590, 1591 (Daicel UCB), CYRACURE UVI-6990 (manufactured by Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103 and NDS-103 (manufactured by Midori Chemical Co., Ltd.), and the like.
これらの中でも、実用面と光感度の観点から、芳香族ヨードニウム塩、芳香族スルホニウム塩、鉄-アレーン錯体を用いることが好ましい。
Among these, aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferably used from the viewpoint of practical use and light sensitivity.
上記光アニオン重合開始剤としては、光により塩基を発生するものを用いることができ、光アニオン重合開始剤として公知のものを用いることができる。
上記光アニオン重合開始剤としては、例えば、アセトフェノン O-アロイルオキシム(acetophenone O-aroyloxime)、ニフェジピン(nifedipine)等を挙げることができる。 As said photoanion polymerization initiator, what generate | occur | produces a base with light can be used, and what is well-known as a photoanion polymerization initiator can be used.
Examples of the photoanion polymerization initiator include acetophenone O-aroyloxime (acetophenone O-aroyloxime), nifedipine and the like.
上記光アニオン重合開始剤としては、例えば、アセトフェノン O-アロイルオキシム(acetophenone O-aroyloxime)、ニフェジピン(nifedipine)等を挙げることができる。 As said photoanion polymerization initiator, what generate | occur | produces a base with light can be used, and what is well-known as a photoanion polymerization initiator can be used.
Examples of the photoanion polymerization initiator include acetophenone O-aroyloxime (acetophenone O-aroyloxime), nifedipine and the like.
(b)熱重合開始剤
上記熱重合開始剤としては、加熱することにより重合性化合物を重合可能なものであればよく、ラジカル重合開始剤、カチオン重合開始剤、アニオン重合開始剤等を挙げることができる。 (B) Thermal polymerization initiator As the above-mentioned thermal polymerization initiator, any one capable of polymerizing a polymerizable compound by heating may be used, and a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, etc. may be mentioned. Can.
上記熱重合開始剤としては、加熱することにより重合性化合物を重合可能なものであればよく、ラジカル重合開始剤、カチオン重合開始剤、アニオン重合開始剤等を挙げることができる。 (B) Thermal polymerization initiator As the above-mentioned thermal polymerization initiator, any one capable of polymerizing a polymerizable compound by heating may be used, and a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, etc. may be mentioned. Can.
上記熱ラジカル重合開始剤としては、加熱によりラジカルを発生するものを用いることができ、熱ラジカル重合開始剤として公知のものを用いることができる。
上記熱ラジカル重合開始剤としては、例えば、アゾ系化合物、過酸化物及び過硫酸塩等を好ましいものとして例示することができる。 As said thermal radical polymerization initiator, what generate | occur | produces a radical can be used by heating, and a well-known thing can be used as a thermal radical polymerization initiator.
As said thermal radical polymerization initiator, an azo compound, a peroxide, a persulfate, etc. can be illustrated as a preferable thing, for example.
上記熱ラジカル重合開始剤としては、例えば、アゾ系化合物、過酸化物及び過硫酸塩等を好ましいものとして例示することができる。 As said thermal radical polymerization initiator, what generate | occur | produces a radical can be used by heating, and a well-known thing can be used as a thermal radical polymerization initiator.
As said thermal radical polymerization initiator, an azo compound, a peroxide, a persulfate, etc. can be illustrated as a preferable thing, for example.
上記アゾ系化合物としては、2,2′-アゾビスイソブチロニトリル、2,2′-アゾビス(メチルイソブチレ-ト)、2,2’-アゾビス-2,4-ジメチルバレロニトリル、1,1’-アゾビス(1-アセトキシ-1-フェニルエタン)等が挙げられる。
Examples of the above azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1 ' And -azobis (1-acetoxy-1-phenylethane) and the like.
過酸化物としては、ベンゾイルパーオキサイド、ジ-t-ブチルベンゾイルパーオキサイド、t-ブチルパーオキシピバレート及びジ(4-t-ブチルシクロヘキシル)パーオキシジカーボネート等が挙げられる。
Examples of peroxides include benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxy dicarbonate.
上記過硫酸塩としては、過硫酸アンモニウム、過硫酸ナトリウム及び過硫酸カリウム等の過硫酸塩等が挙げられる。
Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
上記熱カチオン重合開始剤としては、加熱によりカチオン種又はルイス酸を発生するものを用いることができ、熱カチオン重合開始剤として公知のものを用いることができる。
上記熱カチオン重合開始剤としては、具体的には、スルホニウム塩、チオフェニウム塩、チオラニウム塩、ベンジルアンモニウム、ピリジニウム塩及びヒドラジニウム塩等の塩;ジエチレントリアミン、トリエチレントリアミン及びテトラエチレンペンタミン等のポリアルキルポリアミン類;1,2-ジアミノシクロヘキサン、1,4-ジアミノ-3,6-ジエチルシクロヘキサン及びイソホロンジアミン等の脂環式ポリアミン類;m-キシリレンジアミン、ジアミノジフェニルメタン及びジアミノジフェニルスルホン等の芳香族ポリアミン類;上記ポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールA-ジグリシジルエーテル及びビスフェノールF-ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ樹脂とを常法によって反応させることによって製造されるポリエポキシ付加変性物;上記有機ポリアミン類と、フタル酸、イソフタル酸及びダイマー酸等のカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物;上記ポリアミン類とホルムアルデヒド等のアルデヒド類及びフェノール、クレゾール、キシレノール、第三ブチルフェノール及びレゾルシン等の核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを常法によって反応させることによって製造されるマンニッヒ化変性物;多価カルボン酸(シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、2-メチルコハク酸、2-メチルアジピン酸、3-メチルアジピン酸、3-メチルペンタン二酸、2-メチルオクタン二酸、3,8-ジメチルデカン二酸、3,7-ジメチルデカン二酸、水添ダイマー酸及びダイマー酸等の脂肪族ジカルボン酸類;フタル酸、テレフタル酸、イソフタル酸及びナフタレンジカルボン酸等の芳香族ジカルボン酸類;シクロヘキサンジカルボン酸等の脂環式ジカルボン酸類;トリメリット酸、トリメシン酸及びひまし油脂肪酸等の三量体等のトリカルボン酸類;ピロメリット酸等のテトラカルボン酸類等)の酸無水物;ジシアンジアミド、イミダゾール類、カルボン酸エステル、スルホン酸エステル及びアミンイミド等を挙げることができる。
上記熱カチオン重合開始剤としては、市販品を用いることもでき、例えば、アデカオプトンCP-77、アデカオプトンCP-66(ADEKA社製)、CI-2639、CI-2624(日本曹達社製)、サンエイドSI-60L、サンエイドSI-80L、サンエイド SI-100L(三新化学工業社製)等が挙げられる。 As said thermal cationic polymerization initiator, what generate | occur | produces cationic seed | species or a Lewis acid by heating can be used, and a well-known thing can be used as a thermal cationic polymerization initiator.
Specific examples of the thermal cationic polymerization initiator include salts such as sulfonium salts, thiophenium salts, thiolanium salts, benzyl ammonium, pyridinium salts and hydrazinium salts; and polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine. Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophorone diamine; Aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenyl sulfone Glycidyl ethers such as the above polyamines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether Or a polyepoxy adduct modified product produced by reaction with various epoxy resins such as glycidyl esters of carboxylic acid according to a conventional method; the above organic polyamines and carboxylic acids such as phthalic acid, isophthalic acid and dimer acid Amidated modified products produced by reaction according to a conventional method; the above-mentioned polyamines and aldehydes such as formaldehyde and the like, having at least one aldehyded reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol and resorcin Mannich modified products produced by reacting phenols in a usual manner; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid) , Dodecanedioic acid, 2 Methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer Aliphatic dicarboxylic acids such as acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; trimellitic acid, trimesic acid and castor oil fatty acid Etc .; acid anhydrides of tetracarboxylic acids such as pyromellitic acid etc.); dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides and the like.
A commercial item can also be used as said thermal cationic polymerization initiator, For example, Adeka opton CP-77, Adeka opton CP-66 (made by ADEKA), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun Aid SI -60 L, San Aid SI-80 L, San Aid SI-100 L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.
上記熱カチオン重合開始剤としては、具体的には、スルホニウム塩、チオフェニウム塩、チオラニウム塩、ベンジルアンモニウム、ピリジニウム塩及びヒドラジニウム塩等の塩;ジエチレントリアミン、トリエチレントリアミン及びテトラエチレンペンタミン等のポリアルキルポリアミン類;1,2-ジアミノシクロヘキサン、1,4-ジアミノ-3,6-ジエチルシクロヘキサン及びイソホロンジアミン等の脂環式ポリアミン類;m-キシリレンジアミン、ジアミノジフェニルメタン及びジアミノジフェニルスルホン等の芳香族ポリアミン類;上記ポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールA-ジグリシジルエーテル及びビスフェノールF-ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ樹脂とを常法によって反応させることによって製造されるポリエポキシ付加変性物;上記有機ポリアミン類と、フタル酸、イソフタル酸及びダイマー酸等のカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物;上記ポリアミン類とホルムアルデヒド等のアルデヒド類及びフェノール、クレゾール、キシレノール、第三ブチルフェノール及びレゾルシン等の核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを常法によって反応させることによって製造されるマンニッヒ化変性物;多価カルボン酸(シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、2-メチルコハク酸、2-メチルアジピン酸、3-メチルアジピン酸、3-メチルペンタン二酸、2-メチルオクタン二酸、3,8-ジメチルデカン二酸、3,7-ジメチルデカン二酸、水添ダイマー酸及びダイマー酸等の脂肪族ジカルボン酸類;フタル酸、テレフタル酸、イソフタル酸及びナフタレンジカルボン酸等の芳香族ジカルボン酸類;シクロヘキサンジカルボン酸等の脂環式ジカルボン酸類;トリメリット酸、トリメシン酸及びひまし油脂肪酸等の三量体等のトリカルボン酸類;ピロメリット酸等のテトラカルボン酸類等)の酸無水物;ジシアンジアミド、イミダゾール類、カルボン酸エステル、スルホン酸エステル及びアミンイミド等を挙げることができる。
上記熱カチオン重合開始剤としては、市販品を用いることもでき、例えば、アデカオプトンCP-77、アデカオプトンCP-66(ADEKA社製)、CI-2639、CI-2624(日本曹達社製)、サンエイドSI-60L、サンエイドSI-80L、サンエイド SI-100L(三新化学工業社製)等が挙げられる。 As said thermal cationic polymerization initiator, what generate | occur | produces cationic seed | species or a Lewis acid by heating can be used, and a well-known thing can be used as a thermal cationic polymerization initiator.
Specific examples of the thermal cationic polymerization initiator include salts such as sulfonium salts, thiophenium salts, thiolanium salts, benzyl ammonium, pyridinium salts and hydrazinium salts; and polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine. Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophorone diamine; Aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenyl sulfone Glycidyl ethers such as the above polyamines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether Or a polyepoxy adduct modified product produced by reaction with various epoxy resins such as glycidyl esters of carboxylic acid according to a conventional method; the above organic polyamines and carboxylic acids such as phthalic acid, isophthalic acid and dimer acid Amidated modified products produced by reaction according to a conventional method; the above-mentioned polyamines and aldehydes such as formaldehyde and the like, having at least one aldehyded reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol and resorcin Mannich modified products produced by reacting phenols in a usual manner; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid) , Dodecanedioic acid, 2 Methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer Aliphatic dicarboxylic acids such as acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; trimellitic acid, trimesic acid and castor oil fatty acid Etc .; acid anhydrides of tetracarboxylic acids such as pyromellitic acid etc.); dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides and the like.
A commercial item can also be used as said thermal cationic polymerization initiator, For example, Adeka opton CP-77, Adeka opton CP-66 (made by ADEKA), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun Aid SI -60 L, San Aid SI-80 L, San Aid SI-100 L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.
上記熱アニオン重合開始剤としては、熱により塩基を発生するものを用いることができ、熱アニオン重合開始剤として公知のものを用いることができる。
上記アニオン重合開始剤としては、具体的には、脂肪族アミン系化合物、芳香族アミン系化合物、二級又は三級アミン系化合物、イミダゾール系化合物、ポリメルカプタン系化合物、三フッ化ホウ素-アミン錯体、ジシアンジアミド、有機酸ヒドラジッド等を用いることができる。 As said thermal anion polymerization initiator, what generate | occur | produces a base by heat can be used, and what is well-known as a thermal anion polymerization initiator can be used.
Specific examples of the anionic polymerization initiator include aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, and boron trifluoride-amine complex. , Dicyandiamide, organic acid hydrazide and the like can be used.
上記アニオン重合開始剤としては、具体的には、脂肪族アミン系化合物、芳香族アミン系化合物、二級又は三級アミン系化合物、イミダゾール系化合物、ポリメルカプタン系化合物、三フッ化ホウ素-アミン錯体、ジシアンジアミド、有機酸ヒドラジッド等を用いることができる。 As said thermal anion polymerization initiator, what generate | occur | produces a base by heat can be used, and what is well-known as a thermal anion polymerization initiator can be used.
Specific examples of the anionic polymerization initiator include aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, and boron trifluoride-amine complex. , Dicyandiamide, organic acid hydrazide and the like can be used.
(c)重合開始剤の含有量
上記重合開始剤の含有量としては、所望の硬化性等を付与できるものであればよいが、例えば、固形分100質量部中、0.1質量部以上30質量部以下とすることができ、0.5質量部以上10質量部以下であることが好ましい。上記含有量であることで、組成物は、硬化性等に優れ、また、分散性等にも優れるからである。
上記重合開始剤の含有量としては、所望の硬化性や感光性を付与できるものであればよいが、例えば、重合性化合物100質量部に対して、0.001質量部以上20質量部以下とすることができ、0.1質量部以上30質量部以下であることが好ましく、0.5質量部以上10質量部以下であることが好ましい。上記含有量であることで、組成物は、硬化性等に優れ、また、分散性等にも優れるからである。 (C) Content of Polymerization Initiator The content of the polymerization initiator may be any as long as it can impart desired curability and the like, and for example, 0.1 parts by mass or more and 30 parts by mass in 100 parts by mass of solid content. It can be made into parts by mass or less and preferably 0.5 parts by mass or more and 10 parts by mass or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
The content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity, and for example, 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound It is preferable that it is 0.1 mass part or more and 30 mass parts or less, and it is preferable that it is 0.5 mass part or more and 10 mass parts or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
上記重合開始剤の含有量としては、所望の硬化性等を付与できるものであればよいが、例えば、固形分100質量部中、0.1質量部以上30質量部以下とすることができ、0.5質量部以上10質量部以下であることが好ましい。上記含有量であることで、組成物は、硬化性等に優れ、また、分散性等にも優れるからである。
上記重合開始剤の含有量としては、所望の硬化性や感光性を付与できるものであればよいが、例えば、重合性化合物100質量部に対して、0.001質量部以上20質量部以下とすることができ、0.1質量部以上30質量部以下であることが好ましく、0.5質量部以上10質量部以下であることが好ましい。上記含有量であることで、組成物は、硬化性等に優れ、また、分散性等にも優れるからである。 (C) Content of Polymerization Initiator The content of the polymerization initiator may be any as long as it can impart desired curability and the like, and for example, 0.1 parts by mass or more and 30 parts by mass in 100 parts by mass of solid content. It can be made into parts by mass or less and preferably 0.5 parts by mass or more and 10 parts by mass or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
The content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity, and for example, 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound It is preferable that it is 0.1 mass part or more and 30 mass parts or less, and it is preferable that it is 0.5 mass part or more and 10 mass parts or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
(3)その他
上記他の成分としては、樹脂成分、重合開始剤以外に、必要に応じて、着色剤、溶剤、連鎖移動剤、増感剤、界面活性剤、シランカップリング剤、メラミン化合物等を含むことができる。
また、上記他の成分は、これら以外にも必要に応じて、p-アニソール、ハイドロキノン、ピロカテコール、t-ブチルカテコール、フェノチアジン等の熱重合抑制剤;可塑剤;接着促進剤;充填剤;消泡剤;レベリング剤;表面調整剤;フェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤等の酸化防止剤;上記化合物I-1で表される化合物以外の紫外線吸収剤;分散助剤;凝集防止剤;触媒;効果促進剤;架橋剤;増粘剤等の添加剤を含むことができる。 (3) Others As the above other components, in addition to the resin component and the polymerization initiator, if necessary, a colorant, a solvent, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, etc. Can be included.
In addition to the above, the other components may be, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol or phenothiazine; plasticizer; adhesion promoter; filler; Foaming agents; leveling agents; surface conditioners; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants, etc .; UV absorbers other than the compounds represented by the above compound I-1; Dispersion aids; aggregation inhibitors; catalysts; effects accelerators; crosslinkers; additives such as thickeners etc. can be included.
上記他の成分としては、樹脂成分、重合開始剤以外に、必要に応じて、着色剤、溶剤、連鎖移動剤、増感剤、界面活性剤、シランカップリング剤、メラミン化合物等を含むことができる。
また、上記他の成分は、これら以外にも必要に応じて、p-アニソール、ハイドロキノン、ピロカテコール、t-ブチルカテコール、フェノチアジン等の熱重合抑制剤;可塑剤;接着促進剤;充填剤;消泡剤;レベリング剤;表面調整剤;フェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤等の酸化防止剤;上記化合物I-1で表される化合物以外の紫外線吸収剤;分散助剤;凝集防止剤;触媒;効果促進剤;架橋剤;増粘剤等の添加剤を含むことができる。 (3) Others As the above other components, in addition to the resin component and the polymerization initiator, if necessary, a colorant, a solvent, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, etc. Can be included.
In addition to the above, the other components may be, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol or phenothiazine; plasticizer; adhesion promoter; filler; Foaming agents; leveling agents; surface conditioners; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants, etc .; UV absorbers other than the compounds represented by the above compound I-1; Dispersion aids; aggregation inhibitors; catalysts; effects accelerators; crosslinkers; additives such as thickeners etc. can be included.
