JP2010132804A - Copolymer and photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer useful as a photosensitive resin having excellent adhesivity to substrates and forming patterns having high sensitivity and high resolution. <P>SOLUTION: The copolymer is obtained by polymerizing a monomer mixture comprising at least a vinyl monomer containing a plurality of carbon-carbon double bonds in the molecule [except a (meth) acrylate derivative and a (meth)acrylamide derivative] (vinyl monomer A) and a carboxy group- or carboxylic acid anhydride group-containing vinyl monomer (vinyl monomer B). The vinyl monomer A includes a compound represented by formula (1) (wherein R<SP>1</SP>is hydrogen or hydrocarbon that may contain a substituent; R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>may be the same as or different from each other and are each hydrogen or methyl; X is connecting group; and n is an integer of 1-3). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention has a vinyl monomer having a plurality of carbon-carbon double bonds in its molecule [excluding (meth) acrylic acid ester derivatives and (meth) acrylic acid amide derivatives] and a carboxyl group or a carboxylic acid anhydride group. Copolymer with vinyl monomer, curable resin composition and photosensitive resin composition containing the copolymer, color filter produced using the photosensitive resin composition, and photosensitive resin composition The present invention relates to a color filter manufacturing method using

  Photosensitive resins used for displays are required to have high brightness and high contrast, and are particularly required for television applications. In Japanese Patent No. 4090292, a high resolution is realized by using a dye for high brightness and high contrast and using a highly sensitive resin having a radical polymerization group as the resin. However, since the developer is a dilute alkaline aqueous solution, it is essential to introduce a carboxylic acid component for dissolving in the developer. Therefore, in reality, it is impossible to introduce a functional group such as an epoxy group in the final form of the resin, so problems such as adhesion to the substrate and color residue during development actually occur. A one-layer undercoat is provided between the two to solve the problem. Further, most of the resin synthesis steps require two steps, ie, a resin polymerization step and a radical polymerization group introduction step, so that the productivity is not good.

Japanese Patent No. 4090292

An object of the present invention is to provide a copolymer useful as a photosensitive resin having excellent adhesion to a substrate and capable of forming a pattern with high sensitivity and high resolution, a curable resin composition containing the copolymer, and a photosensitive resin composition. Another object of the present invention is to provide a color filter using the photosensitive resin composition and a method for producing the color filter.
Another object of the present invention is useful as a photosensitive resin that is excellent in adhesion to a substrate, can form a pattern with high sensitivity and high resolution, and has a functional group such as a radical polymerizable group and an epoxy group at the time of resin synthesis ( Copolymers that can be introduced in a single step and can be produced with good productivity, curable resin compositions and photosensitive resin compositions containing the copolymers, and color filters and color filters using the photosensitive resin compositions It is to provide a method.

  As a result of intensive studies to achieve the above object, the present inventors have found that vinyl monomers having a plurality of carbon-carbon double bonds in the molecule [(meth) acrylic acid ester derivatives and (meth) acrylic acid amide derivatives]. And a vinyl monomer having a carboxyl group or a carboxylic acid anhydride group can be used to introduce a functional group such as a radical polymerizable group and an epoxy group (in one step) at the time of resin synthesis, resulting in high productivity. The present inventors have found that a copolymer can be obtained, and that when such a copolymer is used as a photosensitive resin, it has excellent adhesion to a substrate and can form a pattern with high sensitivity and high resolution.

  That is, the present invention is a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [excluding (meth) acrylic acid ester derivatives and (meth) acrylic acid amide derivatives] (vinyl monomer A), Provided is a copolymer obtained by polymerizing a monomer mixture containing at least a vinyl monomer having a carboxyl group or a carboxylic anhydride group (vinyl monomer B).

（式中、Ｒ¹は水素原子又は置換基を有していてもよい炭化水素基を示し、Ｒ²、Ｒ³及びＲ⁴は、同一又は異なって、水素原子又はメチル基を示し、Ｘは連結基を示す。ｎは１〜３の整数を示す）
で表される化合物が含まれる。 The vinyl monomer A has the following formula (1)

(Wherein R ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group, R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or a methyl group, and X represents Represents a linking group, n represents an integer of 1 to 3)
The compound represented by these is included.

In the vinyl monomer A, (i) in the formula (1), R ¹ is a hydrocarbon group which may have a substituent, and R ² , R ³ and R ⁴ may be the same or different. , A hydrogen atom or a methyl group, X is a —COO— group (the left end is bonded to the carbon atom to which R ² is bonded), and n = 1, (ii) in formula (1): R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom or a methyl group, X is a residue of a polycarboxylic acid, n is an integer of 1 to 3, and ( iii) In the formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom or a methyl group, and X is an n-valent hydrocarbon which may have a substituent. It is possible to use at least one compound selected from the group consisting of compounds which are groups and n is an integer of 1 to 3.

  The copolymer is obtained by polymerizing a monomer mixture containing at least a vinyl monomer A, a vinyl monomer B, and a vinyl monomer C having a 3- to 5-membered cyclic ether group. Copolymers are included.

  As the vinyl monomer C, a vinyl monomer having an alicyclic epoxy group is preferable.

  The copolymer includes a vinyl monomer A, a vinyl monomer B, a vinyl monomer C, a (meth) acrylic ester D, an aromatic monovinyl compound E, a vinyl alkoxysilane compound F, and A copolymer obtained by polymerizing a monomer mixture containing at least one monomer selected from the group consisting of hydroxyl group-containing monomers G is included.

  The present invention also provides a curable resin composition containing at least the copolymer.

  The curable resin composition further comprises at least one compound selected from the group consisting of a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. May be included.

  The present invention further provides a photosensitive resin composition comprising the copolymer and a photopolymerization initiator.

  The photosensitive resin composition further comprises at least one compound selected from the group consisting of a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. May be included.

  Moreover, said photosensitive resin composition may contain the pigment further. The photosensitive resin composition can be used for forming a liquid resist, a dry film, a pigment resist or a coating protective film.

  The present invention further provides a color filter produced using the photosensitive resin composition.

  The present invention also provides a method for producing a color filter, wherein the photosensitive resin composition is coated on a support, exposed through a mask, and developed to form a pattern.

  According to the copolymer of the present invention, a functional group such as a radical polymerizable group and an epoxy group can be introduced at the time of resin synthesis (in one step), and a resin can be synthesized with high productivity. In addition, the coating film obtained from the curable resin composition or the photosensitive resin composition containing the copolymer of the present invention has high adhesion to the base material and the substrate, and is excellent in solvent resistance and alkali resistance. . For this reason, a pattern with high sensitivity and high resolution can be formed by using the photosensitive resin composition. The photosensitive resin composition of the present invention can be suitably used for forming a dry film, a pigment resist or a coating protective film.

  The copolymer of the present invention is a vinyl monomer having a plurality of carbon-carbon double bonds in its molecule [excluding (meth) acrylic acid ester derivatives and (meth) acrylic acid amide derivatives] (vinyl monomer A). And a monomer mixture containing at least a vinyl monomer having a carboxyl group or a carboxylic acid anhydride group (vinyl monomer B) (vinyl polymerization). The copolymer of the present invention may be a random copolymer or a block copolymer. The plurality of carbon-carbon double bonds have polymerizability (particularly radical polymerizability). The type of polymerization for polymerizing the monomer mixture is not particularly limited, but radical polymerization is preferred. During this polymerization, any double bond among the plurality of carbon-carbon double bonds in the vinyl monomer A may participate in the polymerization. The vinyl monomer A can be used alone or in combination of two or more.

