TW201026723A - Copolymer and photosensitive resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a copolymer can be used as photosensitive resin composition, in which the said photosensitive resin is able to form a pattern having excellent adherence property to substrate and high sensitive, high resolution. The said copolymer is obtained by copolymerizing monomer mixtures, which the said monomer mixtures at least comprise vinyl based monomer having plural C-C double bond in molecular [except (meth)acrylate derivative and (meth)acrylic amide derivative] (vinyl monomer A), and vinyl based monomer having carboxyl group or carboxylic anhydride (vinyl monomer B). The vinyl based monomer A comprises the compound represented by following formula (1). (In the formula, R1 represents hydrogen atom or hydrocarbon group which can also have substituent group; R2, R3 and R4 are identical or different and represent hydrogen atom or methyl group; X represents linking group; and n represents the integral of 1 to 3.)

Description

201026723 VI. Description of the Invention: [Technical Field] The present invention relates to a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [except for (meth) acrylate derivatives and (meth) acrylamide derivatives) a copolymer containing a carboxyl group or a carboxylic acid anhydride group, a curable resin composition containing the copolymer, and a photosensitive resin composition, a color filter prepared using the photosensitive resin composition, and used A method of producing a color filter of the photosensitive resin composition. Q [Prior Art] Photosensitive resins for displays are required to have high brightness and high contrast. In Japanese Patent No. 4090292, a dye is used for high brightness and high contrast, and a high-sensitivity resin having a free radical polymer group is used for the resin to achieve high resolution. However, it is necessary to introduce a carboxylic acid component into the developing solution because the developing solution is a thin alkaline aqueous 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 coloration during development are actually caused, and a primer layer is provided between the φ substrate and the photoresist. To solve the problem. Further, since almost all of the resins must be subjected to the steps of the resin polymerization step and the radical polymerization group introduction step in the synthesis step, the productivity is also low. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a copolymer which can be used as a photosensitive resin which can form adhesion to a substrate. A high-sensitivity, high-sensitivity pattern copolymer containing a curable 201026723 resin composition and a photosensitive resin composition of the copolymer, and a color filter and a color filter using the photosensitive resin composition method. 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 the color filter Q. Means for Solving the Problems 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 [(meth) acrylate derivative and (meth) propylene] In addition to a phthalamide derivative, when a vinyl monomer having a carboxyl group or a carboxylic acid anhydride group is polymerized, 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). When the copolymer is used as a photosensitive resin, a copolymer having excellent adhesion to a φ substrate and high sensitivity and high resolution can be formed, 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 a molecule [except for a (meth) acrylate derivative and a (meth) acrylamide derivative] (Vinyl monomer A) is obtained by polymerizing a monomer mixture of a monomer having a carboxyl group or a carboxylic anhydride group (vinyl monomer B). The vinyl monomer A contains a compound represented by the following formula (1): 201026723

Wherein Ri represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R2, R3 and R4 are the same or different and each represents a hydrogen atom or a methyl group, and X represents a linking group; η represents an integer of the above-mentioned vinyl monomer. Α At least one compound selected from the group consisting of the following (i) to (in) compounds may be used: © (1) In the formula (1), R1 is a hydrocarbon group which may have a substituent, R2, R3 and R4 The same or different represents a hydrogen atom or a methyl group, 乂 is a _〇〇〇_ group (the left end is bonded to a carbon atom bonded to R2), a compound of η=1; (11) 'Rl in the formula (1), R2, R3 and R4 are the same or different and are a hydrogen atom or a methyl group, 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), R1, R2, and R4 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 η is at least one compound of a group consisting of a compound of an integer of 1 to 3 Å. 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 body C is preferably a vinyl monomer having an alicyclic epoxy group. Further, the copolymer contains at least a vinyl monomer A, a vinyl monomer B, and a vinyl monomer C. Polymerization of a monomer mixture of at least one monomer selected from the group consisting of acrylate D, aromatic monovinyl compound E, vinyl alkoxy decane compound F, and monomer having a hydroxyl group of 201026723 The present invention further provides a curable resin composition containing at least the above copolymer. The curable resin composition may further contain a compound having a radical polymerizable double bond, a polyfunctional thiol compound, and a hindered amine. At least one compound selected from the group consisting of a compound, an epoxy compound, an oxetane compound, and a vinyl ether compound. 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 compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, or an oxetane. At least one compound selected from the group consisting of a compound and a vinyl ether compound. Further, the photosensitive resin composition may further contain a pigment. Further, the photosensitive resin composition may be used as a liquid photoresist or a dry film. The present invention also provides a color filter β produced by using the above-mentioned photosensitive resin composition. The present invention also provides a method for producing a color filter, which is characterized in that the above-mentioned photosensitivity is used. A method of producing a color filter in which a resin composition is applied onto a support and then exposed by a mask to develop a pattern. Advantageous Effects of Invention The copolymer of the present invention can be introduced into the resin during synthesis (in 1 step). A functional group such as a base polymerizable group or an epoxy group, and a tree of 201026723 fat is synthesized by the ruthenium 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, 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. [Embodiment] The copolymer of the present invention contains 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) acryl oxime derivative] ( A polymer obtained by polymerizing (vinyl polymerization) a vinyl monomer A) and 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 ethylenic monomer A may be polymerized in any of them. The vinyl monomer A may be used alone or in combination of two or more. ❹ If the above-mentioned B is a monomer A, there are a plurality of vinyl monomers in the molecule (for example, 2 to 4 '2 or 3, preferably 2, preferably) carbon-carbon double bonds [but (methyl The acrylate 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), Ri represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R2, R3 and R4 are the same or different and each represents a hydrogen atom or a methyl group, and X represents a linking group. η represents an integer from 1 to 3. The "hydrocarbon group" of the hydrocarbon group which may have a substituent in R1 may, for example, be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and these two or more bonds may be bonded to the group of 201026723. The aliphatic hydrocarbon group is, for example, 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 1 ,, preferably an alkyl group having 1 to 6 carbon atoms; 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~) An alkenyl group of 10, 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 2 to 2 carbon atoms) 6 alkynyl) and the like. The alicyclic hydrocarbon group is, for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group or the like, a 3 to 15 φ member cycloalkyl group; a cyclohexenyl group; and a 3 to 15 membered cycloalkenyl group; a thiol group, an adamantyl group or the like having 4 carbon atoms; ~15 cross-linked ring base and so on. The aromatic hydrocarbon group has, 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 (Ci-4 alkyl group or the like), an alkenyl group (C2-4 alkenyl group, etc.), a haloalkyl group (Ci-4 haloalkyl group, etc.), a halogen atom, an alkoxy group. (Cl -4 alkoxy), hydroxy, hydroxyalkyl (hydroxy-Ci-4 alkyl φ, etc.), carboxyl group, alkoxycarbonyl group (Ci-4 alkoxy-carbonyl group, etc.), fluorenyl group (Cmo fluorenyl group) and many more. R1 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, or carbon. The aralkyl group having 7 to 15 atomic 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. R2, R3 and R4 may each be a hydrogen atom or a methyl group, and a hydrogen atom is preferred. .201026723 The linking group of hydrazine has a linear or branched chain alkyl group such as methylene, vinyl, propenyl, trimethylene, tetramethylene or hexamethylene (carbon number 1~6) a straight chain or a branched chain of an alkyl group, etc.; a linear or branched chain perfluoroalkylene group such as a perfluorohexamethylene group (a linear or branched chain having a carbon number of about 1 to 6) Fluorine alkyl, etc.; linear or branched chain-like alkenyl groups such as vinyl, propylene, and butenyl groups (linear or branched chain alkenyl groups having a carbon number of 2 to 6 or the like) ); linear or branched chain fluorinated alkenyl group (linear or branched chain fluorinated alkenyl group having a carbon number of 2 to 6 or the like); 1,3-cyclopentyl group, 1,4-Q a divalent alicyclic hydrocarbon group such as a cyclohexyl group, a 1,3 -cyclohexylene group or a cyclohexene group; a phenyl group, a naphthyl group or the like; or a Cl 4 alkyl group, an aromatic group, a halogen atom, or a Ci- Arylene of a substituent such as 4 alkoxy group; -COO-; -OCO-; -CONH-; -NHCO-; -Ο-; -S-; -CO-; -CS-; -NH- These are two or more valence groups which are combined by 2 or more. n is preferably 1 or 2, and particularly preferably 1. Representative examples of vinyl monomer oxime At least one compound selected from the group consisting of the following compounds (i) to (iii), φ (1) in the formula (1), R1 is a hydrocarbon group which may have a substituent, and R2, R3 and R4 are the same or different And a hydrogen atom or a methyl group, Xg_c thiol (the left end is bonded to a carbon atom bonded to R2), a compound of 1;

