WO2006059564A1 - 脂環式エポキシ(メタ)アクリレート及びその製造方法、並びに共重合体 - Google Patents
脂環式エポキシ(メタ)アクリレート及びその製造方法、並びに共重合体 Download PDFInfo
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- WO2006059564A1 WO2006059564A1 PCT/JP2005/021794 JP2005021794W WO2006059564A1 WO 2006059564 A1 WO2006059564 A1 WO 2006059564A1 JP 2005021794 W JP2005021794 W JP 2005021794W WO 2006059564 A1 WO2006059564 A1 WO 2006059564A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
- C07D303/06—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
- C07D303/17—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals containing oxirane rings condensed with carbocyclic ring systems having three or more relevant rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/31—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/402—Alkyl substituted imides
Definitions
- the present invention relates to an alicyclic epoxy unsaturated carboxylic acid ester such as an alicyclic epoxy (meth) acrylate having an epoxy group in the structure (3, 4 epoxy tricyclo [5. 2. 1. 0 2 [ 6 ] An unsaturated carboxylic acid ester having a decane skeleton) and a method for producing the same.
- the cycloaliphatic epoxy (meth) acrylate and the fats obtained from them are coating agents, inks
- the present invention also relates to a copolymer containing a structural unit having a 3,4 epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane skeleton and a method for producing the same. More specifically, lithography using actinic rays such as deep ultraviolet rays, electron beams, ion beams, and X-rays in semiconductor processes, insulating films provided on electronic components such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, A copolymer containing a structural unit having a 3,4-epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane ring suitable as a radiation-sensitive resin used as a material for forming a protective film or the like And its manufacturing method.
- Aliphatic (meth) acrylate and (meth) acrylates having alicyclic epoxy groups are generally used in coatings, inks, It is a useful compound in fields such as adhesives and sealants, and in particular, polymers and cured products obtained from (meth) acrylates containing an alicyclic structure and an epoxy group have excellent weather resistance and are used outdoors. It has characteristics suitable for use.
- the polymer and the cured product are caused by the ring-opening reactivity of the epoxy group existing in the alicyclic structure or the reactivity of the radical polymerizable double bond in the (meth) acrylate structure. This is to exhibit predetermined performance.
- unsaturated carboxylic acid esters having an epoxy group in the molecule include, for example, terminal epoxy group-containing (meth) such as glycidyl methacrylate and 1-methyl-1,2-epoxyethyl methacrylate.
- terminal epoxy group-containing (meth) such as glycidyl methacrylate and 1-methyl-1,2-epoxyethyl methacrylate.
- Atalylate; 3 Epoxycyclohexylmethyl talylate (Daicel Engineering Co., Ltd .: trade name “Cyclomer A—200”)
- 3 Epoxycyclo (Meth) acrylate having an alicyclic epoxy group such as hexyl methyl metatalylate (manufactured by Daicel Chemical Industries, Ltd .: “Cyclomer M-100”) is known.
- 3,536,687 also discloses a cyclohexene-alkyl alkyl alcohol, an ester compound of an alkyl cyclohexane-alkyl alkyl and an ⁇ , ⁇ unsaturated acid, and the ester compound as a monomer component. Homopolymers and copolymers are disclosed.
- Japanese Patent Application Laid-Open No. 2-18410 describes the production of a coating for an erasable white plate obtained by curing siloxane metatalylate with 3,4 epoxycyclohexylmethyl metatalylate.
- JP-A-57-47365 discloses that a copolymer containing acrylic acid or 3,4-epoxycyclohexylmethyl (meth) acrylate as a structural unit is more effective than a thermosetting powder coating composition. It has been disclosed! RU
- the alicyclic epoxy (meth) acrylate which is represented by the above-mentioned cyclomer is used as a raw material for polymers and the like.
- the epoxy group in the compound is an acid and a glycidyl type epoxy group. Therefore, after an acrylic polymer having an epoxy group is obtained by addition polymerization of an alicyclic epoxy (meth) acrylate, an acid group-containing curing agent is added to the acrylate polymer having the epoxy group. There was a problem in storage stability when trying to preserve it in the added state.
- a TFT type thin film transistor TFT
- an interlayer insulating film to form a back plate
- a polarizing plate is provided on a glass plate
- a black matrix layer and a color are provided as necessary.
- a filter layer pattern is formed, and a transparent conductive circuit layer and an interlayer insulating film are formed in sequence to form a top plate.
- the back plate and the top plate face each other via a spacer, and liquid crystal is sealed between the two plates.
- the photosensitive resin composition used therein is required to have excellent transparency, light resistance, developability and flatness.
- a chemically amplified resist using a photoacid generator as a photosensitizer is well known.
- a resin composition containing a resin containing a structural unit having an epoxy group and a photoacid generator a protonic acid is generated from the photoacid generator by exposure, and the epoxy group is cleaved to cause a crosslinking reaction.
- the resin becomes insoluble in the developer and a pattern is formed.
- the heat treatment after the exposure moves through the resist solid phase, and the acid causes the chemical change such as the resist resin to catalyze. Amplify.
- the insulating film provided in the THT type liquid crystal display element and the integrated circuit element needs to be finely processed. Therefore, as a material for forming the insulating film, a radiation sensitive film is generally used. A fat composition is used, and such a radiation-sensitive grease composition is required to have high radiation sensitivity in order to obtain high productivity. In addition, when the insulating film has low solvent resistance, the insulating film is swelled or deformed by an organic solvent, peeling of the substrate force, and the like, which may cause liquid crystal display elements and integrated circuit elements. Serious obstacles occur in manufacturing. Therefore, such an insulating film is required to have excellent solvent resistance. Furthermore, an insulating film provided on a liquid crystal display element, a solid-state imaging element, etc. Therefore, high transparency is required as necessary.
- Japanese Patent Application Laid-Open No. 2003-7612 discloses a photosensitive resin composition containing a copolymer of an alicyclic epoxy group-containing polymerizable unsaturated compound and a radical polymerizable compound.
- An unsaturated carboxylic acid or the like is used as a radical polymerizable compound.
- Epoxy compounds are effective for obtaining a film having good etching resistance by easily crosslinking with an acid generated by a photoacid generator and subsequent heating (post-bake) in a light-amplified resist.
- alicyclic epoxy group-containing polymerizable unsaturated compounds are rich in thione polymerizability, but react with the carboxyl group derived from unsaturated carboxylic acid used to impart alkali solubility and are poor in storage stability. Therefore, it was necessary to store it at a low temperature of 20 ° C or less, and there was a big problem in practicality.
- Patent No. 305549 discloses a monomer unit having an epoxy group-containing hydrocarbon group and a monomer unit corresponding to a (meth) acrylate ester in which an organic cyclic hydrocarbon group is directly bonded to an oxygen atom of the ester.
- a photosensitive resin composition comprising a unit and a monomer unit having a carboxyl group and a powerful copolymer is disclosed.
- (meth) acrylic acid esters in which an organic cyclic hydrocarbon group is directly bonded to the oxygen atom of the ester have a very bulky group adjacent to the ester group, so that monomer synthesis is difficult.
- it is difficult to handle the polymerization reaction due to poor solubility in organic solvents.
- (meth) acrylic acid ester in which an organic hydrocarbon group is directly bonded to the oxygen atom of the ester is very low in polarity, so it is highly polar and co-polymerized with unsaturated carboxylic acid and epoxy group-containing monomers.
- the monomer composition of the polymer is biased and a uniform polymer cannot be obtained, and thus the desired resist performance cannot be obtained.