  As the vinyl monomer A, a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule (for example, 2 to 4, preferably 2 or 3, particularly preferably 2) [provided that ( Although it will not specifically limit if it removes a (meth) acrylic acid ester derivative and a (meth) acrylic acid amide derivative], a representative example includes a compound represented by the formula (1).

In formula (1), R ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group, R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or a methyl group, X represents a linking group. n shows the integer of 1-3.

Examples of the “hydrocarbon group” of the hydrocarbon group which may have a substituent in R ¹ include, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination of two or more of these Group. Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl and decyl groups (for example, alkyl groups having 1 to 10 carbon atoms, preferably Are alkyl groups having 1 to 6 carbon atoms, etc .; alkenyl groups such as vinyl, 1-propenyl, 1-butenyl and 1-hexenyl groups (for example, alkenyl groups having 2 to 10 carbon atoms, preferably alkenyl groups having 2 to 6 carbon atoms) Group); alkynyl groups such as ethynyl and 1-propynyl groups (for example, alkynyl groups having 2 to 10 carbon atoms, preferably alkynyl groups having 2 to 6 carbon atoms) and the like.

  Examples of the alicyclic hydrocarbon group include 3 to 15 membered cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl groups; 3 to 15 membered cycloalkenyl groups such as cyclohexenyl groups; norbornyl groups and adamantyl groups. Examples thereof include a bridged cyclic group having 4 to 15 carbon atoms.

  Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 20 carbon atoms such as phenyl and naphthyl groups. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include aralkyl groups such as benzyl and 2-phenylethyl groups.

Examples of the substituent that these hydrocarbon groups may have include, for example, an alkyl group (C _1-4 alkyl group etc.), an alkenyl group (C _2-4 alkenyl group etc.), and a haloalkyl group (C _1-4 ). Haloalkyl group, etc.), halogen atom, alkoxy group (C _1-4 alkoxy group), hydroxyl group, hydroxyalkyl group (hydroxy-C _1-4 alkyl group etc.), carboxyl group, alkoxycarbonyl group (C _1-4 alkoxy-) Carbonyl group and the like), acyl group (C _1-10 acyl group and the like), and the like.

R ¹ includes a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 15 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aralkyl group having 7 to 15 carbon atoms is preferable, and among them, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms are preferable.

R ² , R ³ , and R ⁴ may each be a hydrogen atom or a methyl group, but a hydrogen atom is particularly preferable.

Examples of the linking group in X include linear or branched alkylene groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, and hexamethylene groups (linear or branched chain having about 1 to 6 carbon atoms). A linear or branched fluoroalkylene group such as a perfluorohexamethylene group (a linear or branched fluoroalkylene group having about 1 to 6 carbon atoms); vinylene, propenylene, Linear or branched alkenylene group such as butenylene group (linear or branched alkenylene group having about 2 to 6 carbon atoms); linear or branched fluoroalkenylene group (carbon A linear or branched fluoroalkenylene group of about 2 to 6); 1,3-pentylene, 1,4-hexylene, 1,3-hexylene, hexylidene group Divalent alicyclic hydrocarbon group; phenylene, such as a naphthylene group, C _1-4 alkyl group, an aryl group, a halogen atom, C _1-4 alkoxy which may arylene have a substituent group such as ( -COO-; -OCO-; -CONH-; -NHCO-; -O-; -S-; -CO-; -CS-; -NH-; a divalent group in which two or more of these are bonded Etc.

  n is preferably 1 or 2, particularly preferably 1.

As a typical example of the vinyl monomer A, (i) in the formula (1), R ¹ is a hydrocarbon group which may have a substituent, and R ² , R ³ and R ⁴ are the same. Or a hydrogen atom or a methyl group, a compound in which X is a —COO— group (the left end is bonded to a carbon atom to which R ² is bonded), and n = 1, (ii) Formula (1 ), R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom or a methyl group, X is a residue of a polycarboxylic acid, and n is an integer of 1 to 3 , (Iii) In the formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and each is a hydrogen atom or a methyl group, and X may have a substituent. And at least one compound selected from the group consisting of compounds which are hydrocarbon groups and n is an integer of 1 to 3.

  Examples of the compound corresponding to the above (i) include, for example, vinyl crotonate, vinyl cinnamate, vinyl sorbate and the like.

  Examples of the compound corresponding to the above (ii) include divinyl oxalate, divinyl succinate, divinyl malonate, divinyl adipate, divinyl 1,4-cyclohexanecarboxylate, divinyl terephthalate, and the like.

  As an example of the compound corresponding to the formula (iii), for example, it may have a fluorine atom having a carbon-carbon double bond (vinyl group) at both ends, such as 1,6-divinyl (perfluorohexane). Aliphatic hydrocarbons; divinylbenzene, 1,2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,2-divinyl-3,4-dimethylbenzene, 2,4-divinyl Aromatic polyvinyl compounds such as biphenyl, 3,5,4'-trivinylbiphenyl, 1,3,5-trivinylbenzene and the like can be mentioned.

  As said vinyl monomer B, unsaturated carboxylic acid or its acid anhydride is mentioned. Examples of unsaturated carboxylic acids and acid anhydrides include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid, and acid anhydrides thereof (maleic anhydride). , Itaconic anhydride, etc.). Among these, acrylic acid and methacrylic acid are particularly preferable. The vinyl monomer B can be used alone or in combination of two or more.

  The copolymer of the present invention has at least a monomer unit corresponding to the vinyl monomer A and a monomer unit corresponding to the vinyl monomer B. Each of these monomer units may be one kind or two or more kinds.

  The proportion of the monomer unit corresponding to the vinyl monomer A in the copolymer is, for example, 1 to 99% by weight, preferably 2 to 90% by weight, more preferably, based on all monomer units constituting the copolymer. Is from 2 to 70% by weight. If this ratio is too small, the sensitivity tends to decrease, and if it is too large, the hydrophobicity of the resin itself increases, so that it is difficult to dissolve in the developer.

  The proportion of the monomer unit corresponding to the vinyl monomer B in the copolymer varies depending on the type of the vinyl monomer B used. It is -99 weight%, Preferably it is 2-90 weight%, More preferably, it is 2-70 weight%. If this ratio is too small, the hydrophilicity of the resin is low and it is difficult to dissolve in the developer. If it is too high, the hydrophilicity of the resin is high and the chemical resistance of the coating film tends to be lowered.

  The proportion of the total monomer units corresponding to vinyl monomer A and the monomer units corresponding to vinyl monomer B in the copolymer is, for example, 5 to 100 with respect to all monomer units constituting the copolymer. % By weight, preferably 10 to 100% by weight, more preferably 12 to 100% by weight.

  The copolymer of the present invention may be a copolymer obtained by polymerizing a monomer mixture containing another vinyl monomer together with the vinyl monomer A and the vinyl monomer B. Other vinyl monomers can be used alone or in combination of two or more.

  Examples of such other vinyl monomers include a vinyl monomer C having a 3- to 5-membered cyclic ether group, a (meth) acrylic acid ester D, an aromatic monovinyl compound E, a vinylalkoxysilane compound F, Examples thereof include a hydroxyl group-containing monomer G.

  The vinyl monomer C having a 3- to 5-membered cyclic ether group includes an oxirane ring (epoxy group) -containing polymerizable unsaturated compound, an oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound, and an oxolane ring (oxolanyl group). Contains polymerizable unsaturated compounds.