(a)着色剤
上記着色剤としては、例えば組成物又はその硬化物等に所望の着色を付与できるものであればよく、染料又は顔料が挙げられる。
染料としては、380~1200nmに吸収を有する化合物を用いることができ、例えば、アゾ化合物、アントラキノン化合物、インジゴイド化合物、トリアリールメタン化合物、キサンテン化合物、アリザリン化合物、アクリジン化合物、スチルベン化合物、チアゾール化合物、ナフトール化合物、キノリン化合物、ニトロ化合物、インダミン化合物、オキサジン化合物、フタロシアニン化合物、シアニン化合物、ジインモニウム化合物、シアノエテニル化合物、ジシアノスチレン化合物、ローダミン化合物、ペリレン化合物、ポリエンナフトラクタム化合物、クマリン化合物、スクアリリウム化合物、クロコニウム化合物、スピロピラン化合物、スピロオキサジン化合物、メロシアニン化合物、オキソノール化合物、スチリル化合物、ピリリウム化合物、ローダニン化合物、オキサゾロン化合物、フタルイミド化合物、シンノリン化合物、ナフトキノン化合物、アザアントラキノン化合物、ポルフィリン化合物、アザポルフィリン化合物、ピロメテン化合物、キナクリドン化合物、ジケトピロロピロール化合物、インジゴ化合物、アクリジン化合物、アジン化合物、アゾメチン化合物、アニリン化合物、キナクリドン化合物、キノフタロン化合物、キノンイミン化合物、イリジウム錯体化合物、ユーロピウム錯体化合物等の染料等が挙げられ、これらは複数を混合して用いてもよい。 (A) Colorant As the above-mentioned colorant, for example, a dye or a pigment may be mentioned as long as it can impart a desired color to a composition or a cured product thereof or the like.
As the dye, a compound having absorption at 380 to 1200 nm can be used, and for example, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazole compound, naphthol Compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound, perylene compound, polyene naphtholactam compound, coumarin compound, squalilium compound, squarylium compound, Spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pi Lithium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyromethene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, Azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinone imine compounds, iridium complex compounds, dyes such as europium complex compounds, and the like may be mentioned, and a plurality of these may be mixed and used.
上記着色剤としては、例えば組成物又はその硬化物等に所望の着色を付与できるものであればよく、染料又は顔料が挙げられる。
染料としては、380~1200nmに吸収を有する化合物を用いることができ、例えば、アゾ化合物、アントラキノン化合物、インジゴイド化合物、トリアリールメタン化合物、キサンテン化合物、アリザリン化合物、アクリジン化合物、スチルベン化合物、チアゾール化合物、ナフトール化合物、キノリン化合物、ニトロ化合物、インダミン化合物、オキサジン化合物、フタロシアニン化合物、シアニン化合物、ジインモニウム化合物、シアノエテニル化合物、ジシアノスチレン化合物、ローダミン化合物、ペリレン化合物、ポリエンナフトラクタム化合物、クマリン化合物、スクアリリウム化合物、クロコニウム化合物、スピロピラン化合物、スピロオキサジン化合物、メロシアニン化合物、オキソノール化合物、スチリル化合物、ピリリウム化合物、ローダニン化合物、オキサゾロン化合物、フタルイミド化合物、シンノリン化合物、ナフトキノン化合物、アザアントラキノン化合物、ポルフィリン化合物、アザポルフィリン化合物、ピロメテン化合物、キナクリドン化合物、ジケトピロロピロール化合物、インジゴ化合物、アクリジン化合物、アジン化合物、アゾメチン化合物、アニリン化合物、キナクリドン化合物、キノフタロン化合物、キノンイミン化合物、イリジウム錯体化合物、ユーロピウム錯体化合物等の染料等が挙げられ、これらは複数を混合して用いてもよい。 (A) Colorant As the above-mentioned colorant, for example, a dye or a pigment may be mentioned as long as it can impart a desired color to a composition or a cured product thereof or the like.
As the dye, a compound having absorption at 380 to 1200 nm can be used, and for example, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazole compound, naphthol Compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound, perylene compound, polyene naphtholactam compound, coumarin compound, squalilium compound, squarylium compound, Spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pi Lithium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyromethene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, Azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinone imine compounds, iridium complex compounds, dyes such as europium complex compounds, and the like may be mentioned, and a plurality of these may be mixed and used.
顔料としては、無機顔料或いは有機顔料を用いることができ、例えば、ニトロソ化合物、ニトロ化合物、アゾ化合物、ジアゾ化合物、キサンテン化合物、キノリン化合物、アントラキノン化合物、クマリン化合物、フタロシアニン化合物、イソインドリノン化合物、イソインドリン化合物、キナクリドン化合物、アンタンスロン化合物、ペリノン化合物、ペリレン化合物、ジケトピロロピロール化合物、チオインジゴ化合物、ジオキサジン化合物、トリフェニルメタン化合物、キノフタロン化合物、ナフタレンテトラカルボン酸;アゾ染料、シアニン染料の金属錯体化合物;レーキ顔料;ファーネス法、チャンネル法、サーマル法によって得られるカーボンブラック、或いはアセチレンブラック、ケッチェンブラック又はランプブラック等のカーボンブラック;上記カーボンブラックをエポキシ樹脂で調整、被覆したもの、上記カーボンブラックを予め溶媒中で樹脂により分散処理し、20~200mg/gの樹脂を吸着させたもの、上記カーボンブラックを酸性又はアルカリ性表面処理したもの、平均粒径が8nm以上でDBP吸油量が90ml/100g以下のもの、950℃における揮発分中のCO、CO2から算出した全酸素量が、カーボンブラックの表面積100m2当たり9mg以上であるもの;黒鉛、黒鉛化カーボンブラック、活性炭、炭素繊維、カーボンナノチューブ、カーボンマイクロコイル、カーボンナノホーン、カーボンエアロゲル、フラーレン;アニリンブラック、ピグメントブラック7、チタンブラック;疎水性樹脂、酸化クロム緑、ミロリブルー、コバルト緑、コバルト青、マンガン系、フェロシアン化物、リン酸塩群青、紺青、ウルトラマリン、セルリアンブルー、ピリジアン、エメラルドグリーン、硫酸鉛、黄色鉛、亜鉛黄、べんがら(赤色酸化鉄(III))、カドミウム赤、合成鉄黒、アンバー等の無機含量又は有機顔料を用いることができる。これらの顔料は単独で、或いは複数を混合して用いることができる。
As the pigment, an inorganic pigment or an organic pigment can be used. For example, nitroso compound, nitro compound, azo compound, diazo compound, xanthene compound, quinoline compound, anthraquinone compound, coumarin compound, phthalocyanine compound, isoindolinone compound, iso Indoline compounds, quinacridone compounds, anthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes, cyanine dyes; Lake pigment; carbon black obtained by furnace method, channel method, thermal method, or acetylene black, ketjen black or lamp black -Carbon black prepared by coating the above carbon black with an epoxy resin, coated with the carbon black in advance in a solvent, and adsorbed with a resin of 20 to 200 mg / g, the carbon black having an acidic or alkaline surface Treated, with an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in volatiles at 950 ° C., total oxygen amount calculated from CO 2 is 9 mg or more per 100 m 2 of surface area of carbon black Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue , Co Ruthe green, cobalt blue, manganese base, ferrocyanide, phosphate group blue, bitumen, ultramarine, cerulian blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), Inorganic contents such as cadmium red, synthetic iron black, amber and organic pigments can be used. These pigments may be used alone or in combination of two or more.
上記無機顔料又は有機顔料としては、市販の顔料を用いることもでき、例えば、ピグメントレッド1、2、3、9、10、14、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254;ピグメントオレンジ13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;ピグメントイエロー1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185;ピグメントグリ-ン7、10、36;ピグメントブルー15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、56、60、61、62、64;ピグメントバイオレット1、19、23、27、29、30、32、37、40、50等が挙げられる。
Commercially available pigments can also be used as the above-mentioned inorganic pigment or organic pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 22, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment oranges 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 154, 154, 154, 154, 154, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 36; pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.
上記着色剤の含有量としては、組成物の固形分100質量部に対して0.01質量部以上50質量部以下とすることができる。
上記着色剤の含有量としては、組成物100質量部中に0.01質量部以上20質量部以下とすることができる。 As content of the said coloring agent, it can be referred to as 0.01 mass part or more and 50 mass parts or less with respect to 100 mass parts of solid content of a composition.
The content of the coloring agent can be 0.01 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.
上記着色剤の含有量としては、組成物100質量部中に0.01質量部以上20質量部以下とすることができる。 As content of the said coloring agent, it can be referred to as 0.01 mass part or more and 50 mass parts or less with respect to 100 mass parts of solid content of a composition.
The content of the coloring agent can be 0.01 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.
(b)溶剤
上記溶剤としては、上記の各成分を溶解又は分散し得るものであればよく、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノン等のケトン類;エチルエーテル、ジオキサン、テトラヒドロフラン、1,2-ジメトキシエタン、1,2-ジエトキシエタン、ジプロピレングリコールジメチルエーテル等のエーテル系溶媒;酢酸メチル、酢酸エチル、酢酸-n-プロピル、酢酸イソプロピル、酢酸n-ブチル、酢酸シクロヘキシル、乳酸エチル、コハク酸ジメチル、テキサノール等のエステル系溶媒;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のセロソルブ系溶媒;メタノール、エタノール、イソ-又はn-プロパノール、イソ-又はn-ブタノール、アミルアルコール、ジアセトンアルコール等のアルコール系溶媒;エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート(PGMEA)、ジプロピレングリコールモノメチルエーテルアセテート、3-メトキシブチルアセテート、エトキシエチルプロピオネート、1-t-ブトキシ-2-プロパノール、3-メトキシブチルアセテート、シクロヘキサノールアセテート等のエーテルエステル系溶媒;ベンゼン、トルエン、キシレン等のBTX系溶媒;ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒;テレピン油、D-リモネン、ピネン等のテルペン系炭化水素油;ミネラルスピリット、スワゾール#310(コスモ松山石油(株))、ソルベッソ#100(エクソン化学(株))等のパラフィン系溶媒;四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、1,2-ジクロロエタン等のハロゲン化脂肪族炭化水素系溶媒;クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒;カルビトール系溶媒、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン、ジメチルスルホキシド、水等が挙げられ、これらの溶媒は1種又は2種以上の混合溶媒として使用することができる。
上記溶剤の含有量としては、上記組成物の用途等に応じて異なるものであるが、組成物100質量部中に1質量部以上99質量部以下とすることができ、10質量部以上70質量部以下であることが好ましい。塗布性等に優れたものとすることが容易だからである。 (B) Solvent The solvent may be any solvent as long as it can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2- Ketones such as heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, Ester solvents such as isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol and diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2 -Ether ester solvents such as acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate, etc. BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine oil, D-limonene, Terpene-based hydrocarbon oils such as Nene; paraffin spirits such as Mineral Spirit, Swazor # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water and the like can be mentioned, and these solvents can be used as one or two or more mixed solvents.
The content of the solvent varies depending on the application of the composition, etc., and can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass or more and 70 parts by mass It is preferable that it is less than part. It is because it is easy to make it excellent in coating property etc.
上記溶剤としては、上記の各成分を溶解又は分散し得るものであればよく、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノン等のケトン類;エチルエーテル、ジオキサン、テトラヒドロフラン、1,2-ジメトキシエタン、1,2-ジエトキシエタン、ジプロピレングリコールジメチルエーテル等のエーテル系溶媒;酢酸メチル、酢酸エチル、酢酸-n-プロピル、酢酸イソプロピル、酢酸n-ブチル、酢酸シクロヘキシル、乳酸エチル、コハク酸ジメチル、テキサノール等のエステル系溶媒;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のセロソルブ系溶媒;メタノール、エタノール、イソ-又はn-プロパノール、イソ-又はn-ブタノール、アミルアルコール、ジアセトンアルコール等のアルコール系溶媒;エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール-1-モノメチルエーテル-2-アセテート(PGMEA)、ジプロピレングリコールモノメチルエーテルアセテート、3-メトキシブチルアセテート、エトキシエチルプロピオネート、1-t-ブトキシ-2-プロパノール、3-メトキシブチルアセテート、シクロヘキサノールアセテート等のエーテルエステル系溶媒;ベンゼン、トルエン、キシレン等のBTX系溶媒;ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒;テレピン油、D-リモネン、ピネン等のテルペン系炭化水素油;ミネラルスピリット、スワゾール#310(コスモ松山石油(株))、ソルベッソ#100(エクソン化学(株))等のパラフィン系溶媒;四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、1,2-ジクロロエタン等のハロゲン化脂肪族炭化水素系溶媒;クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒;カルビトール系溶媒、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン、ジメチルスルホキシド、水等が挙げられ、これらの溶媒は1種又は2種以上の混合溶媒として使用することができる。
上記溶剤の含有量としては、上記組成物の用途等に応じて異なるものであるが、組成物100質量部中に1質量部以上99質量部以下とすることができ、10質量部以上70質量部以下であることが好ましい。塗布性等に優れたものとすることが容易だからである。 (B) Solvent The solvent may be any solvent as long as it can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2- Ketones such as heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, Ester solvents such as isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol and diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2 -Ether ester solvents such as acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate, etc. BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine oil, D-limonene, Terpene-based hydrocarbon oils such as Nene; paraffin spirits such as Mineral Spirit, Swazor # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water and the like can be mentioned, and these solvents can be used as one or two or more mixed solvents.
The content of the solvent varies depending on the application of the composition, etc., and can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass or more and 70 parts by mass It is preferable that it is less than part. It is because it is easy to make it excellent in coating property etc.
(c)連鎖移動剤及び増感剤
上記連鎖移動剤、増感剤としては、組成物の感度等を調整できるものとすることができ、一般的に硫黄原子含有化合物が用いられる。例えばチオグリコール酸、チオリンゴ酸、チオサリチル酸、2-メルカプトプロピオン酸、3-メルカプトプロピオン酸、3-メルカプト酪酸、N-(2-メルカプトプロピオニル)グリシン、2-メルカプトニコチン酸、3-[N-(2-メルカプトエチル)カルバモイル]プロピオン酸、3-[N-(2-メルカプトエチル)アミノ]プロピオン酸、N-(3-メルカプトプロピオニル)アラニン、2-メルカプトエタンスルホン酸、3-メルカプトプロパンスルホン酸、4-メルカプトブタンスルホン酸、ドデシル(4-メチルチオ)フェニルエーテル、2-メルカプトエタノール、3-メルカプト-1,2-プロパンジオール、1-メルカプト-2-プロパノール、3-メルカプト-2-ブタノール、メルカプトフェノール、2-メルカプトエチルアミン、2-メルカプトイミダゾール、2-メルカプトベンゾイミダゾール、2-メルカプト-3-ピリジノール、2-メルカプトベンゾチアゾール、メルカプト酢酸、トリメチロールプロパントリス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)等のメルカプト化合物、該メルカプト化合物を酸化して得られるジスルフィド化合物、ヨード酢酸、ヨードプロピオン酸、2-ヨードエタノール、2-ヨードエタンスルホン酸、3-ヨードプロパンスルホン酸等のヨード化アルキル化合物、トリメチロールプロパントリス(3-メルカプトイソブチレート)、ブタンジオールビス(3-メルカプトイソブチレート)、ヘキサンジチオール、デカンジチオール、1,4-ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、下記化合物No.C1、トリメルカプトプロピオン酸トリス(2-ヒドロキシエチル)イソシアヌレート等の脂肪族多官能チオール化合物、昭和電工社製カレンズMT BD1、PE1、NR1等が挙げられる。 (C) Chain Transfer Agent and Sensitizer As the chain transfer agent and the sensitizer, the sensitivity of the composition can be adjusted, and a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-Mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- 3- Mercapto compounds such as mercapto propionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, iodomethane such as 3-iodopropanesulfonic acid Alkylated compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris hydroxyethyl tris thiopropionate, compound No. 1 below. C1, aliphatic polyfunctional thiol compounds, such as tri-mercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, manufactured by Showa Denko KK Karenz MT BD1, PE1, NR 1, and the like.
上記連鎖移動剤、増感剤としては、組成物の感度等を調整できるものとすることができ、一般的に硫黄原子含有化合物が用いられる。例えばチオグリコール酸、チオリンゴ酸、チオサリチル酸、2-メルカプトプロピオン酸、3-メルカプトプロピオン酸、3-メルカプト酪酸、N-(2-メルカプトプロピオニル)グリシン、2-メルカプトニコチン酸、3-[N-(2-メルカプトエチル)カルバモイル]プロピオン酸、3-[N-(2-メルカプトエチル)アミノ]プロピオン酸、N-(3-メルカプトプロピオニル)アラニン、2-メルカプトエタンスルホン酸、3-メルカプトプロパンスルホン酸、4-メルカプトブタンスルホン酸、ドデシル(4-メチルチオ)フェニルエーテル、2-メルカプトエタノール、3-メルカプト-1,2-プロパンジオール、1-メルカプト-2-プロパノール、3-メルカプト-2-ブタノール、メルカプトフェノール、2-メルカプトエチルアミン、2-メルカプトイミダゾール、2-メルカプトベンゾイミダゾール、2-メルカプト-3-ピリジノール、2-メルカプトベンゾチアゾール、メルカプト酢酸、トリメチロールプロパントリス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)等のメルカプト化合物、該メルカプト化合物を酸化して得られるジスルフィド化合物、ヨード酢酸、ヨードプロピオン酸、2-ヨードエタノール、2-ヨードエタンスルホン酸、3-ヨードプロパンスルホン酸等のヨード化アルキル化合物、トリメチロールプロパントリス(3-メルカプトイソブチレート)、ブタンジオールビス(3-メルカプトイソブチレート)、ヘキサンジチオール、デカンジチオール、1,4-ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、下記化合物No.C1、トリメルカプトプロピオン酸トリス(2-ヒドロキシエチル)イソシアヌレート等の脂肪族多官能チオール化合物、昭和電工社製カレンズMT BD1、PE1、NR1等が挙げられる。 (C) Chain Transfer Agent and Sensitizer As the chain transfer agent and the sensitizer, the sensitivity of the composition can be adjusted, and a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-Mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- 3- Mercapto compounds such as mercapto propionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, iodomethane such as 3-iodopropanesulfonic acid Alkylated compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris hydroxyethyl tris thiopropionate, compound No. 1 below. C1, aliphatic polyfunctional thiol compounds, such as tri-mercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, manufactured by Showa Denko KK Karenz MT BD1, PE1, NR 1, and the like.
