KR20100065115A - Copolymer and photosensitive resin composition - Google Patents

Abstract

PURPOSE: A copolymer and a photosensitive resin composition including thereof are provided to use the copolymer as a photosensitive resin capable of producing a pattern with a high definition and the high-sensitivity. CONSTITUTION: A copolymer is obtained by polymerizing a monomer compound including a vinyl monomer A with a carbon double bond, and a vinyl monomer B with a carboxyl group, or a carboxylic anhydride group. The vinyl monomer A is a compound marked with chemical formula 1. In the chemical formula 1, R1 is a hydrogen atom or a hydrocarbon group. R2, R3, and R4 are the hydrogen atom or a methyl group. X refers to a coupling element, and n is a linker of 1~3.

Description

Copolymer and Photosensitive Resin Composition {COPOLYMER AND PHOTOSENSITIVE RESIN COMPOSITION}

The present invention is a copolymer of a vinyl monomer having a plurality of carbon carbon double bonds in a molecule (excluding (meth) acrylic acid ester derivative and (meth) acrylic acid amide derivative) with a vinyl monomer having a carboxyl group or a carboxylic anhydride group, The present invention relates to a curable resin composition and a photosensitive resin composition containing a copolymer, a color filter produced using the photosensitive resin composition, and a method for producing a color filter using the photosensitive resin composition.

As a photosensitive resin used for a display, high brightness and high contrast are calculated | required, and especially the level required for television use is high. In Japanese Patent No. 4090292, a high resolution is achieved by using a dye for high brightness and high contrast, and using a highly sensitive resin having a radical polymerizer as the resin. However, since the developer is a thin aqueous alkali solution, introduction of the carboxylic acid component is essential for dissolving in the developer. As a result, it is impossible to introduce functional groups such as epoxy groups into the resin of the final form, and in reality, problems such as adhesion to the substrate and residual color at the time of development occur, and the one-layer undercoating between the substrate and the resist ink occurs. The problem is solved by installing. In addition, productivity of resin synthesis is also poor because most resins require two steps, a resin polymerization step and a radical polymerizer introduction step.

[Patent Document 1] Japanese Patent No. 4090292

SUMMARY OF THE INVENTION An object of the present invention is a copolymer useful as a photosensitive resin having excellent adhesion to a substrate and capable of forming a pattern of high sensitivity and high resolution, a curable resin composition and a photosensitive resin composition comprising the copolymer, and the photosensitive resin composition. It is providing the color filter and the manufacturing method of a color filter.

It is another object of the present invention to be useful as a photosensitive resin which is excellent in adhesion to a substrate, capable of forming a pattern of high sensitivity and high resolution, and also introduces functional groups such as a radical polymerizable group and an epoxy group during resin synthesis (in one step). It is possible to provide a copolymer which can be produced with high productivity, a curable resin composition and a photosensitive resin composition containing the copolymer, a color filter and a method for producing the color filter using the photosensitive resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, As a result, the vinyl monomer which has a some carbon carbon double bond in a molecule | numerator (except a (meth) acrylic acid ester derivative and a (meth) acrylic acid amide derivative), and a carboxyl group or carboxylic acid When the vinyl monomer having an anhydride group is polymerized, functional groups such as a radical polymerizable group and an epoxy group can be introduced (in one step) at the time of resin synthesis, and a copolymer can be obtained with high productivity, and such a copolymer is used as the photosensitive resin. The present invention was found to be able to form a pattern having high sensitivity and high resolution while being excellent in adhesion to a substrate, thereby completing the present invention.

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

The vinyl monomer A includes a compound represented by the following formula (1).

(Wherein R ¹ represents a hydrocarbon group which may have a hydrogen atom or a substituent, R ² , R ³ and R ⁴ are the same or different, represent a hydrogen atom or a methyl group, X represents a linking group, n is 1 Represents an integer of 3 to 3)

As the vinyl monomer A, (i) in Formula 1, R ¹ is a hydrocarbon group which may have a substituent, R ² , R ³ and R ⁴ are the same or different, and are a hydrogen atom or a methyl group, X is -COO A compound having a group (left of which is bonded to a carbon atom to which R ² is bonded) and n = 1, (ii) in formula (1), wherein R ¹ , R ² , R ³ and R ⁴ are the same or different; , 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 formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or At least 1 type of compound chosen from the group which consists of a compound which is different, is a hydrogen atom or a methyl group, X is an n-valent hydrocarbon group which may have a substituent, and n is an integer of 1-3 can be used.

The copolymer includes a copolymer obtained by polymerizing a monomer mixture including at least a vinyl monomer A, a vinyl monomer B, and a vinyl monomer C having a 3 to 5 membered cyclic ether group.

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

In addition, the copolymer includes a vinyl monomer A, a vinyl monomer B, a vinyl monomer C, a (meth) acrylic acid ester D, an aromatic monovinyl compound E, a vinylalkoxysilane compound F and a hydroxyl group-containing monomer G. Included are copolymers obtained by polymerizing a monomer mixture comprising at least one selected monomer.

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

This curable resin composition further contains at least one compound selected from the group consisting of a compound having a radically polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound and a vinyl ether compound. There may be.

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

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

In addition, the photosensitive resin composition may further contain a pigment. In addition, 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.

This invention further provides the manufacturing method of the color filter characterized by apply | coating the said photosensitive resin composition on a support body, exposing through a mask, developing and forming a pattern.

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

The copolymer of the present invention has a vinyl monomer having a plurality of carbon carbon double bonds in the molecule (excluding (meth) acrylic acid ester derivative and (meth) acrylic acid amide derivative) (vinyl monomer A), and a carboxyl group or a carboxylic anhydride group. It is a polymer obtained by superposing | polymerizing (vinyl polymerization) the monomer mixture containing a vinyl monomer (vinyl monomer B) at least. The copolymer of the present invention may be a random copolymer or a block copolymer. The plurality of carbon carbon double bonds have polymerizable (particularly radical polymerizable). Although the kind of superposition | polymerization at the time of superposing | polymerizing a monomer mixture is not specifically limited, A radical polymerization is preferable. At the time of the said superposition | polymerization, any double bond of the some carbon carbon double bond in vinyl monomer A may be involved in superposition | polymerization. Vinyl monomer A can be used individually by 1 type or in combination of 2 or more type.

As the vinyl monomer A, a vinyl monomer having a plurality of carbon carbon double bonds (for example, 2 to 4, preferably 2 or 3, particularly preferably 2) in a molecule [wherein, (meth) acrylic acid ester Derivatives and (meth) acrylic acid amide derivatives] are not particularly limited, and examples thereof include compounds represented by the formula (1).

In formula (1), R ¹ represents a hydrocarbon group which may have a hydrogen atom or a substituent, R ² , R ³ and R ⁴ are the same or different, represent a hydrogen atom or a methyl group, and X represents a linking group. n represents the integer of 1-3.

As a "hydrocarbon group" of the hydrocarbon group which may have a substituent in R <^1> , an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, the group which these couple | bonded two or more is mentioned, for example. As the aliphatic hydrocarbon group, for example, 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 Is an alkyl group having 1 to 6 carbon atoms; 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); Alkynyl groups (for example, a C2-C10 alkynyl group, Preferably, a C2-C6 alkynyl group), such as an ethynyl and a 1-propynyl group, etc. are mentioned.