Ui) in the formula (1), wherein R1, R2, R3 and R4 are the same or different and are a hydrogen atom or a methyl group, X is a residue of a polycarboxylic acid, and η is an integer of 1 to 3; (1) wherein V, R2, R3 and R4 are the same or different and are a hydrogen atom or a methyl group 'X is an 11-valent hydrocarbon group which may have a substituent, and 11 is a group of a compound of an integer of 1 to 3, at least 1 Kind of compound. -10-201026723 The compound corresponding to the above (1) 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, 1,8-0 divinylnaphthalene, 1,2-divinyl-3,4-xylene, 2,4-divinylbiphenyl, 3, An aromatic polyethylene compound such as 5,4'-triethylenebiphenyl or 1,3,5-trivinylbenzene. The vinyl monomer B may be 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, etc., α-unsaturated carboxylic acid and anhydride thereof (hundene)

Especially good. The vinyl monomer oxime 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 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 corresponding to the vinyl monomer A to the copolymer is, for example, 1 to 99% by weight, preferably 2 to 90% by weight, based on the total monomer units constituting the copolymer, of '2 to 70% by weight. . /. Better yet. If the ratio is too low, the sensitivity tends to be low. When the resin is too hydrophobic, 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 entire monomer unit of the copolymer constituting -11 to 201026723. For example, 1 to 99% by weight, 2 to 90% by weight. /. Preferably, 2 to 70% by weight is more preferred. 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 resin is high, the hydrophilicity of the resin is high and the chemical resistance of the coating film is liable to be low. 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 weight. /. Preferably, 12 to 100% by weight is more preferably. φ The copolymer of the present invention may 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. Examples of 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 having 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 epoxy φ ethane ring (epoxy group) and an oxetane ring (oxetanyl 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 containing an oxirane ring (monocyclic) such as 3-glycidoxypropoxide or (meth)acrylic acid propyloxypropionate-12- 201026723 ((meth) acrylate derivative Etc.); 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)(meth)acrylate Ethyl ester, 2-(3,4-epoxycyclohexylmethoxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethoxy)propyl (meth)acrylate, etc. a polymerizable unsaturated compound (such as a (meth) acrylate derivative) having an epoxy group-containing cycloalkane ring such as a 4-epoxycyclohexane ring; (meth)acrylic acid 5,6-epoxy-2-bicyclic ring; [2.2.1] Heptyl ester and the like contain 5,6-epoxy-2-bicyclo[2 .2.1] polymerizable unsaturated compound of heptane ring ((meth) acrylate derivative, etc.); epoxidized {methyl cyano) dicyclopentenyl acrylate [(meth)acrylic acid 3,4-epoxy III Ring [5.2.1.〇2,6]癸-9-ester, (methyl}acrylic acid 3,4-epoxytricyclo[5.2.1.02,6]癸-8-ester or a mixture of these, epoxidation Dicyclopenteneoxyethyl (meth) acrylate [2-(3,4-epoxytricyclo[5.2.1.02,6]癸-9-oxy)ethyl ester, (meth)acrylic acid 2-(3) , 4-epoxytricyclo[5.2.1.02,6]癸- 8-oxy)ethyl ester or a mixture of these], epoxidized dicyclopentenyloxybutyl (methyl > acrylate, etc. containing 3,4- An epoxy-tricyclic [5.2.1.02.6] anthracene ring-containing polymerizable unsaturated compound (such as a (meth} acrylate derivative)), etc., as another polymerizable property containing a φ oxirane ring (epoxy group) As the saturated compound, an epoxy group-containing ethyl ether compound, an epoxy group-containing allyl ether compound, an epoxy group-containing aromatic vinyl compound, etc. may be used. The epoxy group-containing aromatic vinyl compound has 4 -vinylbenzyl epoxidized ether, 4-vinylbenzyl epoxy B a styrene derivative such as an alkane or a 4-vinylethylbenzene oxide. A polymerizable unsaturated compound containing an oxetane ring (oxetanyl group) is, for example, an oxetane (meth)acrylate. Ester, 3-methyl-3-oxetane (meth)acrylate, 3_b_3_oxetanyl (meth)acrylate, (meth)acrylic acid (3-methyl-3- Oxetane) methyl ester, (meth) propylene-13- 201026723 'acid (3-ethyl-3-oxetanyl) methyl ester, (meth)acrylic acid 2-(3-methyl- 3-oxetanyl)ethyl ester, 2-(3-ethyl-3-oxetanyl)ethyl (meth)acrylate, 2-[(3-methyl-3)(meth)acrylate -oxetanyl)methoxy]ethyl ester, 3-[(3-methyl-3-oxetanyl)methoxyl-propyl (meth)acrylate, (meth)acrylic acid 3 -[(3-Ethyl-3-oxetanyl)methoxy]propyl ester, a vinyl ether compound containing an oxetane group, an allyl ether compound containing an oxetanyl group, and the like. The polymerizable unsaturated compound 0 containing an oxolane (oxocyclopentyl) group is, for example, tetrahydrofuran (meth) acrylate, a vinyl ether compound containing an oxolyl group, and an allylic group containing an oxolyl group. Ether compounds and the like. 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 3 to 5 member cyclic ether group may be used alone or in combination of two or more. φ A vinyl monomer having a 3 to 5 membered cyclic ether group is preferably a polymerizable unsaturated compound containing an oxirane ring (epoxy group), wherein the cycloalkyl ring containing an epoxy group is contained. a polymerizable unsaturated compound, a polymerizable unsaturated compound containing 5,6-epoxy-2-bicyclo[2.2.11 heptane ring, containing 3,4-epoxytricyclic guanidine 5.2.2.02,6] decane A vinyl monomer having an alicyclic epoxy group such as a polymerizable unsaturated compound of the 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, 2~85 is -14-201026723% is better. When the ratio is too low, the coating film is resistant to drug resistance and adhesion, and if it 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): R5 CH^CC—0 — R6 (2) 0 (wherein R 5 represents a hydrogen atom or a methyl group, and R 6 represents a hydrocarbon group; a substituted hydrocarbon group having 1 to 25 carbon atoms).烃 R6 has a hydrocarbon group having 1 to 25 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, 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 , 10-- phenyl fluorenyl, 12-phenyldodecyl, 14-phenyltetradecyl, 16-phenylhexadecyl and the like aralkyl; these two or more bonded groups and the like. 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 1 carbon atom): an aryloxy group such as a phenoxy group. Hydrocarbyl group-substituted oxy group such as cyclohexyloxy group or dicyclopentyloxy group; hydrocarbyl group having 1 to 15 carbon atoms (preferably having 1 to 12 carbon atoms) such as an aralkoxy group such as a benzyloxy group; Base. Representative examples of the (meth) acrylate represented by the formula (2) are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (methyl) -15 - 201026723 2-ethylhexyl acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyloxy (meth) acrylate, (meth) acrylate Isodecyl ester, benzyl (meth)acrylate, phenethyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate, etc. (meth)acrylate D has, for example, a (meth) acrylate having an isocyanate group or a blocked isocyanate group, a (meth) acrylate having an alkoxyalkyl group, and a group having a hindered amine structure. (meth) ❹ acrylate, etc. The (meth) acrylate having an isocyanate group or a blocked isocyanate group is, for example, 2-[0-(1'-i-propylidino)carboxyamino]ethyl methacrylate (= 2-(1-wayaramine oxycarbonylamine ethyl) methacrylate [Product name "Karenz MOI-BM", manufactured by Showa Denko Co., Ltd.], 2-(3,5-dimethylpyrazole-1-yl)carbonylamine ethyl methacrylate [trade name "Karenz MOI-BP", Showa Denko Electric Co., Ltd., etc. The (meth) acrylate having an alkoxyalkyl group has, for example, r -(methyl} ^ propylene oxypropyl trimethoxy decane, r-(methyl) propyl lanthanum Oxypropyl triethoxy decane, r-(methyl) propylene methoxypropyl methyl dimethoxy decane, r - (meth) propylene oxiranyl methyl diethoxy decane, r- ( Methyl) propylene oxypropyl triethoxy decane, /3-(methyl) propylene oxiranyloxyethyl trimethoxy decane, (meth) propylene oxiranyl ethyl triethoxy decane, r- (a a polymerizable unsaturated compound containing an alkoxyalkyl group such as propylene oxybutyl butyl dimethoxy decane or r-(methyl) propylene oxy oxy phenyl diethoxy decane. The (meth) acrylate having a hindered amine structure is, for example, 16-201026723, trade name "AdekaStab LA-82", "AdekaStab LA-87" (above, ADEKA), etc. Aromatic monoethylene Compound E is, for example, styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, ethylene biphenyl, etc. The vinyl alkoxydecane compound F is, for example, vinyltrimethoxydecane, vinyltriethoxydecane, vinyl Dimethoxy decane, vinyl methyl diethoxy decane, etc. The hydroxyl group-containing monomer G is, for example, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth) acrylate, (methyl) } 2,3-dihydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, etc. An alkyl ester, 4-hydroxymethylcyclohexyl (meth)acrylate, a polyalkylene glycol mono(meth)acrylate, or the like, a monoester of a polyhydric alcohol with acrylic acid or methacrylic acid, the above polyol and acrylic acid Or a compound obtained by ring-opening polymerization of ε-caprolactone with monoester of methacrylic acid (DAICEL Chemical Industry Co., Ltd., PLAKCEL FA series, PLAKCEL FM series, etc.), ethylene oxide or propylene oxide through open loop A compound or the like which is polymerized to have a hydroxy φ group. The copolymer of the present invention has at least 1 selected from the group consisting of (meth)acrylate D, an aromatic monovinyl compound fluorene, a vinyl alkoxy decane compound F, and a 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, more 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 ethylenic monomer A and a monomer unit corresponding to the vinyl monomer B in an amount of 5 parts by weight based on the total of the monomer units. /. The above (especially 1% by weight or more 'specifically -17-201026723 50% by weight or more) copolymer, (2) containing a monomer unit corresponding to the vinyl monomer A, corresponding to the vinyl monomer B The bulk unit and the monomer unit corresponding to the vinyl monomer C having a 3 to 5 member cyclic ether group account for 40% by weight or more (especially 50% by weight or more) of the total monomer unit of the copolymer '(3) a monomer unit corresponding to the monomer unit of the vinyl monomer A, a monomer unit corresponding to the vinyl monomer B, and a vinyl monomer C corresponding to a cyclic ether group having 3 to 5 members, and corresponding to Total of monomer units of at least one monomer selected from the group consisting of (meth) acrylate D, aromatic monovinyl compound E, vinyl alkoxy decane compound F, and hydroxyl group-containing single Q body 0 A copolymer containing 40% by weight or more (especially 50% by weight or more) of all monomer units. The copolymer of the present invention may contain the vinyl monomer B having a carboxyl group or an acid anhydride group, and, if necessary, a vinyl monomer C having 3 to 5 member cyclic ether groups, and (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 copolymerized (vinyl polymerization) to be produced by φ. 