(d)界面活性剤
上記界面活性剤としては、組成物の分散安定性、塗工性等を改善できるものを用いることができ、パーフルオロアルキルリン酸エステル、パーフルオロアルキルカルボン酸塩等のフッ素界面活性剤、高級脂肪酸アルカリ塩、アルキルスルホン酸塩、アルキル硫酸塩等のアニオン系界面活性剤、高級アミンハロゲン酸塩、第四級アンモニウム塩等のカチオン系界面活性剤、ポリエチレングリコールアルキルエーテル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリド等の非イオン界面活性剤、両性界面活性剤、シリコーン系界面活性剤等の界面活性剤を用いることができ、これらは組み合わせて用いてもよい。 (D) Surfactant As said surfactant, what can improve the dispersion stability of a composition, coating property, etc. can be used, Fluorine, such as perfluoro alkyl phosphate ester and perfluoro alkyl carboxylic acid salt Surfactants, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, cationic surfactants such as higher amine halides and quaternary ammonium salts, polyethylene glycol alkyl ether, polyethylene Nonionic surfactants such as glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, surfactants such as amphoteric surfactants and silicone surfactants can be used, and these may be used in combination.
上記界面活性剤としては、組成物の分散安定性、塗工性等を改善できるものを用いることができ、パーフルオロアルキルリン酸エステル、パーフルオロアルキルカルボン酸塩等のフッ素界面活性剤、高級脂肪酸アルカリ塩、アルキルスルホン酸塩、アルキル硫酸塩等のアニオン系界面活性剤、高級アミンハロゲン酸塩、第四級アンモニウム塩等のカチオン系界面活性剤、ポリエチレングリコールアルキルエーテル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリド等の非イオン界面活性剤、両性界面活性剤、シリコーン系界面活性剤等の界面活性剤を用いることができ、これらは組み合わせて用いてもよい。 (D) Surfactant As said surfactant, what can improve the dispersion stability of a composition, coating property, etc. can be used, Fluorine, such as perfluoro alkyl phosphate ester and perfluoro alkyl carboxylic acid salt Surfactants, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, cationic surfactants such as higher amine halides and quaternary ammonium salts, polyethylene glycol alkyl ether, polyethylene Nonionic surfactants such as glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, surfactants such as amphoteric surfactants and silicone surfactants can be used, and these may be used in combination.
(e)シランカップリング剤
上記シランカップリング剤としては、ガラスなどの無機材料と化学結合する反応基と、合成樹脂などの有機材料と化学結合する反応基と、を有するシラン化合物であり、組成物又はその硬化物の密着性等を改善できるものを用いることができる。シランカップリング剤としては、例えば信越化学社製シランカップリング剤を用いることができ、その中でもKBE-9007、KBM-502、KBE-403等、イソシアネート基、メタクリロイル基、エポキシ基を有するシランカップリング剤が好適に用いられる。 (E) Silane Coupling Agent The above silane coupling agent is a silane compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material such as a synthetic resin, What can improve the adhesiveness etc. of a thing or its hardened | cured material can be used. As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc., silane coupling having an isocyanate group, methacryloyl group or epoxy group An agent is preferably used.
上記シランカップリング剤としては、ガラスなどの無機材料と化学結合する反応基と、合成樹脂などの有機材料と化学結合する反応基と、を有するシラン化合物であり、組成物又はその硬化物の密着性等を改善できるものを用いることができる。シランカップリング剤としては、例えば信越化学社製シランカップリング剤を用いることができ、その中でもKBE-9007、KBM-502、KBE-403等、イソシアネート基、メタクリロイル基、エポキシ基を有するシランカップリング剤が好適に用いられる。 (E) Silane Coupling Agent The above silane coupling agent is a silane compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material such as a synthetic resin, What can improve the adhesiveness etc. of a thing or its hardened | cured material can be used. As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc., silane coupling having an isocyanate group, methacryloyl group or epoxy group An agent is preferably used.
(f)メラミン化合物
上記メラミン化合物としては、硬化性を改善できるものを用いることができ、例えば、(ポリ)メチロールメラミン、(ポリ)メチロールグリコールウリル、(ポリ)メチロールベンゾグアナミン、(ポリ)メチロールウレア等の窒素化合物中の活性メチロール基(CH2OH基)の全部又は一部(少なくとも2つ)がアルキルエーテル化された化合物を挙げることができる。ここで、アルキルエーテルを構成するアルキル基としては、メチル基、エチル基又はブチル基が挙げられ、互いに同一である場合もあるし、異なる場合もある。また、アルキルエーテル化されていないメチロール基は、一分子内で自己縮合していてもよく、二分子間で縮合して、その結果オリゴマー成分が形成されていてもよい。具体的には、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等を用いることができる。これらの中でも、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン等のアルキルエーテル化されたメラミンが好ましい。 (F) Melamine compound As the above-mentioned melamine compound, those which can improve the curability can be used, for example, (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, (poly) methylolurea and the like of active methylol groups of the nitrogen compound (CH 2 OH groups) of all or part (at least two) can be exemplified compounds alkyl etherified. Here, as an alkyl group which comprises an alkyl ether, a methyl group, an ethyl group, or a butyl group is mentioned, It may mutually be same or different. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.
上記メラミン化合物としては、硬化性を改善できるものを用いることができ、例えば、(ポリ)メチロールメラミン、(ポリ)メチロールグリコールウリル、(ポリ)メチロールベンゾグアナミン、(ポリ)メチロールウレア等の窒素化合物中の活性メチロール基(CH2OH基)の全部又は一部(少なくとも2つ)がアルキルエーテル化された化合物を挙げることができる。ここで、アルキルエーテルを構成するアルキル基としては、メチル基、エチル基又はブチル基が挙げられ、互いに同一である場合もあるし、異なる場合もある。また、アルキルエーテル化されていないメチロール基は、一分子内で自己縮合していてもよく、二分子間で縮合して、その結果オリゴマー成分が形成されていてもよい。具体的には、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等を用いることができる。これらの中でも、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン等のアルキルエーテル化されたメラミンが好ましい。 (F) Melamine compound As the above-mentioned melamine compound, those which can improve the curability can be used, for example, (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, (poly) methylolurea and the like of active methylol groups of the nitrogen compound (CH 2 OH groups) of all or part (at least two) can be exemplified compounds alkyl etherified. Here, as an alkyl group which comprises an alkyl ether, a methyl group, an ethyl group, or a butyl group is mentioned, It may mutually be same or different. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.
3.組成物
上記組成物の粘度としては、例えば、塗工性を有するものとする観点からは、例えば、200mPa・s以下とすることができ、1mPa・s以上200mPa・s以下とすることができる。上記組成物は、塗工性に優れるからである。
上記粘度は、JIS Z 8803:2011に準じて、回転式粘度計(例えば、アントンパール社製、Physica MCR301等)を用いて、測定される値のことを指す。また、本明細書で、特に、温度の指定がない処理、測定は、25℃で行うものとすることができる。 3. Composition The viscosity of the composition may be, for example, 200 mPa · s or less, and 1 mPa · s or more and 200 mPa · s or less from the viewpoint of having coatability. It is because the said composition is excellent in coatability.
The viscosity, JIS Z 8803: according to the 2011, rotational viscometer (e.g., Anton Paar, Physica MCR 3 01, etc.) using, refers to the measured values. In the present specification, in particular, processing without temperature designation and measurement may be performed at 25 ° C.
上記組成物の粘度としては、例えば、塗工性を有するものとする観点からは、例えば、200mPa・s以下とすることができ、1mPa・s以上200mPa・s以下とすることができる。上記組成物は、塗工性に優れるからである。
上記粘度は、JIS Z 8803:2011に準じて、回転式粘度計(例えば、アントンパール社製、Physica MCR301等)を用いて、測定される値のことを指す。また、本明細書で、特に、温度の指定がない処理、測定は、25℃で行うものとすることができる。 3. Composition The viscosity of the composition may be, for example, 200 mPa · s or less, and 1 mPa · s or more and 200 mPa · s or less from the viewpoint of having coatability. It is because the said composition is excellent in coatability.
The viscosity, JIS Z 8803: according to the 2011, rotational viscometer (e.g., Anton Paar, Physica MCR 3 01, etc.) using, refers to the measured values. In the present specification, in particular, processing without temperature designation and measurement may be performed at 25 ° C.
上記組成物の製造方法は、上記各成分を所望の含有量で配合可能な方法であればよく、上記各成分を同時に添加して混合する方法であってもよく、各成分を順次添加しながら混合する方法であってもよい。
The method for producing the above composition may be any method as long as the above-mentioned components can be blended at a desired content, and may be a method in which the above-mentioned components are simultaneously added and mixed. It may be a method of mixing.
上記組成物の用途は、熱硬化性塗料、光硬化性塗料或いはワニス、熱硬化性接着剤、光硬化性接着剤、プリント基板、或いはカラーテレビ、PCモニタ、携帯情報端末、デジタルカメラ等のカラー表示の液晶表示パネルにおけるカラーフィルタ、CCDイメージセンサのカラーフィルタ、フォトスペーサ、ブラックカラムスペーサ、プラズマ表示パネル用の電極材料、タッチパネル、タッチセンサ、粉末コーティング、印刷インク、印刷版、接着剤、歯科用組成物、光造形用樹脂、ゲルコート、電子工学用のフォトレジスト、電気メッキレジスト、エッチングレジスト、液状及び乾燥膜の双方、はんだレジスト、種々の表示用途用のカラーフィルタを製造するための或いはプラズマ表示パネル、電気発光表示装置、及びLCDの製造工程において構造を形成するためのレジスト、電気及び電子部品を封入するための組成物、ソルダーレジスト、磁気記録材料、微小機械部品、導波路、光スイッチ、メッキ用マスク、エッチングマスク、カラー試験系、ガラス繊維ケーブルコーティング、スクリーン印刷用ステンシル、ステレオリトグラフィによって三次元物体を製造するための材料、ホログラフィ記録用材料、画像記録材料、微細電子回路、脱色材料、画像記録材料のための脱色材料、マイクロカプセルを使用する画像記録材料用の脱色材料、印刷配線板用フォトレジスト材料、UV及び可視レーザー直接画像系用のフォトレジスト材料、プリント回路基板の逐次積層における誘電体層形成に使用するフォトレジスト材料、3D実装用フォトレジスト材料或いは保護膜等の各種の用途に使用することができ、その用途に特に制限はない。
また、上記用途としては、製品としての使用時等に紫外線に対する耐久性が要求される用途に限定されず、例えば、製造過程において紫外線照射等を受ける部材にも好適に用いることができる。
製造過程において紫外線照射等を受ける部材としては、例えば、表面の濡れ性向上、密着性向上等の表面改質を図るために、紫外線等の照射を受ける部材を挙げることができる。
上述の濡れ性向上、密着性向上等が要求される部材としては、他の部材と積層される部材を挙げることができ、例えば、プラズマ表示パネル、有機エレクトロルミネッセンス表示装置、液晶表示装置等の各種画像表示、タッチパネル等の各種センサ、回路基板等を構成する部材としてカラーフィルタ、フォトスペーサ、輝度向上板、導光板、TFT基板、配向膜、液晶層、絶縁膜、スピーカーなどの音響素子、撮像用レンズ、キーパッド、HDD用磁気ヘッドなどの製造過程での表面改質や部材の劣化防止が要求される部材が挙げられる。
上述の製造過程での表面改質や部材の劣化防止が要求される部材としては、接着剤を介して他の部材と積層される部材、塗料等により他の部材により被覆される部材も挙げることができ、例えば、自動車、航空機の内外装部材等の運搬機器、冷蔵庫、洗濯機等の家電製品、住宅建材等の各種用途の構成部材も挙げることができる。
また、基材上にパターン状の部材を形成した後、露出する基材の表面改質等のために基材と共に上記部材に対して紫外線照射等を実施する場合がある。上記用途としては、このような製造過程において表面改質等が要求される部材と共に用いられる部材にも好ましく用いることができる。上記用途としては、例えば、プラスチックフィルムやガラス、シリコンウエハー、各種エンジニアリングプラスチック、光学レンズ、金属表面、メッキ、セラミック、金型などの表面洗浄や表面改質などが要求される部材と共に用いられる部材が挙げられる。 Applications of the above composition are thermosetting coatings, photocurable coatings or varnishes, thermosetting adhesives, photocurable adhesives, printed circuit boards, or color televisions such as color televisions, PC monitors, personal digital assistants, digital cameras, etc. Color filters for liquid crystal display panels for display, color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, for dental use Composition, resin for photolithography, gel coat, photoresist for electronics, electroplating resist, etching resist, both liquid and dry film, solder resist, for manufacturing color filters for various display applications or plasma display In the manufacturing process of panels, electroluminescent displays, and LCDs Resists for forming optical structures, compositions for encapsulating electric and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass Fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronics, bleaching materials, bleaching materials for image recording materials, microcapsules Decoloring materials for image recording materials using the same, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used for forming a dielectric layer in sequential lamination of printed circuit boards, For various uses such as photoresist material or protective film for 3D mounting It can be used, and there is no particular limitation on the application.
Further, the application is not limited to the application in which the durability to ultraviolet light is required at the time of use as a product etc. For example, it can be suitably used also for a member which receives ultraviolet irradiation or the like in the manufacturing process.
As a member which receives ultraviolet irradiation etc. in a manufacturing process, in order to aim at surface modification of surface wettability improvement, adhesion improvement, etc., a member which receives irradiation, such as ultraviolet light, can be mentioned, for example.
Examples of the members required to have the above-mentioned wettability improvement and adhesion improvement include members laminated with other members. For example, various members such as a plasma display panel, an organic electroluminescence display, a liquid crystal display, etc. Image display, various sensors such as touch panels, color filters, photo spacers, brightness enhancement plates, light guide plates, light guide plates, TFT substrates, alignment films, liquid crystal layers, insulating films, acoustic elements such as speakers, members for constituting circuit boards etc. Examples of such a member include a surface modification in the manufacturing process of a lens, a keypad, a magnetic head for an HDD, and the like, and the prevention of deterioration of the member.
As members required to prevent surface modification and deterioration of members in the above-mentioned manufacturing process, members to be laminated with other members via an adhesive, members to be covered with other members by paints, etc. should also be mentioned. For example, components of various uses such as vehicles, transport devices such as interior and exterior members of aircraft, household appliances such as refrigerators and washing machines, and housing materials can also be mentioned.
In addition, after forming a pattern-like member on a base material, the base material may be irradiated with ultraviolet light or the like together with the base material for surface modification of the exposed base material. As said use, it can use preferably also for the member used with the member by which surface modification etc. are requested | required in such a manufacturing process. As the above applications, for example, members used together with members that require surface cleaning or surface modification such as plastic film, glass, silicon wafer, various engineering plastics, optical lenses, metal surfaces, plating, ceramics, dies etc. It can be mentioned.
また、上記用途としては、製品としての使用時等に紫外線に対する耐久性が要求される用途に限定されず、例えば、製造過程において紫外線照射等を受ける部材にも好適に用いることができる。
製造過程において紫外線照射等を受ける部材としては、例えば、表面の濡れ性向上、密着性向上等の表面改質を図るために、紫外線等の照射を受ける部材を挙げることができる。
上述の濡れ性向上、密着性向上等が要求される部材としては、他の部材と積層される部材を挙げることができ、例えば、プラズマ表示パネル、有機エレクトロルミネッセンス表示装置、液晶表示装置等の各種画像表示、タッチパネル等の各種センサ、回路基板等を構成する部材としてカラーフィルタ、フォトスペーサ、輝度向上板、導光板、TFT基板、配向膜、液晶層、絶縁膜、スピーカーなどの音響素子、撮像用レンズ、キーパッド、HDD用磁気ヘッドなどの製造過程での表面改質や部材の劣化防止が要求される部材が挙げられる。
上述の製造過程での表面改質や部材の劣化防止が要求される部材としては、接着剤を介して他の部材と積層される部材、塗料等により他の部材により被覆される部材も挙げることができ、例えば、自動車、航空機の内外装部材等の運搬機器、冷蔵庫、洗濯機等の家電製品、住宅建材等の各種用途の構成部材も挙げることができる。
また、基材上にパターン状の部材を形成した後、露出する基材の表面改質等のために基材と共に上記部材に対して紫外線照射等を実施する場合がある。上記用途としては、このような製造過程において表面改質等が要求される部材と共に用いられる部材にも好ましく用いることができる。上記用途としては、例えば、プラスチックフィルムやガラス、シリコンウエハー、各種エンジニアリングプラスチック、光学レンズ、金属表面、メッキ、セラミック、金型などの表面洗浄や表面改質などが要求される部材と共に用いられる部材が挙げられる。 Applications of the above composition are thermosetting coatings, photocurable coatings or varnishes, thermosetting adhesives, photocurable adhesives, printed circuit boards, or color televisions such as color televisions, PC monitors, personal digital assistants, digital cameras, etc. Color filters for liquid crystal display panels for display, color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, for dental use Composition, resin for photolithography, gel coat, photoresist for electronics, electroplating resist, etching resist, both liquid and dry film, solder resist, for manufacturing color filters for various display applications or plasma display In the manufacturing process of panels, electroluminescent displays, and LCDs Resists for forming optical structures, compositions for encapsulating electric and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass Fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronics, bleaching materials, bleaching materials for image recording materials, microcapsules Decoloring materials for image recording materials using the same, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used for forming a dielectric layer in sequential lamination of printed circuit boards, For various uses such as photoresist material or protective film for 3D mounting It can be used, and there is no particular limitation on the application.