As an alicyclic hydrocarbon group, For example, 3-15 membered cycloalkyl groups, such as a cyclopentyl, a cyclohexyl, a cyclooctyl group; 3 to 15 membered cycloalkenyl groups such as cyclohexenyl group; And a C4-C15 temporary exchange group such as a norbornyl group and adamantyl group.

As an aromatic hydrocarbon group, C6-C20 aromatic hydrocarbon groups, such as a phenyl and a naphthyl group, are mentioned, for example. As group which the aliphatic hydrocarbon group and the aromatic hydrocarbon group couple | bonded, aralkyl groups, such as benzyl and 2-phenylethyl group, are mentioned, for example.

As a substituent which these hydrocarbon groups may have, for example, an alkyl group (C _1-4 alkyl group etc.), an alkenyl group (C _2-4 alkenyl group etc.), a haloalkyl group (C _1-4 haloalkyl group etc.), a 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, etc.), acyl group (C _{1- 10} acyl group etc.) etc. are mentioned.

As R ^{1, 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, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 15 carbon atoms is preferable. Especially, a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, and a C6-C10 aromatic hydrocarbon group are preferable.

Although R <^2> , R <^3> and R <^4> may be either a hydrogen atom or a methyl group, respectively, Especially a hydrogen atom is 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 alkylene groups having 1 to 6 carbon atoms, etc.). ); Linear or branched fluoroalkylene groups such as perfluorohexamethylene group (such as linear or branched fluoroalkylene groups having 1 to 6 carbon atoms); Linear or branched alkenylene groups such as vinylene, propenylene and butenylene groups (such as linear or branched alkenylene groups having 2 to 6 carbon atoms); Linear or branched fluoroalkenylene groups (such as linear or branched fluoroalkenylene groups having 2 to 6 carbon atoms); Divalent alicyclic hydrocarbon groups such as 1,3-cyclopentylene, 1,4-cyclohexylene, 1,3-cyclohexylene, and cyclohexylidene groups; Arylene groups which may have substituents such as C _1-4 alkyl groups such as phenylene and naphthylene groups, aryl groups, halogen atoms, and C _1-4 alkoxy groups; -COO-; -OCO-; -CONH-; -NHCO-; -O-; -S-; -CO-; -CS-; -NH-; And divalent groups in which two or more thereof are bonded to each other.

As n, 1 or 2 is preferable and 1 is especially preferable.

As a representative example of the vinyl monomer A, (i) in formula (1), R ¹ is a hydrocarbon group which may have a substituent, R ² , R ³ and R ⁴ are the same or different, are a hydrogen atom or a methyl group, X Is a -COO- group (the left ^end is bonded to a 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 Or different, a hydrogen atom or a methyl group, X is a residue of a polycarboxylic acid, n is an integer from 1 to 3, (iii) in Formula 1, R ¹ , R ² , R ³ and R ⁴ are the same Or at least one compound selected from the group consisting of compounds having a hydrogen atom or a methyl group, an n-valent hydrocarbon group in which X may have a substituent, and n is an integer of 1 to 3, and the like.

As an example of the compound corresponding to said (i), vinyl crotonate, a vinyl cinnamate, a vinyl sorbate, etc. are mentioned, for example.

As an example of the compound corresponding to said (ii), divinyl oxalate, divinyl succinate, divinyl malonate, divinic adipic acid, 1, 4- cyclohexanedicarboxylic acid divinyl, diterephthalate divinyl, etc. are mentioned, for example. Can be.

As an example of the compound corresponding to the above formula (iii), for example, an aliphatic which may have a fluorine atom having a carbon carbon double bond (vinyl group) at both terminals, such as 1,6-divinyl (perfluorohexane) hydrocarbon; 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 a biphenyl, 3,5,4'- trivinyl biphenyl, 1,3,5- trivinylbenzene, etc. are mentioned.

As said vinyl monomer B, unsaturated carboxylic acid or its acid anhydride is mentioned. The unsaturated carboxylic acid and its acid anhydride include, for example, 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 and ita anhydride). Cornic acid, etc.), and the like. Among these, acrylic acid and methacrylic acid are particularly preferable. Vinyl monomer B can be used individually by 1 type or in combination of 2 or more types.

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

The proportion to the copolymer of the monomer unit corresponding to the vinyl monomer A is, for example, 1 to 99% by weight, preferably 2 to 90% by weight, more preferably 2 to the total monomer units constituting the copolymer. To 70% by weight. If the ratio is too small, the sensitivity tends to be lowered, and if too large, the hydrophobicity of the resin itself increases, making it difficult to dissolve in the developer.

Although the ratio which occupies to the copolymer of the monomeric unit corresponding to the vinyl monomer B varies also with the kind of vinyl monomer B to be used, it is 1-99 weight% normally with respect to the all monomeric units which comprise a copolymer normally, Preferably Is 2 to 90% by weight, more preferably 2 to 70% by weight. When the ratio is too small, the hydrophilicity of the resin is low, so that it is difficult to dissolve in the developer, and when too large, the hydrophilicity of the resin is increased, and the chemical resistance of the coating film tends to be lowered.

The ratio of the monomer unit corresponding to the vinyl monomer A to the copolymer of the sum total of the monomer units corresponding to the vinyl monomer B is, for example, 5 to 100% by weight relative to all monomer units constituting the copolymer. 10 to 100% by weight, more preferably 12 to 100% by weight.

The copolymer of this invention may be a copolymer obtained by superposing | polymerizing the monomer mixture containing another vinyl monomer with vinyl monomer A and the vinyl monomer B. FIG. Another vinyl monomer can be used individually by 1 type or in combination of 2 or more types.

As such another vinyl monomer, the vinyl monomer C which has a 3 to 5 membered cyclic ether group, (meth) acrylic acid ester D, an aromatic monovinyl compound E, a vinyl alkoxysilane compound F, a hydroxyl group containing monomer G, etc. are mentioned, for example. Can be.

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 oxolan ring (oxoranyl group) -containing polymerizable unsaturated group. Compound is included.

As an oxirane ring (epoxy group) containing polymerizable unsaturated compound, for example, oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycid Di (meth) acrylate, 2-oxyranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl ( Polymerizable unsaturated compounds ((meth) acrylic acid ester derivative etc.) containing oxirane ring (monocyclic), such as meth) acrylate; 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2- (3, Epoxy-group containing cycloalkanes, such as 3, 4- epoxy cyclohexane ring, such as 4-epoxy cyclohexyl methyloxy) ethyl (meth) acrylate and 3- (3, 4- epoxy cyclohexyl methyloxy) propyl (meth) acrylate Polymerizable unsaturated compounds ((meth) acrylic acid ester derivative etc.) containing a ring; A polymerizable unsaturated compound containing a 5,6-epoxy-2-bicyclo [2.2.1] heptane ring such as 5,6-epoxy-2-bicyclo [2.2.1] heptyl (meth) acrylate ((meth ) Acrylic acid ester derivatives); Epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^{2 , 6} ] decane-8-yl (meth) acrylate, or mixtures thereof], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decane-9-yloxy) ethyl (meth) acrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl (meth) acrylate, or mixtures thereof ], 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring, such as epoxidized dicyclopentenyl oxybutyl (meth) acrylate and epoxidized dicyclopentenyl oxyhexyl (meth) acrylate A polymerizable unsaturated compound ((meth) acrylic acid ester derivative etc.) mentioned above is mentioned. As another oxirane ring (epoxy group) containing polymerizable unsaturated compound, the vinyl ether compound containing an epoxy group, the allyl ether compound containing an epoxy group, the aromatic vinyl compound containing an epoxy group, etc. can also be used. As an aromatic vinyl compound containing an epoxy group, styrene derivatives, such as 4-vinyl benzyl glycidyl ether, 4-vinyl benzyl oxirane, and 4-vinyl phenethyl oxirane, are mentioned.