Examples of the oxirane ring (epoxy group) -containing polymerizable unsaturated compound include oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, and 2-oxy Polymerizable unsaturated compounds containing an oxirane ring (monocyclic) such as ranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate, etc. ((Meth) acrylic acid ester derivatives, etc.); 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate Epoxy group-containing cyclohexane such as 3,4-epoxycyclohexane ring such as 2- (3,4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate and 3- (3,4-epoxycyclohexylmethyloxy) propyl (meth) acrylate Polymerizable unsaturated compounds containing an alkane ring (such as (meth) acrylic acid ester derivatives); 5,6-epoxy-2 such as 5,6-epoxy-2-bicyclo [2.2.1] heptyl (meth) acrylate A polymerizable unsaturated compound containing a bicyclo [2.2.1] heptane ring (such as a (meth) acrylic acid ester derivative); an epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5.2] 1.0 ^2,6 ] decan-9-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1. 0 ^2,6 ] decan-8-yl (meth) acrylate, or mixtures thereof], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1. 0 ^2,6 ] decan-9-yloxy) ethyl (meth) acrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate Or a mixture thereof], 3,4-epoxytricyclo [5.2.1.0 ^2,6 such as epoxidized dicyclopentenyloxybutyl (meth) acrylate, epoxidized dicyclopentenyloxyhexyl (meth) acrylate, etc. And polymerizable unsaturated compounds containing a decane ring (such as (meth) acrylic acid ester derivatives). As another oxirane ring (epoxy group) -containing polymerizable unsaturated compound, a vinyl ether compound containing an epoxy group, an allyl ether compound containing an epoxy group, an aromatic vinyl compound containing an epoxy group, or the like can also be used. Examples of the aromatic vinyl compound containing an epoxy group include styrene derivatives such as 4-vinylbenzylglycidyl ether, 4-vinylbenzyloxirane, 4-vinylphenethyloxirane.

  Examples of the oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound include oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, (3- Methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-oxetanyl) ethyl (meth) acrylate, 2- (3-ethyl -3-Oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[(3-ethyl-3-oxetanyl) methyloxy] ethyl (meta ) Acrylate, 3-[(3-Methyl-3-oxetanyl) methyloxy] propyl Pill (meth) acrylate, 3 - and [(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, vinyl ether compounds containing oxetanyl group, and allyl ether compounds containing oxetanyl group.

  Examples of the oxolane ring (oxolanyl group) -containing polymerizable unsaturated compound include tetrahydrofurfuryl (meth) acrylate, vinyl ether compounds containing an oxolanyl group, and allyl ether compounds containing an oxolanyl group.

  When the copolymer of the present invention has a 3- to 5-membered cyclic ether group [oxirane ring (epoxy group), oxetane ring (oxetanyl group), oxolane ring (oxolanyl group)], these groups are used as curable groups. Works. The 3- to 5-membered cyclic ether group mainly contributes to improvement of chemical resistance (solvent resistance, alkali resistance, etc.). The vinyl monomer C which has a 3-5 membered cyclic ether group can be used individually by 1 type or in combination of 2 or more types.

As the vinyl monomer C having a 3- to 5-membered cyclic ether group, an oxirane ring (epoxy group) -containing polymerizable unsaturated compound is particularly preferable, and in particular, a polymerizable unsaturated compound containing an epoxy group-containing cycloalkane ring. A polymerizable unsaturated compound containing a 5,6-epoxy-2-bicyclo [2.2.1] heptane ring, and a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring A vinyl monomer having an alicyclic epoxy group such as a polymerizable unsaturated compound is preferred.

  When the copolymer of the present invention has a monomer unit corresponding to the vinyl monomer C, the proportion of the monomer unit in the copolymer is, for example, 1 to 1 with respect to all the monomer units constituting the copolymer. It is 99 weight%, Preferably it is 2-90 weight%, More preferably, it is 2-85 weight%. If this ratio is too small, the chemical resistance and adhesion of the coating film are likely to be lowered, and if it is too large, the hydrophobicity of the resin is increased and it is difficult to dissolve in the developer.

（式中、Ｒ⁵は水素原子又はメチル基を示し、Ｒ⁶は炭化水素基置換オキシ基を有していてもよい炭素数１〜２５の炭化水素基を示す）
で表される化合物が挙げられる。 Examples of the (meth) acrylic acid ester D include the following formula (2):

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrocarbon-substituted oxy group)
The compound represented by these is mentioned.

Examples of the hydrocarbon group having 1 to 25 carbon atoms in R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, Alkyl groups such as hexadecyl (cetyl), heptadecyl, octadecyl (stearyl), nonadecyl, icosyl and docosyl (behenyl) groups; alicyclic hydrocarbon groups such as cyclohexyl, dicyclopentanyl and isobornyl groups; 10-cyclohexyldecyl, 12 A group in which an alicyclic hydrocarbon group such as cyclohexyldodecyl, 14-cyclohexyltetradecyl, or 16-cyclohexylhexadecyl group is bonded to an alkyl group; an aryl group such as a phenyl group; benzyl, 1-phenylethyl, 2-phenyl Ethyl, 4-phenyl Aralkyl groups such as til, 6-phenylhexyl, 8-phenyloctyl, 10-phenyldecyl, 12-phenyldodecyl, 14-phenyltetradecyl, 16-phenylhexadecyl; groups in which two or more of these are bonded .

  Examples of the hydrocarbon group-substituted oxy group that the hydrocarbon group having 1 to 25 carbon atoms may have include, for example, alkoxy groups such as methoxy and ethoxy groups (for example, alkoxy groups having 1 to 10 carbon atoms); phenoxy groups Aryloxy groups such as cyclohexyloxy groups, alicyclic hydrocarbon group-substituted oxy groups such as cyclohexyloxy groups, dicyclopentanyloxy groups, etc .; C 1-15 such as aralkyloxy groups such as benzyloxy groups (preferably 1 carbon atoms) -12) hydrocarbon group-substituted oxy groups and the like.

  Representative examples of the (meth) acrylic acid ester represented by the formula (2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (Meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, Examples include cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.

  In addition to the above, (meth) acrylic acid ester D includes, for example, (meth) acrylic acid ester having an isocyanate group or blocked isocyanate group, (meth) acrylic acid ester having alkoxysilyl group, and a group having a hindered amine structure. Examples include (meth) acrylic acid esters.

  Examples of the (meth) acrylic acid ester having an isocyanate group or a blocked isocyanate group include, for example, 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (= 2- (1-methylpropylideneamino). Oxycarbonylaminoethyl) methacrylate) [trade name “Karenz MOI-BM”, manufactured by Showa Denko KK], 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl methacrylate [trade name “Karenz MOI- BP ", manufactured by Showa Denko KK] and the like.

  Examples of (meth) acrylic acid ester having an alkoxysilyl group include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and γ- (meth) acryloyloxypropylmethyldimethoxy. Silane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane And alkoxysilyl group-containing polymerizable unsaturated compounds such as γ- (meth) acryloyloxybutylphenyldimethoxysilane and γ- (meth) acryloyloxybutylphenyldiethoxysilane.

  Examples of the (meth) acrylic acid ester having a group having a hindered amine structure include trade names “ADK STAB LA-82” and “ADEKA STAB LA-87” [manufactured by ADEKA Corporation].

  Examples of the aromatic monovinyl compound E include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, and vinyl biphenyl.