Further, the application is not limited to the application in which the durability to ultraviolet light is required at the time of use as a product etc. For example, it can be suitably used also for a member which receives ultraviolet irradiation or the like in the manufacturing process.
As a member which receives ultraviolet irradiation etc. in a manufacturing process, in order to aim at surface modification of surface wettability improvement, adhesion improvement, etc., a member which receives irradiation, such as ultraviolet light, can be mentioned, for example.
Examples of the members required to have the above-mentioned wettability improvement and adhesion improvement include members laminated with other members. For example, various members such as a plasma display panel, an organic electroluminescence display, a liquid crystal display, etc. Image display, various sensors such as touch panels, color filters, photo spacers, brightness enhancement plates, light guide plates, light guide plates, TFT substrates, alignment films, liquid crystal layers, insulating films, acoustic elements such as speakers, members for constituting circuit boards etc. Examples of such a member include a surface modification in the manufacturing process of a lens, a keypad, a magnetic head for an HDD, and the like, and the prevention of deterioration of the member.
As members required to prevent surface modification and deterioration of members in the above-mentioned manufacturing process, members to be laminated with other members via an adhesive, members to be covered with other members by paints, etc. should also be mentioned. For example, components of various uses such as vehicles, transport devices such as interior and exterior members of aircraft, household appliances such as refrigerators and washing machines, and housing materials can also be mentioned.
In addition, after forming a pattern-like member on a base material, the base material may be irradiated with ultraviolet light or the like together with the base material for surface modification of the exposed base material. As said use, it can use preferably also for the member used with the member by which surface modification etc. are requested | required in such a manufacturing process. As the above applications, for example, members used together with members that require surface cleaning or surface modification such as plastic film, glass, silicon wafer, various engineering plastics, optical lenses, metal surfaces, plating, ceramics, dies etc. It can be mentioned.
D.硬化物
次に、本発明の硬化物について説明する。
本発明の硬化物は、本発明の化合物I-1と重合性化合物とを含有する組成物の硬化物である。 D. Cured Product Next, the cured product of the present invention will be described.
The cured product of the present invention is a cured product of a composition containing the compound I-1 of the present invention and a polymerizable compound.
次に、本発明の硬化物について説明する。
本発明の硬化物は、本発明の化合物I-1と重合性化合物とを含有する組成物の硬化物である。 D. Cured Product Next, the cured product of the present invention will be described.
The cured product of the present invention is a cured product of a composition containing the compound I-1 of the present invention and a polymerizable compound.
本発明の組成物は、上述の組成物を用いているため、良好な紫外線吸収能等を有する。
Since the composition of the present invention uses the above-mentioned composition, it has a good ultraviolet absorbing ability and the like.
本発明の硬化物は、上述の組成物を用いるものである。
以下、本発明の硬化物について詳細に説明する。 The cured product of the present invention uses the composition described above.
Hereinafter, the cured product of the present invention will be described in detail.
以下、本発明の硬化物について詳細に説明する。 The cured product of the present invention uses the composition described above.
Hereinafter, the cured product of the present invention will be described in detail.
上記組成物は、上記化合物I-1と、重合性化合物と、を含むものである。また、上記組成物は、上記化合物I-1及び重合性化合物以外の成分を含むものであってもよい。
このような組成物の各成分の内容については、上記「C.組成物」の「2.その他の成分」の項に記載の内容と同様とすることができる。 The composition contains the compound I-1 and a polymerizable compound. The composition may also contain components other than the compound I-1 and the polymerizable compound.
About the content of each component of such a composition, it can be made to be the same as the content as described in the term of "2. other components" of the above-mentioned "C. composition".
このような組成物の各成分の内容については、上記「C.組成物」の「2.その他の成分」の項に記載の内容と同様とすることができる。 The composition contains the compound I-1 and a polymerizable compound. The composition may also contain components other than the compound I-1 and the polymerizable compound.
About the content of each component of such a composition, it can be made to be the same as the content as described in the term of "2. other components" of the above-mentioned "C. composition".
上記組成物に含まれる上記化合物I-1は、硬化物中で、光脱離基Bの脱離前であっても、脱離後であってもよいが、脱離後であることが好ましい。上記硬化物は、優れた紫外線吸収能を有するものとなるからである。
The compound I-1 contained in the composition may be before or after elimination of the photoleaving group B in the cured product, but is preferably after elimination . It is because the said hardened | cured material will have the outstanding ultraviolet absorptivity.
上記硬化物は、通常、重合性化合物の重合物を含むものである。
上記硬化物に含まれる重合性化合物の残存量としては、硬化物の用途等に応じて適宜設定されるものであるが、例えば、硬化物100質量部中、10質量部以下であり、1質量部以下であることが好ましい。 The above-mentioned cured product usually contains a polymer of a polymerizable compound.
The remaining amount of the polymerizable compound contained in the cured product is appropriately set according to the application of the cured product and the like, and is, for example, 10 parts by mass or less in 100 parts by mass of the cured product, and 1 part It is preferable that it is less than part.
上記硬化物に含まれる重合性化合物の残存量としては、硬化物の用途等に応じて適宜設定されるものであるが、例えば、硬化物100質量部中、10質量部以下であり、1質量部以下であることが好ましい。 The above-mentioned cured product usually contains a polymer of a polymerizable compound.
The remaining amount of the polymerizable compound contained in the cured product is appropriately set according to the application of the cured product and the like, and is, for example, 10 parts by mass or less in 100 parts by mass of the cured product, and 1 part It is preferable that it is less than part.
上記硬化物としては、溶剤を実質的に含まないものとすることができる。
上記硬化物に含まれる溶剤の含有量としては、例えば、硬化物100質量部中、1質量部以下とすることができ、0.5質量部以下とすることができる。 The cured product may be substantially free of a solvent.
As content of the solvent contained in the said hardened | cured material, it can be 1 mass part or less in 100 mass parts of hardened | cured material, for example, can be 0.5 mass part or less.
上記硬化物に含まれる溶剤の含有量としては、例えば、硬化物100質量部中、1質量部以下とすることができ、0.5質量部以下とすることができる。 The cured product may be substantially free of a solvent.
As content of the solvent contained in the said hardened | cured material, it can be 1 mass part or less in 100 mass parts of hardened | cured material, for example, can be 0.5 mass part or less.
上記硬化物の弾性率は、通常、上記組成物より高いものであり、例えば、10-3M以上とすることができ、10MPa以上とすることができる。上記弾性率であることで、上記硬化物は、安定的に化合物I-1等を保持できるからである。
上記弾性率の上限については、硬化物の用途等に応じて適宜設定できるが、例えば、106MPa以下とすることができる。
なお以下、弾性率は、圧縮弾性率をいうものであり、JIS K7181に準拠して、23℃で、測定することができる。
測定サンプルについては、例えば、一辺の長さが6mmの立方体の試験片を作成又は切り出し、JISK7181に準じ、試験速度1±0.2mm/分の条件で測定することができる。 The elastic modulus of the cured product is usually higher than that of the composition, and can be, for example, 10 -3 M or more, and can be 10 MPa or more. With the elastic modulus, the cured product can stably hold the compound I-1 and the like.
About the upper limit of the above-mentioned elastic modulus, although it can set suitably according to the use etc. of hardened material, it can be made into 10 6 MPa or less, for example.
Hereinafter, the elastic modulus refers to the compressive elastic modulus and can be measured at 23 ° C. in accordance with JIS K7181.
For the measurement sample, for example, a cube-shaped test piece having a side length of 6 mm can be prepared or cut out, and measurement can be performed at a test speed of 1 ± 0.2 mm / min according to JIS K7181.
上記弾性率の上限については、硬化物の用途等に応じて適宜設定できるが、例えば、106MPa以下とすることができる。
なお以下、弾性率は、圧縮弾性率をいうものであり、JIS K7181に準拠して、23℃で、測定することができる。
測定サンプルについては、例えば、一辺の長さが6mmの立方体の試験片を作成又は切り出し、JISK7181に準じ、試験速度1±0.2mm/分の条件で測定することができる。 The elastic modulus of the cured product is usually higher than that of the composition, and can be, for example, 10 -3 M or more, and can be 10 MPa or more. With the elastic modulus, the cured product can stably hold the compound I-1 and the like.
About the upper limit of the above-mentioned elastic modulus, although it can set suitably according to the use etc. of hardened material, it can be made into 10 6 MPa or less, for example.
Hereinafter, the elastic modulus refers to the compressive elastic modulus and can be measured at 23 ° C. in accordance with JIS K7181.
For the measurement sample, for example, a cube-shaped test piece having a side length of 6 mm can be prepared or cut out, and measurement can be performed at a test speed of 1 ± 0.2 mm / min according to JIS K7181.
上記硬化物の製造方法としては、上述の組成物を硬化させることができる方法であればよく、例えば、後述する「F.硬化物の製造方法」の項に記載の方法と同様とすることができる。
The method for producing the above-mentioned cured product may be any method as long as the above-mentioned composition can be cured, for example, it may be the same as the method described in “F. Method for producing a cured product” described later. it can.
上記硬化物の用途等については、上記「C.組成物」の項に記載の内容と同様とすることができる。
About the use etc. of the said hardened | cured material, it can be made to be the same as that of the content as described in the term of the said "C. composition".
E.組成物
次に、本発明の第2組成物について説明する。
本発明の第2組成物は、下記一般式(I-2)で表される化合物(以下、「化合物I-2と称する場合がある。)と、光脱離基由来の脱離物(以下、「化合物B´」と称する場合がある。)と、を含むことを特徴とするものである。 E. Composition Next, the second composition of the present invention will be described.
The second composition of the present invention comprises a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound I-2”) , And may be referred to as "compound B '").
次に、本発明の第2組成物について説明する。
本発明の第2組成物は、下記一般式(I-2)で表される化合物(以下、「化合物I-2と称する場合がある。)と、光脱離基由来の脱離物(以下、「化合物B´」と称する場合がある。)と、を含むことを特徴とするものである。 E. Composition Next, the second composition of the present invention will be described.
The second composition of the present invention comprises a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound I-2”) , And may be referred to as "compound B '").
(式中、Aは、紫外線吸収能を有する原子団であり、kは1~10の整数を表す。)
(In the formula, A represents an atomic group having an ultraviolet absorbing ability, and k represents an integer of 1 to 10)
本発明によれば、上記第2組成物は、例えば、上述の組成物を用いて、容易に形成できる。また、上記第2組成物は、容易に紫外線吸収能等を付与できる。
According to the present invention, the second composition can be easily formed, for example, using the composition described above. In addition, the second composition can easily impart ultraviolet absorbing ability and the like.
本発明の第2組成物は、化合物I-2及び化合物B´を有するものである。
以下、本発明の第2組成物について詳細に説明する。 The second composition of the present invention comprises the compound I-2 and the compound B ′.
Hereinafter, the second composition of the present invention will be described in detail.
以下、本発明の第2組成物について詳細に説明する。 The second composition of the present invention comprises the compound I-2 and the compound B ′.
Hereinafter, the second composition of the present invention will be described in detail.
1.化合物I-2
上記化合物I-2は、紫外線吸収能を発揮するものである。
上記化合物I-2は、上記化合物I-1における上記B-O-が-OH基に置換されたものである。
このような化合物I-1の内容については、上記「A.化合物」の項に記載の内容と同様とすることができるので、ここでの説明は省略する。 1. Compound I-2
The compound I-2 exhibits ultraviolet absorbing ability.
The compound I-2 is a compound in which the B-O- in the compound I-1 is substituted with an -OH group.
The contents of such compound I-1 can be the same as the contents described in the section “A. Compound” above, so the description thereof is omitted here.
上記化合物I-2は、紫外線吸収能を発揮するものである。
上記化合物I-2は、上記化合物I-1における上記B-O-が-OH基に置換されたものである。
このような化合物I-1の内容については、上記「A.化合物」の項に記載の内容と同様とすることができるので、ここでの説明は省略する。 1. Compound I-2
The compound I-2 exhibits ultraviolet absorbing ability.
The compound I-2 is a compound in which the B-O- in the compound I-1 is substituted with an -OH group.
The contents of such compound I-1 can be the same as the contents described in the section “A. Compound” above, so the description thereof is omitted here.
上記化合物I-2の組成物中の含有量としては、所望の紫外線吸収能等を付与できるものであればよいが、例えば、化合物I-2及び化合物B´の合計が、上記「C.組成物」の項に記載の上記化合物I-1の固形分中の含有量と同じとすることができる。
The content of the compound I-2 in the composition may be any as long as it can impart a desired ultraviolet absorbing ability and the like. For example, the total of the compound I-2 and the compound B ′ corresponds to the “C. It can be made the same as the content in the solid content of the above-mentioned compound I-1 described in the item of Article].
2.化合物B´
上記化合物B´は、光脱離基由来の脱離物である。
また、光脱離基は、フェノール性水酸基に対して保護基として結合可能な基であればよく、上記「A.化合物」の「1.光脱離基B」に記載の内容と同様とすることができる。
このような化合物B´としては、上記光脱離基がフェノール性水酸基から脱離した後にとり得るものであればよい。
なお、フェノール性水酸基から脱離した後の光脱離基Bは、通常、反応性が高く、様々な構造をとり得る。
上記化合物B´としては、光脱離基Bが、上記一般式(B-1-a)、(B-2)、(B-3)、(B-4)、(B-5)、(B-6)、(B-7)等で表されるものである場合には、それぞれ例えば、下記一般式(B-111-a)、(B-112)、(B-113)、(B-114)、(B-115)、(B-116)、(B-117)で表される化合物等を含むことができる。 2. Compound B '
The compound B ′ is a leaving substance derived from a photoleaving group.
The photoleaving group may be any group capable of binding to the phenolic hydroxyl group as a protecting group, and the same as the contents described in “1. Photoleaving group B” of the above “A. Compound”. be able to.
As such a compound B ′, any compound can be used as long as it can be taken after the photoleaving group is eliminated from the phenolic hydroxyl group.
The photoleaving group B after leaving the phenolic hydroxyl group is usually highly reactive and can have various structures.
As the compound B ′, the photoleaving group B is preferably a compound represented by the general formulas (B-1-a), (B-2), (B-3), (B-4), (B-5), When it is represented by B-6), (B-7), etc., for example, the following general formulas (B-111-a), (B-112), (B-113), (B) -114), (B-115), (B-116), (B-117) and the like can be included.
上記化合物B´は、光脱離基由来の脱離物である。
また、光脱離基は、フェノール性水酸基に対して保護基として結合可能な基であればよく、上記「A.化合物」の「1.光脱離基B」に記載の内容と同様とすることができる。
このような化合物B´としては、上記光脱離基がフェノール性水酸基から脱離した後にとり得るものであればよい。
なお、フェノール性水酸基から脱離した後の光脱離基Bは、通常、反応性が高く、様々な構造をとり得る。
上記化合物B´としては、光脱離基Bが、上記一般式(B-1-a)、(B-2)、(B-3)、(B-4)、(B-5)、(B-6)、(B-7)等で表されるものである場合には、それぞれ例えば、下記一般式(B-111-a)、(B-112)、(B-113)、(B-114)、(B-115)、(B-116)、(B-117)で表される化合物等を含むことができる。 2. Compound B '
The compound B ′ is a leaving substance derived from a photoleaving group.
The photoleaving group may be any group capable of binding to the phenolic hydroxyl group as a protecting group, and the same as the contents described in “1. Photoleaving group B” of the above “A. Compound”. be able to.
As such a compound B ′, any compound can be used as long as it can be taken after the photoleaving group is eliminated from the phenolic hydroxyl group.
The photoleaving group B after leaving the phenolic hydroxyl group is usually highly reactive and can have various structures.
As the compound B ′, the photoleaving group B is preferably a compound represented by the general formulas (B-1-a), (B-2), (B-3), (B-4), (B-5), When it is represented by B-6), (B-7), etc., for example, the following general formulas (B-111-a), (B-112), (B-113), (B) -114), (B-115), (B-116), (B-117) and the like can be included.
上記化合物B´に含まれるR11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26及びR27並びにb1、b2、b3、b4、b5、b6、b7及びb8については、上記「A.化合物」の項に記載の内容と同じであるもで、ここでの説明は省略する。
R 11 contained in the compound B', R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25 , R 26 and R 27 and b 1, b 2, b 3, b 4, b 5, b 6, b 7 and b 8 are the same as the contents described in the section “A. I omit it.
上記化合物B´の種類は、1種類のみであってもよく、2種類以上の組み合わせであってもよい。
The type of the compound B ′ may be only one type or a combination of two or more types.
3.その他
上記第2組成物は、化合物I-2及び化合物B´を有するものであるが、通常、その他の成分を含むものである。
このようなその他の成分としては、上記「C.組成物」の「2.その他の成分」の項に記載の内容等を挙げることができる。
上記その他の成分は、なかでも、樹脂成分を含むことが好ましく、特に、重合性化合物の重合物等の重合性基を有しない重合体を含むことが好ましい。上記第2組成物は、例えば、硬化物等に対して容易に紫外線吸収能等を付与できるとの効果を効果的に発揮できるからである。
なお、樹脂成分の種類は、1種類のみであってもよく、2種類以上を組み合わせて用いてもよい。 3. Others The above-mentioned second composition comprises the compound I-2 and the compound B ′, and usually comprises other components.
Examples of such other components include the contents described in the section "2. Other components" of the above "C. composition".