Examples of the oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound include oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, and 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 (meth) acrylate, 3-[(3-methyl-3-oxetanyl) methyloxy] propyl (meth ) Acrylate, 3-[(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, a vinyl ether compound containing an oxetanyl group, an allyl ether compound containing an oxetanyl group, and the like. Can be mentioned.

As an oxoran ring (oxoranyl group) containing polymeric unsaturated compound, For example, tetrahydrofurfuryl (meth) acrylate, the vinyl ether compound containing an oxoranyl group, the allyl ether compound containing an oxoranyl group, etc. are mentioned. Can be mentioned.

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

Especially as vinyl monomer C which has a 3-5 membered cyclic ether group, an oxirane ring (epoxy group) containing polymerizable unsaturated compound is preferable, and the polymerizable unsaturated compound containing an epoxy group containing cycloalkane ring especially, 5, 6- epoxy- It has alicyclic epoxy groups, such as a polymerizable unsaturated compound containing a 2-bicyclo [2.2.1] heptane ring, and a polymerizable unsaturated compound containing a 3, 4- epoxy cyclocyclo [5.2.1.0 ^2,6 ] decane ring. Vinyl monomers are preferred.

When the copolymer of this invention has the monomer unit corresponding to vinyl monomer C, the ratio which occupies for the copolymer of the said monomer unit is 1 to 99 weight%, for example with respect to all the monomer units which comprise a copolymer. Preferably it is 2 to 90 weight%, More preferably, it is 2 to 85 weight%. If the ratio is too small, the chemical resistance and adhesiveness of the coating film tend to be lowered, and if too large, the hydrophobicity of the resin becomes high, making it difficult to dissolve in the developer.

As said (meth) acrylic acid ester D, the compound represented by following formula (2) is mentioned, for example.

(Wherein 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 group substituted oxy group)

As a C1-C25 hydrocarbon group in R <^6> , For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, Alkyl groups such as decyl, dodecyl, hexadecyl (cetyl), heptadecyl, octadecyl (stearyl), nonadecyl, isocyl, and docosyl (behenyl) groups; Alicyclic hydrocarbon groups such as cyclohexyl, dicyclopentanyl, isobornyl group; Groups in which an alicyclic hydrocarbon group such as 10-cyclohexyldecyl, 12-cyclohexyldodecyl, 14-cyclohexyl tetradecyl, or 16-cyclohexyl hexadecyl group is bonded to an alkyl group; Aryl groups such as phenyl group; Benzyl, 1-phenylethyl, 2-phenylethyl, 4-phenylbutyl, 6-phenylhexyl, 8-phenyloctyl, 10-phenyldecyl, 12-phenyldodecyl, 14-phenyltetradecyl, 16-phenylhexadecyl group Aralkyl groups such as; The group which these couple | bonded two or more, etc. are mentioned.

As a hydrocarbon group substituted oxy group which a C1-C25 hydrocarbon group may have, For example, Alkoxy groups, such as a methoxy and an ethoxy group (for example, C1-C10 alkoxy group); Aryloxy groups such as phenoxy group; Alicyclic hydrocarbon group-substituted oxy groups such as cyclohexyloxy group and dicyclopentanyloxy group; C1-C15 (preferably C1-C12) hydrocarbon group substituted oxy group etc., such as aralkyloxy groups, such as a benzyloxy group, are mentioned.

As a representative example of the (meth) acrylic acid ester represented by General formula (2), 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, phenyl Ethyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. are mentioned.

Moreover, as (meth) acrylic acid ester D, (meth) which has the group which has (meth) acrylic acid ester which has an isocyanate group or a block isocyanate group, the (meth) acrylic acid ester which has an alkoxysilyl group, and a hindered amine structure, for example. Acrylic acid ester etc. are mentioned.

As the (meth) acrylic acid ester having an isocyanate group or a block isocyanate group, for example, methacrylic acid 2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl (= 2- (1-methylpropylideneamino) Oxycarbonylaminoethyl) methacrylate) (brand name "Karens MOI-BM", Showa Denko Co., Ltd. product), methacrylic acid 2- (3,5-dimethylpyrazol-1-yl) carbonylamino Ethyl (brand name "Karens MOI-BP", Showa Denko Co., Ltd. product) etc. are mentioned.

As (meth) acrylic acid ester which has an alkoxy silyl group, (gamma)-(meth) acryloyloxypropyl trimethoxysilane, (gamma)-(meth) acryloyloxypropyl triethoxysilane, (gamma)-(meth) acryl Loyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, β- (meth) acryloyloxyethyltri Methoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxybutylphenyldimethoxysilane, γ- (meth) acryloyloxybutylphenyldiethoxysilane, etc. And alkoxysilyl group-containing polymerizable unsaturated compounds.

Moreover, as (meth) acrylic acid ester which has a group which has a hindered amine structure, For example, brand name "adecasta LA-82", "adecasta LA-87" [above, made by Adeka Corporation] etc. are mentioned. Can be mentioned.

As aromatic monovinyl compound E, styrene, (alpha) -methylstyrene, vinyltoluene, vinyl naphthalene, vinyl biphenyl etc. are mentioned, for example.

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

As the hydroxyl group-containing monomer G, for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl Hydroxyalkyl (meth) acrylates, such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate Polycyclic alcohols such as polyalkylene glycol mono (meth) acrylate, and mono-esterified products of acrylic acid or methacrylic acid, and mono-esterified compounds of polyhydric alcohol and acrylic acid or methacrylic acid. Manufactured by Daicel Kagaku Kogyo Co., Ltd., Fraxel FA series, Fraxel FM series, and the like, and hydroxyl group-containing compounds obtained by ring-opening polymerization of ethylene oxide or propylene oxide. .

When the copolymer of the present invention has a monomer unit corresponding 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, The ratio to the copolymer of the said monomeric unit is generally 2 to 60 weight% in total, Preferably it is 2 to 50 weight%, More preferably, it is 5 to 40 weight%.

As a preferable embodiment of the copolymer of this invention, (1) 5 weight% or more (especially 10 weight% or more, especially 50) of all the monomer units totaling the monomer unit corresponding to vinyl monomer A and the monomer unit corresponding to vinyl monomer B (% By weight or more), (2) a monomer unit corresponding to vinyl monomer A, a monomer unit corresponding to vinyl monomer B, and a monomer unit corresponding to vinyl monomer C having 3 to 5 membered cyclic ether groups in total. A copolymer comprising 40% by weight or more (particularly 50% by weight or more) of all monomer units, (3) 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 With a monomer unit corresponding to vinyl monomer C, (meth) acrylic acid ester D, aromatic monovinyl compound E, vinylalkoxysilane compound F, and hydroxyl group containing monomer G Bait which may be a copolymer comprising at least about 40% by weight of the monomer unit of the monomer unit corresponding to a monomer in a total amount of at least one member selected from the group (especially at least 50% by weight).