- Patent Document 1 US Pat. No. 3,536,687
- Patent Document 2 German Patent No. 1063808
- Patent Document 3 Japanese Patent Laid-Open No. 2-18410
- Patent Document 4 JP-A-57-47364
- Patent Document 6 Japanese Patent Laid-Open No. 2003-7612
- Patent Document 6 Japanese Patent No. 3055495
- Non-Patent Document 1 "Journal 'Ob' American 'Chemical Society'" No. 81, No. 335 Page 0 (1959)
- An object of the present invention is to provide a novel compound having a radical polymerizable double bond and an alicyclic epoxy group, a method for producing the same, and a copolymer having a monomer unit corresponding to the compound.
- Another object of the present invention is a high-performance skin having excellent solvent solubility and transparency, heat resistance, etching resistance, flatness and developability when used as a radiation sensitive resin. It is an object of the present invention to provide a polymer that can form a film, has a very high storage stability of a resin composition containing the resin, and is easy to synthesize, and a method for producing the same.
- the inventors of the present invention have been paying attention to unsaturated carboxylic acid esters having a dicyclopentalel group in earnest studies to solve the above problems.
- a compound having a dicyclopentenyl group such as dicyclopentayl (meth) ate, for example, is derived using dicyclopentagen (DCPD) which is generally commercially available, it corresponds to dicyclopentadiene in the compound.
- DCPD dicyclopentagen
- the dicyclopentenyl group is a group represented by the following formula (5)
- the main product is a compound having a structure represented by either (a) or (b) and having a group represented by structure (b).
- the introduced epoxy group has a structure that wraps around the inside of the ring and is inhibited by the tricyclodecane ring, making it difficult to react. I can expect that.
- the epoxy group in the 3,4-epoxytricyclo [5.2.1.0 2 ' 6 ] decane ring is, for example, a conventional alicyclic ring such as 3,4 epoxytricyclohexyl (meth) acrylate. Reactivity compared to epoxy groups in formula epoxy compounds Can be expected to be lower.
- a polymer using a 3,4-epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane ring-containing polymerizable compound as a monomer component has an epoxy group reactive for the reasons described above. Since it is suppressed, it can be expected that storage stability, in particular, stability in the state of a composition to which an acid group-containing curing agent is added is improved. Further, the bulky skeleton of the tricyclodecane ring has a higher Tg of the polymer having the compound having the ring as a monomer component, and thus the coconut resin obtained from a conventional alicyclic epoxy (meth) acrylate compound, for example. Compared to the above, effects such as improvement of transparency, heat resistance, etc., and prevention of stickiness when rosin is used as a coating film can be expected.
- a novel compound having a radical-polymerizable double bond and an alicyclic epoxy group can be obtained, and a specific amount of the radical polymerization can be obtained.
- Monomer mixture comprising a compound having an ionic double bond and an alicyclic epoxy group and a polymerizable unsaturated compound having an alcoholic soluble group, or a monomer comprising these and a specific polymerizable unsaturated compound.
- the polymer obtained by copolymerization of the mixture is excellent in solvent solubility, has a very good storage stability of the solution, and has a film excellent in transparency, heat resistance, etching resistance, flatness, developability, etc.
- the present invention has been completed by finding that it can be formed.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group, and A may contain a single bond or a hetero atom.
- R 2 is represented by the following formula (lb)
- any one of R 3 , R 4 , R 5 , and R 6 represents a bond with A in the formula (la), and the others are hydrogen atoms or carbon atoms of 1 to 10 Represents an alkyl group
- 4-epoxytricyclo [5. 2. 1. 0 2 ' 6 ] is a group having a decane skeleton] represented by 3, 4-epoxytricyclo [5. 2. 1. 0 2 '6] provides decane skeleton-containing unsaturated carboxylic acid ester.
- R 7 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 0 or more).
- R 7 is particularly preferably an ethylene group. is there.
- N is preferably an integer of 0 to 5.
- the present invention also provides the following formula (3a)
- R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group
- A represents a single bond or a hetero atom which may contain a divalent carbon atom.
- R 2 represents the following formula (3b)
- R 3 , R 4 , R 5 , and R 6 represents a bond with A in Formula (3a), and the others are hydrogen atoms or carbon atoms of 1 to 10 A tricyclo [5. 2. 1. 0 2 ' 6 ] deca-3-ene skeleton represented by an alkyl group]
- R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group, and A may contain a single bond or a hetero atom.
- R 2 is represented by the following formula (lb)
- any one of R 3 , R 4 , R 5 , and R 6 represents a bond with A in the formula (la), and the others are hydrogen atoms or carbon atoms of 1 to 10 Represents an alkyl group
- 4-epoxytricyclo [5. 2. 1. 0 2 ' 6 ] is a group having a decane skeleton] represented by 3, 4-epoxytricyclo [5. 2. 1. 0 2 '6] decane skeleton-containing unsaturated carboxylic
- peracetic acid can be preferably used.
- the present invention also provides the formula (la)
- R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group, and A may contain a single bond or a hetero atom.
- R 2 is represented by the following formula (lb)
- any one of R 3 , R 4 , R 5 , and R 6 represents a bond with A in the formula (la), and the others are hydrogen atoms or carbon atoms of 1 to 10 Represents an alkyl group
- 4-epoxytricyclo [5. 2. 1. 0 2 ' 6 ] is a group having a decane skeleton] represented by 3, 4-epoxytricyclo [5. 2. 1. 0 2 '6] a copolymer having a monomer unit corresponding to decane skeleton-containing unsaturated carboxylic acid ester, (a) monomer units and (B) an epoxy group-containing polymerizable unsaturated compound containing an alkali-soluble group (C) (cl) styrene optionally substituted with an alkyl group in addition to the monomer units (A) and (B), (c2) the following formula (4)
- R 8 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms
- R 9 represents a primary or secondary alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and aryl.
- a divalent hydrocarbon group having a prime number of 1 to 12 R 11 is a hydrogen atom or a hydrocarbon group, and m is an integer of 1 or more.
- (c3) a copolymer consisting of monomer units corresponding to at least one epoxy group-free polymerizable unsaturated compound selected from the group consisting of N-substituted maleimidoca.
- the proportion of the monomer units (B) is 40 to 90% by weight with respect to the total monomer units, and 30% by weight or more of the monomer units (B) is represented by the formula (la) 3, 4— Epoxy tricyclo [5. 2. 1. 0 2 ' 6 ]
- a copolymer characterized by being a monomer unit corresponding to an unsaturated force rubonic acid ester containing a decane skeleton.
- the ratio of the monomer unit (A) is 10% with respect to the total monomer units.
- the copolymer of the present invention can be suitably used as an alkaline aqueous solution-soluble photoresist resin.
- the present invention also provides a monomer mixture comprising (a) a polymerizable unsaturated compound having an alkali-soluble group and (b) an epoxy group-containing polymerizable unsaturated compound, or (a) and (b) above. (C) (cl) styrene optionally substituted with an alkyl group, (c2) the following formula (4)
- R 8 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms
- R 9 represents a primary or secondary alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and aryl.
- a divalent hydrocarbon group having a prime number of 1 to 12 R 11 is a hydrogen atom or a hydrocarbon group, and m is an integer of 1 or more.
- (c3) a monomer mixture comprising at least one epoxy group-free polymerizable unsaturated compound selected from the group consisting of (c3) N-substituted maleimidoca, the epoxy group
- the content of the polymerizable unsaturated compound (b) is 40 to 90% by weight with respect to the total amount of monomers, and 30% by weight or more of the epoxy group-containing polymerizable unsaturated compound (b) is Formula (la)
- R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group, and A may contain a single bond or a hetero atom.