Among the above, the other components preferably include a resin component, and particularly preferably include a polymer having no polymerizable group such as a polymer of a polymerizable compound. This is because, for example, the second composition can effectively exert the effect of being able to easily impart the ultraviolet absorptivity and the like to a cured product and the like.
In addition, the number of kinds of resin components may be one, or two or more kinds may be used in combination.
上記第2組成物は、化合物I-2及び化合物B´を有するものであるが、通常、その他の成分を含むものである。
このようなその他の成分としては、上記「C.組成物」の「2.その他の成分」の項に記載の内容等を挙げることができる。
上記その他の成分は、なかでも、樹脂成分を含むことが好ましく、特に、重合性化合物の重合物等の重合性基を有しない重合体を含むことが好ましい。上記第2組成物は、例えば、硬化物等に対して容易に紫外線吸収能等を付与できるとの効果を効果的に発揮できるからである。
なお、樹脂成分の種類は、1種類のみであってもよく、2種類以上を組み合わせて用いてもよい。 3. Others The above-mentioned second composition comprises the compound I-2 and the compound B ′, and usually comprises other components.
Examples of such other components include the contents described in the section "2. Other components" of the above "C. composition".
Among the above, the other components preferably include a resin component, and particularly preferably include a polymer having no polymerizable group such as a polymer of a polymerizable compound. This is because, for example, the second composition can effectively exert the effect of being able to easily impart the ultraviolet absorptivity and the like to a cured product and the like.
In addition, the number of kinds of resin components may be one, or two or more kinds may be used in combination.
上記第2組成物は、溶剤、重合性化合物等を含み、塗工性を有するものであってもよく、その場合の粘度としては、上記「C.組成物」の項に記載の内容と同様とすることができる。
また、上記第2組成物は、重合性化合物の重合物を含む硬化物である場合、上記第2組成物の弾性率については、上記「D.硬化物」の項に記載の内容と同様とすることができる。 The second composition contains a solvent, a polymerizable compound, etc., and may have a coating property, and the viscosity in that case is the same as the content described in the above-mentioned "C. composition". It can be done.
When the second composition is a cured product containing a polymer of a polymerizable compound, the elastic modulus of the second composition is the same as the content described in the section "D. cured product". can do.
また、上記第2組成物は、重合性化合物の重合物を含む硬化物である場合、上記第2組成物の弾性率については、上記「D.硬化物」の項に記載の内容と同様とすることができる。 The second composition contains a solvent, a polymerizable compound, etc., and may have a coating property, and the viscosity in that case is the same as the content described in the above-mentioned "C. composition". It can be done.
When the second composition is a cured product containing a polymer of a polymerizable compound, the elastic modulus of the second composition is the same as the content described in the section "D. cured product". can do.
上記第2組成物の用途等については、上記「D.硬化物」の項に記載の内容と同様とすることができる。
About the use etc. of the said 2nd composition, it can be made to be the same as that of the content as described in the term of said "D. hardened | cured material".
F.硬化物の製造方法
次に、本発明の硬化物の製造方法について説明する。
本発明の硬化物の製造方法は、上述の化合物I-1と重合性化合物とを含む組成物を硬化させて硬化物を形成する工程と、上記硬化物に対して光を照射して、上記化合物に含まれる光脱離基Bを脱離する工程とを有するものである。 F. Method of Producing Cured Product Next, a method of producing the cured product of the present invention will be described.
The method for producing a cured product of the present invention comprises the steps of curing the composition containing the compound I-1 and the polymerizable compound described above to form a cured product, and irradiating the cured product with light. And d) removing the photoleaving group B contained in the compound.
次に、本発明の硬化物の製造方法について説明する。
本発明の硬化物の製造方法は、上述の化合物I-1と重合性化合物とを含む組成物を硬化させて硬化物を形成する工程と、上記硬化物に対して光を照射して、上記化合物に含まれる光脱離基Bを脱離する工程とを有するものである。 F. Method of Producing Cured Product Next, a method of producing the cured product of the present invention will be described.
The method for producing a cured product of the present invention comprises the steps of curing the composition containing the compound I-1 and the polymerizable compound described above to form a cured product, and irradiating the cured product with light. And d) removing the photoleaving group B contained in the compound.
本発明によれば、上記製造方法は、上述の組成物を用い、且つ、上記工程を有することにより、硬化が容易であり、また、容易に紫外線吸収能等を付与できる。
According to the present invention, by using the above-mentioned composition and having the above-described steps, the above-mentioned production method can be easily cured and can easily impart ultraviolet absorbing ability and the like.
本発明の製造方法は、硬化物を形成する工程及び脱離する工程を含むものである。
以下、本発明の製造方法の各工程について詳細に説明する。 The production method of the present invention includes the steps of forming a cured product and removing it.
Hereinafter, each process of the manufacturing method of this invention is demonstrated in detail.
以下、本発明の製造方法の各工程について詳細に説明する。 The production method of the present invention includes the steps of forming a cured product and removing it.
Hereinafter, each process of the manufacturing method of this invention is demonstrated in detail.
1.硬化物を形成する工程
上記硬化物を形成する工程は、上述の組成物の硬化物を形成する工程である。 1. Step of forming a cured product The step of forming the cured product is a step of forming a cured product of the composition described above.
上記硬化物を形成する工程は、上述の組成物の硬化物を形成する工程である。 1. Step of forming a cured product The step of forming the cured product is a step of forming a cured product of the composition described above.
本工程における組成物の硬化物を形成する方法としては、所望の硬度の硬化物を形成可能な方法であればよく、組成物に含まれる成分に応じて異なるものである。
上記硬化方法は、例えば、組成物が、重合性化合物と共に重合開始剤として光重合開始剤を含む場合には、組成物に対して光照射を行い、重合性化合物同士を重合する方法を用いることができる。
組成物に照射される光としては、波長300nm~450nmの光を含むものとすることができる。
上記光照射の光源としては、例えば、超高圧水銀、水銀蒸気アーク、カーボンアーク、キセノンアーク等を挙げることができる。
上記照射される光としては、レーザー光を用いてもよい。レーザー光としては、波長340~430nmの光を含むものを用いることができる。
レーザー光の光源としては、アルゴンイオンレーザー、ヘリウムネオンレーザー、YAGレーザー、及び半導体レーザー等の可視から赤外領域の光を発するものも用いることができる。
なお、これらのレーザーを使用する場合には、上記組成物は、可視から赤外の当該領域を吸収する増感色素を含むことができる。 As a method of forming the hardened | cured material of the composition in this process, what is necessary is just a method which can form the hardened | cured material of desired hardness, and it changes according to the component contained in a composition.
For example, when the composition contains a photopolymerization initiator as a polymerization initiator together with a polymerizable compound, the curing method uses a method of irradiating the composition with light to polymerize the polymerizable compounds. Can.
The light irradiated to the composition may include light with a wavelength of 300 nm to 450 nm.
As a light source of the said light irradiation, an ultra-high pressure mercury, a mercury vapor arc, a carbon arc, a xenon arc etc. can be mentioned, for example.
Laser light may be used as the light to be irradiated. As the laser light, one containing light with a wavelength of 340 to 430 nm can be used.
As a light source of laser light, those emitting light in the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser can also be used.
In addition, when using these lasers, the said composition can contain the sensitizing dye which absorbs the said area | region of visible to infrared.
上記硬化方法は、例えば、組成物が、重合性化合物と共に重合開始剤として光重合開始剤を含む場合には、組成物に対して光照射を行い、重合性化合物同士を重合する方法を用いることができる。
組成物に照射される光としては、波長300nm~450nmの光を含むものとすることができる。
上記光照射の光源としては、例えば、超高圧水銀、水銀蒸気アーク、カーボンアーク、キセノンアーク等を挙げることができる。
上記照射される光としては、レーザー光を用いてもよい。レーザー光としては、波長340~430nmの光を含むものを用いることができる。
レーザー光の光源としては、アルゴンイオンレーザー、ヘリウムネオンレーザー、YAGレーザー、及び半導体レーザー等の可視から赤外領域の光を発するものも用いることができる。
なお、これらのレーザーを使用する場合には、上記組成物は、可視から赤外の当該領域を吸収する増感色素を含むことができる。 As a method of forming the hardened | cured material of the composition in this process, what is necessary is just a method which can form the hardened | cured material of desired hardness, and it changes according to the component contained in a composition.
For example, when the composition contains a photopolymerization initiator as a polymerization initiator together with a polymerizable compound, the curing method uses a method of irradiating the composition with light to polymerize the polymerizable compounds. Can.
The light irradiated to the composition may include light with a wavelength of 300 nm to 450 nm.
As a light source of the said light irradiation, an ultra-high pressure mercury, a mercury vapor arc, a carbon arc, a xenon arc etc. can be mentioned, for example.
Laser light may be used as the light to be irradiated. As the laser light, one containing light with a wavelength of 340 to 430 nm can be used.
As a light source of laser light, those emitting light in the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser can also be used.
In addition, when using these lasers, the said composition can contain the sensitizing dye which absorbs the said area | region of visible to infrared.
上記照射される光の合計光量としては、光脱離基Bの脱離を抑制できるものであることが好ましく、例えば、1000mJ/cm2未満とすることができ、800mJ/cm2以下とすることができ、500mJ/cm2以下とすることができる。
The total light quantity of the irradiated light is preferably one that can suppress the detachment of the photoleaving group B, and can be, for example, less than 1000 mJ / cm 2 and not more than 800 mJ / cm 2. And can be 500 mJ / cm 2 or less.
上記硬化方法は、例えば、組成物が、重合性化合物と共に重合開始剤として熱重合開始剤を含む場合には、組成物に対して加熱処理を行い、重合性化合物同士を重合する方法を用いることができる。
加熱温度としては、上記組成物を安定的に硬化できるものであればよく、60℃以上、好ましくは100℃以上300℃以下とすることができる。
なお、加熱温度は、組成物の塗膜表面の温度とすることができる。
加熱時間としては、10秒~3時間程度行うことができる。 When the composition contains a thermal polymerization initiator as a polymerization initiator together with a polymerizable compound, for example, the above curing method uses a method of subjecting the composition to a heat treatment to polymerize the polymerizable compounds. Can.
The heating temperature may be any temperature as long as the composition can be cured stably, and can be 60 ° C. or more, preferably 100 ° C. or more and 300 ° C. or less.
In addition, heating temperature can be made into the temperature of the coating-film surface of a composition.
The heating time can be about 10 seconds to 3 hours.
加熱温度としては、上記組成物を安定的に硬化できるものであればよく、60℃以上、好ましくは100℃以上300℃以下とすることができる。
なお、加熱温度は、組成物の塗膜表面の温度とすることができる。
加熱時間としては、10秒~3時間程度行うことができる。 When the composition contains a thermal polymerization initiator as a polymerization initiator together with a polymerizable compound, for example, the above curing method uses a method of subjecting the composition to a heat treatment to polymerize the polymerizable compounds. Can.
The heating temperature may be any temperature as long as the composition can be cured stably, and can be 60 ° C. or more, preferably 100 ° C. or more and 300 ° C. or less.
In addition, heating temperature can be made into the temperature of the coating-film surface of a composition.
The heating time can be about 10 seconds to 3 hours.
上記硬化方法の種類は、1種類のみを含むものであってもよく、2種類以上を含むものであってもよい。
The type of the curing method may include only one type, or may include two or more types.
本工程に用いられる組成物は、上記化合物I-1と、重合性化合物と、を含むものである。
また、上記組成物は、上記化合物I-1及び重合性化合物以外のその他の成分を含むものであってもよい。
このような組成物の各成分の内容については、上記「C.組成物」の「2.その他の成分」の項に記載の内容と同様とすることができるため、ここでの説明は省略する。 The composition used in this step contains the compound I-1 and a polymerizable compound.
In addition, the composition may include other components other than the compound I-1 and the polymerizable compound.
About the content of each component of such a composition, since it can be made to be the same as the content as described in the item of "2. other components" of the above-mentioned "C. composition", explanation here is omitted. .
また、上記組成物は、上記化合物I-1及び重合性化合物以外のその他の成分を含むものであってもよい。
このような組成物の各成分の内容については、上記「C.組成物」の「2.その他の成分」の項に記載の内容と同様とすることができるため、ここでの説明は省略する。 The composition used in this step contains the compound I-1 and a polymerizable compound.
In addition, the composition may include other components other than the compound I-1 and the polymerizable compound.
About the content of each component of such a composition, since it can be made to be the same as the content as described in the item of "2. other components" of the above-mentioned "C. composition", explanation here is omitted. .
2.脱離する工程
上記脱離する工程は、上記化合物I-1に含まれる光脱離基Bを脱離する工程である。
上記化合物I-1に含まれる光脱離基Bを脱離する方法としては、上記硬化物に対して光照射する方法であればよい。
硬化物に対して照射される光及びその合計光量としては、光脱離基Bを脱離可能なものであれば特に限定されるものではないが、上記「A.化合物」の「1.光脱離基B」の項に記載の内容と同様とすることができる。
なお、光照射の光源としては、照射される光の波長に応じて適宜選択されるものであるが、例えば、上記「1.硬化物を形成する工程」の項に記載の内容と同様とすることができる。 2. Step of Leaving The step of leaving is a step of leaving the photoleaving group B contained in the compound I-1.
As a method of removing the photoleaving group B contained in the compound I-1, any method may be used as long as the cured product is irradiated with light.
The light irradiated to the cured product and the total light amount thereof are not particularly limited as long as the light leaving group B can be eliminated, but the light of “1. light of the above-mentioned“ A. The same contents as those described in the section of "Leaving group B" can be adopted.
In addition, as a light source of light irradiation, although it is suitably selected according to the wavelength of the light irradiated, it shall be the same as the content as described in the term of said "1. Process of forming hardened material", for example. be able to.
上記脱離する工程は、上記化合物I-1に含まれる光脱離基Bを脱離する工程である。
上記化合物I-1に含まれる光脱離基Bを脱離する方法としては、上記硬化物に対して光照射する方法であればよい。
硬化物に対して照射される光及びその合計光量としては、光脱離基Bを脱離可能なものであれば特に限定されるものではないが、上記「A.化合物」の「1.光脱離基B」の項に記載の内容と同様とすることができる。
なお、光照射の光源としては、照射される光の波長に応じて適宜選択されるものであるが、例えば、上記「1.硬化物を形成する工程」の項に記載の内容と同様とすることができる。 2. Step of Leaving The step of leaving is a step of leaving the photoleaving group B contained in the compound I-1.
As a method of removing the photoleaving group B contained in the compound I-1, any method may be used as long as the cured product is irradiated with light.
The light irradiated to the cured product and the total light amount thereof are not particularly limited as long as the light leaving group B can be eliminated, but the light of “1. light of the above-mentioned“ A. The same contents as those described in the section of "Leaving group B" can be adopted.
In addition, as a light source of light irradiation, although it is suitably selected according to the wavelength of the light irradiated, it shall be the same as the content as described in the term of said "1. Process of forming hardened material", for example. be able to.
本工程における硬化物の温度としては、硬化物や硬化物を支持する基材の耐熱性等に応じて適宜設定することができるが、例えば、200℃以下とすることができ、0℃以上、150℃以下であることが好ましく、なかでも、0℃以上100℃以下であることが好ましい。上記温度が上述の範囲であることで、光脱離基Bの脱離が容易となるからである。また、その結果、例えば、硬化物及び基材等のその周辺部材に対して加熱によるダメージの少ないものとすることができるからである。
なお、上記硬化物の温度は、硬化物表面の温度である。 The temperature of the cured product in this step can be appropriately set according to the heat resistance and the like of the cured product and the substrate supporting the cured product, but can be, for example, 200 ° C. or less, 0 ° C. or more, The temperature is preferably 150 ° C. or less, and more preferably 0 ° C. or more and 100 ° C. or less. It is because detachment | desorption of the photoleaving group B becomes easy because the said temperature is the above-mentioned range. Also, as a result, for example, the cured product and its peripheral members such as the substrate can be less damaged by heating.
The temperature of the cured product is the temperature of the surface of the cured product.
なお、上記硬化物の温度は、硬化物表面の温度である。 The temperature of the cured product in this step can be appropriately set according to the heat resistance and the like of the cured product and the substrate supporting the cured product, but can be, for example, 200 ° C. or less, 0 ° C. or more, The temperature is preferably 150 ° C. or less, and more preferably 0 ° C. or more and 100 ° C. or less. It is because detachment | desorption of the photoleaving group B becomes easy because the said temperature is the above-mentioned range. Also, as a result, for example, the cured product and its peripheral members such as the substrate can be less damaged by heating.
The temperature of the cured product is the temperature of the surface of the cured product.
3.その他の工程
上記製造方法は、硬化物を形成する工程及び脱離する工程を含むものであるが、必要に応じてその他の工程を含むものであってもよい。
上記その他の工程としては、例えば、上記組成物を基材上に塗布する工程等を挙げることができる。
組成物を塗布する方法としては、スピンコーター、ロールコーター、バーコーター、ダイコーター、カーテンコーター、各種の印刷、浸漬等の公知の方法を用いることができる。
上記基材としては、硬化物の用途等に応じて適宜設定することができ、ソーダガラス、石英ガラス、半導体基板、金属、紙、プラスチック等を含むものを挙げることができる。
また、上記硬化物は、基材上で形成された後、基材から剥離して用いても、基材から他の被着体に転写して用いてもよい。 3. Other Steps The above-mentioned production method includes the step of forming a cured product and the step of desorbing, but may include other steps as required.
As said other process, the process of apply | coating the said composition on a base material etc. can be mentioned, for example.
As a method of applying the composition, known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like can be used.
The substrate can be appropriately set depending on the application of the cured product and the like, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics and the like.
In addition, after the cured product is formed on a substrate, it may be used after being peeled off from the substrate or may be transferred from the substrate to another adherend.
