WO2023176680A1 - Composition and cured product - Google Patents

Composition and cured product Download PDF

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Publication number
WO2023176680A1
WO2023176680A1 PCT/JP2023/009027 JP2023009027W WO2023176680A1 WO 2023176680 A1 WO2023176680 A1 WO 2023176680A1 JP 2023009027 W JP2023009027 W JP 2023009027W WO 2023176680 A1 WO2023176680 A1 WO 2023176680A1
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group
mass
parts
carbon atoms
composition
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PCT/JP2023/009027
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French (fr)
Japanese (ja)
Inventor
尭大 井上
涼平 佐藤
萩乃 森田
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株式会社Adeka
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Publication of WO2023176680A1 publication Critical patent/WO2023176680A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a composition and a cured product thereof.
  • Patent Document 1 describes the use of a light shielding filter to adjust illuminance in an exposure apparatus for lithography such as a semiconductor integrated circuit.
  • Patent Document 2 describes the use of a gray colored layer that weakens light intensity at a certain rate as a light shielding filter used in an antireflection film.
  • Patent Document 3 proposes a composition containing a cationically polymerizable compound, a black pigment, a photoacid generator, and a solvent as a material for forming a black matrix used in color filters for liquid crystal displays and video cameras.
  • the light-shielding filters used in Patent Documents 1 and 2 are made of metal thin films or metal meshes, and are difficult to form on uneven surfaces or on large-area light-shielding objects. There may be restrictions.
  • the cured product obtained by curing the composition of Patent Document 3 still has unsatisfactory heat and humidity resistance and weather resistance.
  • the present inventors have conducted intensive studies on the causes of the above-mentioned problems, and have found that by using a composition containing a specific cationic polymerizable compound and a specific antioxidant, the present inventors have improved heat-and-moisture resistance and weather resistance. It has been found that a cured product with excellent properties can be formed.
  • the present disclosure provides a composition comprising a cationically polymerizable component and an antioxidant, wherein the cationically polymerizable component is selected from an alicyclic epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, and an oxetane compound.
  • the present invention provides a composition including at least one type of sulfur-based antioxidant, wherein the antioxidant includes a sulfur-based antioxidant.
  • the above composition can form a cured product with excellent heat and humidity resistance and weather resistance.
  • the alicyclic epoxy compound has a chemical formula selected from the following general formulas (1-1), (1-2), (1-3), (1-4), and (1-5). It is preferable that at least one of the compounds represented by the above is included. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a carbon atom, Represents an alkyl group having 1 to 20 atoms or an alkoxy group having 1 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 and R 26 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms
  • X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which two or more of these are linked.
  • the content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the aliphatic epoxy compound includes a polyfunctional aliphatic epoxy compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is preferably 5 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the oxetane compound is preferably 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur-based antioxidant is preferably a compound represented by the following general formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • A represents a carbon atom or a sulfur atom
  • X 2 is a single bond, an alkylene group having 1 to 4 carbon atoms, a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide group, or more than one of these represents a linked group
  • R B1 represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • m1 represents 2
  • X 2 represents a group containing a thioether bond in its structure.
  • the content of the sulfur-based antioxidant is preferably 10 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the composition further includes a black coloring material. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the composition further includes a photoacid generator. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the present disclosure provides a cured product of the above composition.
  • the present disclosure relates to a composition and a cured product using the same.
  • the composition and cured product of the present disclosure will be explained in detail.
  • the number of carbon atoms in a group when a hydrogen atom in the group is substituted with a substituent, defines the number of carbon atoms in the group after the substitution.
  • 1 to 20 carbon atoms refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the previous number of carbon atoms.
  • the definition of the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group shall be defined as the number of carbon atoms in the group after the substitution. do.
  • solid content of the composition refers to the content of all components in the composition excluding the solvent.
  • composition comprising a cationically polymerizable component and an antioxidant, wherein the cationically polymerizable component is selected from an alicyclic epoxy compound, an aliphatic epoxy compound, an oxetane compound, and an aromatic epoxy compound.
  • the antioxidant includes a sulfur-based antioxidant.
  • the composition of the present disclosure can form a cured product with excellent moist heat resistance and weather resistance.
  • heat and humidity resistance is a function that can maintain the light transmittance of a cured product after being exposed to a high humidity and high temperature environment. Specifically, when exposed to a high humidity and high temperature environment for a long period of time, It can be expressed by evaluating the transmittance of the cured product to light at 540 nm.
  • Weather resistance is durability against sunlight exposure, and specifically can be expressed by evaluating the transmittance of a cured product to 540 nm light after a weather resistance test using a xenon lamp.
  • the cationically polymerizable component is a compound that undergoes a polymerization or crosslinking reaction with an acid.
  • the cationically polymerizable component includes two or more cationically polymerizable compounds having a cationically polymerizable group.
  • Examples of the above-mentioned cationic polymerizable groups include epoxy groups, oxetanyl groups, cyclic lactone groups, cyclic acetal groups, cyclic thioether groups, cyclic ether groups such as spiro-orthoester groups, and vinyl ether groups.
  • examples of the cationically polymerizable compound include epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, cyclic ether compounds such as spiro-orthoester compounds, and vinyl ether compounds.
  • the epoxy compound is a compound having an epoxy group as a cationically polymerizable group.
  • a compound having both an epoxy group and an oxetanyl group corresponds to an epoxy compound.
  • the oxetane compound is a compound having an oxetanyl group as a cationic polymerizable group and not having an epoxy group.
  • the cationically polymerizable compounds other than the epoxy compound and the oxetane compound are compounds having neither an epoxy group nor an oxetanyl group.
  • the cationically polymerizable component includes an alicyclic epoxy compound and at least one selected from an aliphatic epoxy compound, an aromatic epoxy compound, and an oxetane compound. That is, the cationically polymerizable component contains an alicyclic epoxy compound as an essential component, and further contains at least one selected from aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds as an essential component.
  • the above-mentioned cationically polymerizable component contains only an alicyclic epoxy compound and an aliphatic epoxy compound among alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds, Often, it may contain only an alicyclic epoxy compound and an oxetane compound, it may contain only an alicyclic epoxy compound and an aromatic epoxy compound, and it may contain only an alicyclic epoxy compound and an aromatic epoxy compound.
  • the cationic polymerizable component contains at least one selected from an aliphatic epoxy compound and an oxetane compound together with an alicyclic epoxy compound. It is particularly preferable to contain an alicyclic epoxy compound, an aliphatic epoxy compound, and an oxetane compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the lower limit of the total content of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound is preferably 50 parts by mass in 100 parts by mass of the cationically polymerizable component, and especially 60 parts by mass. It is preferably 70 parts by mass, particularly preferably 80 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the total of the alicyclic epoxy compound, the aliphatic epoxy compound, the aromatic epoxy compound, and the oxetane compound refers to the alicyclic epoxy compound, the aliphatic epoxy compound contained in the cationically polymerizable component. , refers to the total of aromatic epoxy compounds and oxetane compounds.
  • the cationically polymerizable component is an alicyclic epoxy compound among alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds.
  • Alicyclic epoxy compound is a compound having at least one alicyclic epoxy group in the molecule, that is, a compound having a cycloalkene oxide structure, and has multiple alicyclic epoxy groups in one molecule. It may have a formula epoxy group, or it may have an epoxy group other than an alicyclic epoxy group. Moreover, the above-mentioned alicyclic epoxy compounds may be used in combination of two or more types. A compound having an aromatic ring also falls under the category of an alicyclic epoxy compound if it has an alicyclic epoxy group.
  • a cycloalkene oxide structure is a cyclohexene oxide structure or a cyclopentene oxide structure obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. This is a structure in which parts are shared.
  • examples of compounds having one cycloalkene oxide structure include 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentadiene diepoxide, and epoxyhexahydro Examples include dioctyl phthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, and 1,2-epoxy-2-epoxyethylcyclohexane.
  • compounds having two cycloalkene oxide structures include compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure, and compounds in which two cycloalkene oxide structures are connected by a linking group.
  • examples include compounds having the following.
  • Specific examples of compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure include compounds represented by any of the following formulas (1-1) to (1-4).
  • Specific examples of compounds having a structure in which two cycloalkene oxide structures are connected by a linking group include compounds represented by the following formula (1-5).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a carbon atom, Represents an alkyl group having 1 to 20 atoms or an alkoxy group having 1 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 and R 26 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms
  • X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which two or more of these are linked.
  • a group in which two or more of these are connected refers to a group in which two or more groups selected from alkylene groups, carbonyl groups, ether bonds, ester bonds, carbonate groups, and amide groups are not adjacent to each other other than the alkylene groups. It can be a group bonded like this. Furthermore, two or more groups of the same type may be combined, such as ester bond-alkylene group-ester bond-alkylene group.
  • Examples of the halogen atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include fluorine, chlorine, bromine, and iodine.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include a methyl group, an ethyl group, and a propyl group.
  • Examples of the alkoxy group having 1 to 20 carbon atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Examples of the alkyl group include groups having a predetermined number of carbon atoms among the alkyl groups listed as the alkyl groups represented by R 1 to R 10 in formula (1-1) above. Specific examples include methylene group, methylmethine group, isopropylidene group, ethylene group, trimethylene group, and tetramethylene group.
  • X is a group in which a plurality of groups selected from an alkylene group, a carbonyl group, an ether bond, an ester bond, a carbonate group, and an amide group having 1 to 4 carbon atoms are connected
  • the total number of carbon atoms in can be 2 or more and 20 or less.
  • a single bond is one in which carbon atoms to which X is connected are directly bonded to each other.
  • Examples of compounds in which two cycloalkene oxide rings are bonded via such a single bond include a compound represented by the following formula (A1-4).
  • Examples of methods for producing the compounds represented by formulas (1-1) to (1-5) include the production method described in JP-A No. 2019-189844.
  • commercially available compounds include, for example, THI-DE (manufactured by ENEOS Corporation).
  • commercially available compounds include, for example, DE-102 (manufactured by ENEOS Corporation).
  • commercially available compounds include, for example, DE-103 (manufactured by ENEOS Corporation).
  • Examples of commercially available compounds represented by the above formula (1-5) include Celloxide 2021P and Celloxide 8000 (manufactured by Daicel Corporation).
  • the alicyclic epoxy compound has two or more cycloalkene oxide structures. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the number of functional groups in the alicyclic epoxy compound is preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Note that the number of functional groups of the alicyclic epoxy compound includes the number of epoxy groups other than the cycloalkene oxide structure.
  • the alicyclic epoxy compound preferably includes a compound having a structure in which two cycloalkene oxide structures are directly condensed, or a compound having a structure in which two cycloalkene oxide structures are connected by a linking group. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the alicyclic epoxy compound has a chemical formula selected from the above formulas (1-1), (1-2), (1-3), (1-4) and (1-5).
  • it contains at least one compound represented by the formula (1-1), (1-2), and (1-5).
  • R 1 to R 10 in the above formula (1-1), R 11 to R 26 in the above formula (1-2), R 31 to R 48 in the above formula (1-3), and the above formula (1- R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • X in the above formula (1-5) may be a single bond, an alkylene group having 1 to 4 carbon atoms, an ester bond, or a group in which an alkylene group having 1 to 4 carbon atoms and an ester bond are connected.
  • it is a group in which a single bond or an alkylene group having 1 to 4 carbon atoms and an ester bond are connected, particularly a group in which a single bond or an alkylene group having 1 to 2 carbon atoms and an ester bond are connected. It is preferable that it is a group in which these are connected, and a single bond is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the alicyclic epoxy compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the epoxy equivalent of the above alicyclic epoxy compound is 50 g/eq. More than 200g/eq. It is preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above epoxy equivalent, the composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the alicyclic epoxy compound is 0.5 parts by mass or more in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. It is preferably 80 parts by mass or less, particularly preferably 1 part by mass or more and 50 parts by mass or less, particularly preferably 2 parts by mass or more and 30 parts by mass or less, especially 3 parts by mass. It is preferably 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less, particularly 1 part by mass or more and 50 parts by mass or less, in 100 parts by mass of the cationically polymerizable component. It is preferably 2 parts by mass or more and 30 parts by mass or less, particularly preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less. It is preferable that there be. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less, particularly 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the solid content of the composition. It is preferably 2 parts by mass or more and 30 parts by mass or less, particularly preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass. It is preferable that it is below. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above-mentioned aliphatic epoxy compound represents a compound having an epoxy group having neither an alicyclic epoxy group nor an aromatic ring. Moreover, the above-mentioned aliphatic epoxy compounds may be used in combination of two or more types. Examples of the aliphatic epoxy compounds include polyfunctional epoxy compounds and monofunctional aliphatic epoxy compounds. In the present disclosure, it is preferable that the aliphatic epoxy compound includes a polyfunctional aliphatic epoxy compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • polyfunctional aliphatic epoxy compound is a compound that has at least two epoxy groups in its molecule and has neither an alicyclic epoxy group nor an aromatic ring. Moreover, the above-mentioned polyfunctional aliphatic epoxy compounds may be used in combination of two or more types.
  • Examples of the polyfunctional aliphatic epoxy compound include compounds represented by the following formula (1-6).
  • Y 1 is an alkylene group having 1 to 20 carbon atoms, a divalent aliphatic hydrocarbon group having 6 to 20 carbon atoms having a cycloalkyl ring, or the alkylene group or the divalent aliphatic hydrocarbon group having cycloalkyl rings. It represents a group having a structure in which one or more methylene groups in a valent aliphatic hydrocarbon group are substituted with oxygen atoms.
  • the alkylene group having 1 to 20 carbon atoms used in Y 1 in the above formula (1-6) is the alkyl group having 1 to 20 carbon atoms used in R 1 to R 10 in the above formula (1-1). Examples include groups obtained by removing one hydrogen atom from the groups listed above.
  • the divalent aliphatic hydrocarbon group having 6 to 20 carbon atoms and having a cycloalkyl ring used for Y 1 in (1-6) above is a cycloalkylene group obtained by removing one hydrogen atom from a cycloalkyl group. , a combination of a cycloalkylene group and an alkylene group.
  • cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a methylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, Monocyclic aliphatic hydrocarbon groups such as tetramethylcyclohexyl group, pentamethylcyclohexyl group, ethylcyclohexyl group and methylcycloheptyl group; bicyclo[2.1.1]hexyl group, bicyclo[2.2.1]heptyl group , bicyclo[2.2.2]octyl group, bicyclo[4.3.1]decyl
  • the above Y 1 is preferably an alkylene group having 1 to 20 carbon atoms, particularly preferably an alkylene group having 2 to 8 carbon atoms, and particularly an alkylene group having 3 to 6 carbon atoms. It is more preferable that This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the alkylene group used for Y 1 may be linear or branched, but is preferably branched. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Y 1 is a divalent aliphatic hydrocarbon group having a cycloalkyl ring and having 6 to 20 carbon atoms
  • the number of carbon atoms in Y 1 is preferably 3 or more and 20 or less, and 6 or more. It is more preferably 18 or less, particularly preferably 10 or more and 15 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • examples of the polyfunctional aliphatic epoxy compound include compounds represented by the following formula (1-7).
  • R is a t-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, s represents an integer of 1 to 30, and t represents an integer of 1 to 10. represent.
  • t is 2 or more, the plurality of s may be different from each other. Further, the sum of s and t is 2 or more.
  • the t-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R in the above formula (1-7) is obtained by removing t-1 hydrogen atoms from an alkyl group having 1 to 10 carbon atoms.
  • the following groups are mentioned.
  • a predetermined number of carbon atoms can be used. Examples include groups having
  • R in the above formula (1-7) is preferably an alkyl group having 2 to 10 carbon atoms, particularly preferably a branched alkyl group having 3 to 8 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • t is preferably an integer of 1 or more and 10 or less in terms of ease of obtaining the compound, more preferably an integer of 2 or more and 8 or less, particularly preferably an integer of 2 or more and 6 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the compound represented by the above formula (1-7) may be any one that can form a cured product with excellent heat and humidity resistance and weather resistance, and is between 1,000 and 5,000. It is preferably 1,500 or more and 4,000 or less, particularly preferably 2,000 or more and 3,000 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the above molecular weight means a weight average molecular weight (Mw). Further, the weight average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.
  • the above weight average molecular weights are, for example, using GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, and using polystyrene standards for the calibration curve as Mw 1,110,000, 707,000, 397,000, 189,
  • the measurement columns were KF-804 and KF-803. , KF-802 (manufactured by Showa Denko).
  • the measurement temperature can be 40° C.
  • the flow rate can be 1.0 mL/min.
  • the sample concentration during measurement can be 0.1% by mass to 0.2% by mass.
  • the number of functional groups in the polyfunctional aliphatic epoxy compound is preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the polyfunctional aliphatic epoxy compound is at least one compound selected from compounds represented by the above formula (1-6) and in which Y 1 is an alkylene group having 1 to 20 carbon atoms. It is preferable to include. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the polyfunctional aliphatic epoxy compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the epoxy equivalent of the polyfunctional aliphatic epoxy compound is 50 g/eq. More than 200g/eq. It is preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above-mentioned epoxy equivalent, the composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • polyfunctional aliphatic epoxy compounds examples include 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, and trimethylol.
  • Glycidyl ethers of polyhydric alcohols such as triglycidyl ether of propane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, propylene glycol, trimethylolpropane,
  • Examples include polyglycidyl etherified polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids.
  • Further examples include epoxidized soybean oil, epoxidized polybutadiene, and the like.
  • the content of the polyfunctional aliphatic epoxy compound is preferably 0 parts by mass or more and 98 parts by mass or less based on a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. Among these, it is preferably 10 parts by mass or more and 50 parts by mass or less, and particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the polyfunctional aliphatic epoxy compound is preferably 0 parts by mass or more and 98 parts by mass or less, especially 10 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. Preferably, it is particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the total content of the alicyclic epoxy compound and polyfunctional aliphatic epoxy compound is preferably 8 parts by mass or more and 100 parts by mass or less, particularly 10 parts by mass or more and 100 parts by mass, based on 100 parts by mass of the cationically polymerizable component. It is more preferably at most 20 parts by mass and at most 70 parts by mass, particularly preferably at least 25 parts by mass and at most 60 parts by mass. In particular, it is preferably 32 parts by mass or more and 55 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the monofunctional aliphatic epoxy compound is a compound having one epoxy group in the molecule. Moreover, the above-mentioned monofunctional aliphatic epoxy compounds may be used in combination of two or more types. Examples of the monofunctional epoxy compound include compounds represented by the following formula (1-8).
  • R A1 represents an alkyl group having 1 to 20 carbon atoms
  • X 1 represents an ether bond or an ester bond.
  • Examples of the alkyl group used for R A1 in the above general formula (1-8) include alkyl groups having 1 to 20 carbon atoms used for R 1 to R 10 in the above formula (1-1). Groups similar to those described above can be used.
  • R A1 is preferably an alkyl group having 6 to 20 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Examples of the monofunctional aliphatic epoxy compound include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, and the like.
  • Commercially available monofunctional aliphatic epoxy compounds include ADEKA Glycilol ED-502 (manufactured by ADEKA, a compound in which R A1 in the above formula (1-8) is an alkyl group having 12 to 13 carbon atoms), Denacol Examples include EX-1113 (manufactured by Nagase ChemteX, a compound in which R A1 in the above formula (1-8) has an alkyl group having 17 carbon atoms).
  • the monofunctional aliphatic epoxy compound When the monofunctional aliphatic epoxy compound is contained, its content is preferably 0.5 parts by mass or more and 30 parts by mass or less, particularly 1 part by mass or more and 20 parts by mass, based on 100 parts by mass of the cationically polymerizable component. It is preferably at most 2 parts by mass and at most 10 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is 0 parts by mass or more and 90 parts by mass or less in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. It is preferably 5 parts by mass or more and 70 parts by mass or less, particularly preferably 10 parts by mass or more and 50 parts by mass or less, especially 15 parts by mass or more and 40 parts by mass or less. It is preferable that This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is preferably 0 parts by mass or more and 90 parts by mass or less, particularly preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. , preferably 10 parts by mass or more and 50 parts by mass or less, particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is preferably 0 parts by mass or more and 90 parts by mass or less, and particularly preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 10 parts by mass or more and 40 parts by mass or less, particularly preferably 15 parts by mass or more and 30 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Aromatic epoxy compound represents a compound that has an epoxy group and an aromatic ring, and does not have an alicyclic epoxy group. Moreover, the above-mentioned aromatic epoxy compounds may be used in combination of two or more types.
  • aromatic epoxy compounds examples include monohydric phenols such as phenol, cresol, butylphenol, glycidyl etherified products of alkylene oxide adducts thereof, polyhydric phenols having two or more aromatic rings, and alkylene phenols thereof.
  • Polyglycidyl ethers of polyhydric phenols such as oxide adducts, phenol novolak type epoxy compounds; Glycidyl ethers of phenols having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; benzenedimethanol, benzenediethanol and benzene
  • Polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups such as dibutanol
  • Glycidyl esters of benzoic acids such as benzoic acid, toluic acid and naphthoic acid; epoxidized products of styrene oxide and divinylbenzene; and the like.
  • the content of the aromatic epoxy compound is preferably 30 parts by mass or less, preferably 20 parts by mass or less, particularly 10 parts by mass in 100 parts by mass of the cationically polymerizable component. It is preferably at most 5 parts by mass, particularly preferably at most 5 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Further, when an aromatic epoxy compound is contained, the content thereof may be 0.1 parts by mass or more, 0.3 parts by mass or more, and 0.3 parts by mass or more, based on 100 parts by mass of the cationically polymerizable component. May be 5 parts by mass or more
  • the content thereof is preferably 0.5 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the solid content of the composition, particularly 0.5 parts by mass. It is preferably at least 1 part by mass and at most 20 parts by mass, particularly preferably at least 1 part by mass and at most 10 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • oxetane compound represents a compound that has at least one oxetanyl group in the molecule and does not have an epoxy group.
  • examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and the like. Further, two or more oxetane compounds may be used in combination.
  • the monofunctional oxetane compound described above represents an oxetane compound having only one oxetanyl group in the molecule.
  • Examples of the monofunctional oxetane compound include compounds represented by the following formula (1-9).
  • R A2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R A3 represents an alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R A2 and R A3 in the above formula (1-9) are the carbon atoms used in R 1 to R 10 in the above formula (1-1).
  • Examples of the alkyl group having a number of 1 to 20 include groups having a predetermined number of carbon atoms.
  • the above R A2 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly an alkyl group having 1 to 3 carbon atoms. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above R A3 is preferably an alkyl group having 3 to 10 carbon atoms, more preferably an alkyl group having 5 to 10 carbon atoms, particularly an alkyl group having 6 to 9 carbon atoms. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Specific examples of the compound represented by the above formula (1-9) include 3-ethyl-3-(methoxymethyl)oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-( Examples include 2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, and 3-ethyl-3-(butyloxymethyl)oxetane.
  • the content of the monofunctional oxetane compound is 1 part by mass out of 100 parts by mass of the total amount of the monofunctional oxetane compound and the bifunctional oxetane compound described below. It is preferably at least 50 parts by mass, particularly preferably at least 5 parts by mass and at most 40 parts by mass, particularly preferably at least 10 parts by mass and at most 30 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • bifunctional Oxetane Compound represents an oxetane compound having two oxetanyl groups in the molecule.
  • Examples of the above-mentioned bifunctional oxetane compound include compounds represented by the following formula (1-10).
  • R A4 and R A5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • Z represents a linking group having 2 to 20 carbon atoms
  • n2 represents an integer from 0 to 3.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R A4 and R A5 in the above formula (1-10) are the carbon atoms represented by R 1 to R 10 in the above formula (1-1).
  • Examples of the alkyl group having 1 to 20 atoms include groups having a predetermined number of carbon atoms.
  • the linking group having 2 to 20 carbon atoms represented by Z in the above formula (1-10) includes an alkylene group having 2 to 10 carbon atoms, an aromatic ring-containing group having 8 to 20 carbon atoms, etc. Can be mentioned.
  • the above R A4 and R A5 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly an alkyl group having 1 to 5 carbon atoms. It is preferable that it is an alkyl group of 3. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Examples of the alkylene group having 2 to 10 carbon atoms represented by Z in the above formula (1-10) include a group obtained by removing one hydrogen atom from an alkyl group having 2 to 10 carbon atoms; Examples of the group include groups having a predetermined number of carbon atoms among the alkyl groups listed as the alkyl groups represented by R 1 to R 10 in formula (1-1) above. Specific examples include methylmethine group, isopropylidene group, ethylene group, trimethylene group, and tetramethylene group.
  • the aromatic ring-containing group having 8 to 20 carbon atoms represented by Z in the above formula (1-10) includes 1 to 2 benzene rings, an alkylene group, a carbonate group, an amide group, or more than one of these. Examples include groups that are a combination of groups in which are linked.
  • the hydrogen atom of the benzene ring may be substituted with an alkyl group having 1 to 4 carbon atoms or a hydroxy group.
  • Specific examples of the aromatic ring-containing group include groups represented by any of the following formulas (2a) to (2d).
  • Specific examples of the compound represented by the above formula (1-10) include 3,7-bis(3-oxetanyl)-5-oxanonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy) ) methyl]benzene, 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-oxetanyl
  • Examples of commercially available oxetane compounds include aron oxetane OXT-212, OXT-121, OXT-221 (manufactured by Toagosei Co., Ltd.), HBOX, OXBP, and OXIPA (manufactured by Ube Industries, Ltd.). .
  • the content of the bifunctional oxetane compound is 50 parts by mass or more out of 100 parts by mass of the total amount of the monofunctional oxetane compound and the bifunctional oxetane compound.
  • the content is preferably 100 parts by mass or less, particularly preferably 55 parts by mass or more and 95 parts by mass or less, and particularly preferably 70 parts by mass or more and 88 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the oxetane compound contains at least one type of monofunctional oxetane compound or a difunctional oxetane compound, and it is particularly preferable that the oxetane compound contains a bifunctional oxetane compound, and especially a monofunctional oxetane compound and a difunctional oxetane compound. Preferably, it contains an oxetane compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the total amount of monofunctional oxetane compounds and difunctional oxetane compounds in the oxetane compound is preferably 50% by mass or more, and 80% by mass or more. is more preferable, and particularly preferably 95% by mass or more.
  • the oxetane compound contains at least one compound selected from the compounds represented by the above formula (1-9) and the above formula (1-10). It is preferable to contain at least one compound represented by formula (10), and particularly preferably to contain at least one compound each of formula (1-9) and formula (1-10). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the oxetane compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the oxetane equivalent of the above oxetane compound is 250 g/eq.
  • the following is preferable, 50g/eq. More than 200g/eq. It is more preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above-mentioned oxetane equivalent, the composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the content of the oxetane compound may be 0 parts by mass or more and 92 parts by mass or less in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound.
  • the content is preferably 10 parts by mass or more and 80 parts by mass or less, particularly preferably 40 parts by mass or more and 80 parts by mass or less, particularly preferably 50 parts by mass or more and 75 parts by mass or less. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the oxetane compound is preferably 0 parts by mass or more and 92 parts by mass or less, particularly preferably 0.5 parts by mass or more and 80 parts by mass or less, in 100 parts by mass of the cationically polymerizable component.
  • it is preferably 10 parts by mass or more and 80 parts by mass or less, particularly preferably 40 parts by mass or more and 80 parts by mass or less, and even more preferably 50 parts by mass or more and 75 parts by mass or less.
  • the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above cationically polymerizable components include other cationically polymerizable compounds that are cationically polymerizable compounds other than alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds. can be included.
  • the content of the other cationically polymerizable compounds is preferably 50 parts by mass or less, particularly 40 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. It is particularly preferable that the amount is 10 parts by mass or less, and it is especially preferable that it is not included.
  • the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the cationically polymerizable component contains another cationically polymerizable compound
  • examples of the other cationically polymerizable compound include vinyl ether compounds.
  • Vinyl ether compound is a compound that has a vinyl ether group and does not have an epoxy group or an oxetane group.
  • 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, Examples include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether.
  • antioxidants examples include compounds that suppress thermal decomposition, oxidative decomposition, coloring due to heat, etc. of the resin.
  • antioxidants include sulfur-based antioxidants, phenolic antioxidants, phosphorus-based antioxidants, and the like.
  • the above-mentioned antioxidants may be used in combination of two or more types.
  • the antioxidant contains a sulfur-based antioxidant as an essential component, and may contain other antioxidants such as a phenolic antioxidant and a phosphorus-based antioxidant as an optional component. .
  • the above antioxidant may contain only a sulfur-based antioxidant, or may contain only a sulfur-based antioxidant and a phenolic antioxidant, or may contain only a sulfur-based antioxidant and a phenolic antioxidant. It may contain only a sulfur-based antioxidant and a phosphorus-based antioxidant, or it may contain a sulfur-based antioxidant, a phenol-based antioxidant, and a phosphorus-based antioxidant.
  • the antioxidant preferably contains a sulfur-based antioxidant, and particularly preferably contains a sulfur-based antioxidant and a phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • sulfur-based antioxidant represents an antioxidant containing a thioether in the molecule. Moreover, the above-mentioned sulfur-based antioxidants can be used alone or in combination of two or more.
  • the above-mentioned sulfur-based antioxidant may be any known sulfur-based antioxidant, including, for example, the sulfur-based antioxidant described in JP-A No. 2022-11537.
  • the sulfur-based antioxidant preferably contains a compound represented by the following formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • A represents a carbon atom or a sulfur atom
  • X 2 is a single bond, an alkylene group having 1 to 4 carbon atoms, a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide group, or more than one of these represents a linked group
  • R B1 represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • m1 represents 2
  • X 2 represents a group containing a thioether bond in its structure.
  • the alkylene group having 1 to 4 carbon atoms represented by X 2 in formula (2-1) is the same as the alkylene group having 1 to 4 carbon atoms represented by X in formula (1-5). It can be done.
  • the phenylene group having 6 to 18 carbon atoms represented by The above may be substituted with an alkyl group having 1 to 4 carbon atoms.
  • an alkylene group having 1 to 4 carbon atoms represented by X 2 a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide
  • the group in which a plurality of these are connected is selected from an alkylene group, a phenylene group, a carbonyl group, an ether group, a thioether bond, an ester bond, a carbonate group, and an amide group.
  • a plurality of groups may be bonded together such that oxygen atoms are not adjacent to each other.
  • the alkyl group having 6 to 20 carbon atoms represented by R B1 in formula (2-1) is the alkyl group having 1 to 20 carbon atoms represented by R 1 in formula (1-1). , a group having a predetermined number of carbon atoms.
  • the aryl group having 6 to 20 carbon atoms represented by R B1 in formula (2-1), has the hydrogen atom of the aryl group substituted with an alkyl group or hydroxy group having 1 to 4 carbon atoms. Good too. Specific examples of the above aryl group having 6 to 20 carbon atoms include 3,5-di-tert-butyl-4-hydroxyphenyl group, 3-tert-butyl-4-hydroxy-5-methylphenyl group, 3, Examples include 4-di-tert-butyl-4-hydroxyphenyl group.
  • the compound represented by the above formula (2-1) include didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, ditetradecyl 3,3'-thiodipropionate, 3,3'- Dipentadecyl thiodipropionate, diotadecyl 3,3'-thiodipyropionate, dodecyl-3-((3-octadecyloxy-3-oxopropyl)thio)propionate, 2,2-bis ⁇ [3-(dodecylthio)-1-oxo propoxy]methyl ⁇ propane-1,3-diyl bis[3-(dodecylthio)propionate], (thiobis(ethane-2,1-diyl))bis(2-tert-butyl)-5-methyl-4,1- phenylene)bis(3-dodecylthio)propionate
  • sulfur-based antioxidants examples include ADEKA STAB (registered trademark) AO-412S, AO-503, AO-26 (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) TPM, TPS, and TP. -D (manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) PS 800 FL, PS 802FL, 1035, 1081, 1192, 1726 (manufactured by BASF), Cyanox (registered trademark) 1212 (manufactured by Solbey) ) etc.
  • the composition of the present disclosure is not limited to the exemplified commercial products, and known sulfur-based antioxidants can be used.
  • X 2 in formula (2-1) is a direct bond, an alkylene group having 1 to 4 carbon atoms, a group in which an alkylene group having 1 to 4 carbon atoms and an ester bond are connected, or a group having a number of carbon atoms
  • a group in which a 6 to 18 phenylene group, an ester bond, an alkylene group having 1 to 4 carbon atoms, and a thioether bond are connected is preferable, and among them, an alkylene group having 1 to 4 carbon atoms and an ester bond are preferable.