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

As a polymerization initiator used for superposition | 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- Azo compounds such as methyl propionate) and dibutyl-2,2'-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1- Organic peroxides, such as bis (t-butylperoxy) cyclohexane, hydrogen peroxide, etc. are mentioned. When using a peroxide as a radical polymerization initiator, it can also be set as a redox initiator by combining a reducing agent. Among these, an azo compound is preferable, and especially 2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), and 2, 2- azobis (isobutyric acid) Dimethyl is preferred.

Although the usage-amount of a polymerization initiator can be suitably selected in the range which does not impair smooth copolymerization, Usually, it is about 1-30 weight% with respect to the total amount of all the monomer components and a polymerization initiator, Preferably it is about 5-25 weight%. .

In this invention, the chain transfer agent generally used in radical polymerization can also be used together. Specific examples include thiols (n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan, etc.). ), Thiol acids (mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, thiomalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), α- Methyl styrene dimer, tabinorene, myrcene, limonene, (alpha) -pinene, (beta) -pinene etc. are mentioned, The quantity of a chain transfer agent is preferably 0.001 to 3 weight% with respect to the quantity of a full radically polymerizable monomer. When using a chain transfer agent, it is preferable to mix with a polymerizable vinyl monomer beforehand.

Polymerization can be performed by the conventional method used when manufacturing a styrene polymer or an acrylic polymer, such as solution polymerization, block polymerization, suspension polymerization, block-suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable. The monomer and the polymerization initiator may be collectively supplied to the reaction system, respectively, or a part or all of them may be added dropwise to the reaction system. For example, a method in which a solution obtained by dissolving a polymerization initiator in a polymerization solvent is added dropwise into a mixed solution of a monomer and a polymerization solvent maintained at a constant temperature, and a solution in which the monomer and the polymerization initiator are dissolved in a polymerization solvent in advance is maintained at a constant temperature. A method of dropwise addition and polymerization in one polymerization solvent (dropping polymerization method) may be employed.

The polymerization solvent can be appropriately selected depending on the monomer composition and the like. As the polymerization solvent, for example, ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether (such as diethylene glycol dialkyl ether such as diethylene glycol methyl ethyl ether)) and 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 Linear ethers such as glycol ethers such as propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono, di or trialkyl ether; Cyclic ethers such as hydrofuran and dioxane, etc., esters (methyl acetate, ethyl acetate, butyl acetate, ace Acid is a carboxylic acid, such as isoamyl, ethyl lactate, 3-methoxy methyl propionate, 3-ethoxy propionate, ethyl, C _5-6 cycloalkane diol mono- or di-acetate, C _5-6 cycloalkanediyl methanol mono- or di-acetate Esters: 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 mono 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 monoalkyl ether acetate, 1,3-butanediol Mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4- Tan diol mono- or di-acetate, 1,6-mono- or di-acetate, glycerol mono-, di- or triacetate, glycerin mono- or di-C _1-4 alkyl ether di- or mono-acetates, tripropylene glycol monoalkyl ether acetate, triethylene Glycol acetates such as propylene glycol mono or diacetate or glycol ether acetates), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexene-1 -Ones), amides (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohols (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkane dimethanol, etc.), hydrocarbons (aromatic hydrocarbons, such as benzene, toluene, xylene, aliphatic hydrocarbons, such as hexane, alicyclic hydrocarbons, such as cyclohexane), these mixed solvents, etc. Can be mentioned. Polymerization temperature can be suitably selected, for example in the range of about 30-150 degreeC.

The above method produces the copolymer of the present invention. The weight average molecular weight of the copolymer is, for example, 500 to 1000000, preferably 5000 to 500000, more preferably about 10000 to 200000. Dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of a copolymer is about 1-3.

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

Curable resin composition of this invention contains the copolymer of this invention at least. Curable resin composition of this invention adjusts solid content concentration as needed, solvent-exchanges, or performs a filtration process with respect to the polymerization liquid obtained by the said method, and also a curing catalyst [thermal acid generator (thermal curing catalyst) as needed. , Thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization initiator)], radical photoinitiator, curing agent, curing accelerator, additive (filler, antifoaming agent, flame retardant, antioxidant, ultraviolet absorber, low stress agent, flexible It can be prepared by blending the imparting agent, waxes, resins, crosslinking agents, halogen trapping agents, leveling agents, leakage improvers and the like), pigments and the like. The curable resin composition and the 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 high molecular compounds, organic metal complexes, C60 / carbon nanotubes, and the like. Carbon compounds and the like can be blended. Moreover, curable resin composition can also be obtained by refine | purifying the polymer produced | generated by superposition | polymerization by precipitation or reprecipitation, etc., and dissolving this refined polymer with the said suitable additive in the solvent according to a use.

The curable resin composition may include at least one compound selected from the group consisting of a compound having a radically polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. . As a solvent which comprises curable resin composition, what was illustrated as said polymerization solvent can be used. 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 this invention contains the 1 type (s) or 2 or more types of said copolymer of this invention, and a photoinitiator. The photosensitive resin composition may further include at least one compound selected from the group consisting of a compound having a radically polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. Can be.

As a compound which has a radically polymerizable double bond, vinyl aromatic compounds, such as (meth) acrylic acid ester and styrene, an amide type unsaturated compound, etc. are mentioned. As typical (meth) acrylic acid ester, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) (Meth) acrylic-acid alkylesters, such as an acrylate; (Meth) which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone modified 2-hydroxyethyl (meth) acrylate Acrylic acid esters; Methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) (Meth) acrylates (polyalkylene glycol monoether mono (meth) acrylates) such as acrylate and methoxy polyethylene glycol # 400- (meth) acrylate; Difunctional (meth) acrylic acid esters such as 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate; Polyfunctional (meth) acrylic acid esters, such as trifunctional (meth) acrylic acid esters, such as a trimethylol propane tri (meth) acrylate, etc. are mentioned.

As the compound having a radical polymerizable double bond, a polymerizable prepolymer may be used. Examples of the polymerizable prepolymer include (meth) acrylic acid esters of polyester polyols, (meth) acrylic acid esters of polyether polyols, adducts of polyepoxy compounds and (meth) acrylic acid, and polyols. The resin etc. which introduce | transduced hydroxy (meth) acrylate through are mentioned.

As a compound which has a radically polymerizable double bond, polyfunctional vinyl compounds, such as polyfunctional (meth) acrylic acid ester, are preferable. The compound which has a radically polymerizable double bond can be used individually by 1 type or in combination of 2 or more types. By mix | blending the compound which has a radically polymerizable double bond in the photosensitive resin composition, high sensitivity and high resolution can be implement | achieved and a film | membrane physical property also improves. Moreover, since the compound which has a radically polymerizable double bond can also be used as a substitute for a dilution solvent, it is effective also for viscosity adjustment and high solidification.

As a polyfunctional thiol compound, what is necessary is just a compound which has two or more thiol groups, For example, hexanedithiol, decandithiol, 1, 4- butanediol bisthio propionate, 1, 4- butanediol bisthioglycolate, ethylene glycol bisty Oglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristyopionate, trimethylolpropane tris-3-mercaptobutyrate, pentaerythritol tetrakisthioglycolate, penta Erythritol tetraquistiopionopionate, pentaerythritol tetrakis-3-mercaptobutyrate, trimercaptopropionate tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4, 6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, tetraethyleneglycolbis-3-mercapto propionate, Trimethylolpropane tris 3-mercaptopropionate, tris (3-mercaptopropionyloxyethyl) isocyanurate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis 3- Mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2, 4,6- (1H, 3H, 5H) -trione etc. are mentioned. A polyfunctional thiol compound can be used individually by 1 type or in combination of 2 or more types. By mix | blending a polyfunctional thiol compound in the photosensitive resin composition, high sensitivity and high resolution can be implement | achieved, and a film | membrane physical property also improves. Moreover, since a polyfunctional thiol compound can be used also as a substitute for a dilution solvent, it is effective also for viscosity adjustment and high solidification.