上記製造方法は、硬化物を形成する工程及び脱離する工程を含むものであるが、必要に応じてその他の工程を含むものであってもよい。
上記その他の工程としては、例えば、上記組成物を基材上に塗布する工程等を挙げることができる。
組成物を塗布する方法としては、スピンコーター、ロールコーター、バーコーター、ダイコーター、カーテンコーター、各種の印刷、浸漬等の公知の方法を用いることができる。
上記基材としては、硬化物の用途等に応じて適宜設定することができ、ソーダガラス、石英ガラス、半導体基板、金属、紙、プラスチック等を含むものを挙げることができる。
また、上記硬化物は、基材上で形成された後、基材から剥離して用いても、基材から他の被着体に転写して用いてもよい。 3. Other Steps The above-mentioned production method includes the step of forming a cured product and the step of desorbing, but may include other steps as required.
As said other process, the process of apply | coating the said composition on a base material etc. can be mentioned, for example.
As a method of applying the composition, known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like can be used.
The substrate can be appropriately set depending on the application of the cured product and the like, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics and the like.
In addition, after the cured product is formed on a substrate, it may be used after being peeled off from the substrate or may be transferred from the substrate to another adherend.
4.その他
上記製造方法により製造される硬化物及び用途等については、上記「D.硬化物」の項に記載の内容と同様とすることができる。 4. Others The cured product produced according to the above-mentioned production method, the use and the like can be the same as the contents described in the section of "D.
上記製造方法により製造される硬化物及び用途等については、上記「D.硬化物」の項に記載の内容と同様とすることができる。 4. Others The cured product produced according to the above-mentioned production method, the use and the like can be the same as the contents described in the section of "D.
本発明は、上記実施形態に限定されるものではない。上記実施形態は、例示であり、本発明に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
The present invention is not limited to the above embodiment. The above embodiment is an exemplification, has substantially the same configuration as the technical idea described in the present invention, and exhibits the same operation and effect as that of the technical scope of the present invention. Is included in
以下、実施例等を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
[実施例1]
下記のスキーム1中のフェノール化合物(化合物I-2)0.005mol、炭酸カリウム0.005mol及びDMF12gを混合し、窒素雰囲気下、室温でo-ニトロベンジルクロリド0.0075molを滴下し、80℃で2時間撹拌し、下記反応により化合物I-1に該当する化合物I-1-2を得た。反応液に酢酸エチル50g、イオン交換水50gを加えて油水分離を行った。有機層を無水硫酸ナトリウムで乾燥後、溶媒を留去し、メタノールで晶析を行った。得られた白色固体を45℃で2時間減圧乾燥させ、目的物(化合物I-1-2)を得た。得られた白色固体が目的物であることは、H-NMR、IRにて確認した。 Example 1
0.005 mol of the phenol compound (compound I-2) in scheme 1 below, 0.005 mol of potassium carbonate and 12 g of DMF are mixed, and 0.0075 mol of o-nitrobenzyl chloride is added dropwise at room temperature under a nitrogen atmosphere, and at 80 ° C. The mixture was stirred for 2 hours, and the following reaction gave compound I-1-2 corresponding to compound I-1. Oil-water separation was performed by adding 50 g of ethyl acetate and 50 g of ion-exchanged water to the reaction solution. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and crystallization was performed with methanol. The obtained white solid was dried under reduced pressure at 45 ° C. for 2 hours to obtain the desired product (Compound I-1-2). It was confirmed by H-NMR and IR that the obtained white solid was the desired product.
下記のスキーム1中のフェノール化合物(化合物I-2)0.005mol、炭酸カリウム0.005mol及びDMF12gを混合し、窒素雰囲気下、室温でo-ニトロベンジルクロリド0.0075molを滴下し、80℃で2時間撹拌し、下記反応により化合物I-1に該当する化合物I-1-2を得た。反応液に酢酸エチル50g、イオン交換水50gを加えて油水分離を行った。有機層を無水硫酸ナトリウムで乾燥後、溶媒を留去し、メタノールで晶析を行った。得られた白色固体を45℃で2時間減圧乾燥させ、目的物(化合物I-1-2)を得た。得られた白色固体が目的物であることは、H-NMR、IRにて確認した。 Example 1
0.005 mol of the phenol compound (compound I-2) in scheme 1 below, 0.005 mol of potassium carbonate and 12 g of DMF are mixed, and 0.0075 mol of o-nitrobenzyl chloride is added dropwise at room temperature under a nitrogen atmosphere, and at 80 ° C. The mixture was stirred for 2 hours, and the following reaction gave compound I-1-2 corresponding to compound I-1. Oil-water separation was performed by adding 50 g of ethyl acetate and 50 g of ion-exchanged water to the reaction solution. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and crystallization was performed with methanol. The obtained white solid was dried under reduced pressure at 45 ° C. for 2 hours to obtain the desired product (Compound I-1-2). It was confirmed by H-NMR and IR that the obtained white solid was the desired product.
[実施例2~7]
o-ニトロベンジルクロリドを変更した以外は、実施例1と同様にして下記化合物I-1-3、I-1-40、I-1-32、I-1-35、I-1-28、I-1-34を得た。具体的には、下記の方法で実施例2~7の化合物I-1-3、I-1-40、I-1-32、I-1-35、I-1-28及び1-34を製造した。
また、実施例2~7で得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例2]
2-エチルニトロベンゼンに対して、1.1当量のN-ブロモスクシンイミドと0.01当量のAIBNを使用し、クロロベンゼン溶媒中、90℃で4時間加熱撹拌した。酢酸エチルで油水分離し、水洗後、シリカカラムにて精製し、ベンジルブロマイド化合物を得た。このベンジルブロマイド化合物をo-ニトロベンジルクロリドの代わりに用いた以外は実施例1と同様にして、化合物I-1-3を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例3]
2-エチルニトロベンゼンの代わりに、4-クロロ-2-ニトロトルエンを用いた以外は実施例2と同様にして、化合物I-1-40を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例4]
o-ニトロベンジルクロリドの代わりに4'-メトキシフェナシルブロミドを用いた以外は実施例1と同様にして、化合物I-1-32を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例5]
o-ニトロベンジルクロリドの代わりに2-ブロモ-2-フェニルアセトフェノンを用いた以外は実施例1と同様にして、化合物I-1-35を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例6]
o-ニトロベンジルクロリドの代わりに2-ブロモ-2’-ニトロアセトフェノンを用いた以外は実施例1と同様にして、化合物I-1-28を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例7]
o-ニトロベンジルクロリドの代わりに4-ブロモメチル-7-メトキシクマリンを用いた以外は実施例1と同様にして、化合物I-1-34を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。 [Examples 2 to 7]
The following compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28, in the same manner as in Example 1, except that o-nitrobenzyl chloride was changed Obtained I-1-34. Specifically, compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28 and 1-34 of Examples 2-7 are prepared by the following method. Manufactured.
In addition, it was confirmed by H-NMR that the white solid obtained in Examples 2 to 7 was the desired product.
Example 2
The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN with respect to 2-ethylnitrobenzene. Oil-water separation was carried out with ethyl acetate, and after washing with water, purification was carried out using a silica column to obtain a benzyl bromide compound. Compound I-1-3 was obtained in the same manner as in Example 1 except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 3]
Compound I-1-40 was obtained in the same manner as in Example 2 except that 4-chloro-2-nitrotoluene was used instead of 2-ethylnitrobenzene. It was confirmed by H-NMR that the obtained white solid was the desired product.
Example 4
Compound I-1-32 was obtained in the same manner as in Example 1 except that 4'-methoxyphenacyl bromide was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 5]
Compound I-1-35 was obtained in the same manner as in Example 1 except that 2-bromo-2-phenylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 6]
Compound I-1-28 was obtained in the same manner as in Example 1 except that 2-bromo-2'-nitroacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 7]
Compound I-1-34 was obtained in the same manner as in Example 1 except that 4-bromomethyl-7-methoxycoumarin was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
o-ニトロベンジルクロリドを変更した以外は、実施例1と同様にして下記化合物I-1-3、I-1-40、I-1-32、I-1-35、I-1-28、I-1-34を得た。具体的には、下記の方法で実施例2~7の化合物I-1-3、I-1-40、I-1-32、I-1-35、I-1-28及び1-34を製造した。
また、実施例2~7で得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例2]
2-エチルニトロベンゼンに対して、1.1当量のN-ブロモスクシンイミドと0.01当量のAIBNを使用し、クロロベンゼン溶媒中、90℃で4時間加熱撹拌した。酢酸エチルで油水分離し、水洗後、シリカカラムにて精製し、ベンジルブロマイド化合物を得た。このベンジルブロマイド化合物をo-ニトロベンジルクロリドの代わりに用いた以外は実施例1と同様にして、化合物I-1-3を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例3]
2-エチルニトロベンゼンの代わりに、4-クロロ-2-ニトロトルエンを用いた以外は実施例2と同様にして、化合物I-1-40を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例4]
o-ニトロベンジルクロリドの代わりに4'-メトキシフェナシルブロミドを用いた以外は実施例1と同様にして、化合物I-1-32を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例5]
o-ニトロベンジルクロリドの代わりに2-ブロモ-2-フェニルアセトフェノンを用いた以外は実施例1と同様にして、化合物I-1-35を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例6]
o-ニトロベンジルクロリドの代わりに2-ブロモ-2’-ニトロアセトフェノンを用いた以外は実施例1と同様にして、化合物I-1-28を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例7]
o-ニトロベンジルクロリドの代わりに4-ブロモメチル-7-メトキシクマリンを用いた以外は実施例1と同様にして、化合物I-1-34を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。 [Examples 2 to 7]
The following compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28, in the same manner as in Example 1, except that o-nitrobenzyl chloride was changed Obtained I-1-34. Specifically, compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28 and 1-34 of Examples 2-7 are prepared by the following method. Manufactured.
In addition, it was confirmed by H-NMR that the white solid obtained in Examples 2 to 7 was the desired product.
Example 2
The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN with respect to 2-ethylnitrobenzene. Oil-water separation was carried out with ethyl acetate, and after washing with water, purification was carried out using a silica column to obtain a benzyl bromide compound. Compound I-1-3 was obtained in the same manner as in Example 1 except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 3]
Compound I-1-40 was obtained in the same manner as in Example 2 except that 4-chloro-2-nitrotoluene was used instead of 2-ethylnitrobenzene. It was confirmed by H-NMR that the obtained white solid was the desired product.
Example 4
Compound I-1-32 was obtained in the same manner as in Example 1 except that 4'-methoxyphenacyl bromide was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 5]
Compound I-1-35 was obtained in the same manner as in Example 1 except that 2-bromo-2-phenylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 6]
Compound I-1-28 was obtained in the same manner as in Example 1 except that 2-bromo-2'-nitroacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 7]
Compound I-1-34 was obtained in the same manner as in Example 1 except that 4-bromomethyl-7-methoxycoumarin was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[実施例8]
4-メトキシ-2-ニトロトルエンに対して、1.1当量のN-ブロモスクシンイミドと0.01当量のAIBNを使用し、クロロベンゼン溶媒中で90℃で4時間加熱撹拌した。酢酸エチルで油水分離し、水洗後、シリカカラムにて精製し、対応するベンジルブロマイド化合物を得た。このベンジルブロマイド化合物をo-ニトロベンジルクロリドの代わりに用いた以外は実施例1と同様にして、化合物I-1-4を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例9]
4-メトキシ-2-ニトロトルエンの代わりに3-クロロ-2-ニトロトルエンを用いた以外は実施例8と同様にして、化合物I-1-41を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例10]
4-メトキシ-2-ニトロトルエンの代わりに3-メトキシ-2-ニトロトルエンを用いた以外は実施例8と同様にして、化合物I-1-42を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例11]
4-メトキシ-2-ニトロトルエンの代わりに3-メトキシ-2-ニトロ-6-ブロモトルエンを用いた以外は実施例8と同様にして、化合物I-1-43を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例12]
o-ニトロベンジルクロリドの代わりに2-ブロモ-2‘-メチルアセトフェノンを用いた以外は実施例1と同様にして、化合物I-1-44を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。 [Example 8]
The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN based on 4-methoxy-2-nitrotoluene. After oil-water separation with ethyl acetate and washing with water, purification with a silica column gave the corresponding benzyl bromide compound. Compound I-1-4 was obtained in the same manner as in Example 1 except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 9]
Compound I-1-41 was obtained in the same manner as in Example 8 except that 3-chloro-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 10]
Compound I-1-42 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 11]
Compound I-1-43 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitro-6-bromotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 12]
Compound I-1-44 was obtained in the same manner as in Example 1 except that 2-bromo-2′-methylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
4-メトキシ-2-ニトロトルエンに対して、1.1当量のN-ブロモスクシンイミドと0.01当量のAIBNを使用し、クロロベンゼン溶媒中で90℃で4時間加熱撹拌した。酢酸エチルで油水分離し、水洗後、シリカカラムにて精製し、対応するベンジルブロマイド化合物を得た。このベンジルブロマイド化合物をo-ニトロベンジルクロリドの代わりに用いた以外は実施例1と同様にして、化合物I-1-4を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例9]
4-メトキシ-2-ニトロトルエンの代わりに3-クロロ-2-ニトロトルエンを用いた以外は実施例8と同様にして、化合物I-1-41を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例10]
4-メトキシ-2-ニトロトルエンの代わりに3-メトキシ-2-ニトロトルエンを用いた以外は実施例8と同様にして、化合物I-1-42を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例11]
4-メトキシ-2-ニトロトルエンの代わりに3-メトキシ-2-ニトロ-6-ブロモトルエンを用いた以外は実施例8と同様にして、化合物I-1-43を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。
[実施例12]
o-ニトロベンジルクロリドの代わりに2-ブロモ-2‘-メチルアセトフェノンを用いた以外は実施例1と同様にして、化合物I-1-44を得た。得られた白色固体が目的物であることは、H-NMRにて確認した。 [Example 8]
The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN based on 4-methoxy-2-nitrotoluene. After oil-water separation with ethyl acetate and washing with water, purification with a silica column gave the corresponding benzyl bromide compound. Compound I-1-4 was obtained in the same manner as in Example 1 except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 9]
Compound I-1-41 was obtained in the same manner as in Example 8 except that 3-chloro-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 10]
Compound I-1-42 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 11]
Compound I-1-43 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitro-6-bromotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
[Example 12]
Compound I-1-44 was obtained in the same manner as in Example 1 except that 2-bromo-2′-methylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
[実施例13]
o-ニトロベンジルクロリドの代わりに4-(2-ブロモアセチル)フェニルt-ブチルカーボネートを用いた以外は実施例1と同様にして中間体化合物を得た。該中間体化合物0.0035molを酢酸エチル5mlに溶解させ、4M HCl酢酸エチル溶液5mL入れ、50℃で10時間加熱撹拌した。反応液の溶媒を留去し、シリカカラム(酢酸エチル:ヘキサン=1:2)にて単離し、目的物(化合物I-1-45)を得た。得られた白色固体が目的物であることを、H-NMRで確認した。
[実施例14]
フェノール化合物(スキーム1中のフェノール化合物)0.004molをピリジン40mLに溶解させ、NPPOC-Cl(2-(2-ニトロフェニル)プロピルクロロホルメ-ト)0.006molを滴下し、6時間室温で撹拌した。反応液に酢酸エチル200g、イオン交換水50gを加えて油水分離を行った。有機層を希塩酸で2回、イオン交換水で3回洗浄し、溶媒を留去し、シリカカラム(酢酸エチル:ヘキサン=1:4)にて単離した。得られた白色固体をヘキサンで分散後、45℃で2時間減圧乾燥させ、目的物(化合物I-1-46)を得た。得られた白色固体が目的物であることを、H-NMRにて確認した。
[実施例15~17]
フェノール化合物として下記式(1)~(3)の化合物を用いた以外は、実施例1と同様にして下記化合物I-1-8、I-1-47及びI-1-48を得た。 [Example 13]
An intermediate compound was obtained in the same manner as in Example 1 except that 4- (2-bromoacetyl) phenyl t-butyl carbonate was used instead of o-nitrobenzyl chloride. The intermediate compound (0.0035 mol) was dissolved in 5 ml of ethyl acetate, 5 mL of 4 M HCl ethyl acetate solution was added, and the mixture was heated and stirred at 50 ° C. for 10 hours. The solvent of the reaction mixture was distilled off, and the residue was isolated on a silica column (ethyl acetate: hexane = 1: 2) to obtain the desired product (compound I-1-45). It was confirmed by H-NMR that the obtained white solid was the desired product.
Example 14
Dissolve 0.004 mol of a phenol compound (phenol compound in scheme 1) in 40 mL of pyridine, add 0.006 mol of NPPOC-Cl (2- (2-nitrophenyl) propyl chloroformate) dropwise, and stir for 6 hours at room temperature It stirred. 200 g of ethyl acetate and 50 g of ion-exchanged water were added to the reaction solution to conduct oil-water separation. The organic layer was washed twice with dilute hydrochloric acid and three times with ion-exchanged water, the solvent was evaporated, and the residue was isolated on a silica column (ethyl acetate: hexane = 1: 4). The obtained white solid was dispersed in hexane and then dried under reduced pressure at 45 ° C. for 2 hours to obtain the desired product (Compound I-1-46). It was confirmed by H-NMR that the obtained white solid was the desired product.