  • a group in which a phenylene group having 6 to 18 carbon atoms, an ester bond, an alkylene group having 1 to 4 carbon atoms, and a thioether bond are connected and in particular, a group in which a phenylene group having 6 to 18 carbon atoms is connected to 2, a group in which an alkylene group and an ester bond are connected, a group in which a phenylene group having 6 to 18 carbon atoms, an ester bond, an alkylene group having 1 to 2 carbon atoms and a thioether bond are connected, Among these, a group in which an alkylene group having 1 to 2 carbon atoms and an ester bond are connected is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur-based antioxidant contains a compound represented by formula (2-2) among the compounds represented by formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R B2 and R B3 each independently represent an alkyl group having 6 to 20 carbon atoms.
  • the alkyl group having 6 to 20 carbon atoms represented by R B2 and R B3 in formula (2-2) is the alkyl group having 1 to 20 carbon atoms represented by R 1 in formula (1-1).
  • Examples of the alkyl group include groups having a predetermined number of carbon atoms.
  • R B2 and R B3 in formula (2-2) are both preferably an alkyl group having 6 to 18 carbon atoms, particularly an alkyl group having 8 to 18 carbon atoms. It is particularly preferred to be an alkyl group having 12 to 18 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the sulfur-based antioxidant is preferably 200 or more and 1,200 or less, particularly preferably 300 or more and 1,000 or less, particularly preferably 350 or more and 600 or less, In particular, it is preferably 350 or more and 550 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur content of the sulfur-based antioxidant is preferably within the range of 3% by mass to 20% by mass, particularly preferably within the range of 4% by mass to 15% by mass, and particularly, It is preferably within the range of 5% by mass to 13% by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur content can be measured in accordance with JIS K 2541.
  • the content of the sulfur-based antioxidant is equal to the amount of the sulfur-based antioxidant and the phenolic antioxidant.
  • the total amount of 100 parts by mass it is preferably 10 parts by mass or more and 99 parts by mass, particularly preferably 15 parts by mass or more and 90 parts by mass or less, and especially 20 parts by mass or more and 80 parts by mass or less. It is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant is preferably 10 parts by mass or more and 100 parts by mass or less, particularly preferably 20 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the antioxidant. In particular, it is preferably 30 parts by mass or more and 70 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant is preferably 0.001 parts by mass or more and 10 parts by mass or less, particularly 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component.
  • the content is preferably 0.5 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant is preferably 0.01 parts by mass or more and 10 parts by mass or less, particularly 0.1 parts by mass or more and 5 parts by mass, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably at least 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Phenolic antioxidant represents an antioxidant that does not contain a thioether and contains a phenolic hydroxyl group in its molecule.
  • Specific examples of the above-mentioned phenolic antioxidant include, for example, the phenolic antioxidant described in JP-A No. 2022-11537.
  • ADEKA STAB registered trademark
  • AO-20 AO-30
  • AO-40 AO-60
  • AO-80 AO-330
  • Sumilizer registered trademark
  • GP manufactured by Sumitomo Chemical Co., Ltd.
  • Irganox registered trademark
  • BASF BASF
  • the phenolic antioxidant is preferably a compound having a hindered phenol group. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above-mentioned hindered phenol group represents a group in which one hydrogen atom has been extracted from a benzene ring containing two tert-butyl groups and a hydroxyl group, and specifically, 3,5-di-tert-butyl- A preferred example is a 4-hydroxyphenyl group.
  • phenolic antioxidant having a hindered phenol group examples include Adekastab (registered trademark) AO-20, AO-50, AO-60, AO-330, and the like.
  • the content of the phenolic antioxidant is preferably 10 parts by mass or more and 100 parts by mass or less, based on 100 parts by mass of the antioxidant. However, it is preferably 20 parts by mass or more and 90 parts by mass or less, particularly preferably 30 parts by mass or more and 80 parts by mass or less, particularly preferably 30 parts by mass or more and 75 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the phenolic antioxidant is 0.001 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the cationically polymerizable component. is preferable, and more preferably 0.01 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, especially 0.2 parts by mass.
  • the amount is preferably 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the phenolic antioxidant is 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 0.05 parts by mass or more and 5 parts by mass or less, particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Phosphorus-based antioxidant represents an antioxidant that contains a phosphorus atom and does not contain a thioether or phenolic hydroxyl group in its molecule.
  • Commercially available products of the above-mentioned phosphorus antioxidants include ADEKA STAB (registered trademark) TPP, 3010, 135A, C, 1500, 1178, 2112, HP-10, PEP-36, and PEP-8 (manufactured by ADEKA Co., Ltd.). ) etc.
  • the antioxidant contains a compound represented by the above formula (2-1) and the above phenolic antioxidant, and in particular, a compound represented by the above formula (2-2). It is preferable to contain the represented compound and the above-mentioned phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the antioxidant includes a sulfur-based antioxidant and a phenolic antioxidant
  • the content of the sulfur-based antioxidant is higher than that of the phenolic antioxidant.
  • the mass ratio of inhibitor/phenolic antioxidant is preferably within the range of 0.1 to 20, particularly preferably within the range of 0.2 to 10, particularly 0.3 to 20. It is preferably within the range of 5. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant and the phenolic antioxidant relative to 100 parts by mass of the antioxidant is preferably 50 parts by mass or more, particularly preferably 70 parts by mass or more, and particularly , is preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, that is, the antioxidant contains only the sulfur-based antioxidant and the phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the antioxidant including a sulfur-based antioxidant and a phenolic antioxidant as the above-mentioned antioxidant is preferably 0.01 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the cationic polymerizable component. Among them, it is preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Further, the content of the antioxidant including a sulfur-based antioxidant and a phenolic antioxidant as the above-mentioned antioxidant is 0.001 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the solid content of the composition. The content is preferably 0.1 parts by mass or more and 5 parts by mass or less, particularly preferably 0.2 parts by mass or more and 4 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the antioxidant is 0 in 100 parts by mass of the cationic polymerizable component.
  • the content is preferably .01 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the antioxidant is based on 100 parts by mass of the solid content of the composition. , preferably 0.001 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, particularly 0.2 parts by mass or more and 3 parts by mass or less. It is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the black coloring material includes one or more selected from the group consisting of black pigments and black dyes.
  • the above black coloring materials may be used alone or in combination of two or more.
  • a black coloring material may be obtained by combining a plurality of coloring agents that cannot be used alone as a black coloring material and adjusting the coloring agent to produce a black color as a whole.
  • a black pigment as a pigment that expresses black color by itself
  • a plurality of pigments each having a color other than black may be used in combination as a black pigment.
  • a plurality of dyes having colors other than black may be used in combination as a black dye.
  • the black coloring material refers to a coloring material that can absorb light with a wavelength of 400 nm to 700 nm.
  • a composition is prepared that contains a coloring material, a transparent resin matrix (acrylic resin, etc.), and a solvent, and the content of the coloring material is 60% by mass based on the total solid content.
  • the obtained composition is applied onto a glass substrate so that the coating film after drying has a thickness of 1 ⁇ m to form a coating film.
  • the light-shielding properties of the dried coating film are evaluated using an ultraviolet-visible-near-infrared spectrophotometer (V-670, manufactured by JASCO Corporation). If the maximum value of the transmittance of the dried coating film in the wavelength range of 400 nm to 700 nm is less than 10%, it can be determined that the composition is useful for applications requiring light-shielding properties, for example.
  • the black coloring material is preferably a black pigment.
  • a black pigment a known black pigment can be used.
  • the black pigment may be an inorganic pigment or an organic pigment, but a pigment that alone expresses black color is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • pigments that express black color by themselves include Group 4 metal elements such as titanium and zirconium, Group 5 metal elements such as vanadium and niobium, cobalt, chromium, copper, manganese, ruthenium, iron, nickel, Examples include metal oxides, metal nitrides, metal oxynitrides, etc. containing metal elements such as tin and silver.
  • the black pigment include carbon black. Specific examples of carbon black include commercially available C. I. Pigment Black 1 and other organic pigments, and C.I. I. Examples include inorganic pigments such as Pigment Black 7.
  • the content of the black pigment is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the cationic polymerizable component.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the black pigment is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • a black dye is preferable because it dissolves in the composition of the present disclosure and is easily dispersed, so that it is easy to form a uniformly colored cured product. Further, it is preferable because it has excellent transparency and haze.
  • the above-mentioned black dye is soluble in a solvent and can be colored black by absorbing light in the wavelength range of visible light.
  • the black dye is at least one selected from azo black dyes and nigrosine black dyes.
  • DirectFastBlackAB C.I.DirectBlack32, manufactured by Sumitomo Chemical Industries, Ltd.
  • DirectDeepBlackEX C.I.DirectBlack38, manufactured by Sumitomo Chemical Industries, Ltd.
  • DirectFastBlackConc. C.I. Direct Black 51, manufactured by Hodogaya Chemical Industry Co., Ltd.
  • KayarusSupra Gray VGN C.I. Direct Black 71, manufactured by Nippon Kayaku Co., Ltd.
  • Acid BlueBlack 10B C.I. Acid Black 1
  • Sumino l Milling Black 8BX C.I. Acid Black 24, manufactured by Sumitomo Chemical Co., Ltd.
  • Kayanol Milling Black VLG C.I.
  • Acid Black 109 manufactured by Nippon Kayaku Co., Ltd.
  • Suminol Milling Black B C.I. Acid Black 109 , manufactured by Sumitomo Chemical Industries, Ltd.
  • Kayanol Milling Black TLR C.I. Acid Black 110, manufactured by Nippon Kayaku Co., Ltd.
  • the nigrosine black dye is a compound having a phenazine skeleton obtained by condensing aniline and nitrobenzene, such as a compound having a triphenazine oxazine structure represented by the following chemical formula (I) or (II), or a compound having the following chemical formula (III).
  • Examples include compounds having a phenazineazine structure represented by (VI). Note that X ⁇ in formulas (I) to (VI) represents a counter anion.
  • R 90 , R 91 , R 92 and R 93 are each independently a hydrogen atom or a phenyl group.
  • the nigrosine black dye mentioned above includes C.I. I. No. Examples include Acid Black 2, Solvent Black 5, Solvent Black 7, Solvent Black 22, Solvent Black 27, Solvent Black 29, and Solvent Black 34.
  • Examples of commercially available nigrosine black dyes include NUBIAN BLACK NH-805, NH-815 (manufactured by Orient Chemical Industry Co., Ltd.) (C.I.Solvent Black 5)), NUBIAN BLACK TN-870, TH-807 (manufactured by Orient Chemical Industry Co., Ltd.) (C.I. Solvent Black 7), VALIFAST BLACK1821 (organic acid salt (salt-forming dye) of C.I. Solvent Black 7), oil-soluble dye manufactured by Orient Chemical Industry Co., Ltd. dyes), etc.
  • the black dye includes a nigrosine-based black dye. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the black dye is a metal complex dye in which a metal such as chromium, cobalt, nickel, copper, or iron is complexed in the skeleton, or a salt-forming dye in which an acidic dye and a basic dye are reacted.
  • salt-forming dyes such as salt-forming dyes produced by salt-forming an acidic dye with a base such as an organic amine
  • salt-forming dyes such as salt-forming dyes produced by salt-forming a basic dye with an acid such as an organic acid.
  • salt-forming dyes are preferable.
  • the dye is preferably a salt-forming dye obtained by salt-forming a basic dye with an acid such as an organic acid. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • organic acids used to form the salt-forming dye include alkylbenzenesulfonic acids, naphthalenesulfonic acids, naphthalenesulfonic acid-formaldehyde condensates, alkyldiphenyl ether disulfonic acids, and polyoxyethylene alkylphenyl ether phosphoric acids.
  • alkylbenzenesulfonic acids are particularly preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the metal complex dye C.I. I. Solvent Black 21, 22, 23, 27, 28, 29, 31 etc., C.I. I. Acid Black 52, 60, 99, etc. are mentioned.
  • the salt forming dye include VALIFAST BLACK 1807, 1821, 3804, 3806, 3808, 3810, 3820, 3830, 3840, 3870, 3877 (manufactured by Orient Chemical Industry Co., Ltd.).
  • the black dye is a nigrosine-based black dye and contains a dye that is a metal complex salt dye or a salt-forming dye, particularly a nigrosine-based black dye, and a dye that is a salt-forming dye. It is preferred to include dyes that are salt dyes, especially C.I. I. An organic acid salt of Solvent Black 7 is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the black dye is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the black dye is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Photoacid generator The photoacid generator described above generates acid upon irradiation with active energy rays (hereinafter sometimes simply referred to as "energy rays") such as visible light, ultraviolet rays, X-rays, electron beams, and high frequency waves. It is a compound that can.
  • energy rays active energy rays
  • the above-mentioned photoacid generators include double salts that are onium salts or derivatives thereof, oxime sulfonate compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, diazomethane compounds, nitrobenzyl compounds, benzointosylate compounds, iron. -arene complexes, acetophenone derivative compounds, etc., and these can be used alone or in combination of two or more.
  • the photoacid generator is a double salt that is an onium salt or a derivative thereof. This is because, by using such a photoacid generator, the composition can yield a cured product with excellent sensitivity and adhesion.
  • double salts that are onium salts or derivatives thereof include salts of cations and anions represented by the following formula (i).
  • the cation [A] m+ is onium, and its structure can be represented by the following formula, for example.
  • R 300 represents an organic group having 1 to 60 carbon atoms and which may contain any number of atoms other than carbon atoms.
  • a represents an integer from 1 to 5.
  • the a pieces of R 300 are each independent and may be the same or different.
  • At least one of a R 300 represents the above organic group having an aromatic ring.
  • anion [B] m- is preferably a halide complex, and its structure can be represented by, for example, the following formula (iii). This is because the composition of the present disclosure has excellent sensitivity.
  • L represents a metal or metalloid that is the central atom of the halide complex, and includes B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn. , Sc, V, Cr, Mn or Co.
  • X 3 represents a halogen atom.
  • b represents an integer from 3 to 7.
  • anion [LX 3 b ] m- in formula (iii) above include tetrakis(pentafluorophenyl)borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) -, hexafluoroborate (BF 4 ) - , Fluorophosphate (PF 6 ) - , hexafluoroantimonate (SbF 6 ) - , hexafluoroarsenate (AsF 6 ) - , hexachloroantimonate (SbCl 6 ) - , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion) ) etc.
  • anion [B] m- may have a structure represented by the following formula (iv).
  • L, X3 and b are the same as above.
  • Other anions include perchlorate ion (ClO 4 ) - , trifluoromethylsulfite ion (CF 3 SO 3 ) - , fluorosulfonate ion (FSO 3 ) - , toluenesulfonate anion, and trinitrobenzene.
  • Sulfonic acid anions, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like can be mentioned.
  • onium salts it is particularly effective to use the following aromatic onium salts (a) to (c).
  • aromatic onium salts (a) to (c) one kind can be used alone or two or more kinds can be used in combination.
  • Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
  • Diaryl such as diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tolylcumyliodonium tetrakis(pentafluorophenyl)borate, etc. iodonium salt
  • photoacid generators include ( ⁇ 5-2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6- ⁇ )-(1-methylethyl)benzene] - Iron-arene complexes such as iron-hexafluorophosphate, aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, tris(salicylaldehydato)aluminum, and silanols such as triphenylsilanol. Also included are mixtures with other types.
  • aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferable as photoacid generators, and aromatic sulfonium salts are especially preferable.
  • a triarylsulfonium salt having a structure in which three aromatic rings are bonded to a sulfur atom (S) is more preferable, and a triarylsulfonium salt represented by the following formula (4) is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 are Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R 115 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any substituent selected from the following formulas (4a) to (4c), An q- represents a q-valent anion, p represents a coefficient that neutralizes the charge.
  • R 116 , R 117 , R 118 , R 119 , R 120 , R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 are each independently, Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, * represents the bonding position with S.
  • Examples of the alkyl group having 1 to 10 carbon atoms include those listed as the ⁇ al
  • the alkoxy group having numbers 1 to 10 is a predetermined one among those listed as the "alkoxy group having 1 to 20
  • Examples of the q-valent anion represented by pAn q- in the above formula (4) include anions with a predetermined valence among those listed as the above-mentioned anion [B] m- .
  • Examples of the q-valent anion represented by pAn q- include tetrakis(pentafluorophenyl)borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) - , hexafluorophosphate (PF 6 ) - , hexafluoroantimonate (SbF 6 ) - , hexafluoroarsenate (AsF 6 ) - , hexachloroantimonate (SbCl 6 ) - , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion), perchloric acid ion (ClO 4 ) - ,
  • R 115 is preferably selected from the above formulas (4a) to (4c), more preferably the above formula (4a) or (4c). This is because when R 115 has the above-described structure, the composition can form a cured product with better heat-and-moisture resistance and weather resistance.
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 are hydrogen atom, halogen atom, carbon It is preferably an alkyl group having 1 to 10 atoms or an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R116 , R117 , R118 , R119 , R120, R121 , R122, R123, R124 , R125 , R126 , R127 , R128 , R129 , R130 , R131 , R132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. or an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the photoacid generator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. It is more preferably 1 part by mass or more and 7 parts by mass or less, particularly preferably 1 part by mass or more and 4.5 parts by mass or less. This is because by setting the content within such a range, the composition can form a cured product with better heat and humidity resistance and weather resistance.
  • the content of the photoacid generator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 7 parts by mass, based on 100 parts by mass of the solid content of the composition. It is more preferably at most 1 part by mass and at most 5 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Note that commercially available photoacid generators are sometimes sold in a state dispersed or dissolved in a solvent, but the content of the photoacid generator in this disclosure refers to the content as a solid content excluding the solvent. It represents.
  • composition of the present disclosure contains a cationic polymerizable component and an antioxidant, and further contains a photoacid generator and a black coloring material as necessary, but as long as the effects of the present invention are not impaired.
  • Other ingredients may be included depending on the requirements.
  • Other ingredients include sensitizers, solvents, leveling agents, fillers, silane coupling agents, antifoaming agents, thickeners, thixotropic agents, surfactants, dispersants, flame retardants, plasticizers, stabilizers, Examples include various additives such as polymerization inhibitors, ultraviolet absorbers, antistatic agents, fluidity regulators, and adhesion promoters.
  • the composition of the present disclosure preferably contains a sensitizer and a leveling agent as additives. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Sensitizer The above composition preferably contains a sensitizer together with the above-mentioned cationically polymerizable component and antioxidant in order to improve the sensitivity and curability of the composition.
  • a carbazole-based sensitizer made of a compound having a carbazole skeleton can be preferably used as the sensitizer. This is because the above composition can be easily cured. Further, the above composition can form a cured product having better heat and humidity resistance and weather resistance.
  • carbazole-based sensitizers examples include compounds represented by chemical formulas selected from the following formulas (5-1), (5-2), (5-3), and (5-4). Can be mentioned.
  • R 201 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, or a group having 6 to 30 carbon atoms; 30 aryl group, an alkoxy group having 1 to 30 carbon atoms, a cyano group, a hydroxyl group, or a carboxyl group.
  • R 211 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.
  • R 231 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.
  • R 251 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.
  • alkyl group having 1 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1),
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1) For example, in addition to those exemplified as the "alkyl group having 1 to 20 carbon atoms" in formula (1-1) described in the section "1.
  • Cationically polymerizable component above, n-tricosyl groups and Examples include n-tetracosyl group.
  • the aryl group having 6 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1) is Examples include phenyl group, tolyl group, 3,4,5-trimethoxyphenyl group, 4-tert-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, and phenanthryl group.
  • alkoxy group having 1 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1),
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1)
  • alkoxy group having 1 to 20 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1)
  • alkoxy group having 1 to 20 carbon atoms represented by R 201 , R 202 , R 203 ,
  • the number of carbon atoms represented by R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 in the above formula (5-2) is 1 to
  • the alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 in the above formula (5-2) is 6 or more
  • the aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 231 , R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 in the above formula (5-3) is 1 to
  • the alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 231 , R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 in the above formula (5-3) is 6 or more
  • the aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 251 , R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 in the above formula (5-4) is 1 to
  • the alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 251 , R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 in the above formula (5-4) is 6 or more
  • the aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
  • R 201 in the above formula (5-1) is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, In particular, an alkyl group having 1 to 5 carbon atoms is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 211 in the above formula (5-2), R 231 in the above formula (5-3), and R 251 in the above formula (5-4) may be an alkyl group having 1 to 30 carbon atoms. It is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 5 to 12 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 202 , R 203 , R 204 and R 205 and at least one of R 206 , R 207 , R 208 and R 209 each independently have a carbon atom number of 1 to It is preferable that R 203 and R 208 are each independently an alkoxy group having 1 to 30 carbon atoms, and is preferably an alkoxy group having 1 to 10 carbon atoms. More preferably, it is an alkoxy group having 1 to 5 carbon atoms, and particularly preferably an alkoxy group having 1 to 3 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 203 and R 208 are alkoxy groups
  • R 202 , R 204 , R 205 , R 206 , R 207 and R 209 are preferably hydrogen atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sensitizer is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the solid content of the composition. More preferably 2 parts by mass or more and 3 parts by mass or less, particularly preferably 0.5 parts by mass or more and 2 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sensitizer is preferably 1 part by mass or more and 70 parts by mass or less, and 5 parts by mass or more, based on 100 parts by mass of the photoacid generator. It is more preferably 50 parts by mass or less, particularly preferably 10 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the composition of the present disclosure can contain a solvent as necessary.
  • the above-mentioned solvent is liquid at room temperature (25° C.) under atmospheric pressure, is capable of dispersing or dissolving each component in the composition, and does not react with the above-mentioned cationically polymerizable component. Therefore, even if it is liquid at room temperature (25° C.) and atmospheric pressure, the cationically polymerizable compound described in the above “A1. Cationically polymerizable component” is not included in the above solvent.
  • the antioxidant described in "A2. Antioxidant” and the antioxidant described in "A3. Black coloring material” above are used.
  • a solvent either water or an organic solvent can be used, and an organic solvent can be preferably used.
  • organic solvents examples include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, , 2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc.
  • ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl
  • Ester solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethylpropionate, 1-t-butoxy Ether ester solvents such as -2-propanol, 3-methoxybutyl acetate, and cyclohexanol acetate; Aromatic solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, oc
  • ketones, ether ester solvents, etc. especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. can be mentioned, and these solvents can be used as a single type or a mixed solvent of two or more types. can.
  • organic solvents ketones, alcohol solvents, ether ester solvents, aromatic solvents, etc. are preferred, and ether ester solvents and alcohol solvents are particularly preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the above-mentioned solvent may be such that the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the content of the above-mentioned solvent in 100 parts by mass of the above-mentioned composition is 50 parts by mass or less, which provides excellent drying properties and the above-mentioned composition. It is preferable in that the degree of freedom in selecting the destination for forming the cured film is widened, and it is particularly preferable that the amount is 30 parts by mass or less, and particularly preferably 10 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • composition of the present disclosure may contain a filler as another component.
  • the filler include fumed silica, particulate silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, Examples include mica, minnesotaite, pyrophyllite, silica, glass fiber, and calcium carbonate.
  • the content of the filler can be appropriately set depending on the use of the composition of the present disclosure.
  • components other than the cationic polymerizable component, antioxidant, black coloring material, photoacid generator, and sensitizer is preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less, based on 100 parts by mass of the solid content of the composition of the present disclosure. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the amount thereof is preferably 20 parts by mass or less, particularly 10 parts by mass or less, per 100 parts by mass of the cationically polymerizable component. The amount is preferably 5 parts by mass or less, particularly preferably 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • compositions There is no problem in producing the above composition as long as it is possible to form a composition containing the desired amounts of each of the above components, and examples include methods using known mixing means.
  • the composition of the present invention can be produced by mixing each component using a mixer such as a homodisper, a homomixie, a universal mixer, a planetary mixer, a kneader, or a three-roll mixer.
  • the use of the above composition preferably requires a cured product with excellent heat and humidity resistance and weather resistance, such as optical filters including light blocking filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, etc.
  • color filters, electrode materials for plasma display panels, printing inks, dental compositions, stereolithography resins, both liquid and dry films, micromechanical components, glass fiber cable coatings, and holographic recording materials. can be mentioned.
  • the cured product of the present disclosure is obtained by curing the above-mentioned composition.
  • the composition is used as an optical filter, particularly as a light-blocking filter (ND filter) that reduces the transmittance of visible light as a whole, and in particular, as an image filter.
  • ND filter light-blocking filter
  • a light-shielding film such as a black matrix used in a display device; a color adjustment filter for an image display device; a light-shielding filter for improving antireflection properties, etc. This is because the cured product can exhibit excellent light-shielding properties in the form of a thin film, and is particularly useful in the above-mentioned applications where thin films are highly demanded.
  • the composition described above can be preferably used for solder resists used in printed circuit boards. This is because it provides excellent protection for the wiring.
  • the cured product may be used to achieve two purposes at the same time.
  • the thicker portion may be used as a black matrix, and the thinner portion may be used as a color adjustment filter.
  • reducing the transmittance of the entire visible light means, for example, when a cured film of the above composition is formed so that the transmittance at 500 nm is 45%, the transmittance at 400 nm is reduced.
  • the transmittance and transmittance at 600 nm may be in the range of 40% to 50%.
  • the transmittance at 700 nm is also preferably within the range of 40% to 50%.
  • the color adjustment filter can be one that adjusts each color of light. More specifically, the color adjustment filter is the color of light transmitted through a color filter used as an optical filter, in which pixels of R (red), G (green), B (blue) and other colors are arranged.
  • the light emitters of each color are arranged so as to overlap with the color filter in plan view. Examples include those arranged so as to overlap in plan view.
  • the material of the adherend on which the cured product of the above composition is formed is not particularly limited, and commonly used materials can be used, such as metal bases such as aluminum, titanium, stainless steel, mild steel, and plated steel.
  • Inorganic materials such as wood, glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate; Polyesters such as polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene , polyolefins such as polymethylpentene; vinyl compounds such as polyvinyl a
  • the cured product of the present disclosure is characterized by being a cured product of the above-mentioned composition. Since the cured product is obtained by curing the composition described above, it has excellent heat-humidity resistance and weather resistance. The cured product has a long service life in a high-humidity, high-temperature environment.
  • the cured product of the present disclosure will be explained in detail. Note that the above-mentioned composition is the same as described in the section "A. Composition" above.
  • the above-mentioned cured product usually contains a polymer of a cationically polymerizable component.
  • the planar shape, thickness, etc. of the cured product can be appropriately set depending on the intended use of the cured product.
  • the thickness may be, for example, 0.05 ⁇ m or more and 300 ⁇ m or less.
  • the total light transmittance and Haze value of the cured product are appropriately set depending on the use of the cured product, and are adjusted depending on the thickness, concentration of the black coloring material, etc.
  • the method for producing the cured product is not particularly limited as long as it can form the cured product of the composition into a desired shape.
  • the step of curing the composition described above may be mentioned.
  • the step of curing is a step of curing the above-mentioned composition.
  • the method for curing the composition may be any method as long as the cationically polymerizable components can be polymerized with each other, such as a method of irradiating the coating film of the composition with light (energy rays). This is because the cationically polymerizable component can be easily polymerized.
  • the light sources of energy rays used for polymerizing the cationically polymerizable component include ultra-high pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, and carbon arc lamps.
  • electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., and high-energy rays such as electron beams, X-rays, and radiation. can be used.
  • an ultra-high pressure mercury lamp a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a light emitting diode, etc. that emit light with a wavelength of 300 to 450 nm is used.
  • a mercury vapor arc lamp a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a light emitting diode, etc. that emit light with a wavelength of 300 to 450 nm
  • the cationically polymerizable component can be easily polymerized.
  • the amount of energy ray irradiation is preferably in the range of 100 mJ/cm 2 to 2000 mJ/cm 2 at 365 nm from the viewpoint of preventing deterioration of the components in the composition.
  • the curing method is a method that uses a method of irradiating energy rays and a method of heating in combination, and more specifically, a method of irradiating energy rays and a method of heating are performed in this order. It is preferable. This is because the polymerization of the cationically polymerizable component can proceed efficiently.
  • Examples of the method for heating the coating film of the composition in this step include methods using a hot plate such as a hot plate, an atmospheric oven, an inert gas oven, a vacuum oven, a hot air circulation oven, and the like.
  • the heating temperature when heating the coating film is not particularly limited, but from the viewpoint of facilitating polymerization of the cationic polymerizable component, it is preferably 70°C or more and 200°C or less, and especially 90°C or more and 150°C or less. It is preferable that there be.
  • the heating time when heating the coating film is not particularly limited, but from the viewpoint of improving productivity, it is preferably in the range of 1 minute to 60 minutes, particularly in the range of 1 minute to 30 minutes. is preferred.
  • the above manufacturing method may include other steps as necessary.
  • Such a step may include a step of applying the composition to a substrate before the step of curing the composition.
  • known methods such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, and dipping methods can be used.
  • the above-mentioned base material can be appropriately selected depending on the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like. Moreover, after the cured product is formed on a base material, it may be peeled off from the base material and used, or it may be used after being transferred from the base material to another adherend.
  • Examples 1 to 28 and Comparative Examples 1 to 5 Each component was blended according to the formulations in Tables 1 to 5 below to obtain a composition. In addition, the following materials were used for each component. Note that the blending amounts in the table represent parts by mass of each component.
  • the compounding amount of the photoacid generator represents the compounding amount including the solvent.
  • A1-1 Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-1), epoxy equivalent 80 g/eq., THI-DE manufactured by JXTG Energy)
  • A1-2 Alicyclic epoxy compound ( Bifunctional, compound represented by the following formula (A1-2), epoxy equivalent: 122 g/eq., manufactured by JXTG Energy DE-102)
  • A1-3 Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-3), epoxy equivalent 128 to 145 g/eq., Celoxide 2021P manufactured by Daicel)
  • A1-4 Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-4), epoxy equivalent 100 g/eq., Celoxide 8000 manufactured by Daicel)
  • A2-1 Polyfunctional aliphatic epoxy compound (bifunctional, compound represented by the following formula (A2-1).
  • A2-2 Monofunctional aliphatic epoxy compound (monofunctional, compound represented by the following formula (A2-2).
  • R A6 is an alkyl group having 12 to 13 carbon atoms
  • A3-1 Adeka Resin (registered trademark) EP-4100 (manufactured by ADEKA Co., Ltd., bisphenol A type epoxy resin (epoxy equivalent: 190 g/eq.))
  • A4-1 Aronoxetane (registered trademark) OXT-221 (manufactured by Toagosei Co., Ltd., bifunctional oxetane compound represented by the following formula (A4-1))
  • A4-2 Aronoxetane (registered trademark) OXT-212 (manufactured by Toagosei Co., Ltd., monofunctional oxetane compound represented by the following formula (A4-2))
  • B1-1 Compound represented by the following formula (B1-1) (compound represented by formula (2-1) and formula (2-2), sulfur content: 5.91% by mass)
  • B1-2 Compound represented by the following formula (B1-2) (compound represented by formula (2-1), sulfur content: 11.04% by mass)
  • B1-3 Compound represented by the following formula (B1-3) (sulfur content: 10.43% by mass)
  • Antioxidant phenolic antioxidant
  • B2-1 ADEKA STAB (registered trademark) AO-60 (manufactured by ADEKA Co., Ltd., compound represented by the following formula (B2-1)) "tBu” in formula (B2-1) represents a tert-butyl group. represent.
  • black color material C1-1 Nigrosine black dye (compound represented by the following formula (C1-1))
  • Leveling agent F1-1 Megafac (registered trademark) F-554 (manufactured by DIC Corporation)
  • compositions of Examples and Comparative Examples were spin-coated onto a 10 cm x 10 cm glass substrate to form a coating film (hereinafter sometimes referred to as "pre-cured coating film").
  • pre-cured coating film a coating film
  • each composition was cured by irradiating 2,000 mJ/cm 2 of 365 nm light using a UV-LED light source to form a cured film.
  • the thickness of the coating film before curing was adjusted to 4 ⁇ m.
  • a double-sided adhesive tape (manufactured by 3M, thickness: 25 ⁇ m, manufacturer product number: 8146-1) was applied on the obtained cured film, and a PET film (manufactured by Toyobo Co., Ltd., thickness: 100 ⁇ m, Lumirror T60) was applied on top of it. ) to prepare a test piece.
  • the obtained test piece was left in a constant temperature and humidity tester at 60° C. and 90% RH for 1,000 hours.