  Examples of the vinylalkoxysilane compound F include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane.

  Examples of the hydroxyl group-containing monomer G include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Polyhydric alcohols and acrylics such as hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, etc. A compound obtained by ring-opening polymerization of ε-caprolactone to a monoesterified product of acid or methacrylic acid or a monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid (product of Daicel Chemical Industries, Ltd. Le FA series, PLACCEL FM series, etc.), ethylene oxide, or propylene oxide ring-opening polymerization with hydroxyl group-containing compounds, and the like.

  The copolymer of the present invention corresponds to at least one monomer selected from the group consisting of (meth) acrylic acid ester D, aromatic monovinyl compound E, vinylalkoxysilane compound F, and hydroxyl group-containing monomer G. In the case where the monomer unit is used, the proportion of the monomer unit in the copolymer is generally 2 to 60% by weight, preferably 2 to 50% by weight, and more preferably 5 to 40% by weight.

  As a preferred embodiment of the copolymer of the present invention, (1) a monomer unit corresponding to vinyl monomer A and a monomer unit corresponding to vinyl monomer B total 5% by weight or more (particularly 10% by weight) of the total monomer units. (2) a vinyl having a monomer unit corresponding to vinyl monomer A, a monomer unit corresponding to vinyl monomer B, and a 3- to 5-membered cyclic ether group A copolymer containing 40% by weight or more (particularly 50% by weight or more) of the total monomer units corresponding to the monomer C, and (3) a monomer unit and a vinyl monomer corresponding to the vinyl monomer A A monomer unit corresponding to B, a monomer unit corresponding to a vinyl monomer C having a 3- to 5-membered cyclic ether group, a (meth) acrylate ester D, an aromatic monovinyl compound E, a vinyl alkoxysilane Copolymers containing 40% by weight or more (particularly 50% by weight or more) of the total monomer units corresponding to at least one monomer selected from the group consisting of a monomer group F and a hydroxyl group-containing monomer G A polymer is mentioned.

  The copolymer of the present invention comprises the vinyl monomer A, a vinyl monomer B having a carboxyl group or an acid anhydride group, and a vinyl monomer having a 3- to 5-membered cyclic ether group, if necessary. Copolymerization of a monomer mixture containing the compound C, (meth) acrylic acid ester D, aromatic monovinyl compound E, vinylalkoxysilane compound F, and other copolymerizable monomers such as hydroxyl group-containing monomer G It can be produced by attaching to (vinyl polymerization).

  As the polymerization initiator used for polymerization, a normal radical initiator can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), Dimethyl-2,2'-azobis (2-methylpropionate), 2,2-azobis (isobutyric acid) dimethyl, diethyl-2,2'-azobis (2-methylpropionate), dibutyl-2,2 Azo compounds such as' -azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, organic peroxides such as 1,1-bis (t-butylperoxy) cyclohexane, peroxide Examples include hydrogen. When a peroxide is used as a radical polymerization initiator, a redox initiator may be combined with a reducing agent. Of these, azo compounds are preferred, and in particular, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (isobutyric acid) dimethyl. preferable.

  The amount of the polymerization initiator used can be appropriately selected within a range that does not impair smooth copolymerization, but is usually about 1 to 30% by weight, preferably based on the total amount of all monomer components and polymerization initiator. It is about 5 to 25% by weight.

  In the present invention, a chain transfer agent generally used in radical polymerization may be used in combination. Specific examples include thiols (such as n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan). Mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, thiomalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), α-methylstyrene dimer , Terbinolene, myrcene, limonene, α-pinene, β-pinene and the like, and the amount of the chain transfer agent is preferably 0.001 to 3% by weight based on the amount of the total radical polymerizable monomer. is there. When using a chain transfer agent, it is preferable to mix with a polymerizable vinyl monomer in advance.

  The polymerization can be performed 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. For example, a method in which a solution in which a polymerization initiator is dissolved in a polymerization solvent is dropped into a mixed solution of a monomer and a polymerization solvent kept at a constant temperature, or the monomer and the polymerization initiator are dissolved in the polymerization solvent in advance. A method in which the solution 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 according to the monomer composition and the like. As a polymerization solvent, for example, ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether (diethylene glycol dialkyl ether such as diethylene glycol methyl ethyl ether), propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, Dipropylene glycol mono or dialkyl ether (such as dipropylene glycol dialkyl ether such as dipropylene glycol dimethyl ether), tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl Ether, 1,4-butanediol mono- or dialkyl Chain ethers such as glycol ethers such as ether, glycerin mono, di or trialkyl ethers; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, 3- Carboxylic acid esters such as methyl methoxypropionate, ethyl 3-ethoxypropionate, C _5-6 cycloalkanediol mono- or diacetate, C _5-6 cycloalkane dimethanol mono- or diacetate; ethylene glycol monoalkyl ether acetate, Ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol Rumono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propanediol mono or diacetate, 1,3-butanediol mono Alkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, 1,6-hexanediol mono or diacetate, glycerin mono , Di or triacetate, glycerin mono or di C _1-4 alkyl ether di or mono acetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate Glycol acetates or glycol ether acetates, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amides (N, N-dimethyl) Acetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanedimethanol, etc.), hydrocarbon (benzene, Aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, and a mixed solvent thereof. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.

  The copolymer of this invention produces | generates by the said method. The weight average molecular weight of a copolymer is 500-1 million, for example, Preferably it is 5000-500000, More preferably, it is about 10,000-200000. The degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer is about 1 to 3.

  The produced copolymer can be purified by precipitation or reprecipitation. Known or well-known methods can be applied to precipitation and reprecipitation.

  The curable resin composition of the present invention contains at least the copolymer of the present invention. The curable resin composition of the present invention is further adjusted as necessary after adjusting the solid content concentration, exchanging the solvent, or performing a filtration treatment on the polymerization solution obtained by the above method as necessary. , Curing catalyst [thermal acid generator (thermal curing catalyst, thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization initiator)], photo radical initiator, curing agent, curing accelerator, addition Agents (fillers, antifoaming agents, flame retardants, antioxidants, UV absorbers, stress reducing agents, flexibility imparting agents, waxes, resins, crosslinking agents, halogen trapping agents, leveling agents, wetting improvers, etc. ), Pigments and the like. The curable resin composition and photosensitive resin composition of the present invention include fine particles such as glass, silica, ceramics, metal oxides, metal nitrides, metal carbides, metals, clay minerals, rubber, and polymer compounds, and organic compounds. Metal complexes, carbon compounds such as C60 / carbon nanotubes, and the like can be blended. Moreover, the polymer produced | generated by superposition | polymerization can be refine | purified by precipitation or reprecipitation, etc., The curable resin composition can also be obtained by melt | dissolving this refine | purified polymer in the solvent according to a use with the said appropriate additive. .

  The curable resin composition contains at least one compound selected from the group consisting of a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. Also good. As the solvent constituting the curable resin composition, those exemplified as the polymerization solvent can be used. The curable resin composition of this invention can be used as a photosensitive resin composition by selecting the component to mix | blend.

  The photosensitive resin composition of the present invention contains one or more of the copolymers of the present invention and a photopolymerization initiator. The photosensitive resin composition further includes at least one compound selected from the group consisting of a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. You may go out.