As a hindered amine compound, the compound generally called a hindered amine light stabilizer (HALS) can be used, For example, the following compound is illustrated. In addition, in general formula (3h), (3i), (3o), (3q), (3r), m represents an integer of 1 or more. A hindered amine compound can be used individually by 1 type or in combination of 2 or more types. By mix | blending a hindered amine compound in the photosensitive resin composition, high sensitivity and high resolution can be implement | achieved and a film | membrane physical property improves.

Examples of the epoxy compound include unsaturated group-containing epoxidized resins such as epoxidized polybutadiene and epoxidized butadiene styrene block copolymers (the commercially available products of which are manufactured by Daicel Chemical Co., Ltd. epoxide PB, ESBS, etc.). , Alicyclic epoxy resin (for example, Daicel Chemical Co., Ltd. make, Celoxide 2021, EHPE; Mitsui Sekiyu Chemical Co., Ltd. make, Epomic VG-3101; Yuka Shell Epoxy Co., Ltd. make, E -1031S; manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X, TETRAD-C; manufactured by Nihon Soda Co., Ltd., EPB-13, EPB-27, etc.), copolymerized epoxy resin (e.g., glycine Nippon Yushi Co., Ltd., a copolymer of dimethyl methacrylate and styrene, a copolymer of glycidyl methacrylate, styrene and methyl methacrylate, CP-50M, CP-50S, or glycidyl methacrylate Copolymers such as cyclohexyl maleimide, etc.), and other, having special structures There may be mentioned epoxy resin and the like.

Moreover, as an epoxy compound, the novolak, epichlorohydrin and / or methyl which are obtained by reacting a novolak-type epoxy resin [for example, phenols, such as a phenol, a cresol, a halogenated phenol, and an alkylphenol, and formaldehyde under an acidic catalyst] What is obtained by reacting epichlorohydrin (as a commercial item, the Nippon Kayaku Co., Ltd. make, EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN-S; Dow Chemical company make) , DEN-431, DEN-439; Dai Nippon Ink Chemical Co., Ltd., N-73, VH-4150 and the like)], bisphenol-type epoxy resin (for example, bisphenol A, bisphenol F, bisphenol S And those obtained by reacting bisphenols such as tetrabrombisphenol A with epichlorohydrin, or those obtained by reacting diglycidyl ether of bisphenol A with a condensate of the bisphenols and epichlorohydrin (as its commercially available product, Yucca Shell Co., Ltd. , Epicoat 1004, Epicoat 1002; Dow Chemical Co., DER-330, DER-337 and the like)], epichlorohydrin and / or methyl epichlorohydrin such as trisphenolmethane and triscresolmethane Obtained as a result of commercially available products (such as Nippon Kayaku Co., EPPN-501, EPPN-502, etc.), tris (2,3-epoxypropyl) isocyanurate, biphenyl diglycidyl ether, etc. Can be used.

These epoxy compounds (epoxy resin) can be used individually by 1 type or in combination of 2 or more types. By mix | blending an epoxy compound in the photosensitive resin composition, high sensitivity and high resolution can be implement | achieved and a film | membrane physical property improves.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Chemical Co., Ltd., "OXT-101") and 2-ethylhexyl oxetane [Toagosei Chemical Co., Ltd. ( Corporation) production, "OXT-212"], xylylenebisoxetane [Toagosei Kagaku Kogyo Co., Ltd. make, "OXT-121"], 3-ethyl-3- [3-ethyloxetane-3- Ilmethoxymethyl] oxetane (Toagosei Kagaku Kogyo Co., Ltd. make, "OXT-221") etc. are mentioned.

These oxetane compounds can be used individually by 1 type or in combination of 2 or more types. By mix | blending an oxetane compound in the photosensitive resin composition, high sensitivity and high resolution can be implement | achieved and a film | membrane physical property also improves.

As a vinyl ether compound, for example, pentaerythritol tetravinyl ether, trimethylol propane trivinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexanediol divinyl ether, nonanediol divinyl ether, 1,4-butanediol divinyl ether, allyl vinyl ether, triethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether, 4- Hydroxycyclohexyl vinyl ether, etc. are mentioned.

These vinyl ether compounds can be used individually by 1 type or in combination of 2 or more types. By mix | blending a vinyl ether compound in the photosensitive resin composition, high sensitivity and high resolution can be implement | achieved and a film | membrane physical property also improves.

The amount of the compound having a radically polymerizable double bond to the curable resin composition or the photosensitive resin composition, the polyfunctional thiol compound, the hindered amine compound, the epoxy compound, the oxetane compound, and the vinyl ether compound may be the copolymer 100 of the present invention, respectively. It is 0.1-40 weight part with respect to a weight part, Preferably it is 1-25 weight part, More preferably, it is 1.5-15 weight part. The total blending amount of these compounds in the curable resin composition or the photosensitive resin composition is, for example, 0.1 to 40 parts by weight, preferably 1 to 25 parts by weight, more preferably based on 100 parts by weight of the copolymer of the present invention. Is 1.5 to 15 parts by weight.

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

As an optical radical initiator, benzophenone, acetophenone benzyl ketal, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxy acetophenone, dimethoxyphenyl acetophenone, Diethoxyacetophenone, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethyl thioxanthone (Nipbon Kayaku Co., Ltd.) ) Manufactured Kayacure DETX, etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (Ilgacure 907, manufactured by Ciba-Geigi Co., Ltd.), 2-dimethyl 2-amino-2-benzoyl-1-phenylalkane compounds such as amino-2- (4-morpholino) benzoyl-1-phenylpropane, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2- Aminobenzene derivatives such as hydroxy-2-methyl-1-phenyl-propan-1-one and 4,4-bisdiethylaminobenzophenone, 2,2'-bis (2-chlorophenyl) -4, Imidazole compounds, such as 5,4 ', 5'- tetraphenyl- 1,2'- biimidazole (B-CIM by Hodogaya Chemical Co., Ltd.), 2, 6-bis (trichloromethyl)- Halomethylated triazine compounds such as 4- (4-methoxynaphthalen-1-yl) -1,3,5-triazine, 2-trichloromethyl-5- (2-benzofuran2-yl-ethenyl) Halomethyloxa diazole compounds, such as -1,3,4-oxadiazole, etc. can be used individually or in mixture, A photosensitizer can be added as needed.

As a photo-acid generator, for example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, Union Carbide Corporation make, brand name), Irgacure 261 (Shiba specialty chemicals company make, brand name), SP-150, SP-151, SP-170, Optimer SP-171 (above, Asahi Denka Kogyo Co., Ltd. make, brand name), CG-24-61 (Shiba specialty Chemicals company make, brand name), DAICATII (the Daicel Chemical Industries, Ltd. make, brand name), UVAC1591 (the Daicel Cytec Co., Ltd. make, brand name), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758 (above, Nihon Soda Co., Ltd. product, brand name), PI-2074 (Ronufuran company make, brand name, pentafluorophenyl borate toluyl cumyl iodonium salt), FFC509 (3M company product, brand name), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (manufactured by Midori Chemical Co., Ltd.) , CD-1012 (USA, Sartomer) Diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, oxonium salt, ammonium salt, etc. represented by (Sartomer) make, brand names) etc. can be used.