  • the transmittance of the test piece at 540 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-670, manufactured by JASCO Corporation), and the transmittance at 540 nm was compared with that of the test piece before the test. For comparison, when the transmittance before the test is A and the transmittance after the test is B, (BA) (%) is the change in transmittance, and the evaluation was made according to the following evaluation criteria.
  • a test piece was prepared in the same manner as in "1. Moisture and Heat Resistance” above. The obtained test piece was subjected to a weather resistance test for 200 hours using SUN TEST The transmittance at 540 nm of the test piece was measured in the same manner as in "1. Humid heat resistance”, and compared with the transmittance at 540 nm of the test piece before the test, the transmittance before the test was A, and the transmittance after the test was A. When the transmittance is B, (B-A) (%) is the change in transmittance, and the evaluation was made according to the following evaluation criteria.

Abstract

A composition containing a cationic polymerizable component and an antioxidant, wherein the cationic polymerizable component contains at least one selected from alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds and the antioxidant contains a sulfur-based antioxidant. The content of the alicyclic epoxy compound is preferably from 0.5 mass part to 80 mass parts per 100 mass parts of the cationic polymerizable component.

Description

組成物及び硬化物Composition and cured product
　本発明は、組成物及びその硬化物に関する。 The present invention relates to a composition and a cured product thereof.
　光量の調整方法として遮光フィルタを使用する方法が知られている。
　特許文献１には、半導体集積回路等のリソグラフィ用露光装置における照度調整のために遮光フィルタを用いることが記載されている。
　特許文献２には、反射防止膜に用いる遮光フィルタとして一定の割合で光強度を弱めるグレイ着色層を使用することが記載されている。
　特許文献３には、液晶ディスプレイ用やビデオカメラ用のカラーフィルタに用いるブラックマトリックスを形成する材料として、カチオン重合性化合物、黒色顔料、光酸発生剤及び溶剤を含む組成物が提案されている。 A method of using a light blocking filter is known as a method of adjusting the amount of light.
Patent Document 1 describes the use of a light shielding filter to adjust illuminance in an exposure apparatus for lithography such as a semiconductor integrated circuit.
Patent Document 2 describes the use of a gray colored layer that weakens light intensity at a certain rate as a light shielding filter used in an antireflection film.
Patent Document 3 proposes a composition containing a cationically polymerizable compound, a black pigment, a photoacid generator, and a solvent as a material for forming a black matrix used in color filters for liquid crystal displays and video cameras.
特開２００７－２６６０９８号公報JP2007-266098A 特開平１－１９８７０１号公報Japanese Patent Application Publication No. 198701/1999 特開平９－１３３８０７号公報Japanese Patent Application Publication No. 9-133807
　特許文献１～２で用いられている遮光フィルタは、金属薄膜や金属メッシュからなるものであり、凹凸形状の表面への形成や、大面積の遮光対象への形成が困難であり、形成箇所に制限を受ける場合がある。
　特許文献３の組成物を硬化させた硬化物は、耐湿熱性及び耐候性が未だ満足できるものではなかった。 The light-shielding filters used in Patent Documents 1 and 2 are made of metal thin films or metal meshes, and are difficult to form on uneven surfaces or on large-area light-shielding objects. There may be restrictions.
The cured product obtained by curing the composition of Patent Document 3 still has unsatisfactory heat and humidity resistance and weather resistance.
　本発明者らは、上記課題を解決すべく、上記問題の原因等について鋭意検討した結果、特定のカチオン重合性化合物と特定の酸化防止剤を含む組成物を用いることで、耐湿熱性及び耐候性に優れる硬化物を形成できることを見出した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the causes of the above-mentioned problems, and have found that by using a composition containing a specific cationic polymerizable compound and a specific antioxidant, the present inventors have improved heat-and-moisture resistance and weather resistance. It has been found that a cured product with excellent properties can be formed.
　すなわち、本開示は、カチオン重合性成分及び酸化防止剤を含む組成物であって、前記カチオン重合性成分は、脂環式エポキシ化合物と、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物から選択される少なくとも１種と、を含み、前記酸化防止剤が、硫黄系酸化防止剤を含む組成物を提供する。 That is, the present disclosure provides a composition comprising a cationically polymerizable component and an antioxidant, wherein the cationically polymerizable component is selected from an alicyclic epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, and an oxetane compound. The present invention provides a composition including at least one type of sulfur-based antioxidant, wherein the antioxidant includes a sulfur-based antioxidant.
　本開示によれば、上記組成物は、耐湿熱性及び耐候性に優れる硬化物を形成することができる。 According to the present disclosure, the above composition can form a cured product with excellent heat and humidity resistance and weather resistance.
　本開示においては、前記脂環式エポキシ化合物が、下記一般式（１－１）、（１－２）、（１－３）、（１－４）及び（１－５）から選択される化学式で表される化合物のうち少なくとも１種を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the alicyclic epoxy compound has a chemical formula selected from the following general formulas (1-1), (1-2), (1-3), (1-4), and (1-5). It is preferable that at least one of the compounds represented by the above is included. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（１－１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－２）中、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９、Ｒ２０、Ｒ２１、Ｒ２２、Ｒ２３、Ｒ２４、Ｒ２５及びＲ２６は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－３）中、Ｒ３１、Ｒ３２、Ｒ３３、Ｒ３４、Ｒ３５、Ｒ３６、Ｒ３７、Ｒ３８、Ｒ３９、Ｒ４０、Ｒ４１、Ｒ４２、Ｒ４３、Ｒ４４、Ｒ４５、Ｒ４６、Ｒ４７及びＲ４８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－４）中、Ｒ５１、Ｒ５２、Ｒ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７、Ｒ５８、Ｒ５９、Ｒ６０、Ｒ６１、Ｒ６２、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－５）中、Ｒ７１、Ｒ７２、Ｒ７３、Ｒ７４、Ｒ７５、Ｒ７６、Ｒ７７、Ｒ７８、Ｒ７９、Ｒ８０、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４、Ｒ８５、Ｒ８６、Ｒ８７及びＲ８８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表し、
　Ｘは、単結合又は炭素原子数１～４のアルキレン基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド基若しくはこれらのうちの複数が連結した基を表す。 In formula (1-1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a carbon atom, Represents an alkyl group having 1 to 20 atoms or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-2), 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 and R 26 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-3), R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-4), R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-5), R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms,
X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which two or more of these are linked.
　本開示においては、上記脂環式エポキシ化合物の含有量が、上記カチオン重合性成分１００質量部中、０．５質量部以上８０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記脂肪族エポキシ化合物が、多官能脂肪族エポキシ化合物を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the aliphatic epoxy compound includes a polyfunctional aliphatic epoxy compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記脂肪族エポキシ化合物の含有量が、上記カチオン重合性成分１００質量部中、５質量部以上７０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the content of the aliphatic epoxy compound is preferably 5 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記オキセタン化合物の含有量が、上記カチオン重合性成分１００質量部中、０．５質量部以上８０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the content of the oxetane compound is preferably 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記硫黄系酸化防止剤が、下記一般式（２－１）で表される化合物であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the sulfur-based antioxidant is preferably a compound represented by the following general formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（２－１）中、Ａは、炭素原子又は硫黄原子を表し、
Ｘ２は、単結合又は炭素原子数１～４のアルキレン基、炭素原子数６～１８のフェニレン基、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、カーボネート基、アミド基若しくはこれらのうち複数が連結した基を表し、
ＲＢ１は、炭素原子数６～２０のアルキル基又は、炭素原子数６～２０のアリール基を表し、
Ａが、硫黄原子の場合、ｍ１は、２を表し、
Ａが、炭素原子の場合、ｍ１は、４を表し、且つ、Ｘ２は、構造中にチオエーテル結合を含む基を表す。 In formula (2-1), A represents a carbon atom or a sulfur atom,
X 2 is a single bond, an alkylene group having 1 to 4 carbon atoms, a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide group, or more than one of these represents a linked group,
R B1 represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms,
When A is a sulfur atom, m1 represents 2,
When A is a carbon atom, m1 represents 4, and X 2 represents a group containing a thioether bond in its structure.
　本開示においては、上記硫黄系酸化防止剤の含有量が、酸化防止剤１００質量部中、１０質量部以上９０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the content of the sulfur-based antioxidant is preferably 10 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記組成物は、さらに、黒色色材を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the composition further includes a black coloring material. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記組成物は、さらに、光酸発生剤を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the composition further includes a photoacid generator. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示は、上述の組成物の硬化物を提供する。 The present disclosure provides a cured product of the above composition.
　本開示によれば、耐湿熱性及び耐候性に優れた硬化物を形成できる組成物を提供できる。 According to the present disclosure, it is possible to provide a composition that can form a cured product with excellent heat and humidity resistance and weather resistance.
　本開示は、組成物、それを用いた硬化物に関するものである。
　以下、本開示の組成物及び硬化物について詳細に説明する。 The present disclosure relates to a composition and a cured product using the same.
Hereinafter, the composition and cured product of the present disclosure will be explained in detail.
　本明細書において、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、炭素原子数１～２０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１～２０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。また、本明細書において所定の炭素原子数の基中のメチレン基が二価の基で置き換えられた基に係る炭素原子数の規定は、その置換後の基の炭素原子数を規定するものとする。 In this specification, the number of carbon atoms in a group, when a hydrogen atom in the group is substituted with a substituent, defines the number of carbon atoms in the group after the substitution. For example, when a hydrogen atom of an alkyl group having 1 to 20 carbon atoms is substituted, 1 to 20 carbon atoms refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the previous number of carbon atoms. In addition, in this specification, the definition of the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group shall be defined as the number of carbon atoms in the group after the substitution. do.
　本明細書において、「組成物の固形分」とは、組成物中の溶剤を除く全成分の含有量を表す。 In this specification, the "solid content of the composition" refers to the content of all components in the composition excluding the solvent.
Ａ．組成物
　本発明は、カチオン重合性成分及び酸化防止剤を含む組成物であって、上記カチオン重合性成分は、脂環式エポキシ化合物と、脂肪族エポキシ化合物、オキセタン化合物及び芳香族エポキシ化合物から選択される少なくとも１種と、を含み、上記酸化防止剤が、硫黄系酸化防止剤を含むことを特徴の一つとする。 A. Composition The present invention provides a composition comprising a cationically polymerizable component and an antioxidant, wherein the cationically polymerizable component is selected from an alicyclic epoxy compound, an aliphatic epoxy compound, an oxetane compound, and an aromatic epoxy compound. One of the characteristics is that the antioxidant includes a sulfur-based antioxidant.
　本開示の組成物は、耐湿熱性及び耐候性に優れる硬化物を形成できる。
　なお、耐湿熱性は、高湿高温環境下に曝された後の、硬化物の光透過性を維持できる機能であり、具体的には、長期間の高湿高温環境下に曝したときの、硬化物の５４０ｎｍの光の透過率による評価によって表すことができる。
　耐候性は、太陽光暴露に対する耐久性であり、具体的には、キセノンランプを用いた耐候性試験後における硬化物の５４０ｎｍの光の透過率による評価によって表すことができる。 The composition of the present disclosure can form a cured product with excellent moist heat resistance and weather resistance.
In addition, heat and humidity resistance is a function that can maintain the light transmittance of a cured product after being exposed to a high humidity and high temperature environment. Specifically, when exposed to a high humidity and high temperature environment for a long period of time, It can be expressed by evaluating the transmittance of the cured product to light at 540 nm.
Weather resistance is durability against sunlight exposure, and specifically can be expressed by evaluating the transmittance of a cured product to 540 nm light after a weather resistance test using a xenon lamp.
　以下、本開示の組成物を構成する各成分について詳細に説明する。 Hereinafter, each component constituting the composition of the present disclosure will be explained in detail.
Ａ１．カチオン重合性成分
　上記カチオン重合性成分は、酸により重合又は架橋反応を起こす化合物である。
　本開示においては、カチオン重合性成分として、カチオン重合性基を有するカチオン重合性化合物を２種以上含む。 A1. Cationically polymerizable component The cationically polymerizable component is a compound that undergoes a polymerization or crosslinking reaction with an acid.
In the present disclosure, the cationically polymerizable component includes two or more cationically polymerizable compounds having a cationically polymerizable group.
　上記カチオン重合性基は、例えばエポキシ基、オキセタニル基、環状ラクトン基、環状アセタール基、環状チオエーテル基、スピロオルトエステル基等の環状エーテル基、及びビニルエーテル基等が挙げられる。
　すなわち、上記カチオン重合性化合物としては、例えばエポキシ化合物、オキセタン化合物、環状ラクトン化合物、環状アセタール化合物、環状チオエーテル化合物、スピロオルトエステル化合物等の環状エーテル化合物、及びビニルエーテル化合物等が挙げられる。
　ここで、エポキシ化合物は、カチオン重合性基としてエポキシ基を有する化合物とする。従って、エポキシ基及びオキセタニル基の両者を有する化合物は、エポキシ化合物に該当する。
　オキセタン化合物は、カチオン重合性基として、オキセタニル基を有し、エポキシ基を有しない化合物とする。
　エポキシ化合物、オキセタン化合物以外のカチオン重合性化合物は、エポキシ基、オキセタニル基のいずれも有しない化合物とする。 Examples of the above-mentioned cationic polymerizable groups include epoxy groups, oxetanyl groups, cyclic lactone groups, cyclic acetal groups, cyclic thioether groups, cyclic ether groups such as spiro-orthoester groups, and vinyl ether groups.
That is, examples of the cationically polymerizable compound include epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, cyclic ether compounds such as spiro-orthoester compounds, and vinyl ether compounds.
Here, the epoxy compound is a compound having an epoxy group as a cationically polymerizable group. Therefore, a compound having both an epoxy group and an oxetanyl group corresponds to an epoxy compound.
The oxetane compound is a compound having an oxetanyl group as a cationic polymerizable group and not having an epoxy group.
The cationically polymerizable compounds other than the epoxy compound and the oxetane compound are compounds having neither an epoxy group nor an oxetanyl group.
　本開示においては、カチオン重合性成分は、脂環式エポキシ化合物と、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物から選択される少なくとも１種と、を含むものである。
　すなわち、カチオン重合性成分は、脂環式エポキシ化合物を必須成分として含有し、さらに、必須成分として脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物から選ばれる少なくとも１種を含むものである。
　したがって、上記カチオン重合性成分は、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物のうち、脂環式エポキシ化合物と、脂肪族エポキシ化合物とのみを含むものであってもよく、脂環式エポキシ化合物と、オキセタン化合物とのみを含むものであってもよく、脂環式エポキシ化合物と、芳香族エポキシ化合物とのみを含むものであってもよく、脂環式エポキシ化合物と、脂肪族エポキシ化合物及びオキセタン化合物とのみを含むものであってもよく、脂環式エポキシ化合物と、脂肪族エポキシ化合物及び芳香族エポキシ化合物とのみを含むものであってもよく、脂環式エポキシ化合物と、芳香族エポキシ及びオキセタン化合物とのみを含むものであってもよく、脂環式エポキシ化合物と、脂肪族エポキシ化合物と、オキセタン化合物及び芳香族エポキシ化合物と、の全てを含むものであってもよい。 In the present disclosure, the cationically polymerizable component includes an alicyclic epoxy compound and at least one selected from an aliphatic epoxy compound, an aromatic epoxy compound, and an oxetane compound.
That is, the cationically polymerizable component contains an alicyclic epoxy compound as an essential component, and further contains at least one selected from aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds as an essential component.
Therefore, even if the above-mentioned cationically polymerizable component contains only an alicyclic epoxy compound and an aliphatic epoxy compound among alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds, Often, it may contain only an alicyclic epoxy compound and an oxetane compound, it may contain only an alicyclic epoxy compound and an aromatic epoxy compound, and it may contain only an alicyclic epoxy compound and an aromatic epoxy compound. may contain only an aliphatic epoxy compound and an oxetane compound, or may contain only an alicyclic epoxy compound, an aliphatic epoxy compound, and an aromatic epoxy compound; It may contain only a compound, an aromatic epoxy compound, and an oxetane compound, or it may contain all of an alicyclic epoxy compound, an aliphatic epoxy compound, an oxetane compound, and an aromatic epoxy compound. Good too.
　本開示においては、カチオン重合性成分が、脂環式エポキシ化合物とともに、脂肪族エポキシ化合物及びオキセタン化合物から選ばれる少なくとも１種を含むことが好ましく、なかでも、脂環式エポキシ化合物と、オキセタン化合物とを含むことが好ましく、特に、脂環式エポキシ化合物と、脂肪族エポキシ化合物及びオキセタン化合物とを含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the cationic polymerizable component contains at least one selected from an aliphatic epoxy compound and an oxetane compound together with an alicyclic epoxy compound. It is particularly preferable to contain an alicyclic epoxy compound, an aliphatic epoxy compound, and an oxetane compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物の合計の含有量の下限は、カチオン重合性成分１００質量部中、５０質量部であることが好ましく、なかでも、６０質量部であることが好ましく、特に、７０質量部であることが好ましく、なかでも特に、８０質量部であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The lower limit of the total content of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound is preferably 50 parts by mass in 100 parts by mass of the cationically polymerizable component, and especially 60 parts by mass. It is preferably 70 parts by mass, particularly preferably 80 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　以下、本明細書において、「脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物の合計」は、カチオン重合性成分中に含まれる、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物の合計をいうものであり、例えば、カチオン重合性成分が、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物のうち、脂環式エポキシ化合物、脂肪族エポキシ化合物及びオキセタン化合物のみを含み、芳香族エポキシ化合物を含まない場合には、脂環式エポキシ化合物、脂肪族エポキシ化合物及びオキセタン化合物の合計をいうものである。 Hereinafter, in this specification, "the total of the alicyclic epoxy compound, the aliphatic epoxy compound, the aromatic epoxy compound, and the oxetane compound" refers to the alicyclic epoxy compound, the aliphatic epoxy compound contained in the cationically polymerizable component. , refers to the total of aromatic epoxy compounds and oxetane compounds. For example, the cationically polymerizable component is an alicyclic epoxy compound among alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds. , when it contains only an aliphatic epoxy compound and an oxetane compound and does not contain an aromatic epoxy compound, it refers to the total of the alicyclic epoxy compound, the aliphatic epoxy compound, and the oxetane compound.
（１）脂環式エポキシ化合物
　上記脂環式エポキシ化合物は、分子中に少なくとも１つの脂環式エポキシ基を有する化合物、すなわちシクロアルケンオキサイド構造を有する化合物であり、１分子中に複数の脂環式エポキシ基を有していてもよく、脂環式エポキシ基以外のエポキシ基を有していてもよい。また、上記脂環式エポキシ化合物は、２種以上を組み合わせて用いてもよい。
　芳香族環を有する化合物も、脂環式エポキシ基を有するものであれば、脂環式エポキシ化合物に該当する。
　シクロアルケンオキサイド構造は、シクロヘキセン環含有化合物やシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られる、シクロヘキセンオキサイド構造やシクロペンテンオキサイド構造のように、脂肪族環とエポキシ環とが環構造の一部を共有する構造である。 (1) Alicyclic epoxy compound The above-mentioned alicyclic epoxy compound is a compound having at least one alicyclic epoxy group in the molecule, that is, a compound having a cycloalkene oxide structure, and has multiple alicyclic epoxy groups in one molecule. It may have a formula epoxy group, or it may have an epoxy group other than an alicyclic epoxy group. Moreover, the above-mentioned alicyclic epoxy compounds may be used in combination of two or more types.
A compound having an aromatic ring also falls under the category of an alicyclic epoxy compound if it has an alicyclic epoxy group.
A cycloalkene oxide structure is a cyclohexene oxide structure or a cyclopentene oxide structure obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. This is a structure in which parts are shared.
　上記脂環式エポキシ化合物のうち、シクロアルケンオキサイド構造を１つ有する化合物としては、例えば、３，４－エポキシシクロヘキシルメチルアクリレート、３，４－エポキシシクロヘキシルメチルメタクリレート、ジシクロペンタジエンジエポキサイド、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ－２－エチルヘキシル、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等が挙げられる。 Among the above alicyclic epoxy compounds, examples of compounds having one cycloalkene oxide structure include 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentadiene diepoxide, and epoxyhexahydro Examples include dioctyl phthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, and 1,2-epoxy-2-epoxyethylcyclohexane.
　また、シクロアルケンオキサイド構造を２つ有する化合物としては、２つのシクロアルケンオキサイド構造が直接又はシクロアルカン構造を介して縮合した構造を有する化合物、及び２つのシクロアルケンオキサイド構造が連結基により連結した構造を有する化合物が挙げられる。
　２つのシクロアルケンオキサイド構造が直接又はシクロアルカン構造を介して縮合した構造を有する化合物の具体例としては、下記式（１－１）～（１－４）のいずれかで表される化合物が挙げられ、２つのシクロアルケンオキサイド構造が連結基により連結した構造を有する化合物の具体例としては、下記式（１－５）で表される化合物が挙げられる。 In addition, compounds having two cycloalkene oxide structures include compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure, and compounds in which two cycloalkene oxide structures are connected by a linking group. Examples include compounds having the following.
Specific examples of compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure include compounds represented by any of the following formulas (1-1) to (1-4). Specific examples of compounds having a structure in which two cycloalkene oxide structures are connected by a linking group include compounds represented by the following formula (1-5).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（１－１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－２）中、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９、Ｒ２０、Ｒ２１、Ｒ２２、Ｒ２３、Ｒ２４、Ｒ２５及びＲ２６は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－３）中、Ｒ３１、Ｒ３２、Ｒ３３、Ｒ３４、Ｒ３５、Ｒ３６、Ｒ３７、Ｒ３８、Ｒ３９、Ｒ４０、Ｒ４１、Ｒ４２、Ｒ４３、Ｒ４４、Ｒ４５、Ｒ４６、Ｒ４７及びＲ４８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－４）中、Ｒ５１、Ｒ５２、Ｒ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７、Ｒ５８、Ｒ５９、Ｒ６０、Ｒ６１、Ｒ６２、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
　式（１－５）中、Ｒ７１、Ｒ７２、Ｒ７３、Ｒ７４、Ｒ７５、Ｒ７６、Ｒ７７、Ｒ７８、Ｒ７９、Ｒ８０、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４、Ｒ８５、Ｒ８６、Ｒ８７及びＲ８８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表し、
　Ｘは、単結合又は炭素原子数１～４のアルキレン基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド基若しくはこれらのうちの複数が連結した基を表す。
　また「これらのうちの複数が連結した基」とは、アルキレン基、カルボニル基、エーテル結合、エステル結合、カーボネート基及びアミド基から選ばれる複数の基が、アルキレン基以外の基同士が互いに隣接しないように結合した基とすることができる。
　また、エステル結合－アルキレン基－エステル結合－アルキレン基のように、同一種類の基を２以上組み合わせてもよい。 In formula (1-1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a carbon atom, Represents an alkyl group having 1 to 20 atoms or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-2), 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 and R 26 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-3), R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-4), R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
In formula (1-5), R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms,
X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which two or more of these are linked.
In addition, "a group in which two or more of these are connected" refers to a group in which two or more groups selected from alkylene groups, carbonyl groups, ether bonds, ester bonds, carbonate groups, and amide groups are not adjacent to each other other than the alkylene groups. It can be a group bonded like this.
Furthermore, two or more groups of the same type may be combined, such as ester bond-alkylene group-ester bond-alkylene group.
　上記式（１－１）中のＲ１～Ｒ１０、上記式（１－２）中のＲ１１～Ｒ２６、上記式（１－３）中のＲ３１～Ｒ４８、上記式（１－４）中のＲ５１～Ｒ６８及び上記式（１－５）中のＲ７１～Ｒ８８で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等が挙げられる。 R 1 to R 10 in the above formula (1-1), R 11 to R 26 in the above formula (1-2), R 31 to R 48 in the above formula (1-3), and the above formula (1- Examples of the halogen atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include fluorine, chlorine, bromine, and iodine.
　上記式（１－１）中のＲ１～Ｒ１０、上記式（１－２）中のＲ１１～Ｒ２６、上記式（１－３）中のＲ３１～Ｒ４８、上記式（１－４）中のＲ５１～Ｒ６８及び上記式（１－５）中のＲ７１～Ｒ８８で表される炭素原子数１～２０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソブチル基、ペンチル基、イソペンチル基、ｔｅｒｔ－ペンチル基、ヘキシル基、２－ヘキシル基、３－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、ｔｅｒｔ－ヘプチル基、オクチル基、イソオクチル基、ｔｅｒｔ－オクチル基、２－エチルヘキシル基、ノニル基、イソノニル基、デシル基、ｎ－ウンデシル基、１－メチルデシル基、ｎ－ドデシル基、４－エチルオクチル基、１，３，５，７－テトラメチルオクチル基、トリデシル基、１－ヘキシルヘプチル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基、ｎ－エイコシル基等が挙げられる。 R 1 to R 10 in the above formula (1-1), R 11 to R 26 in the above formula (1-2), R 31 to R 48 in the above formula (1-3), and the above formula (1- Examples of the alkyl group having 1 to 20 carbon atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include a methyl group, an ethyl group, and a propyl group. , isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group group, 3-heptyl group, isoheptyl group, tert-heptyl group, octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, 4-ethyloctyl group, 1,3,5,7-tetramethyloctyl group, tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- Examples include heptadecyl group, n-octadecyl group, n-eicosyl group, and the like.
　上記式（１－１）中のＲ１～Ｒ１０、上記式（１－２）中のＲ１１～Ｒ２６、上記式（１－３）中のＲ３１～Ｒ４８、上記式（１－４）中のＲ５１～Ｒ６８及び上記式（１－５）中のＲ７１～Ｒ８８で表される炭素原子数１～２０のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、アミルオキシ基、イソアミルオキシ基、ｔｅｒｔ－アミルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、イソオクチルオキシ基、２－エチルヘキシルオキシ基、ｔｅｒｔ－オクチルオキシ基、ノニルオキシ基、イソノニルオキシ基、デシルオキシ基、イソデシルオキシ基、ｎ－ウンデシルオキシ基、１－メチルデシルオキシ基、ｎ－ドデシルオキシ基、４－エチルオクチルオキシ基、１，３，５，７－テトラメチルオクチルオキシ基、ｎ－トリデシルオキシ基、１－ヘキシルヘプチルオキシ基、ｎ－テトラデシルオキシ基、ｎ－ペンタデシルオキシ基、ｎ－ヘキサデシルオキシ基、ｎ－ヘプタデシルオキシ基、ｎ－オクタデシルオキシ基、ｎ－エイコシルオキシ基等が挙げられる。 R 1 to R 10 in the above formula (1-1), R 11 to R 26 in the above formula (1-2), R 31 to R 48 in the above formula (1-3), and the above formula (1- Examples of the alkoxy group having 1 to 20 carbon atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. group, isobutoxy group, sec-butoxy group, tert-butoxy group, amyloxy group, isoamyloxy group, tert-amyloxy group, hexyloxy group, heptyloxy group, octyloxy group, isooctyloxy group, 2-ethylhexyloxy group, tert-octyloxy group, nonyloxy group, isononyloxy group, decyloxy group, isodecyloxy group, n-undecyloxy group, 1-methyldecyloxy group, n-dodecyloxy group, 4-ethyloctyloxy group, 1 , 3,5,7-tetramethyloctyloxy group, n-tridecyloxy group, 1-hexylheptyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n- Examples include heptadecyloxy group, n-octadecyloxy group, n-eicosyloxy group and the like.
　上記式（１－５）中のＸで表される、炭素原子数１～４のアルキレン基としては、炭素原子数１～４のアルキル基から水素原子を１個除いた基が挙げられ、該アルキル基としては、上記式（１－１）のＲ１～Ｒ１０で表されるアルキル基として挙げたアルキル基のうち、所定の炭素原子数を有する基が挙げられる。具体的には、メチレン基、メチルメチン基、イソプロピリデン基、エチレン基、トリメチレン基、テトラメチレン基等が挙げられる。
　上記Ｘが、炭素原子数１～４のアルキレン基、カルボニル基、エーテル結合、エステル結合、カーボネート基及びアミド基から選択される基が複数連結した基である場合、Ｘの全体の炭素原子数としては、２以上２０以下とすることができる。
　なお、単結合とは、Ｘが連結する炭素原子同士が直接結合するものである。このような単結合により、２つのシクロアルケンオキサイド環が結合された化合物としては、例えば、下記式（Ａ１－４）で表される化合物が挙げられる。 Examples of the alkylene group having 1 to 4 carbon atoms, represented by X in the above formula (1-5), include a group obtained by removing one hydrogen atom from an alkyl group having 1 to 4 carbon atoms; Examples of the alkyl group include groups having a predetermined number of carbon atoms among the alkyl groups listed as the alkyl groups represented by R 1 to R 10 in formula (1-1) above. Specific examples include methylene group, methylmethine group, isopropylidene group, ethylene group, trimethylene group, and tetramethylene group.
When the above X is a group in which a plurality of groups selected from an alkylene group, a carbonyl group, an ether bond, an ester bond, a carbonate group, and an amide group having 1 to 4 carbon atoms are connected, the total number of carbon atoms in can be 2 or more and 20 or less.
Note that a single bond is one in which carbon atoms to which X is connected are directly bonded to each other. Examples of compounds in which two cycloalkene oxide rings are bonded via such a single bond include a compound represented by the following formula (A1-4).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記式（１－１）～（１－５）で表される化合物の製造方法としては、特開２０１９－１８９８４４号公報に記載の製造方法等が挙げられる。
　上記式（１－１）で表される化合物のうち市販されているものとしては、例えば、ＴＨＩ－ＤＥ（ＥＮＥＯＳ（株）製）等が挙げられる。
　上記式（１－２）で表される化合物のうち市販されているものとしては、例えば、ＤＥ－１０２（ＥＮＥＯＳ（株）製）等が挙げられる。
　上記式（１－３）で表される化合物のうち市販されているものとしては、例えば、ＤＥ－１０３（ＥＮＥＯＳ（株）製）等が挙げられる。
　上記式（１－５）で表される化合物のうち市販されているものとしては、例えば、セロキサイド２０２１Ｐ、セロキサイド８０００（（株）ダイセル製）等が挙げられる。 Examples of methods for producing the compounds represented by formulas (1-1) to (1-5) include the production method described in JP-A No. 2019-189844.
Among the compounds represented by the above formula (1-1), commercially available compounds include, for example, THI-DE (manufactured by ENEOS Corporation).
Among the compounds represented by the above formula (1-2), commercially available compounds include, for example, DE-102 (manufactured by ENEOS Corporation).
Among the compounds represented by the above formula (1-3), commercially available compounds include, for example, DE-103 (manufactured by ENEOS Corporation).
Examples of commercially available compounds represented by the above formula (1-5) include Celloxide 2021P and Celloxide 8000 (manufactured by Daicel Corporation).
　本開示においては、上記脂環式エポキシ化合物が、シクロアルケンオキサイド構造を２つ以上有することが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the alicyclic epoxy compound has two or more cycloalkene oxide structures. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂環式エポキシ化合物の官能基数は、２以上５以下であることが好ましく、２以上３以下であることがより好ましく、２であることが特に好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。なお、脂環式エポキシ化合物の官能基数は、シクロアルケンオキサイド構造以外のエポキシ基の数も含むものである。 The number of functional groups in the alicyclic epoxy compound is preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Note that the number of functional groups of the alicyclic epoxy compound includes the number of epoxy groups other than the cycloalkene oxide structure.