  Examples of the compound having a radical polymerizable double bond include (meth) acrylic acid esters, vinyl aromatic compounds such as styrene, amide unsaturated compounds, and the like. As typical (meth) acrylic acid esters, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters; having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone-modified 2-hydroxyethyl (meth) acrylate (meta ) Acrylic acid esters; methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy (Meth) acrylates (polyalkylene glycol monoether mono (meth) acrylates) such as reethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypolyethylene glycol # 400- (meth) acrylate; 1,6 -Bifunctional (meth) acrylates such as hexanediol di (meth) acrylate and neopentylglycol di (meth) acrylate; Trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate Polyfunctional (meth) acrylic acid ester etc. are mentioned.

  A polymerizable prepolymer can also be used as the compound having a radically polymerizable double bond. Examples of the polymerizable prepolymer include (meth) acrylic acid esters of polyester polyol, (meth) acrylic acid esters of polyether polyol, an adduct of a polyepoxy compound and (meth) acrylic acid, and a polyol. Examples thereof include a resin in which hydroxy (meth) acrylate is introduced through an isocyanate.

  As the compound having a radical polymerizable double bond, a polyfunctional vinyl compound such as a polyfunctional (meth) acrylic acid ester is preferable. The compounds having a radical polymerizable double bond can be used singly or in combination of two or more. By blending a compound having a radical polymerizable double bond in the photosensitive resin composition, higher sensitivity and higher resolution can be realized, and film properties are also improved. Furthermore, since a compound having a radical polymerizable double bond can be used as a substitute for a diluting solvent, it is also effective for viscosity adjustment and high solidification.

  The polyfunctional thiol compound may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate , Ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris-3-mercaptobutyrate, pentaerythritol tetrakisthioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis-3-mercaptobutyrate, tris (2-hydroxyethyl) isocyanine trimercaptopropionate 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, tetraethylene glycol bis- 3-mercaptopropionate, trimethylolpropane tris 3-mercaptopropionate, tris (3-mercaptopropionyloxyethyl) isocyanurate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis 3-mercaptopropio 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like. A polyfunctional thiol compound can be used individually by 1 type or in combination of 2 or more types. By blending a polyfunctional thiol compound in the photosensitive resin composition, higher sensitivity and higher resolution can be realized, and film properties can be improved. Furthermore, since the polyfunctional thiol compound can be used as a substitute for a diluting solvent, it is effective for viscosity adjustment and high solidification.

  As the hindered amine compound, a compound generally referred to as a hindered amine light stabilizer (HALS) can be used. For example, the following compounds are exemplified. In the formulas (3h), (3i), (3o), (3q), and (3r), m represents an integer of 1 or more. A hindered amine type compound can be used individually by 1 type or in combination of 2 or more types. By blending a hindered amine compound in the photosensitive resin composition, higher sensitivity and higher resolution can be realized, and film physical properties are also improved.

  Examples of the epoxy compound include unsaturated group-containing epoxidized resins such as epoxidized polybutadiene and epoxidized butadiene styrene block copolymers (there are commercially available products such as Epolide PB and ESBS manufactured by Daicel Chemical Industries), and fats. Cyclic epoxy resins (for example, Daicel Chemical Co., Ltd., Celoxide 2021, EHPE; Mitsui Petrochemical Co., Ltd., Epomic VG-3101; Yuka Shell Epoxy Co., Ltd., E-1031S; Mitsubishi Gas Chemical Co., Ltd.) ), TETRAD-X, TETRAD-C; Nippon Soda Co., Ltd., EPB-13, EPB-27, etc.), copolymer type epoxy resin (for example, glycidyl methacrylate and styrene copolymer, glycidyl methacrylate and CP made by Nippon Oil & Fats Co., Ltd., which is a copolymer of styrene and methyl methacrylate 50M, CP-50S, or there copolymers such as glycidyl methacrylate and cyclohexyl maleimide), others, and epoxy resin or the like having a special structure.

  In addition, as an epoxy compound, a novolak type epoxy resin [for example, a novolak obtained by reacting phenols such as phenol, cresol, halogenated phenol and alkylphenol with formaldehyde in the presence of an acidic catalyst, and epichlorohydrin and / or methyl epichlorohydrin] Products obtained by reaction (as commercial products, Nippon Kayaku Co., Ltd., EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN-S; manufactured by Dow Chemical Co., Ltd., DEN-431, DEN-439; manufactured by Dainippon Ink & Chemicals, Inc., N-73, VH-4150, etc.)], bisphenol type epoxy resins (for example, bisphenol A, bisphenol F, bisphenol S, and tetrabromobis) F A product obtained by reacting bisphenols such as Nord A with epichlorohydrin, or a product obtained by reacting a diglycidyl ether of bisphenol A, a condensate of the bisphenols with epichlorohydrin (as a commercial product, an oiled shell ( Co., Ltd., Epicoat 1004, Epicoat 1002; Dow Chemical Co., Ltd., DER-330, DER-337, etc.)], trisphenolmethane, triscresol methane and other epichlorohydrin and / or methyl epichlorohydrin. (Commercially available from Nippon Kayaku Co., Ltd., EPPN-501, EPPN-502, etc.), tris (2,3-epoxypropyl) isocyanurate, biphenyldiglycidyl ether, etc. can also be used. .

  These epoxy compounds (epoxy resins) can be used alone or in combination of two or more. By blending an epoxy compound in the photosensitive resin composition, higher sensitivity and higher resolution can be realized, and film physical properties are also improved.

  As the oxetane compound, for example, 3-ethyl-3-hydroxymethyloxetane [manufactured by Toagosei Chemical Industry Co., Ltd., “OXT-101”], 2-ethylhexyloxetane [manufactured by Toagosei Chemical Industry Co., Ltd., “OXT- 212 "], xylylenebisoxetane [manufactured by Toagosei Chemical Co., Ltd.," OXT-121 "], 3-ethyl-3- [3-ethyloxetane-3-ylmethoxymethyl] oxetane [Toagosei Chemical Industry ( Co., Ltd., "OXT-221"] etc. are mentioned.

  These oxetane compounds can be used alone or in combination of two or more. By blending an oxetane compound in the photosensitive resin composition, higher sensitivity and higher resolution can be realized, and film physical properties are also improved.

  Examples of the vinyl ether compound include pentaerythritol tetravinyl ether, trimethylolpropane trivinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexanediol divinyl ether, nonanediol divinyl ether, 1,4-butanediol divinyl ether, allyl Examples include vinyl ether, triethylene glycol monovinyl ether, cyclohexanedimethanol monovinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and the like.

  These vinyl ether compounds can be used alone or in combination of two or more. By blending a vinyl ether compound in the photosensitive resin composition, higher sensitivity and higher resolution can be realized, and film properties are also improved.

  The compounding amount of the compound having a radical polymerizable double bond, the polyfunctional thiol compound, the hindered amine compound, the epoxy compound, the oxetane compound, and the vinyl ether compound to the curable resin composition or the photosensitive resin composition is the above-mentioned present invention. For example, 0.1 to 40 parts by weight, preferably 1 to 25 parts by weight, and more preferably 1.5 to 15 parts by weight with respect to 100 parts by weight of the copolymer. Moreover, the total compounding amount of these compounds in the curable resin composition and the photosensitive resin composition is, for example, 0.1 to 40 parts by weight, preferably 1 with respect to 100 parts by weight of the copolymer of the present invention. -25 parts by weight, more preferably 1.5-15 parts by weight.