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, 2'-azobis(2-methylpropionate), dibutyl-2,2'-azobis(2-methylpropionate) and other azo compounds, benzalkonium peroxide, peroxidized laurel An organic peroxide such as a mercapto group, a tributyl peroxyacetate, a 1,1-bis(t-butylperoxy)cyclohexane, or a hydrogen peroxide. When the oxide is used as a base polymerization initiator from -18 to 201026723, it may be a reduction oxidative initiator which is a combination of a reducing agent. 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 particularly preferred. The amount of the polymerization initiator can be appropriately selected in the range of not inhibiting smooth copolymerization, and usually accounts for about 1 to 30% by weight of the total monomer component and the total amount of the polymerization initiator, 5 to 25 It is preferably about weight%. In the present invention, a chain transfer agent generally used for radical polymerization can also be used. Specific examples are mercaptans (n-dodecyl mercaptan, n-octadecyl mercaptan, n-butyl mercaptan, third butanol, n-lauryl mercaptan, antimony ethanol, mercapto alcohol, triethylene glycol dithiol, Mercaptans (propionic acid, phthalic acid, decanediol, phthalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.) ), α-methyl styrene dimer, decene ene, citronene, nin, α decene, fluorene-decene, etc., the amount of chain transfer agent relative to the total amount of free radical polymerizable monomer is 0.001 ~ 3 wt% is preferred. When a chain transfer agent is used, it is preferred to mix it with a polymerizable vinyl monomer in advance. φ Polymerization can be carried out by solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, emulsion polymerization, and the like. A method for producing a styrene-based polymer or a propylene-based polymer is carried out. Among these, solution polymerization is preferred. The monomer and the polymerization initiator may be supplied to the reaction system at a time, and some or all of them may be dropped. Into the reaction system, for example, a mixture of a monomer and a polymerization solvent maintained at a certain temperature can be used. In the method of dissolving a solution in which a polymerization initiator is dissolved in a polymerization solvent, or a solution in which a monomer, a polymerization initiator, and a polymerization initiator are dissolved in a polymerization solvent maintained at a certain temperature to be polymerized ( Into the polymerization method, etc. -19- 201026723 The polymerization solvent can be appropriately selected depending on the monomer composition, etc. The polymerization solvent is, for example, an ether (diethyl ether; ethylene glycol mono or di yard acid, diethylene glycol mono or dioxane). 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 (two Propylene glycol dimethyl ether or the like, dipropylene glycol, di- 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 and other glycol ethers and other chain ethers; tetrahydrofuran, dioxane and other cyclic ethers, etc., 0 esters (methyl acetate, Ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, 3-ethoxypropionic acid Carboxyl esters such as ester, Cs-6 cycloalkane mono or diacetate, C5-6 cycloalkanediethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol single Or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate 'propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkane Ethyl acetate, dipropylene glycol mono or diacetate, U-propylene di-monoalkyl ether acetate, iota, 3-propanediol mono or diacetate, hydrazine, 3-butanediol monoalkyl Ethyl ethylene phthalate, 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 Ci-4 alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether acetate, a diol acetate such as tripropylene glycol mono- or diacetate or a glycol ether acetate, etc.), a ketone (acetone, butanone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl) -2-cyclohexen-1-one, etc.), guanamines (Ν, Ν-dimethylacetamide, ν, Ν-dimethylformamide, etc. , alkaloids (dimethyl sulphide, etc.), alcohols (methanol, ethanol, propanol, C5-6 cycloalkanediol, Cs·6 ring dimethanol, etc.), hydrocarbons (benzene, toluene, xylene) 20-201026723, such as an aromatic hydrocarbon, an aliphatic hydrocarbon such as hexane, an alicyclic hydrocarbon such as cyclohexane, or the like, a mixed solvent thereof, or the like. 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 500-1000000, preferably 5,000 to 500,000, more preferably about 10,000 to 2,000 Å. The degree of dispersion of the copolymer (weight average molecular weight Mw / number average molecular weight Μη) is about 1 to 3. The resulting copolymer can be purified by precipitation or reprecipitation or the like. Conventional methods can be employed for precipitation and reprecipitation. 0 The curable resin composition of the present invention contains at least the above-mentioned 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 (dipping agent, antifoaming agent, Flame retardant, antioxidant, UV absorber, low stress agent, flexibility imparting agent, wax, resin, crosslinker, ^halogen collector, leveling agent, wetting improver, etc.), pigment, etc. And modulation. 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, and the like, and organic metals. A complex compound, a carbon compound such as a C60/carbon nanotube, or the like. 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 compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxidized-21-201026723 compound, an oxetane compound, and a vinyl ether compound. At least one compound selected from the group consisting of. 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 comprise 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 by the group. Examples of the compound having a radical polymerizable double bond include a vinyl aromatic compound such as (meth) acrylate or styrene, and a guanamine compound. Representative (meth) acrylates are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (methyl > acrylic acid (meth)acrylic acid alkyl esters such as amyl ester and hexyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid hydroxybutyrate Ester, caprolactone modified (2-hydroxyethyl (meth) acrylate, etc., having a hydroxyl group (meth) acrylate; methoxy diethylene glycol (meth) acrylate, ethoxy diethylene glycol (Meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polymerization (meth) acrylate such as ethylene glycol #400-(meth) acrylate (polyalkylene glycol monoether mono(meth) acrylate); L, 6-hexanediol di(methyl) Difunctional (meth) acrylates such as acrylate and neopentyl glycol di(meth)acrylate; trimethylolpropane tris(methyl) a polyfunctional (meth) acrylate such as a trifunctional (meth) acrylate such as an acrylate, etc. -22- 201026723 A polymerizable prepolymer can also be used as a compound having a radical polymerizable double bond. The polymer is, for example, a (meth)acrylic acid vinegar of a polyester polyol, a (meth) acrylate of a polyether polyol, an adduct of a polyepoxide and a (meth)acrylic acid, and a poly The alcohol is introduced into a resin of a hydroxy ester of (meth) acrylate by a polyisocyanate, etc. The compound having a radical polymerizable double bond is preferably a polyfunctional vinyl compound such as a polyfunctional (meth) acrylate. The compound of the bond may be used singly or in combination of two or more kinds. In the photosensitive Q resin composition, a compound having a radical polymerizable double bond is blended, whereby 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 a polyfunctional thiol compound has two or more thiols The compound may be, for example, hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol disulfide Glycol ester, ethylene glycol dithiopropionate, trimethylolpropane thioethylene glycol ester, trimethylolpropane φ alkyl thiopropionate, trimethylolpropane -3- butyl butyrate, new Pentaerythritol thioglycolate, pentaerythritol thiopropionate, pentaerythritol sulfonium-3-hydrazine butyrate, trimethyl propionic acid ginseng (2-hydroxyethyl) iso-cyanide Acid ester, iota, dimethyl phthalic acid, 2,4,6-triterpene-s-three tillage, 2-(N,N-dibutylaminodibu-4,6-dioxin-s-three tillage , tetraethylene glycol bis-3-indolyl propionate, trimethylolpropane ginseng 3-indole propionate, ginseng (3 - fluorene oxyethyl) iso-cyanate, neopentyl pentoxide - 3-propionic acid vinegar, dipentaerythritol 肆3-thiopropionate, 1,4-bis(3-thiobutoxy)butane, 1,3,5-gin (3-butoxy) Ethyl)-1,3,5-tris-2,4,6-(1Η, 3H,5H)trione and the like. The polyfunctional thiol compound may be used alone or in combination of two or more of -23-201026723. By blending a polyol compound into the photosensitive resin composition, higher sensitivity and resolution can be achieved, and the belly can be improved, and the polyfunctional thiol compound can be used instead of the dilution solvent, which is effective for the whole and high solid content. . As the hindered amine compound, a compound generally referred to as hindered amine light (HALS) can be used, and for example, the following compounds can be used. In the formulas (3h), (3〇), (3 q), and (3 r), m represents an integer of 1 or more. The hindered amines may be used alone or in combination of two or more. By incorporating a hindered amine compound into the photosensitive tree φ, a higher degree of sensitivity can be achieved and the film properties can be improved. Functional sulfur. Viscosity adjustment stabilizer (3i), compound composition, analysis