　本開示においては、上記脂環式エポキシ化合物が、２つのシクロアルケンオキサイド構造が直接縮合した構造を有する化合物又は２つのシクロアルケンオキサイド構造が連結基により連結した構造を有する化合物を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the alicyclic epoxy compound preferably includes a compound having a structure in which two cycloalkene oxide structures are directly condensed, or a compound having a structure in which two cycloalkene oxide structures are connected by a linking group. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記脂環式エポキシ化合物が、上記式（１－１）、（１－２）、（１－３）、（１－４）及び（１－５）から選択される化学式で表される化合物のうち少なくとも１種を含むことが好ましく、上記式（１－１）、（１－２）及び（１－５）から選択される化学式で表される化合物のうち少なくとも１種を含むことがより好ましく、特に、上記式（１－１）及び（１－２）で表される化合物のうち少なくとも１種を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the alicyclic epoxy compound has a chemical formula selected from the above formulas (1-1), (1-2), (1-3), (1-4) and (1-5). Preferably, it contains at least one compound represented by the formula (1-1), (1-2), and (1-5). It is more preferable to include at least one of the compounds represented by formulas (1-1) and (1-2) above. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記式（１－１）中のＲ１～Ｒ１０、上記式（１－２）中のＲ１１～Ｒ２６、上記式（１－３）中のＲ３１～Ｒ４８、上記式（１－４）中のＲ５１～Ｒ６８及び上記式（１－５）中のＲ７１～Ｒ８８は、それぞれ独立に、水素原子又は炭素原子数１～１０のアルキル基であることが好ましく、水素原子又は炭素原子数１～３のアルキル基であることがより好ましく、特に、水素原子であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　上記式（１－５）中のＸは、単結合、炭素原子数１～４のアルキレン基、エステル結合、又は炭素原子数１～４のアルキレン基とエステル結合とが連結した基であることが好ましく、なかでも、単結合又は炭素原子数１～４のアルキレン基とエステル結合とが連結した基であることが好ましく、特に、単結合、又は、炭素原子数１～２のアルキレン基とエステル結合とが連結した基であることが好ましく、なかでも特に、単結合であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 R 1 to R 10 in the above formula (1-1), R 11 to R 26 in the above formula (1-2), R 31 to R 48 in the above formula (1-3), and the above formula (1- R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
X in the above formula (1-5) may be a single bond, an alkylene group having 1 to 4 carbon atoms, an ester bond, or a group in which an alkylene group having 1 to 4 carbon atoms and an ester bond are connected. Preferably, it is a group in which a single bond or an alkylene group having 1 to 4 carbon atoms and an ester bond are connected, particularly a group in which a single bond or an alkylene group having 1 to 2 carbon atoms and an ester bond are connected. It is preferable that it is a group in which these are connected, and a single bond is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂環式エポキシ化合物の分子量としては、１００以上４００以下であることが好ましく、１２０以上３００以下であることがより好ましく、特に、１５０以上２５０以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The molecular weight of the alicyclic epoxy compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂環式エポキシ化合物のエポキシ当量としては、５０ｇ／ｅｑ．以上２００ｇ／ｅｑ．以下であることが好ましく、６０ｇ／ｅｑ．以上１５０ｇ／ｅｑ．以下であることがより好ましく、特に、７０ｇ／ｅｑ．以上１３０ｇ／ｅｑ．以下であることが好ましい。上記エポキシ当量であることで、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The epoxy equivalent of the above alicyclic epoxy compound is 50 g/eq. More than 200g/eq. It is preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above epoxy equivalent, the composition can form a cured product with better moist heat resistance and weather resistance.
（１）－２．脂環式エポキシ化合物の含有量
　上記脂環式エポキシ化合物の含有量は、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物の合計１００質量部中、０．５質量部以上８０質量部以下であることが好ましく、なかでも、１質量部以上５０質量部以下であることが好ましく、特に、２質量部以上３０質量部以下であることが好ましく、なかでも特に、３質量部以上２０質量部以下であることが好ましく、さらに一層、５質量部以上２０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (1)-2. Content of alicyclic epoxy compound The content of the alicyclic epoxy compound is 0.5 parts by mass or more in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. It is preferably 80 parts by mass or less, particularly preferably 1 part by mass or more and 50 parts by mass or less, particularly preferably 2 parts by mass or more and 30 parts by mass or less, especially 3 parts by mass. It is preferably 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂環式エポキシ化合物の含有量は、カチオン重合性成分１００質量部中に、０．５質量部以上８０質量部以下であることが好ましく、なかでも、１質量部以上５０質量部以下であることが好ましく、特に、２質量部以上３０質量部以下であることが好ましく、なかでも特に、３質量部以上２０質量部以下であることが好ましく、さらに一層、５質量部以上２０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less, particularly 1 part by mass or more and 50 parts by mass or less, in 100 parts by mass of the cationically polymerizable component. It is preferably 2 parts by mass or more and 30 parts by mass or less, particularly preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less. It is preferable that there be. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂環式エポキシ化合物の含有量は、上記組成物の固形分１００質量部中に、０．５質量部以上８０質量部以下であることが好ましく、なかでも、１質量部以上５０質量部以下であることが好ましく、特に、２質量部以上３０質量部以下であることが好ましく、なかでも特に、３質量部以上２０質量部以下であることが好ましく、さらに一層、５質量部以上２０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less, particularly 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the solid content of the composition. It is preferably 2 parts by mass or more and 30 parts by mass or less, particularly preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass. It is preferable that it is below. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（２）脂肪族エポキシ化合物
　上記脂肪族エポキシ化合物は、脂環式エポキシ基及び芳香族環の何れも有しないエポキシ基を有する化合物を表す。また、上記脂肪族エポキシ化合物は、２種以上を組み合わせて用いてもよい。
　上記脂肪族エポキシ化合物としては、多官能エポキシ化合物、単官能脂肪族エポキシ化合物が挙げられる。
　本開示においては、上記脂肪族エポキシ化合物が、多官能脂肪族エポキシ化合物を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (2) Aliphatic epoxy compound The above-mentioned aliphatic epoxy compound represents a compound having an epoxy group having neither an alicyclic epoxy group nor an aromatic ring. Moreover, the above-mentioned aliphatic epoxy compounds may be used in combination of two or more types.
Examples of the aliphatic epoxy compounds include polyfunctional epoxy compounds and monofunctional aliphatic epoxy compounds.
In the present disclosure, it is preferable that the aliphatic epoxy compound includes a polyfunctional aliphatic epoxy compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（２）－１．多官能脂肪族エポキシ化合物
　上記多官能脂肪族エポキシ化合物は、分子中に少なくとも２つのエポキシ基を有し、且つ、脂環式エポキシ基及び芳香族環をいずれも有しない化合物である。また、上記多官能脂肪族エポキシ化合物は、２種以上を組み合わせて用いてもよい。 (2)-1. Polyfunctional Aliphatic Epoxy Compound The polyfunctional aliphatic epoxy compound is a compound that has at least two epoxy groups in its molecule and has neither an alicyclic epoxy group nor an aromatic ring. Moreover, the above-mentioned polyfunctional aliphatic epoxy compounds may be used in combination of two or more types.
　上記多官能脂肪族エポキシ化合物としては、例えば、下記式（１－６）で表される化合物が挙げられる。 Examples of the polyfunctional aliphatic epoxy compound include compounds represented by the following formula (1-6).
Figure JPOXMLDOC01-appb-C000007
 　上記式（１－６）中、Ｙ１は、炭素原子数１～２０のアルキレン基、シクロアルキル環を有する炭素原子数６～２０の二価の脂肪族炭化水素基又は該アルキレン基若しくは該二価の脂肪族炭化水素基中のメチレン基の１つ又は２つ以上が酸素原子で置換された構造の基を表す。
Figure JPOXMLDOC01-appb-C000007
 In the above formula (1-6), Y 1 is an alkylene group having 1 to 20 carbon atoms, a divalent aliphatic hydrocarbon group having 6 to 20 carbon atoms having a cycloalkyl ring, or the alkylene group or the divalent aliphatic hydrocarbon group having cycloalkyl rings. It represents a group having a structure in which one or more methylene groups in a valent aliphatic hydrocarbon group are substituted with oxygen atoms.
　上記式（１－６）中のＹ１に用いられる炭素原子数１～２０のアルキレン基は、上記式（１－１）中のＲ１～Ｒ１０で用いられる炭素原子数１～２０のアルキル基として挙げた基から水素原子を１つ除いた基が挙げられる。
　上記（１－６）中のＹ１に用いられるシクロアルキル環を有する炭素原子数６～２０の二価の脂肪族炭化水素基としては、シクロアルキル基から水素原子を１つ除いたシクロアルキレン基、シクロアルキレン基とアルキレン基とを組み合わせた基が挙げられる。
　上記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、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、メチルシクロペンチル基、メチルシクロヘキシル基、ジメチルシクロヘキシル基、トリメチルシクロヘキシル基、テトラメチルシクロヘキシル基、ペンタメチルシクロヘキシル基、エチルシクロヘキシル基及びメチルシクロヘプチル基等の単環式脂肪族炭化水素基；ビシクロ［２．１．１］ヘキシル基、ビシクロ［２．２．１］ヘプチル基、ビシクロ［２．２．２］オクチル基、ビシクロ［４．３．１］デシル基、ビシクロ［３．３．１］ノニル基、ボルニル基、ボルネニル基、ノルボルニル基、ノルボルネニル基、６，６－ジメチルビシクロ［３．１．１］ヘプチル基、トリシクロブチル基、アダマンチル基等の多環式脂肪族炭化水素基等が挙げられる。
　脂肪族炭化水素基中のメチレン基の１つ又は２つ以上が酸素原子で置換された構造の基及び当該基を含む化合物において、酸素原子同士は隣り合わないものとする。 The alkylene group having 1 to 20 carbon atoms used in Y 1 in the above formula (1-6) is the alkyl group having 1 to 20 carbon atoms used in R 1 to R 10 in the above formula (1-1). Examples include groups obtained by removing one hydrogen atom from the groups listed above.
The divalent aliphatic hydrocarbon group having 6 to 20 carbon atoms and having a cycloalkyl ring used for Y 1 in (1-6) above is a cycloalkylene group obtained by removing one hydrogen atom from a cycloalkyl group. , a combination of a cycloalkylene group and an alkylene group.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a methylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, Monocyclic aliphatic hydrocarbon groups such as tetramethylcyclohexyl group, pentamethylcyclohexyl group, ethylcyclohexyl group and methylcycloheptyl group; bicyclo[2.1.1]hexyl group, bicyclo[2.2.1]heptyl group , bicyclo[2.2.2]octyl group, bicyclo[4.3.1]decyl group, bicyclo[3.3.1]nonyl group, bornyl group, bornenyl group, norbornyl group, norbornenyl group, 6,6- Examples include polycyclic aliphatic hydrocarbon groups such as dimethylbicyclo[3.1.1]heptyl group, tricyclobutyl group, and adamantyl group.
In a group having a structure in which one or more methylene groups in an aliphatic hydrocarbon group are substituted with an oxygen atom, and in a compound containing the group, the oxygen atoms are not adjacent to each other.
　上記Ｙ１としては、炭素原子数１～２０のアルキレン基であることが好ましく、なかでも、炭素原子数２～８のアルキレン基であることが好ましく、特に、炭素原子数３～６のアルキレン基であることがより好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　上記Ｙ１に用いられるアルキレン基は、直鎖状であってもよく、分岐状であってもよいが、分岐状であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The above Y 1 is preferably an alkylene group having 1 to 20 carbon atoms, particularly preferably an alkylene group having 2 to 8 carbon atoms, and particularly an alkylene group having 3 to 6 carbon atoms. It is more preferable that This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
The alkylene group used for Y 1 may be linear or branched, but is preferably branched. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記Ｙ１が、シクロアルキル環を有する炭素原子数６～２０の二価の脂肪族炭化水素基である場合、Ｙ１の炭素原子数としては、３以上２０以下であることが好ましく、６以上１８以下であることがより好ましく、特に、１０以上１５以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When Y 1 is a divalent aliphatic hydrocarbon group having a cycloalkyl ring and having 6 to 20 carbon atoms, the number of carbon atoms in Y 1 is preferably 3 or more and 20 or less, and 6 or more. It is more preferably 18 or less, particularly preferably 10 or more and 15 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　また、上記多官能脂肪族エポキシ化合物としては、下記式（１－７）で表される化合物も挙げられる。 Further, examples of the polyfunctional aliphatic epoxy compound include compounds represented by the following formula (1-7).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記式（１－７）中、Ｒは、炭素原子数１～１０のｔ価の脂肪族炭化水素基であり、ｓは、１～３０の整数を表し、ｔは、１～１０の整数を表す。ｔが２以上の場合、複数のｓはそれぞれ異なっていてもよい。
　また、ｓ及びｔの合計は、２以上である。 In the above formula (1-7), R is a t-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, s represents an integer of 1 to 30, and t represents an integer of 1 to 10. represent. When t is 2 or more, the plurality of s may be different from each other.
Further, the sum of s and t is 2 or more.
　上記式（１－７）中のＲで表される炭素原子数１～１０のｔ価の脂肪族炭化水素基としては、炭素原子数１～１０のアルキル基から水素原子をｔ－１個除いた基が挙げられる。
　上記炭素原子数１～１０のアルキル基の例としては、上記式（１－１）中のＲ１～Ｒ１０で表される炭素原子数１～２０のアルキル基において、所定の炭素原子数を有する基が挙げられる。 The t-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R in the above formula (1-7) is obtained by removing t-1 hydrogen atoms from an alkyl group having 1 to 10 carbon atoms. The following groups are mentioned.
As an example of the alkyl group having 1 to 10 carbon atoms, in the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 10 in the above formula (1-1), a predetermined number of carbon atoms can be used. Examples include groups having
　上記式（１－７）中のＲは、炭素原子数２～１０のアルキル基が好ましく、特に、炭素原子数３～８の分岐状のアルキル基が好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　ｔは、１以上１０以下の整数であることが化合物の入手容易性の点で好ましく、２以上８以下の整数であることがより好ましく、特に、２以上６以下の整数であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 R in the above formula (1-7) is preferably an alkyl group having 2 to 10 carbon atoms, particularly preferably a branched alkyl group having 3 to 8 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
t is preferably an integer of 1 or more and 10 or less in terms of ease of obtaining the compound, more preferably an integer of 2 or more and 8 or less, particularly preferably an integer of 2 or more and 6 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記式（１－７）で表される化合物の分子量としては、耐湿熱性及び耐候性が優れた硬化物を形成可能とすることができるものであればよく、１，０００以上５，０００以下であることが好ましく、１，５００以上４，０００以下であることがより好ましく、特に、２，０００以上３，０００以下であることが好ましい。上述の分子量であることで、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　なお、上記式（１－７）で表される化合物が、モノマーやオリゴマーが重合した部位を有する場合、上記分子量は、重量平均分子量（Ｍｗ）を意味する。また、重量平均分子量の測定は、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 represented by the above formula (1-7) may be any one that can form a cured product with excellent heat and humidity resistance and weather resistance, and is between 1,000 and 5,000. It is preferably 1,500 or more and 4,000 or less, particularly preferably 2,000 or more and 3,000 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
In addition, when the compound represented by the above formula (1-7) has a site where a monomer or oligomer is polymerized, the above molecular weight means a weight average molecular weight (Mw). Further, the weight average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.
　上記重量平均分子量は、例えば、日本分光製のＧＰＣ（ＬＣ－２０００ｐｌｕｓシリーズ）を用い、溶出溶剤をテトラヒドロフランとし、校正曲線用ポリスチレンスタンダードをＭｗ１，１１０，０００、７０７，０００、３９７，０００、１８９，０００、９８，９００、３７，２００、１３，７００、９，４９０、５，４３０、３，１２０、１，０１０、５８９（東ソー製　ＴＳＫｇｅｌ標準ポリスチレン）とし、測定カラムをＫＦ－８０４、ＫＦ－８０３、ＫＦ－８０２（昭和電工製）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。
　測定時の試料濃度としては、０．１質量％～０．２質量％とすることができる。 The above weight average molecular weights are, for example, using GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, and using polystyrene standards for the calibration curve as Mw 1,110,000, 707,000, 397,000, 189, The measurement columns were KF-804 and KF-803. , KF-802 (manufactured by Showa Denko).
Further, the measurement temperature can be 40° C., and the flow rate can be 1.0 mL/min.
The sample concentration during measurement can be 0.1% by mass to 0.2% by mass.
　上記多官能脂肪族エポキシ化合物の官能基数としては、２以上５以下であることが好ましく、２以上３以下であることがさらに好ましく、２であることが特に好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The number of functional groups in the polyfunctional aliphatic epoxy compound is preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記多官能脂肪族エポキシ化合物が、上記式（１－６）で表され、且つ、Ｙ１が、炭素原子数１～２０のアルキレン基である化合物から選択される少なくとも１種を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the polyfunctional aliphatic epoxy compound is at least one compound selected from compounds represented by the above formula (1-6) and in which Y 1 is an alkylene group having 1 to 20 carbon atoms. It is preferable to include. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記多官能脂肪族エポキシ化合物の分子量としては、１００以上４００以下であることが好ましく、１２０以上３００以下であることがより好ましく、特に、１５０以上２５０以下であることが好ましい。上述の分子量であることで、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The molecular weight of the polyfunctional aliphatic epoxy compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
　上記多官能脂肪族エポキシ化合物のエポキシ当量としては、５０ｇ／ｅｑ．以上２００ｇ／ｅｑ．以下であることが好ましく、６０ｇ／ｅｑ．以上１５０ｇ／ｅｑ．以下であることがより好ましく、特に、７０ｇ／ｅｑ．以上１３０ｇ／ｅｑ．以下であることが好ましい。上述のエポキシ当量であることで、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The epoxy equivalent of the polyfunctional aliphatic epoxy compound is 50 g/eq. More than 200g/eq. It is preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above-mentioned epoxy equivalent, the composition can form a cured product having better heat-and-moisture resistance and weather resistance.
　上述のような多官能脂肪族エポキシ化合物としては、例えば、１，４－ブタ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、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、ポリプロピレングリコールのジグリシジルエーテル等の多価アルコールのグリシジルエーテル、またプロピレングリコール、トリメチロールプロパン、グリセリン等の脂肪族多価アルコールに１種又は２種以上のアルキレンオキサイドを付加することによって得られるポリエーテルポリオールのポリグリシジルエーテル化物、脂肪族長鎖二塩基酸のジグリシジルエステルが挙げられる。さらに、エポキシ化大豆油、エポキシ化ポリブタジエン等が挙げられる。 Examples of the above-mentioned polyfunctional aliphatic epoxy compounds include 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, and trimethylol. Glycidyl ethers of polyhydric alcohols such as triglycidyl ether of propane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, propylene glycol, trimethylolpropane, Examples include polyglycidyl etherified polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include epoxidized soybean oil, epoxidized polybutadiene, and the like.
　上記多官能脂肪族エポキシ化合物の含有量は、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物の合計１００質量部中、０質量部以上９８質量部以下であることが好ましく、なかでも、１０質量部以上５０質量部以下であることが好ましく、特に、１５質量部以上４０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the polyfunctional aliphatic epoxy compound is preferably 0 parts by mass or more and 98 parts by mass or less based on a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. Among these, it is preferably 10 parts by mass or more and 50 parts by mass or less, and particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記多官能脂肪族エポキシ化合物の含有量は、カチオン重合性成分１００質量部中、０質量部以上９８質量部以下であることが好ましく、なかでも、１０質量部以上５０質量部以下であることが好ましく、特に、１５質量部以上４０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the polyfunctional aliphatic epoxy compound is preferably 0 parts by mass or more and 98 parts by mass or less, especially 10 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. Preferably, it is particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂環式エポキシ化合物及び多官能脂肪族エポキシ化合物の合計の含有量は、カチオン重合性成分１００質量部中、８質量部以上１００質量部以下であることが好ましく、なかでも１０質量部以上１００質量部以下であることがより好ましく、特に、２０質量部以上７０質量部以下であることが好ましく、なかでも特に、２５質量部以上６０質量部以下であることが好ましい。とりわけ、３２質量部以上５５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The total content of the alicyclic epoxy compound and polyfunctional aliphatic epoxy compound is preferably 8 parts by mass or more and 100 parts by mass or less, particularly 10 parts by mass or more and 100 parts by mass, based on 100 parts by mass of the cationically polymerizable component. It is more preferably at most 20 parts by mass and at most 70 parts by mass, particularly preferably at least 25 parts by mass and at most 60 parts by mass. In particular, it is preferably 32 parts by mass or more and 55 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（２）－２．単官能脂肪族エポキシ化合物
　上記単官能脂肪族エポキシ化合物は、分子中に１個のエポキシ基を有する化合物である。また、上記単官能脂肪族エポキシ化合物は、２種以上を組み合わせて用いてもよい。
　上記単官能エポキシ化合物としては、例えば、下記式（１－８）で表される化合物が挙げられる。 (2)-2. Monofunctional aliphatic epoxy compound The monofunctional aliphatic epoxy compound is a compound having one epoxy group in the molecule. Moreover, the above-mentioned monofunctional aliphatic epoxy compounds may be used in combination of two or more types.
Examples of the monofunctional epoxy compound include compounds represented by the following formula (1-8).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（１－８）中、ＲＡ１は、炭素原子数１～２０のアルキル基を表し、Ｘ１は、エーテル結合又はエステル結合を表す。 In formula (1-8), R A1 represents an alkyl group having 1 to 20 carbon atoms, and X 1 represents an ether bond or an ester bond.
　上記一般式（１－８）中のＲＡ１に用いられるアルキル基としては、上記式（１－１）中のＲ１～Ｒ１０に用いられる炭素原子数１～２０のアルキル基の例として挙げた基と同様の基を用いることができる。
　本開示においては、ＲＡ１が、炭素原子数６～２０のアルキル基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 Examples of the alkyl group used for R A1 in the above general formula (1-8) include alkyl groups having 1 to 20 carbon atoms used for R 1 to R 10 in the above formula (1-1). Groups similar to those described above can be used.
In the present disclosure, R A1 is preferably an alkyl group having 6 to 20 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記単官能脂肪族エポキシ化合物としては、ブ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、２－メチルオクチルグリシジルエーテル等が挙げられる。
　上記単官能脂肪族エポキシ化合物の市販品としては、アデカグリシロールＥＤ－５０２（ＡＤＥＫＡ社製、上記式（１－８）中のＲＡ１が炭素数１２～１３のアルキル基である化合物）、デナコールＥＸ－１１１３（ナガセケムテックス社製、上記式（１－８）中のＲＡ１が炭素原子数１７のアルキル基を有する化合物）が挙げられる。 Examples of the monofunctional aliphatic epoxy compound include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, and the like.
Commercially available monofunctional aliphatic epoxy compounds include ADEKA Glycilol ED-502 (manufactured by ADEKA, a compound in which R A1 in the above formula (1-8) is an alkyl group having 12 to 13 carbon atoms), Denacol Examples include EX-1113 (manufactured by Nagase ChemteX, a compound in which R A1 in the above formula (1-8) has an alkyl group having 17 carbon atoms).
　上記単官能脂肪族エポキシ化合物を含有する場合、その含有量は、カチオン重合性成分１００質量部中、０．５質量部以上３０質量部以下であることが好ましく、なかでも、１質量部以上２０質量部以下であることが好ましく、特に、２質量部以上１０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the monofunctional aliphatic epoxy compound is contained, its content is preferably 0.5 parts by mass or more and 30 parts by mass or less, particularly 1 part by mass or more and 20 parts by mass, based on 100 parts by mass of the cationically polymerizable component. It is preferably at most 2 parts by mass and at most 10 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（２）－３．脂肪族エポキシ化合物の含有量
　上記脂肪族エポキシ化合物の含有量は、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物の合計１００質量部中、０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５質量部以上７０質量部以下であることが好ましく、特に、１０質量部以上５０質量部以下であることが好ましく、なかでも特に、１５質量部以上４０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (2)-3. Content of aliphatic epoxy compound The content of the aliphatic epoxy compound is 0 parts by mass or more and 90 parts by mass or less in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. It is preferably 5 parts by mass or more and 70 parts by mass or less, particularly preferably 10 parts by mass or more and 50 parts by mass or less, especially 15 parts by mass or more and 40 parts by mass or less. It is preferable that This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂肪族エポキシ化合物の含有量は、カチオン重合性成分１００質量部中、０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５質量部以上７０質量部以下であることが好ましく、特に、１０質量部以上５０質量部以下であることが好ましく、なかでも特に、１５質量部以上４０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the aliphatic epoxy compound is preferably 0 parts by mass or more and 90 parts by mass or less, particularly preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. , preferably 10 parts by mass or more and 50 parts by mass or less, particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記脂肪族エポキシ化合物の含有量は、上記組成物の固形分１００質量部中、０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、５質量部以上７０質量部以下であることが好ましく、特に、１０質量部以上４０質量部以下であることが好ましく、なかでも特に、１５質量部以上３０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the aliphatic epoxy compound is preferably 0 parts by mass or more and 90 parts by mass or less, and particularly preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the solid content of the composition. The content is preferably 10 parts by mass or more and 40 parts by mass or less, particularly preferably 15 parts by mass or more and 30 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（３）芳香族エポキシ化合物
　上記芳香族エポキシ化合物は、エポキシ基及び芳香族環を有し、且つ、脂環式エポキシ基を有しない化合物を表す。また、上記芳香族エポキシ化合物は、２種以上を組み合わせて用いてもよい。 (3) Aromatic epoxy compound The above-mentioned aromatic epoxy compound represents a compound that has an epoxy group and an aromatic ring, and does not have an alicyclic epoxy group. Moreover, the above-mentioned aromatic epoxy compounds may be used in combination of two or more types.
　このような芳香族エポキシ化合物としては、例えば、フェノール、クレゾール、ブチルフェノール等の一価フェノール、及びそのアルキレンオキサイド付加物のグリシジルエーテル化物、２個以上の芳香族環を有する多価フェノール、及びそのアルキレンオキサイド付加物等の多価フェノール類のポリグリシジルエーテル、フェノールノボラック型エポキシ化合物；レゾルシノール、ハイドロキノン及びカテコール等の２個以上のフェノール性水酸基を有するフェノール類のグリシジルエーテル；ベンゼンジメタノール、ベンゼンジエタノール及びベンゼンジブタノール等のアルコール性水酸基を２個以上有する芳香族化合物のポリグリシジルエーテル；フタル酸、テレフタル酸及びトリメリット酸等の２個以上のカルボン酸を有する多塩基酸芳香族化合物のポリグリシジルエステル；安息香酸、トルイル酸及びナフトエ酸等の安息香酸類のグリシジルエステル；スチレンオキサイド及びジビニルベンゼンのエポキシ化物等が挙げられる。 Examples of such aromatic epoxy compounds include monohydric phenols such as phenol, cresol, butylphenol, glycidyl etherified products of alkylene oxide adducts thereof, polyhydric phenols having two or more aromatic rings, and alkylene phenols thereof. Polyglycidyl ethers of polyhydric phenols such as oxide adducts, phenol novolak type epoxy compounds; Glycidyl ethers of phenols having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; benzenedimethanol, benzenediethanol and benzene Polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups such as dibutanol; polyglycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid; Glycidyl esters of benzoic acids such as benzoic acid, toluic acid and naphthoic acid; epoxidized products of styrene oxide and divinylbenzene; and the like.
（３）－１．芳香族エポキシ化合物の含有量
　上記芳香族エポキシ化合物の含有量は、カチオン重合性成分１００質量部中に、３０質量部以下であることが好ましく、２０質量部以下であることが好ましく、特に１０質量部以下であることが好ましく、なかでも特に５質量部以下が好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。また芳香族エポキシ化合物を含有する場合はその含有量はカチオン重合性成分１００質量部中に、０．１質量部以上であってもよく、０．３質量部以上であってもよく、０．５質量部以上であってもよい (3)-1. Content of aromatic epoxy compound The content of the aromatic epoxy compound is preferably 30 parts by mass or less, preferably 20 parts by mass or less, particularly 10 parts by mass in 100 parts by mass of the cationically polymerizable component. It is preferably at most 5 parts by mass, particularly preferably at most 5 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Further, when an aromatic epoxy compound is contained, the content thereof may be 0.1 parts by mass or more, 0.3 parts by mass or more, and 0.3 parts by mass or more, based on 100 parts by mass of the cationically polymerizable component. May be 5 parts by mass or more
　上記芳香族エポキシ化合物を含有する場合、その含有量は、上記組成物の固形分１００質量部中に、０．５質量部以上５０質量部以下であることが好ましく、なかでも、０．５質量部以上２０質量部以下であることが好ましく、特に、１質量部以上１０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the aromatic epoxy compound is contained, the content thereof is preferably 0.5 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the solid content of the composition, particularly 0.5 parts by mass. It is preferably at least 1 part by mass and at most 20 parts by mass, particularly preferably at least 1 part by mass and at most 10 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（４）オキセタン化合物
　上記オキセタン化合物は、分子中に少なくとも１つのオキセタニル基を有し、エポキシ基を有しない化合物を表す。
　上記オキセタン化合物としては、単官能オキセタン化合物、二官能オキセタン化合物等が挙げられる。また、オキセタン化合物は、２種以上を組み合わせて用いてもよい。 (4) Oxetane Compound The above oxetane compound represents a compound that has at least one oxetanyl group in the molecule and does not have an epoxy group.
Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and the like. Further, two or more oxetane compounds may be used in combination.
（４）－１．単官能オキセタン化合物
　上記単官能オキセタン化合物は、分子中にオキセタニル基を１つのみ有するオキセタン化合物を表す。
　上記単官能オキセタン化合物としては、例えば、下記式（１－９）で表される化合物が挙げられる。 (4)-1. Monofunctional Oxetane Compound The monofunctional oxetane compound described above represents an oxetane compound having only one oxetanyl group in the molecule.
Examples of the monofunctional oxetane compound include compounds represented by the following formula (1-9).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記式（１－９）中、ＲＡ２は、水素原子又は炭素原子数１～１０のアルキル基を表し、ＲＡ３は、炭素原子数１～１０のアルキル基を表す。 In the above formula (1-9), R A2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R A3 represents an alkyl group having 1 to 10 carbon atoms.
　上記式（１－９）中のＲＡ２及びＲＡ３で表される炭素原子数１～１０のアルキル基の例は、上記式（１－１）中のＲ１～Ｒ１０に用いられる炭素原子数１～２０のアルキル基において、所定の炭素原子数を有する基が挙げられる。 Examples of the alkyl group having 1 to 10 carbon atoms represented by R A2 and R A3 in the above formula (1-9) are the carbon atoms used in R 1 to R 10 in the above formula (1-1). Examples of the alkyl group having a number of 1 to 20 include groups having a predetermined number of carbon atoms.
　上記ＲＡ２は、炭素原子数１～１０のアルキル基であることが好ましく、炭素原子数１～５のアルキル基であることがより好ましく、特に、炭素原子数１～３のアルキル基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The above R A2 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly an alkyl group having 1 to 3 carbon atoms. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記ＲＡ３は、炭素原子数３～１０のアルキル基であることが好ましく、炭素原子数５～１０のアルキル基であることがより好ましく、特に、炭素原子数６～９のアルキル基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The above R A3 is preferably an alkyl group having 3 to 10 carbon atoms, more preferably an alkyl group having 5 to 10 carbon atoms, particularly an alkyl group having 6 to 9 carbon atoms. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記式（１－９）で表される化合物の具体例としては、３－エチル－３－（メトキシメチル）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－（シクロヘキシルオキシメチル）オキセタン、３－エチル－３－（ブチロキシメチル）オキセタン等が挙げられる。 Specific examples of the compound represented by the above formula (1-9) include 3-ethyl-3-(methoxymethyl)oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-( Examples include 2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, and 3-ethyl-3-(butyloxymethyl)oxetane.
　本開示の組成物において、上記単官能オキセタン化合物を含有する場合、上記単官能オキセタン化合物の含有量は、上記単官能オキセタン化合物及び後述する二官能オキセタン化合物の合計量１００質量部中、１質量部以上５０質量部以下であることが好ましく、なかでも、５質量部以上４０質量部以下であることが好ましく、特に、１０質量部以上３０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure contains the monofunctional oxetane compound, the content of the monofunctional oxetane compound is 1 part by mass out of 100 parts by mass of the total amount of the monofunctional oxetane compound and the bifunctional oxetane compound described below. It is preferably at least 50 parts by mass, particularly preferably at least 5 parts by mass and at most 40 parts by mass, particularly preferably at least 10 parts by mass and at most 30 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（４）－２．二官能オキセタン化合物
　上記二官能オキセタン化合物は、分子中にオキセタニル基を２つ有するオキセタン化合物を表す。
　上記二官能オキセタン化合物としては、例えば、下記式（１－１０）で表される化合物等が挙げられる。 (4)-2. Bifunctional Oxetane Compound The above bifunctional oxetane compound represents an oxetane compound having two oxetanyl groups in the molecule.
Examples of the above-mentioned bifunctional oxetane compound include compounds represented by the following formula (1-10).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（１－１０）中、ＲＡ４及びＲＡ５は、それぞれ独立に、水素原子又は炭素原子数１～１０のアルキル基を表し、Ｚは、炭素原子数２～２０の連結基を表し、ｎ２は、０～３の整数を表す。 In formula (1-10), R A4 and R A5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Z represents a linking group having 2 to 20 carbon atoms, and n2 represents an integer from 0 to 3.
