TWI461448B - Copolymer and photosensitive resin composition - Google Patents

Description

Copolymer and photosensitive resin composition

The present invention relates to a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [except for a (meth) acrylate derivative and a (meth) acrylamide derivative] and a vinyl monomer having a carboxyl group or a carboxylic anhydride group. Copolymer, a curable resin composition containing the copolymer, a photosensitive resin composition, a color filter prepared using the photosensitive resin composition, and a color filter using the photosensitive resin composition method.

Photosensitive resins for displays are required to have high brightness and high contrast, and are particularly required for television use. In Japanese Patent No. 4090292, a dye is used for high brightness and high contrast, and a high-sensitivity resin having a radical polymerizable group is used for the resin to achieve high resolution. However, since the developing solution is a dilute aqueous alkali solution, it is necessary to introduce a carboxylic acid component in order to dissolve in the developing solution. Therefore, it is practically impossible to introduce a functional group such as an epoxy group into the resin of the final form, so that adhesion to the substrate and coloring during development are actually caused, and a primer layer is provided between the substrate and the photoresist. Solve the problem. And since almost all of the resin must have the steps of the resin polymerization step and the radical polymerization group introduction step in the synthesis step, the productivity is also low.

Patent Document 1 Japanese Patent No. 4090292

An object of the present invention is to provide a copolymer which can be used as a photosensitive resin which can form a pattern copolymer excellent in adhesion to a substrate and which has high sensitivity and high resolution, and contains curability of the copolymer. A resin composition and a photosensitive resin composition, a color filter using the photosensitive resin composition, and a method of producing a color filter.

Another object of the present invention is to provide a copolymer which can be used as a photosensitive resin, wherein the photosensitive resin can form a pattern having excellent adhesion to a substrate and having high sensitivity and high resolution, and can be used in resin synthesis ( 1 step) introducing a functional group such as a radical polymerizable group or an epoxy group to produce a high productivity; a curable resin composition containing the copolymer; and a photosensitive resin composition; and a color filter using the photosensitive resin composition And a method of manufacturing a color filter.

In order to achieve the above object, the present inventors have intensively studied and found that a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [except for a (meth) acrylate derivative and a (meth) acrylamide derivative] When it is polymerized with a vinyl monomer having a carboxyl group or a carboxylic anhydride group, a functional group such as a radical polymerizable group or an epoxy group can be introduced during the synthesis of the resin (in one step), and the copolymer can be obtained with high productivity. When the copolymer is used as a photosensitive resin, it is possible to form a pattern excellent in adhesion to a substrate while having high sensitivity and high resolution, and the present invention has been completed.

That is, the present invention provides a copolymer which can contain at least a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [except for a (meth) acrylate derivative and a (meth) acrylamide derivative] (Vinyl monomer A) is obtained by polymerizing a monomer mixture with a monomer having a carboxyl group or a carboxylic anhydride group (vinyl monomer B).

The above vinyl monomer A contains a compound represented by the following formula (1):

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

The vinyl monomer A may be at least one compound selected from the group consisting of the following compounds (i) to (iii): (i) in the formula (1), R ¹ may have a substituent. a hydrocarbon group, wherein R ² , R ³ and R ^{4 are the} same or different and each represents 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 a compound of n=1; 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 a compound of an integer of from 1 to 3; 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, X is an n-valent hydrocarbon group which may have a substituent, and n is an integer of 1 to 3 At least one compound of the group consisting of the compounds.

The above copolymer contains a copolymer 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 member cyclic ether group.

The vinyl monomer C is preferably a vinyl monomer having an alicyclic epoxy group.

Further, the above copolymer contains at least a vinyl monomer A, a vinyl monomer B, a vinyl monomer C, and a (meth) acrylate D, an aromatic monovinyl compound E, a vinyl alkoxy decane. A copolymer obtained by polymerizing a monomer mixture of at least one monomer selected from the group consisting of the compound F and the hydroxyl group-containing monomer G.

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

The curable resin composition may further contain a group 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. At least one compound selected from the group.

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

The photosensitive resin composition may further contain a group 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. At least one compound selected from the group.

Further, the photosensitive resin composition may further contain a pigment. Further, the above-mentioned photosensitive resin composition can be used for liquid photoresist, dry film, pigment photoresist or coated protective film.

The present invention also provides a color filter produced by using the above photosensitive resin composition.

The present invention also provides a method of producing a color filter, which is characterized in that the photosensitive resin composition is applied onto a support, and then a photomask is formed by exposure to a photomask to form a pattern.

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

The copolymer of the present invention will contain at least a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [except for (meth) acrylate derivatives and (meth) acrylamide derivatives] (vinyl monomer A) a polymer obtained by polymerizing (vinyl polymerization) a monomer mixture of a vinyl monomer (vinyl monomer B) having a carboxyl group or a carboxylic anhydride group. The copolymer of the present invention may be a random copolymer or a block copolymer. The above plurality of carbon-carbon double bonds have polymerizability (especially radical polymerizability). The type of polymerization at the time of polymerizing the monomer mixture is not particularly limited, and radical polymerization is preferred. In the case of such polymerization, a plurality of carbon-carbon double bonds in the vinyl monomer A may be polymerized in any of them. The vinyl monomer A may be used alone or in combination of two or more.

The above vinyl monomer A is a vinyl monomer having a plurality of (for example, 2 to 4, 2 or 3, preferably 2) carbon-carbon double bonds in the molecule [but (meth) acrylate The derivative and the (meth) acrylamide derivative are not particularly limited, and representative examples thereof include the compound represented by the above formula (1).

In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R ² , R ³ and R ^{4 are the} same or different and each represents a hydrogen atom or a methyl group, and X represents a linking group. n represents an integer from 1 to 3.

The "hydrocarbon group" of the hydrocarbon group which may have a substituent in R ¹ may, for example, be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, or a group in which two or more of these groups are bonded. The aliphatic hydrocarbon group has an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group or a decyl group (for example, a carbon number of 1~) An alkyl group of 10, preferably an alkyl group having 1 to 6 carbon atoms; etc.; an alkenyl group such as a vinyl group, a 1-propenyl group, a 1-butenyl group or a 1-hexenyl group (for example, a carbon number of 2 to 10) An alkenyl group, preferably an alkenyl group having 2 to 6 carbon atoms; an alkynyl group such as an ethynyl group or a 1-propynyl group (for example, an alkynyl group having 2 to 10 carbon atoms, preferably a carbon number of 2 to 6) Alkynyl) and the like.

The alicyclic hydrocarbon group is, for example, a cyclopentyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group; a cyclohexenyl group having 3 to 15 members such as a cyclohexenyl group; and a carbon atom number such as a thiol group and an amyl group; 15 cross-linked ring base and so on.

The aromatic hydrocarbon group is, for example, an aromatic hydrocarbon group having about 6 to 20 carbon atoms such as a phenyl group or a naphthyl group. The aliphatic hydrocarbon group and the aromatic hydrocarbon group are bonded to an aralkyl group such as a benzyl group or a 2-phenylethyl group.

These hydrocarbon groups may have a substituent such as an alkyl group (C _1-4 alkyl group or the like), an alkenyl group (C _2-4 alkenyl group or the like), a haloalkyl group (C _1-4 haloalkyl group, etc.), a halogen atom. , alkoxy (C _1-4 alkoxy), hydroxy, hydroxyalkyl (hydroxy-C _1-4 alkyl, etc.), carboxyl, alkoxycarbonyl (C _1-4 alkoxy-carbonyl, etc.), hydrazine Base (C _1-10 thiol, etc.) and the like.