As a photoinitiator, a combination of an imidazole compound and an aminobenzene derivative, a 2-amino-2-benzoyl-1-phenyl alkane compound, a halomethylated triazine compound, a halomethyl oxadiazole compound, etc. from a viewpoint of a sensitivity, chemical resistance, etc. This is preferred.

The photosensitive resin composition of this invention may contain the thermal acid generator as needed. As a thermal acid generator, for example, sunaid SI-45, the seat SI-47, the seat SI-60, the seat SI-60L, the seat SI-80, the seat SI-80L, the seat SI-100, the seat SI-100L, the seat SI-145, seat SI-150, seat SI-160, seat SI-110L, seat SI-180L (above, Sanshin Kagaku Kogyo Co., Ltd. product, brand name), CI-2921, CI-2920, CI-2946, CI- 3128, CI-2624, CI-2639, CI-2064 (above, Nihon Soda Co., Ltd. product, brand name), CP-66, CP-77 (Asahi Denka Kogyo Co., Ltd. product name), FC-520 (Three company Manufactured products, brand names) and the like, diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, oxonium salt, ammonium salt and the like can be used.

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

These photoinitiators may also contain a synergist, for example, a tertiary amine, for enhancing the conversion of light absorption energy into a polymerization initiation free group. In addition, when hardening curable resin composition of this invention by electron beam irradiation, addition of an initiator is not necessarily required.

Thus, the photosensitive resin composition obtained by hardening has high sensitivity and high resolution, has high adhesiveness with respect to a base material and a board | substrate, and can obtain the hardened | cured material (hardened film etc.) excellent in chemical resistance, such as solvent resistance and alkali resistance. . Therefore, it is useful as a coating material, a coating agent, an adhesive agent, etc., Especially it can use suitably as a resin composition for liquid resist, dry film, and coating protective film formation which are the fields 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, and the like, added and mixed in the photosensitive resin composition, and used as color filters for liquid crystal displays. And pigment resists such as black matrices can be produced.

As said 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, various inorganic pigments can also be used as the structure, in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxane, indanthrene and perinone. Hereinafter, the specific example of the pigment which can be used is shown by a pigment number. "C.I. Pigment Red 2 ”and the like mean a color index (C.I.).

As a red pigment, C.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, 179, 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. Among these, Preferably C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment Red 177, 209, 224 and 254.

As a blue pigment, C.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. Among these, Preferably C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. Pigment Blue 15: 6.

As a green pigment, C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among these, Preferably C.I. Pigment Green 7, 36.

As a yellow pigment, C.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, 173, 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, and 208. Among these, Preferably C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. Pigment Yellow 83, 138, 139, 150, 180.

As an orange pigment, C.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. Pigment Orange 38, 71.

As a purple pigment, C.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 and 50. Among these, Preferably C.I. Pigment violet 19, 23, more preferably C.I. Pigment Violet 23.

In addition, when forming the resin black matrix of a color filter using a pigment composition (pigment), a black color 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. Moreover, these color materials can be suitably selected from pigments of an inorganic or organic. In the case of inorganic and organic pigments, it is preferable to disperse | distribute to an average particle diameter of 1 micrometer or less, Preferably it is 0.5 micrometer or less.

Color materials that can be mixed and used to produce a black color material include Victoria Pure Blue (42595), Oramine O (41000), Catyl Brilliant Flavin (Basic 13), Rhodamine 6 GCP (45160), Rhodamine B (45170), Sapranine OK70: 100 (50240), eryoglausin X (42080), No.120 / Leonol Yellow (21090), Leonol Yellow GRO (21090), Sima First Yellow 8GF (21105), Benzidine Yellow 4T- 564D (21095), Sima First Red 4015 (12355), Lionol Red 7B4401 (15850), Pastogen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6 ), A lynogen red GD (pigment red 168), a lionol green 2YS (pigment green 36), etc. (In addition, the number in () mentioned above means color index (CI)).

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

Moreover, as a black color material which can be used independently, carbon black, acetylene black, lamp black, this black, graphite, iron black, aniline black, cyanine black, titanium black, etc. are mentioned. Among them, carbon black is preferable in view of light blocking rate and image characteristics. Examples of the carbon blacks include the following carbon blacks.

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.

Degussa Company: Printex 3, Printtex 3OP, Printtex 30, Printtex 30OP, Printtex 40, Printtex 45, Printtex 55, Printtex 60, Printtex 75, Printtex 80, Printtex 85, Printtex 90, Printtex A, Printtex L, Printtex G, Printtex P, Printtex U, Printtex V, Printtex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170.

Cabot Company: Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, Regal 99, Regal 99R, Regal 415, Regal 415R, Regal 250, Regal 250R, Regal 330, Regal 400R, Regal 55R0, Regal 660R, BLACK PEARLS 480, Pearls 130, VULCAN XC72R, Elftex-8 (ELFTEX- 8).

Colombiyan carbon company: Raven 11, Raven 14, Raven 15, Raven 16, Raven 22, Raven 30, Raven 35, Raven 40, Raven 410, Raven 420, Raven 450, Raven 500, Raven 780, Raven 850 , Raven 890H, Raven 1000, Raven 1020, Raven 1040, Raven 1060U, Raven 1080U, Raven 1170, Raven 1190U, Raven 1250, Raven 1500, Raven 2000, Raven 2500U, Raven 3500, Raven 5000, Raven 5250, Raven 5750, Raven 7000.

As an example of another black pigment, titanium black, aniline black, an iron oxide type black pigment, and three organic pigments of red, green, and blue can be mixed and used as a black pigment.

Moreover, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, etc. can also be used as a pigment. These various pigments can also use multiple types together. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used together as a pigment, or a blue pigment and a purple pigment can be used together.

In addition, these pigments preferably have an average particle diameter of 1 μm, preferably 0.5 μm or less (eg, 0.005 to 0.5 μm), more preferably 0.25 μm or less (eg, 0.01 to 0.25 μm).

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. Moreover, in the case of compositions for black matrices containing black pigments, such as carbon black, the compounding quantity of a pigment is preferably 50-150 weight part with respect to 100 weight part of total solids except a pigment, and 70-140 weight The range of parts is more preferable, and the range of 90-130 weight part is especially preferable.

As a dispersing agent, in order to disperse | distribute a pigment favorably, it mix | blends as needed in the photosensitive resin composition. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based compounds can be used. Among the surfactants, polymer surfactants (polymer dispersants) as illustrated below are preferable.

Namely, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid-modified polyesters; Polymeric surfactants, such as tertiary amine modified polyurethanes, are used preferably.

Specific examples of the polymer dispersant include EFKA (manufactured by Efka Chemicals Viv (EFKA)), Disperbyk (manufactured by BIC Chemical Co., Ltd.), dispalon (manufactured by Kusumoto Kasei Co., Ltd.), SOLSPERSE (manufactured by Geneca), KP ( Shin-Etsu Chemical Co., Ltd. make), polyflow (Kyoeisha Chemical Co., Ltd. make), etc. are mentioned. These may be used individually by 1 type, and may mix and use 2 or more types.