　上記式（１－１０）中のＲＡ４及びＲＡ５で表される炭素原子数１～１０のアルキル基の例は、上記式（１－１）中のＲ１～Ｒ１０で表される炭素原子数１～２０のアルキル基において、所定の炭素原子数を有する基が挙げられる。 Examples of the alkyl group having 1 to 10 carbon atoms represented by R A4 and R A5 in the above formula (1-10) are the carbon atoms represented by R 1 to R 10 in the above formula (1-1). Examples of the alkyl group having 1 to 20 atoms include groups having a predetermined number of carbon atoms.
　上記式（１－１０）中のＺで表される炭素原子数２～２０の連結基としては、炭素原子数２～１０のアルキレン基又は炭素原子数８～２０の芳香族環含有基等が挙げられる。
　上記ＲＡ４及びＲＡ５は、それぞれ独立に、炭素原子数１～１０のアルキル基であることが好ましく、炭素原子数１～５のアルキル基であることがより好ましく、特に、炭素原子数１～３のアルキル基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The linking group having 2 to 20 carbon atoms represented by Z in the above formula (1-10) includes an alkylene group having 2 to 10 carbon atoms, an aromatic ring-containing group having 8 to 20 carbon atoms, etc. Can be mentioned.
The above R A4 and R A5 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly an alkyl group having 1 to 5 carbon atoms. It is preferable that it is an alkyl group of 3. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記式（１－１０）中のＺで表される炭素原子数２～１０のアルキレン基としては、炭素原子数２～１０のアルキル基から水素原子を１個除いた基が挙げられ、該アルキル基としては、上記式（１－１）のＲ１～Ｒ１０で表されるアルキル基として挙げたアルキル基のうち、所定の炭素原子数を有する基が挙げられる。具体的には、メチルメチン基、イソプロピリデン基、エチレン基、トリメチレン基、テトラメチレン基等が挙げられる。 Examples of the alkylene group having 2 to 10 carbon atoms represented by Z in the above formula (1-10) include a group obtained by removing one hydrogen atom from an alkyl group having 2 to 10 carbon atoms; Examples of the group include groups having a predetermined number of carbon atoms among the alkyl groups listed as the alkyl groups represented by R 1 to R 10 in formula (1-1) above. Specific examples include methylmethine group, isopropylidene group, ethylene group, trimethylene group, and tetramethylene group.
　上記式（１－１０）中のＺで表される炭素原子数８～２０の芳香族環含有基としては、ベンゼン環１～２個と、アルキレン基、カーボネート基、アミド基若しくはこれらのうち複数が連結した基を組み合わせた基が挙げられる。ベンゼン環の水素原子が、炭素原子数１～４のアルキル基、ヒドロキシ基で置換されていてもよい。上記芳香族環含有基の具体例としては、例えば、下記式（２ａ）～（２ｄ）の何れかで表される基等が挙げられる。 The aromatic ring-containing group having 8 to 20 carbon atoms represented by Z in the above formula (1-10) includes 1 to 2 benzene rings, an alkylene group, a carbonate group, an amide group, or more than one of these. Examples include groups that are a combination of groups in which are linked. The hydrogen atom of the benzene ring may be substituted with an alkyl group having 1 to 4 carbon atoms or a hydroxy group. Specific examples of the aromatic ring-containing group include groups represented by any of the following formulas (2a) to (2d).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記式（１－１０）で表される化合物の具体例としては、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－（３－エチル－３－オキセタニルメチルオキシメチル）オキセタン、キシリレンビスオキセタン等が挙げられる。 Specific examples of the compound represented by the above formula (1-10) include 3,7-bis(3-oxetanyl)-5-oxanonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy) ) methyl]benzene, 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-(3-ethyl-3-oxetanylmethyloxymethyl)oxetane, xylylenebisoxetane etc.
　上記オキセタン化合物の市販品としては、例えば、アロンオキセタンＯＸＴ－２１２、ＯＸＴ－１２１、ＯＸＴ－２２１（東亜合成（株）製）、ＨＢＯＸ、ＯＸＢＰ、ＯＸＩＰＡ（宇部興産（株）製）等が挙げられる。 Examples of commercially available oxetane compounds include aron oxetane OXT-212, OXT-121, OXT-221 (manufactured by Toagosei Co., Ltd.), HBOX, OXBP, and OXIPA (manufactured by Ube Industries, Ltd.). .
　本開示の組成物において、上記二官能オキセタン化合物を含有する場合、上記二官能オキセタン化合物の含有量は、上記単官能オキセタン化合物及び上記二官能オキセタン化合物の合計量１００質量部中、５０質量部以上１００質量部以下であることが好ましく、なかでも、５５質量部以上９５質量部以下であることが好ましく、特に、７０質量部以上８８質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure contains the bifunctional oxetane compound, the content of the bifunctional oxetane compound is 50 parts by mass or more out of 100 parts by mass of the total amount of the monofunctional oxetane compound and the bifunctional oxetane compound. The content is preferably 100 parts by mass or less, particularly preferably 55 parts by mass or more and 95 parts by mass or less, and particularly preferably 70 parts by mass or more and 88 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（４）－３．オキセタン化合物
　上記オキセタン化合物は、一部の水素原子がヒドロキシ基で置換されていてもよい。
　本開示においては、上記オキセタン化合物が、単官能オキセタン化合物又は二官能オキセタン化合物を少なくとも一種を含むことが好ましく、なかでも、二官能オキセタン化合物を含むことが好ましく、特に、単官能オキセタン化合物及び二官能オキセタン化合物を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　耐湿熱性及び耐候性がより優れる硬化物を形成する点から、オキセタン化合物中、単官能オキセタン化合物及び二官能オキセタン化合物の合計量は５０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９５質量％以上であることが特に好ましい。 (4)-3. Oxetane Compound In the oxetane compound, some of the hydrogen atoms may be substituted with hydroxy groups.
In the present disclosure, it is preferable that the oxetane compound contains at least one type of monofunctional oxetane compound or a difunctional oxetane compound, and it is particularly preferable that the oxetane compound contains a bifunctional oxetane compound, and especially a monofunctional oxetane compound and a difunctional oxetane compound. Preferably, it contains an oxetane compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
From the viewpoint of forming a cured product with better heat and humidity resistance and weather resistance, the total amount of monofunctional oxetane compounds and difunctional oxetane compounds in the oxetane compound is preferably 50% by mass or more, and 80% by mass or more. is more preferable, and particularly preferably 95% by mass or more.
　本開示においては、上記オキセタン化合物が、上記式（１－９）及び上記式（１－１０）で表される化合物から選択される少なくとも１種を含むことが好ましく、中でも、上記式（１－１０）で表される化合物を少なくとも１種含むことが好ましく、特に、上記式（１－９）及び上記式（１－１０）で表される化合物をそれぞれ少なくとも１種含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the oxetane compound contains at least one compound selected from the compounds represented by the above formula (1-9) and the above formula (1-10). It is preferable to contain at least one compound represented by formula (10), and particularly preferably to contain at least one compound each of formula (1-9) and formula (1-10). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記オキセタン化合物の分子量としては、１００以上４００以下であることが好ましく、１２０以上３００以下であることがより好ましく、特に、１５０以上２５０以下であることが好ましい。上述の分子量であることで、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The molecular weight of the oxetane compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
　上記オキセタン化合物のオキセタン当量としては、２５０ｇ／ｅｑ．以下が好ましく、５０ｇ／ｅｑ．以上２００ｇ／ｅｑ．以下であることがより好ましく、６０ｇ／ｅｑ．以上１５０ｇ／ｅｑ．以下であることが更に好ましく、特に、７０ｇ／ｅｑ．以上１３０ｇ／ｅｑ．以下であることが好ましい。上述のオキセタン当量であることで、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The oxetane equivalent of the above oxetane compound is 250 g/eq. The following is preferable, 50g/eq. More than 200g/eq. It is more preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above-mentioned oxetane equivalent, the composition can form a cured product having better heat-and-moisture resistance and weather resistance.
（４）－４．オキセタン化合物の含有量
　上記オキセタン化合物の含有量は、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物の合計１００質量部中、０質量部以上９２質量部以下であることが好ましく、なかでも、１０質量部以上８０質量部以下であることが好ましく、特に、４０質量部以上８０質量部以下であることが好ましく、なかでも特に、５０質量部以上７５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (4)-4. Content of Oxetane Compound The content of the oxetane compound may be 0 parts by mass or more and 92 parts by mass or less in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. Preferably, the content is preferably 10 parts by mass or more and 80 parts by mass or less, particularly preferably 40 parts by mass or more and 80 parts by mass or less, particularly preferably 50 parts by mass or more and 75 parts by mass or less. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記オキセタン化合物の含有量は、カチオン重合性成分１００質量部中に、０質量部以上９２質量部以下であることが好ましく、なかでも、０．５質量部以上８０質量部以下であることが好ましく、特に、１０質量部以上８０質量部以下であることが好ましく、なかでも特に、４０質量部以上８０質量部以下であることが好ましく、さらに一層、５０質量部以上７５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the oxetane compound is preferably 0 parts by mass or more and 92 parts by mass or less, particularly preferably 0.5 parts by mass or more and 80 parts by mass or less, in 100 parts by mass of the cationically polymerizable component. In particular, it is preferably 10 parts by mass or more and 80 parts by mass or less, particularly preferably 40 parts by mass or more and 80 parts by mass or less, and even more preferably 50 parts by mass or more and 75 parts by mass or less. preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（５）その他のカチオン重合性化合物
　上記カチオン重合性成分は、脂環式エポキシ化合物、脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物以外のカチオン重合性化合物である、その他のカチオン重合性化合物を含むことができる。
　上記その他のカチオン重合性化合物を含む場合、その他のカチオン重合性化合物の含有量は、カチオン重合性成分１００質量部中、５０質量部以下であることが好ましく、なかでも、４０質量部以下であることが好ましく、特に、１０質量部以下であることが好ましく、なかでも特に、含まないことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　上記カチオン重合性成分が、その他のカチオン重合性化合物を含む場合、その他のカチオン重合性化合物としては、ビニルエーテル化合物等が挙げられる。 (5) Other cationically polymerizable compounds The above cationically polymerizable components include other cationically polymerizable compounds that are cationically polymerizable compounds other than alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds. can be included.
When the other cationically polymerizable compounds mentioned above are included, the content of the other cationically polymerizable compounds is preferably 50 parts by mass or less, particularly 40 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. It is particularly preferable that the amount is 10 parts by mass or less, and it is especially preferable that it is not included. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
When the cationically polymerizable component contains another cationically polymerizable compound, examples of the other cationically polymerizable compound include vinyl ether compounds.
（５）－１．ビニルエーテル化合物
　上記ビニルエーテル化合物は、ビニルエーテル基を有し、エポキシ基、オキセタン基を有しない化合物である。
　このような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、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。 (5)-1. Vinyl ether compound The above vinyl ether compound is a compound that has a vinyl ether group and does not have an epoxy group or an oxetane group.
Examples of such 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, Examples include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether.
Ａ２．酸化防止剤
　上記酸化防止剤は、樹脂の熱分解、酸化分解、熱による着色等を抑制する化合物が挙げられる。上記酸化防止剤としては、例えば、硫黄系酸化防止剤、フェノール系酸化防止剤、リン系酸化防止剤等が挙げられる。また、上記酸化防止剤は、２種以上を組み合わせて用いてもよい。 A2. Antioxidant Examples of the above-mentioned antioxidant include compounds that suppress thermal decomposition, oxidative decomposition, coloring due to heat, etc. of the resin. Examples of the antioxidant include sulfur-based antioxidants, phenolic antioxidants, phosphorus-based antioxidants, and the like. Moreover, the above-mentioned antioxidants may be used in combination of two or more types.
　本開示においては、酸化防止剤は、硫黄系酸化防止剤を必須成分として含有し、任意の成分として、フェノール系酸化防止剤、リン系酸化防止剤等のその他の酸化防止剤を含むことができる。 In the present disclosure, the antioxidant contains a sulfur-based antioxidant as an essential component, and may contain other antioxidants such as a phenolic antioxidant and a phosphorus-based antioxidant as an optional component. .
　従って、上記酸化防止剤は、硫黄系酸化防止剤のみを含むものであってもよく、硫黄系酸化防止剤と、フェノール系酸化防止剤とのみを含むものであってもよく、硫黄系酸化防止剤と、リン系酸化防止剤とのみを含むものであってもよく、硫黄系酸化防止剤と、フェノール系酸化防止剤及びリン系酸化防止剤とを含むものであってもよい。 Therefore, the above antioxidant may contain only a sulfur-based antioxidant, or may contain only a sulfur-based antioxidant and a phenolic antioxidant, or may contain only a sulfur-based antioxidant and a phenolic antioxidant. It may contain only a sulfur-based antioxidant and a phosphorus-based antioxidant, or it may contain a sulfur-based antioxidant, a phenol-based antioxidant, and a phosphorus-based antioxidant.
　本開示においては、上記酸化防止剤が、硫黄系酸化防止剤を含むものであることが好ましく、なかでも、硫黄系酸化防止剤と、フェノール系酸化防止剤とを含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the antioxidant preferably contains a sulfur-based antioxidant, and particularly preferably contains a sulfur-based antioxidant and a phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（１）硫黄系酸化防止剤
　上記硫黄系酸化防止剤は、分子中にチオエーテルを含む酸化防止剤を表す。また、上記硫黄系酸化防止剤は、１つ又は２つ以上を組み合わせて用いることができる。 (1) Sulfur-based antioxidant The above-mentioned sulfur-based antioxidant represents an antioxidant containing a thioether in the molecule. Moreover, the above-mentioned sulfur-based antioxidants can be used alone or in combination of two or more.
　上記硫黄系酸化防止剤は公知の硫黄系酸化防止剤であればよく、例えば、特開２０２２－１１５３７号公報等に記載の硫黄系酸化防止剤が挙げられる。 The above-mentioned sulfur-based antioxidant may be any known sulfur-based antioxidant, including, for example, the sulfur-based antioxidant described in JP-A No. 2022-11537.
　本開示においては、硫黄系酸化防止剤は、下記式（２－１）で表される化合物を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the sulfur-based antioxidant preferably contains a compound represented by the following formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（２－１）中、Ａは、炭素原子又は硫黄原子を表し、
Ｘ２は、単結合又は炭素原子数１～４のアルキレン基、炭素原子数６～１８のフェニレン基、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、カーボネート基、アミド基若しくはこれらのうち複数が連結した基を表し、
ＲＢ１は、炭素原子数６～２０のアルキル基又は、炭素原子数６～２０のアリール基を表し、
Ａが硫黄原子の場合、ｍ１は、２を表し、
Ａが炭素原子の場合、ｍ１は、４を表し、且つ、Ｘ２は、構造中にチオエーテル結合を含む基を表す。 In formula (2-1), A represents a carbon atom or a sulfur atom,
X 2 is a single bond, an alkylene group having 1 to 4 carbon atoms, a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide group, or more than one of these represents a linked group,
R B1 represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms,
When A is a sulfur atom, m1 represents 2,
When A is a carbon atom, m1 represents 4, and X 2 represents a group containing a thioether bond in its structure.
　式（２－１）中のＸ２で表される炭素原子数１～４のアルキレン基としては、式（１－５）中のＸで表される炭素原子数１～４のアルキレン基と同様とすることができる。 The alkylene group having 1 to 4 carbon atoms represented by X 2 in formula (2-1) is the same as the alkylene group having 1 to 4 carbon atoms represented by X in formula (1-5). It can be done.
　式（２－１）中のＸ２で表される炭素原子数６～１８のフェニレン基は、ベンゼン環から水素原子を２個引き抜いた基を表し、ベンゼン環の水素原子の１つ又は２つ以上が、炭素原子数１～４のアルキル基で置換されていてもよい。 The phenylene group having 6 to 18 carbon atoms represented by The above may be substituted with an alkyl group having 1 to 4 carbon atoms.
　式（２－１）中、Ｘ２で表される炭素原子数１～４のアルキレン基、炭素原子数６～１８のフェニレン基、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、カーボネート基、アミド基若しくはこれらのうち複数が連結した基において、これらのうちの複数が連結した基とは、アルキレン基、フェニレン基、カルボニル基、エーテル基、チオエーテル結合、エステル結合、カーボネート基、アミド基から選ばれる複数の基が、酸素原子同士が互いに隣接しないように接合した基とすることができる。 In formula (2-1), an alkylene group having 1 to 4 carbon atoms represented by X 2 , a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide In a group or a group in which a plurality of these are connected, the group in which a plurality of these are connected is selected from an alkylene group, a phenylene group, a carbonyl group, an ether group, a thioether bond, an ester bond, a carbonate group, and an amide group. A plurality of groups may be bonded together such that oxygen atoms are not adjacent to each other.
　式（２－１）中のＲＢ１で表される、炭素原子数６～２０のアルキル基は、式（１－１）中、Ｒ１で表される炭素原子数１～２０のアルキル基において、所定の炭素原子数を有する基が挙げられる。 The alkyl group having 6 to 20 carbon atoms represented by R B1 in formula (2-1) is the alkyl group having 1 to 20 carbon atoms represented by R 1 in formula (1-1). , a group having a predetermined number of carbon atoms.
　式（２－１）中のＲＢ１で表される、炭素原子数６～２０のアリール基は、アリール基の水素原子が、炭素原子数１～４のアルキル基又はヒドロキシ基で置換されていてもよい。
　上記炭素原子数６～２０のアリール基の具体例としては、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル基、３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル基、３，４－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル基等が挙げられる。 The aryl group having 6 to 20 carbon atoms, represented by R B1 in formula (2-1), has the hydrogen atom of the aryl group substituted with an alkyl group or hydroxy group having 1 to 4 carbon atoms. Good too.
Specific examples of the above aryl group having 6 to 20 carbon atoms include 3,5-di-tert-butyl-4-hydroxyphenyl group, 3-tert-butyl-4-hydroxy-5-methylphenyl group, 3, Examples include 4-di-tert-butyl-4-hydroxyphenyl group.
　上記式（２－１）で表される化合物の具体例としては、３，３’－チオジピロピオン酸ジドデシル、３，３’－チオジピロピオン酸ジトリデシル、３，３’－チオジピロピオン酸ジテトラデシル、３，３’－チオジピロピオン酸ジペンタデシル、３，３’－チオジピロピオン酸ジオクタデシル、ドデシル－３－（（３－オクタデシルオキシ－３－オキソプロピル）チオ）プロピオナート、２，２－ビス｛［３－（ドデシルチオ）－１－オキソプロポキシ］メチル｝プロパン－１，３－ジイル　ビス［３－（ドデシルチオ）プロピオナート］、（チオビス（エタン－２，１－ジイル））ビス（２－ｔｅｒｔ－ブチル）－５－メチル－４，１－フェニレン）ビス（３－ドデシルチオ）プロピオナート）、６，６’－チオビス（２，４－ジ－ｔｅｒｔ－ブチルフェノール）、６，６’－（チオビス（２－ｔｅｒｔ－ブチル）－４－メチルフェノール）、６，６’－（チオビス（メチレン）ビス（２－ｔｅｒｔ－ブチル）－４－メチルフェノール）、チオビス（エタン－２，１－ジイル）ビス（３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート）等が挙げられる。 Specific examples of the compound represented by the above formula (2-1) include didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, ditetradecyl 3,3'-thiodipropionate, 3,3'- Dipentadecyl thiodipropionate, diotadecyl 3,3'-thiodipyropionate, dodecyl-3-((3-octadecyloxy-3-oxopropyl)thio)propionate, 2,2-bis{[3-(dodecylthio)-1-oxo propoxy]methyl}propane-1,3-diyl bis[3-(dodecylthio)propionate], (thiobis(ethane-2,1-diyl))bis(2-tert-butyl)-5-methyl-4,1- phenylene)bis(3-dodecylthio)propionate), 6,6'-thiobis(2,4-di-tert-butylphenol), 6,6'-(thiobis(2-tert-butyl)-4-methylphenol), 6,6'-(thiobis(methylene)bis(2-tert-butyl)-4-methylphenol), thiobis(ethane-2,1-diyl)bis(3-(3,5-di-tert-butyl- 4-hydroxyphenyl) propionate) and the like.
　上記硫黄系酸化防止剤の市販品としては、例えば、アデカスタブ（登録商標）ＡＯ－４１２Ｓ、ＡＯ－５０３、ＡＯ－２６（以上、（株）ＡＤＥＫＡ製）、スミライザー（登録商標）ＴＰＭ、ＴＰＳ、ＴＰ－Ｄ（以上、住友化学（株）製）、Ｉｒｇａｎｏｘ（登録商標）ＰＳ　８００　ＦＬ、ＰＳ　８０２ＦＬ、１０３５、１０８１、１１９２、１７２６（以上、ＢＡＳＦ社製）、Ｃｙａｎｏｘ（登録商標）１２１２（Ｓｏｌｂｅｙ社製）等が挙げられる。但し、本開示の組成物は、例示した市販品に限定されるものではなく、公知の硫黄系酸化防止剤を用いることができる。 Examples of commercially available sulfur-based antioxidants include ADEKA STAB (registered trademark) AO-412S, AO-503, AO-26 (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) TPM, TPS, and TP. -D (manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) PS 800 FL, PS 802FL, 1035, 1081, 1192, 1726 (manufactured by BASF), Cyanox (registered trademark) 1212 (manufactured by Solbey) ) etc. However, the composition of the present disclosure is not limited to the exemplified commercial products, and known sulfur-based antioxidants can be used.
　本開示においては、式（２－１）中のＸ２が、直接結合、炭素原子数１～４のアルキレン基、炭素原子数１～４のアルキレン基及びエステル結合が連結した基、炭素原子数６～１８のフェニレン基と、エステル結合と、炭素原子数１～４のアルキレン基及びチオエーテル結合とが連結した基であることが好ましく、なかでも、炭素原子数１～４のアルキレン基及びエステル結合が連結した基、炭素原子数６～１８のフェニレン基と、エステル結合と、炭素原子数１～４のアルキレン基及びチオエーテル結合とが連結した基であることが好ましく、特に、炭素原子数１～２のアルキレン基及びエステル結合が連結した基、炭素原子数６～１８のフェニレン基と、エステル結合と、炭素原子数１～２のアルキレン基及びチオエーテル結合とが連結した基であることが好ましく、なかでも特に、炭素原子数１～２のアルキレン基及びエステル結合が連結した基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, X 2 in formula (2-1) is a direct bond, an alkylene group having 1 to 4 carbon atoms, a group in which an alkylene group having 1 to 4 carbon atoms and an ester bond are connected, or a group having a number of carbon atoms A group in which a 6 to 18 phenylene group, an ester bond, an alkylene group having 1 to 4 carbon atoms, and a thioether bond are connected is preferable, and among them, an alkylene group having 1 to 4 carbon atoms and an ester bond are preferable. A group in which a phenylene group having 6 to 18 carbon atoms, an ester bond, an alkylene group having 1 to 4 carbon atoms, and a thioether bond are connected, and in particular, a group in which a phenylene group having 6 to 18 carbon atoms is connected to 2, a group in which an alkylene group and an ester bond are connected, a group in which a phenylene group having 6 to 18 carbon atoms, an ester bond, an alkylene group having 1 to 2 carbon atoms and a thioether bond are connected, Among these, a group in which an alkylene group having 1 to 2 carbon atoms and an ester bond are connected is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記硫黄系酸化防止剤が、式（２－１）で表される化合物の中でも、式（２－２）で表される化合物を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the sulfur-based antioxidant contains a compound represented by formula (2-2) among the compounds represented by formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（２－２）中、ＲＢ２及びＲＢ３は、それぞれ独立に、炭素原子数６～２０のアルキル基を表す。 In formula (2-2), R B2 and R B3 each independently represent an alkyl group having 6 to 20 carbon atoms.
　式（２－２）中のＲＢ２及びＲＢ３で表される、炭素原子数６～２０のアルキル基は、式（１－１）中、Ｒ１で表される炭素原子数１～２０のアルキル基において、所定の炭素原子数を有する基が挙げられる。 The alkyl group having 6 to 20 carbon atoms represented by R B2 and R B3 in formula (2-2) is the alkyl group having 1 to 20 carbon atoms represented by R 1 in formula (1-1). Examples of the alkyl group include groups having a predetermined number of carbon atoms.
　本開示においては、式（２－２）中のＲＢ２及びＲＢ３が、ともに炭素原子数６～１８のアルキル基であることが好ましく、なかでも、炭素原子数８～１８のアルキル基であることが好ましく、特に、炭素原子数１２～１８のアルキル基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, R B2 and R B3 in formula (2-2) are both preferably an alkyl group having 6 to 18 carbon atoms, particularly an alkyl group having 8 to 18 carbon atoms. It is particularly preferred to be an alkyl group having 12 to 18 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記硫黄系酸化防止剤の分子量としては、２００以上１，２００以下であることが好ましく、なかでも、３００以上１，０００以下であることが好ましく、特に、３５０以上６００以下であることが好ましく、なかでも特に、３５０以上５５０以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The molecular weight of the sulfur-based antioxidant is preferably 200 or more and 1,200 or less, particularly preferably 300 or more and 1,000 or less, particularly preferably 350 or more and 600 or less, In particular, it is preferably 350 or more and 550 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記硫黄系酸化防止剤の硫黄含有率としては、３質量％～２０質量％の範囲内であることが好ましく、なかでも、４質量％～１５質量％の範囲内であることが好ましく、特に、５質量％～１３質量％の範囲内であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　上記硫黄含有率は、ＪＩＳ　Ｋ　２５４１に準拠して測定することができる。 The sulfur content of the sulfur-based antioxidant is preferably within the range of 3% by mass to 20% by mass, particularly preferably within the range of 4% by mass to 15% by mass, and particularly, It is preferably within the range of 5% by mass to 13% by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
The sulfur content can be measured in accordance with JIS K 2541.
　本開示の組成物が、上記硫黄系酸化防止剤と後述するフェノール系酸化防止剤との組み合わせを含む場合、上記硫黄系酸化防止剤の含有量は、硫黄系酸化防止剤及びフェノール系酸化防止剤の合計量１００質量部中、１０質量部以上９９質量部であることが好ましく、なかでも、１５質量部以上９０質量部以下であることが好ましく、特に、２０質量部以上８０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure includes a combination of the sulfur-based antioxidant and the phenolic antioxidant described below, the content of the sulfur-based antioxidant is equal to the amount of the sulfur-based antioxidant and the phenolic antioxidant. Of the total amount of 100 parts by mass, it is preferably 10 parts by mass or more and 99 parts by mass, particularly preferably 15 parts by mass or more and 90 parts by mass or less, and especially 20 parts by mass or more and 80 parts by mass or less. It is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記硫黄系酸化防止剤の含有量は、酸化防止剤１００質量部中、１０質量部以上１００質量部以下であることが好ましく、なかでも、２０質量部以上８０質量部以下であることが好ましく、特に、３０質量部以上７０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the sulfur-based antioxidant is preferably 10 parts by mass or more and 100 parts by mass or less, particularly preferably 20 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the antioxidant. In particular, it is preferably 30 parts by mass or more and 70 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記硫黄系酸化防止剤の含有量は、上記カチオン重合性成分１００質量部中、０．００１質量部以上１０質量部以下であることが好ましく、なかでも、０．１質量部以上５質量部以下であることが好ましく、特に、０．５質量部以上３質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the sulfur-based antioxidant is preferably 0.001 parts by mass or more and 10 parts by mass or less, particularly 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. The content is preferably 0.5 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記硫黄系酸化防止剤の含有量は、上記組成物の固形分１００質量部中、０．０１質量部以上１０質量部以下であることが好ましく、なかでも、０．１質量部以上５質量部以下であることが好ましく、特に、０．２質量部以上３質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the sulfur-based antioxidant is preferably 0.01 parts by mass or more and 10 parts by mass or less, particularly 0.1 parts by mass or more and 5 parts by mass, based on 100 parts by mass of the solid content of the composition. The content is preferably at least 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（２）フェノール系酸化防止剤
　上記フェノール系酸化防止剤は、チオエーテルを含まず、分子中にフェノール性水酸基を含む酸化防止剤を表す。
　上記フェノール系酸化防止剤の具体例としては、例えば、特開２０２２－１１５３７号公報に記載のフェノール系酸化防止剤が挙げられる。 (2) Phenolic antioxidant The above phenolic antioxidant represents an antioxidant that does not contain a thioether and contains a phenolic hydroxyl group in its molecule.
Specific examples of the above-mentioned phenolic antioxidant include, for example, the phenolic antioxidant described in JP-A No. 2022-11537.
　上記フェノール系酸化防止剤の市販品としては、例えば、アデカスタブ（登録商標）ＡＯ－２０、ＡＯ－３０、ＡＯ－４０、ＡＯ－６０、ＡＯ－８０、ＡＯ－３３０（以上、（株）ＡＤＥＫＡ製）、スミライザー（登録商標）ＧＰ　（以上、住友化学（株）製）、Ｉｒｇａｎｏｘ（登録商標）２４５、２５９、４２０、５６５、８５８、１１３５、２２４６、３１１４（以上、ＢＡＳＦ社製）等が挙げられる。 Commercially available products of the above-mentioned phenolic antioxidants include, for example, ADEKA STAB (registered trademark) AO-20, AO-30, AO-40, AO-60, AO-80, AO-330 (manufactured by ADEKA Co., Ltd.). ), Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 245, 259, 420, 565, 858, 1135, 2246, 3114 (manufactured by BASF), etc. .
　本開示においては、上記フェノール系酸化防止剤は、ヒンダードフェノール基を有する化合物であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　上記ヒンダードフェノール基は、２個のｔｅｒｔ－ブチル基とヒドロキシ基を含むベンゼン環から、１個の水素原子を引き抜いた基を表し、具体的には、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル基が好適に挙げられる。 In the present disclosure, the phenolic antioxidant is preferably a compound having a hindered phenol group. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
The above-mentioned hindered phenol group represents a group in which one hydrogen atom has been extracted from a benzene ring containing two tert-butyl groups and a hydroxyl group, and specifically, 3,5-di-tert-butyl- A preferred example is a 4-hydroxyphenyl group.
　上記ヒンダードフェノール基を有するフェノール系酸化防止剤としては、例えば、アデカスタブ（登録商標）ＡＯ－２０、ＡＯ－５０、ＡＯ－６０、ＡＯ－３３０等が挙げられる。 Examples of the above-mentioned phenolic antioxidant having a hindered phenol group include Adekastab (registered trademark) AO-20, AO-50, AO-60, AO-330, and the like.
　本開示の組成物が上記フェノール系酸化防止剤を含む場合、上記フェノール系酸化防止剤の含有量は、酸化防止剤１００質量部中、１０質量部以上１００質量部以下であることが好ましく、なかでも、２０質量部以上９０質量部以下であることが好ましく、特に、３０質量部以上８０質量部以下であることが好ましく、なかでも特に、３０質量部以上７５質量部以下が好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure contains the phenolic antioxidant, the content of the phenolic antioxidant is preferably 10 parts by mass or more and 100 parts by mass or less, based on 100 parts by mass of the antioxidant. However, it is preferably 20 parts by mass or more and 90 parts by mass or less, particularly preferably 30 parts by mass or more and 80 parts by mass or less, particularly preferably 30 parts by mass or more and 75 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示の組成物が上記フェノール系酸化防止剤を含む場合、上記フェノール系酸化防止剤の含有量は、上記カチオン重合性成分１００質量部中、０．００１質量部以上１０質量部以下であることが好ましく、なかでも、０．０１質量部以上１０質量部以下であることがより好ましく、特に、０．１質量部以上５質量部以下であることが好ましく、なかでも特に、０．２質量部以上３質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure includes the phenolic antioxidant, the content of the phenolic antioxidant is 0.001 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the cationically polymerizable component. is preferable, and more preferably 0.01 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, especially 0.2 parts by mass. The amount is preferably 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示の組成物が上記フェノール系酸化防止剤を含む場合、上記フェノール系酸化防止剤の含有量は、上記組成物の固形分１００質量部中、０．０１質量部以上１０質量部以下であることが好ましく、なかでも、０．０５質量部以上５質量部以下であることが好ましく、特に、０．２質量部以上３質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure includes the phenolic antioxidant, the content of the phenolic antioxidant is 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the solid content of the composition. The content is preferably 0.05 parts by mass or more and 5 parts by mass or less, particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（３）リン系酸化防止剤
　上記リン系酸化防止剤は、リン原子を含み、分子中にチオエーテル及びフェノール性水酸基を含まない酸化防止剤を表す。
　上記リン系酸化防止剤の市販品としては、アデカスタブ（登録商標）ＴＰＰ、３０１０、１３５Ａ、Ｃ、１５００、１１７８、２１１２、ＨＰ－１０、ＰＥＰ－３６、ＰＥＰ－８（以上、（株）ＡＤＥＫＡ製）等が挙げられる。 (3) Phosphorus-based antioxidant The above-mentioned phosphorus-based antioxidant represents an antioxidant that contains a phosphorus atom and does not contain a thioether or phenolic hydroxyl group in its molecule.