  As the photopolymerization initiator, a photo radical initiator, a photo acid generator, or the like can be used. A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  Examples of the photo radical initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, orthobenzoyl. Methyl benzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd. Kayacure EPA), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd. Kayacure DETX etc.), 2-methyl-1 -[4- (Methyl) phenyl] -2-morpholinopropanone-1 (Irgacure 907, etc., manufactured by Ciba-Gaigi Co., Ltd.), 2-dimethylamino-2- (4-morpholino) benzoyl-1-pheni 2-amino-2-benzoyl-1-phenylalkane compounds such as propane, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4, Aminobenzene derivatives such as 4-bisdiethylaminobenzophenone, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (Hodogaya Chemical Co., Ltd.) Imidazole compounds such as B-CIM etc.), halomethylated triazine compounds such as 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-triazine, 2 -Halomethyl oxadi, such as trichloromethyl-5- (2-benzofuran-2-yl-ethenyl) -1,3,4-oxadiazole Tetrazole compounds etc. alone or in combination can be used, it can be added photosensitizer, if necessary.

  Examples of the photoacid generator include Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, trade name of Union Carbide, USA), Irgacure 261 (Ciba Specialty Chemicals) Product name), SP-150, SP-151, SP-170, Optomer SP-171 (above, manufactured by Asahi Denka Kogyo Co., Ltd., product name), CG-24-61 (manufactured by Ciba Specialty Chemicals, Product name), DAICATII (manufactured by Daicel Chemical Industries, Ltd., product name), UVAC1591 (manufactured by Daicel-Cytec Co., Ltd., product name), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734 , CI-2855, CI-2823, CI-2758 , Nippon Soda Co., Ltd., trade name), PI-2074 (Rhone-Poulenc, trade name, pentafluorophenyl borate toluylcumyl iodonium salt), FFC509 (3M product, trade name), BBI-102, BBI-101 , BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (trade name, manufactured by Midori Chemical Co., Ltd.), CD-1012 (trade name, manufactured by Sartomer, USA) ) And the like, and diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, and the like can be used.

  As a photopolymerization initiator, from the viewpoint of sensitivity and chemical resistance, a combination of an imidazole compound and an aminobenzene derivative, 2-amino-2-benzoyl-1-phenylalkane compound, halomethylated triazine compound, halomethyloxadiazole Compounds and the like are preferred.

  The photosensitive resin composition of this invention may contain the thermal acid generator as needed. Examples of the thermal acid generator include Sun-Aid SI-45, Same as left SI-47, Same as left SI-60, Same as left SI-60L, Same as left SI-80, Same as left SI-80L, Same as left SI-100, Same as left SI-100L, Same as left SI-145, SI-150, LE-SI-160, SI-110L, SI-180L, SI-180L (product of Sanshin Chemical Co., Ltd., trade name), CI-2921, CI-2920, CI-2946, CI -3128, CI-2624, CI-2639, CI-2064 (above, Nippon Soda Co., Ltd., product name), CP-66, CP-77 (Asahi Denka Kogyo Co., product name), FC-520 Diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, etc. You can use.

  The addition amount of a photoinitiator is 0.05-10 weight% with respect to the said copolymer (resin content) in the photosensitive resin composition, for example, Preferably it is 0.5-5 weight%.

  These photopolymerization initiators can also contain a synergist, such as a tertiary amine, to enhance the conversion of light absorption energy into polymerization initiation free radicals. In addition, when hardening the curable resin composition of this invention by electron beam irradiation, addition of an initiator is not necessarily required.

  The photosensitive resin composition thus obtained has high sensitivity and high resolution by curing, has high adhesion to a substrate and a substrate, and is excellent in chemical resistance such as solvent resistance and alkali resistance. A cured product (cured film or the like) can be obtained. Therefore, it is useful as a paint, a coating agent, an adhesive, and the like, and can be suitably used as a resin composition for forming a liquid resist, a dry film, and a coating protective film that are particularly in the field of electronic materials.

  Moreover, it can be used suitably also for pigment resists, such as a color filter and a black matrix, by containing a pigment in the photosensitive resin composition. For example, pigments and dispersants are dispersed using paint conditioners, sand grinders, ball mills, roll mills, stone mills, jet mills, homogenizers, etc. and added to the photosensitive resin composition and used for liquid crystal displays. Pigment resists such as color filters and black matrices can be prepared.

  As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perinone, various inorganic pigments are also used. Is possible. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” listed below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment Blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, Preferably, C.I. I. Pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. Pigment Violet 23.

  Moreover, when forming the resin black matrix of a color filter using a pigment composition (pigment), a black coloring material (pigment) can be used. The black color material may be a black color material alone or a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. [Note that the numbers in parentheses above indicate the color index (CI)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B.

  Made by Degussa: Printex 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 85, Printex 85, Printex 85, Printex 85, Printex 85, Printex 85 P, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 5, Speck Black, Special Black 350, Special Black 350, Special Black 250, Special Black 350, Special Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170.

  Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8.

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

  As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment. These various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

  These pigments have an average particle diameter of 1 μm, preferably 0.5 μm or less (for example, 0.005 to 0.5 μm), and more preferably 0.25 μm or less (for example, 0.01 to 0.25 μm). Is preferred.

  As a compounding quantity of a pigment, the range of 15-60 weight part is preferable with respect to 100 weight part of total solids except a pigment. In the case of a composition for a black matrix containing a black pigment such as carbon black, the blending amount of the pigment is preferably in the range of 50 to 150 parts by weight with respect to 100 parts by weight of the total solid content excluding the pigment. The range of 70 to 140 parts by weight is more preferable, and the range of 90 to 130 parts by weight is particularly preferable.

  As a dispersing agent, in order to disperse | distribute a pigment favorably, it mix | blends with the photosensitive resin composition as needed. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.

  That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymer surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.

  Specific examples of the polymer dispersant include trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), and SOLPERSE (manufactured by GENECA). , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. These may be used individually by 1 type, and may mix and use 2 or more types.

  The weight average molecular weight (Mw) in terms of polystyrene by GPC of these polymer dispersants is 700 or more, preferably 1000 or more and 100,000 or less, preferably 50,000 or less. In particular, as the urethane-based and acrylic polymer dispersant, Disperbyk 160 to 166 series, Disperbyk 2000, 2001, etc. (both manufactured by Big Chemie) are preferable.

  As the acrylic polymer dispersant, it is preferable to use a random copolymer, a graft copolymer, or a block copolymer. These copolymers can be produced by a known method.

  The dispersant may be a pigment derivative, and examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, and indanthrene. , Perylene-based, perinone-based, diketopyrrolopyrrole-based and dioxazine-based derivatives, among which quinophthalone-based is preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in a combination of two or more. Further, it is preferable to use a polymer dispersant and a pigment derivative in combination as the dispersant.

  Moreover, solid content other than the said component can be mix | blended with the photosensitive resin composition of this invention as needed. Examples of these components include surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, development improvers, and the like. As the solvent for the photosensitive resin composition, those exemplified as the polymerization solvent can be used.

  Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but nonionic surfactants are used because they are unlikely to adversely affect various properties. It is preferable to use it.

  The concentration range of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, most preferably, based on the total amount of the composition. It is in the range of 0.03 to 0.3% by weight.

  As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight with respect to the total solid content of the composition.

  Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The blending amount of these plasticizers is preferably in the range of 10% by weight or less with respect to the total solid content of the composition.