The weight average molecular weight (Mw) of polystyrene conversion by GPC of these polymer dispersing agents is 700 or more, Preferably it is 1000 or more and 100,000 or less, Preferably it is 50,000 or less. In particular, as the urethane-based and acrylic polymer dispersants, Disperbyk 160 to 166 series, Disperbyk 2000, 2001 and the like (both manufactured by Big Chemistry Co., Ltd.) are preferable.

It is preferable to use a random copolymer, a graft copolymer, and a block copolymer as the acrylic polymer dispersant. These copolymers can be manufactured by a well-known method.

Further, the dispersant may be a pigment derivative, and the pigment derivative may be azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, Although derivatives, such as a perylene system, a perinone system, a diketopyrrolopyrrole system, a dioxazine system, are mentioned, Especially, a quinophthalone system is preferable. As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and quaternary salts thereof, phthalimide methyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group and the like are bonded directly to the pigment skeleton or through an alkyl group, an aryl group, a heterocyclic group or the like. These are mentioned, Preferably it is a sulfonic acid group. In addition, these substituents may be substituted by one pigment skeleton. As a specific example of a pigment derivative, the sulfonic acid derivative of phthalocyanine, the sulfonic acid derivative of quinophthalone, the sulfonic acid derivative of anthraquinone, the sulfonic acid derivative of quinacridone, the sulfonic acid derivative of diketopyrrolopyrrole, the sulfonic acid derivative of dioxazine, etc. are mentioned. These may be used individually by 1 type, and may mix and use 2 or more types. Moreover, it is preferable to use a polymer dispersing agent and a pigment derivative together as a dispersing agent.

Moreover, solid content other than the said component can be mix | blended with the photosensitive resin composition of this invention as needed. As these components, surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protector, an adhesion promoter, a development improving agent, etc. are mentioned. As a solvent of the photosensitive resin composition, what was illustrated as the said polymerization solvent can be used.

Although various things, such as anionic, cationic, nonionic, and amphoteric surfactant, can be used as surfactant, it is preferable to use a nonionic surfactant from the point that the possibility of adversely affecting various characteristics is low.

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 0.03 to 0.3% by weight based on the total amount of the composition.

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. It is preferable that the compounding quantity of a thermal polymerization inhibitor is 0 to 3 weight% with respect to the total solid of a composition.

As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine and the like are used. It is preferable that the compounding quantity of these plasticizers is 10 weight% or less with respect to the total solid of a composition.

By hardening the said curable resin composition, the hardened | cured material excellent in various physical properties is obtained. For example, after apply | coating the said curable resin composition to various base materials or a board | substrate (support body) by methods, such as a spin coater and a slit coater, after forming a coating film, hardened | cured material can be obtained by hardening the said coating film. Examples of the substrate or substrate include glass, ceramics, silicon wafers, metals, plastics, and the like. Coating by a spin coater, a slit coater, etc. can be performed by a well-known method.

Curing of a coating film is performed by heating, irradiating and exposing an active energy ray, or heating after exposure. When hardening the said curable resin composition with heat, heating temperature is the range of 50 degreeC-260 degreeC, Preferably it is the range of 80 degreeC-240 degreeC. In addition, when hardening the said curable resin composition with light, the light ray of various wavelengths, for example, ultraviolet-ray, X-ray, g-ray, i-ray, an excimer laser etc. are used for exposure. Although the thickness of the coating film after hardening can be suitably selected according to a use, it is generally 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 on a support body, a color filter can be manufactured by exposing through a mask, developing, and forming a pattern. The procedure and operation | movement at the time of manufacturing a color filter can apply a well-known or well-known method.

<Examples>

EMBODIMENT OF THE INVENTION Below, although this invention is demonstrated in detail based on an Example, this invention is not limited by 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 copolymer were measured on condition of the following.

Device: Detector: RID-10A (Shimazu Seisakusho)

      Pump: LC-10ADVP (Shimazu Seisakusho)

      System controller: SCL-10AVP (Shimazu Seisakusho)

      Degatsa: DGU-14A (Shimazu Seisakusho)

      Auto injector: SIL-10AF (Shimazu Seisakusho)

Columns: Waters Styragel HR3, Styragel HR4, Styragel HR5

Mobile phase: THF

Flow rate: 1 mL / min

Temperature: Oven (40 ° C), RI (40 ° C)

Detector: RI POLARITY (+)

Injection volume: 50 μL

Synthesis Example 1

Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed into a nitrogen atmosphere, and 235 parts by weight of propylene glycol monomethyl ether and 35 parts by weight of propylene glycol monomethyl ether acetate were heated to 75 ° C while stirring. It was. Subsequently, 250 parts by weight of methacrylic acid and 250 parts by weight of vinyl crotonate (manufactured by Nippon Vinyl Acetate Foam Co., Ltd.) were added dropwise into the flask using a dropping pump for about 4 hours. On the other hand, the solution which melt | dissolved 30 weight part of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 200 weight part of propylene glycol monomethyl ether acetate was dripped over about 4 hours using the other dropping pump. . After completion of the dropwise addition of the polymerization initiator, the mixture was kept 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 [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 -It carried out similarly to the synthesis example 1 except having changed to 385 weight part of mixtures of a monoacrylate [50:50 (molar ratio)], and 25 weight part of vinyl crotonate (made by Nippon vinyl acetate foaming). 50.5 weight% of solid content and the copolymer solution of the acid value 106 mg-KOH / g were obtained. The weight average molecular weight Mw of the produced copolymer was 12000.

Synthesis Example 3

It carried out similarly to the synthesis example 1 except having changed the vinyl crotonate (made by the Nippon-vinyl acetate foaming company) to vinyl sorbate (made by the Nippon-vinyl acetate foaming company). 50.8 weight% of solid content and the copolymer solution of the acid value 113 mg-KOH / g were 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 the crotonate vinyl (made by Nippon vinyl acetate foaming company) to the vinyl cinnamic acid (made by Nippon vinyl acetate foaming company). 50.3 weight% of solid content and the copolymer solution of acid value 104 mg-KOH / g were 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 [5.2.1.0 ^2,6 ] de-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 -Synthesis example 1 except having changed into 285 weight part of mixtures of a monoacrylate [50:50 (molar ratio)], 100 weight part of cyclohexyl methacrylate, and 25 weight part of vinyl crotonate (made by Nippon vinyl acetate foaming). The same procedure was followed. 50.2 weight% of solid content and the copolymer solution of the acid value 110 mg-KOH / g were obtained. The weight average molecular weight Mw of the produced copolymer was 17000.

Synthesis Example 6

Monomer The monomer composition is 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- A mixture of 8-ylacrylate [50:50 (molar ratio)] was carried out in the same manner as in Synthesis example 1 except that it was changed to 410 weight. 49.8 weight% of solid content and the copolymer solution of the acid value 110 mg-KOH / g were obtained. The weight average molecular weight Mw of the produced copolymer was 10000.

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 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator were used to mix the photosensitive resin composition. Got.

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, and 2 parts by weight of dipentaerythritol hexaacrylate ("DPHA", manufactured by Daicel Cytec Co., Ltd.) as a polyfunctional vinyl compound. And 1 weight part of Irgacure 184 (photo radical initiator; Shiva Japan Co., Ltd. product) were mix | blended as a photoinitiator, and the photosensitive resin composition was obtained.