[Examples 15 to 17]
The following compounds I-1-8, I-1-47 and I-1-48 were obtained in the same manner as in Example 1 except that compounds of the following formulas (1) to (3) were used as the phenol compound.
o-ニトロベンジルクロリドの代わりに4-(2-ブロモアセチル)フェニルt-ブチルカーボネートを用いた以外は実施例1と同様にして中間体化合物を得た。該中間体化合物0.0035molを酢酸エチル5mlに溶解させ、4M HCl酢酸エチル溶液5mL入れ、50℃で10時間加熱撹拌した。反応液の溶媒を留去し、シリカカラム(酢酸エチル:ヘキサン=1:2)にて単離し、目的物(化合物I-1-45)を得た。得られた白色固体が目的物であることを、H-NMRで確認した。
[実施例14]
フェノール化合物(スキーム1中のフェノール化合物)0.004molをピリジン40mLに溶解させ、NPPOC-Cl(2-(2-ニトロフェニル)プロピルクロロホルメ-ト)0.006molを滴下し、6時間室温で撹拌した。反応液に酢酸エチル200g、イオン交換水50gを加えて油水分離を行った。有機層を希塩酸で2回、イオン交換水で3回洗浄し、溶媒を留去し、シリカカラム(酢酸エチル:ヘキサン=1:4)にて単離した。得られた白色固体をヘキサンで分散後、45℃で2時間減圧乾燥させ、目的物(化合物I-1-46)を得た。得られた白色固体が目的物であることを、H-NMRにて確認した。
[実施例15~17]
フェノール化合物として下記式(1)~(3)の化合物を用いた以外は、実施例1と同様にして下記化合物I-1-8、I-1-47及びI-1-48を得た。 [Example 13]
An intermediate compound was obtained in the same manner as in Example 1 except that 4- (2-bromoacetyl) phenyl t-butyl carbonate was used instead of o-nitrobenzyl chloride. The intermediate compound (0.0035 mol) was dissolved in 5 ml of ethyl acetate, 5 mL of 4 M HCl ethyl acetate solution was added, and the mixture was heated and stirred at 50 ° C. for 10 hours. The solvent of the reaction mixture was distilled off, and the residue was isolated on a silica column (ethyl acetate: hexane = 1: 2) to obtain the desired product (compound I-1-45). It was confirmed by H-NMR that the obtained white solid was the desired product.
Example 14
Dissolve 0.004 mol of a phenol compound (phenol compound in scheme 1) in 40 mL of pyridine, add 0.006 mol of NPPOC-Cl (2- (2-nitrophenyl) propyl chloroformate) dropwise, and stir for 6 hours at room temperature It stirred. 200 g of ethyl acetate and 50 g of ion-exchanged water were added to the reaction solution to conduct oil-water separation. The organic layer was washed twice with dilute hydrochloric acid and three times with ion-exchanged water, the solvent was evaporated, and the residue was isolated on a silica column (ethyl acetate: hexane = 1: 4). The obtained white solid was dispersed in hexane and then dried under reduced pressure at 45 ° C. for 2 hours to obtain the desired product (Compound I-1-46). It was confirmed by H-NMR that the obtained white solid was the desired product.
[Examples 15 to 17]
The following compounds I-1-8, I-1-47 and I-1-48 were obtained in the same manner as in Example 1 except that compounds of the following formulas (1) to (3) were used as the phenol compound.
[評価]
実施例1、2、5~9、12~14及び16(化合物I-1-2、I-1-3、I-1-35、I-1-28、I-1-34、I-1-4、I-1-41、I-1-44、I-1-45、I-1-46及びI-1-47)の0.01質量%アセトニトリル溶液を調製し、1cm角石英セルに入れた。超高圧水銀ランプUL750(HOYA製)を20mW/cm2に調整し、溶液で満たされた石英セルに100mJ/cm2、3000mJ/cm2、10000mJ/cm2の光量を照射した。
照射後の液を高速液体クロマトグラフィー(HPLC)にて、分析し、脱離率を以下の式から算出した。結果を下記表3に示す。
なお、HPLCによる分析では、化合物I-1に由来する230nmのピークが全て消失した場合に100%脱離したと仮定して算出した。
脱離率(%)=フェノール化合物(化合物I-2)/フェノール化合物(化合物I-2)+化合物I-1)×100 [Evaluation]
Examples 1, 2, 5 to 9, 12 to 14 and 16 (compounds I-1-2, I-1-3, I-1-35, I-1-28, I-1-34, I-1 Acetonitrile solution of 0.01 mass% was prepared into 1cm square quartz cell, and it was prepared. -4, I-1-41, I-1-44, I-1-45, I-1-46 and I-1-47) I put it in. Ultra-high pressure mercury lamp UL750 (manufactured by HOYA) was adjusted to 20 mW / cm 2, in a quartz cell filled with the solution was irradiated with light quantity of 100mJ / cm 2, 3000mJ / cm 2, 10000mJ / cm 2.
The liquid after irradiation was analyzed by high performance liquid chromatography (HPLC), and the desorption rate was calculated from the following equation. The results are shown in Table 3 below.
In the analysis by HPLC, calculation was made on the assumption that 100% desorption occurred when all the 230 nm peak derived from compound I-1 disappeared.
Elimination rate (%) = phenol compound (compound I-2) / phenol compound (compound I-2) + compound I-1) × 100
実施例1、2、5~9、12~14及び16(化合物I-1-2、I-1-3、I-1-35、I-1-28、I-1-34、I-1-4、I-1-41、I-1-44、I-1-45、I-1-46及びI-1-47)の0.01質量%アセトニトリル溶液を調製し、1cm角石英セルに入れた。超高圧水銀ランプUL750(HOYA製)を20mW/cm2に調整し、溶液で満たされた石英セルに100mJ/cm2、3000mJ/cm2、10000mJ/cm2の光量を照射した。
照射後の液を高速液体クロマトグラフィー(HPLC)にて、分析し、脱離率を以下の式から算出した。結果を下記表3に示す。
なお、HPLCによる分析では、化合物I-1に由来する230nmのピークが全て消失した場合に100%脱離したと仮定して算出した。
脱離率(%)=フェノール化合物(化合物I-2)/フェノール化合物(化合物I-2)+化合物I-1)×100 [Evaluation]
Examples 1, 2, 5 to 9, 12 to 14 and 16 (compounds I-1-2, I-1-3, I-1-35, I-1-28, I-1-34, I-1 Acetonitrile solution of 0.01 mass% was prepared into 1cm square quartz cell, and it was prepared. -4, I-1-41, I-1-44, I-1-45, I-1-46 and I-1-47) I put it in. Ultra-high pressure mercury lamp UL750 (manufactured by HOYA) was adjusted to 20 mW / cm 2, in a quartz cell filled with the solution was irradiated with light quantity of 100mJ / cm 2, 3000mJ / cm 2, 10000mJ / cm 2.
The liquid after irradiation was analyzed by high performance liquid chromatography (HPLC), and the desorption rate was calculated from the following equation. The results are shown in Table 3 below.
In the analysis by HPLC, calculation was made on the assumption that 100% desorption occurred when all the 230 nm peak derived from compound I-1 disappeared.
Elimination rate (%) = phenol compound (compound I-2) / phenol compound (compound I-2) + compound I-1) × 100
また、また、実施例1、2及び7(化合物I-1-2、I-1-3及びI-1-34)について、光照射前(0mJ/cm2)及び光照射後(10000mJ/cm2)に、波長250nm以上450nm以下の範囲の光の吸収スペクトルを確認した。その結果、光照射前と比較し、光照射後は、波長250nm以上450nm以下の範囲で長波長側の光を幅広く吸収できることが確認できた。また、最大吸収波長(nm)の測定結果を下記表3及び4に示す。
In addition, for Examples 1, 2 and 7 (Compounds I-1-2, I-1-3 and I-1-34), before (0 mJ / cm 2 ) and after (10 000 mJ / cm) light irradiation. In 2 ), the absorption spectrum of light in the wavelength range of 250 nm to 450 nm was confirmed. As a result, it was confirmed that light having a longer wavelength can be widely absorbed in a wavelength range of 250 nm or more and 450 nm or less after light irradiation, as compared to before light irradiation. The measurement results of the maximum absorption wavelength (nm) are shown in Tables 3 and 4 below.
表3及び4より、化合物I-1は、光照射により光脱離基Bが脱離することが確認できた。
また、表3より、上記化合物I-1は、光照射により、波長250nm以上450nm以下の範囲の幅広い波長の紫外線を効率的に吸収できることが確認できた。また、それに伴って、最大吸収波長の長波長側へのシフトが確認された。
以上より、化合物I-1は、光照射前ではフェノール性水酸基が光脱離基Bにより保護され紫外線吸収能が抑制されており、硬化阻害を抑制できるとともに、光照射により容易に紫外線吸収能を付与できることが確認できた。 From Tables 3 and 4, it was confirmed that compound I-1 was desorbed from the photoleaving group B by light irradiation.
Further, it was confirmed from Table 3 that the compound I-1 was able to efficiently absorb ultraviolet rays having a wide wavelength range of 250 nm or more and 450 nm or less by light irradiation. Moreover, along with that, the shift to the long wavelength side of the maximum absorption wavelength was confirmed.
From the above, compound I-1 has the phenolic hydroxyl group protected by the photoleaving group B before light irradiation and the ultraviolet ray absorbing ability is suppressed, so that the curing inhibition can be suppressed and the ultraviolet ray absorbing ability can be easily made by the light irradiation. It has been confirmed that it can be granted.
また、表3より、上記化合物I-1は、光照射により、波長250nm以上450nm以下の範囲の幅広い波長の紫外線を効率的に吸収できることが確認できた。また、それに伴って、最大吸収波長の長波長側へのシフトが確認された。
以上より、化合物I-1は、光照射前ではフェノール性水酸基が光脱離基Bにより保護され紫外線吸収能が抑制されており、硬化阻害を抑制できるとともに、光照射により容易に紫外線吸収能を付与できることが確認できた。 From Tables 3 and 4, it was confirmed that compound I-1 was desorbed from the photoleaving group B by light irradiation.
Further, it was confirmed from Table 3 that the compound I-1 was able to efficiently absorb ultraviolet rays having a wide wavelength range of 250 nm or more and 450 nm or less by light irradiation. Moreover, along with that, the shift to the long wavelength side of the maximum absorption wavelength was confirmed.
From the above, compound I-1 has the phenolic hydroxyl group protected by the photoleaving group B before light irradiation and the ultraviolet ray absorbing ability is suppressed, so that the curing inhibition can be suppressed and the ultraviolet ray absorbing ability can be easily made by the light irradiation. It has been confirmed that it can be granted.
下記表5に示す成分を、表5に示す割合で混合し、実施例18~20並びに比較例1及び2の組成物を得た。表5中の符号は下記の化合物を示す。なお、表中の数値は、質量部を表す。
The components shown in Table 5 below were mixed in the proportions shown in Table 5 to obtain the compositions of Examples 18 to 20 and Comparative Examples 1 and 2. The symbols in Table 5 indicate the following compounds. In addition, the numerical value in a table represents a mass part.
A-1:重合性化合物(新中村化学工業社製NKオリゴEA-1020(ビスフェノールA型エポキシアクリレート)
A-2:ラジカル重合性化合物(日本化薬社製カヤラッドDPHA(ジペンタエリスリトールペンタ及びヘキサアクリレートの混合物))
B-1:BASF社製イルガキュア907(ラジカル重合開始剤)
C-1:信越化学工業社製シランカップリング剤KBE-403
D-1:2-ブタノン
E-1:下記式(1)で表される化合物(紫外線吸収剤)
F-1:化合物I-1-3
F-2:化合物I-1-35
F-3:化合物I-1-47 A-1: Polymerizable compound (NK Oligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-2: Radically polymerizable compound (Kayarad DPHA (a mixture of dipentaerythritol penta and hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)
B-1: IRGACURE 907 manufactured by BASF (radical polymerization initiator)
C-1: Shine Chemical Industry Co., Ltd. silane coupling agent KBE-403
D-1: 2-butanone E-1: compound represented by the following formula (1) (ultraviolet absorber)
F-1: Compound I-1-3
F-2: Compound I-1-35
F-3: Compound I-1-47
A-2:ラジカル重合性化合物(日本化薬社製カヤラッドDPHA(ジペンタエリスリトールペンタ及びヘキサアクリレートの混合物))
B-1:BASF社製イルガキュア907(ラジカル重合開始剤)
C-1:信越化学工業社製シランカップリング剤KBE-403
D-1:2-ブタノン
E-1:下記式(1)で表される化合物(紫外線吸収剤)
F-1:化合物I-1-3
F-2:化合物I-1-35
F-3:化合物I-1-47 A-1: Polymerizable compound (NK Oligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-2: Radically polymerizable compound (Kayarad DPHA (a mixture of dipentaerythritol penta and hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)
B-1: IRGACURE 907 manufactured by BASF (radical polymerization initiator)
C-1: Shine Chemical Industry Co., Ltd. silane coupling agent KBE-403
D-1: 2-butanone E-1: compound represented by the following formula (1) (ultraviolet absorber)
F-1: Compound I-1-3
F-2: Compound I-1-35
F-3: Compound I-1-47
得られた実施例18~20並びに比較例1及び2の組成物の硬化性及び耐光性を下記の方法で評価した。
The curability and light resistance of the resulting compositions of Examples 18 to 20 and Comparative Examples 1 and 2 were evaluated by the following methods.
[硬化性]
実施例18~20並びに比較例1及び2の組成物をそれぞれ、PETフィルムにバーコーターで約3μmの厚さに塗布した。次いで、80℃で3分間プリベークを行った後、光源として超高圧水銀ランプ(UL750)を用いて露光した(20mW/cm2)。なお、露光は、露光光量が、500mJ/cm2となるように行った。この際、光感度を測定できるように、光透過率が段階的に少なくなるように作られたネガフィルム(光学密度0.05を1段目とし、1段毎に光学密度が0.15ずつ増加するステップタブレット)を用いた。次いで、イソプロパノール(IPA)を用いて、25℃の環境下、10秒間かけ洗いを行って現像した後、80℃で30分間乾燥した。そして、PETフィルム上に形成された硬化物のステップタブレットの段数を測定することにより光感度を評価した。ステップタブレットの段数が高いほど光感度が高く、硬化性が良好なことを示す。結果を下記表5に示す。 [Curable]
The compositions of Examples 18-20 and Comparative Examples 1 and 2 were each applied to a PET film with a bar coater to a thickness of about 3 μm. Next, after prebaking at 80 ° C. for 3 minutes, exposure was performed (20 mW / cm 2 ) using an ultra-high pressure mercury lamp (UL 750) as a light source. The exposure was performed so that the exposure light amount was 500 mJ / cm 2 . Under the present circumstances, the negative film made so that light transmittance might be decreased in steps in order to measure a photosensitivity (The optical density 0.05 is made into the 1st step, The optical density is 0.15 at a time for every step. An increasing step tablet was used. Then, development was carried out by washing with isopropanol (IPA) for 10 seconds in an environment of 25 ° C., followed by drying at 80 ° C. for 30 minutes. And the photosensitivity was evaluated by measuring the number of steps of the step tablet of the hardened | cured material formed on PET film. The higher the number of steps of the step tablet, the higher the photosensitivity and the better the curability. The results are shown in Table 5 below.
実施例18~20並びに比較例1及び2の組成物をそれぞれ、PETフィルムにバーコーターで約3μmの厚さに塗布した。次いで、80℃で3分間プリベークを行った後、光源として超高圧水銀ランプ(UL750)を用いて露光した(20mW/cm2)。なお、露光は、露光光量が、500mJ/cm2となるように行った。この際、光感度を測定できるように、光透過率が段階的に少なくなるように作られたネガフィルム(光学密度0.05を1段目とし、1段毎に光学密度が0.15ずつ増加するステップタブレット)を用いた。次いで、イソプロパノール(IPA)を用いて、25℃の環境下、10秒間かけ洗いを行って現像した後、80℃で30分間乾燥した。そして、PETフィルム上に形成された硬化物のステップタブレットの段数を測定することにより光感度を評価した。ステップタブレットの段数が高いほど光感度が高く、硬化性が良好なことを示す。結果を下記表5に示す。 [Curable]
The compositions of Examples 18-20 and Comparative Examples 1 and 2 were each applied to a PET film with a bar coater to a thickness of about 3 μm. Next, after prebaking at 80 ° C. for 3 minutes, exposure was performed (20 mW / cm 2 ) using an ultra-high pressure mercury lamp (UL 750) as a light source. The exposure was performed so that the exposure light amount was 500 mJ / cm 2 . Under the present circumstances, the negative film made so that light transmittance might be decreased in steps in order to measure a photosensitivity (The optical density 0.05 is made into the 1st step, The optical density is 0.15 at a time for every step. An increasing step tablet was used. Then, development was carried out by washing with isopropanol (IPA) for 10 seconds in an environment of 25 ° C., followed by drying at 80 ° C. for 30 minutes. And the photosensitivity was evaluated by measuring the number of steps of the step tablet of the hardened | cured material formed on PET film. The higher the number of steps of the step tablet, the higher the photosensitivity and the better the curability. The results are shown in Table 5 below.
[耐光性]
実施例18~20並びに比較例1及び2の組成物をそれぞれガラス基板にスピンコーターで塗布し、80℃で3分間プリベークを行った後、光源として超高圧水銀ランプ(UL750)を用いて露光した(20mW/cm2)。露光は、露光光量が、100mJ/cm2となるように行った。その後、更に3000mJ/cm2照射し、耐光性評価用サンプルを作製した。スガ試験機製キセノン耐光性試験機テーブルサンXT-1500Lを用いて、評価用サンプルに対して24時間耐光性試験を実施した。評価用サンプルの耐光性試験前後の波長470nmでの透過率(%)の差((耐光性試験前の透過率(%)-耐光性試験後の透過率(%))を測定し、以下の基準で耐光性評価を行った。
〇:透過率差(%)が耐光性試験前の透過率に対して5%未満である。
×:透過率差(%)が耐光性試験前の透過率に対して5%以上である。
耐光性評価が「〇」であると、硬化物が耐光性に優れることを示す。その結果を下記表5に示す。 [Lightfastness]
The compositions of Examples 18 to 20 and Comparative Examples 1 and 2 were each applied to a glass substrate by a spin coater, prebaked at 80 ° C. for 3 minutes, and then exposed using a super high pressure mercury lamp (UL 750) as a light source. (20 mW / cm 2 ). The exposure was performed so that the exposure light amount was 100 mJ / cm 2 . Thereafter, the sample was further irradiated with 3000 mJ / cm 2 to prepare a sample for light resistance evaluation. A 24-hour light resistance test was performed on the sample for evaluation using a Suga Test Instruments Xenon Light Resistance Tester Table Sun XT-1500L. The difference in transmittance (%) at a wavelength of 470 nm before and after the light resistance test of the sample for evaluation ((transmittance (%) before light resistance test-transmittance (%) after light resistance test) was measured. The light resistance was evaluated on the basis of the standard.