R ¹ is 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, The aralkyl group having 7 to 15 carbon atoms is preferred, and 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 preferred. .

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

The linking group of X has a linear or branched chain alkyl group such as a methylene group, a vinyl group, a propylene group, a trimethylene group, a tetramethylene group or a hexamethylene group (the number of carbon atoms is about 1 to 6). Straight chain or branched chain alkyl group, etc.; linear or branched chain perfluoroalkylene group such as perfluorohexamethylene (linear or branched chain fluorine extension of about 1 to 6 carbon atoms) Alkyl group, etc.; a straight-chain or branched chain-like alkenyl group such as a vinyl group, a propylene group or a butenyl group; a linear or branched chain extending alkenyl group having a carbon number of 2 to 6 or the like; a linear or branched chain fluoro-alkenyl group (linear or branched chain fluorinated alkenyl group having a carbon number of 2 to 6 or the like); 1,3-cyclopentylene group, 1,4-cyclohexylene group a divalent alicyclic hydrocarbon group such as a 1,3-cyclohexylene group or a cyclohexene group; a phenyl group, a naphthyl group or the like, or a C _1-4 alkyl group, an aromatic group, a halogen atom, or a C ₁ group _; Arylene of a substituent such as _-4 alkoxy group; -COO-; -OCO-; -CONH-; -NHCO-; -O-; -S-; -CO-; -CS-;-NH - These are two or more valence groups which are combined by two or more.

n is preferably 1 or 2, and 1 is particularly preferred.

Representative examples of the vinyl monomer A include at least one compound selected from the group consisting of the following compounds (i) to (iii), and (i) in the formula (1), R ¹ may have a substituent. a hydrocarbon group, wherein R ² , R ³ and R ^{4 are the} same or different and represent 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 the compound of n=1; Ii) in the formula (1), wherein 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 a compound of an integer of from 1 to 3; (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, X is an n-valent hydrocarbon group which may have a substituent, and n is an integer of 1 to 3 At least one compound of the group consisting of the compounds.

The compound corresponding to the above (i) is, for example, vinyl crotonate, vinyl cinnamate, vinyl sorbate or the like.

The compound corresponding to the above (ii) is, for example, divinyl oxalate, divinyl succinate, divinyl malonate, divinyl adipate, divinyl 1,4-cyclohexanedicarboxylate, or the like. Divinyl phthalate and the like.

The compound corresponding to the above (iii) is, for example, an aliphatic hydrocarbon which may have a fluorine atom at both terminals, such as 1,6-diethylene (perfluorohexane), having a carbon-carbon double bond (vinyl group); divinylbenzene, 1, 2,4-trivinylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,2-divinyl-3,4-xylene, 2,4-divinylbiphenyl, 3,5 An aromatic polyvinyl compound such as 4'-triethylenebiphenyl or 1,3,5-trivinylbenzene.

The above vinyl monomer B has an unsaturated carboxylic acid or an anhydride thereof. The unsaturated carboxylic acid and its anhydride include, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and the like, α,β-unsaturated carboxylic acid and anhydride thereof (maleic anhydride, Ikon Anhydride, etc.). Among these, acrylic acid and methacrylic acid are particularly preferred. The vinyl monomer B may 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. These monomer units may be used alone or in combination of two or more.

The ratio of the monomer unit to the copolymer of the vinyl monomer A in the copolymer is, for example, 1 to 99% by weight, preferably 2 to 90% by weight, and 2 to 70% by weight, based on the total of the monomer units constituting the copolymer. Better. When the ratio is too low, the sensitivity is liable to be lowered. When the ratio is too high, the resin itself is highly hydrophobic, so that it is difficult to dissolve in the developing solution.

The ratio of the monomer unit to the copolymer of the vinyl monomer B varies depending on the type of the vinyl monomer B to be used, and is usually relative to the composition. The total monomer unit of the copolymer is, for example, 1 to 99% by weight, preferably 2 to 90% by weight, more preferably 2 to 70% by weight. When the ratio is too low, the hydrophilicity of the resin is low and it is difficult to dissolve in the developing solution. When the ratio is too high, the hydrophilicity of the resin is high and the chemical resistance of the coating film is liable to be lowered.

The ratio of the monomer unit corresponding to the vinyl monomer A to the monomer unit corresponding to the vinyl monomer B in the copolymer is, for example, 5 to 100% by weight, based on the total monomer unit constituting the copolymer, 10~ 100% by weight is preferred, and 12 to 100% by weight is more preferred.

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

Such other vinyl monomers include, for example, a vinyl monomer C having 3 to 5 membered cyclic ether groups, a (meth) acrylate D, an aromatic monovinyl compound E, and a vinyl alkoxy decane compound. F, a monomer G containing a hydroxyl group, and the like.

The vinyl monomer C having a 3 to 5 membered cyclic ether group contains a polymerizable unsaturated compound containing an oxirane ring (epoxy group) and an oxetane ring (oxetane group) A polymerizable unsaturated compound or a polymerizable unsaturated compound having an oxylanyl group (oxypentanyl group).

Examples of the polymerizable unsaturated compound containing an oxirane ring (epoxy group) include epoxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 2-methyl epoxy (meth)acrylate. Propyl ester, (meth) acrylate 2-glycidyl propyl ester, 2-epoxyethyl ethyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, (meth) acrylate a polymerizable unsaturated compound ((meth)acrylate derivative, etc.) containing an oxirane ring (monocyclic ring) such as 3-glycidoxypropoxide or (meth)acrylic acid propylene oxide; 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethoxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethoxy)propyl (meth)acrylate, etc., containing 3,4-ring A polymerizable unsaturated compound (such as a (meth) acrylate derivative) containing an epoxy group-containing cycloalkane ring such as an oxycyclohexane ring; (meth)acrylic acid 5,6-epoxy-2-bicyclo[2.2.1 a polymerizable unsaturated compound ((meth) acrylate derivative, etc.) containing a 5,6-epoxy-2-bicyclo[2.2.1]heptane ring, such as heptyl ester; epoxidation (methyl) Acid dicyclopentenyl acrylate [(meth) acrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2,6] dec-9-ester, (meth) acrylate, 3,4-epoxy-tricyclo [5.2 .1.0 ^2,6] decan-8, or a mixture of these ester], epoxidized dicyclopentenyl oxyethyl (meth) acrylates [2- (3,4-epoxy-tricyclo [5.2.1.0 ^{2, 6} ]癸-9-oxy)ethyl ester, 2-(3,4-epoxytricyclo[5.2.1.0 ^2,6 ]癸-8-oxy)ethyl (meth)acrylate or a mixture of these], ring A polymerizable unsaturated compound ((meth) acrylate derivative, etc.) containing a 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] anthracene ring, such as dicyclopentenyloxybutyl (meth) acrylate )Wait. As another polymerizable unsaturated compound containing an oxirane ring (epoxy group), a vinyl ether compound containing an epoxy group, an allyl ether compound containing an epoxy group, or an aromatic vinyl group containing an epoxy group can also be used. Base compound, etc. The aromatic vinyl compound containing an epoxy group is a styrene derivative such as 4-vinylbenzyl epoxidized ether, 4-vinylbenzyloxyethane or 4-ethyleneethylbenzene oxide.