- R 2 is represented by the following formula (lb)
- any one of R 3 , R 4 , R 5 , and R 6 represents a bond with A in the formula (la), and the others are hydrogen atoms or carbon atoms of 1 to 10 Represents an alkyl group
- 4 epoxy tricyclo [5. 2. 1. 0 2 ' 6 ] is a group having a decane skeleton] represented by 3, 4 epoxy tricyclo [5. 2. 1. 0 2 ' 6 ]
- a process for producing a copolymer characterized in that a monomer mixture which is an unsaturated carboxylic acid ester containing a decane skeleton is subjected to copolymerization.
- a novel unsaturated carboxylic acid ester compound having a 3, 4 epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane skeleton (an alicyclic ring having a radical polymerizable double bond) Formula epoxi (meth) acrylate compounds) are provided.
- the unsaturated carboxylic acid ester has suppressed epoxy group reactivity, and is excellent in storage stability when stored in a state where an acid group-containing curing agent is added.
- the solvent solubility is excellent, the storage stability is very good, the transparency (for example, transparency to light of 180 to 400 nm), the heat resistance, and the etching resistance.
- a film excellent in flatness, developability, etc. can be formed. Therefore, it is extremely useful as a resin for photoresist.
- Fig. 1 shows an unsaturated carboxylic acid ester (alicyclic acrylate) containing tricyclo [5. 2. 1. 0 2 ' 6 ] deca -3 skeleton used in Example 1 (Hitachi Chemical chart: 1 H-NMR chart of trade name “FA-511 A”).
- R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group
- A is Each represents a divalent hydrocarbon group that may contain a single bond or a hetero atom
- R 2 is represented by the formula (lb) 3, 4 epoxy tricyclo [5. 2. 1. 0 2 ' 6 ] A group having a decane skeleton.
- alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group in R 1 include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl Alkyl groups such as groups; hydroxymethyl group, 1-hydroxychetyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3 hydroxypropyl group, 1-hydroxy1 methylethyl group, 2 hydroxy group Examples thereof include hydroxyalkyl groups such as 1 methylethyl group, 1-hydroxybutyl group, 2 hydroxybutyl group, 3 hydroxybutyl group and 4-hydroxybutyl group.
- R 1 is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may be substituted with a hydroxyl group, and particularly preferably a hydrogen atom or
- Examples of the divalent hydrocarbon group that may contain a heteroatom in A include a divalent hydrocarbon group, a divalent hydrocarbon group, a divalent hydrocarbon group of 1 or more, and a divalent hydrocarbon group of 1 or more.
- the hetero atom may be interposed between carbon atoms constituting the hydrocarbon group which may be bonded to the terminal of the hydrocarbon group.
- Examples of the hetero atom include nitrogen, oxygen, sulfur atom and the like.
- R 7 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 0 or more).
- Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms in R 7 include divalent hydrocarbon groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, otatamethylene, decamethylene, and dodecamethylene groups. Linear or branched alkylene group; divalent alicyclic hydrocarbon group such as cyclopentylene, cyclohexylene, cyclopentylidene, cyclohexylidene (cycloalkylene group, cycloalkylidene group, divalent bridge Carbocyclic groups, etc.); And divalent hydrocarbon groups in which two or more of these are bonded.
- divalent hydrocarbon groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, otatamethylene, decamethylene, and dodecamethylene groups. Linear or branched alkylene group; divalent alicyclic hydrocarbon group such as cyclopenty
- R 7 is particularly an alkylene group having 1 to 6 carbon atoms such as methylene, ethylene, propylene, tetramethylene or hexamethylene group; a 3 to 6-membered alicyclic hydrocarbon group such as cyclohexylene group, etc. Is preferred.
- n is preferably an integer of 0 to 0, more preferably an integer of 0 to 5, still more preferably an integer of 0 to 4, and particularly preferably 0 or 1.
- alkylene groups such as a methylene group, an ethylene group, a propylene group, and a trimethylene group (for example, an alkylene group having 1 to 12 carbon atoms, particularly an alkylene group having 1 to 6 carbon atoms).
- a thioalkylene group such as a thiomethylene group, a thioethylene group or a thiopropylene group (for example, a thioalkylene group having 1 to 12 carbon atoms, particularly a thioalkylene group having 1 to 6 carbon atoms); an aminomethylene group, an aminoethylene group,
- An aminoalkylene group such as a minopropylene group (for example, an aminoalkylene group having 1 to 12 carbon atoms, particularly an aminoalkylene group having 1 to 6 carbon atoms) and the like can be mentioned.
- A is preferably a single bond [in the above formula (2), when n is 0], an alkylene group having 1 to 6 carbon atoms (particularly 1 to 3 carbon atoms), or 1 to 6 carbon atoms. (Especially 2 to 3 carbon atoms) oxyalkylene group [in the above formula (2), n is 1 and R 7 is a C alkylene group (especially C alkylene
- R 7 is an ethylene group and n is an integer of 0 to 5 in formula (2) is also preferable.
- any one of R 3 , R 4 , R 5 , and R 6 represents a bond with A in the formula (la), and the other is a hydrogen atom or a carbon number of 1 to 10 alkyl groups are shown.
- R 5 and R 6 hydrogen atoms or alkyl groups having 1 to 10 carbon atoms may be the same as or different from each other. Among these, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable.
- the compound represented by the formula (la) is bonded to the group represented by the formula (lb) at R 3 or R 4 (3, 4-epoxytricyclo [5. 2. 1. 0 2 '6] and if to have) attached at the 9-position of decane skeleton, when bound in R 5 or R 6 (3, 4-epoxytricyclo [5.2.2 1.0 2' 6] decane May be bonded at the 8th position of the skeleton).
- a typical example of the former is a compound represented by the following formula (la-1).
- a typical example of the latter is, for example, a compound represented by the following formula (la-2). Can be mentioned. [Chemical 29]
- R 1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydroxyl group
- A represents a single bond or a hetero atom which may contain a divalent carbon atom. Show hydrogen group
- 3,4-Epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane skeleton-containing unsaturated carboxylic acid ester represented by the formula (la) is a typical example of epoxidized dicyclopentenyl.
- the unsaturated double bond between the a-position and the 13-position carbon of the carboxylic carbon in the unsaturated carboxylic acid ester remains almost 100%.
- Tricyclo [5. 2. 1.0 .0 2 ' 6 ] Deca in the 3-ene skeleton Double bonds can be epoxyized.
- the tricyclo [5. 2. 1. 0 2 ' 6 ] deca 3 -ene skeleton-containing unsaturated carboxylic acid ester represented by the formula (3a) as a starting material is, for example, dicyclopentayl (meta ) Atalylate [Tricyclo [5. 2. 1. 0 2 ' 6 ] Deca-3 9-yl (meth) Atylate; Tricyclo [5. 2. 1. 0 2 ' 6 ] Deca 3 -8-yl (meth) acrylate], dicyclopente-loxychetyl (meth) acrylate [2— (tricyclo [5. 2. 1.
- R 1 in formula (3a) is a hydrogen atom, A is a single bond
- R 4 , R 5 , and R 6 are Manufactured by Hitachi Chemical Co., Ltd., all but one of which is a hydrogen atom, trade name “FA-511A”
- R 1 is a hydrogen atom
- A is an oxyethylene group
- the formula (3b) In R 3 , R 5 and R 6 except for one that represents a bond to A, all of which are hydrogen atoms, manufactured by Hitachi Chemical Co., Ltd., trade name “FA 512A”; R 1 is a methyl group, and A is an oxyethylene group
- “512M” and “FA-512MT” are examples. Tricyclo [5. 2. 1.