-24- 201026723

-25- 201026723

(3g)

CH — COO — l (3h) CH2-C00-

-26- 201026723 〇

(3j) (3k)

(31)

(3o) -27- 201026723

Rz Rz (3p)

RZ-NH- (CHg) 3~A- (CH2)2-A-(CH2)3-NH-RZ

❿

NH I tert. CgH17 (3r) (3q) 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 thereof DAICEL chemical (EP) EPOLEAD PB, ESBS, etc., alicyclic epoxy resin (such as DAEREL Chemical Co., Ltd. CEROXIDE 2021, EHPE; Mitsui Petrochemical Co., Ltd. EPOMIC VG-3101; oiled SHELL EPOXY (share) ) E-3013S; Mitsubishi Gas Chemical (TETRAD-X, TETRAD-C; Japan Soda (EPB-13, EPB-27, etc.), copolymerized epoxy resin (such as methacrylic-28) - 201026723 Copolymer of epoxidized propyl acrylate and styrene, glycidyl methacrylate, copolymer of styrene and methyl methacrylate, CP-50M, CP-50S, or A made of Japanese fat (stock) A copolymer of glycidyl acrylate and cyclohexanimide, etc., and an epoxidized resin having a special structure. Epoxy compounds can also be used as varnish-type epoxy resins [for example, phenol, A Phenols such as phenol, halogenated phenol and alkylphenol are reacted with formaldehyde under an acidic catalyst. A product obtained by reacting lacquer with epichlorohydrin and/or methylpichlorohydrin (the commercially available φ product is EOCN-103, EOCN-104S, EOCN-1020' EOCN- 1 027, EPPN manufactured by Nippon Kayaku Co., Ltd. -201 >BREN-S; DEN-431, DEN-439 manufactured by DOW CHEMICAL Co., Ltd.; N-73, VH-4150, etc. manufactured by Dainippon Ink Chemical Industry Co., Ltd.), bisphenol type epoxy resin (for example, a product obtained by reacting bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin to form a condensate of bisphenol A diglycidyl ether and the above bisphenol The product obtained by the reaction of epichlorohydrin (the commercial product is EPICOTE 1004, EPICOTE 1002 made by oily SHELL); DER-330, DER-337, etc. made by DOW ❹ CHEMICAL Co., Ltd.), phenolic methane, ginseng A product obtained by reacting phenol methane with epichlorohydrin and/or methylpichlorohydrin (the commercial products are Nippon Chemical Co., Ltd. (EPPN-501, EPPN-502, etc.), and ginseng (2,3-epoxy). Propyl)iso-p-cyanate, biphenyl diglycidyl ether, etc. These epoxy compounds (epoxy resins) may be used alone or in combination of two or more. In the photosensitive resin composition, epoxy is blended. Compound A higher sensitivity, resolution, and film properties can be achieved. The oxetane compound is, for example, 3-ethyl-3-hydroxymethoxyoxetane [OXT-101, manufactured by East Asian Synthetic Chemical Industry Co., Ltd.] 2-Ethyloxetane [East-29-201026723 Synthetic Chemical Industry Co., Ltd. ΟΧΤ-2 12], Benzene Dioxygen [East Asia Synthetic Chemical Industry Co., Ltd. ΟΧΤ-12 1], 3-Ethyl-3-[3-butan-3-ylmethoxymethyl]oxetane [East Asian Synthetic Chemical Industry ΟΧΤ-22 1]. These oxetane compounds may be used singly or in combination. By blending oxetane into 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, trimethyl ether ether, triethylene glycol divinyl ether, cyclohexane dimethanol dicyclohexanediol divinyl ether, decanediol divinyl ether, 1, 4-butylene ether, allyl vinyl ether, triethylene glycol monovinyl ether, cyclohexane vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 9-hydroxydecyl 4-hydroxycyclohexyl vinyl ether Wait. These vinyl ether compounds may be blended in a photosensitive resin composition in a single or a combination of two to give a higher sensitivity and resolution of the vinyl ether compound, and to enhance the film properties. φ The compound of the curable resin composition, the polymerizable double bond of the photosensitive resin composition, the polyfunctional thiol compound, the acceptor, the epoxy compound, the oxetane compound, and the vinyl ether. The weight of the copolymer 100 of the present invention is 0.1 to 40 parts by weight, preferably 1 to 25 parts by weight, more preferably 1.5 to 15 parts by weight. In addition, the total amount of the curable resin composition and the photosensitive resin composition compound is, for example, 〇. 1 to 40 parts by weight, preferably 1 to 25 parts by weight, based on the copolymer component of the present invention. Better. A compound having two or more kinds of compounds, a hydroxymethylpropane vinyl ether, an alcohol diethylene dimethanol monovinyl ether, or a compound of a heterocyclic butane ethoxycyclohexane product, which has a free-resistance amine compound For example, these 100 parts by weight of the weight of the material • 5~1 5 weight -30- 201026723 Photopolymerization initiator can use a photo radical initiator, a photoacid generator, and the like. The photopolymerization initiator may be used alone or in combination of two or more. The photoradical initiator may, for example, be 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) KAYACURE EPA, etc.), 2,4-diethyloxysulfide D hawthorn (KAYACURE DETX, etc. made by Nippon Chemical Co., Ltd.), 2-methylindole-1-[4-(methyl)benzene 2-pyrylylacetone-1 (IRGACURE 907, etc. manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-dimethylamine-2-(4-tyrosolinyl)benzylidene-1-phenylpropane, etc. 2- Amine-2-benzylindole-1-phenylalkane compound, tetrakis(t-butylperoxycarbonyl)diphenyl ketone, diphenylethylenedione, 2-hydroxy-1-phenylpropan-1-one, 4,4 - an amine benzene derivative such as bisdiethylaminodiphenyl ketone, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole Imidazole compound such as B-CIM (made by Baotu Valley Chemical Co., Ltd.), 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-three Halogen-methylated tri-trap compound, 2-trichloro- 5-(2) A halogen methacrylate compound such as -φ benzofuran-2-vinyl)-1,3,4-oxadiazole may be used singly or in combination, and if necessary, a photo-sensitizer may be added. Such as SAIRACURE UVI-6970, SAIRACURE UVI-6974, SAIRACURE UVI-6990,

SAIRACURE U VI - 9 5 Ο (above U.S. United Carbonation Co., Ltd., trade name), IRGACURE 261 (manufactured by Steam Bart, Inc., trade name), SP-150, SP-151, SP-170, OPTOMER SP-171 (above: Asahi Chemical Industry Co., Ltd., trade name), CG-2 4-61 (manufactured by Steam Bart Chemical Co., Ltd., trade name), DAIACT II (DAICEL Chemical Industry Co., Ltd., trade name), UVAC -31 - 201026723 159 1 (trade name of DAICEL CYTEC), CI-2064, CI-2639 ' CI-2624, CI-248 1, CI-2734, CI-2855, CI-2823, CI-2758 (above, Japan Cao Da Company's products, trade name), PI-2074 (Rhone Poulenc company, trade name, phenylmethyl cumene iodide), FFC509 (3M company products, trade name), BBI-102, BBI-101 , BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS - 1 0 3 (Μ ID Ο RI Chemical Co., Ltd., trade name), CD-1012 (Sartomer, USA) The system is a diazonium salt, a barium salt, a barium salt, a scale salt, a selenium salt, a salt, an ammonium salt, and the like. The photopolymerization initiator is a combination of an imidazole compound and an amine benzene derivative, a 2-amine-2-benzylindole-1-phenylalkane compound, a halomethylated three-till compound, from the viewpoints of sensitivity and chemical resistance. A halomethyl oxadiazole compound or the like is preferred. The photosensitive resin composition of the present invention may contain a thermal acid generator if necessary. The thermal acid generator can be used, 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 same φ, SI-100L with the left, and the left SI-145, SI-150 with the left, SI-160 with the left, SI-110L with the left, SI-180L with the left (the products of the above three new chemical industry companies, trade names), CI-292, 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. product, trade name)' FC-52 0 (3M The company's products, trade names, etc. are represented by diazonium salts, sulfonium salts, strontium salts, scale salts, selenium salts, detailed salts, ammonium salts, etc. The amount of photopolymerization initiator added is, for example, relative to the photosensitive resin composition. The above copolymer (resin component) is preferably from 005 to 10% by weight, preferably from 5% to 5% by weight. These photopolymerization initiators may also contain a synergist, such as a tertiary amine, for enhancing the conversion of absorbed light energy to the initiation of radicals. On the other hand, when the inventive resin composition is hardened by irradiation with an electron beam, an initiator is not necessarily required. The photosensitive resin composition thus obtained is cured to obtain a cured product (hardened film, etc.) having high degree of high resolution, high adhesion to a substrate and a substrate, and excellent chemical resistance such as a medicinal property and an alkali resistance. Further, it is suitably used as a coating material, a coating agent, an adhesive, etc., and is particularly suitable as an electronic liquid photoresist, a dry film, and a resin composition for forming a protective film. Further, a pigment is added to the photosensitive resin composition, that is, a color filter such as a color filter or a black matrix is also used. For example, the pigment is dispersed in a lacquer ware, a sand mill, a ball mill, a roll mill, a stone mill, a jet machine, a homogenizer, etc., and is added to a photosensitive resin composition and mixed to modulate the color filter used for the liquid crystal display. Light resistance of light sheets, black matrices, etc. φ For the above pigments, blue pigments, green pigments, red yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments can be used. Further, the structure may be an organic pigment such as an azo system, a phthalocyanine quinacone system, a benzimidazolone system, an isoindolinone type, a dioxin system, a dansone system, or a purple ring ketone system, and the like. Various inorganic pigments Specific examples of the pigments which can be used are shown below by the pigment number. The following words such as "Pigment Red 2" mean the color index (c. I·). The red pigment has C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32'. Hardening of polymerization Adding high sensitivity and resistance to dissolution. Because the field is mixed with color powder, pigment materials, materials, etc. are ', yin and so on. C. I., 8, -33- 37, 201026723