Commercially available products of the above-mentioned phosphorus antioxidants include ADEKA STAB (registered trademark) TPP, 3010, 135A, C, 1500, 1178, 2112, HP-10, PEP-36, and PEP-8 (manufactured by ADEKA Co., Ltd.). ) etc.
（４）酸化防止剤 (4) Antioxidant
　本開示においては、酸化防止剤として、上記式（２－１）で表される化合物と、上記フェノール系酸化防止剤と、を含有することが好ましく、なかでも、上記式（２－２）で表される化合物と、上記フェノール系酸化防止剤と、を含有することが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable that the antioxidant contains a compound represented by the above formula (2-1) and the above phenolic antioxidant, and in particular, a compound represented by the above formula (2-2). It is preferable to contain the represented compound and the above-mentioned phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（５）酸化防止剤の含有量
　酸化防止剤として、硫黄系酸化防止剤及びフェノール系酸化防止剤を含む場合、硫黄系酸化防止剤の含有量は、フェノール系酸化防止剤に対し、硫黄系酸化防止剤／フェノール系酸化防止剤の質量比が、０．１～２０の範囲内であることが好ましく、なかでも、０．２～１０の範囲内であることが好ましく、特に、０．３～５の範囲内であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　また、酸化防止剤１００質量部に対する、硫黄系酸化防止剤及びフェノール系酸化防止剤の含有量は、５０質量部以上であることが好ましく、なかでも、７０質量部以上であることが好ましく、特に、９０質量部以上であることが好ましく、なかでも特に、１００質量部、すなわち、酸化防止剤が、硫黄系酸化防止剤とフェノール系酸化防止剤のみ含有することが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (5) Content of antioxidant When the antioxidant includes a sulfur-based antioxidant and a phenolic antioxidant, the content of the sulfur-based antioxidant is higher than that of the phenolic antioxidant. The mass ratio of inhibitor/phenolic antioxidant is preferably within the range of 0.1 to 20, particularly preferably within the range of 0.2 to 10, particularly 0.3 to 20. It is preferably within the range of 5. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Further, the content of the sulfur-based antioxidant and the phenolic antioxidant relative to 100 parts by mass of the antioxidant is preferably 50 parts by mass or more, particularly preferably 70 parts by mass or more, and particularly , is preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, that is, the antioxidant contains only the sulfur-based antioxidant and the phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記酸化防止剤として硫黄系酸化防止剤及びフェノール系酸化防止剤を含む酸化防止剤の含有量は、カチオン重合性成分１００質量部中、０．０１質量部以上１０質量部以下であることが好ましく、なかでも、０．１質量部以上５質量部以下であることが好ましく、特に、０．２質量部以上３質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　また、上記酸化防止剤として硫黄系酸化防止剤及びフェノール系酸化防止剤を含む酸化防止剤の含有量は、上記組成物の固形分１００質量部中、０．００１質量部以上１０質量部以下であることが好ましく、なかでも、０．１質量部以上５質量部以下であることが好ましく、特に、０．２質量部以上４質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the antioxidant including a sulfur-based antioxidant and a phenolic antioxidant as the above-mentioned antioxidant is preferably 0.01 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the cationic polymerizable component. Among them, it is preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Further, the content of the antioxidant including a sulfur-based antioxidant and a phenolic antioxidant as the above-mentioned antioxidant is 0.001 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the solid content of the composition. The content is preferably 0.1 parts by mass or more and 5 parts by mass or less, particularly preferably 0.2 parts by mass or more and 4 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記酸化防止剤として、硫黄系酸化防止剤のみ、又は、硫黄系酸化防止剤とリン系酸化防止剤とを含有する場合の酸化防止剤の含有量は、カチオン重合性成分１００質量部中、０．０１質量部以上１０質量部以下であることが好ましく、なかでも、０．１質量部以上５質量部以下であることが好ましく、特に、０．２質量部以上３質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the antioxidant contains only a sulfur-based antioxidant or a sulfur-based antioxidant and a phosphorus-based antioxidant, the content of the antioxidant is 0 in 100 parts by mass of the cationic polymerizable component. The content is preferably .01 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記酸化防止剤として、硫黄系酸化防止剤のみ、又は、硫黄系酸化防止剤とリン系酸化防止剤とを含有する場合の酸化防止剤の含有量は、上記組成物の固形分１００質量部中、０．００１質量部以上１０質量部以下であることが好ましく、なかでも、０．１質量部以上５質量部以下であることが好ましく、特に、０．２質量部以上３質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the antioxidant contains only a sulfur-based antioxidant or a sulfur-based antioxidant and a phosphorus-based antioxidant, the content of the antioxidant is based on 100 parts by mass of the solid content of the composition. , preferably 0.001 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, particularly 0.2 parts by mass or more and 3 parts by mass or less. It is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Ａ３．黒色色材
　上記黒色色材としては、黒色顔料及び黒色染料からなる群から選択される１種以上が挙げられる。上記黒色色材は１種単独で用いてもよく、２種以上を用いてもよい。
　また、単独では黒色色材として使用できない着色剤を複数組み合わせ、全体として黒色になるように調整して黒色色材としてもよい。
　例えば、単独で黒色を発現する顔料を黒色顔料とする他にも、単独では黒色以外の色を有する顔料を複数組み合わせて黒色顔料として使用してもよい。同様に、単独で黒色を発現する染料を黒色染料とする他にも、単独では黒色以外の色を有する染料を複数組み合わせて黒色染料として使用してもよい。
　なお、黒色色材とは、波長４００ｎｍ～７００ｎｍの光を吸収できる色材をいう。 A3. Black Coloring Material The black coloring material includes one or more selected from the group consisting of black pigments and black dyes. The above black coloring materials may be used alone or in combination of two or more.
Alternatively, a black coloring material may be obtained by combining a plurality of coloring agents that cannot be used alone as a black coloring material and adjusting the coloring agent to produce a black color as a whole.
For example, in addition to using a black pigment as a pigment that expresses black color by itself, a plurality of pigments each having a color other than black may be used in combination as a black pigment. Similarly, in addition to using a dye that expresses black color by itself as a black dye, a plurality of dyes having colors other than black may be used in combination as a black dye.
Note that the black coloring material refers to a coloring material that can absorb light with a wavelength of 400 nm to 700 nm.
　より具体的には、例えば、色材と透明な樹脂マトリックス（アクリル樹脂等）と、溶剤とを含有し、全固形分に対する色材の含有量が６０質量％である組成物を調製する。得られた組成物を、ガラス基板上に、乾燥後の塗膜が１μｍになるように塗布し、塗膜を形成する。乾燥後の塗膜の遮光性を、紫外線可視近赤外分光光度計（Ｖ－６７０、日本分光（株）製）を用いて評価する。乾燥後の塗膜の波長４００ｎｍ～７００ｎｍにおける透過率の最大値が１０％未満であることで、例えば、遮光性が求められる用途の組成物に有用であると判断できる。 More specifically, for example, a composition is prepared that contains a coloring material, a transparent resin matrix (acrylic resin, etc.), and a solvent, and the content of the coloring material is 60% by mass based on the total solid content. The obtained composition is applied onto a glass substrate so that the coating film after drying has a thickness of 1 μm to form a coating film. The light-shielding properties of the dried coating film are evaluated using an ultraviolet-visible-near-infrared spectrophotometer (V-670, manufactured by JASCO Corporation). If the maximum value of the transmittance of the dried coating film in the wavelength range of 400 nm to 700 nm is less than 10%, it can be determined that the composition is useful for applications requiring light-shielding properties, for example.
（１）黒色顔料
　反射率が低減された硬化膜を得られる観点から、上記黒色色材は、黒色顔料であることが好ましい。
　黒色顔料は、公知の黒色顔料を使用できる。黒色顔料は、無機顔料であってもよく有機顔料であってもよいが、単独で黒色を発現する顔料が好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (1) Black Pigment From the viewpoint of obtaining a cured film with reduced reflectance, the black coloring material is preferably a black pigment.
As the black pigment, a known black pigment can be used. The black pigment may be an inorganic pigment or an organic pigment, but a pigment that alone expresses black color is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　単独で黒色を発現する顔料としては、例えば、チタン、ジルコニウム等の第４族の金属元素、バナジウム、ニオブ等の第５族の金属元素、コバルト、クロム、銅、マンガン、ルテニウム、鉄、ニッケル、スズ、銀等の金属元素を含む、金属酸化物、金属窒化物、金属酸窒化物等が挙げられる。
　また、黒色顔料としては、カーボンブラックも挙げられる。カーボンブラックの具体例としては、市販品である、Ｃ．Ｉ．ピグメントブラック　１等の有機顔料、及び、Ｃ．Ｉ．ピグメントブラック　７等の無機顔料等が挙げられる。 Examples of pigments that express black color by themselves include Group 4 metal elements such as titanium and zirconium, Group 5 metal elements such as vanadium and niobium, cobalt, chromium, copper, manganese, ruthenium, iron, nickel, Examples include metal oxides, metal nitrides, metal oxynitrides, etc. containing metal elements such as tin and silver.
Furthermore, examples of the black pigment include carbon black. Specific examples of carbon black include commercially available C. I. Pigment Black 1 and other organic pigments, and C.I. I. Examples include inorganic pigments such as Pigment Black 7.
　上記黒色顔料の含有量は、カチオン重合性成分１００質量部に対して、０．１質量部以上１５質量部以下であることが好ましく、なかでも、０．３質量部以上１０質量部以下であることが好ましく、特に、１質量部以上５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the black pigment is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the cationic polymerizable component. The content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記黒色顔料の含有量としては、上記組成物の固形分１００質量部中に、０．１質量部以上１５質量部以下であることが好ましく、なかでも、０．３質量部以上１０質量部以下であることが好ましく、特に、１質量部以上５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the black pigment is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition. The content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（２）黒色染料
　上記黒色色材として、黒色染料は、本開示の組成物に溶解し、分散が容易であるため、着色が均一な硬化物を形成しやすい点で好ましい。また、透明性やヘイズに優れるので好ましい。
　上記黒色染料は、溶剤に可溶であり、可視光線の波長の光を吸収することで、黒色に着色できるものである。
　本開示においては、上記黒色染料が、アゾ系黒色染料及びニグロシン系黒色染料から選択される少なくとも１種からなるものである。 (2) Black Dye As the above-mentioned black coloring material, a black dye is preferable because it dissolves in the composition of the present disclosure and is easily dispersed, so that it is easy to form a uniformly colored cured product. Further, it is preferable because it has excellent transparency and haze.
The above-mentioned black dye is soluble in a solvent and can be colored black by absorbing light in the wavelength range of visible light.
In the present disclosure, the black dye is at least one selected from azo black dyes and nigrosine black dyes.
　上記アゾ系黒色染料としては、アゾ基（－Ｎ＝Ｎ－）を有するものを用いることができ、例えば以下のものを挙げることができる。
Ｃ．Ｉ．ＳｏｌｖｅｎｔＢｌａｃｋ３、同２２、同２３、同１２３、ＪａｐａｎｏｌＦａｓｔＢｌａｃｋＤｃｏｎｃ．（Ｃ．Ｉ．ＤｉｒｅｃｔＢｌａｃｋ１７、住友化学工業（株）製）、ＷａｔｅｒＢｌａｃｋ１００Ｌ（Ｃ．Ｉ．ＤｉｒｅｃｔＢｌａｃｋ１９）、ＷａｔｅｒＢｌａｃｋＬ－２００（Ｃ．Ｉ．ＤｉｒｅｃｔＢｌａｃｋ１９）、ＤｉｒｅｃｔＦａｓｔＢｌａｃｋＢ（Ｃ．Ｉ．ＤｉｒｅｃｔＢｌａｃｋ２２、保土谷化学工業（株）製）、ＤｉｒｅｃｔＦａｓｔＢｌａｃｋＡＢ（Ｃ．Ｉ．ＤｉｒｅｃｔＢｌａｃｋ３２、住友化学工業（株）製）、ＤｉｒｅｃｔＤｅｅｐＢｌａｃｋＥＸ（Ｃ．Ｉ．ＤｉｒｅｃｔＢｌａｃｋ３８、住友化学工業（株）製）、ＤｉｒｅｃｔＦａｓｔＢｌａｃｋＣｏｎｃ．（Ｃ．Ｉ．ＤｉｒｅｃｔＢｌａｃｋ５１、保土谷化学工業（株）製）、ＫａｙａｒｕｓＳｕｐｒａ　Ｇｒｅｙ　ＶＧＮ（Ｃ．Ｉ．Ｄｉｒｅｃｔ　Ｂｌａｃｋ　７１、日本化薬（株）製）、Ａｃｉｄ　ＢｌｕｅＢｌａｃｋ　１０Ｂ（Ｃ．Ｉ．ＡｃｉｄＢｌａｃｋ１）、Ｓｕｍｉｎｏｌ　Ｍｉｌｌｉｎｇ　Ｂｌａｃｋ　８ＢＸ（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　２４、住友化学工業（株）製）、Ｋａｙａｎｏｌ　ＭｉｌｌｉｎｇＢｌａｃｋ　ＶＬＧ（Ｃ．Ｉ．ＡｃｉｄＢｌａｃｋ　２６、日本化薬（株）製）、ＳｕｍｉｎｏｌＦａｓｔ　Ｂｌａｃｋ　ＢＲ　ｃｏｎｃ．（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ３１、住友化学工業(株)製）、Ｍｉｔｓｕｉ Ｎｙｌｏｎ Ｂｌａｃｋ ＧＬ（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ ５２、三井ＢＡＳＦ(株)製）、Ａｉｚｅｎ　ＯｐａｌＢｌａｃｋ　ＷＨ　ｅｘｔｒａ　ｃｏｎｃ．（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　５２、保土谷化学工業（株）製）、Ｓｕｍｉｌａｎ　Ｂｌａｃｋ　ＷＡ（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ５２、住友化学工業（株）製）、ＬａｎｙｌＢｌａｃｋ　ＢＧ，ｅｘｔｒａ　ｃｏｎｃ．（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　１０７、三菱化成工業（株）製）、ＫａｙａｎｏｌＭｉｌｌｉｎｇ　Ｂｌａｃｋ　ＴＬＢ（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　１０９、日本化薬（株）製）、Ｓｕｍｉｎｏｌ　Ｍｉｌｌｉｎｇ　Ｂｌａｃｋ　Ｂ（Ｃ．Ｉ．ＡｃｉｄＢｌａｃｋ　１０９、住友化学工業（株）製）、Ｋａｙａｎｏｌ　Ｍｉｌｌｉｎｇ　Ｂｌａｃｋ　ＴＬＲ（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　１１０、日本化薬（株）製）、ＡｉｚｅｎＯｐａｌ　Ｂｌａｃｋ　ｎｅｗ　ｃｏｎｃ．（Ｃ．Ｉ．ＡｃｉｄＢｌａｃｋ　１１９、保土谷化学工業（株）製）、ＶＡＬＩＦＡＳＴＢｌａｃｋ３８０４（ＡｚｏＣｈｒｏｍｉｕｍＣｏｍｐｌｅｘＳｏｌｖｅｎｔＢｌａｃｋ３４とアミンの混合物）、ＶＡＬＩＦＡＳＴＢＬＡＣＫ１８０７（ＡｃｉｄＢｌａｃｋ５２）、同３８０４（ＳｏｌｖｅｎｔＢｌａｃｋ３４とアミンの混合物）、同３８１０（ＳｏｌｖｅｎｔＢｌａｃｋ２９）、同３８２０（ＳｏｌｖｅｎｔＢｌａｃｋ２７）、同３８３０（ＳｏｌｖｅｎｔＢｌａｃｋ２７）、同３８４０（ＳｏｌｖｅｎｔＢｌａｃｋ２７）、同３８６６（ＳｏｌｖｅｎｔＢｌａｃｋ２９）、同３８７０（ＳｏｌｖｅｎｔＢｌａｃｋ２９）（以上、オリヱント化学工業（株）製） As the above-mentioned azo black dye, those having an azo group (-N=N-) can be used, and examples thereof include the following.
C. I. SolventBlack3, 22, 23, 123, JapanolFastBlackDconc. (C.I.DirectBlack17, manufactured by Sumitomo Chemical Co., Ltd.), WaterBlack100L (C.I.DirectBlack19), WaterBlackL-200 (C.I.DirectBlack19), DirectFastBlackB (C.I.Dir ectBlack22, Hodogaya Chemical Industry Co., Ltd. ), DirectFastBlackAB (C.I.DirectBlack32, manufactured by Sumitomo Chemical Industries, Ltd.), DirectDeepBlackEX (C.I.DirectBlack38, manufactured by Sumitomo Chemical Industries, Ltd.), DirectFastBlackConc. (C.I. Direct Black 51, manufactured by Hodogaya Chemical Industry Co., Ltd.), KayarusSupra Gray VGN (C.I. Direct Black 71, manufactured by Nippon Kayaku Co., Ltd.), Acid BlueBlack 10B (C.I. Acid Black 1), Sumino l Milling Black 8BX (C.I. Acid Black 24, manufactured by Sumitomo Chemical Co., Ltd.), Kayanol Milling Black VLG (C.I. Acid Black 26, manufactured by Nippon Kayaku Co., Ltd.), SuminolFast Black BR con c. (C.I. Acid Black 31, manufactured by Sumitomo Chemical Industries, Ltd.), Mitsui Nylon Black GL (C.I. Acid Black 52, manufactured by Mitsui BASF, Ltd.), Aizen OpalBlack WH extra conc. (C.I. Acid Black 52, manufactured by Hodogaya Chemical Industries, Ltd.), Sumilan Black WA (C.I. Acid Black 52, manufactured by Sumitomo Chemical Industries, Ltd.), LanylBlack BG, extra conc. (C.I. Acid Black 107, manufactured by Mitsubishi Chemical Industries, Ltd.), Kayanol Milling Black TLB (C.I. Acid Black 109, manufactured by Nippon Kayaku Co., Ltd.), Suminol Milling Black B (C.I. Acid Black 109 , manufactured by Sumitomo Chemical Industries, Ltd.), Kayanol Milling Black TLR (C.I. Acid Black 110, manufactured by Nippon Kayaku Co., Ltd.), Aizen Opal Black new conc. (C.I.AcidBlack 119, manufactured by Hodogaya Chemical Industry Co., Ltd.), VALIFASTBlack3804 (mixture of AzoChromium Complex SolventBlack34 and amine), VALIFASTBLACK1807 (AcidBlack52), 804 (mixture of SolventBlack34 and amine), 3810 (SolventBlack29), 3820 (SolventBlack27), 3830 (SolventBlack27), 3840 (SolventBlack27), 3866 (SolventBlack29), 3870 (SolventBlack29) (manufactured by Orient Chemical Industry Co., Ltd.)
　上記ニグロシン系黒色染料としては、アニリン・ニトロベンゼンを縮合したフェナジン骨格を有する化合物であり、例えば、下記化学式（Ｉ）又は（ＩＩ）で表されるトリフェナジンオキサジン構造を有する化合物、下記化学式（ＩＩＩ）～（ＶＩ）で表されるフェナジンアジン構造を有する化合物等が挙げられる。
　なお、式（Ｉ）～（ＶＩ）中のＸ－は、対アニオンを表す。 The nigrosine black dye is a compound having a phenazine skeleton obtained by condensing aniline and nitrobenzene, such as a compound having a triphenazine oxazine structure represented by the following chemical formula (I) or (II), or a compound having the following chemical formula (III). Examples include compounds having a phenazineazine structure represented by (VI).
Note that X − in formulas (I) to (VI) represents a counter anion.
Figure JPOXMLDOC01-appb-C000015
 （Ｒ９０、Ｒ９１、Ｒ９２及びＲ９３はそれぞれ独立に、水素原子又はフェニル基である。）
Figure JPOXMLDOC01-appb-C000015
 (R 90 , R 91 , R 92 and R 93 are each independently a hydrogen atom or a phenyl group.)
　上記ニグロシン系黒色染料としては、具体的には、Ｃ．Ｉ．Ｎｏ．Ａｃｉｄ　Ｂｌａｃｋ　２、Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　５、Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　７、Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　２２、Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　２７、Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　２９、Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　３４等が挙げられる。
　上記ニグロシン系黒色染料の市販品としては、例えば、ＮＵＢＩＡＮ　ＢＬＡＣＫ　ＮＨ－８０５、同ＮＨ－８１５（オリヱント化学工業（株）製）（Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌａｃｋ ５））、ＮＵＢＩＡＮ　ＢＬＡＣＫ　ＴＮ－８７０、同ＴＨ－８０７（オリヱント化学工業（株）製）（Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　７）、ＶＡＬＩＦＡＳＴ　ＢＬＡＣＫ１８２１（Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　７の有機酸塩（造塩染料）、オリヱント化学工業社製の油溶性染料）等が挙げられる。 Specifically, the nigrosine black dye mentioned above includes C.I. I. No. Examples include Acid Black 2, Solvent Black 5, Solvent Black 7, Solvent Black 22, Solvent Black 27, Solvent Black 29, and Solvent Black 34.
Examples of commercially available nigrosine black dyes include NUBIAN BLACK NH-805, NH-815 (manufactured by Orient Chemical Industry Co., Ltd.) (C.I.Solvent Black 5)), NUBIAN BLACK TN-870, TH-807 (manufactured by Orient Chemical Industry Co., Ltd.) (C.I. Solvent Black 7), VALIFAST BLACK1821 (organic acid salt (salt-forming dye) of C.I. Solvent Black 7), oil-soluble dye manufactured by Orient Chemical Industry Co., Ltd. dyes), etc.
　本開示においては、なかでも、上記黒色染料が、ニグロシン系黒色染料を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is particularly preferable that the black dye includes a nigrosine-based black dye. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記黒色染料が、骨格にクロム、コバルト、ニッケル、銅、鉄等の金属が錯塩化されている金属錯塩染料、又は、酸性染料と塩基性染料とを反応させた造塩染料、酸性染料を有機アミン等の塩基によって造塩した造塩染料、塩基性染料を有機酸等の酸によって造塩した造塩染料等の造塩染料であることが好ましく、なかでも、造塩染料であることが好ましく、特に、塩基性染料を有機酸等の酸によって造塩した造塩染料であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, the black dye is a metal complex dye in which a metal such as chromium, cobalt, nickel, copper, or iron is complexed in the skeleton, or a salt-forming dye in which an acidic dye and a basic dye are reacted. , salt-forming dyes such as salt-forming dyes produced by salt-forming an acidic dye with a base such as an organic amine, and salt-forming dyes such as salt-forming dyes produced by salt-forming a basic dye with an acid such as an organic acid. Among these, salt-forming dyes are preferable. The dye is preferably a salt-forming dye obtained by salt-forming a basic dye with an acid such as an organic acid. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示において、造塩染料の形成に用いられる有機酸としては、アルキルベンゼンスルホン酸、ナフタレンスルホン酸、ナフタレンスルホン酸-ホルムアルデヒド縮合物、アルキルジフェニルエーテルジスルホン酸、ポリオキシエチレンアルキルフェニルエーテルリン酸が挙げられる。
　本開示においては、なかでも、アルキルベンゼンスルホン酸であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, organic acids used to form the salt-forming dye include alkylbenzenesulfonic acids, naphthalenesulfonic acids, naphthalenesulfonic acid-formaldehyde condensates, alkyldiphenyl ether disulfonic acids, and polyoxyethylene alkylphenyl ether phosphoric acids.
In the present disclosure, alkylbenzenesulfonic acids are particularly preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記金属錯塩染料としては、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　２１、２２、２３、２７、２８、２９、３１等、Ｃ．Ｉ．Ａｃｉｄ　Ｂｌａｃｋ　５２、６０、９９等が挙げられる。
　上記造塩染料としては、ＶＡＬＩＦＡＳＴ　ＢＬＡＣＫ　１８０７、１８２１、３８０４、３８０６、３８０８、３８１０、３８２０、３８３０、３８４０、３８７０、３８７７等（オリヱント化学工業社製）等が挙げられる。 As the metal complex dye, C.I. I. Solvent Black 21, 22, 23, 27, 28, 29, 31 etc., C.I. I. Acid Black 52, 60, 99, etc. are mentioned.
Examples of the salt forming dye include VALIFAST BLACK 1807, 1821, 3804, 3806, 3808, 3810, 3820, 3830, 3840, 3870, 3877 (manufactured by Orient Chemical Industry Co., Ltd.).
　本開示においては、なかでも、上記黒色染料が、ニグロシン系黒色染料であり、且つ、金属錯塩染料又は造塩染料である染料を含むことが好ましく、特に、ニグロシン系黒色染料であり、且つ、造塩染料である染料を含むことが好ましく、なかでも特に、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌａｃｋ　７の有機酸塩であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is particularly preferable that the black dye is a nigrosine-based black dye and contains a dye that is a metal complex salt dye or a salt-forming dye, particularly a nigrosine-based black dye, and a dye that is a salt-forming dye. It is preferred to include dyes that are salt dyes, especially C.I. I. An organic acid salt of Solvent Black 7 is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記黒色染料の含有量は、カチオン重合性成分１００質量部に対して、０．１質量部以上１５質量部以下であることが好ましく、なかでも、０．３質量部以上１０質量部以下であることが好ましく、特に、１質量部以上５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the black dye is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. The content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記黒色染料の含有量としては、上記組成物の固形分１００質量部中に、０．１質量部以上１５質量部以下であることが好ましく、なかでも、０．３質量部以上１０質量部以下であることが好ましく、特に、１質量部以上５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the black dye is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition. The content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Ａ４．光酸発生剤
　上記光酸発生剤は、可視光線、紫外線、Ｘ線、電子線、高周波のような活性エネルギー線（以下、単に「エネルギー線」と称する場合がある。）照射により酸を発生させることが可能な化合物である。 A4. Photoacid generator The photoacid generator described above generates acid upon irradiation with active energy rays (hereinafter sometimes simply referred to as "energy rays") such as visible light, ultraviolet rays, X-rays, electron beams, and high frequency waves. It is a compound that can.
　上記光酸発生剤としては、オニウム塩である複塩又はその誘導体、あるいはオキシムスルホネート化合物、ハロゲン含有化合物、ジアゾケトン化合物、スルホン化合物、スルホン酸化合物、ジアゾメタン化合物、ニトロベンジル化合物、ベンゾイントシレート化合物、鉄－アレーン錯体、アセトフェノン誘導体化合物等が挙げられ、これらは単独で又は２種以上を混合して使用することができる。
　本開示においては、光酸発生剤が、オニウム塩である複塩又はその誘導体であることが好ましい。このような光酸発生剤であることで、上記組成物は、感度に優れ、密着性にも優れた硬化物が得られるものとなるからである。 The above-mentioned photoacid generators include double salts that are onium salts or derivatives thereof, oxime sulfonate compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, diazomethane compounds, nitrobenzyl compounds, benzointosylate compounds, iron. -arene complexes, acetophenone derivative compounds, etc., and these can be used alone or in combination of two or more.
In the present disclosure, it is preferable that the photoacid generator is a double salt that is an onium salt or a derivative thereof. This is because, by using such a photoacid generator, the composition can yield a cured product with excellent sensitivity and adhesion.
　オニウム塩である複塩又はその誘導体としては、例えば、下記式（ｉ）で表される陽イオンと陰イオンの塩が挙げられる。 Examples of double salts that are onium salts or derivatives thereof include salts of cations and anions represented by the following formula (i).
［Ａ］ｍ＋［Ｂ］ｍ－　　（ｉ） [A] m+ [B] m- (i)
　ここで、陽イオン［Ａ］ｍ＋はオニウムであり、その構造は、例えば、下記式で表すことができる。 Here, the cation [A] m+ is onium, and its structure can be represented by the following formula, for example.
［（Ｒ３００）ａＱ］ｍ＋　　（ｉｉ） [(R 300 ) a Q] m+ (ii)
　上記式（ｉｉ）中、Ｒ３００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含んでいてもよい有機基を表す。
　ａは１～５の整数を表す。
　ａ個のＲ３００は各々独立で、同一でも異なっていてもよい。
　ａ個のＲ３００のうち、少なくとも１つが、芳香族環を有する上記有機基を表す。
　ＱはＳ、Ｎ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｏ、Ｉ、Ｂｒ、Ｃｌ、Ｆ及びＮ＝Ｎからなる群から選ばれる原子又は原子団を表す。また、陽イオン［Ａ］ｍ＋中のＱの原子価をｑとしたとき、ｍ＝ａ－ｑなる関係が成り立つことが必要である。ただし、Ｎ＝Ｎは原子価０として扱う。 In the above formula (ii), R 300 represents an organic group having 1 to 60 carbon atoms and which may contain any number of atoms other than carbon atoms.
a represents an integer from 1 to 5.
The a pieces of R 300 are each independent and may be the same or different.
At least one of a R 300 represents the above organic group having an aromatic ring.
Q represents 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. Further, when the valence of Q in the cation [A] m+ is q, it is necessary that the relationship m=aq holds true. However, N=N is treated as a valence of 0.
　また、陰イオン［Ｂ］ｍ－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、下記式（ｉｉｉ）で表すことができる。本開示の組成物が、感度に優れたものとなるからである。 Further, the anion [B] m- is preferably a halide complex, and its structure can be represented by, for example, the following formula (iii). This is because the composition of the present disclosure has excellent sensitivity.
［ＬＸ３ ｂ］ｍ－　　（ｉｉｉ） [LX 3 b ] m- (iii)
　上記式（ｉｉｉ）中、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）を表し、Ｂ、Ｐ、Ａｓ、Ｓｂ、Ｆｅ、Ｓｎ、Ｂｉ、Ａｌ、Ｃａ、Ｉｎ、Ｔｉ、Ｚｎ、Ｓｃ、Ｖ、Ｃｒ、Ｍｎ又はＣｏである。
　Ｘ３はハロゲン原子を表す。
　ｂは３～７の整数を表す。また、陰イオン［Ｂ］ｍ－中のＬの原子価をｐとしたとき、ｍ＝ｂ－ｐなる関係が成り立つことが必要である。 In the above formula (iii), L represents a metal or metalloid that is the central atom of the halide complex, and includes B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn. , Sc, V, Cr, Mn or Co.
X 3 represents a halogen atom.
b represents an integer from 3 to 7. Further, when the valence of L in the anion [B] m- is set to p, it is necessary that the relationship m=bp holds true.
　上記式（ｉｉｉ）の陰イオン［ＬＸ３ ｂ］ｍ－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［（Ｃ６Ｆ５）４Ｂ］－、テトラフルオロボレート（ＢＦ４）－、ヘキサフルオロホスフェート（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）－、ヘキサクロロアンチモネート（ＳｂＣｌ６）－、トリス（ペンタフルオロメチル）トリフルオロリン酸イオン（ＦＡＰアニオン）等が挙げられる。 Specific examples of the anion [LX 3 b ] m- in formula (iii) above include tetrakis(pentafluorophenyl)borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) -, hexafluoroborate (BF 4 ) - , Fluorophosphate (PF 6 ) - , hexafluoroantimonate (SbF 6 ) - , hexafluoroarsenate (AsF 6 ) - , hexachloroantimonate (SbCl 6 ) - , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion) ) etc.
　また、陰イオン［Ｂ］ｍ－は、下記式（ｉｖ）で表される構造であってもよい。 Further, the anion [B] m- may have a structure represented by the following formula (iv).
［ＬＸ３ ｂ－１（ＯＨ）］ｍ－　　（ｉｖ） [LX 3 b-1 (OH)] m- (iv)
　ここで、Ｌ、Ｘ３及びｂは上記と同様である。
　また、その他の陰イオンとしては、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、テトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Here, L, X3 and b are the same as above.
Other anions include perchlorate ion (ClO 4 ) - , trifluoromethylsulfite ion (CF 3 SO 3 ) - , fluorosulfonate ion (FSO 3 ) - , toluenesulfonate anion, and trinitrobenzene. Sulfonic acid anions, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like can be mentioned.