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, and a polyfunctional thiol compound, dipentaerythritol tetrakis-3-mercaptopropionic acid ("DPMP", Sakai Chemical Co., Ltd.) 2 parts by weight of Irgacure 184 (Photoradical Initiator; manufactured by Ciba Japan, Inc.) as a photopolymerization initiator, 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, and adecastab LA-57 (a compound of formula (3e), manufactured by Adeka Co., Ltd.) as a hindered amine compound 2 weight part and 1 weight part of Irgacure 184 (photo radical initiator; Ciba Japan Co., Ltd. product) were mix | blended as a photoinitiator, and the photosensitive resin composition was obtained.

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 ceoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.) as an epoxy compound, Irgacure as a photopolymerization initiator 184 (photo radical initiator; Ciba Japan Corporation make) 1 weight part was mix | blended, and the photosensitive resin composition was obtained.

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, and 2 parts by weight of dipentaerythritol hexaacrylate ("DPHA", manufactured by Daicel Cytec Co., Ltd.) as a polyfunctional vinyl compound. And 1 weight part of Irgacure 184 (photo radical initiator; Shiva Japan Co., Ltd. product) were mix | blended as a photoinitiator, and the photosensitive resin composition was obtained.

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, and dipentaerythritol tetrakis-3-mercaptopropionic acid ("DPMP", Sakai Chemical Industries, Ltd.) as a polyfunctional thiol compound 2 parts by weight of Irgacure 184 (Photoradical Initiator; manufactured by Ciba Japan, Inc.) as a photopolymerization initiator, 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, and adecastab LA-57 (a compound of formula (3e), manufactured by Adeka Co., Ltd.) as a hindered amine compound 2 weight part and 1 weight part of Irgacure 184 (photo radical initiator; Ciba Japan Co., Ltd. product) were mix | blended as a photoinitiator, and the photosensitive resin composition was obtained.

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 Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.) as an epoxy compound, Irgacure 184 as a photoinitiator. (Photoradical initiator; Shiva Japan Co., Ltd. product) 1 weight part was mix | blended and the photosensitive resin composition was obtained.

Evaluation test

(1) Preparation of Test Specimens for Evaluation

After apply | coating the photosensitive resin composition obtained by each Example and the comparative example to a glass plate (base material) with a spin coater, it heats for 3 minutes on a 100 degreeC hotplate, and exposes the obtained coating film in 30 degreeC oven 200 The coating film was obtained by hardening for a minute. As an exposure amount, the light quantity of 2 conditions of 200 mJ / cm <2> and 800 mJ / cm <2> was irradiated.

(2) adhesion

In an Example and a comparative example, adhesiveness was measured by peeling from a base material based on JISK-5600-5-6. Moreover, it evaluated based on the following criteria according to the classification prescribed | regulated by JIS K5600-5-6 8.3 Table 1 Classification of the test result.

◎… It was "0" in the classification of the test result.

○… It was "1" in the classification of the test result.

? It was "2" in the classification of the test result.

×… It was "3" "4" in the classification of the test result.

(3) solvent resistance

In Examples and Comparative Examples, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and N-methylpyrrolidone (NMP) were respectively added dropwise to the test specimen for evaluation made from a glass plate, and left for 10 minutes. . ◎, traces of solvent remain after rinsing with water, and dropping solvent is not changed at all, but ○ if trace disappears, trace of solvent remains, △, if discolored entirely It was set as x. Moreover, the same result was obtained also when the test piece for evaluation manufactured by the stainless plate was used instead of the glass plate.

(4) alkali resistance

In the Example and the comparative example, 1 weight% NaOH aqueous solution was dripped at the test piece for evaluation manufactured by the glass plate one by one, and it was left to stand for 10 minutes. After washing with water, the place where the 1% by weight aqueous solution of NaOH was added is not changed at all. ◎, a slight dropping trace remains, but if it is wiped off, ○, the dropping trace remains, and if it does not seem to disappear even after wiping, △, the whole area When it changed into color, it was set as x.

The results of the evaluation test are shown in Table 1. In the table, "DPHA", "DPMP", "Adecastab LA-57", and "Celoxide 2021P" are the compounds described in the Example and the comparative example, respectively.

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

Claims (14)

Vinyl monomers having a plurality of carbon carbon double bonds in a molecule [excluding (meth) acrylic acid ester derivatives and (meth) acrylic acid amide derivatives] (vinyl monomer A) and vinyl monomers having a carboxyl group or a carboxylic anhydride group (vinyl monomer B A copolymer obtained by polymerizing the monomer mixture containing at least). The copolymer according to claim 1, wherein the vinyl monomer A is a compound represented by the following general formula (1). <Formula 1>

(Wherein R ¹ represents a hydrocarbon group which may have a hydrogen atom or a substituent, R ² , R ³ and R ⁴ are the same or different, represent a hydrogen atom or a methyl group, X represents a linking group, n is 1 Represents an integer of 3 to 3) The vinyl monomer A according to claim 2, wherein (i) in formula (1), R ¹ is a hydrocarbon group which may have a substituent, R ² , R ³ and R ⁴ are the same or different, and a hydrogen atom or a methyl group. And X is a -COO- group (the left ^end is bonded to a carbon atom to which R ² is bonded) and n = 1, (ii) in formula (1), R ¹ , R ² , R ³ and R ⁴ Is the same or different, is a hydrogen atom or a methyl group, X is a residue of a polycarboxylic acid, n is an integer from 1 to 3, and (iii) in formula (1), R ¹ , R ² , R ³ and A copolymer wherein R ⁴ is the same or different and is a hydrogen atom or a methyl group, X is an n-valent hydrocarbon group which may have a substituent, and at least one compound selected from the group consisting of compounds wherein n is an integer of 1 to 3. The copolymer obtained in any one of Claims 1-3 by superposing | polymerizing the monomer mixture containing vinyl monomer A, the vinyl monomer B, and the vinyl monomer C which has a 3 to 5 membered cyclic ether group at least. The copolymer according to claim 4, wherein the vinyl monomer C is a vinyl monomer having an alicyclic epoxy group. The vinyl monomer A, the vinyl monomer B, the vinyl monomer C, the (meth) acrylic acid ester D, the aromatic monovinyl compound E, the vinylalkoxysilane compound F and the hydroxyl group containing monomer G of Claim 4 or 5 The copolymer obtained by superposing | polymerizing the monomer mixture containing at least 1 sort (s) of monomer chosen from the group which consists of. Curable resin composition containing at least the copolymer of any one of Claims 1-6. The compound according to claim 7, further comprising at least one compound selected from the group consisting of a compound having a radically polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. Curable resin composition. The photosensitive resin composition containing the copolymer as described in any one of Claims 1-6, and a photoinitiator. The compound of claim 9, further comprising at least one compound selected from the group consisting of a compound having a radically polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. The photosensitive resin composition. The photosensitive resin composition of Claim 9 or 10 which further contains a pigment. The photosensitive resin composition of Claim 9 or 10 used for forming a liquid resist, a dry film, a pigment resist, or a coating protective film. The color filter manufactured using the photosensitive resin composition of Claim 11. After apply | coating the photosensitive resin composition of Claim 11 on a support body, it exposes through a mask, and develops and forms a pattern, The manufacturing method of the color filter characterized by the above-mentioned.