38, 4 1, 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, 8 1 , 8 1 : 1, 8 1:2, 8 1: 3, 8 1 : 4, 83, 88, 9 0 : 1, 10 1 , 1 0 1 : 1, 104, 108, L08: 1, 109 112, 113, 114, 122, 123 144, 146 147, 149 151, 166, 168, 169, 170 172, 1 73, 174, 175, 176, 177, 178, 179, 18 1 , 184, 185 187, 1 88 > 190, 193, 194 , 200, 202, 206, 207 > 208, 209 210, 214 '216' 220, 22 1 224, 230, 23 1 , 2 32 233 , 235 , 236 , 237 , 238 , 239 , 242 , 243 , 245 247 , 249 , 250 , 25 1 , 2 53 , 254 , 2 55 256 , 2 57 , 258 , 259 , 260 , 262 , 263 , 264 , 265 266 , 2 67 , 268 , 269 , 270 , 27 1 , 272 273 , 274, 275, 276. Among these, preferred are CI Pigment Red: 48: 1, 1 22 '168' 177, 202, 206 ' 207 ' 209 ' 224 , 242, 254 » Better CI Pigment Red 177, 209, 224, 254. The blue pigment has C _ .I. Pigment Blue 1, 1 : 2, 9, 14, 15 , 15 : 1 ' 15 : 2 ' 1 5 : 3 , 15: 4 , 15 : 6, 16, 17, 19 25 , 27 ' 28 , 29 , 33 , 35 , 36 , 56 , 56 : 1, 60, 6 1 > 6 1: 1 ' 62, 63, 66, 67, 68, 7 1, 72, 73, 74, 75 76, 7 8 ' '79. Among these, preferred are CI Pigment Blue 15 ' 1 5 : 1, 1 5 : : 2, 15. 3, 1 5 : 4, 15: 6, and more preferably CI Pigment Blue 15 : : 6 ° Green The pigments are C.I. Pigment Green 1 > 2, 4, 7, 8, 10 13, -34- 201026723 ❹ 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 5 1 54, 55. Among these, the preferred ones are: CI Pigment Green 7, 36 » Yellow pigments have c.I. Pigment Yellow 1 ' • 1 : 1, 2, 3, 4, 5, 6, 9, 1 0, 12, 13 , 14, 1 6, 1 7, 24 '31' 32, 34, 35, 3 5: 1, 36, 36 :] L, 37, 37 : 1 ' 40 '41' 42, 43 ' 4 8' 53, 55 ' 6 1' 62, 62 : 1 ' .63, 65 , 73 , 74 , 75 , 8 1 , 83 , 87 , 93 ' 94- • 95' 97, 1 00, 1 0 1 , 104, 105, 108 109, 110 '111' 116, 117, 119, 12 0, 126, 1 27, 127: 1, 128, 129 ' 133, 134, 136 138, 139, 142, 147, 148, 150, 15 1 , 153 , 154 155 , 157 ' 158 ' 159 , 160 , 16 1 , 162 , 163 , 164 165 , 166 ' 16 7 ' 168 , 169 , 170 ' 172 , 173 , 174 175 , 176 , 180 , 18 1 , 182 , 183 , 184, 185, 188, 189, 190, 1 9 1 , 1 9 1:1' 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 2 05 > 206 207, 208 ° of 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. Orange pigments have C.I. Pigment orange 1, 2, 5, 1 3, 1 6 ' 1 7 , 19, 20, 2 1 , 22 , 23 , 24 , 34 blue 36 '38*39 ' 43 , 46 , 48, 49, 6 1, 62, 64 > 65, 67, 68 '69, 70, 7 1, 72, 73, 74, 75, 77 '78, 79 <> For C. I. . Pigment Orange 38, 71 » Purple pigments have C.I. Pigment Violet 1, 1, 1, 2, 2:2, 3, 3: 1 ' 3 i : 3, 5 > 5: 1, 14, 15, 5, 1 6, 19, 23, 25, 27, 29, -35- 201026723 31, 32, 37, 39, 42, 44, 47, 49, 50. Among these, the preferred one is 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 made of black color material alone or a mixture of red, green and blue. Further, these color materials may be appropriately selected from inorganic or organic pigments. Inorganic and organic pigments are preferably dispersed to an average particle diameter of 1/m or less, preferably 5% or less. The color materials that can be mixed for the modulation of black color materials are Victoria Pure Blue (42595), Auramine 0 (41000), Catilon Brilliant

Flavin (Basic 13), Rose Red 6GCP (45160), Rose Red B (45 1 70) 'Saffron Red OK70: 100 (50240}, Alice Sea Blue X (42080), No. 1 20/RIONOL YELLOW (2 1 090), RIONOL YELLOW GRO (2 1090), SIMURA FAST YELLOW 8GF (21105), benzidine yellow 4T-564D (2 1095), SIMURA FAST RED 40 15 (12355), RIONOL RED 7B440 1 (15850), Fastogen Blue TGR-L (74 160), RIONOL BLUE SM (26 150)' RIONOL BLUE ES (pigment blue 1 5 : 6 ), RI 〇 NOGEN RED (pigment red 168), RIONOL GREEN 2YS (pigment green 36), etc. The number in () means the color index (C. I·)]. In addition, the pigments which can be mixed and used are indicated by CI number, and there are C. I. yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, C·I. Red pigment 9, 97, 122, 123, 149, 168 , 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI violet pigment-36-201026723 19, 23, 29, 30, 37, 40, 50, CI blue Color pigment 15, i5: 1, 15: 4, 22, 60, 64, CI green pigment 7, C. 1_ brown pigment 23, 25, 26, etc. Also, the black color materials that can be used alone are carbon black, acetylene black, lamp black, bone black, graphite, iron Black, aniline black, cyanine black, titanium black, etc. Among these, carbon black is preferable from the viewpoint of light blocking ratio and image characteristics. Carbon black has, for example, the following carbon black.

Mitsubishi Chemical Corporation: ΜΑ7, ΜΑ8, ΜΑ11, ΜΑ100, MA100R, ΜA 2 2 0, Μ A 2 3 Ο, Μ Α 6 0 0, # 5, # 1 0, # 2 0, #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 company: Printex 3, Printex 30P, 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 S 160 ' Color Black S 1 70 ° -37- 201026723

Cabot company: Monarchl20, Monarch280, Monarch460, Monarch800, Monarch880,

Monarch900, MonarchlOOO, Monarchl100,

Monarch 1 300, Monarch 1400, Monarch463 0, REGAL99, REGAL99R > REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS 130, VULCAN XC72R, ELFTEX-8.