  By curing the curable resin composition, a cured product having excellent physical properties can be obtained. For example, the curable resin composition is applied to various substrates or substrates (supports) by a method such as a spin coater or a slit coater to form a coating film, and then cured by curing the coating film. You can get things. Examples of the base material or substrate include glass, ceramic, silicon wafer, metal, and plastic. Coating with a spin coater, slit coater, or the like can be performed by a known method.

  Curing of the coating film is performed by heating, irradiating and irradiating active energy rays, or heating after exposure. When the curable resin composition is cured by heat, the heating temperature is in the range of 50 ° C to 260 ° C, preferably in the range of 80 ° C to 240 ° C. When the curable resin composition is cured by light, light of various wavelengths, for example, ultraviolet rays, X-rays, g-rays, i-rays, excimer lasers, etc. are used for exposure. Although the thickness of the coating film after hardening can be suitably selected according to a use, generally it is 0.1-40 micrometers, Preferably it is 0.3-20 micrometers, More preferably, it is about 0.5-10 micrometers.

  Moreover, when using the said photosensitive resin composition, after apply | coating this to a support body, it can expose through a mask, can develop, and can develop a color filter by forming. Known or well-known methods can be applied to procedures and operations for producing the color filter.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the weight average molecular weight (polystyrene conversion) and dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the produced | generated copolymer were measured on condition of the following.
Device: Detector: RID-10A (Shimadzu Corporation)
Pump: LC-10ADVP (Shimadzu Corporation)
System controller: SCL-10AVP (Shimadzu Corporation)
Degasser: DGU-14A (Shimadzu Corporation)
Autoinjector: SIL-10AF (Shimadzu Corporation)
Column: Waters Styragel HR3, Styragel HR4, Styragel HR5, 3 in total Mobile phase: THF
Flow rate: 1mL / min
Temperature: Oven (40 ° C), RI (40 ° C)
Detector: RI POLARITY (+)
Injection volume: 50μL

Synthesis example 1
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer is flowed with a suitable amount of nitrogen to form a nitrogen atmosphere. 235 parts by weight of propylene glycol monomethyl ether and 35 parts by weight of propylene glycol monomethyl ether acetate are added and stirred at 75 ° C. Until heated. Subsequently, 250 parts by weight of methacrylic acid and 250 parts by weight of vinyl crotonate (manufactured by Nippon Vinyl Biological Poval Co., Ltd.) were dropped into the flask over about 4 hours using a dropping pump. On the other hand, a solution prepared by dissolving 30 parts by weight of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 200 parts by weight of propylene glycol monomethyl ether acetate was dropped over about 4 hours using another dropping pump. did. After completion of the dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 50.5% by weight and an acid value of 290 mg-KOH / g. The weight average molecular weight Mw of the produced copolymer was 19000.

Synthesis example 2
The monomer composition was 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo [5.2.1.02,6] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1. Synthetic Example 1 except that the mixture was changed to 385 parts by weight of a mixture of [02,6] decan-8-yl acrylate [50:50 (molar ratio)] and 25 parts by weight of vinyl crotonate (manufactured by Nihon Acetate / Poval). It carried out like. A copolymer solution having a solid content of 50.5% by weight and an acid value of 106 mg-KOH / g was obtained. The weight average molecular weight Mw of the produced copolymer was 12000.

Synthesis example 3
The same procedure as in Synthesis Example 1 was performed except that vinyl crotonate (Nippon Acetate / Poval) was changed to vinyl sorbate (Nippon Acetate / Poval). A copolymer solution having a solid content of 50.8% by weight and an acid value of 113 mg-KOH / g was obtained. The weight average molecular weight Mw of the produced copolymer was 19000.

Synthesis example 4
It carried out similarly to the synthesis example 1 except having changed vinyl crotonate (Nippon Vinegar-Poval Co., Ltd. product) into vinyl cinnamate (Nippon Acetate-Poval Co., Ltd. product). A copolymer solution having a solid content of 50.3% by weight and an acid value of 104 mg-KOH / g was obtained. The weight average molecular weight Mw of the produced copolymer was 15000.

Synthesis example 5
The monomer composition was 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo [5.2.1.02,6] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1. [02: 6] Mixture of decan-8-yl acrylate [50:50 (molar ratio)] 285 parts by weight, cyclohexyl methacrylate 100 parts by weight, vinyl crotonate (Nippon Acetate / Poval) 25 parts by weight The same procedure as in Synthesis Example 1 was performed except that. A copolymer solution having a solid content of 50.2% by weight and an acid value of 110 mg-KOH / g was obtained. The weight average molecular weight Mw of the produced copolymer was 17000.

Synthesis Example 6
The monomer monomer composition was 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo [5.2.1.02,6] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1]. .02,6] Decan-8-yl acrylate mixture [50:50 (molar ratio)] It was carried out in the same manner as in Synthesis Example 1 except that the weight was changed to 410 weight. A copolymer solution having a solid content of 49.8% by weight and an acid value of 110 mg-KOH / g was obtained. The produced copolymer had a weight average molecular weight Mw of 10,000.

Example 1
50 parts by weight of the copolymer solution obtained in Synthesis Example 1, 49 parts by weight of propylene glycol monomethyl ether acetate, and 1 part by weight of Irgacure 184 (photo radical initiator; manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator were blended. A photosensitive resin composition was obtained.

Example 2
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the copolymer solution was changed to the copolymer solution obtained in Synthesis Example 2.

Example 3
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the copolymer solution was changed to the copolymer solution obtained in Synthesis Example 3.

Example 4
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the copolymer solution was changed to the copolymer solution obtained in Synthesis Example 4.

Example 5
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the copolymer solution was changed to the copolymer solution obtained in Synthesis Example 5.

Example 6
49 parts by weight of the copolymer solution obtained in Synthesis Example 2, 48 parts by weight of propylene glycol monomethyl ether acetate, 2 parts by weight of dipentaerythritol hexaacrylate (“DPHA”, manufactured by Daicel Cytec Co., Ltd.) as a polyfunctional vinyl compound, As a photopolymerization initiator, 1 part by weight of Irgacure 184 (photo radical initiator; manufactured by Ciba Japan Co., Ltd.) was blended to obtain a photosensitive resin composition.

Example 7
49 parts by weight of the copolymer solution obtained in Synthesis Example 2, 48 parts by weight of propylene glycol monomethyl ether acetate, dipentaerythritol tetrakis-3-mercaptopropionic acid (“DPMP”, manufactured by Sakai Chemical Industry Co., Ltd.) as a polyfunctional thiol compound ) 2 parts by weight, 1 part by weight of Irgacure 184 (photo radical initiator; manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator was blended to obtain a photosensitive resin composition.

Example 8
49 parts by weight of the copolymer solution obtained in Synthesis Example 2, 48 parts by weight of propylene glycol monomethyl ether acetate, 2 parts by weight of ADEKA STAB LA-57 (compound of formula (3e), manufactured by ADEKA Corporation) as a hindered amine compound, As a photopolymerization initiator, 1 part by weight of Irgacure 184 (photo radical initiator; manufactured by Ciba Japan Co., Ltd.) was blended to obtain a photosensitive resin composition.

Example 9
49 parts by weight of the copolymer solution obtained in Synthesis Example 2, 48 parts by weight of propylene glycol monomethyl ether acetate, 2 parts by weight of Celoxide 2021P (manufactured by Daicel Chemical Industries) as an epoxy compound, and Irgacure 184 (light) as a photopolymerization initiator 1 part by weight of a radical initiator (manufactured by Ciba Japan Co., Ltd.) was blended to obtain a photosensitive resin composition.

Comparative Example 1
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the copolymer solution was changed to the copolymer solution obtained in Synthesis Example 6.

Comparative Example 2
49 parts by weight of the copolymer solution obtained in Synthesis Example 6, 48 parts by weight of propylene glycol monomethyl ether acetate, 2 parts by weight of dipentaerythritol hexaacrylate (“DPHA”, manufactured by Daicel Cytec Co., Ltd.) as a polyfunctional vinyl compound, As a photopolymerization initiator, 1 part by weight of Irgacure 184 (photo radical initiator; manufactured by Ciba Japan Co., Ltd.) was blended to obtain a photosensitive resin composition.

Comparative Example 3
49 parts by weight of the copolymer solution obtained in Synthesis Example 6, 48 parts by weight of propylene glycol monomethyl ether acetate, dipentaerythritol tetrakis-3-mercaptopropionic acid (“DPMP”, manufactured by Sakai Chemical Industry Co., Ltd.) as a polyfunctional thiol compound ) 2 parts by weight, 1 part by weight of Irgacure 184 (photo radical initiator; manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator was blended to obtain a photosensitive resin composition.

Comparative Example 4
49 parts by weight of the copolymer solution obtained in Synthesis Example 6, 48 parts by weight of propylene glycol monomethyl ether acetate, 2 parts by weight of ADEKA STAB LA-57 (compound of formula (3e), manufactured by ADEKA Corporation) as a hindered amine compound, As a photopolymerization initiator, 1 part by weight of Irgacure 184 (photo radical initiator; manufactured by Ciba Japan Co., Ltd.) was blended to obtain a photosensitive resin composition.

Comparative Example 5
49 parts by weight of the copolymer solution obtained in Synthesis Example 6, 48 parts by weight of propylene glycol monomethyl ether acetate, 2 parts by weight of ceroxide 2021P (manufactured by Daicel Chemical Industries, Ltd.) as an epoxy compound, and Irgacure 184 (photoradical) as a photoinitiator 1 part by weight of initiator (manufactured by Ciba Japan Co., Ltd.) was blended to obtain a photosensitive resin composition.

Evaluation Test (1) Preparation of Test Specimen for Evaluation After the photosensitive resin composition obtained in each Example and Comparative Example was applied to a glass plate (base material) with a spin coater, it was subjected to a hot plate at 100 ° C. for 3 minutes. After heating, exposure was performed, and the obtained coating film was cured in an oven at 200 ° C. for 30 minutes to obtain a coating film. As the exposure amount, ^two light amounts of 200 mJ / cm ² and 800 mJ / cm ² were irradiated.

(2) Adhesiveness In Examples and Comparative Examples, adhesiveness was measured by peeling from a base material in accordance with JIS K-5600-5-6. Moreover, it evaluated based on the following reference | standard in accordance with the classification | category prescribed | regulated by the classification | category of JIS K5600-5-6 8.3 Table 1 test result classification.
A: The test result classification was “0”.
○: It was “1” in the classification of the test results.
Δ: “2” in the classification of test results.
X: “3” and “4” in the classification of the test results.

(3) Solvent resistance In Examples and Comparative Examples, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and N-methylpyrrolidone (NMP) were dropped on each of the test pieces prepared with glass plates, Left for 10 minutes. After washing with water, if the location where the solvent has been dripped has not changed at all ◎, a trace of the solvent will remain, but if it disappears if wiped off, ○ will leave a trace of the solvent and will not disappear even if wiped off. △, if it was completely discolored, x. In addition, the same result was obtained also when the test piece for evaluation produced with the stainless steel plate instead of the glass plate was used.

(4) Alkali resistance In Examples and Comparative Examples, a 1 wt% NaOH aqueous solution was dropped dropwise onto an evaluation test piece made of a glass plate and allowed to stand for 10 minutes. After washing with water, if the location where the 1 wt% NaOH aqueous solution was dripped was not changed at all, ◎, a trace of dripping remains, but if it disappears if wiped off, ○, the trace of dripping remains and disappears even if wiped off If it was not, Δ, and if it was completely discolored, x.

  The results of the evaluation test are shown in Table 1. In the table, “DPHA”, “DPMP”, “ADK STAB LA-57”, and “Celoxide 2021P” are the compounds described in Examples and Comparative Examples, respectively.

  As is clear from the table, the coating films obtained from the photosensitive resin compositions of the examples were excellent in all of the adhesion to the substrate (glass), solvent resistance, and alkali resistance. On the other hand, all the coating films obtained from the photosensitive resin compositions of the comparative examples were inferior in solvent resistance and alkali resistance. Moreover, the coating film obtained from the photosensitive resin composition of Comparative Examples 3 and 4 was inferior also in the point of the adhesiveness with respect to a base material.

Claims (14)

  Vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [excluding (meth) acrylic acid ester derivatives and (meth) acrylic acid amide derivatives] (vinyl monomer A) and a carboxyl group or carboxylic acid anhydride A copolymer obtained by polymerizing a monomer mixture containing at least a vinyl monomer having a physical group (vinyl monomer B). The vinyl monomer A is represented by the following formula (1)

(Wherein R ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group, R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or a methyl group, and X represents Represents a linking group, n represents an integer of 1 to 3)
The copolymer of Claim 1 which is a compound represented by these. The vinyl monomer A is (i) a hydrocarbon group in which R ¹ may have a substituent in formula (1), and R ² , R ³ and R ⁴ may be the same or different, and hydrogen A compound that is an atom or a methyl group, X is a —COO— group (the left end is bonded to the carbon atom to which R ² is bonded), and n = 1, (ii) In the formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom or a methyl group, X is a residue of a polycarboxylic acid, and n is an integer of 1 to 3, and (iii) In the formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom or a methyl group, and X is an n-valent hydrocarbon group which may have a substituent. The copolymer according to claim 2, which is at least one compound selected from the group consisting of compounds wherein n is an integer of 1 to 3.   Any of Claims 1-3 obtained by superposing | polymerizing the monomer mixture which contains at least the vinyl monomer A, the vinyl monomer B, and the vinyl monomer C which has a 3-5 membered cyclic ether group. A copolymer according to any of the above items.   The copolymer according to claim 4, wherein the vinyl monomer C is a vinyl monomer having an alicyclic epoxy group.   It consists of vinyl monomer A, vinyl monomer B, vinyl monomer C, (meth) acrylic ester D, aromatic monovinyl compound E, vinyl alkoxysilane compound F and hydroxyl group-containing monomer G. The copolymer according to claim 4 or 5, which is obtained by polymerizing a monomer mixture containing at least one monomer selected from the group.   A curable resin composition comprising at least the copolymer according to claim 1.   The curability according to claim 7, further comprising at least one compound selected from the group consisting of a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound and a vinyl ether compound. Resin composition.   The photosensitive resin composition containing the copolymer and photoinitiator in any one of Claims 1-6.   And a photosensitive resin composition comprising at least one compound selected from the group consisting of a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound and a vinyl ether compound.   Furthermore, the photosensitive resin composition of Claim 9 or 10 containing a pigment.   The photosensitive resin composition according to claim 9 or 10, which is used for forming a liquid resist, a dry film, a pigment resist or a coating protective film.   A color filter produced using the photosensitive resin composition according to claim 11.   A method for producing a color filter, comprising: applying a photosensitive resin composition according to claim 11 on a support; exposing through a mask; and developing to form a pattern.