- the amount of the polymerization inhibitor used is not particularly limited, but the tricyclo [5. 2. 1. 0 2 ' 6 ] deca-3-ene skeleton-containing unsaturated carboxylic acid represented by the formula (3a) charged as a starting material is used.
- a range of 0.03 to 5 parts by weight, preferably 0.05 to 3 parts by weight, can be selected with respect to 100 parts by weight of the acid ester.
- the tricyclo [5. 2. 1. 0 2 ' 6 ] deca-3-ene skeleton-containing unsaturated carboxylic acid ester represented by the formula (3a) is represented by the formula (la) 3, 4-Epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane skeleton-containing unsaturated carboxylic acid ester can be produced.
- molecular oxygen is present together with the polymerization inhibitor.
- peracids and hide-mouth peroxides can be used.
- the peracid may be synthesized by force, or may be generated in a reaction system.
- Examples of peracids include organic peracids such as performic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid.
- Examples of the hydride peroxides include hydrogen peroxide, tertiary butyl hydride peroxide, cumium oxide, and the like.
- An epoxy method using hydrogen peroxide, a phase transfer catalyst and a metal salt of tungstic acid can also be used.
- Examples of the phase transfer catalyst include trioctylmethyl ammonium chloride, trioctylmethyl ammonium sulfate, tetrahexyl ammonium sulfate, and trihexylmethyl ammonium.
- trialkyl ammonium salts such as sulfite salts.
- the amount of the phase transfer catalyst used is 0.1 to 20 parts by weight, preferably 0.5 to 18 parts by weight, more preferably 1 to 15 parts by weight per 100 parts by weight of hydrogen peroxide.
- the metal salt of tungstic acid include sodium tandastenate.
- the amount of tungstic acid metal salt used is not particularly limited. For example, 1 to 30 parts by weight, preferably 2 to 18 parts by weight, more preferably 3 to 15 parts by weight per 100 parts by weight of hydrogen peroxide. It is.
- phosphoric acid or a salt thereof, aminomethylsulfonic acid, sodium sulfate, etc. in combination the reaction can proceed more rapidly.
- the amount of these used can be selected from a range force of, for example, 1 to 80 parts by weight, preferably 5 to 75 parts by weight with respect to 100 parts by weight of the metal salt of tungstic acid. If the amount of the phase transfer catalyst and the metal salt of tungstic acid is outside the above range, the appropriate epoxidation reaction may not proceed.
- the metal salt of tungstic acid molybdic acid or metal salt of molybdic acid can be used. In this method, the reaction can be carried out in a water-organic solvent two-phase system.
- One or two or more epoxidizing agents can be selected and used.
- the amount of epoxidizing agent depends on the type of epoxidizing agent used, the desired epoxy level, the tricyclo [5. 2. 1. 0 2 ' 6 ] deca 3-ene skeleton containing unsaturated carboxylic acid ester used. It can be selected appropriately according to the type.
- a catalyst can be used as necessary.
- an alkali such as sodium carbonate or an acid such as sulfuric acid or an organic acid
- a hydride peroxide such as hydrogen peroxide
- tungstic acid and caustic soda can be used.
- a catalytic effect can be obtained by using an organic acid and hydrogen peroxide in combination with molybdenum hexacarbonyl and tertiary butyroxide mouth peroxide.
- An epoxy reaction can also be carried out using a combination of an alkali metal salt of tandastenoic acid, phosphoric acid or a phosphate ester, alkyl ammonium, and hydrogen peroxide.
- tricyclo of the formula (3a) [5. 2. 1. 0 2 '6] dec - molar ratio of epoxidizing agent to 3-E down skeleton-containing unsaturated carboxy phosphate esters, alicyclic It is preferable to cover equimolar or more with respect to the double bond in the skeleton.
- it is a problem of economy and side reaction It is usually disadvantageous to exceed 2 times mol, and when peracetic acid is used as an epoxidizing agent, a range force of usually equimolar or more, preferably 1 to 1.5 times mol can be selected.
- the epoxidation reaction may be performed using a solvent!
- the solvent is used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxy agent.
- an inert solvent can be preferably used.
- the inert solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; and halogenated carbon such as carbon tetrachloride and chloroform.
- Examples include hydrogens; esters such as ethyl acetate; ethers such as jetyl ether and 1,4 dioxane.
- peracetic acid is used as the epoxyting agent, it is preferable to use aromatic hydrocarbons, ethers or esters as the solvent.
- the temperature of the epoxy reaction is preferably 0 to 70 ° C when peracetic acid is used as the epoxidizing agent. This is because peracetic acid may decompose at 70 ° C.
- a tertiary butyl hydride peroxide Z-molybdenum diacid diacetyl acetonate compound which is an example of a hydrated peroxide
- 20 to 150 ° C is preferable for the same reason.
- no special operation is required during the reaction.
- the mixture may be stirred for 1 to 8 hours. Thereby, the 3,4 epoxy tricyclo [5. 2. 1. 0 2 ′ 6 ] decane skeleton-containing unsaturated carboxylic acid ester of the present invention can be produced.
- a polymer having a monomer unit corresponding to an unsaturated carboxylic acid ester containing a 3,4 epoxy tricyclo [5. 2. 1. 0 2 ' 6 ] decane skeleton represented by the formula (la) is a curable resin. It is useful as a radiation-sensitive fat.
- Monomers of various functional polymers include, among others, epoxidized dicyclopentayl (meth) acrylate and epoxidized dicyclopentaol luxe. Chill (meta) atelate is particularly preferred!
- the monomer unit (A) containing an alkali-soluble group has a function of imparting alkali solubility to the polymer.
- the polymer dissolves in an aqueous alkaline solution (developer) during development.
- the monomer unit (A) cures the polymer upon exposure by crosslinking with a crosslinking agent or by reaction with a cyclic ether-containing group such as an epoxy group or an oxetane ring in the polymer molecule.
- a crosslinking agent or by reaction with a cyclic ether-containing group such as an epoxy group or an oxetane ring in the polymer molecule.
- the copolymer of the present invention is particularly useful as a negative type photoresist resin.
- the monomer unit (A) containing an alkali-soluble group can be introduced into a polymer by subjecting the polymerizable unsaturated compound (a) having an alkali-soluble group to copolymerization.
- the alkali-soluble group may be any group that is usually used in the resist field. Examples thereof include a carboxyl group and a phenolic hydroxyl group.
- Typical examples of the polymerizable unsaturated compound (a) having an alkali-soluble group include, but are not limited to, an unsaturated carboxylic acid or an acid anhydride thereof, hydroxystyrene or a derivative thereof. Of these, unsaturated carboxylic acids or acid anhydrides thereof are particularly preferred.
- Examples of unsaturated carboxylic acids or acid anhydrides thereof include a, ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid, and acid anhydrides (anhydrous anhydride). Maleic acid, itaconic anhydride, etc.). Of these, acrylic acid and methacrylic acid are particularly preferable.
- the polymerizable unsaturated compound (a) having an alkali-soluble group can be used alone or in combination of two or more.
- the proportion of the monomer unit (A) containing an alkali-soluble group in the copolymer varies depending on the type of monomer used and the type of resist (negative or positive type). Usually, it constitutes a copolymer. It is 10 to 50% by weight, preferably 12 to 40% by weight, more preferably 14 to 30% by weight based on the total monomer units. If this ratio is too small, it is difficult to dissolve in an alkali image solution, and developability deteriorates. Conversely, if it is too large, etching resistance after development deteriorates, which is not preferable.