The polymerizable unsaturated compound containing an oxetane ring (oxetanyl group) is, for example, (meth)acrylic acid oxetane, (meth)acrylic acid 3-methyl-3-oxetane Alkyl ester, 3-ethyl-3-oxetane (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate, (meth) propylene Acid (3-ethyl-3-oxetanyl) methyl ester, 2-(3-methyl-3-oxetanyl)ethyl (meth)acrylate, 2-((meth)acrylate) 3-ethyl-3-oxetanyl)ethyl ester, 2-[(3-methyl-3-oxetanyl)methoxy](meth)acrylate, (meth)acrylic acid 3-[(3-methyl-3-oxetanyl)methoxy]propyl ester, 3-[(3-ethyl-3-oxetanyl)methoxy](meth)acrylate] A propyl ester, a vinyl ether compound containing an oxetane group, an allyl ether compound containing an oxetane group, or the like.

The polymerizable unsaturated compound containing an oxolane (oxocyclopentyl) group is, for example, tetrahydrofuran (meth) acrylate, a vinyl ether compound containing an oxolyl group, and an allyl ether containing an oxolyl group. Compounds, etc.

The copolymer of the present invention has a cyclic ether group of 3 to 5 members [oxirane ring (epoxy group), oxetane ring (oxetanyl group), oxolane ring (oxalate) When cyclopentyl)], these groups function as a hardening group. The 3~5 member cyclic ether group mainly contributes to the improvement of drug resistance (solvent resistance, alkali resistance, etc.). The vinyl monomer C having a cyclic ether group of 3 to 5 members may be used alone or in combination of two or more.

The vinyl monomer C having a 3 to 5 membered cyclic ether group is preferably a polymerizable unsaturated compound containing an oxirane ring (epoxy group), which contains a cycloalkyl ring containing an epoxy group. A polymerizable unsaturated compound, 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 ]癸A vinyl monomer having an alicyclic epoxy group such as a polymerizable unsaturated compound of an alkane ring is preferred.

When the copolymer of the present invention has a monomer unit corresponding to the vinyl monomer C, the ratio of the monomer unit to the copolymer is, for example, 1 to 99% by weight, and 2 to 90% by weight based on the total of the monomer units constituting the copolymer. % is better, and 2 to 85% by weight is more preferable. When the ratio is too low, the drug resistance and adhesion of the coating film are liable to be low. When the ratio is too high, the resin is highly hydrophobic and difficult to dissolve in the developing solution.

The (meth) acrylate D is, for example, a compound represented by the following formula (2).

(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 hydrocarbyl-substituted oxy group).

R ⁶ carbon atoms, the hydrocarbon group of 1 to 25, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, butyl S-, T-butyl, pentyl, hexyl, octyl , 2-ethylhexyl, decyl, dodecyl, hexadecyl (cetyl), heptadecyl, octadecyl (stearyl), nineteen, twenty, twenty-two An alkyl group; an alicyclic hydrocarbon group such as a cyclohexyl group, a dicyclopentyl group or an isodecyl group; a 10-cyclohexyl decyl group, a 12-cyclohexadecanyl group, a 14-cyclohexyltetradecyl group, and a 16-cyclohexene group An alicyclic hydrocarbon group bonded to an alkyl group; an aryl group such as phenyl; benzyl, 1-phenylethyl, 2-phenylethyl, 4-phenylbutyl, 6-phenylhexyl, 8-phenyloctyl An aralkyl group such as 10-phenylhydrazino group, 12-phenyldodecyl group, 14-phenyltetradecyl group or 16-phenylhexadecyl group; or a group obtained by bonding these two or more groups.

Further, the hydrocarbyl-substituted oxy group having a hydrocarbon group having 1 to 25 carbon atoms may have an alkoxy group such as a methoxy group or an ethoxy group (e.g., an alkoxy group having 1 to 10 carbon atoms); an aryloxy group such as a phenoxy group; a cycloalkyloxy group such as a cyclohexyloxy group or a dicyclopentyloxy group; an aryloxy group such as a benzyloxy group; a hydrocarbyl-substituted oxy group having 1 to 15 carbon atoms (preferably having 1 to 12 carbon atoms); Wait.

Representative examples of the (meth) acrylate represented by the formula (2) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Ester, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyloxy (meth) acrylate, isodecyl (meth) acrylate, Benzyl (meth)acrylate, phenylethyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, or (meth)acrylate.

Further, the (meth) acrylate D may have, for example, a (meth) acrylate having an isocyanate group or a blocked isocyanate group, a (meth) acrylate having an alkoxyalkyl group, and a hindered amine structure. (meth) acrylate or the like.

The (meth) acrylate having an isocyanate group or a blocked isocyanate group is, for example, 2-[O-(1'-i-propylidino)carboxyamino]ethyl methacrylate (= 2-(methacrylic acid) acrylate) Methyl propylamine oxycarbonylamine ethyl ester) [trade name "Karenz MOI-BM", manufactured by Showa Denko Co., Ltd.], 2-(3,5-dimethylpyrazole-1-yl)carbonylamine methacrylate Ester [trade name "Karenz MOI-BP", Showa Denko (share) system] and so on.

The (meth) acrylate having an alkoxyalkyl group is, for example, γ-(meth) propylene oxypropyl trimethoxy decane, γ-(meth) propylene oxypropyl triethoxy decane, γ- (Meth) propylene oxime propyl methyl dimethoxy decane, γ-(methyl) propylene oxiranyl methyl diethoxy decane, γ-(methyl) propylene oxypropyl triethoxy Baseline, β-(meth)acryloyloxyethyltrimethoxydecane, β-(meth)acryloyloxyethyltriethoxydecane, γ-(methyl)propene oxiranyl phenyl phenyl A polymerizable unsaturated compound containing an alkoxyalkyl group such as methoxydecane or γ-(meth)acryloyloxybutyl phenyl diethoxy decane.

Further, the (meth) acrylate having a hindered amine structure is, for example, a trade name "AdekaStab LA-82" or "AdekaStab LA-87" (above, ADEKA Co., Ltd.).

The aromatic monovinyl compound E is, for example, styrene, α-methyl styrene, vinyl toluene, vinyl naphthalene, ethylene biphenyl or the like.

The vinyl alkoxydecane compound F is, for example, vinyltrimethoxydecane, vinyltriethoxydecane, vinylmethyldimethoxydecane, vinylmethyldiethoxydecane or the like.

The hydroxyl group-containing monomer G is, for example, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2,3-dihydroxybutyl (meth)acrylate, 4-hydroxy(meth)acrylate. Butyl methacrylate, 6-hydroxyhexyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 8-hydroxyoctyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, and polycondensation An alkanediol mono(meth)acrylate or the like, which is obtained by ring-opening polymerization of a monoester of a polyhydric alcohol with acrylic acid or methacrylic acid, a monoester of the above polyhydric alcohol with acrylic acid or methacrylic acid, and ε-caprolactone. A compound (manufactured by DAICEL Chemical Industry Co., Ltd., PLAKCEL FA series, PLAKCEL FM series, etc.), a compound containing a hydroxyl group by ring-opening polymerization of ethylene oxide or propylene oxide, or the like.

The copolymer of the present invention has at least 1 selected corresponding to the group consisting of (meth) acrylate D, aromatic monovinyl compound E, vinyl alkoxy decane compound F, and hydroxyl group-containing monomer G. When the monomer unit of the monomer is used, the ratio of the monomer unit to the copolymer is generally 2 to 60% by weight, preferably 2 to 50% by weight, more preferably 5 to 40% by weight.