Good: The difference in transmittance (%) is less than 5% relative to the transmittance before the light resistance test.
X: The difference in transmittance (%) is 5% or more with respect to the transmittance before the light resistance test.
It shows that a cured | curing material is excellent in light resistance in light resistance evaluation being "O". The results are shown in Table 5 below.
実施例18~20並びに比較例1及び2の組成物をそれぞれガラス基板にスピンコーターで塗布し、80℃で3分間プリベークを行った後、光源として超高圧水銀ランプ(UL750)を用いて露光した(20mW/cm2)。露光は、露光光量が、100mJ/cm2となるように行った。その後、更に3000mJ/cm2照射し、耐光性評価用サンプルを作製した。スガ試験機製キセノン耐光性試験機テーブルサンXT-1500Lを用いて、評価用サンプルに対して24時間耐光性試験を実施した。評価用サンプルの耐光性試験前後の波長470nmでの透過率(%)の差((耐光性試験前の透過率(%)-耐光性試験後の透過率(%))を測定し、以下の基準で耐光性評価を行った。
〇:透過率差(%)が耐光性試験前の透過率に対して5%未満である。
×:透過率差(%)が耐光性試験前の透過率に対して5%以上である。
耐光性評価が「〇」であると、硬化物が耐光性に優れることを示す。その結果を下記表5に示す。 [Lightfastness]
The compositions of Examples 18 to 20 and Comparative Examples 1 and 2 were each applied to a glass substrate by a spin coater, prebaked at 80 ° C. for 3 minutes, and then exposed using a super high pressure mercury lamp (UL 750) as a light source. (20 mW / cm 2 ). The exposure was performed so that the exposure light amount was 100 mJ / cm 2 . Thereafter, the sample was further irradiated with 3000 mJ / cm 2 to prepare a sample for light resistance evaluation. A 24-hour light resistance test was performed on the sample for evaluation using a Suga Test Instruments Xenon Light Resistance Tester Table Sun XT-1500L. The difference in transmittance (%) at a wavelength of 470 nm before and after the light resistance test of the sample for evaluation ((transmittance (%) before light resistance test-transmittance (%) after light resistance test) was measured. The light resistance was evaluated on the basis of the standard.
Good: The difference in transmittance (%) is less than 5% relative to the transmittance before the light resistance test.
X: The difference in transmittance (%) is 5% or more with respect to the transmittance before the light resistance test.
It shows that a cured | curing material is excellent in light resistance in light resistance evaluation being "O". The results are shown in Table 5 below.
表5から、化合物I-1を含有する実施例18~20の組成物は、紫外線吸収剤を含有しない比較例1の組成物に比べて耐光性が良好なものである。また、実施例18~20の組成物は、公知の紫外線吸収剤を含有する比較例2の組成物に比べて硬化性が良好なものである。このことから、本発明によれば、硬化阻害が少なく、優れた耐光性を有する組成物が得られることが分かる。
From Table 5, the compositions of Examples 18 to 20 containing the compound I-1 have better light resistance as compared with the composition of Comparative Example 1 which does not contain a UV absorber. Further, the compositions of Examples 18 to 20 have better curability as compared with the composition of Comparative Example 2 containing a known ultraviolet absorber. From this, it can be seen that according to the present invention, a composition having less curing inhibition and having excellent light resistance can be obtained.
本発明の化合物によれば、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる化合物を提供することができる。
本発明の潜在性紫外線吸収剤は、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる。
本発明の組成物によれば、硬化阻害が少なく、優れた紫外線吸収能を有する硬化物が得られる組成物を提供することができる。
本発明の硬化物によれば、優れた紫外線吸収能を有する硬化物を提供することができる。
本発明の硬化物の製造方法によれば、硬化阻害を起こすことなく、優れた紫外線吸収能等を有する硬化物を製造することができる。
本発明の第2組成物によれば、硬化阻害を起こさずに、優れた紫外線吸収能を有する硬化物が得られる組成物を提供すことができる。 According to the compound of the present invention, it is possible to provide a compound which is less in inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
The latent ultraviolet absorber of the present invention has little inhibition of curing and can easily impart ultraviolet absorptivity and the like to a cured product.
According to the composition of the present invention, it is possible to provide a composition capable of obtaining a cured product having excellent curing performance and having excellent ultraviolet absorptivity.
According to the hardened | cured material of this invention, the hardened | cured material which has the outstanding ultraviolet absorptivity can be provided.
According to the method for producing a cured product of the present invention, a cured product having excellent ultraviolet absorptivity and the like can be produced without causing inhibition of curing.
According to the second composition of the present invention, it is possible to provide a composition capable of obtaining a cured product having excellent ultraviolet absorption ability without causing inhibition of curing.
本発明の潜在性紫外線吸収剤は、硬化阻害が少なく、硬化物に対して容易に紫外線吸収能等を付与できる。
本発明の組成物によれば、硬化阻害が少なく、優れた紫外線吸収能を有する硬化物が得られる組成物を提供することができる。
本発明の硬化物によれば、優れた紫外線吸収能を有する硬化物を提供することができる。
本発明の硬化物の製造方法によれば、硬化阻害を起こすことなく、優れた紫外線吸収能等を有する硬化物を製造することができる。
本発明の第2組成物によれば、硬化阻害を起こさずに、優れた紫外線吸収能を有する硬化物が得られる組成物を提供すことができる。 According to the compound of the present invention, it is possible to provide a compound which is less in inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
The latent ultraviolet absorber of the present invention has little inhibition of curing and can easily impart ultraviolet absorptivity and the like to a cured product.
According to the composition of the present invention, it is possible to provide a composition capable of obtaining a cured product having excellent curing performance and having excellent ultraviolet absorptivity.
According to the hardened | cured material of this invention, the hardened | cured material which has the outstanding ultraviolet absorptivity can be provided.
According to the method for producing a cured product of the present invention, a cured product having excellent ultraviolet absorptivity and the like can be produced without causing inhibition of curing.
According to the second composition of the present invention, it is possible to provide a composition capable of obtaining a cured product having excellent ultraviolet absorption ability without causing inhibition of curing.
Claims (9)
- 前記一般式(I-1)におけるBが、下記一般式(B-1)、(B-2)、(B-3)、(B-4)、(B-5)、(B-6)、(B-7)、(B-8)、(B-9)及び(B-10)で表される基の少なくとも1種を含む請求項1に記載の化合物。
R12、R14、R17、R21、R22、R24、R25、R27、R29及びR30は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R15は、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29及びR30で表されるアルキル基及びアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があり、
前記アルキル基、アリール基、アリールアルキル基及び複素環含有基は、置換基を有している場合があり、
R’は、水素原子又は炭素原子数1~8のアルキル基を表し、
複数のR11同士、複数のR13同士、複数のR16同士、複数のR18同士、複数のR19同士、複数のR20同士、複数のR23同士、複数のR26同士及び複数のR28同士は、それぞれ結合してベンゼン環又はナフタレン環を形成している場合があり、
複数のR11、R12、R13、R14、R16、R17、R18、R19、R20、R23、R25、R26、R27、R28、R29及びR30は、それぞれ同じである場合があり、異なる場合があり、
b1、b2、b3、b6、b7、b8及びb9は、それぞれ独立に0~4の整数を表し、
b4及びb5は、それぞれ独立に0~5の整数を表し、
**は、前記A-O-との結合位置を表す。)
R32、R33、R41、R42、R43及びR44は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R31、R32、R33、R40、R41、R42、R43及びR44で表されるアルキル基及びアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があり、
前記アルキル基、アリール基、アリールアルキル基及び複素環含有基は、置換基を有している場合があり、
c1は、0~5の整数を表し、
c2は、0~4の整数を表し、
**は、前記A-O-との結合位置を表す。) In the general formula (I-1), B is a group represented by the following general formula (B-1), (B-2), (B-3), (B-4), (B-5), (B-6) The compound according to claim 1, comprising at least one of the groups represented by (B-7), (B-8), (B-9) and (B-10).
R 12, R 14, R 17 , R 21, R 22, R 24, R 25, R 27, R 29 and R 30 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl A group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 15 represents an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms,
R 11, R 12, R 13 , R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27 And the methylene group in the alkyl group and arylalkyl group represented by R 28 , R 29 and R 30 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof, Yes,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Multiple R 11 each other, multiple R 13 each other, multiple R 16 each other, multiple R 18 each other, multiple R 19 each other, multiple R 20 each other, multiple R 23 each other, multiple R 26 each other and multiple R 28 may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R 11 , R 12 , R 13 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , R 23 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 , Each may be the same, may be different,
b1, b2, b3, b6, b7, b8 and b9 each independently represent an integer of 0 to 4;
b4 and b5 each independently represent an integer of 0 to 5;
** represents the bonding position with the AO-. )
R 32 , R 33 , R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
The methylene group in the alkyl group and arylalkyl group represented by R 31 , R 32 , R 33 , R 40 , R 41 , R 42 , R 43 and R 44 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO 2 -or a combination of these may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
c1 represents an integer of 0 to 5;
c2 represents an integer of 0 to 4;
** represents the bonding position with the AO-. ) - 上記一般式(I-1)で表される化合物が下記一般式(A-1)、(A-2)又は(A-3)で表される化合物であり、
前記光脱離基Bとして、下記一般式(B-1-a)を含む、請求項2に記載の化合物。
R1及びR2の少なくとも一方は、前記-O-Bであり、
R3、R4、R5、R6、R7及びR8は、それぞれ独立に、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R1、R2、R3、R4、R5、R6、R7及びR8で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合もあり、
前記アルキル基、アリール基、アリールアルキル基及び複素環含有基は、置換基を有している場合があり、
R’は、水素原子又は炭素原子数1~8のアルキル基を表し、
複数のR3同士、複数のR4同士、複数のR5同士、複数のR6同士及び複数のR7同士は、それぞれ結合してベンゼン環又はナフタレン環を形成している場合があり、
複数のR3、R4、R5、R6、R7及びR8は、それぞれ同じ場合があり、異なる場合があり、
m1及びm2は、それぞれ独立に、1~10の整数を表し、
nは、1~3の整数を表し、
a1は、0~4の整数を表し、
a2は、0~2の整数を表し、
a3は、0~4の整数を表し、
a4は、0~3の整数を表し、
a5は、0~3の整数を表し、
a6は、0~3-nの整数を表し、
X1及びX2は、それぞれm1価及びm2価の結合基を表す。)
R11は、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、炭素原子数1~40のアルキル基、炭素原子数6~20のアリール基、炭素原子数7~20のアリールアルキル基又は炭素原子数2~20の複素環含有基を表し、
R11及びR12で表されるアルキル基又はアリールアルキル基中のメチレン基は、炭素-炭素二重結合、-O-、-S-、-CO-、-O-CO-、-CO-O-、-O-CO-O-、-O-CO-O-、-S-CO-、-CO-S-、-S-CO-O-、-O-CO-S-、-CO-NH-、-NH-CO-、-NH-CO-O-、-NR'-、>P=O、-S-S-、-SO2-又はこれらの組み合わせで置き換わっている場合があり、
前記アルキル基、アリール基、アリールアルキル基及び複素環含有基は、置換基を有している場合があり、
R’は、水素原子又は炭素原子数1~8のアルキル基を表し、
複数のR11同士は結合してベンゼン環又はナフタレン環を形成している場合があり、
R11及びR12は、それぞれ同じ場合があり、異なる場合があり、
b1は、0~4の整数を表し、
**は、前記A-O-との結合位置を表す。) The compound represented by the above general formula (I-1) is a compound represented by the following general formula (A-1), (A-2) or (A-3),
The compound according to claim 2, comprising the following general formula (B-1-a) as the photoleaving group B:
At least one of R 1 and R 2 is the above-mentioned -O-B
R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, the number of carbon atoms An aryl group of 6 to 20, an arylalkyl group of 7 to 20 carbon atoms, or a heterocycle-containing group of 2 to 20 carbon atoms,
The methylene group in the alkyl group or arylalkyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S -CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -SS-, -SO 2 -or a combination of these may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R 3 's , a plurality of R 4' s , a plurality of R 5 's , a plurality of R 6' s and a plurality of R 7 's may be bonded to each other to form a benzene ring or a naphthalene ring,
Plural R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be the same or different.
m1 and m2 each independently represent an integer of 1 to 10,
n represents an integer of 1 to 3;
a1 represents an integer of 0 to 4;
a2 represents an integer of 0 to 2;
a3 represents an integer of 0 to 4;
a4 represents an integer of 0 to 3;
a5 represents an integer of 0 to 3;
a6 represents an integer of 0 to 3-n,
X 1 and X 2 each represent an m1 monovalent or m2 divalent linking group. )
R 11 represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or carbon Represents a heterocycle-containing group having 2 to 20 atoms,
The methylene group in the alkyl group or arylalkyl group represented by R 11 and R 12 is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O -, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH -, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof may be substituted,
The alkyl group, aryl group, arylalkyl group and heterocycle-containing group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Several R 11 may be combined to form a benzene ring or a naphthalene ring,
R 11 and R 12 may be the same or different.
b1 represents an integer of 0 to 4;
** represents the bonding position with the AO-. ) - 請求項1~3のいずれか1項に記載の化合物を含む潜在性紫外線吸収剤。 A latent ultraviolet absorber comprising the compound according to any one of claims 1 to 3.
- 請求項1~3のいずれか1項に記載の化合物を含む組成物。 A composition comprising a compound according to any one of claims 1 to 3.
- 更に樹脂成分を含む請求項5に記載の組成物。 The composition according to claim 5, further comprising a resin component.
- 請求項1~3のいずれか1項に記載の化合物と、重合性化合物とを含む組成物の硬化物。 A cured product of a composition comprising the compound according to any one of claims 1 to 3 and a polymerizable compound.
- 請求項1~3のいずれか1項に記載の化合物と重合性化合物とを含む組成物を硬化させて硬化物を形成する工程と、
前記硬化物に対して光を照射して、前記化合物に含まれる光脱離基を脱離する工程と、
を有する硬化物の製造方法。 Curing the composition containing the compound according to any one of claims 1 to 3 and a polymerizable compound to form a cured product;
Irradiating the cured product with light to release a photoleaving group contained in the compound;
A method of producing a cured product having: - 下記一般式(I-2)で表される化合物と、光脱離基由来の脱離物とを含む組成物。
Priority Applications (3)
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CN201880046837.6A CN111094256A (en) | 2017-10-05 | 2018-10-02 | Compound, latent ultraviolet absorber, composition, cured product, and method for producing cured product |
KR1020197036459A KR20200064029A (en) | 2017-10-05 | 2018-10-02 | Compound, latent ultraviolet absorber, composition, cured product and method for producing cured product |
JP2019546747A JP7393205B2 (en) | 2017-10-05 | 2018-10-02 | Compound, latent ultraviolet absorber, composition, cured product, and method for producing cured product |
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JP2017-195515 | 2017-10-05 | ||
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PCT/JP2018/036958 WO2019069960A1 (en) | 2017-10-05 | 2018-10-02 | Compound, latent ultraviolet light absorber, composition, cured product, and cured product production method |
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JP (1) | JP7393205B2 (en) |
KR (1) | KR20200064029A (en) |
CN (1) | CN111094256A (en) |
TW (2) | TW201922717A (en) |
WO (1) | WO2019069960A1 (en) |
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US11760764B2 (en) | 2020-05-22 | 2023-09-19 | Aligos Therapeutics, Inc. | Methods and compositions for targeting PD-L1 |
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US4728599A (en) * | 1985-12-02 | 1988-03-01 | Eastman Kodak Company | Sterically hindered phenolic ester photographic coupler dispersion addenda and photographic elements employing same |
JPH06191155A (en) * | 1992-12-25 | 1994-07-12 | Fuji Photo Film Co Ltd | Recording material |
EP0711804A3 (en) * | 1994-11-14 | 1999-09-22 | Ciba SC Holding AG | Latent light stabilizers |
JP3512911B2 (en) * | 1995-07-11 | 2004-03-31 | 富士写真フイルム株式会社 | Ultraviolet absorber precursor compound, photosensitive resin composition containing the same and image forming method |
EP1026152B1 (en) * | 1997-03-31 | 2006-07-26 | Daikin Industries, Limited | Process for producing perfluorovinyl ethersulfonic acid derivatives |
IT1301973B1 (en) * | 1998-07-31 | 2000-07-20 | Ausimont Spa | HYDRO-FLUOROALKYLVINYLETERS AND PROCEDURE FOR THEIR OBTAINING |
JP3590345B2 (en) * | 2000-11-27 | 2004-11-17 | 三井化学株式会社 | Optical recording medium |
EP1482904B1 (en) * | 2002-03-12 | 2008-04-02 | Ciba SC Holding AG | Uv absorber compositions comprising a hydroxyphenyltriazine compound |
JP2004018454A (en) * | 2002-06-14 | 2004-01-22 | Daikin Ind Ltd | Method for producing fluorine-containing fluorosulfonylalkyl vinyl ether |
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Cited By (1)
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US11760764B2 (en) | 2020-05-22 | 2023-09-19 | Aligos Therapeutics, Inc. | Methods and compositions for targeting PD-L1 |
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KR20200064029A (en) | 2020-06-05 |
TW201922717A (en) | 2019-06-16 |
TW202325698A (en) | 2023-07-01 |
CN111094256A (en) | 2020-05-01 |
JP7393205B2 (en) | 2023-12-06 |
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