- the monomer unit (B) corresponding to the epoxy group-containing polymerizable unsaturated compound is used during exposure.
- the polymer is cured by cross-linking using a cross-linking agent or by reaction with an alkali-soluble group (for example, carboxyl group, phenolic hydroxyl group, etc.) in the polymer molecule, to give the film the necessary hardness as a resist, It has the function of increasing etching resistance and changing the polymer to alkali-insoluble.
- an alkali-soluble group for example, carboxyl group, phenolic hydroxyl group, etc.
- the monomer unit (B) corresponding to the epoxy group-containing polymerizable unsaturated compound can be introduced into the polymer by subjecting the epoxy group-containing polymerizable unsaturated compound (b) to copolymerization.
- the epoxy group-containing polymerizable unsaturated compound (b) a compound having a polycyclic aliphatic group having an epoxy group on the ring and a group having an unsaturated bond is preferable.
- the polycyclic aliphatic group include a dicyclopental group and a tricyclodecyl group.
- Examples of the unsaturated bond include a carbon-carbon double bond, and examples of the group having an unsaturated bond include a vinyl group, a allyl group, a methallyl group, an allyloyl group, and a methacryloyl group.
- the epoxy group-containing polymerizable unsaturated compound (b) at least one 3, 4 epoxy tricyclo represented by the formula (la) [5. 2. 1. 0 2 ' 6 ]
- An unsaturated carboxylic acid ester containing a decane skeleton is used.
- the formula 3 is expressed by (la), 4 epoxytricyclo [5.2.2 1.0 2 '6] one or more decane bone rated containing unsaturated carboxylic acid ester and
- other epoxy group-containing polymerizable unsaturated compounds hereinafter sometimes referred to as “other epoxy group-containing polymerizable unsaturated compounds” may be used in combination.
- epoxy group-containing polymerizable unsaturated compounds include, for example, oxyl (meth) acrylate, glycidyl (meth) acrylate, 2-sila-ruethyl (meth) acrylate, 2 glycidyl oxetyl (meta ) Polymerizable unsaturated compounds ((meth) acrylic acid esters) containing an oxysilane ring (monocyclic) such as acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate Derivatives, etc.); 3, 4-Epoxycyclohexyl (meth) acrylate, 3, 4-Epoxy silane Chlohexylmethyl (meth) acrylate, 2- (3,4 epoxy cyclohexyl) ethyl (meth) acrylate, 2- (3, 4 epoxy cyclohexyl methyloxy) ethyl (me
- the proportion of the monomer unit (B) corresponding to the epoxy group-containing polymerizable unsaturated compound in the copolymer is 40 to 90% by weight, preferably 45 to 85% by weight, based on the total monomer units. More preferably, it is 50 to 80% by weight. If the ratio force is less than 0% by weight, the crosslinking reaction at the time of exposure does not proceed sufficiently, resulting in poor heat resistance and etching resistance. On the other hand, if the proportion exceeds 90% by weight, the alkali solubility becomes insufficient, and a good pattern cannot be formed.
- the proportion of monomer units corresponding to the unsaturated carboxylic acid ester containing a 0 2 ' 6 ] decane skeleton is 30% by weight or more in total.
- this ratio is less than 30% by weight, for example, when used in combination with a polymerizable unsaturated compound containing an epoxy group-containing alicyclic carbocyclic ring, the storage stability is deteriorated, and the polymerizable unsaturated compound containing an oxysilane ring (monocyclic) is deteriorated.
- saturated compounds such as glycidyl group-containing monomers
- the performance required for radiation-sensitive resins is insufficient, such as insufficient heat resistance.
- the monomer unit (C) is (cl) styrene optionally substituted with an alkyl group, (c2) an unsaturated carboxylic acid ester represented by the formula (4), and (c3 ) N-substituted monomer unit corresponding to at least one epoxy group-free polymerizable unsaturated compound selected from the group consisting of maleimides.
- Monomer unit (C) is required as a resist in the film.
- the corresponding monomer has the function of facilitating the copolymerization reaction.
- it also has a function of increasing the hardness of the film by a crosslinking reaction or the like.
- alkyl groups in styrene (cl) include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl groups, and the like And an alkyl group having about 1 to 7 carbon atoms.
- an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
- the alkyl group may be bonded to either the styrene butyl group or the benzene ring! /.
- styrene (cl) which may be substituted with an alkyl group include styrene, a-methylstyrene, butyltoluene (o-butyltoluene, m-butyltoluene, p-butyltoluene) and the like. . These can be used alone or in combination of two or more.
- R 8 is particularly preferably a hydrogen atom or a methyl group.
- Examples of the primary or secondary alkyl group having 1 to 12 carbon atoms in R 9 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, hexyl, octyl, and decyl. And dodecyl group.
- Examples of the alkenyl group having 2 to 12 carbon atoms include primary or secondary alkenyl groups such as allyl, 3-butyl, 5-hexyl and the like.
- Examples of aryl groups include phenyl groups.
- Examples of the aralkyl group include a benzyl group.
- Examples of the 4- or higher-membered cyclic ether-containing group include groups containing a cyclic ether structure such as an oxetane ring, an oxolane ring, an oxane ring, and an oxepane ring.
- Examples of the oxetane ring-containing group include an oxetal group, a 3-methyl-3-oxetal group, a 3-ethyl-3-oxetal group, a (3-methyl-3-oxetal) methyl group, ( 3-ethyl-3-ethyl), 2- (3-methyl-3-oxeta-yl) ethyl, 2- (3-ethyl-3-oxeta-ethyl), 2- [(3 —Methyl—3—oxeta-l) methyloxy] ethyl group, 2— [(3—eth Ru-3-oxeta-l) methyloxy] ethyl group, 3-[(3-methyl-3-oxetal) methyloxy] propyl group, 3-[(3-ethyl-3-oxeta-l) methyloxy] propyl group, etc.
- Examples of the oxolane ring-containing group include a tetrahydrofurfuryl group, a 3-oxoral group, a 3-methyl-3-oxoral group, a 3-ethyl-3-oxoral group, and a (2-methyl-2-oxolael) methyl group.
- (2-Ethyl-2-oxolael) methyl group 2- (2-Methyl-2-oxolayl) ethyl group, 2- (2-Ethyl-2-oxolayl) ethyl group, 2- [(2— Methyl-2-oxolaer) methyloxy] ethyl, 2-[(2-Ethyl-2-oxolaer) methyloxy] ethyl, 3-[((2-Methyl-2-oxolaer) methyloxy] propyl, 3 [( 2- Ethyl-2-oxolaer) Methyloxy] propyl group, and the like.
- R 1Q is a divalent hydrocarbon group having 1 to 12 carbon atoms
- m represents an integer of 1 or more.
- the divalent hydrocarbon group having 1 to 12 carbon atoms include those similar to the divalent hydrocarbon group having 1 to 12 carbon atoms in R 6 .
- an alkylene group having 2 to 6 carbon atoms such as ethylene, propylene, tetramethylene and hexamethylene groups; a 3 to 6-membered alicyclic hydrocarbon group such as cyclohexylene group and the like are particularly preferable.
- the hydrocarbon group for R 11 include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl groups (for example, C alkyl).
- Aliphatic hydrocarbon groups such as 1-6 groups); cyclopentyl groups such as cyclopentyl groups such as cyclohexyl groups, norbornyl groups (bicyclo [2. 2. 1] heptyl groups) and tricyclo [5. 2. 1. 0 2 ' 6 ]
- An alicyclic hydrocarbon group such as a bridged carbocyclic group such as a decyl group; a group in which two or more of these are bonded.
- m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and particularly preferably 1.
- Representative examples of the unsaturated carboxylic acid ester (c2) represented by the formula (4) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth ) Atalylate, butyl (meth) acrylate, aryl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate, oxetal (meth) acrylate, 3-methyl-3 —oxeta -(R) (Meth) Atalylate, 3-Ethyl-3-methoxal (Meth) Atalylate, (3-Methyl-3-Oxetal) Methyl (Meth) Atalylate, (3-Ethyl-3-Oxeta -(L) methyl (meth) ate, 2- (3-methyl-3-oxeta-ethyl) ethyl (methyl
- the organic group includes a hydrocarbon group and a heterocyclic group.
- the hydrocarbon group include aliphatic hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl groups (for example, C alkyl groups); cyclopentyl groups, cyclohexyl groups, and the like.
- Cycloalkyl groups such as syl group and cyclooctyl group, alicyclic hydrocarbon groups such as bridged carbocyclic group such as adamantyl group and norbornyl group; Aryl groups such as phenyl group; Aralkyl groups such as benzyl group; etc. A group in which two or more are bonded.
- the heterocyclic group for example, a 5- to 10-membered non-aromatic or aromatic complex containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. And cyclic groups.
- N-substituted maleimide for example, N cyclopentylmaleimide N-Cyclohexylmaleimide, N-Cyclooctylmaleimide and other N-Cycloalkylmaleimides; N-Adamantylmaleimide, N-Norbol-Maleylimides and other N-Bridged carbocyclic substituted maleimides; N-Methylmaleimide N-alkylmaleimides such as N-ethylmaleimide and N-propylmaleimide; N-arylmaleimides such as N-phenolmaleimide; N-aralkylmaleimides such as N-benzylmaleimide and the like.
- N-cycloalkylmaleimides such as N-cyclohexylmaleimide, N-bridged carbocyclic group-substituted maleimides, and the like are preferable.
- N-substituted maleimides (c3) can be used alone or in combination of two or more.
- the copolymer of the present invention may contain a small amount of other monomer units in addition to the monomer unit (A), the monomer unit (B), and the monomer unit (C).
- the monomer unit include units corresponding to (meth) acrylamide, (meth) acryl-tolyl and the like.
- the copolymer of the present invention contains the monomer unit (A) and the monomer unit (B) and does not contain the monomer unit (C)
- the monomer unit (A) and the monomer unit (B) The total amount is usually 98% by weight or more, preferably 99% by weight or more, more preferably substantially 100% by weight, based on all monomer units.
- the total amount of these three types of monomer units is based on the total monomer units. For example, it is 90% by weight or more, preferably 95% by weight or more, more preferably 98% by weight or more, and particularly preferably substantially 100% by weight.
- the copolymer of the present invention includes a monomer mixture having a polymerizable unsaturated compound (a) having an alkali-soluble group and an epoxy group-containing polymerizable unsaturated compound (b), or (a) And a monomer mixture comprising the epoxy group-free polymerizable unsaturated compound (c) in addition to (b), wherein the proportion of the epoxy group-containing polymerizable unsaturated compound (b) is a monomer. 40 to 90% by weight with respect to the total amount, and 30% by weight or more of the epoxy group-containing polymerizable unsaturated compound (b) is represented by the formula (2a) and Z or (2b) 3, 4-Epoxytricyclo [5. 2. 1. 0 2 ' 6 ] Can be produced by subjecting a monomer mixture that is an unsaturated carboxylic acid ester containing a decane skeleton to copolymerization.
- a normal radical polymerization initiator can be used.
- Examples thereof include organic peroxides such as benzoyl peroxide, lauroyl belloxide, t-butyl peroxybivalate, 1,1 bis (t-butyl peroxy) cyclohexane, and hydrogen peroxide.
- organic peroxides such as benzoyl peroxide, lauroyl belloxide, t-butyl peroxybivalate, 1,1 bis (t-butyl peroxy) cyclohexane, and hydrogen peroxide.
- a peroxide is used as a radical polymerization initiator
- a redox initiator may be combined with a reducing agent.
- azo compounds are particularly preferred: 2,2'-azobisisobutyric-tolyl, 2,2'-azobis (2,4 dimethylvale-tolyl), dimethyl-2,2'-azobis (2-methylpropionate) is preferred.
- the amount of the polymerization initiator used can be appropriately selected within the range that does not impair smooth copolymerization, but usually 1 to 10 weights relative to the total amount of monomers (all monomer components) and polymerization initiator. %, Preferably about 2 to 8% by weight.
- the copolymerization can be carried out by a conventional method used for producing a styrene polymer or an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable.
- the monomer and the polymerization initiator may be supplied all at once to the reaction system, or a part or all of them may be dropped into the reaction system.
- a method in which a solution obtained by dissolving a polymerization initiator in a polymerization solvent is dropped into a mixed solution of a monomer and a polymerization solvent maintained at a constant temperature for polymerization, or a monomer and a polymerization initiator are previously added to the polymerization solvent For example, a method in which a solution dissolved in is dropped into a polymerization solvent maintained at a constant temperature for polymerization (drop polymerization method) can be employed.
- the polymerization solvent can be appropriately selected depending on the monomer composition and the like.
- a polymerization solvent for example, ether (jetyl ether, 3-methoxy 1-butanol, propylene glycol monomethylenoatenore diethylene glycolenoreethinoremethinoreatenole and other chain ethers such as glyconoreatenore, tetrahydrofuran, Cyclic ethers such as dioxane), ester (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, ethynoleate 3-ethoxypropionate, propylene glycol monomethyl ether Glycol ether esters such as a enormity, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides (N, N-dimethyl
- the copolymer of the present invention is produced by the above method.
- the number average molecular weight of the copolymer is, for example, about 3000 to 50000, preferably ⁇ is 3500 to 40000, and more preferably ⁇ is about 4000 to 30000.
- the degree of dispersion (weight average molecular weight MwZ number average molecular weight Mn) of the copolymer is about 1 to 3.
- the polymerization solution obtained by the above method is adjusted to a solid content concentration or subjected to a filtration treatment as necessary, and then a photoacid generator, a crosslinking agent (in the case of a negative resist), By adding appropriate additives such as a resin and a coloring agent, it can be used as a radiation-sensitive resin composition such as a resin composition for photoresist.
- the polymer produced by the polymerization is purified by precipitation or reprecipitation, and the purified polymer is dissolved in a solvent such as a resist solvent together with the appropriate additives to obtain a resin composition for photoresist. It can also be used as a radiation-sensitive rosin composition.
- the additive such as the photoacid generator and the crosslinking agent and the resist solvent, those generally used in the resist field can be used depending on the monomer composition and the like.
- the solvent used for the precipitation or reprecipitation of the polymer may be either an organic solvent or water, or a mixed solvent thereof.
- organic solvents include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene.
- Halogenated hydrocarbons halogenated aliphatic hydrocarbons such as methylene chloride, black mouth form, and tetrasalt ⁇ carbon; halogen ⁇ aromatic hydrocarbons such as black mouth benzene and dichlorobenzene), nitro compounds (nitromethane) , Nitroethane, etc.), nitrile (acetonitrile, benzo-tolyl, etc.), ether (jetyl ether, diisopropyl ether, dimethoxy) Chain ethers such as ethane; Cyclic ethers such as tetrahydrofuran and dioxane), Ketone (acetone, methyl ethyl ketone, diisoptyl ketone, etc.), Ester (ethyl acetate, butyl acetate, etc.), Carbonate (dimethyl carbonate, Jetyl) Carbonate, ethylene carbonate, propylene carbonate, etc.), alcohol (methanol, ethanol, propano
- Tricyclo [5. 2. 1. 0 2 ' 6 ] deca-l 3 atylate (manufactured by Hitachi Chemical Co., Ltd .; trade name “FA-511A”; molecular weight 204.3) lOOg and acetic acid 100 g of ethyl acetate
- the temperature inside the reaction system was adjusted to 50 ° C while blowing air, and the perethyl acetate solution of peracetic acid (peracetic acid concentration; 29.6%, moisture content; 0 2%) 156 g was added dropwise. After completion of peracetic acid addition, the reaction was terminated by aging at 50 ° C for 4 hours.
- Tricyclo [5. 2. 1. 0 2 ' 6 ] decal 3 tert acrylate (manufactured by Hitachi Chemical; trade name “FA-511A”; molecular weight 204.3); 100 g of toluene 100 g, phosphoric acid 0.24 g, trimethyloctylammonium chloride 4.65 g, sodium tungstate 6.60 g, the temperature inside the reaction system is 30 ° C while blowing air, about 1 Over time, 83.5 g of 30% hydrogen peroxide was added dropwise. After completion of the hydrogen peroxide addition, the reaction was terminated by aging at 40 ° C for 2 hours.
- reaction crude liquid was washed with water at 40 ° C, deboiling was performed at 70 ° C / 10mmH g, and 3, 4-epoxytricyclo [5. 2. 1. 0 2 ' 6 ] Atarylate 91.6 g was obtained.
- Its properties are oxysilane oxygen concentration 6.62%, viscosity 103cPZ25 ° C, and when NMR was measured, it was derived from the internal double bond of ⁇ 5.5 to 5.8 ppm observed in the chart of Fig. 1.
- a proton peak derived from an epoxy group was generated in the vicinity of S3.2 to 3.6 ppm.
- reaction crude liquid was washed with water at 50 ° C, and deboiling was performed at 70 ° C Zl0mmHg.
- reaction crude liquid was washed with water at 50 ° C, and de-boiling operation was performed at 70 ° C Zl0mmHg to give 2- (3, 4-epoxytricyclo [5. 2. 1. 0 2 ' 6 ] strength) Atarylate 88.4 g was obtained. Its properties are oxysilane oxygen concentration 5.67% and viscosity 160cPZ25 ° C.
- the peak derived from the internal double bond of ⁇ 5.5 to 5.8 ppm observed in the chart of FIG. 1 almost disappeared, and in the chart of FIG. 2, S 3.2 to 3.6 ppm or so.
- a proton peak derived from an epoxy group was generated.
- the viscosities of the copolymer solution and the radiation-sensitive resin composition solution were measured with a B-type viscometer.
- the weight average molecular weight (polystyrene conversion) and dispersity (weight average molecular weight) of the copolymer MwZ number average molecular weight Mn is a GPC (gel permeation chromatography) device (trade name) manufactured by Shimadzu Corporation. “K2479”).
- the analysis conditions are as follows.
- a 1 L flask equipped with a reflux condenser, dropping funnel and stirrer is used to flow a suitable amount of nitrogen to create a nitrogen atmosphere, and 200 parts by weight of 3-methoxy-1-butanol and 105 parts by weight of 3-methoxybutyl acetate are added and stirred. While heating to 70 ° C. Next, in the flask, 55 parts by weight of methacrylic acid (MAA), 3, 4 epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane-9-ylatarylate (compound contained in formula (la-1)) ) And 3, 4 epoxy tricyclo [5. 2. 1.
- MAA methacrylic acid
- decane a mixture of 8-yl acrylate (compounds contained in formula (la— 2)) [50:50 (molar ratio)] — 0? 8)
- a solution prepared by dissolving 175 parts by weight and 70 parts by weight of N cyclohexylmaleimide (CHMI) in 140 parts by weight of 3-methoxybutyl acetate was added dropwise over about 4 hours using a dropping pump.
- a solution prepared by dissolving 30 parts by weight of a polymerization initiator 2,2′-azobis (2,4-dimethylbareto-tolyl) in 225 parts by weight of 3-methoxybutyl acetate was dropped over about 5 hours using another dropping pump. did.
- a 1 L flask equipped with a reflux condenser, dropping funnel and stirrer is used to flow an appropriate amount of nitrogen to create a nitrogen atmosphere, and 150 parts by weight of 3-methoxy-1-butanol and 110 parts by weight of 3-methoxybutylacetate are added and stirred. While heating to 70 ° C. Next, in the flask, 60 parts by weight of methacrylic acid (MAA) and 3, 4 epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane-9-yl acrylate (included in formula (la-1)) Compound) and 3, 4 epoxy trisic mouth [5. 2. 1.
- MAA methacrylic acid
- a 1 L flask equipped with a reflux condenser, dropping funnel and stirrer is used to flow a suitable amount of nitrogen to create a nitrogen atmosphere, and 160 parts by weight of 3-methoxy-1-butanol and 110 parts by weight of 3-methoxybutyl acetate are added and stirred. While heating to 65 ° C. Next, in the flask, 50 parts by weight of methacrylic acid (MAA), 3, 4 epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane —9-ylatarylate (compound contained in formula (la-1)) ) And 3, 4-epoxytricyclo [5. 2. 1.
- MAA methacrylic acid
- decane— 8-yl acrylate (compounds contained in formula (la— 2)) [50: 50 (molar ratio)] — 0? 8)
- a solution prepared by dissolving 30 parts by weight of polymerization initiator 2, 2′-azobis (2,4 dimethylvale-tolyl) in 225 parts by weight of 3-methoxybutyl acetate was added to another dropping bonnet. The solution was added dropwise over 5 hours.
- the temperature is kept at the same temperature for about 4 hours, and then cooled to room temperature.
- the viscosity (23 ° C) is 50 mPa's, the solid content is 31.6% by weight, and the solution acid value is 34.
- a copolymer solution of 3 mg-KOHZg was obtained.
- the produced copolymer had a weight average molecular weight Mw of 7230 and a dispersity of 1.63.
- a 1 L flask equipped with a reflux condenser, dropping funnel and stirrer is used to flow a suitable amount of nitrogen to create a nitrogen atmosphere, and 200 parts by weight of 3-methoxy-1-butanol and 105 parts by weight of 3-methoxybutyl acetate are added and stirred. While heating to 90 ° C. Next, in the flask, 55 parts by weight of methacrylic acid (MAA), 3, 4 epoxy tricyclo [5. 2. 1. 0 2 ' 6 ] decane —9—yl acrylate (compounds contained in formula (la-1)) and 3, 4-epoxytricyclo [5. 2. 1.
- MAA methacrylic acid
- decane—8-yl acrylate (included in formula (la-2)) (50:50 (molar ratio)) — 0 times? 8)
- a solution in which 105 parts by weight, 40 parts by weight of (3-ethyl-3-oxeta-l) methyl metatalylate (OXMA), and 100 parts by weight of N cyclohexylmaleimide (CHMI) are dissolved in 140 parts by weight of 3-methoxybutyl acetate. was dropped over about 5 hours using a dropping pump.
- the copolymer solution having a viscosity (23 ° C.) of 93 mPa's, a solid content of 31.3% by weight, and a solution acid value of 32.5 mg-KOH / g was obtained by the same procedure as described above.
- the produced copolymer had a weight average molecular weight Mw of 12530 and a degree of dispersion of 2.51.
- a 1 L flask equipped with a reflux condenser, dropping funnel and stirrer is used to flow an appropriate amount of nitrogen to create a nitrogen atmosphere, and 150 parts by weight of 3-methoxy-1-butanol and 110 parts by weight of 3-methoxybutylacetate are added and stirred. While heating to 90 ° C. Next, in the flask, 60 parts by weight of methacrylic acid (MAA), 3, 4 epoxytricyclo [5. 2. 1. 0 2 ' 6 ] decane —9-ylatarylate (compound contained in the formula (la-1)) ) And 3, 4-epoxytricyclo [5. 2. 1.
- MAA methacrylic acid
- decane-8-yl acrylate (compounds in formula (la-2)) [ 50:50 (molar ratio)] —0? 8)
- a solution prepared by dissolving 50 parts by weight of polymerization initiator 2, 2′-azobis (2,4-dimethylbareto-tolyl) in 220 parts by weight of 3-methoxybutyl acetate was dropped over about 5 hours using another dropping pump. did.
- the temperature is kept at the same temperature for about 3 hours, and then cooled to room temperature.
- the viscosity (23 ° C) is 98 mPa's
- the solid content is 31.5% by weight
- the solution acid value is 36.
- a copolymer solution of 3 mg—KOHZg was obtained.
- the resulting copolymer had a weight average molecular weight Mw of 8700 and a dispersity of 2.06.
- Example 5 As monomers, 55 parts by weight of methacrylic acid (MAA), 175 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (E—CHM), and 70 parts by weight of N-cyclohexylmaleimide (CH Ml) were used. Otherwise, the same operation as in Example 5 was carried out to obtain a copolymer solution having a viscosity (23 ° C.) of 125 mPa ⁇ s, a solid content of 32.3% by weight, and a solution acid value of 34. Omg-KOHZg. The resulting copolymer had a weight average molecular weight Mw of 14700 and a dispersity of 2.47.
- MAA methacrylic acid
- E—CHM 3,4-epoxycyclohexylmethyl methacrylate
- CH Ml N-cyclohexylmaleimide
- a copolymer solution having a viscosity (23 ° C.) of 115 mPa's, a solid content of 31.9% by weight, and a solution acid value of 35.8 mg-KOHZg was obtained.
- the produced copolymer had a weight average molecular weight Mw of 11,800 and a dispersity of 2.15.
- a radiation-sensitive rosin composition solution was prepared in the same manner as in the above (1) storage stability test. After filtering this solution with a 0.2 m Teflon (registered trademark) filter, the film thickness is 3 ⁇ m on a glass substrate 1737 (Corning Co., Ltd., 0.7 mm thickness x 150 mm diameter). The sample was applied with a spinner, dried on a hot plate at 90 ° C for 3 minutes, and fully exposed using a high-pressure mercury lamp. Next, the entire surface of the coating film was exposed using an ultra-high pressure mercury lamp without passing through a positive mask pattern, and dried by heating at 120 ° C. for 30 minutes in a clean oven.
- Teflon registered trademark
- the substrate with the cured film thus obtained has a wavelength of 4 ⁇ !
- the minimum transmittance of ⁇ 800 nm was measured. ⁇ when the minimum transmittance is 95% or more, ⁇ when less than 85% and less than 95%, and X when less than 85%.
- a radiation-sensitive rosin composition solution was prepared in the same manner as in the above (1) storage stability test. After filtering this solution with a 0.2 m Teflon (registered trademark) filter, the film thickness is 3 ⁇ m on a glass substrate 1737 (Corning Co., Ltd., 0.7 mm thickness x 150 mm diameter). The sample was applied with a spinner, dried on a hot plate at 90 ° C for 3 minutes, and fully exposed using a high-pressure mercury lamp. Next, the coating film was heat-cured at 200 ° C. for 30 minutes in a clean oven, and then heat-treated again at 230 ° C. for 1 hour to measure the film thickness. The change in film thickness after reheating treatment is calculated as the film thickness reduction rate with respect to the film thickness after heat curing at 200 ° C for 30 minutes, and when the film thickness reduction rate is less than 3% The case is X.
- reaction solution containing epoxy (meth) acrylate) can also be used as a reactive solvent, that is, as a reactive diluent that can be cured with an active energy ray such as ultraviolet rays. It can also be used as an additive for various polymers and other compounds, either isolated or in solution.
- halogens are reacted with epoxy groups to use as halogenated alicyclic group-containing unsaturated carboxylic acid esters as flame retardant radically polymerizable monomers, or to react with other compounds to form various curable coatings. It can also be used as an intermediate for synthesizing raw materials for producing inks, adhesives, sealants, and molded articles. For example, it can be copolymerized with various radical polymerizable monomers and used as an acrylic resin having an alicyclic epoxy group in the side chain, or acrylic acid can be added to all or part of the alicyclic epoxy group in the side chain.
- curable acrylic resin having an unsaturated group or an alicyclic epoxy group and an unsaturated group in the side chain by reacting with a carboxylic acid having such an unsaturated group, for example, active energy rays for photoresists and the like It can also be used as a cured resin.
- acid-removing agent furniture coating agent, decorative coating agent, automotive primer, sealer, finish coating agent, beverage can and other can coating agent, ink for character information or image information, and electronic parts as curable monomer It can be used as a sealant.
- the resin can be incorporated into the resin and used as a photoresist resin suitable for developing a printed board or printed circuit board, a cast printing roll, or the like. Furthermore, it can be a molding compound mainly composed of unsaturated polyester and styrene and reinforced with glass, carbon, graphite or other fibers. In addition, a sheet-forming compound can be further added to obtain a molded product.
- the copolymer of the present invention is a radiation-sensitive resin, for example, g-line, i-line, excimerray for exposure.
- the one for example, XeCl, KrF, KrCl, ArF, ArCl, F
- photoresist resin in particular, an alkaline aqueous soluble photoresist resin (negative type photoresist resin).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Compounds (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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KR1020077015001A KR101255866B1 (ko) | 2004-11-30 | 2005-11-28 | 지환식 에폭시(메트)아크릴레이트 및 그의 제조 방법, 및공중합체 |
CN200580040592.9A CN101065371B (zh) | 2004-11-30 | 2005-11-28 | 脂环式环氧(甲基)丙烯酸酯及其制备方法、以及共聚物 |
US11/666,943 US20090124776A1 (en) | 2004-11-30 | 2005-11-28 | Cycloaliphatic epoxy (meth)acrylates, preparation processes thereof, and copolymers |
EP05809648A EP1818327A4 (en) | 2004-11-30 | 2005-11-28 | ALICYCLIC EPOXY (METH) ACRYLATES, PROCESS FOR THEIR PREPARATION AND COPOLYMERS |
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JP2004346860A JP2006151900A (ja) | 2004-11-30 | 2004-11-30 | 脂環式エポキシ(メタ)アクリレート及びその製造方法 |
JP2004-346860 | 2004-11-30 | ||
JP2004361381 | 2004-12-14 | ||
JP2004-361381 | 2004-12-14 |
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US (1) | US20090124776A1 (ja) |
EP (1) | EP1818327A4 (ja) |
KR (1) | KR101255866B1 (ja) |
TW (2) | TWI417286B (ja) |
WO (1) | WO2006059564A1 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
TWI417286B (zh) | 2013-12-01 |
TW201313694A (zh) | 2013-04-01 |
EP1818327A1 (en) | 2007-08-15 |
KR101255866B1 (ko) | 2013-04-17 |
TWI417287B (zh) | 2013-12-01 |
US20090124776A1 (en) | 2009-05-14 |
EP1818327A4 (en) | 2010-02-24 |
KR20070086833A (ko) | 2007-08-27 |
TW200626569A (en) | 2006-08-01 |
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