Columbian Carbon Company: RAVEN 1 1 , 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, the pigment may also use barium sulfate, sulfuric acid, oxidized, chrome yellow, iron oxide red, chromium oxide or the like. These pigments can also be used in a plurality of types. For example, to adjust the color, you can use green and yellow pigments, or you can use blue pigments and purple pigments. The average particle diameter of these pigments is preferably 1/zm, more preferably 〇5//111 or less (e.g., 0.005 to 0.5//m>, 0.; 25/zm or less) (for example, 0.01 to 〇25 mils m) The blending amount of the pigment is preferably 15 to 60 parts by weight based on the total solid content of the pigment except for the pigment. The composition of the black matrix containing the black pigment such as carbon black is -38-201026723 The blending amount of the pigment is preferably from 50 to 150 parts by weight, more preferably from 70 to 140 parts by weight, even more preferably from 90 to 130 parts by weight, based on the total solid content of the pigment except for the pigment. If necessary, a dispersing agent may be blended in the photosensitive resin composition. For the dispersing agent, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric, polyfluorene-based or fluorine-based surfactant may be used. Among them, the polymer surfactant (polymer dispersant) exemplified below is preferable. That is, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleic acid, etc. Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene and octyl phenyl ether Polyethylene glycol diesters such as polyethylene glycol dilaurate, polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; third amine modified polyamines Polymeric surfactants such as carboxylic acid esters are suitable. Specific examples of the polymer dispersant include EFKA (manufactured by EFKA Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and DISPERON (manufactured by Nanben Chemical Co., Ltd.). SOLSPERSE (manufactured by ZENEKA), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more. The weight average molecular weight (Mw) of the GPC polystyrene is 700 or more, and it is preferably 1000 or more, preferably 1,000,000 or less, and preferably 50,000 or less. In particular, the urethane-based polymer and the propylene-based polymer are dispersed. The solvent is preferably Disperbyk 160-166, IJ, Disperbyk 2000, 2001, etc. (all manufactured by BYK Chemical Co., Ltd.). The propylene-based polymer dispersant is a random copolymer, grafted with a total of -39- 201026723 Block copolymers are preferred. These copolymers are It is produced by a conventional method. The 'dispersant can also be a pigment derivative. The pigment derivatives are azo, phthalocyanine, quinophthalone, benzimidazolone, quinoline yellow, isoporphyrin. a derivative of a ketone system, a diterpenoid system, an anthraquinone system, an indanthrene system, an anthraquinone system, a purple ketone-based system, or a diketopyrrolpyrrole, wherein a quinoline yellow system is preferred. The substituent includes 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, an aryl group, or a hetero group. The ring group or the like is 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 an anthrone, and a sulfonic acid of a diketopyrrolpyrrole. Derivatives, sulfonic acid derivatives, etc. 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 contain a solid content other than the above components as necessary. These components include surfactants, thermal polymerization Q inhibitors, plasticizers, storage stabilizers, surface protectants, adhesion promoters, and imaging modifiers. As the solvent of the photosensitive resin composition, those exemplified above may be used as the polymerization solvent. As the surfactant, various surfactants such as an anionic, cationic, nonionic or amphoteric surfactant can be used, and the possibility of adversely affecting the properties is low, and a nonionic surfactant is preferably used. 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, more preferably 0.03 to 0.3% by weight, based on the total amount of the composition. -40-201026723 As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, gallic phenol, catechol, 2,6-tributyl-p-cresol, cold-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(dodecyl) phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, cresol 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 having excellent physical properties can be obtained. For example, the curable resin composition is applied to various substrates or substrates (supports) by a spin coater or a gap coater. After the film, the coating film is cured to obtain a cured product. The substrate or substrate has glass, ceramic, twin crystal, 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, Q or by heating after exposure. When the above 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 coating film after hardening can be appropriately selected depending on the use, and is generally 0.1 to 40//m, preferably 0.3 to 20 μmη, preferably about 0.5 to l〇vm. 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-41 - 201026723 filter. The order and operation of the color filter can be carried out. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The weight average molecular weight (polystyrene) and the degree of dispersion (weight average molecular weight Mw/number average molecular weight) of the resulting copolymer were determined according to the following conditions. Apparatus: Detector: RID-10A (Shimadzu Corporation) Pump: LC-10ADVP (Shimadzu φ System controller: SCL-10AVP (Shimadzu degasser: DGU-14A (Shimadzu Corporation automatic injector: SIL-10AF (Shimadzu Corporation column: Waters Styragel HR3, Styragel S tyragel H R5 3 mobile phases: THF Flow rate: lmL/min Temperature: oven (40 ° C }, RI (4 (TC ) φ detector: RI POLARITY ( + ) Injection volume: 5 0 # L Synthesis Example 1 with reflux cooler, dropping funnel and mixer The amount of nitrogen in a 1 L flask was passed through a nitrogen atmosphere, and 35 parts by weight of propylene glycol monomethyl ether 235 weight of diol monomethyl ether acetate was placed, and the mixture was stirred while stirring. Next, a drop pump was used for about 4 hours in the flask. 250 parts by weight of olefinic acid and 200 parts by weight of vinyl crotonate (manufactured by JAPAN VAM & CO., LTD.) were added dropwise. Further, the polymerization polymerization agent 2 was dissolved. The method was limited to this ethylene exchange Μ) ) HR4, internal , B-Bound to 75 Methylpropionate POVAL 2 '-Azo-42- 201026723 Bis(2,4-Dimethylvaleronitrile) 30 parts by weight of a solution of 200 parts by weight of propylene glycol monomethyl ether acetate using individual drip pumps After dropwise addition for about 4 hours, the polymerization initiator 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 a strontium hydride of 290 mg-KOH/g. The weight average molecular weight Mw of the resulting copolymer was 19000. Synthesis Example 2 The monomer composition was changed to 90 parts by weight of methacrylic acid, and 3,4-epoxytricyclo[5_2.1.0 2,6]fluoren-9-ylacrylic acid was used. Mixture of ester with 3,4-epoxytricyclo 0 [5.2·1·0 2,6]癸-8-yl acrylate [50: 50 (mole ratio)] 385 parts by weight and vinyl crotonate (JAPAN) VAM & POVAL C Ο., 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 50.5 wt% and a cerium acid content of 106 mg-KOH/g was obtained. The molecular weight Mw was 12,000. Synthesis Example 3 Vinyl crotonate (JAPAN VAM & POVAL CO., LTD. manufactured as J was changed to vinyl sorbate (JAPAN VAM & PO) Other than