Preferably, the copolymer of the present invention has (1) a monomer unit corresponding to the vinyl monomer A and a monomer unit corresponding to the vinyl monomer B in an amount of 5% by weight or more based on the total of all the monomer units ( Especially 10% by weight or more, especially 50% by weight or more of the copolymer, (2) containing a monomer unit corresponding to the vinyl monomer A, a monomer unit corresponding to the vinyl monomer B, and an ethylene corresponding to a cyclic ether group having 3 to 5 members The monomer unit of the base monomer C accounts for 40% by weight or more (especially 50% by weight or more) of the copolymer of all the monomer units, and (3) contains the monomer unit corresponding to the vinyl monomer A, corresponding to ethylene. a monomer unit of the base monomer B, a monomer unit corresponding to the vinyl monomer C having a 3 to 5 member cyclic ether group, and corresponding to (meth)acrylate D, an aromatic monovinyl compound E, The monomer unit of at least one monomer selected from the group consisting of the vinyl alkoxydecane compound F and the hydroxyl group-containing monomer G accounts for 40% by weight or more (especially 50% by weight or more) of all the monomer units. Copolymer.

The copolymer of the present invention may have the above-mentioned vinyl monomer A having a vinyl group A, a carboxyl group or an acid anhydride group, and, if necessary, a vinyl monomer C having a cyclic ether group of 3 to 5 members, (methyl group) A monomer mixture of another copolymerizable monomer such as acrylate D, aromatic monovinyl compound E, vinyl alkoxy decane compound F, or hydroxyl group-containing monomer G is produced by copolymerization (vinyl polymerization).

The polymerization initiator used for the polymerization may be a usual radical initiator. 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(isobutyrate) dimethyl ester, diethyl-2, An azo compound such as 2'-azobis(2-methylpropionate) or dibutyl-2,2'-azobis(2-methylpropionate), benzalkonium peroxide, lauric peroxide An organic peroxide such as a mercapto group, a tributyl peroxyacetate, a 1,1-bis(t-butoxy)cyclohexane, or a hydrogen peroxide. Use peroxide as self In the case of a base polymerization initiator, a reducing oxidative initiator which combines a reducing agent may also be used. Among the above, an azo compound is preferred, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis ( Isobutyric acid) dimethyl ester is especially preferred.

The amount of the polymerization initiator to be used may be appropriately selected so as not to impair the smooth copolymerization, and is usually about 1 to 30% by weight, preferably about 5 to 25% by weight based on the total of the total monomer components and the polymerization initiator.

In the present invention, a chain transfer agent generally used for radical polymerization can also be used in combination. Specific examples are mercaptans (n-dodecyl mercaptan, n-octadecyl mercaptan, n-butyl mercaptan, third butanol, n-lauric mercaptan, antimony ethanol, mercapto alcohol, triethylene glycol dithiol, Mercaptans (such as thiopropionic acid, benzoic acid, decanediol, phthalic acid, etc.), alcohols (such as isopropanol), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.) ), α-methylstyrene dimer, decene, cuminene, anthracene, α-pinene, β-pinene, etc., the amount of the chain transfer agent is 0.001 relative to the total amount of the radical polymerizable monomer. It is preferable that it is 3% by weight. When a chain transfer agent is used, it is preferred to mix it with a polymerizable vinyl monomer in advance.

The polymerization can be carried out by a method conventionally used for the production of a styrene-based polymer or a propylene-based polymer by solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, or emulsion polymerization. Among these, solution polymerization is preferred. The monomer and the polymerization initiator may be supplied to the reaction system in a single gas, or a part or all of the monomer 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 mixture of a monomer and a polymerization solvent maintained at a certain temperature, or a monomer or a polymerization initiator is previously dissolved in a polymerization solvent may be used. The solution is dropped into a polymerization solvent maintained at a certain temperature to be polymerized (drop polymerization method) or the like.

The polymerization solvent can be appropriately selected depending on the monomer composition and the like. The polymerization solvent is, for example, an 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, etc.) ), propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether (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 ether, glycerol mono, di or trialkyl ether Chain ethers such as glycol ethers; tetrahydrofuran, Alkyl and other cyclic ethers, etc., esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C _a carboxylic acid ester such as _5-6 cycloalkane mono or diacetate, C _5-6 cycloalkanediethanol 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 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-butanediol mono or diacetate, 1,6 - hexanediol mono or diacetate, glycerol mono, di or triacetate, glycerol mono or di C _1-4 alkyl ether di or mono acetate, tripropylene glycol monoalkyl ether acetate, three a diol acetate such as propylene glycol mono- or diacetate or a glycol ether acetate, etc.), a ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone) Cyclohexanone, 3,5,5-trimethyl-2-cyclohexene-1-one, etc., guanamines (N,N-dimethylacetamide, N,N-dimethylformamide, etc.) ), anthraquinones (dimethyl hydrazine, etc.), alcohols (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanediethanol, etc.), hydrocarbons (benzene, toluene, An aromatic hydrocarbon such as xylene or an aliphatic hydrocarbon such as hexane or an alicyclic hydrocarbon such as cyclohexane, or a mixed solvent thereof. The polymerization temperature can be appropriately selected, for example, in the range of about 30 to 150 °C.

The copolymer of the present invention is produced by the above method. The weight average molecular weight of the copolymer is about 500 to 1,000,000, preferably 5,000 to 500,000, and more preferably about 10,000 to 200,000. The degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer is about 1 to 3.

The resulting copolymer can be purified by precipitation or reprecipitation or the like. Precipitation and reprecipitation can be carried out by conventional methods.

The curable resin composition of the present invention contains at least the above copolymer of the present invention. The curable resin composition of the present invention is subjected to a solid content concentration adjustment, a solvent exchange, a filtration treatment, and, if necessary, a curing catalyst [thermal acid generator (thermosetting). Catalyst, thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization initiator), photoradical initiator, hardener, hardening accelerator, additive (filler, defoamer, hard Modification of a fuel, an antioxidant, an ultraviolet absorber, a low-stressing agent, a flexibility imparting agent, a wax, a resin, a crosslinking agent, a halogen trapping agent, a leveling agent, a wetting modifier, etc., and a pigment . The curable resin composition and the photosensitive resin composition of the present invention may be blended with particles of glass, vermiculite, ceramics, metal oxides, metal nitrides, metals, clay minerals, rubbers, polymer compounds, etc., and organometallics. Carbon compounds such as C60/carbon nanotubes. Further, the polymer produced by the polymerization is purified by precipitation or reprecipitation, and the purified polymer together with the above-mentioned appropriate additive is dissolved in a solvent required for the use to obtain a curable resin composition.

The curable resin composition may also contain a 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. At least one compound selected. The solvent constituting the curable resin composition may be exemplified as the above-mentioned polymerization solvent. The curable resin composition of the present invention can be used as a photosensitive resin composition by selecting a component to be blended.

The photosensitive resin composition of the present invention contains one or more kinds of the above-mentioned copolymers of the present invention and a photopolymerization initiator. The photosensitive resin composition may further contain a 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. At least one compound selected.

Examples of the compound having a radical polymerizable double bond include a (meth) acrylate, a vinyl aromatic compound such as styrene, and a guanamine compound. Representative (meth) acrylates are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, butyl (meth) acrylate (meth)acrylic acid alkyl esters such as esters and hexyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, The lactone is modified with 2-hydroxyethyl (meth)acrylate, etc., having a hydroxyl group (meth) acrylate; methoxydiethylene glycol (meth) acrylate, ethoxy diethylene glycol (methyl) Acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol #400-(Meth)acrylate and other (meth)acrylates (polyalkylene glycol monoether mono(meth)acrylates); 1,6-hexanediol di(meth)acrylate, a difunctional (meth) acrylate such as neopentyl glycol di(meth)acrylate; a polyfunctional (meth) acrylate such as trimethylolpropane tri(meth)acrylate or the like (methyl) Acrylate and the like.

It is also possible to use a polymerizable prepolymer as a compound having a radical polymerizable double bond. The polymerizable prepolymer is, for example, a (meth) acrylate of a polyester polyol, a (meth) acrylate of a polyether polyol, an adduct of a polyepoxide and a (meth)acrylic acid, and The polyol is introduced into a resin of a hydroxy (meth) acrylate by a polyisocyanate.

The compound having a radical polymerizable double bond is preferably a polyfunctional vinyl compound such as a polyfunctional (meth) acrylate. The compound having a radically polymerizable double bond may be used alone or in combination of two or more. When a compound having a radical polymerizable double bond is blended in the photosensitive resin composition, higher sensitivity and resolution can be achieved, and film properties can be improved. Further, since a compound having a radical polymerizable double bond can be used in place of a diluent solvent, it is also effective in viscosity adjustment and high solid content.

If the polyfunctional thiol compound is a compound having two or more thiol groups, for example, hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4- Butylene glycol dithioethylene glycol ester, ethylene glycol dithioethylene glycol ester, ethylene glycol dithiopropionate, trimethylolpropane thioethylene glycol ester, trimethylolpropane thiopropionate, Trimethylolpropane -3-butyrate, neopentyl thioglycolate, pentaerythritol thiopropionate, pentaerythritol sulphur-3-n-butyrate, triterpenoid Propionate (2-hydroxyethyl)isocyanate, 1,4-dimethylindole, 2,4,6-tris-s-three , 2-(N,N-dibutylamino)-4,6-diterpene-s-three , tetraethylene glycol bis-3-indolyl propionate, trimethylolpropane ginseng 3-indole propionate, ginseng (3-indolyl oxyethyl) iso-cyanate, neopentyl pentoxide - 3-巯propionate, dipentaerythritol 肆3-thiopropionate, 1,4-bis(3-indolyloxy)butane, 1,3,5-gin (3-indeneoxy) Ethyl)-1,3,5-three -2,4,6-(1H,3H,5H)trione and the like. The polyfunctional thiol compound may be used alone or in combination of two or more. By blending a polyfunctional thiol compound into the photosensitive resin composition, higher sensitivity, resolution, and film properties can be achieved. Further, since the polyfunctional thiol compound can be used in place of the dilution solvent, it is also effective in viscosity adjustment and high solid content.

As the hindered amine compound, a compound generally called a hindered amine light stabilizer (HALS) can be used, and for example, the following compounds can be used. In the formulas (3h), (3i), (3o), (3q), and (3r), m represents an integer of 1 or more. The hindered amine compound may be used alone or in combination of two or more. When a hindered amine compound is blended in the photosensitive resin composition, higher sensitivity and resolution can be achieved, and film properties can be improved.

The epoxy compound is, for example, an epoxidized resin containing an unsaturated group such as an epoxidized polybutadiene or an epoxidized butadiene styrene block copolymer (a commercially available product is EPICEAD PB, ESBS, etc. manufactured by DAICEL Chemical Co., Ltd.). ), alicyclic epoxy resin (for example, CEROXIDE 2021, EHPE manufactured by DAICEL Chemical Co., Ltd.; EPOMIC VG-3101 manufactured by Mitsui Petrochemical Co., Ltd.; E-3013S manufactured by SHELL EPOXY); Mitsubishi Gas Chemical Co., Ltd. ) TETRAD-X, TETRAD-C; Japan's Soda (EPB-13, EPB-27, etc.), copolymerized epoxy resin (for example, copolymer of glycidyl methacrylate and styrene, methyl Glycidyl acrylate, copolymer of styrene and methyl methacrylate, CP-50M, CP-50S, or glycidyl methacrylate and cycloheximinimide, manufactured by Nippon Oil & Fats Co., Ltd. Such as copolymers, etc., as well as epoxidized resins having a special structure.

The epoxy compound may also be a varnish-type epoxy resin [having varnishes such as phenol, cresol, halogenated phenol, and alkylphenol, and aldehydes reacted with formaldehyde under an acidic catalyst to obtain varnish and epichlorohydrin and/or a watch. The product obtained by the reaction of chlorohydrin (the commercial product is EOCN-103, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN-S manufactured by Nippon Kayaku Co., Ltd.) DEN-made by DOW CHEMICAL Co., Ltd. 431, DEN-439; Nippon Ink Chemical Industry Co., Ltd. N-73, VH-4150, etc.), bisphenol type epoxy resin (for example, bisphenol A, bisphenol F, bisphenol S and tetrabromo a product obtained by reacting a bisphenol A such as bisphenol A with epichlorohydrin, a product obtained by reacting a condensed product of bisphenol A diglycidyl ether with the above bisphenol and epichlorohydrin (a commercially available product thereof Oiled SHELL (stock) EPICOTE 1004, EPICOTE 1002; DOW CHEMICAL DER-330, DER-337, etc.), reacting phenolic methane, cresyl methane, etc. with epichlorohydrin and / or methyl chlorohydrin And the products obtained (the commercial products are EPPN-501, EPPN-502, etc. made by Nippon Chemical Co., Ltd.), ginseng (2,3-epoxypropyl) isocyanurate, biphenyl epoxide Propyl ether and the like.

These epoxy compounds (epoxy resins) may be used alone or in combination of two or more. When an epoxy compound is blended in the photosensitive resin composition, higher sensitivity and resolution can be achieved, and the film properties can be improved.

The oxetane compound is, for example, 3-ethyl-3-hydroxymethoxyoxetane [OXT-101, manufactured by East Asian Synthetic Chemical Industry Co., Ltd.], 2-hexyloxetane [East Asia Synthetic Chemical Industry Co., Ltd. OXT-212], benzodimethyloxetane [OXT-121, manufactured by East Asian Synthetic Chemical Industry Co., Ltd.], 3-ethyl-3-[3-ethoxyoxet-3-yl Methoxymethyl]oxetane [OXT-221 manufactured by East Asian Synthetic Chemical Industry Co., Ltd.] and the like.

These oxetane compounds may be used alone or in combination of two or more. When an oxetane compound is blended in the photosensitive resin composition, higher sensitivity and resolution can be achieved, and film properties can be improved.

The vinyl ether compound is, for example, neopentyl alcohol tetravinyl ether, trimethylolpropane trivinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexanediol divinyl ether, decanediol two Vinyl ether, 1,4-butanediol divinyl ether, allyl vinyl ether, triethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9 - hydroxydecyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and the like.

These vinyl ether compounds may be used alone or in combination of two or more. When a vinyl ether compound is blended in the photosensitive resin composition, higher sensitivity and resolution can be achieved, and film properties can be improved.

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 in a curable resin composition or a photosensitive resin composition The amount is preferably 0.1 to 40 parts by weight, preferably 1 to 25 parts by weight, more preferably 1.5 to 15 parts by weight per 100 parts by weight of the copolymer of the present invention. In addition, the total 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 to 25 parts by weight, based on 100 parts by weight of the copolymer of the present invention. More preferably ~15 parts by weight.

As the photopolymerization initiator, a photo radical initiator, a photoacid generator, or the like can be used. The photopolymerization initiator may be used alone or in combination of two or more.

The photoradical initiator may be, for example, diphenyl ketone, acetophenone ketal, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, methyl benzalkonium bromide, ethyl 4-dimethylamine benzylate (Japanese KA(stock) system KAYACURE EPA, etc.), 2,4-diethyl oxysulfide (KAYACURE DETX, etc.), 2-methyl-1-[4-(methyl)phenyl]-2- 2-Amino-2-benzyl hydrazine, such as 2-aminoamine-2-(4-tyrosolinyl)benzylidene-1-phenylpropane, is morpholinedone-1 (IRGACURE 907, etc. made by Ciba Specialty Chemicals Co., Ltd.) -1-phenylalkane compound, tetrakis(t-butylperoxycarbonyl)diphenyl ketone, diphenylethylenedione, 2-hydroxy-1-phenylpropan-1-one, 4,4-bisdiethylamine Amine benzene derivative such as diphenyl ketone, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole An imidazole compound such as B-CIM, etc., 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-three Isohalogen methylation Compound, 2-trichloromethyl-5-(2-benzofuran-2-vinyl)-1,3,4- Halogen methyl group The oxadiazole compound or the like may be used singly or in combination, and if necessary, a sensitizer may be added.

The photoacid generator may be, for example, SAIRACURE UVI-6970, SAIRACURE UVI-6974, SAIRACURE UVI-6990, SAIRACURE UVI-950 (manufactured by U.S. Union Carbide Co., Ltd., trade name), IRGACURE 261 (manufactured by Steam Bartification Co., Ltd.). Product name), SP-150, SP-151, SP-170, OPTOMER SP-171 (the above-mentioned Asahi Chemical Industry Co., Ltd., trade name), CG-24-61 (manufactured by Steam Bart Chemical Co., Ltd., trade name), DAIACTII (DAICEL Chemical Industry Co., Ltd., trade name), UVAC 1591 (DAICEL CYTEC (stock), trade name), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI- 2855, CI-2823, CI-2758 (above, product of Japan Soda Co., trade name), PI-2074 (manufactured by Rhone Poulenc, trade name, benzyl cumene pentafluorobenzene), FFC509 (3M company) Product, trade 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., trade name) , CD-1012 (manufactured by American Sartomer Co., Ltd., trade name), etc., represented by diazonium salt, barium salt, barium salt, barium salt, selenium salt, Salt, ammonium salt, etc.

The photopolymerization initiator is a combination of an imidazole compound and an amine benzene derivative, a 2-amine-2-benzylindole-1-phenylalkane compound, or a halomethylation three from the viewpoints of sensitivity and drug resistance. Compound, halomethyl The oxadiazole compound or the like is preferred.

The photosensitive resin composition of the present invention may contain a thermal acid generator if necessary. For the thermal acid generator, for example, SANAID SI-45, SI-47 with the left, SI-60 with the left, SI-60L with the left, SI-80 with the left, SI-80L with the left, SI-100 with the left, SI-100L with the left, and SI- with the left can be used. 145, the same left SI-150, the same left SI-160, the same left SI-110L, the same left SI-180L (the above three new chemical industry company products, trade names), CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (above Japanese Caoda (share) products, trade name), CP-66, CP-77 (asahi Chemical Industry Co., Ltd. products, trade name), FC-520 (3M company products, The product name) is represented by diazonium salt, strontium salt, strontium salt, strontium salt, selenium salt, Salt, ammonium salt, etc.

The amount of the photopolymerization initiator to be added is, for example, 0.05 to 10% by weight, preferably 0.5 to 5% by weight based on the copolymer (resin component) in the photosensitive resin composition.

These photopolymerization initiators may also contain a synergist, such as a tertiary amine, for enhancing the conversion of absorbed light energy to polymerization-initiated radicals. On the other hand, when the curable resin composition of the present invention is hardened by irradiation with an electron beam, it is not necessary to add an initiator.

The photosensitive resin composition thus obtained is cured to obtain a cured product (hardened film, etc.) which has high sensitivity and high resolution, has high adhesion to a substrate and a substrate, and is excellent in solvent resistance such as solvent resistance and alkali resistance. ). Therefore, it is suitably used as a coating material, a coating agent, an adhesive, etc., and is especially suitable as a resin composition for liquid-resistance, dry film, and coating-protection film formation of an electronic field.

Further, by adding a pigment to the photosensitive resin composition, it is also suitable for a pigment filter such as a color filter or a black matrix. For example, the pigment and the dispersing agent are dispersed in a varnishing machine, a sand mill, a ball mill, a roll mill, a stone mill, a jet mixer, a homogenizer, etc., and are added to a photosensitive resin composition and mixed, and can be used for liquid crystal display. A color filter such as a color filter or a black matrix.

As the above pigment, a pigment of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, a brown pigment, and a black pigment can be used. Further, the structure may be azo, phthalocyanine, quinophthalone, benzimidazolone, isoindolinone, or Organic pigments such as phthalic acid, indanthrene, and purple ketone, and various other inorganic pigments. Specific examples of the pigment that can be used are shown below by the pigment number. The following terms such as "CI Pigment Red 2" mean the color index (CI).

The red pigments are CI 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, 52:2, 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. Of these, preferred are C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, and more preferably C.I. Pigment Red 177, 209, 224, 254.

Blue pigments are CI 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, preferred are C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and more preferably C.I. Pigment Blue 15:6.

The green pigments are 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, C. I. Pigment Green 7, 36 is preferred.

The yellow pigment has C. 1. 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, 6162, 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, 208. Of these, preferred are C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C. I. Pigment Yellow 83, 138, 139, 150, 180.

Orange pigments are CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34 blue 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, C. I. Pigment Orange 38, 71 is preferred.

The purple pigments are CI 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. Among these, preferred are C.I. Pigment Violet 19, 23, and more preferably C. I. Pigment Violet 23.

Further, when a pigment composition (pigment) is used to form a resin black matrix of a color filter, a black color material (pigment) can be used. The black color material can be a black color material alone, or a mixture of red, green, blue, and the like. Further, these color materials may be appropriately selected from inorganic or organic pigments. The inorganic or organic pigments are preferably dispersed to an average particle diameter of 1 μm or less, more preferably 0.5 μm or less.

The color materials that can be mixed for the modulation of black color materials are Victoria Pure Blue (42595), Aurora O (41000), Catilon Brilliant Flavin (Basic 13), Rose Red 6GCP (45160), Rose Red B (45170), Tibetan Red OK 70: 100 (50240), Alice Sea Blue X (42080), No. 120 / RIONOL YELLOW (21090), RIONOL YELLOW GRO (21090), SIMURA FAST YELLOW 8GF (21105), benzidine yellow 4T-564D ( 21095), SIMURA FAST RED 4015 (12355), RIONOL RED 7B4401 (15850), Fastogen Blue TGR-L (74160), RIONOL BLUE SM (26150), RIONOL BLUE ES (Pigment Blue 15:6), RIONOGEN RED (Pigment Red) 168), RIONOL GREEN 2YS (pigment green 36), etc. [and the number in the above () means color index (CI)].

Further, in addition, pigments which can be used in combination, represented by CI numbers, are CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange Pigments 36, 43, 51, 55, 59, 61, CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI violet pigments 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15:1, 15:4, 22, 60, 64, CI green pigment 7, CI brown pigment 23 , 25, 26, etc.

Further, the black color materials which can be used alone are carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and the like. Among these, carbon black is preferred from the viewpoint of light blocking rate and image characteristics. Carbon black has, for example, 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, #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 Corporation: Printex 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex 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: 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.

Columbian Carbon: RAVEN 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

Other black pigments are, for example, titanium black, aniline black, iron oxide black pigment, and can be mixed with red, green, and blue organic pigments.

Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, chrome yellow, iron oxide red, chromium oxide or the like can be used. These pigments may also be used in combination. For example, to adjust the color, a green pigment and a yellow pigment may be used in combination, and a blue pigment and a violet pigment may be used in combination.

The average particle diameter of these pigments is preferably 1 μm, preferably 0.5 μm or less (for example, 0.005 to 0.5 μm), more preferably 0.25 μm or less (for example, 0.01 to 0.25 μm).

The blending amount of the pigment is preferably 15 to 60 parts by weight based on 100 parts by weight of the total solid content excluding the pigment. In the case of a composition for a black matrix containing a black pigment such as carbon black, the amount of the pigment is preferably 50 to 150 parts by weight, more preferably 70 to 140 parts by weight, based on 100 parts by weight of the total solid content of the pigment. 90~130 parts by weight is especially good.

For the good dispersion of the pigment, a dispersant may be blended in the photosensitive resin composition as necessary. As the dispersant, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, a polyfluorene-based or a fluorine-based surfactant can be used. Among the surfactants, a polymer surfactant (polymer dispersant) exemplified below is preferred.

That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl benzene such as polyoxyethylene octyl phenyl ether and polyoxyethylene phenyl ether Ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate, polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; third amine modification Polymeric surfactants such as polyurethanes are suitable.

Specific examples of the polymer dispersant include EFKA (manufactured by EFKA Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), DISPERON (manufactured by Kanemoto Kasei Co., Ltd.), SOLSPERSE (manufactured by ZENEKA Co., Ltd.), and KP (Shin-Etsu Chemical Co., Ltd.) System), POLYFLOW (Kyoeisha Chemical Co., Ltd.) and so on. These may be used alone or in combination of two or more.

The polymer dispersant has a weight average molecular weight (Mw) of 700 or more in terms of polystyrene by GPC, preferably 1,000 or more, 100,000 or less, and 50,000 or less. In particular, the urethane-based and acryl-based polymer dispersing agents are preferably Disperbyk 160-166 series, Disperbyk 2000, 2001, etc. (all manufactured by BYK Chemical Co., Ltd.).

The propylene-based polymer dispersant is preferably a random copolymer, a graft copolymer or a block copolymer. These copolymers can be produced by a known method.

Further, the dispersant may be a pigment derivative, and the pigment derivative may be an azo system, an anthocyanine system, a quinophthalone type, a benzimidazolone type, a quinoline yellow type, an isoindolinone type, or a second. Derivatives of the genus, lanthanide, indanthrene, lanthanide, perhexanone, diketopyrrolpyrrole, etc., of which quinoline yellow is preferred. The substituent of the pigment derivative is a sulfonic acid group, a sulfonylamino group and a fourth salt thereof, a quinone imine methyl group, a dialkylamine alkyl group, a hydroxyl group, a carboxyl group, a decylamino group, etc., directly or through an alkyl group, The aryl group, the heterocyclic group and the like are bonded to the pigment skeleton, preferably a sulfonic acid group. Further, these substituents may have a complex substitution in a pigment skeleton. Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinoline yellow, a sulfonic acid derivative of hydrazine, a sulfonic acid derivative of quinacridone, and a sulfonic acid of diketopyrrolpyrrole. Derivative, two Sulfonic acid derivatives and the like. These may be used alone or in combination of two or more. Further, the dispersant is preferably a combination of a polymer dispersant and a pigment derivative.

Further, the photosensitive resin composition of the present invention may be blended with a solid content other than the above components as necessary. These components include a surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, an adhesion enhancer, a development improver, and the like. As the solvent of the photosensitive resin composition, those exemplified above as the polymerization solvent can be used.

As the surfactant, various surfactants such as an anionic, cationic, nonionic or amphoteric surfactant can be used, and it is preferable to use a nonionic surfactant because it is less likely to adversely affect the properties.

The concentration 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, even more preferably 0.03 to 0.3% by weight, based on the total amount of the composition.

As the thermal polymerization preventive agent, for example, hydroquinone, p-methoxyphenol, gallic phenol, catechol, 2,6-tributyl-p-cresol, β-naphthol or the like can be used. The amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight based on the total solid content of the composition.

For the plasticizer, for example, dioctyl phthalate, di(didecanoate), triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresol phosphate, dioctyl adipate can be used. Ester, dibutyl sebacate, triethylene glycol glycerin, and the like. The compounding amount of these plasticizers is preferably in the range of 10% by weight or less based on the total solid content of the composition.

When the curable resin composition is cured, a cured product excellent in physical properties can be obtained. For example, the curable resin composition is applied to various substrates or substrates (supports) by a spin coater, a gap coater or the like to form a coating film, and then the coating film is cured to obtain a cured product. The substrate or substrate has glass, ceramic, germanium wafer, metal, plastic, and the like. Coating by a spin coater, a gap coater or the like can be carried out by a conventional method.

The hardening of the coating film is carried out by heating, or by exposure with an active energy ray, or by heating after exposure. When the curable resin composition is thermally cured, the heating temperature is in the range of 50 ° C to 260 ° C, and preferably in the range of 80 ° C to 240 ° C. Further, when the curable resin composition is cured by light, light rays of various wavelengths such as ultraviolet rays, X-rays, g-lines, i-lines, excimer lasers, and the like are used for exposure. The thickness of the film after hardening can be appropriately selected depending on the use, and is generally 0.1 to 40 μm, preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm.

Further, when the photosensitive resin composition is used, it is applied onto a support, and then exposed to a mask to develop a pattern to form a color filter. The order in which the color filters are produced and the operation can be carried out by conventional methods.

Example

The invention is illustrated in more detail in the following examples, but the invention is not limited to the examples. The weight average molecular weight (in terms of polystyrene) and the degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the produced copolymer were measured under the following conditions.

Device: Detector: RID-10A (Shimadzu Corporation)

Pump: LC-10ADVP (Shimadzu Corporation)

System controller: SCL-10AVP (Shimadzu Corporation)

Deaerator: DGU-14A (Shimadzu Corporation)

Autoinjector: SIL-10AF (Shimadzu Corporation)

Column: Waters Styragel HR3, Styragel HR4, Styragel HR5

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 was passed through an appropriate amount of nitrogen to form 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 added, and the mixture was heated to 75 ° C while stirring. . Next, 250 parts by weight of methacrylic acid and 250 parts by weight of vinyl crotonate (manufactured by JAPAN VAM & POVAL CO., LTD.) were dropped into the flask over a period of about 4 hours using a drip pump. Further, a solution of 30 parts by weight of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 200 parts by weight of propylene glycol monomethyl ether acetate was pumped through an individual dropping solution for about 4 hours. In. After the 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 wt% and an acid value of 290 mg-KOH/g. The resulting copolymer had a weight average molecular weight Mw of 19000.

Synthesis Example 2

The monomer composition was changed to 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6]fluoren-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2 , a mixture of 3858-yl acrylate (50:50 (mole ratio)] 385 parts by weight and 25 parts by weight of vinyl crotonate (manufactured by JAPAN VAM & POVAL CO., LTD.), as in the synthesis example 1 implementation. A copolymer solution having a solid content of 50.5 wt% and an acid value of 106 mg-KOH/g was obtained. The resulting copolymer had a weight average molecular weight Mw of 12,000.

Synthesis Example 3

The crotonic acid vinyl ester (manufactured by JAPAN VAM & POVAL CO., LTD.) was changed to Synthesis Example 1 except that it was changed to vinyl sorbate (manufactured by JAPAN VAM & POVAL CO., LTD.). A copolymer solution having a solid content of 50.8 wt% and an acid value of 113 mg-KOH/g was obtained. The resulting copolymer had a weight average molecular weight Mw of 19000.

Synthesis Example 4

The crotonic acid vinyl ester (manufactured by JAPAN VAM & POVAL CO., LTD.) was changed to Synthesis Example 1 except that it was changed to vinyl cinnamate (manufactured by JAPAN VAM & POVAL CO., LTD.). A copolymer solution having a solid content of 50.3 wt% and an acid value of 104 mg-KOH/g was obtained. The resulting copolymer had a weight average molecular weight Mw of 15,000.

Synthesis Example 5

The monomer composition was changed to 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6]fluoren-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2 , 6] mixture of 癸-8-yl acrylate [50:50 (mole ratio)] 285 parts by weight, 100 parts by weight of cyclohexyl methacrylate, and vinyl crotonate (JAPAN VAM & POVAL CO., LTD. In addition to 25 parts by weight, it was carried out as in Synthesis Example 1. A copolymer solution having a solid content of 50.2% by weight and an acid value of 110 mg-KOH/g was obtained. The resulting copolymer had a weight average molecular weight Mw of 17,000.

Synthesis Example 6

The monomer composition was changed to 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6]fluoren-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2 In the same manner as in Synthesis Example 1, except that the mixture of 6: 癸-8-yl acrylate [50:50 (mole ratio)] was 410 parts by 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 resulting 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 a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) were mixed. A photosensitive resin composition is obtained.

Example 2

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

Example 3

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

Example 4

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

Example 5

The photosensitive resin composition was obtained 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 polyfunctional vinyl compound dipentaerythritol hexaacrylate (DPHA, manufactured by DAICEL CYTEC Co., Ltd.) 1 part by weight of a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) was mixed 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, and a polyfunctional thiol compound dipentaerythritol 肆-3-mercaptopropionic acid (DPMP, 堺Chemical Industries Co., Ltd.) 2 parts by weight of a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) was mixed 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 2 parts by weight of a hindered amine compound ADEKASTAB LA-57 (a compound of the above formula (3e), manufactured by ADEKA Co., Ltd.) , photopolymerization initiator IRGACURE 184 (photoradical initiator; Ciba Japan (Unit) 1 part by weight was mixed 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 epoxy compound CELOXIDE 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.), and photopolymerization initiator IRGACURE 184 (light) 1 part by weight of a free radical initiator; manufactured by Ciba Japan Co., Ltd. was mixed to obtain a photosensitive resin composition.

Comparative example 1

The photosensitive resin composition was obtained 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 polyfunctional vinyl compound dipentaerythritol hexaacrylate (DPHA, manufactured by DAICEL CYTEC Co., Ltd.) 1 part by weight of a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) was mixed 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, and a polyfunctional thiol compound dipentaerythritol 肆-3-mercaptopropionic acid (DPMP, 堺Chemical Industries Co., Ltd.) 2 parts by weight of a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) was mixed 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 2 parts by weight of a hindered amine compound ADEKASTAB LA-57 (a compound of the above formula (3e), manufactured by ADEKA Co., Ltd.) 1 part by weight of a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) was mixed 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 epoxy compound CELOXIDE 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.), and photopolymerization initiator IRGACURE 184 (light) 1 part by weight of a free radical initiator; manufactured by Ciba Japan Co., Ltd. was mixed to obtain a photosensitive resin composition.

Evaluation test (1) Production of evaluation test pieces

After spin-coating the photosensitive resin composition obtained in each of the examples and the comparative examples on a glass plate (substrate), the film was heated by a hot plate at 100 ° C for 3 minutes, and then exposed, and the film was hardened in an oven at 200 ° C. . The exposure was irradiated with a light amount of 200 mJ/cm ² and 800 mJ/cm ² .

(2) Adhesion

In the examples and comparative examples, the adhesion from the substrate was measured in accordance with JIS K-5600-5-6. Based on the classification specified in the classification of test results in Table 1 of JIS K5600-5-6 8.3, the evaluation is based on the following criteria.

◎‧‧‧ is equivalent to "0" of the classification of test results.

○‧‧‧ corresponds to "1" of the classification of test results.

△‧‧‧ corresponds to "2" of the classification of test results.

╳‧‧‧ is equivalent to "3" and "4" of the classification of test results.

(3) Solvent resistance

In the examples and comparative examples, the test pieces prepared for evaluation on a glass plate were each dropped with isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and N-methylpyrrolidone (NMP), and left for 10 minutes. Then, the water was washed, and the solvent was completely left unchanged. The solvent trace was retained and the erased one was ○, the solvent trace was retained and the rewritable was Δ, and the total color change was ╳. The same result was obtained when using an evaluation test piece made of a stainless steel plate instead of a glass plate.

(4) Alkali resistance

In the examples and comparative examples, the evaluation test piece prepared on a glass plate was dropped dropwise with a 1% by weight aqueous NaOH solution, and left for 10 minutes. Then, the water was washed, and the 1% by weight aqueous solution of NaOH was completely changed to ◎, and the trace was left to be retained, and the eliminator was ○, and the solvent trace was retained and the rewritable was Δ, and the total color was ╳.

The results of the evaluation test are shown in Table 1. In the table, "DPHA", "DPMP", "ADEKASTAB LA-57", and "CELOXIDE 2021P" are the compounds described in the examples and comparative examples.

As is clear from the table, the coating film of the photosensitive resin composition of the example is excellent in adhesion to a substrate, solvent resistance, and alkali resistance. On the other hand, any coating film obtained from the photosensitive resin composition of the comparative example was inferior in solvent resistance and alkali resistance. Further, the coating films of the photosensitive resin compositions obtained in Comparative Examples 3 and 4 were also inferior in adhesion to the substrate.

Claims (12)

A copolymer characterized by containing at least a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [except for a (meth) acrylate derivative and a (meth) acrylamide derivative] (vinyl monomer) A) A monomer mixture of a vinyl monomer having a carboxyl group or a carboxylic anhydride group (vinyl monomer B) and a vinyl monomer having an alicyclic epoxy group (vinyl monomer C) is obtained by polymerization. The copolymer of claim 1, wherein the vinyl monomer A is a compound represented by the following formula (1): (wherein R ¹ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R ² , R ³ and R ^{4 are the} same or different and each represents a hydrogen atom or a methyl group, and X represents a linking group; and n represents an integer of 1 to 3). The copolymer of claim 2, wherein the vinyl monomer A is at least one compound selected from the group consisting of the following compounds (i) to (iii): (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 different and represent a hydrogen atom or a methyl group, and X is a -COO- group (the left end is bonded to a carbon atom bonded to R ² ) a compound of 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, and X is a residue of a polycarboxylic acid, n is a compound of 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 group which may have a substituent. A hydrocarbon group, and n is a compound of an integer of from 1 to 3. The copolymer of any one of claims 1 to 3 which will contain at least a vinyl monomer A, a vinyl monomer B, a vinyl monomer C and a (meth) acrylate D, aroma A monomer mixture of at least one monomer selected from the group consisting of a group monovinyl compound E, a vinyl alkoxy decane compound F, and a hydroxyl group-containing monomer G is obtained by polymerization. A curable resin composition characterized by containing at least a copolymer according to any one of claims 1 to 4. The curable resin composition of claim 5, which further comprises a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and At least one compound selected from the group consisting of vinyl ether compounds. A photosensitive resin composition characterized by containing the copolymer and the photopolymerization initiator according to any one of claims 1 to 4. The photosensitive resin composition of claim 7, which further comprises a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane compound, and At least one compound selected from the group consisting of vinyl ether compounds. A photosensitive resin composition as claimed in claim 7 or 8, which further contains a pigment. The photosensitive resin composition of claim 7 or 8 is used for forming a liquid photoresist, a dry film, a pigment photoresist or a coated protective film. A color filter produced by using the photosensitive resin composition according to any one of claims 7 to 9 of the patent application. A method for manufacturing a color filter, which is characterized by a patent application The photosensitive resin composition according to any one of items 7 to 9 is applied to a support, exposed to a mask, and developed to form a pattern.