　本開示においては、このようなオニウム塩の中でも、下記の（イ）～（ハ）の芳香族オニウム塩を使用することが特に有効である。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 disclosure, among such onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one kind can be used alone or two or more kinds can be used in combination.
（イ）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、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 (a) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
（ロ）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、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 (b) Diaryl such as diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tolylcumyliodonium tetrakis(pentafluorophenyl)borate, etc. iodonium salt
（ハ）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 (c) Sulfonium cations represented by Group I or Group II below and sulfonium salts such as hexafluoroantimony ion, tetrakis(pentafluorophenyl)borate ion, etc.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　また、その他の光酸発生剤としては、（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－アレーン錯体や、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と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られる。 In addition, other photoacid generators include (η5-2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl)benzene] - Iron-arene complexes such as iron-hexafluorophosphate, aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, tris(salicylaldehydato)aluminum, and silanols such as triphenylsilanol. Also included are mixtures with other types.
　これらの中でも、実用面と光感度の観点から、光酸発生剤としては、芳香族ヨードニウム塩、芳香族スルホニウム塩及び鉄－アレーン錯体が好ましく、なかでも、芳香族スルホニウム塩であることが好ましく、硫黄原子（Ｓ）に芳香族環が３つ結合した構造を有するトリアリールスルホニウム塩であることがより好ましく、特に、下記式（４）で表されるトリアリールスルホニウム塩であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 Among these, from the viewpoint of practical use and photosensitivity, aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferable as photoacid generators, and aromatic sulfonium salts are especially preferable. A triarylsulfonium salt having a structure in which three aromatic rings are bonded to a sulfur atom (S) is more preferable, and a triarylsulfonium salt represented by the following formula (4) is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記式（４）中、Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２、Ｒ１１３及びＲ１１４は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基又は炭素原子数１～１０のアルコキシ基を表し、
　Ｒ１１５は、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基又は下記式（４ａ）～（４ｃ）より選択されるいずれかの置換基を表し、
　Ａｎｑ－はｑ価の陰イオンを表し、
　ｐは電荷を中性にする係数を表す。 In the above formula (4), R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 are Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
R 115 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any substituent selected from the following formulas (4a) to (4c),
An q- represents a q-valent anion,
p represents a coefficient that neutralizes the charge.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記式（４ａ）～（４ｃ）中、Ｒ１１６、Ｒ１１７、Ｒ１１８、Ｒ１１９、Ｒ１２０、Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３、Ｒ１３４、Ｒ１３５、Ｒ１３６、Ｒ１３７、Ｒ１３８、Ｒ１３９、Ｒ１４０、Ｒ１４１、Ｒ１４２及びＲ１４３は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基又は炭素原子数１～１０のアルコキシ基を表し、
　＊は、Ｓとの結合位置を表す。 In the above formulas (4a) to (4c), R 116 , R 117 , R 118 , R 119 , R 120 , R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 are each independently, Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
* represents the bonding position with S.
　上記式（４）中のＲ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２、Ｒ１１３、Ｒ１１４及びＲ１１５並びに上記式（４ａ）～（４ｃ）中のＲ１１６、Ｒ１１７、Ｒ１１８、Ｒ１１９、Ｒ１２０、Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３、Ｒ１３４、Ｒ１３５、Ｒ１３６、Ｒ１３７、Ｒ１３８、Ｒ１３９、Ｒ１４０、Ｒ１４１、Ｒ１４２及びＲ１４３で表されるハロゲン原子は、上記「１．カチオン重合性成分」の項に記載した、式（１－１）中の「ハロゲン原子」と同様である。 R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 and R in the above formula (4) 115 and R 116 , R 117 , R 118 , R 119 , R 120 , R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R in the above formulas (4a) to (4c) 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 The halogen atom is the same as the "halogen atom" in formula (1-1) described in the section "1. Cationically polymerizable component" above.
　上記式（４）中のＲ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２、Ｒ１１３、Ｒ１１４及びＲ１１５、並びに上記式（４ａ）～（４ｃ）中のＲ１１６、Ｒ１１７、Ｒ１１８、Ｒ１１９、Ｒ１２０、Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３、Ｒ１３４、Ｒ１３５、Ｒ１３６、Ｒ１３７、Ｒ１３８、Ｒ１３９、Ｒ１４０、Ｒ１４１、Ｒ１４２及びＲ１４３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．カチオン重合性成分」の項に記載した、式（１－１）中の「炭素原子数１～２０のアルキル基」として挙げたもののうち、所定の炭素原子数を有する基が挙げられる。 R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 , R 114 and R in the above formula (4) 115 , as well as R 116 , R 117 , R 118 , R 119 , R 120 , R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 in the above formulas (4a) to (4c), Represented by R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 Examples of the alkyl group having 1 to 10 carbon atoms include those listed as the ``alkyl group having 1 to 20 carbon atoms'' in formula (1-1) described in the section ``1. Cationically polymerizable component'' above. Among them, groups having a predetermined number of carbon atoms can be mentioned.
　上記式（４）中のＲ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２、Ｒ１１３及びＲ１１４、並びに上記式（４ａ）～（４ｃ）中のＲ１１６、Ｒ１１７、Ｒ１１８、Ｒ１１９、Ｒ１２０、Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３、Ｒ１３４、Ｒ１３５、Ｒ１３６、Ｒ１３７、Ｒ１３８、Ｒ１３９、Ｒ１４０、Ｒ１４１、Ｒ１４２及びＲ１４３で表される炭素原子数１～１０のアルコキシ基は、上記「１．カチオン重合性成分」の項に記載した、式（１－１）中の「炭素原子数１～２０のアルコキシ基」として挙げたもののうち、所定の炭素原子数を有する基が挙げられる。 R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 in the above formula (4), and R 116 , R 117 , R 118 , R 119 , R 120 , R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 in the above formulas (4a) to (4c), Carbon atoms represented by R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 The alkoxy group having numbers 1 to 10 is a predetermined one among those listed as the "alkoxy group having 1 to 20 carbon atoms" in formula (1-1) described in the section "1. Cationically polymerizable component" above. Examples include groups having the number of carbon atoms.
　上記式（４）中のｐＡｎｑ－で表されるｑ価のアニオンとしては、上述の陰イオン［Ｂ］ｍ－として挙げたもののうち、所定の価数のアニオンが挙げられる。
　ｐＡｎｑ－で表されるｑ価のアニオンとしては、例えば、テトラキス（ペンタフルオロフェニル）ボレート［（Ｃ６Ｆ５）４Ｂ］－、テトラフルオロボレート（ＢＦ４）－、ヘキサフルオロホスフェート（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）－、ヘキサクロロアンチモネート（ＳｂＣｌ６）－、トリス（ペンタフルオロメチル）トリフルオロリン酸イオン（ＦＡＰアニオン）、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、テトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the q-valent anion represented by pAn q- in the above formula (4) include anions with a predetermined valence among those listed as the above-mentioned anion [B] m- .
Examples of the q-valent anion represented by pAn q- include tetrakis(pentafluorophenyl)borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) - , hexafluorophosphate (PF 6 ) - , hexafluoroantimonate (SbF 6 ) - , hexafluoroarsenate (AsF 6 ) - , hexachloroantimonate (SbCl 6 ) - , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion), perchloric acid ion (ClO 4 ) - , trifluoromethyl sulfite ion (CF 3 SO 3 ) - , fluorosulfonate ion (FSO 3 ) - , toluenesulfonate anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluoro Examples include butane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like.
　本開示においては、Ｒ１１５が、上記式（４ａ）～（４ｃ）より選択されるものであることが好ましく、上記式（４ａ）又は（４ｃ）であることがより好ましい。Ｒ１１５が上述の構造を有することにより、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, R 115 is preferably selected from the above formulas (4a) to (4c), more preferably the above formula (4a) or (4c). This is because when R 115 has the above-described structure, the composition can form a cured product with better heat-and-moisture resistance and weather resistance.
　Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７、Ｒ１０８、Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２、Ｒ１１３及びＲ１１４は、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基又は炭素原子数１～１０のアルコキシ基であることが好ましく、特に、水素原子又はハロゲン原子であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 are hydrogen atom, halogen atom, carbon It is preferably an alkyl group having 1 to 10 atoms or an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　Ｒ１１６、Ｒ１１７、Ｒ１１８、Ｒ１１９、Ｒ１２０、Ｒ１２１、Ｒ１２２、Ｒ１２３、Ｒ１２４、Ｒ１２５、Ｒ１２６、Ｒ１２７、Ｒ１２８、Ｒ１２９、Ｒ１３０、Ｒ１３１、Ｒ１３２、Ｒ１３３、Ｒ１３４、Ｒ１３５、Ｒ１３６、Ｒ１３７、Ｒ１３８、Ｒ１３９、Ｒ１４０、Ｒ１４１、Ｒ１４２及びＲ１４３は、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基又は炭素原子数１～１０のアルコキシ基であることが好ましく、特に、水素原子又はハロゲン原子であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 R116 , R117 , R118 , R119 , R120, R121 , R122, R123, R124 , R125 , R126 , R127 , R128 , R129 , R130 , R131 , R132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. or an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記光酸発生剤の含有量は、単独又は複数種の合計で、上記カチオン重合性成分１００質量部に対して、０．１質量部以上１０質量部以下が好ましく、０．５質量部以上８質量部以下がより好ましく、特に、１質量部以上７質量部以下が好ましく、中でも特に、１質量部以上４．５質量部以下が好ましい。含有量をこのような範囲とすることで、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the photoacid generator, either alone or in the total of multiple types, is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. It is more preferably 1 part by mass or more and 7 parts by mass or less, particularly preferably 1 part by mass or more and 4.5 parts by mass or less. This is because by setting the content within such a range, the composition can form a cured product with better heat and humidity resistance and weather resistance.
　上記光酸発生剤の含有量は、単独又は複数種の合計で、上記組成物の固形分１００質量部中に、０．１質量部以上１０質量部以下が好ましく、０．５質量部以上７質量部以下がより好ましく、特に、１質量部以上５質量部以下が好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　なお、光酸発生剤の市販品は、溶剤に分散又は溶解された状態で販売されることがあるが、本開示における光酸発生剤の含有量は、溶剤を除いた固形分としての含有量を表すものである。 The content of the photoacid generator, either alone or in total, is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 7 parts by mass, based on 100 parts by mass of the solid content of the composition. It is more preferably at most 1 part by mass and at most 5 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Note that commercially available photoacid generators are sometimes sold in a state dispersed or dissolved in a solvent, but the content of the photoacid generator in this disclosure refers to the content as a solid content excluding the solvent. It represents.
Ａ５．その他の成分
　本開示の組成物は、カチオン重合性成分及び酸化防止剤を含み、さらに必要に応じて、光酸発生剤、黒色色材を含むものであるが、本発明の効果を損なわない限り、必要に応じてその他の成分を含むことができる。
　その他の成分としては、増感剤、溶剤、レベリング剤、充填剤、シランカップリング剤、消泡剤、増粘剤、チクソ剤、界面活性剤、分散剤、難燃剤、可塑剤、安定剤、重合禁止剤、紫外線吸収剤、静電防止剤、流動調整剤及び接着促進剤等の各種添加物等が挙げられる。
　本開示の組成物は、添加剤として、増感剤、レベリング剤を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 A5. Other Components The composition of the present disclosure contains a cationic polymerizable component and an antioxidant, and further contains a photoacid generator and a black coloring material as necessary, but as long as the effects of the present invention are not impaired. Other ingredients may be included depending on the requirements.
Other ingredients include sensitizers, solvents, leveling agents, fillers, silane coupling agents, antifoaming agents, thickeners, thixotropic agents, surfactants, dispersants, flame retardants, plasticizers, stabilizers, Examples include various additives such as polymerization inhibitors, ultraviolet absorbers, antistatic agents, fluidity regulators, and adhesion promoters.
The composition of the present disclosure preferably contains a sensitizer and a leveling agent as additives. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（１）増感剤
　上記組成物は、組成物の感度及び硬化性を向上させるために、上述のカチオン重合性成分及び酸化防止剤とともに、増感剤を含むことが好ましい。
　本開示においては、上記増感剤が、カルバゾール骨格を有する化合物からなるカルバゾール系増感剤を好ましく用いることができる。上記組成物は、硬化が容易になるからである。また、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (1) Sensitizer The above composition preferably contains a sensitizer together with the above-mentioned cationically polymerizable component and antioxidant in order to improve the sensitivity and curability of the composition.
In the present disclosure, a carbazole-based sensitizer made of a compound having a carbazole skeleton can be preferably used as the sensitizer. This is because the above composition can be easily cured. Further, the above composition can form a cured product having better heat and humidity resistance and weather resistance.
　このようなカルバゾール系増感剤としては、例えば、下記式（５－１）、（５－２）、（５－３）及び（５－４）から選択される化学式で表される化合物等が挙げられる。 Examples of such carbazole-based sensitizers include compounds represented by chemical formulas selected from the following formulas (5-1), (5-2), (5-3), and (5-4). Can be mentioned.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記式（５－１）中、Ｒ２０１は水素原子、炭素原子数１～３０のアルキル基、ビニル基又は炭素原子数６～３０のアリール基を表し、
　Ｒ２０２、Ｒ２０３、Ｒ２０４、Ｒ２０５、Ｒ２０６、Ｒ２０７、Ｒ２０８及びＲ２０９は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～３０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数１～３０のアルコキシ基、シアノ基、水酸基又はカルボキシル基を表す。 In the above formula (5-1), R 201 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms,
R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, or a group having 6 to 30 carbon atoms; 30 aryl group, an alkoxy group having 1 to 30 carbon atoms, a cyano group, a hydroxyl group, or a carboxyl group.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記式（５－２）中、Ｒ２１１は水素原子、炭素原子数１～３０のアルキル基、ビニル基又は炭素原子数６～３０のアリール基を表し、
　Ｒ２１２、Ｒ２１３、Ｒ２１４、Ｒ２１５、Ｒ２１６、Ｒ２１７、Ｒ２１８、Ｒ２１９、Ｒ２２０及びＲ２２１は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～３０のアルキル基、炭素原子数６～３０のアリール基、シアノ基、水酸基又はカルボキシル基を表す。 In the above formula (5-2), R 211 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms,
R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms. , represents an aryl group, cyano group, hydroxyl group or carboxyl group having 6 to 30 carbon atoms.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記式（５－３）中、Ｒ２３１は水素原子、炭素原子数１～３０のアルキル基、ビニル基又は炭素原子数６～３０のアリール基を表し、
　Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３５、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４０及びＲ２４１は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～３０のアルキル基、炭素原子数６～３０のアリール基、シアノ基、水酸基又はカルボキシル基を表す。 In the above formula (5-3), R 231 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms,
R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms. , represents an aryl group, cyano group, hydroxyl group or carboxyl group having 6 to 30 carbon atoms.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　上記式（５－４）中、Ｒ２５１は水素原子、炭素原子数１～３０のアルキル基、ビニル基又は炭素原子数６～３０のアリール基を表し、
　Ｒ２５２、Ｒ２５３、Ｒ２５４、Ｒ２５５、Ｒ２５６、Ｒ２５７、Ｒ２５８、Ｒ２５９、Ｒ２６０及びＲ２６１は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～３０のアルキル基、炭素原子数６～３０のアリール基、シアノ基、水酸基又はカルボキシル基を表す。 In the above formula (5-4), R 251 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms,
R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms. , represents an aryl group, cyano group, hydroxyl group or carboxyl group having 6 to 30 carbon atoms.
　上記式（５－１）中のＲ２０１、Ｒ２０２、Ｒ２０３、Ｒ２０４、Ｒ２０５、Ｒ２０６、Ｒ２０７、Ｒ２０８及びＲ２０９で表される炭素原子数１～３０のアルキル基としては、例えば、上記「１．カチオン重合性成分」の項に記載した、式（１－１）中の「炭素原子数１～２０のアルキル基」として例示したものに加えて、ｎ－トリコシル基及びｎ－テトラコシル基等が挙げられる。 As the alkyl group having 1 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1), For example, in addition to those exemplified as the "alkyl group having 1 to 20 carbon atoms" in formula (1-1) described in the section "1. Cationically polymerizable component" above, n-tricosyl groups and Examples include n-tetracosyl group.
　上記式（５－１）中のＲ２０１、Ｒ２０２、Ｒ２０３、Ｒ２０４、Ｒ２０５、Ｒ２０６、Ｒ２０７、Ｒ２０８及びＲ２０９で表される炭素原子数６～３０のアリール基としては、例えば、フェニル基、トリル基、３，４，５－トリメトキシフェニル基、４－ｔｅｒｔ－ブチルフェニル基、ビフェニル基、ナフチル基、メチルナフチル基、アントラセニル基及びフェナントリル基等を挙げることができる。 The aryl group having 6 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1) is Examples include phenyl group, tolyl group, 3,4,5-trimethoxyphenyl group, 4-tert-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, and phenanthryl group.
　上記式（５－１）中のＲ２０１、Ｒ２０２、Ｒ２０３、Ｒ２０４、Ｒ２０５、Ｒ２０６、Ｒ２０７、Ｒ２０８及びＲ２０９で表される炭素原子数１～３０のアルコキシ基としては、例えば、上記「１．カチオン重合性成分」の項に記載した、式（１－１）中の「炭素原子数１～２０のアルコキシ基」として例示したものに加えて、ｎ－トリコシルオキシ基及びｎ－テトラコシルオキシ基等が挙げられる。 As the alkoxy group having 1 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1), For example, in addition to those exemplified as the "alkoxy group having 1 to 20 carbon atoms" in formula (1-1) described in the section "1. Cationically polymerizable component" above, n-tricosyloxy and n-tetracosyloxy group.
　上記式（５－２）中のＲ２１１、Ｒ２１２、Ｒ２１３、Ｒ２１４、Ｒ２１５、Ｒ２１６、Ｒ２１７、Ｒ２１８、Ｒ２１９、Ｒ２２０及びＲ２２１で表される炭素原子数１～３０のアルキル基は、式（５－１）中のＲ２０１で表される炭素原子数１～３０のアルキル基と同じである。 The number of carbon atoms represented by R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 in the above formula (5-2) is 1 to The alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
　上記式（５－２）中のＲ２１１、Ｒ２１２、Ｒ２１３、Ｒ２１４、Ｒ２１５、Ｒ２１６、Ｒ２１７、Ｒ２１８、Ｒ２１９、Ｒ２２０及びＲ２２１で表される炭素原子数６～３０のアリール基は、式（５－１）中のＲ２０１で表される炭素原子数６～３０のアリール基と同じである。 The number of carbon atoms represented by R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 in the above formula (5-2) is 6 or more The aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
　上記式（５－３）中のＲ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３５、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４０及びＲ２４１で表される炭素原子数１～３０のアルキル基は、式（５－１）中のＲ２０１で表される炭素原子数１～３０のアルキル基と同じである。 The number of carbon atoms represented by R 231 , R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 in the above formula (5-3) is 1 to The alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
　上記式（５－３）中のＲ２３１、Ｒ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３５、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４０及びＲ２４１で表される炭素原子数６～３０のアリール基は、式（５－１）中のＲ２０１で表される炭素原子数６～３０のアリール基と同じである。 The number of carbon atoms represented by R 231 , R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 in the above formula (5-3) is 6 or more The aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
　上記式（５－４）中のＲ２５１、Ｒ２５２、Ｒ２５３、Ｒ２５４、Ｒ２５５、Ｒ２５６、Ｒ２５７、Ｒ２５８、Ｒ２５９、Ｒ２６０及びＲ２６１で表される炭素原子数１～３０のアルキル基は、式（５－１）中のＲ２０１で表される炭素原子数１～３０のアルキル基と同じである。 The number of carbon atoms represented by R 251 , R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 in the above formula (5-4) is 1 to The alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
　上記式（５－４）中のＲ２５１、Ｒ２５２、Ｒ２５３、Ｒ２５４、Ｒ２５５、Ｒ２５６、Ｒ２５７、Ｒ２５８、Ｒ２５９、Ｒ２６０及びＲ２６１で表される炭素原子数６～３０のアリール基は、式（５－１）中のＲ２０１で表される炭素原子数６～３０のアリール基と同じである。 The number of carbon atoms represented by R 251 , R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 in the above formula (5-4) is 6 or more The aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
　上記式（５－１）中のＲ２０１は、水素原子又は炭素原子数１～１０のアルキル基であることが好ましく、水素原子又は炭素原子数１～５のアルキル基であることがより好ましく、特に、炭素原子数１～５のアルキル基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 R 201 in the above formula (5-1) is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, In particular, an alkyl group having 1 to 5 carbon atoms is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記式（５－２）中のＲ２１１、上記式（５－３）中のＲ２３１及び上記式（５－４）中のＲ２５１は、炭素原子数１～３０のアルキル基であることが好ましく、炭素原子数３～１５のアルキル基であることがより好ましく、特に、炭素原子数５～１２のアルキル基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 R 211 in the above formula (5-2), R 231 in the above formula (5-3), and R 251 in the above formula (5-4) may be an alkyl group having 1 to 30 carbon atoms. It is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 5 to 12 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記式（５－１）中のＲ２０２、Ｒ２０３、Ｒ２０４及びＲ２０５の少なくとも１つと、Ｒ２０６、Ｒ２０７、Ｒ２０８及びＲ２０９の少なくとも１つが、それぞれ独立に、炭素原子数１～３０のアルコキシ基であることが好ましく、なかでも、Ｒ２０３及びＲ２０８が、それぞれ独立に、炭素原子数１～３０のアルコキシ基であることが好ましく、炭素原子数１～１０のアルコキシ基であることがより好ましく、炭素原子数１～５のアルコキシ基であることがさらに好ましく、特に、炭素原子数１～３のアルコキシ基であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　また、Ｒ２０３及びＲ２０８がアルコキシ基である場合、Ｒ２０２、Ｒ２０４、Ｒ２０５、Ｒ２０６、Ｒ２０７及びＲ２０９が水素原子であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the above formula (5-1), at least one of R 202 , R 203 , R 204 and R 205 and at least one of R 206 , R 207 , R 208 and R 209 each independently have a carbon atom number of 1 to It is preferable that R 203 and R 208 are each independently an alkoxy group having 1 to 30 carbon atoms, and is preferably an alkoxy group having 1 to 10 carbon atoms. More preferably, it is an alkoxy group having 1 to 5 carbon atoms, and particularly preferably an alkoxy group having 1 to 3 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Furthermore, when R 203 and R 208 are alkoxy groups, R 202 , R 204 , R 205 , R 206 , R 207 and R 209 are preferably hydrogen atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記式（５－２）中のＲ２１２、Ｒ２１３、Ｒ２１４、Ｒ２１５、Ｒ２１６、Ｒ２１７、Ｒ２１８、Ｒ２１９、Ｒ２２０及びＲ２２１、上記式（５－３）中のＲ２３２、Ｒ２３３、Ｒ２３４、Ｒ２３５、Ｒ２３６、Ｒ２３７、Ｒ２３８、Ｒ２３９、Ｒ２４０及びＲ２４１、並びに上記式（５－４）中のＲ２５２、Ｒ２５３、Ｒ２５４、Ｒ２５５、Ｒ２５６、Ｒ２５７、Ｒ２５８、Ｒ２５９、Ｒ２６０及びＲ２６１は、水素原子又は炭素原子数１～３０のアルキル基であることが好ましく、特に、水素原子であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 in the above formula (5-2), R 232 in the above formula (5-3) , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 , and R 252 , R 253 , R 254 , R 255 in the above formula (5-4), R 256 , R 257 , R 258 , R 259 , R 260 and R 261 are preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and particularly preferably a hydrogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示においては、上記式（５－１）で表される化合物又は上記式（５－２）で表される化合物を含むことが好ましく、特に、上記式（５－２）で表される化合物を含むことが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 In the present disclosure, it is preferable to include a compound represented by the above formula (5-1) or a compound represented by the above formula (5-2), and particularly a compound represented by the above formula (5-2). It is preferable to include. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示の組成物が上記増感剤を含む場合、上記増感剤の含有量は、上記組成物の固形分１００質量部中に、０．１質量部以上５質量部以下が好ましく、０．２質量部以上３質量部以下がより好ましく、特に、０．５質量部以上２質量部以下が好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure includes the sensitizer, the content of the sensitizer is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the solid content of the composition. More preferably 2 parts by mass or more and 3 parts by mass or less, particularly preferably 0.5 parts by mass or more and 2 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　本開示の組成物が上記増感剤を含む場合、上記増感剤の含有量は、上記光酸発生剤１００質量部に対して、１質量部以上７０質量部以下が好ましく、５質量部以上５０質量部以下がより好ましく、特に、１０質量部以上４０質量部以下が好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 When the composition of the present disclosure contains the sensitizer, the content of the sensitizer is preferably 1 part by mass or more and 70 parts by mass or less, and 5 parts by mass or more, based on 100 parts by mass of the photoacid generator. It is more preferably 50 parts by mass or less, particularly preferably 10 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（２）溶剤
　本開示の組成物は、必要に応じて溶剤を含むことができる。
　上記溶剤は、常温（２５℃）大気圧下で液状であり、組成物中の各成分を分散又は溶解可能なものであり、上記カチオン重合性成分と反応しないものである。
　したがって、常温（２５℃）大気圧下で液状であっても、上記「Ａ１．カチオン重合性成分」の項に記載したカチオン重合性化合物は、上記溶剤には含まれない。
　また、上記溶剤は、上記組成物の各成分を分散又は溶解するために用いられるものであるため、上記「Ａ２．酸化防止剤」に記載の酸化防止剤、「Ａ３．黒色色材」に記載の黒色色材、「Ａ４．光酸発生剤」に記載の光酸発生剤、「Ａ５．その他の成分」に記載の増感剤等は、常温大気圧下で液状であっても、上記溶剤には含まれない。 (2) Solvent The composition of the present disclosure can contain a solvent as necessary.
The above-mentioned solvent is liquid at room temperature (25° C.) under atmospheric pressure, is capable of dispersing or dissolving each component in the composition, and does not react with the above-mentioned cationically polymerizable component.
Therefore, even if it is liquid at room temperature (25° C.) and atmospheric pressure, the cationically polymerizable compound described in the above “A1. Cationically polymerizable component” is not included in the above solvent.
In addition, since the above-mentioned solvent is used to disperse or dissolve each component of the above-mentioned composition, the antioxidant described in "A2. Antioxidant" and the antioxidant described in "A3. Black coloring material" above are used. The black coloring material, the photoacid generator described in "A4. Photoacid generator", the sensitizer described in "A5. Other components", etc., even if they are liquid at room temperature and atmospheric pressure, cannot be used with the above solvent. is not included.
　このような溶剤としては、水、有機溶剤のいずれも用いることができるが、有機溶剤を好ましく用いることができる。 As such a solvent, either water or an organic solvent can be used, and an organic solvent can be preferably used.
　上記有機溶剤としては、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剤；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剤；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剤；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剤；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剤；ベンゼン、トルエン、キシレン等の芳香族系溶剤；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剤；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剤；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剤；クロロベンゼン等のハロゲン化芳香族炭化水素系溶剤；カルビトール系溶剤、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、これらの溶剤は１種又は２種以上の混合溶剤として使用することができる。これらの中でも、ケトン類、エーテルエステル系溶剤等、特に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、シクロヘキサノン等が挙げられ、これらの溶剤は１種又は２種以上の混合溶剤として使用することができる。
　上記有機溶剤の中でも、ケトン類、アルコール系溶剤、エーテルエステル系溶剤、芳香族系溶剤等であることが好ましく、なかでも、エーテルエステル系溶剤、アルコール系溶剤であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 Examples of the organic solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, , 2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc. Ester solvents; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethylpropionate, 1-t-butoxy Ether ester solvents such as -2-propanol, 3-methoxybutyl acetate, and cyclohexanol acetate; Aromatic solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Turpentine Terpene hydrocarbon oils such as oil, D-limonene, and pinene; Paraffinic solvents such as mineral spirit, Swasol #310 (Cosmo Matsuyama Oil Co., Ltd.) and Solvesso #100 (Exxon Chemical Co., Ltd.); Carbon tetrachloride; Halogenated aliphatic hydrocarbon solvents such as chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, Examples include carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water, etc., and these solvents can be used alone or as a mixed solvent of two or more. can. Among these, ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. can be mentioned, and these solvents can be used as a single type or a mixed solvent of two or more types. can.
Among the above organic solvents, ketones, alcohol solvents, ether ester solvents, aromatic solvents, etc. are preferred, and ether ester solvents and alcohol solvents are particularly preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
　上記溶剤の含有量は、上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成できるものであればよい。
　本開示の組成物が上記溶剤を含む場合、上記溶剤の含有量が上記組成物１００質量部中に、５０質量部以下であることは乾燥容易性に優れたものとなる点及び上記組成物の硬化膜の形成先の選択の自由度が広くなる点で好ましく、なかでも、３０質量部以下であることが好ましく、特に、１０質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 The content of the above-mentioned solvent may be such that the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
When the composition of the present disclosure contains the above-mentioned solvent, the content of the above-mentioned solvent in 100 parts by mass of the above-mentioned composition is 50 parts by mass or less, which provides excellent drying properties and the above-mentioned composition. It is preferable in that the degree of freedom in selecting the destination for forming the cured film is widened, and it is particularly preferable that the amount is 30 parts by mass or less, and particularly preferably 10 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
（３）その他
　本開示の組成物において、その他の成分として充填剤を含むことができる。上記充填剤としては、例えば、フュームドシリカ、微粒子シリカ、けい石、珪藻土類、クレー、カオリン、珪藻土、シリカゲル、珪酸カルシウム、セリサイト、カオリナイト、フリント、長石粉、蛭石、アタパルジャイト、タルク、マイカ、ミネソタイト、パイロフィライト、シリカ、ガラス繊維、炭酸カルシウム等が挙げられる。
　充填剤の含有量は、本開示の組成物を使用する用途に応じて、適宜設定することができる。 (3) Others The composition of the present disclosure may contain a filler as another component. Examples of the filler include fumed silica, particulate silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, Examples include mica, minnesotaite, pyrophyllite, silica, glass fiber, and calcium carbonate.
The content of the filler can be appropriately set depending on the use of the composition of the present disclosure.
（４）その他の成分の含有量
　本開示の組成物において、カチオン重合性成分、酸化防止剤、黒色色材、光酸発生剤、増感剤以外の成分（但し、溶剤及び充填剤を除く）は、例えば本開示の組成物の固形分１００質量部中５質量部以下であることが好ましく、なかでも、１質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。
　また、本開示の組成物が仮にラジカル重合性成分を含有する場合、その量は、カチオン重合性成分１００質量部に対し２０質量部以下であることが好ましく、なかでも、１０質量部以下であることが好ましく、特に、５質量部以下であることが好ましい。上記組成物は、耐湿熱性及び耐候性がより優れる硬化物を形成することができるからである。 (4) Content of other components In the composition of the present disclosure, components other than the cationic polymerizable component, antioxidant, black coloring material, photoacid generator, and sensitizer (excluding solvents and fillers) is preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less, based on 100 parts by mass of the solid content of the composition of the present disclosure. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Further, if the composition of the present disclosure contains a radically polymerizable component, the amount thereof is preferably 20 parts by mass or less, particularly 10 parts by mass or less, per 100 parts by mass of the cationically polymerizable component. The amount is preferably 5 parts by mass or less, particularly preferably 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
Ａ６．組成物
　上記組成物の製造方法としては、上記各成分を所望量含む組成物を形成可能な方法であれば問題はなく、公知の混合手段を用いる方法を挙げることができる。例えば、本発明の組成物は、ホモディスパー、ホモミキー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、各成分を混合することで製造することができる。 A6. Composition There is no problem in producing the above composition as long as it is possible to form a composition containing the desired amounts of each of the above components, and examples include methods using known mixing means. For example, the composition of the present invention can be produced by mixing each component using a mixer such as a homodisper, a homomixie, a universal mixer, a planetary mixer, a kneader, or a three-roll mixer.
　上記組成物の用途は、耐湿熱性及び耐候性に優れる硬化物が要求されることが好ましく、例えば、遮光フィルタを含む光学フィルタ、塗料、コーティング剤、ライニング剤、接着剤、印刷版、絶縁ワニス、絶縁シート、積層板、プリント基板、半導体装置用・ＬＥＤパッケージ用・液晶注入口用・有機エレクトロルミネッセンス（ＥＬ）用・光素子用・電気絶縁用・電子部品用・分離膜用等の封止剤、成形材料、パテ、ガラス繊維含浸剤、目止め剤、半導体用・太陽電池用等のパッシベーション膜、層間絶縁膜、保護膜、プリント基板、又はカラーテレビ、ＰＣモニタ、携帯情報端末、ＣＣＤイメージセンサのカラーフィルタ、プラズマ表示パネル用の電極材料、印刷インク、歯科用組成物、光造形用樹脂、液状及び乾燥膜の双方、微小機械部品、ガラス繊維ケーブルコーティング、ホログラフィ記録用材料の各種の用途を挙げることができる。 The use of the above composition preferably requires a cured product with excellent heat and humidity resistance and weather resistance, such as optical filters including light blocking filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, etc. Sealants for insulation sheets, laminates, printed circuit boards, semiconductor devices, LED packages, liquid crystal injection ports, organic electroluminescence (EL), optical devices, electrical insulation, electronic components, separation films, etc. , molding materials, putty, glass fiber impregnating agents, fillers, passivation films for semiconductors, solar cells, etc., interlayer insulation films, protective films, printed circuit boards, color televisions, PC monitors, mobile information terminals, CCD image sensors. color filters, electrode materials for plasma display panels, printing inks, dental compositions, stereolithography resins, both liquid and dry films, micromechanical components, glass fiber cable coatings, and holographic recording materials. can be mentioned.
　本開示の硬化物は、上述の組成物を硬化させて得られるものである。
　本開示においては、なかでも、上記組成物の用途が、光学フィルタであることが好ましく、なかでも、可視光全体の透過率を低下させる遮光フィルタ（ＮＤフィルタ）であることが好ましく、特に、画像表示装置に用いられるブラックマトリクス等の遮光膜；画像表示装置の色調整フィルタ；反射防止性向上のための遮光フィルタ等であることが好ましい。上記硬化物は、薄膜で優れた遮光性を発揮でき、薄膜化の要求の高い上述の用途に特に有用だからである。 The cured product of the present disclosure is obtained by curing the above-mentioned composition.
In the present disclosure, it is particularly preferable that the composition is used as an optical filter, particularly as a light-blocking filter (ND filter) that reduces the transmittance of visible light as a whole, and in particular, as an image filter. It is preferable to use a light-shielding film such as a black matrix used in a display device; a color adjustment filter for an image display device; a light-shielding filter for improving antireflection properties, etc. This is because the cured product can exhibit excellent light-shielding properties in the form of a thin film, and is particularly useful in the above-mentioned applications where thin films are highly demanded.
　また、本開示においては、上記組成物の用途が、プリント基板に用いられるソルダーレジスト等にも好ましく用いることができる。配線の保護性に優れたものとなるからである。
　上記硬化物の用途は、同時に２つの目的を達成するものであってもよい。例えば、厚みの厚い部分をブラックマトリクス等として用い、厚みの薄い部分を色調整フィルタとして用いてもよい。
　なお、遮光フィルタにおいて、可視光全体の透過率を低下させるとは、例えば、上記組成物の硬化物膜を、５００ｎｍでの透過率が４５％となるように形成した際に、４００ｎｍでの透過率及び６００ｎｍでの透過率が４０％～５０％の範囲内となるものとすることができる。本開示においては、なかでも、７００ｎｍにおける透過率も４０％～５０％の範囲内となることが好ましい。 Further, in the present disclosure, the composition described above can be preferably used for solder resists used in printed circuit boards. This is because it provides excellent protection for the wiring.
The cured product may be used to achieve two purposes at the same time. For example, the thicker portion may be used as a black matrix, and the thinner portion may be used as a color adjustment filter.
In addition, in a light-blocking filter, reducing the transmittance of the entire visible light means, for example, when a cured film of the above composition is formed so that the transmittance at 500 nm is 45%, the transmittance at 400 nm is reduced. The transmittance and transmittance at 600 nm may be in the range of 40% to 50%. In the present disclosure, the transmittance at 700 nm is also preferably within the range of 40% to 50%.
　ここで、色調整フィルタは、各色の光を調整するものを挙げることができる。色調整フィルタとしては、より具体的には、光学フィルタとして用いられる、Ｒ（赤）、Ｇ（緑）、Ｂ（青）及びその他の色の画素が配置されたカラーフィルタを透過した光の色をさらに調整するために、カラーフィルタと平面視上重なるように配置されるもの、各色のエレクトロルミネッセンス素子等の各色の発光体から照射された光の色をさらに調整するために、各色の発光体と平面視上重なるように配置されるもの等が挙げられる。 Here, the color adjustment filter can be one that adjusts each color of light. More specifically, the color adjustment filter is the color of light transmitted through a color filter used as an optical filter, in which pixels of R (red), G (green), B (blue) and other colors are arranged. In order to further adjust the color of the light emitted from the light emitters of each color, such as the electroluminescent elements of each color, the light emitters of each color are arranged so as to overlap with the color filter in plan view. Examples include those arranged so as to overlap in plan view.
　上記組成物の硬化物が形成される被着体の材料としては、特に制限されず、通常用いられるものを使用することができ、例えば、アルミニウム、チタン、ステンレス、軟鋼、めっき鋼等の金属基材、ガラス等の無機材料；ジアセチルセルロース、トリアセチルセルロース（ＴＡＣ）、プロピオニルセルロース、ブチリルセルロース、アセチルプロピオニルセルロース、ニトロセルロース等のセルロースエステル；ポリアミド；ポリイミド；ポリウレタン；エポキシ樹脂；ポリカーボネート；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリ－１，４－シクロヘキサンジメチレンテレフタレート、ポリエチレン－１，２－ジフェノキシエタン－４，４’－ジカルボキシレート、ポリブチレンテレフタレート等のポリエステル；ポリスチレン；ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン；ポリ酢酸ビニル、ポリ塩化ビニル、ポリフッ化ビニル等のビニル化合物；ポリメチルメタクリレート、ポリアクリレート等のアクリル系樹脂；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルケトン；ポリエーテルイミド；ポリオキシエチレン、ノルボルネン樹脂、シクロオレフィンポリマー（ＣＯＰ）等の高分子材料が挙げられる。
　また、上記組成物の硬化物が形成される被着体としては、例えば、上記組成物の硬化物が色調整フィルタ等に用いられる場合には、カラーフィルタの画素の上面等であってもよい。 The material of the adherend on which the cured product of the above composition is formed is not particularly limited, and commonly used materials can be used, such as metal bases such as aluminum, titanium, stainless steel, mild steel, and plated steel. Inorganic materials such as wood, glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate; Polyesters such as polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene , polyolefins such as polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyether Imide: Examples include polymeric materials such as polyoxyethylene, norbornene resin, and cycloolefin polymer (COP).
Further, the adherend on which the cured product of the composition is formed may be, for example, the upper surface of a pixel of a color filter when the cured product of the composition is used for a color adjustment filter or the like. .
Ｂ．硬化物
　次に、本開示の硬化物について説明する。
　本開示の硬化物は、上述の組成物の硬化物であることを特徴とするものである。
　上記硬化物は、上述の組成物を硬化させたものであることで、耐熱湿性及び耐候性が優れたものになる。上記硬化物は、高湿高温環境下での長寿命化が得られるものとなる。
　以下、本開示の硬化物について詳細に説明する。
　なお、上述の組成物については、上記「Ａ．組成物」の項に記載の内容と同様である。 B. Cured Product Next, the cured product of the present disclosure will be described.
The cured product of the present disclosure is characterized by being a cured product of the above-mentioned composition.
Since the cured product is obtained by curing the composition described above, it has excellent heat-humidity resistance and weather resistance. The cured product has a long service life in a high-humidity, high-temperature environment.
Hereinafter, the cured product of the present disclosure will be explained in detail.
Note that the above-mentioned composition is the same as described in the section "A. Composition" above.
　上記硬化物は、通常、カチオン重合性成分の重合物を含むものである。 The above-mentioned cured product usually contains a polymer of a cationically polymerizable component.
　上記硬化物の平面視形状、厚み等については、上記硬化物の用途等に応じて適宜設定することができる。
　上記厚みとしては、例えば、０．０５μｍ以上３００μｍ以下等とすることができる。 The planar shape, thickness, etc. of the cured product can be appropriately set depending on the intended use of the cured product.
The thickness may be, for example, 0.05 μm or more and 300 μm or less.
　上記硬化物の全光線透過率、Ｈａｚｅ値としては、上記硬化物の用途等に応じて適宜設定されるものであり、厚み、黒色色材の濃度等によって調整されるものである。 The total light transmittance and Haze value of the cured product are appropriately set depending on the use of the cured product, and are adjusted depending on the thickness, concentration of the black coloring material, etc.
　上記硬化物の製造方法としては、上記組成物の硬化物を所望の形状となるように形成できる方法であれば特に限定されるものではない。例えば、上述の組成物を硬化する工程が挙げられる。 The method for producing the cured product is not particularly limited as long as it can form the cured product of the composition into a desired shape. For example, the step of curing the composition described above may be mentioned.
（１）硬化する工程
　上記硬化する工程は、上述の組成物を硬化する工程である。
　上記組成物の硬化方法としては、上記カチオン重合性成分同士を重合可能な方法であればよく、組成物の塗膜に対して光（エネルギー線）を照射する方法等が挙げられる。上記カチオン重合性成分の重合が容易だからである。 (1) Step of Curing The step of curing is a step of curing the above-mentioned composition.
The method for curing the composition may be any method as long as the cationically polymerizable components can be polymerized with each other, such as a method of irradiating the coating film of the composition with light (energy rays). This is because the cationically polymerizable component can be easily polymerized.
　本工程において、カチオン重合性成分の重合に用いられるエネルギー線の光源としては、超高圧水銀ランプ、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、水銀蒸気アーク灯、キセノンアーク灯、カーボンアーク灯、メタルハライドランプ、蛍光灯、タングステンランプ、エキシマーランプ、殺菌灯、発光ダイオード、ＣＲＴ光源等から得られる２０００オングストローム～７０００オングストロームの波長を有する電磁波エネルギーや電子線、Ｘ線、放射線等の高エネルギー線を利用することができる。好ましくは、波長３００～４５０ｎｍの光を発光する超高圧水銀ランプ、水銀蒸気アーク灯、カーボンアーク灯、キセノンアーク灯、発光ダイオード等が用いられる。カチオン重合性成分の重合が容易だからである。 In this process, the light sources of energy rays used for polymerizing the cationically polymerizable component include ultra-high pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, and carbon arc lamps. , electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., and high-energy rays such as electron beams, X-rays, and radiation. can be used. Preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a light emitting diode, etc. that emit light with a wavelength of 300 to 450 nm is used. This is because the cationically polymerizable component can be easily polymerized.
　エネルギー線の照射量に特に制限はなく、組成物の組成によって適宜決定することができる。上記照射量は、組成物中の成分の劣化防止の観点から、照射量は３６５ｎｍにおいて、１００ｍＪ／ｃｍ２～２０００ｍＪ／ｃｍ２の範囲であることが好ましい。 There is no particular restriction on the amount of energy ray irradiation, and it can be appropriately determined depending on the composition of the composition. The above-mentioned irradiation amount is preferably in the range of 100 mJ/cm 2 to 2000 mJ/cm 2 at 365 nm from the viewpoint of preventing deterioration of the components in the composition.
　本工程において、上記硬化方法が、エネルギー線を照射する方法及び加熱する方法を併用する方法であることが好ましく、より具体的には、エネルギー線を照射する方法及び加熱する方法をこの順で行うことが好ましい。カチオン重合性成分の重合を効率的に進めることができるからである。 In this step, it is preferable that the curing method is a method that uses a method of irradiating energy rays and a method of heating in combination, and more specifically, a method of irradiating energy rays and a method of heating are performed in this order. It is preferable. This is because the polymerization of the cationically polymerizable component can proceed efficiently.
　本工程における組成物の塗膜を加熱する方法としては、ホットプレート等の熱板や、大気オーブン、イナートガスオーブン、真空オーブン、熱風循環式オーブン等を用いる方法が挙げられる。
　塗膜を加熱する際の加熱温度としては、特に限定されないが、カチオン重合性成分の重合容易の観点から、７０℃以上２００℃以下であることが好ましく、なかでも、９０℃以上１５０℃以下であることが好ましい。
　塗膜を加熱する際の加熱時間としては、特に限定されないが、生産性向上の点から、１分～６０分の範囲であることが好ましく、なかでも、１分～３０分の範囲であることが好ましい。 Examples of the method for heating the coating film of the composition in this step include methods using a hot plate such as a hot plate, an atmospheric oven, an inert gas oven, a vacuum oven, a hot air circulation oven, and the like.
The heating temperature when heating the coating film is not particularly limited, but from the viewpoint of facilitating polymerization of the cationic polymerizable component, it is preferably 70°C or more and 200°C or less, and especially 90°C or more and 150°C or less. It is preferable that there be.
The heating time when heating the coating film is not particularly limited, but from the viewpoint of improving productivity, it is preferably in the range of 1 minute to 60 minutes, particularly in the range of 1 minute to 30 minutes. is preferred.
（２）その他の工程
　上記製造方法は、必要に応じてその他の工程を有するものであっても構わない。
　このような工程としては、組成物を硬化する工程の前に、上記組成物を基材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。 (2) Other steps The above manufacturing method may include other steps as necessary.
Such a step may include a step of applying the composition to a substrate before the step of curing the composition.
As a method for applying the composition, known methods such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, and dipping methods can be used.
　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構わない。 The above-mentioned base material can be appropriately selected depending on the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like.
Moreover, after the cured product is formed on a base material, it may be peeled off from the base material and used, or it may be used after being transferred from the base material to another adherend.
　上記硬化物の用途等については、上記「Ａ．組成物」の項に記載の内容と同様である。 The uses of the cured product are the same as those described in the "A. Composition" section above.
　本開示は、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、本開示の特許請求の範囲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開示の技術的範囲に包含される。 The present disclosure is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment that has substantially the same configuration as the technical idea stated in the claims of the present disclosure and provides similar effects is the present invention. within the technical scope of the disclosure.
　以下、本発明の組成物を具体的に示して本発明をさらに詳細に説明するが、本発明はこれらの実施例等に限定されるものではない。 Hereinafter, the present invention will be explained in more detail by specifically showing the composition of the present invention, but the present invention is not limited to these Examples.
［実施例１～２８及び比較例１～５］
　下記表１～５の配合に従って、各成分を配合して組成物を得た。
　また、各成分は以下の材料を用いた。
　なお、表中の配合量は、各成分の質量部を表すものである。光酸発生剤の配合量は、溶剤を含む配合量を表す。 [Examples 1 to 28 and Comparative Examples 1 to 5]
Each component was blended according to the formulations in Tables 1 to 5 below to obtain a composition.
In addition, the following materials were used for each component.
Note that the blending amounts in the table represent parts by mass of each component. The compounding amount of the photoacid generator represents the compounding amount including the solvent.
（カチオン重合性成分：脂環式エポキシ化合物）
Ａ１－１：脂環式エポキシ化合物（２官能、下記式（Ａ１－１）で表される化合物、エポキシ当量８０ｇ／ｅｑ．、ＪＸＴＧエネルギー製　ＴＨＩ－ＤＥ）Ａ１－２：脂環式エポキシ化合物（２官能、下記式（Ａ１－２）で表される化合物、エポキシ当量１２２ｇ／ｅｑ．、ＪＸＴＧエネルギー製　ＤＥ－１０２）
Ａ１－３：脂環式エポキシ化合物（２官能、下記式（Ａ１－３）で表される化合物、エポキシ当量１２８～１４５ｇ／ｅｑ．、ダイセル製　セロキサイド２０２１Ｐ）
Ａ１－４：脂環式エポキシ化合物（２官能、下記式（Ａ１－４）で表される化合物、エポキシ当量１００ｇ／ｅｑ．、ダイセル製　セロキサイド８０００） (Cationic polymerizable component: alicyclic epoxy compound)
A1-1: Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-1), epoxy equivalent 80 g/eq., THI-DE manufactured by JXTG Energy) A1-2: Alicyclic epoxy compound ( Bifunctional, compound represented by the following formula (A1-2), epoxy equivalent: 122 g/eq., manufactured by JXTG Energy DE-102)
A1-3: Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-3), epoxy equivalent 128 to 145 g/eq., Celoxide 2021P manufactured by Daicel)
A1-4: Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-4), epoxy equivalent 100 g/eq., Celoxide 8000 manufactured by Daicel)
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（カチオン重合性成分：脂肪族エポキシ化合物）
Ａ２－１：多官能脂肪族エポキシ化合物（２官能、下記式（Ａ２－１）で表される化合物。
Ａ２－２：単官能脂肪族エポキシ化合物（単官能、下記式（Ａ２－２）で表される化合物。ＲＡ６は、炭素原子数１２～１３のアルキル基） (Cationic polymerizable component: aliphatic epoxy compound)
A2-1: Polyfunctional aliphatic epoxy compound (bifunctional, compound represented by the following formula (A2-1).
A2-2: Monofunctional aliphatic epoxy compound (monofunctional, compound represented by the following formula (A2-2). R A6 is an alkyl group having 12 to 13 carbon atoms)
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（カチオン重合性成分：芳香族エポキシ化合物）
Ａ３－１：アデカレジン（登録商標）ＥＰ－４１００（（株）ＡＤＥＫＡ製、ビスフェノールＡ型エポキシ樹脂（エポキシ当量：１９０ｇ／ｅｑ．）） (Cationic polymerizable component: aromatic epoxy compound)
A3-1: Adeka Resin (registered trademark) EP-4100 (manufactured by ADEKA Co., Ltd., bisphenol A type epoxy resin (epoxy equivalent: 190 g/eq.))
（カチオン重合性成分：オキセタン化合物）
Ａ４－１：アロンオキセタン（登録商標）ＯＸＴ－２２１（東亜合成（株）製、下記式（Ａ４－１）で表される二官能オキセタン化合物）
Ａ４－２：アロンオキセタン（登録商標）ＯＸＴ－２１２（東亜合成（株）製、下記式（Ａ４－２）で表される単官能オキセタン化合物） (Cationic polymerizable component: oxetane compound)
A4-1: Aronoxetane (registered trademark) OXT-221 (manufactured by Toagosei Co., Ltd., bifunctional oxetane compound represented by the following formula (A4-1))
A4-2: Aronoxetane (registered trademark) OXT-212 (manufactured by Toagosei Co., Ltd., monofunctional oxetane compound represented by the following formula (A4-2))
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（酸化防止剤：硫黄系酸化防止剤）
Ｂ１－１：下記式（Ｂ１－１）で表される化合物（式（２－１）及び式（２－２）で表される化合物、硫黄含有率：５．９１質量％）
Ｂ１－２：下記式（Ｂ１－２）で表される化合物（式（２－１）で表される化合物、硫黄含有率：１１．０４質量％）
Ｂ１－３：下記式（Ｂ１－３）で表される化合物（硫黄含有率：１０．４３質量％） (Antioxidant: sulfur-based antioxidant)
B1-1: Compound represented by the following formula (B1-1) (compound represented by formula (2-1) and formula (2-2), sulfur content: 5.91% by mass)
B1-2: Compound represented by the following formula (B1-2) (compound represented by formula (2-1), sulfur content: 11.04% by mass)
B1-3: Compound represented by the following formula (B1-3) (sulfur content: 10.43% by mass)
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（酸化防止剤：フェノール系酸化防止剤）
Ｂ２－１：アデカスタブ（登録商標）ＡＯ－６０（（株）ＡＤＥＫＡ製、下記式（Ｂ２－１）で表される化合物）式（Ｂ２－１）中の「ｔＢｕ」は、ｔｅｒｔ－ブチル基を表す。 (Antioxidant: phenolic antioxidant)
B2-1: ADEKA STAB (registered trademark) AO-60 (manufactured by ADEKA Co., Ltd., compound represented by the following formula (B2-1)) "tBu" in formula (B2-1) represents a tert-butyl group. represent.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（黒色色材）
Ｃ１－１：ニグロシン系黒色染料（下記式（Ｃ１－１）で表される化合物） (black color material)
C1-1: Nigrosine black dye (compound represented by the following formula (C1-1))
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
（光酸発生剤）
Ｄ１－１：下記式（Ｄ１ａ）で表される化合物及び下記式（Ｄ１ｂ）で表される化合物を質量比で１：１含む５０質量％炭酸プロピレン溶液） (Photoacid generator)
D1-1: 50% by mass propylene carbonate solution containing a compound represented by the following formula (D1a) and a compound represented by the following formula (D1b) in a mass ratio of 1:1)
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（増感剤）
Ｅ１－１：カルバゾール系増感剤（下記式（Ｅ１－１）で表される化合物） (sensitizer)
E1-1: Carbazole sensitizer (compound represented by the following formula (E1-1))
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
（レベリング剤）
Ｆ１－１：メガファック（登録商標）Ｆ－５５４（ＤＩＣ（株）製） (Leveling agent)
F1-1: Megafac (registered trademark) F-554 (manufactured by DIC Corporation)
「評価」
　得られた各組成物につき、耐湿熱性、耐候性を、下記の手順に従って評価した。結果を表１～表５に示す。 "evaluation"
The moisture and heat resistance and weather resistance of each of the obtained compositions were evaluated according to the following procedure. The results are shown in Tables 1 to 5.
１．耐湿熱性
　実施例、比較例の組成物を、１０ｃｍ×１０ｃｍのガラス基板にスピンコートで塗布し、塗膜（以下、「硬化前塗膜」と称する場合がある。）を形成した。
　次いで、ＵＶ－ＬＥＤ光源を用いて３６５ｎｍの光を２，０００ｍＪ／ｃｍ２照射して各組成物を硬化させて硬化膜を形成した。
　なお、硬化前塗膜の厚みは、４μｍになるように調整した。
　得られた硬化膜上に、両面粘着テープ（３Ｍ社製、厚み：２５μｍ、メーカー製品番号：８１４６－１）を貼付し、さらにその上をＰＥＴフィルム（東洋紡（株）製、厚み１００μｍ、ルミラーＴ６０）で被覆して、試験片を作製した。
　得られた試験片を６０℃、９０％ＲＨの恒温恒湿試験機に１，０００時間放置した。試験終了後の試験片について、紫外線可視近赤外分光光度計（Ｖ－６７０、日本分光（株）製）を用いて、５４０ｎｍの透過率を測定し、試験前試験片の５４０ｎｍの透過率と比較して、試験前の透過率をＡ、試験後の透過率をＢとしたとき、（Ｂ－Ａ）（％）を透過率変化とし、下記評価基準で評価した。 1. Moisture and Heat Resistance The compositions of Examples and Comparative Examples were spin-coated onto a 10 cm x 10 cm glass substrate to form a coating film (hereinafter sometimes referred to as "pre-cured coating film").
Next, each composition was cured by irradiating 2,000 mJ/cm 2 of 365 nm light using a UV-LED light source to form a cured film.
The thickness of the coating film before curing was adjusted to 4 μm.
A double-sided adhesive tape (manufactured by 3M, thickness: 25 μm, manufacturer product number: 8146-1) was applied on the obtained cured film, and a PET film (manufactured by Toyobo Co., Ltd., thickness: 100 μm, Lumirror T60) was applied on top of it. ) to prepare a test piece.
The obtained test piece was left in a constant temperature and humidity tester at 60° C. and 90% RH for 1,000 hours. After the test, the transmittance of the test piece at 540 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-670, manufactured by JASCO Corporation), and the transmittance at 540 nm was compared with that of the test piece before the test. For comparison, when the transmittance before the test is A and the transmittance after the test is B, (BA) (%) is the change in transmittance, and the evaluation was made according to the following evaluation criteria.
（評価基準）
＋＋：透過率変化が１．５％未満。
＋　：透過率変化が１．５％以上２．０％未満。
－　：透過率変化が２．０％以上。
　なお、透過率変化が小さいほど、耐湿熱性に優れた膜が得られたと判断できる。 (Evaluation criteria)
++: Change in transmittance is less than 1.5%.
+: Change in transmittance is 1.5% or more and less than 2.0%.
-: Change in transmittance is 2.0% or more.
Note that it can be judged that the smaller the change in transmittance, the more excellent the film was obtained in heat and humidity resistance.
２．耐候性
　上記「１．耐湿熱性」と同様の方法で、試験片を作製した。
　得られた試験片を、(株)ＡＴＬＡＳ製ＳＵＮ　ＴＥＳＴ　ＸＸＬを用い、光源：キセノンランプ、波長：３００～８００ｎｍ、照度：５０Ｗ／ｍ２、温度：６０℃の条件により、２００時間の耐候性試験を行い、「１．耐湿熱性」と同様の方法で試験片の５４０ｎｍの透過率を測定し、試験前試験片の５４０ｎｍの透過率と比較して、試験前の透過率をＡ、試験後の透過率をＢとしたとき、（Ｂ－Ａ）（％）を透過率変化とし、下記評価基準で評価した。 2. Weather Resistance A test piece was prepared in the same manner as in "1. Moisture and Heat Resistance" above.
The obtained test piece was subjected to a weather resistance test for 200 hours using SUN TEST The transmittance at 540 nm of the test piece was measured in the same manner as in "1. Humid heat resistance", and compared with the transmittance at 540 nm of the test piece before the test, the transmittance before the test was A, and the transmittance after the test was A. When the transmittance is B, (B-A) (%) is the change in transmittance, and the evaluation was made according to the following evaluation criteria.
（評価基準）
＋＋：透過率変化が３．０％未満。
＋　：透過率変化が３．０％以上６．０％未満。
－　：透過率変化が６．０％以上。
　なお、透過率変化が小さいほど、耐候性に優れた膜が得られたと判断できる。 (Evaluation criteria)
++: Change in transmittance is less than 3.0%.
+: Change in transmittance is 3.0% or more and less than 6.0%.
-: Change in transmittance is 6.0% or more.
Note that it can be judged that the smaller the change in transmittance, the more excellent the weather resistance was obtained.
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
　表１～表５の結果より、実施例の組成物は、耐湿熱性及び耐候性に優れることが確認できた。 From the results in Tables 1 to 5, it was confirmed that the compositions of Examples had excellent heat and humidity resistance and weather resistance.

Claims (11)

  1. 　カチオン重合性成分及び酸化防止剤を含む組成物であって、
    　前記カチオン重合性成分は、脂環式エポキシ化合物と、
    脂肪族エポキシ化合物、芳香族エポキシ化合物及びオキセタン化合物とから選択される少なくとも１種と、
    を含み、
    　前記酸化防止剤が、硫黄系酸化防止剤を含む組成物。     A composition comprising a cationically polymerizable component and an antioxidant,
    The cationic polymerizable component includes an alicyclic epoxy compound,
    At least one selected from aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds;
    including;
    A composition in which the antioxidant includes a sulfur-based antioxidant.
  2. 　前記脂環式エポキシ化合物が、下記一般式（１－１）、（１－２）、（１－３）、（１－４）及び（１－５）から選択される化学式で表される化合物のうち少なくとも１種を含む請求項１に記載の組成物。
    Figure JPOXMLDOC01-appb-C000001
     　式（１－１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
    　式（１－２）中、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９、Ｒ２０、Ｒ２１、Ｒ２２、Ｒ２３、Ｒ２４、Ｒ２５及びＲ２６は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
    　式（１－３）中、Ｒ３１、Ｒ３２、Ｒ３３、Ｒ３４、Ｒ３５、Ｒ３６、Ｒ３７、Ｒ３８、Ｒ３９、Ｒ４０、Ｒ４１、Ｒ４２、Ｒ４３、Ｒ４４、Ｒ４５、Ｒ４６、Ｒ４７及びＲ４８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
    　式（１－４）中、Ｒ５１、Ｒ５２、Ｒ５３、Ｒ５４、Ｒ５５、Ｒ５６、Ｒ５７、Ｒ５８、Ｒ５９、Ｒ６０、Ｒ６１、Ｒ６２、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表す。
    　式（１－５）中、Ｒ７１、Ｒ７２、Ｒ７３、Ｒ７４、Ｒ７５、Ｒ７６、Ｒ７７、Ｒ７８、Ｒ７９、Ｒ８０、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４、Ｒ８５、Ｒ８６、Ｒ８７及びＲ８８は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～２０のアルキル基又は炭素原子数１～２０のアルコキシ基を表し、
    　Ｘは、単結合又は炭素原子数１～４のアルキレン基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド基若しくはこれらのうちの複数が連結した基を表す。     The alicyclic epoxy compound is a compound represented by a chemical formula selected from the following general formulas (1-1), (1-2), (1-3), (1-4) and (1-5). The composition according to claim 1, comprising at least one of the following.
    Figure JPOXMLDOC01-appb-C000001
     In formula (1-1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a carbon atom, Represents an alkyl group having 1 to 20 atoms or an alkoxy group having 1 to 20 carbon atoms.
    In formula (1-2), 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 and R 26 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
    In formula (1-3), R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
    In formula (1-4), R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
    In formula (1-5), R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms,
    X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which two or more of these are linked.
  3. 　前記脂環式エポキシ化合物の含有量が、前記カチオン重合性成分１００質量部中、０．５質量部以上８０質量部以下である、請求項１又は請求項２に記載の組成物。 The composition according to claim 1 or 2, wherein the content of the alicyclic epoxy compound is 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component.
  4. 　前記脂肪族エポキシ化合物が、多官能脂肪族エポキシ化合物を含む、請求項１～３の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 3, wherein the aliphatic epoxy compound includes a polyfunctional aliphatic epoxy compound.
  5. 　前記脂肪族エポキシ化合物の含有量が、前記カチオン重合性成分１００質量部中、５質量部以上７０質量部以下である請求項１～４の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 4, wherein the content of the aliphatic epoxy compound is 5 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the cationically polymerizable component.
  6. 　前記オキセタン化合物の含有量が、前記カチオン重合性成分１００質量部中、０．５質量部以上、８０質量部以下である請求項１～５の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 5, wherein the content of the oxetane compound is 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component.
  7. 　前記硫黄系酸化防止剤が、下記一般式（２－１）で表される化合物である請求項１～６の何れか一項に記載の組成物。
    Figure JPOXMLDOC01-appb-C000002
     　（式（２－１）中、Ａは、炭素原子又は硫黄原子を表し、
    　Ｘ２は、炭素原子数１～４のアルキレン基、炭素原子数６～１８のフェニレン基、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、カーボネート基、アミド基若しくはこれらのうちの複数が連結した基を表し、
    　ＲＢ１は、炭素原子数６～２０のアルキル基又は、炭素原子数６～２０のアリール基を表し、
    　Ａが硫黄原子の場合、ｍ１は、２を表し、
    　Ａが炭素原子の場合、ｍ１は、４を表し、且つ、Ｘ２は、構造中にチオエーテル結合を含む基を表す。）     The composition according to any one of claims 1 to 6, wherein the sulfur-based antioxidant is a compound represented by the following general formula (2-1).
    Figure JPOXMLDOC01-appb-C000002
     (In formula (2-1), A represents a carbon atom or a sulfur atom,
    X 2 is an alkylene group having 1 to 4 carbon atoms, a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide group, or a group in which multiple of these are linked. represents the group,
    R B1 represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms,
    When A is a sulfur atom, m1 represents 2,
    When A is a carbon atom, m1 represents 4, and X 2 represents a group containing a thioether bond in its structure. )
  8. 　前記硫黄系酸化防止剤の含有量が、酸化防止剤１００質量部中、１０質量部以上１００質量部以下である請求項１～７の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein the content of the sulfur-based antioxidant is 10 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the antioxidant.
  9. 　さらに、黒色色材を含む請求項１～８の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 8, further comprising a black coloring material.
  10. 　さらに、光酸発生剤を含む請求項１～９の何れか一項に記載の組成物。 The composition according to any one of claims 1 to 9, further comprising a photoacid generator.
  11. 　請求項１～１０の何れか一項に記載の組成物の硬化物。 A cured product of the composition according to any one of claims 1 to 10.
PCT/JP2023/009027 2022-03-14 2023-03-09 Composition and cured product WO2023176680A1 (en)

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JPH10279778A (en) * 1997-04-07 1998-10-20 Hitachi Chem Co Ltd Epoxy resin composition for printed circuit board and prepreg and metal-clad laminated board produced by using the composition
JPH11279375A (en) * 1998-03-27 1999-10-12 Hitachi Chem Co Ltd Resin composition for printed wiring board and printed wiring board using the same
JP2005307148A (en) * 2004-03-24 2005-11-04 Hitachi Chem Co Ltd Prepreg and metal foil-adhered lamination plate and printed circuit board using it
JP2006152044A (en) * 2004-11-26 2006-06-15 Toyo Ink Mfg Co Ltd Sealing composition
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