Q, manufactured by VAL CO., LTD., was carried out as in Synthesis Example 1. A copolymer solution having a solid content of 50.8 wt% and a phosphonium 113 mg-KOH/g was obtained. The resulting copolymer had a weight average molecular weight Mw of 19000. Synthesis Example 4 A vinyl crotonate (manufactured by JAPAN VAM & POVAL CO., LTD.) was changed to a synthetic example 1 except that it was changed to vinyl cinnamate (manufactured by JAPAN VAM & POVAL Co., Ltd.). A copolymer solution having a content of 50% by weight and a cerium acid content of 104 mg-KOH/g. The weight average molecular weight Mw of the resulting copolymer is 15000. -43-.201026723 Synthesis Example 5 Modification of the monomer composition to methacrylic acid 90 Parts by weight, 3,4-epoxytricyclo[5.2.1.0 2,6]non-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6]non-8-yl acrylate a mixture of [50: 50 (mole ratio)] 285 parts by weight, 1 part by weight of cyclohexyl methacrylate, and 25 parts by weight of vinyl crotonate (manufactured by JAPAN VAM & p〇VAL CO., LTD.) In the same manner as in Synthesis Example 1, a copolymer solution having a solid content of 50.2% by weight and an acid hydrazine of 1 1 Omg-KOH / g was obtained. The weight average of the resulting copolymer ❺ molecular weight Mw was 1 7000. Synthesis Example 6 Monomer composition Changed to 90 parts by weight of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6]non-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6]癸-8-based propylene A mixture of acid esters [50: 50 (mole ratio)] was used in the same manner as in Synthesis Example 1. A solid content of 49.8 wt% was obtained, and a copolymer of acid 値1 1 〇mg-KOH / g was dissolved. The resulting copolymer has a weight average molecular weight Mw of 10000. Q Example 1 50 parts by weight of the copolymer solution obtained in Synthesis Example 1, propylene glycol monomethyl ether acetate 49 parts by weight, photopolymerization initiator IRGACURE 184 (Photoradical initiator; manufactured by Ciba Japan Co., Ltd.) 1 part by weight was mixed to obtain a photosensitive resin composition. Example 2 The copolymer solution was changed to the copolymer solution obtained in Synthesis Example 2, as in the examples. (1) A photosensitive resin composition was obtained. Example 3 -44-.201026723 The copolymer solution was changed to the copolymer solution obtained in Synthesis Example 3, and a photosensitive resin composition was obtained as in Example 1. Example 4 Change of copolymer solution The photosensitive resin composition was obtained as in Example 1 except for the copolymer solution obtained in Synthesis Example 4. Example 5 The copolymer solution was changed to the copolymer solution obtained in Synthesis Example 5, and the photosensitivity was obtained as in Example 1. Resin composition. φ 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 a polyfunctional vinyl compound dipentaerythritol hexaacrylate (DPHA, DAICEL CYTEC) (2) parts by weight of a photopolymerization initiator IRGACURE 184 (photoradical initiator; 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Chem Industrial 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 a copolymer solution obtained in Synthesis Example 2, 48 parts by weight of propylene glycol monomethyl ether acetate, and a hindered amine compound ADEKA STAB LA-57 (a compound of the above formula (3e)' ADEKA (manufactured by ADEKA Co., Ltd.) 2 parts by weight of a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan-45-201026723 (manufactured by Co., Ltd.)) 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, epoxy compound CELOXIDE 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.), 2 parts by weight, photopolymerization initiator IRGACURE 184 (photoradical bow; hair agent; manufactured by Ciba Japan Co., Ltd.) 1 part by weight of a photosensitive resin composition was mixed. Comparative Example 1 φ Copolymer solution was changed to a copolymer solution obtained in Synthesis Example 6. A photosensitive resin composition was obtained as in Example 1. 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 a polyfunctional vinyl compound dipentaerythritol 2 parts by weight of a acrylate (DPHA, manufactured by DAICEL CYTEC Co., Ltd.) and a photopolymerization initiator IRGACURE 184 (photoradical initiator; manufactured by Ciba Japan Co., Ltd.) were 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-propionic acid (DPMP, 堺Chem Industrial (share) system 2 parts by weight of a photopolymerization initiator IRGACURE 184 (photo radical initiator; Ciba Japan (shares), Ltd.) 1 parts by weight of the mixed photosensitive resin composition obtained in 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 a hindered amine compound ADEKASTAB - 46 - 201026723 LA-57 (a compound of the above formula (3e), manufactured by ADEKA Co., Ltd. 2 polymerization initiator IRGACURE 184 (manufactured by photo-radical initiator) was mixed to obtain a photosensitive resin composition. Comparative Example 5 Synthetic copolymer solution obtained in Synthesis Example 6 49 parts by weight of methyl ether acetate 48 parts by weight, epoxy compound 2021P (manufactured by DAICEL Chemical Industry Co., Ltd.), 2 parts by weight, light IRGACURE 184 (photoradical bow; hair agent; Ciba Japan (and φ parts were mixed to obtain a photosensitive resin composition). Evaluation test (1) Preparation of evaluation test piece The glass plate (substrate) was spin-coated with each of the examples and the comparative example neutral resin composition, and then heated at 1 ° C for 3 minutes at 200 ° C. The coating film was hardened in an oven. The light amount of the conditions of 200 mJ/cm2 and 800 mJ/cm2 (2) Adhesiveness 0 The adhesion of the examples and the comparative examples according to JIS K-5600-5-6' peeling. And based on the classification specified in the classification of JIS K5600-5-6 8.3, based on the following benchmarks ◎ . · • "相当于" which is equivalent to the classification of the test results. 〇..·相当于" which corresponds to the classification of the test results. △ · ·. The "2" corresponding to the classification of the test results. X· · · "3" corresponding to the classification of the test results (3) Solvent resistance in the examples and comparative examples, evaluated in parts by weight of glass plate, light: Ciba 曰, propylene glycol mono CELOXIDE polymerization initiator t) 1 weight of the obtained photosensitive exposure, more exposure is measured from the test results of the substrate 1 4" ° test strips, each -47- 201026723 with isopropanol (IPA), butanone (oxime), N-methylpyrrolidone (NMP) was dripped dropwise and left for 10 minutes. Then, it was washed with water, and the solvent was completely left unchanged. The solvent trace was left and the solvent was retained. The solvent trace was retained and the solvent could not be erased. The overall discoloration is X. The same result is obtained when the test piece for the evaluation made of stainless steel plate is used instead of the glass plate. (4) Alkali resistance The test piece for the evaluation of the glass plate was carried out in the examples and comparative examples. , drop by 1% by weight of NaOH solution, place 1 0 minutes. Then water φ wash, 1% by weight of NaOH aqueous solution drop no change is ◎, a little dripping trace is retained and can be erased as 〇, there is a solvent trace left and can not be erased △, comprehensive The discoloration was X. The results of the evaluation test are shown in Table 1. In the table, "DPHA", "DPMP", "ADEKASTAB LA-57", "CELOXIDE 202 1P_ each of the examples and comparative examples.

-48 - 201026723

Comparative example 00 00 ◎ 〇〇 X 〇 ◎ 〇〇 X 〇 inch inch rH 00 inch <] 〇 < X <] < 〇 <3 X < CO OJ rH 00 inch < 〇X <] <] 〇<3 X <] (Μ σ\ inch < N 00 inch 〇 ◎ < X < ◎ ◎ 〇〇 1-Η t-1 inch 〇 ◎ < X 0 〇 ◎ < X <3 σ\ σ; (N iH 00 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 00 CN rH 00 inch ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 卜 iH 00 inch ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ r r ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 实施 实施 H H H H H ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ CO H ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ 〇 ◎ CN rH 寸 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ iH 〇 \ inch 〇〇〇〇〇 ◎ ◎ ◎ 〇 ◎ copolymer dissolution Liquid Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 DPHA DPMP ADEKASTAB LA-57 CELOXIDE 202IP Photopolymerization Initiator (Irgacure 184) Solvent (PGMEA) Adhesive Solvent Resistance Isopropyl Ketone N -Methylpyrrolidone alkali-resistant adhesive solvent-resistant isopropanol butanone N-methylpyrrolidone alkali-resistant exposure 200 mJ/cm2 exposure 800 mJ/cm2

On 201026723, it is understood that 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, the coating film of the photosensitive resin composition obtained from 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 inferior in adhesion to the substrate. [Simple description of the diagram] None. [Main component symbol description] ^ None. 〇

Claims (1)

201026723 VII. Patent application scope: 1. A copolymer is characterized in that it contains at least a vinyl monomer having a plurality of carbon-carbon double bonds in the molecule [(meth) acrylate derivative and (meth) acrylonitrile] In addition to the amine derivative] (vinyl monomer A), it is obtained by polymerizing a monomer mixture of a vinyl monomer (vinyl monomer B) having a carboxyl group or a carboxylic anhydride group. 2. The copolymer of claim 1, wherein the vinyl monomer A is a compound represented by the following formula (1): R2 (1) κ1γ^ Η (wherein R1 represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R2, R3 and R4 are the same or different and represent a hydrogen atom or a methyl group, and X represents a linking group; η represents an integer of 1 to 3) . 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) Formula (1) In the formula, R1 is a hydrocarbon group which may have a substituent, and R2, R3 and R4 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 to which R2 is bonded), n a compound of the formula (1) wherein R, R2, R3 and R4 are the same or different and are a hydrogen atom or a methyl group, X is a residue of a polycarboxylic acid, and η is an integer of 1 to 3 And (iii) in the formula (1), 'R1, R2, R3 and R4 are the same or different and are a hydrogen atom or a methyl group. 'X is an η-valent hydrocarbon group which may have a substituent, and η is a 1-5-51- .201026723 Integer compound. 4. The copolymer according to any one of claims 1 to 3, which comprises at least a vinyl monomer A, a vinyl monomer B, and a vinyl monomer having 3 to 5 member cyclic ether groups. The monomer mixture of C is obtained by polymerization. 5. The copolymer of claim 4, wherein the vinyl monomer C has a vinyl monomer having an alicyclic epoxy group. 6. The copolymer of claim 4 or 5, which comprises at least a vinyl monomer A, a vinyl monomer B, a vinyl monomer C, and a (Φ methyl) acrylate D, an aromatic group. A monomer mixture of at least one monomer selected from the group consisting of a 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 6. 8. The curable 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 At least one compound selected from the group consisting of a compound and a vinyl ether compound. A photosensitive resin composition characterized by containing the copolymer and photopolymerization initiator according to any one of claims 1 to 6. (1) The photosensitive resin composition of claim 9 which further contains a compound having a radical polymerizable double bond, a polyfunctional thiol compound, a hindered amine compound, an epoxy compound, an oxetane At least one compound selected from the group consisting of an alkyl compound and a vinyl ether compound. -52- 201026723 11. The photosensitive resin composition of the ninth or first aspect of the patent application 'in which the pigment is further contained' 1 2 . The photosensitive resin composition of the ninth or first aspect of the patent application' Used as a liquid photoresist, dry film, pigment photoresist or coated protective film. A color filter characterized in that it is produced by using a photosensitive resin composition as set forth in claim 11 of the patent application. A method of producing a color filter, characterized in that the photosensitive resin composition of the eleventh aspect of the patent application is applied to a support, and then exposed by a photomask to develop a pattern. Ο ‘ 201026723 ' IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: