JP2007248678A - Colored alkali developing photosensitive resin composition and color filter using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored alkali developing photosensitive resin composition which is excellent in sensitivity, resolution, developing, and adhesiveness, and can form a fine pattern with precision, and a color filter using it. <P>SOLUTION: This colored alkali developing photosensitive resin is an alkali developing resin composition containing a photopolymerizing unsaturated compound (X) in a structure obtained by esterificating polybasic acid anhydride (C) in the epoxy addition product in a structure adding unsaturated monobasic acid (B) to an epoxy resin (A) in a structure alternately polymerizing an epoxy compound expressed in the general formula (I) and a polyhydroxy aromatic compound, and further containing a photopolymerizing initiator (F) and a color material (G). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colored alkali-developable photosensitive resin composition suitably used for producing a color filter used in a liquid crystal display, a plasma display, an electroluminescence panel, a video camera and the like, and the colored alkali-developable photosensitive resin composition The present invention relates to a color filter using an object.

  The colored alkali-developable photosensitive resin composition contains a colorant such as a pigment or a dye and a photopolymerization initiator in an alkali-developable resin composition containing a compound having an ethylenically unsaturated bond. This colored alkali-developable photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or an electron beam, so it is used for photo-curable inks, photosensitive printing plates, printed wiring plates, various photoresists, and the like. ing. Recently, with the progress of miniaturization and high functionality of electronic devices, it is desired to form fine patterns with high accuracy.

  Regarding the alkali-developable resin composition and the alkali-developable photosensitive resin composition, the following Patent Document 1 proposes a photosensitive resin composition containing a prepolymer having an ethylenically unsaturated bond. Patent Document 2 below proposes a photosensitive resin composition containing an unsaturated group-containing polycarboxylic acid resin. However, these known alkali-developable photosensitive resin compositions have insufficient resolution and adhesion, and it has been difficult to obtain appropriate pattern shapes and fine patterns. Therefore, an alkali development type photosensitive resin composition that is excellent in resolution and adhesion and can form a fine pattern with high accuracy has been desired.

  Patent Document 3 below discloses an epoxy resin composition containing a polyfunctional epoxy resin obtained by reacting a bifunctional epoxy resin having a bisphenol skeleton and the like with bisphenols. Discloses an epoxy resin composition containing an epoxy resin having two epoxy groups in one molecule and an epoxy resin obtained by alternately copolymerizing a compound containing a phenolic hydroxyl group in one molecule. However, there is no description or suggestion that these epoxy resin compositions can be used in alkali-developable photosensitive resin compositions.

JP 2000-235261 A JP 2000-355621 A Japanese Examined Patent Publication No. 7-45561 JP 2004-217774 A

  The problem to be solved is that, as described above, there has been no colored alkali development type photosensitive resin composition that is excellent in sensitivity and adhesion and can obtain an appropriate pattern shape and fine pattern. .

  Accordingly, an object of the present invention is to provide a colored alkali-developable photosensitive resin composition that is excellent in sensitivity, resolution, developability, adhesion, etc., and can form a fine pattern with high precision, and the colored alkali-developable photosensitive resin composition. It is to provide a used color filter.

  The present invention has a structure in which an epoxy compound represented by the following general formula (I) and a polyhydroxy aromatic compound (excluding a bisphenol compound represented by the following general formula (II)) are alternately copolymerized. Photopolymerizable unsaturated structure having a structure obtained by esterifying polybasic acid anhydride (C) to an epoxy adduct having a structure in which unsaturated monobasic acid (B) is added to epoxy resin (A) To provide a colored alkali-developable photosensitive resin composition characterized by further containing a photopolymerization initiator (F) and a colorant (G) in an alkali-developable resin composition containing the compound (X). Thus, the above object is achieved.

（式中、Ｃｙは、炭素原子数３〜１０のシクロアルキル基を示し、Ｘは、水素原子、フェニル基又は炭素原子数３〜１０のシクロアルキル基を示し、該フェニル基及び炭素原子数３〜１０のシクロアルキル基は、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基又はハロゲン原子により置換されていてもよく、Ｙ及びＺは、それぞれ独立して、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を示し、アルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、ｐは０〜４の数を示し、ｒは０〜４の数を示す。）

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group and the carbon number 3 -10 cycloalkyl group may be substituted by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and Y and Z are each independently a carbon atom. An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom, wherein the alkyl group, the alkoxy group, and the alkenyl group are substituted with a halogen atom; And p represents a number from 0 to 4, and r represents a number from 0 to 4.)

（式中、Ｃｙ、Ｘ、Ｙ、Ｚ、ｐ及びｒは、上記一般式（Ｉ）と同じである。）

(In the formula, Cy, X, Y, Z, p and r are the same as those in the general formula (I).)

  The present invention also provides a reaction product obtained by esterifying a polybasic acid anhydride (C) with an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to the epoxy resin (A). In addition, an alkali-developable resin composition containing a photopolymerizable unsaturated compound (Y) having a structure obtained by adding an epoxy compound (D) to the product, a photopolymerization initiator (F) and a colorant ( The object is achieved by providing a colored alkali-developable photosensitive resin composition characterized by containing G).

  The present invention also provides a reaction product obtained by esterifying a polybasic acid anhydride (C) with an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to the epoxy resin (A). An alkali-developable resin composition containing a photopolymerizable unsaturated compound (Z) having a structure obtained by adding an epoxy compound (D) to the product and subsequently esterifying the polybasic acid anhydride (E) The object is achieved by providing a colored alkali-developable photosensitive resin composition characterized by further containing a photopolymerization initiator (F) and a coloring material (G).

  Moreover, this invention achieves the said objective by providing the color filter characterized by using the said colored alkali development type photosensitive resin composition.

  The colored alkali-developable photosensitive resin composition of the present invention is excellent in sensitivity, resolution, developability and adhesion, can form a fine pattern with high accuracy, and is suitable as a color filter.

  Hereinafter, the colored alkali development type photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.

  The colored alkali-developable photosensitive resin composition of the present invention includes a photopolymerization initiator (F) and an alkali-developable resin composition containing the photopolymerizable unsaturated compound (X), (Y) or (Z). A coloring material (G) such as a pigment or a dye is contained. Specifically, the content of the photopolymerizable unsaturated compound (X), (Y) or (Z) is the above-mentioned colored alkali developing type 1 to 70% by mass in the photosensitive resin composition, and the content of the photopolymerization initiator (F) is 0.1 to 30% by mass in the colored alkali development type photosensitive resin composition. Content of the said color material (G) is 0.5-70 mass% in the total solid content except a solvent from this colored alkali development type photosensitive resin composition.

  The colored alkali-developable photosensitive resin composition of the present invention is unsaturated with an epoxy resin (A) having a structure in which an epoxy compound represented by the above general formula (I) and a polyhydroxy aromatic compound are alternately copolymerized. The monobasic acid (B) was added at a ratio of 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid (B) to one epoxy group of the epoxy resin (A). Obtained by esterifying an epoxy adduct having a structure with a polybasic acid anhydride (C) at a ratio of 0.1 to 1.0 acid anhydride structure per one hydroxyl group of the epoxy adduct. The photopolymerizable unsaturated compound (X) having the structure as described above, and the epoxy compound (D) as necessary, in a ratio of 0.1 to 1.0 epoxy groups with respect to one hydroxyl group of the epoxy adduct A photopolymerizable polymer having a structure obtained by adding The compound (Y), and then the polybasic acid anhydride (E) are esterified at a ratio of 0.1 to 1.0 acid anhydride structures for one hydroxyl group of the epoxy adduct. The photopolymerizable unsaturated compound (Z) having the structure obtained is contained.

  The ratio of the carboxyl group of the unsaturated monobasic acid (B) to one epoxy group of the epoxy resin (A) is preferably 0.3 to 1.0. The ratio of the acid anhydride structure of the polybasic acid anhydride (C) to one hydroxyl group of the epoxy adduct is preferably 0.3 to 0.95, and the epoxy compound (D) has an epoxy content. The ratio of the group is preferably 0.3 to 0.9, and the ratio of the acid anhydride structure of the polybasic acid anhydride (E) is preferably 0.3 to 0.7.

In the general formula (I), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. .
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by X include those exemplified as the cycloalkyl group having 3 to 10 carbon atoms represented by Cy. As the phenyl group represented by X and the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms and the halogen atom which may be substituted for the cycloalkyl group having 3 to 10 carbon atoms, What is illustrated later as what is shown by Y and Z is mentioned.
Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl Octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. Examples of the alkoxy group having 1 to 10 carbon atoms represented by Y and Z include methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, methoxymethoxy, methoxyethoxy, ethoxyethoxy, propylene Examples include roxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like. Examples of the alkenyl group having 2 to 10 carbon atoms represented by Y and Z include vinyl, allyl, butenyl, propenyl, etc. Examples of the halogen atom represented by Y and Z include fluorine, chlorine, bromine and iodine. It is done.
In addition, the above-mentioned alkyl group and alkoxy group which may be substituted for the phenyl group represented by X and the cycloalkyl group having 3 to 10 carbon atoms, and the above-described alkyl group, alkoxy group and alkenyl group represented by Y and Z May be substituted with a halogen atom, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. For example, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl etc. are mentioned as a C1-C10 alkyl group substituted by the fluorine atom.

  The colored alkali-developable photosensitive resin composition of the present invention has a triarylmonocycloalkylmethane skeleton as the epoxy resin (A) used for its preparation, thereby allowing the cured product to adhere to a substrate, workability, Since the strength and the like are excellent, it is considered that a clear image can be formed with high accuracy even if the pattern is a fine pattern when the uncured portion is developed and removed. As the epoxy resin (A), in the above general formula (I), those in which Cy is cyclohexyl; those in which X is a phenyl group; those in which p and r are 0 are preferable.

  Specific examples of the epoxy compound represented by the general formula (I) include the following compound Nos. 1-No. 9 compounds are mentioned. However, the present invention is not limited by the following compounds.

  Examples of the polyhydroxy aromatic compound include 4,4-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4 -Hydroxyphenyl) butane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 4,4 ′-(1-α-methylbenzylidene) bisphenol, 4, 4 ′-(1-α-ethylbenzylidene) bisphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, α, α′-bis (4-hydroxyphenyl) ) -1,4-diisopropylbenzene, hydrogenated bisphenol compound, resorcinol, hydride Examples include quinone, 2,5-di-tert-butylhydroquinone, 1,4-dihydroxynaphthalene, 1,2,4-trihydroxybenzene, 2- [bis (4-hydroxyphenyl) methyl] benzyl alcohol, and salicylic acid. .

  As the polyhydroxy aromatic compound, an adduct of a polyfunctional epoxy compound described later and the compound exemplified above as the polyhydroxy aromatic compound can also be used.

A polybasic acid anhydride (C) is added to an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to an epoxy resin (A) contained in the colored alkali development type photosensitive resin composition of the present invention. ) And a photopolymerizable unsaturated compound (X) having a structure obtained by esterification, and a light having a structure obtained by further adding an epoxy compound (D) to the photopolymerizable unsaturated compound (X) Polymerizable unsaturated compound (Y), and photopolymerizable unsaturated compound (Z) having a structure obtained by esterifying polybasic acid anhydride (E) to photopolymerizable unsaturated compound (Y) Can be produced, for example, by the method represented by the following reaction formula [Chemical Formula 12].
First, unsaturated monobasic acid (4) as component (B) is added to epoxy resin (3) as component (A) to obtain a resin composition containing compound (5) as an epoxy adduct. The copolymerization reaction between the epoxy compound and the polyhydroxy aromatic compound can be carried out according to a conventional method, but is preferably performed at 50 to 150 ° C. for 5 to 15 hours. Further, the addition reaction of the component (B) to the component (A) can be carried out according to a conventional method, but is preferably performed at 90 to 150 ° C. for 5 to 30 hours.
Subsequently, the compound (5) which is an epoxy adduct is reacted with the polybasic acid anhydride (6) which is the component (C) to carry out an esterification reaction. A resin composition containing the unsaturated compound (X)] is obtained. The esterification reaction between the epoxy adduct and the component (C) can be performed according to a conventional method, but is preferably performed at 50 to 150 ° C. for 5 to 10 hours.
Subsequently, compound (9) [photopolymerizable unsaturated compound (Y)] is obtained by subjecting compound (7) which is an ester compound to addition reaction with compound (8) which is an epoxy compound of component (D). . The addition reaction between the ester compound and the component (D) can be carried out according to a conventional method, but the reaction is preferably carried out at 50 to 150 ° C. for 2 to 30 hours.
Subsequently, the compound (9) is further reacted with the compound (10) which is a polybasic acid anhydride of the component (E) for esterification, and the target reaction product, the compound (11) [photopolymerizable] A resin composition containing the unsaturated compound (Z)] can be obtained. The esterification reaction between the compound (9) and the component (E) can be performed according to a conventional method, but the reaction is preferably performed at 50 to 150 ° C. for 3 to 10 hours.

  The unsaturated monobasic acid (B) used in the preparation of the colored alkali-developable photosensitive resin composition of the present invention is used to improve the sensitivity of the alkali-developable resin composition. For example, acrylic acid, Methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate or one carboxyl group and two The polyfunctional (meth) acrylate etc. which have the above (meth) acryloyl group are mentioned.

  The polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups has, for example, one hydroxyl group and two or more (meth) acryloyl groups in one molecule. It can be obtained by reacting a polyfunctional (meth) acrylate with a dibasic acid anhydride or carboxylic acid.

  Examples of the polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups include the following compound Nos. 10-14 can be mentioned.

  The polybasic acid anhydride (C) used in the preparation of the colored alkali-developable photosensitive resin composition of the present invention increases the acid value of the alkali-developable resin composition to increase the pattern shape, developability and development speed. For example, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2′-3,3′-benzophenone tetracarboxylic anhydride, 3 , 3'-4,4'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, tetrahydro anhydride Phthalic acid, nadic acid anhydride, methyl nadic acid anhydride, trialkyltetrahydrophthalic anhydride, hexa Drophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl anhydride Examples include succinic acid and methyl hymic anhydride. Among these, succinic anhydride, trimellitic anhydride, and hexahydrophthalic anhydride are preferable.

As an epoxy compound (D) used for preparation of the colored alkali development type photosensitive resin composition of this invention, a monofunctional or polyfunctional epoxy compound is mentioned.
The monofunctional epoxy compound is used to adjust the acid value of the alkali-developable resin composition. For example, glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl Glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether Ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2- Tylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4- Nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1, 2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, sucrose Hexene oxide, propylene oxide, the following compound No. 15-No. 18 etc. are mentioned.

The polyfunctional epoxy compound is used to adjust the development speed by increasing the molecular weight of the photopolymerizable unsaturated compound. For example, polyglycidyl ether of polyhydric alcohol or its alkylene oxide adduct, polybasic acid Cyclohexene oxide or a cyclopentene oxide-containing compound obtained by epoxidizing a polyglycidyl ester, a cyclohexene ring or a cyclopentene ring-containing compound with an oxidizing agent can be used, and specific examples include the following compounds.
That is, bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol S type epoxy resin, Alkylidene bisphenol polyglycidyl ether type epoxy resin such as bisphenol Z type epoxy resin; hydrogenated bisphenol type diglycidyl ether obtained by hydrogenating the above alkylidene bisphenol polyglycidyl ether type epoxy resin; ethylene glycol diglycidyl ether, 1,3- Propylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol di Glycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1 , 1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane, glycerin tri Glycidyl ethers of aliphatic polyhydric alcohols such as ricidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether; two or more polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ethers of polyether polyols obtained by adding an alkylene oxide of the following: phenol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolak type epoxy compounds A novolac-type epoxy compound such as 3,4-epoxy-3-methylcyclohexylmethyl-3, 4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3, 4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) Adipate, methylenebis (3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Cycloaliphatic epoxy compounds such as 1,2-epoxy-2-epoxyethylcyclohexane; glycidyl esters of dibasic acids such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer; tetraglycidyl diamino Glycidylamines such as diphenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dicyclopentadiene Dioxide compounds such as dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like.

  Commercially available compounds can also be used as the polyfunctional epoxy compound, for example, BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), Adeka Resin EP-4000, Adeka Resin EP-4003S, Adeka Resin EP-4080, Adeka Resin EP-4085, Adeka Resin EP-4088, Adeka Resin EP-4100, Adeka Resin EP-4900, Adeka Resin ED-505, Adeka Resin ED-506, Adeka Resin KRM-2110, Adeka Resin KR Adeka Resin KRM-2720 (Asahi Denka Kogyo Co., Ltd.), R-508, R-531, R-710 (Mitsui Chemicals Co., Ltd.), Epicoat 190P, Epicoat 191P, Epicoat 604, Epicoat 801, Epico 828, Epicoat 871, Epicoat 872, Epicoat 1031, Epicoat RXE15, Epicoat YX-4000, Epicoat YDE-205, Epicoat YDE-305 (manufactured by Japan Epoxy Resin Co., Ltd.), Sumiepoxy ELM-120, Sumiepoxy ELM-434 (Sumitomo Chemical Co., Ltd.) ), Denacol EM-150, Denacol EX-201, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-322, Denacol EX-411, Denacol EX-421, Denacol EX -512, Denacol EX-521, Denacol EX-614, Denacol EX-711, Denacol EX-721, Denacol EX-731, Denacol EX-811, Denacol E -821, Denacol EX-850, Denacol EX-851, Denacol EX-911 (manufactured by Nagase ChemteX), Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 80MF, Epolite 100MF, Epolite 1500NP, Epolite 1600, Epolite 3002, Epolite 4000, Epolite FR-1500, Epolite M-1230, Epolite EHDG-L (Kyoeisha Chemical Co., Ltd.), SB-20 (Okamura Oil Co., Ltd.), Epiklon 720 (Large) Nippon Ink Chemical Co., Ltd.), UVR-6100, UVR-6105, UVR-6110, UVR-6200, UVR-6228 (Union Carbide), Celoxide 2 000, Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 3000, Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide 401, Epolide 403, Epolide HD300 , EHPE-3150, ETHB, Epo blend (manufactured by Daicel Chemical Industries), PY-306, 0163, DY-022 (manufactured by Ciba Specialty Chemicals), Santo Tote ST0000, Epototo YD-011, Epototo YD-115, Epototo YD -127, Epototo YD-134, Epototo YD-172, Epototo YD-6020, Epototo YD-716, Epototo YD- 011R, EPOTOHTO YD-901, EPOTOHTO YDPN-638, EPOTOHTO YH-300, Neototo PG-202, (manufactured by Tohto Kasei Co., Ltd.) Neototo PG-207, include Blemmer G (manufactured by NOF Corporation) and the like.

As the polybasic acid anhydride (E) used for the preparation of the colored alkali-developable resin composition of the present invention, those mentioned as the polybasic acid anhydride (C) can be used.
The addition of the epoxy compound (D) to the photopolymerizable unsaturated compound (Z) and subsequent esterification of the polybasic acid anhydride (E) may be repeated, and (A) to (E) The epoxy compound (D) is further added to the photopolymerizable unsaturated compound having a structure obtained by reacting each component of), and the lactone compound may be esterified instead of the polybasic acid anhydride (E). Good.

  The photopolymerizable unsaturated compounds (X), (Y) and (Z) have a content of 1 to 70% by mass, particularly 3 to 30% by mass, in the alkali-developable resin composition. The acid value of the solid content is preferably in the range of 35 to 120 mg / KOH, particularly 50 to 110 mg / KOH.

  In addition to the photopolymerizable unsaturated compounds (X), (Y), and (Z), the alkali-developable resin composition may contain a solvent, for example, containing a photopolymerizable unsaturated compound. When the amount is within the above preferred range, a solvent can be used for the remainder other than the photopolymerizable unsaturated compound. Specific examples of the solvent include those exemplified as the solvent used in the alkali-developable photosensitive resin composition described later. Moreover, you may make it contain in the alkali developable resin composition of this invention as it is, without removing the solvent used when synthesize | combining the said photopolymerizable unsaturated compound (X), (Y), and (Z).

  Content of the said photopolymerizable unsaturated compound (X), (Y) and (Z) is a coloring material (G), such as a photoinitiator (F) and a pigment or dye, in the said alkali developable resin composition. 1 to 70% by mass, particularly 3 to 30% by mass, in the colored alkali development type photosensitive resin composition obtained by adding the acid, the acid value of the solid content is 35 to 120 mg / KOH, especially 50 to A range of 110 mg / KOH is preferred.

  As the photopolymerization initiator (F) used in the colored alkali development type photosensitive resin composition of the present invention, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1 -Benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholy-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1- Chlor-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- ( '-Isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2 '-Morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, the following compound no. 19, no. 20 etc. are mentioned. Among these, benzophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are preferable.

（式中、Ｘ¹はハロゲン原子又はアルキル基を表し、Ｒ¹はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ²はＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ³はＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ及びＲ’は、アルキル基、アリール基、アラルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合又はエステル結合により中断されていてもよく、また、Ｒ及びＲ’は一緒になって環を形成していてもよく、ｍは０〜５である。）

Wherein X ¹ represents a halogen atom or an alkyl group, R ¹ represents R, OR, COR, SR, CONRR ′ or CN, R ² represents R, OR, COR, SR or NRR ′, R ³ represents R, OR, COR, SR or NRR ′, R and R ′ represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which are substituted with a halogen atom and / or a heterocyclic group. Among them, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R ′ together form a ring. (M may be 0 to 5).

（式中、Ｘ¹、Ｒ¹、Ｒ²、Ｒ³、Ｒ及びＲ’は上記化合物Ｎｏ．１９と同様であり、Ｘ¹’はハロゲン原子又はアルキル基を表し、Ｚは酸素原子又は硫黄原子を表し、ｓ及びｔはそれぞれ１〜４の数を表し、Ｒ¹’はＲ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ²’はＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ³’はそれぞれＲ、ＯＲ、ＣＯＲ、ＳＲ又はＮＲＲ’を表し、Ｒ⁴はジオール残基又はジチオール残基を表す。）

(In the formula, X ¹ , R ¹ , R ² , R ³ , R and R ′ are the same as in the above compound No. 19, X ¹ ′ represents a halogen atom or an alkyl group, and Z represents an oxygen atom or a sulfur atom. S and t each represent a number from 1 to 4, R ¹ ′ represents R, OR, COR, SR, CONRR ′ or CN, R ² ′ represents R, OR, COR, SR or NRR ′. R ³ ′ represents R, OR, COR, SR or NRR ′, and R ⁴ represents a diol residue or a dithiol residue.

  In the colored alkali development type photosensitive resin composition of the present invention, the content of the photopolymerization initiator (F) is 0.1 to 30% by mass with respect to the colored alkali development type photosensitive resin composition of the present invention. In particular, 0.5 to 5% by mass is preferable.

The solvent contained in the colored alkali-developable photosensitive resin composition of the present invention is not particularly limited as long as it is a solvent that can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl Ketones such as ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate Cellsolv solvents such as methanol, ethanol, iso- or n-propanol, alcohol solvents such as iso- or n-butanol, amyl alcohol; BTX solvents such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane Aliphatic hydrocarbon solvents such as terpene oil, D-limonene, pinene, etc .; Terpene hydrocarbon oils; Mineral Spirit, Swazol # 310 (Cosmo Matsuyama Oil), Solvesso # 100 (Exxon Chemical) Paraffinic solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and other halogenated aliphatic hydrocarbon solvents; chlorobenzene and other halogenated aromatic hydrocarbon solvents; carbitol solvents, aniline, triethylamine, pyridine, Acetic acid, acetonitrile, two Carbon, tetrahydrofuran, N, N- dimethylformamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used as one or a mixture of two or more.
In the colored alkali-developable photosensitive resin composition of the present invention, the content of the solvent is such that the total solid concentration in the colored alkali-developable photosensitive resin composition is 5 to 40% by mass, particularly 15 to 30% by mass. It is good to adjust so that it becomes.

  Examples of the color material (G) used in the colored alkali development type photosensitive resin composition of the present invention include pigments and dyes. Which is added is not particularly limited, and either one of a pigment and a dye may be used, or both may be used in combination.

As the pigment that can be used as the color material (G), any of the known pigments used in the production of conventional color filters can be used. Below, the specific example of an organic pigment is shown with a curry index (CI) number. In the list below, “x” represents C.I. I. It is an integer that can be arbitrarily selected from the numbers.
・ Pigment Blue:
<C. I> 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: x, 56, 60, 61, 62
・ Pigment Green:
<C. I> 1,1: x, 2,2: x, 4,7,10,36
・ Pigment Orange
<C. I> 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64
・ Pigment Red
<C. I> 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: x, 83, 88, 90, 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226
・ Pigment Violet:
<C. I> 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 23, 27, 32, 42
・ Pigment Yellow
<C. I> 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,156,175

  Further, as black pigments, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, diamond black LI, diamond black LH, diamond black N339, diamond Rack SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Curve Inc. Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBl ack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, Pr, 140, etc.

  Other pigments include miloli blue, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate, silica, alumina, cobalt, manganese, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, Inorganic pigments such as phosphate ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridiane, emerald green, and cobalt green can also be used. These pigments can be used alone or in combination.

  The dyes that can be used as the colorant (G) include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes. Examples thereof include dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like, and these may be used alone or in combination.

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the color material (G) is 0. 0% in the total mass of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. 5 to 70%, particularly 5 to 60% by mass is preferable.

  The colored alkali development type photosensitive resin composition of the present invention may further contain a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like.

Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate , Methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate , Tert-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, etc. .
In the colored alkali-developable photosensitive resin composition of the present invention, the content of the monomer having an unsaturated bond is 0% of the total mass of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. 0.01 to 20% by mass, particularly 0.1 to 10% by mass is preferable.

  Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercaptov Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  In the colored alkali development type photosensitive resin composition of the present invention, the properties of the cured product can be improved by further using a thermoplastic organic polymer. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  In addition, the colored alkali development type photosensitive resin composition of the present invention, if necessary, a thermal polymerization inhibitor such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filling Conventional additives such as an agent, an antifoaming agent, a dispersant, a leveling agent, and a silane coupling agent can be added.

  The colored alkali-developable photosensitive resin composition of the present invention is applied onto a support substrate such as metal, paper, or plastic by a known means such as a roll coater, curtain coater, various printing, or immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The colored alkali-developable photosensitive resin composition of the present invention is not particularly limited in its application, and is used for various applications such as a photo-curable paint, a photo-curable adhesive, a printing plate, and a photoresist for a printed wiring board. However, it is particularly suitable for use in forming a pixel portion of a color filter used in a liquid crystal display, a plasma display, an electroluminescence panel, a video camera, or the like.

  A color filter using the colored alkali development type photosensitive resin composition of the present invention can be produced by a conventional method.

  Moreover, as the light source of the active light used when curing the colored alkali development type photosensitive resin composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used. Mercury vapor arc, carbon arc, xenon arc, etc. can be used.

EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the following examples and the like, “%” means mass%.
Production Examples 1 to 8 show the production of a photopolymerizable unsaturated compound and an alkali developable resin composition No. 1 containing the photopolymerizable unsaturated compound. 1-No. Comparative Production Examples 1 to 4 show the production of a comparative photopolymerizable unsaturated compound and comparative alkaline developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. The preparation of 9-12 is shown. Examples 1-8 are the alkali-developable resin composition Nos. Obtained in Production Examples 1-8. 1-No. 8 is obtained by mixing a photopolymerization initiator, a coloring material and a solvent with a colored alkali development type photosensitive resin composition No. 1-No. 8 and Comparative Examples 1 to 4 are comparative alkali-developable resin composition Nos. Obtained in Comparative Production Examples 1 to 4. Comparatively-colored alkali-developable photosensitive resin composition Nos. 9 to 12 obtained by mixing a photopolymerization initiator, a colorant and a solvent with No. 9-12. The preparation of 9-12 is shown.

[Production Example 1] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 1 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, hereinafter also referred to as epoxy compound 1) 554 g, resorcinol 66 g ( Hereinafter, it is also referred to as polyhydroxy aromatic compound 1), 7.2 g of tetrabutylammonium acetate, and 413 g of propylene glycol-1-monomethyl ether-2-acetate, and stirred at 90 ° C. for 2 hours and at 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-1) solution having an epoxy equivalent of 1490 was obtained. This was charged with 50 g of acrylic acid (hereinafter also referred to as compound b), 2.5 g of 2,6-di-tert-butyl-p-cresol, and 33 g of propylene glycol-1-monomethyl ether-2-acetate at 120 ° C. Stir for 15 hours. After cooling to room temperature, 233 g of propylene glycol-1-monomethyl ether-2-acetate and 160 g of succinic anhydride (hereinafter also referred to as compound c) were added and stirred at 100 ° C. for 5 hours. Further, 337 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 was obtained (Mw = 6650, Mn = 3380, acid value (solid content) 107 mgKOH / g).
In addition, alkali developable resin composition No. 1 is an epoxy resin a-1 that is a component (A) having a structure in which an epoxy compound 1 and a polyhydroxy aromatic compound 1 are alternately copolymerized. The epoxy adduct and compound c are reacted at a ratio of 0.8 acid anhydride structure of compound c as component (C) to one hydroxyl group of the epoxy adduct having a structure to which compound b is added. It was obtained. The epoxy resin a-1 has a structure in which the hydroxyl group of the polyhydroxy aromatic compound 1 is alternately copolymerized at a ratio of 0.6 to one epoxy group of the epoxy compound 1.

[Production Example 2] Production of photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 2 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, epoxy compound 1) 554 g, 1,1-bis (4 -Hydroxyphenyl) 134 g of cyclohexane (hereinafter also referred to as polyhydroxy aromatic compound 2), 7.2 g of tetrabutylammonium acetate and 459 g of propylene glycol-1-monomethyl ether-2-acetate were charged at 90 ° C. for 1 hour, 120 ° C. For 5 hours. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-2) solution having an epoxy equivalent of 860 was obtained. This was charged with 97 g of acrylic acid (compound b), 2.8 g of 2,6-di-tert-butyl-p-cresol, and 64 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 12 hours. . After cooling to room temperature, 251 g of propylene glycol-1-monomethyl ether-2-acetate and 160 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. Further, 383 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 2 was obtained (Mw = 2500, Mn = 1810, acid value (solid content) 100 mgKOH / g).
In addition, alkali developable resin composition No. 2 is an epoxy resin a-2 which is a component (A) having a structure in which an epoxy compound 1 and a polyhydroxy aromatic compound 2 are alternately copolymerized, and a component (B) The epoxy adduct and compound c are reacted at a ratio of 0.8 acid anhydride structure of compound c as component (C) to one hydroxyl group of the epoxy adduct having a structure to which compound b is added. It was obtained. In addition, the epoxy resin a-2 has a structure in which one epoxy group of the epoxy compound 1 is alternately copolymerized at a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 2.

[Production Example 3] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 3 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, epoxy compound 1) 554 g, 2,2-bis (4 -Hydroxyphenyl) propane (136 g) (hereinafter also referred to as polyhydroxy aromatic compound 3), tetrabutylammonium acetate (7.2 g) and propylene glycol-1-monomethyl ether-2-acetate (460 g) were charged at 90 ° C. for 1 hour, 120 ° C. For 5 hours. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-3) solution having an epoxy equivalent of 1220 was obtained. This was charged with 68 g of acrylic acid (compound b), 2.8 g of 2,6-di-tert-butyl-p-cresol, and 45 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 12 hours. . After cooling to room temperature, 247 g of propylene glycol-1-monomethyl ether-2-acetate and 160 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. Further, 373 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 3 was obtained (Mw = 5130, Mn = 2630, acid value (solid content) 103 mgKOH / g).
In addition, alkali developable resin composition No. 3 is an epoxy resin a-3 that is a component (A) having a structure in which an epoxy compound 1 and a polyhydroxy aromatic compound 3 are alternately copolymerized, and a component (B) The epoxy adduct and compound c are reacted at a ratio of 0.8 acid anhydride structure of compound c as component (C) to one hydroxyl group of the epoxy adduct having a structure to which compound b is added. It was obtained. In addition, the epoxy resin a-3 has a structure in which one epoxy group of the epoxy compound 1 is alternately copolymerized with a ratio of 0.6 hydroxyl groups of the polyhydroxy aromatic compound 3.

[Production Example 4] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 4 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, epoxy compound 1) 166 g, resorcinol 16.6 g (polyhydroxy Aromatic compound 1), 2.2 g of tetrabutylammonium acetate and 122 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 90 ° C. for 2 hours and at 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-4) solution having an epoxy equivalent of 1090 was obtained. This was charged with 20 g of acrylic acid (compound b), 0.7 g of 2,6-di-tert-butyl-p-cresol, and 14 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. . After cooling to room temperature, 70 g of propylene glycol-1-monomethyl ether-2-acetate and 48 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 65 g of glycidyl methacrylate (hereinafter also referred to as compound d-1) and 0.7 g of 2,6-di-tert-butyl-p-cresol were added and stirred at 120 ° C. for 8 hours. Further, 59 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound e) was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 200 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 4 (Mw = 6330, Mn = 3290, acid value (solid content) 68 mgKOH / g).
In addition, alkali developable resin composition No. 4 is an epoxy resin a-4 which is a component (A) having a structure in which an epoxy compound 1 and a polyhydroxy aromatic compound 1 are alternately copolymerized. The ratio of the acid anhydride structure of the compound c as the component (C) to 0.8 for the hydroxyl group of the epoxy adduct having the structure to which the compound b is added is the compound d as the component (D). -1 epoxy group at a ratio of 0.75, and the acid anhydride structure of compound e as component (E) is at a ratio of 0.65, an epoxy adduct, compound c, compound d-1 and compound e It was obtained by reacting. In addition, the epoxy resin a-4 has a structure in which one epoxy group of the epoxy compound 1 is alternately copolymerized at a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 1.

[Production Example 5] Production of a photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 5 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, epoxy compound 1) 554 g, 2,5-di-tert -112 g of butylhydroquinone (hereinafter also referred to as polyhydroxy aromatic compound 4), 7.2 g of tetrabutylammonium acetate and 444 g of propylene glycol-1-monomethyl ether-2-acetate were charged at 90 ° C for 2 hours and at 120 ° C for 5 hours. Stir for hours. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-5) solution having an epoxy equivalent of 1390 was obtained. This was charged with 57 g of acrylic acid (compound b), 2.5 g of 2,6-di-tert-butyl-p-cresol, and 49 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. . After cooling to room temperature, 244 g of propylene glycol-1-monomethyl ether-2-acetate and 160 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 215 g of glycidyl methacrylate (compound d-1) and 2.5 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 120 ° C. for 7 hours. Further, 198 g of tetrahydrophthalic anhydride (Compound e) was added and stirred at 100 ° C. for 3 hours. The mixture was cooled to room temperature, 694 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 5 was obtained (Mw = 4960, Mn = 2270, acid value (solid content) 74 mgKOH / g).
In addition, alkali developable resin composition No. 5 is an epoxy resin a-5 that is a component (A) having a structure in which an epoxy compound 1 and a polyhydroxy aromatic compound 4 are alternately copolymerized. The ratio of the acid anhydride structure of the compound c as the component (C) to 0.8 for the hydroxyl group of the epoxy adduct having the structure to which the compound b is added is the compound d as the component (D). -1 epoxy group at a ratio of 0.75, and the acid anhydride structure of compound e as component (E) is at a ratio of 0.65, an epoxy adduct, compound c, compound d-1 and compound e It was obtained by reacting. Further, the epoxy resin a-5 has a structure in which one epoxy group of the epoxy compound 1 is alternately copolymerized with a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 4.

[Production Example 6] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 6 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, epoxy compound 1) 554 g, 2,2-bis (4 -Hydroxyphenyl) propane 114 g (polyhydroxyaromatic compound 3), tetrabutylammonium acetate 7.2 g and propylene glycol-1-monomethyl ether-2-acetate 445 g were charged and stirred at 90 ° C. for 2 hours and 120 ° C. for 5 hours. did. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-6) solution having an epoxy equivalent of 1230 was obtained. This was charged with 65 g of acrylic acid (compound b), 2.6 g of 2,6-di-tert-butyl-p-cresol, and 44 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. . After cooling to room temperature, 243 g of propylene glycol-1-monomethyl ether-2-acetate and 160 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. Cool to room temperature, add 300 g of 4-hydroxybutyl acrylate glycidyl ether (hereinafter also referred to as compound d-2) and 2.6 g of 2,6-di-tert-butyl-p-cresol, and stir at 120 ° C. for 8 hours. did. Further, 198 g of tetrahydrophthalic anhydride (Compound e) was added and stirred at 100 ° C. for 3 hours. The mixture was cooled to room temperature, 694 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 6 (Mw = 8010, Mn = 3370, acid value (solid content) 57 mgKOH / g).
In addition, alkali developable resin composition No. 6 is an epoxy resin a-6 that is a component (A) having a structure in which an epoxy compound 1 and a polyhydroxy aromatic compound 3 are alternately copolymerized. The ratio of the acid anhydride structure of the compound c as the component (C) to 0.8 for the hydroxyl group of the epoxy adduct having the structure to which the compound b is added is the compound d as the component (D). -Epoxy group of -2 at a ratio of 0.75, and the acid anhydride structure of compound (e), which is component (E), is at a ratio of 0.65, an epoxy adduct, compound c, compound d-2 and compound e It was obtained by reacting. The epoxy resin a-6 has a structure in which one epoxy group of the epoxy compound 1 is alternately copolymerized at a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 3.

[Production Example 7] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 7 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, epoxy compound 1) 166 g, salicylic acid 21 g (hereinafter, polyhydroxy (Also referred to as aromatic compound 5), tetrabutylammonium acetate 2.2 g and propylene glycol-1-monomethyl ether-2-acetate 124 g were charged and stirred at 90 ° C. for 2 hours and 120 ° C. for 5 hours. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-7) solution having an epoxy equivalent of 1150 was obtained. This was charged with 20 g of acrylic acid (compound b), 0.9 g of 2,6-di-tert-butyl-p-cresol, and 13 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 10 hours. . After cooling to room temperature, 97 g of propylene glycol-1-monomethyl ether-2-acetate and 80 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 108 g of glycidyl methacrylate (compound d-1) and 0.9 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 120 ° C. for 7 hours. Furthermore, 99 g (compound e) of tetrahydrophthalic anhydride was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 281 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 7 was obtained (Mw = 3050, Mn = 1860, acid value (solid content) 62 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 7 is an epoxy resin a-7 that is a component (A) having a structure in which an epoxy compound 1 and a polyhydroxy aromatic compound 5 are alternately copolymerized. The ratio of the acid anhydride structure of the compound c as the component (C) to 0.8 for the hydroxyl group of the epoxy adduct having the structure to which the compound b is added is the compound d as the component (D). -1 epoxy group at a ratio of 0.75, and the acid anhydride structure of compound e as component (E) is at a ratio of 0.53, an epoxy adduct, compound c, compound d-1 and compound e It was obtained by reacting. In addition, the epoxy resin a-7 has a structure in which one hydroxyl group of the epoxy compound 1 is alternately copolymerized with a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 5.

[Production Example 8] Production of photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 8 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, epoxy compound 1) 554 g, 2,5-di-tert -112 g of butylhydroquinone (hereinafter also referred to as polyhydroxy aromatic compound 4), 7.2 g of tetrabutylammonium acetate and 444 g of propylene glycol-1-monomethyl ether-2-acetate were charged at 90 ° C for 2 hours and at 120 ° C for 5 hours. Stir for hours. After cooling to room temperature, an epoxy resin (hereinafter also referred to as compound a-5) solution having an epoxy equivalent of 1390 was obtained. This was charged with 57 g of acrylic acid (compound b), 2.5 g of 2,6-di-tert-butyl-p-cresol, and 49 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. . After cooling to room temperature, 244 g of propylene glycol-1-monomethyl ether-2-acetate and 160 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 123 g of glycidyl methacrylate (compound d-1) and 2.5 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 120 ° C. for 7 hours. The mixture was cooled to room temperature, 694 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the target alkali-developing resin composition No. 1 was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. 8 was obtained (Mw = 6400, Mn = 2800, acid value (solid content) 58 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 8 is an epoxy resin a-5 which is an (A) component obtained by alternately copolymerizing the epoxy compound 1 and the polyhydroxy aromatic compound 4, and the component (B) The ratio of the acid anhydride structure of the compound c as the component (C) to 0.8 for the hydroxyl group of the epoxy adduct having the structure to which the compound b is added is the compound d as the component (D). -1 epoxy group at a ratio of 0.4, the epoxy adduct was obtained by reacting compound c and compound d-1. Further, the epoxy resin a-5 has a structure in which one epoxy group of the epoxy compound 1 is alternately copolymerized with a ratio of 0.5 hydroxyl groups of the polyhydroxy aromatic compound 4.

[Comparative Production Example 1] Production of a comparative photopolymerizable unsaturated compound and comparative alkali-developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of 9 277 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277), 1,1-bis (4′-hydroxysilane) (Phenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane 87 g, tetrabutylammonium acetate 3.6 g and propylene glycol-1-monomethyl ether-2-acetate 243 g were charged at 90 ° C. for 2 hours, 120 ° C. For 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 1060 was obtained. This was charged with 41 g of acrylic acid, 1.5 g of 2,6-di-tert-butyl-p-cresol, and 28 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 127 g of propylene glycol-1-monomethyl ether-2-acetate and 80 g of succinic anhydride were added and stirred at 100 ° C. for 5 hours. Further, 197 g of propylene glycol-1-monomethyl ether-2-acetate was added to prepare a comparative alkali developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 9 was obtained (Mw = 5100, Mn = 3070, acid value (solid content) 116 mgKOH / g).

[Comparative Production Example 2] Production of a comparative photopolymerizable unsaturated compound and comparative alkali-developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of 10 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277) 277 g, 1,1-bis (4′-hydroxysilane) (Phenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane 109 g, tetrabutylammonium acetate 3.6 g and propylene glycol-1-monomethyl ether-2-acetate 257 g were charged at 90 ° C. for 2 hours, 120 ° C. For 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 1380 was obtained. This was charged with 34 g of acrylic acid, 1.3 g of 2,6-di-tert-butyl-p-cresol, and 23 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. The mixture was cooled to room temperature, 129 g of propylene glycol-1-monomethyl ether-2-acetate and 80 g of succinic anhydride were added, and the mixture was stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, 150 g of 4-hydroxybutyl acrylate glycidyl ether and 2.0 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 120 ° C. for 8 hours. Further, 65 g of succinic anhydride was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 343 g of propylene glycol-1-monomethyl ether-2-acetate was added, and a comparative alkali developable resin composition No. 1 was prepared as a propylene glycol-1-monomethyl ether-2-acetate solution. 10 was obtained (Mw = 7920, Mn = 3810, acid value (solid content) 60 mgKOH / g).

[Comparative Production Example 3] Production of a comparative photopolymerizable unsaturated compound and comparative alkali-developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of 11 380 g of 2,2-bis (4-epoxypropyloxyphenyl) propane (epoxy equivalent 190), 114 g of 2,2-bis (4-hydroxyphenyl) propane, 4.8 g of tetrabutylammonium acetate and propylene glycol-1 -329 g of monomethyl ether-2-acetate was charged and stirred at 90 ° C for 2 hours and at 110 ° C for 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 852 was obtained. This was charged with 70 g of acrylic acid, 2.1 g of 2,6-di-tert-butyl-p-cresol, and 47 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. After cooling to room temperature, 217 g of propylene glycol-1-monomethyl ether-2-acetate and 160 g of succinic anhydride were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 215 g of glycidyl methacrylate and 2.0 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 120 ° C. for 8 hours. Further, 198 g of tetrahydrophthalic anhydride was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 623 g of propylene glycol-1-monomethyl ether-2-acetate was added to give a comparative alkali developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 11 (Mw = 3630, Mn = 1510, acid value (solid content) 68 mgKOH / g).

[Comparative Production Example 4] Production of comparative photopolymerizable unsaturated compound and comparative alkaline developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of No. 12 Resorcinol diglycidyl ether (epoxy equivalent 122) 733 g, resorcinol 165 g, tetrabutylammonium acetate 9.6 g and propylene glycol-1-monomethyl ether-2-acetate 599 g were charged at 90 ° C. for 2 hours at 110 ° C. Stir for 5 hours. After cooling to room temperature, an epoxy resin solution having an epoxy equivalent of 509 was obtained. This was charged with 212 g of acrylic acid, 5.3 g of 2,6-di-tert-butyl-p-cresol, and 142 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at 120 ° C. for 15 hours. The mixture was cooled to room temperature, 562 g of propylene glycol-1-monomethyl ether-2-acetate and 480 g of succinic anhydride were added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, 646 g of glycidyl methacrylate and 5.3 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 120 ° C. for 8 hours. Further, 593 g of tetrahydrophthalic anhydride was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 1632 g of propylene glycol-1-monomethyl ether-2-acetate was added, and a comparative alkali-developable resin composition No. 1 was prepared as a propylene glycol-1-monomethyl ether-2-acetate solution. 12 was obtained (Mw = 3890, Mn = 1710, acid value (solid content) 83 mgKOH / g).

[Examples 1 to 8 (colored alkali-developable photosensitive resin compositions No. 1 to No. 8 respectively containing alkali-developable resin compositions No. 1 to No. 8 obtained in Production Examples 1 to 8) Preparation) and Comparative Examples 1-4 (comparative colored alkali-developable photosensitive resin compositions No. 9- containing the comparative alkali-developable resin compositions No. 9-No. 12 obtained in Comparative Production Examples 1-4) Preparation of No. 12)]
Alkali-developable resin composition Nos. Obtained in Production Examples 1-8. 1-No. 8 and Comparative Alkali Developable Resin Composition Nos. Obtained in Comparative Production Examples 1-4. 9-No. 12 to 44 g, trimethylolpropane triacrylate 8.0 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1.8 g, carbon black (“MA100” manufactured by Mitsubishi Chemical Corporation) 3.2 g and propylene glycol-1- Monomethyl ether-2-acetate (75 g) was added, and the mixture was stirred well. 1-No. 8 and comparative colored alkali development type photosensitive resin composition No. 9-No. 12 was obtained.

The colored alkali development type photosensitive resin composition No. 1 prepared in Examples 1 to 8 above. 1-No. 8 and comparative colored alkali-developable photosensitive resin composition No. 1 prepared in Comparative Examples 1 to 4. 9-No. Evaluation of 12 was performed as follows.
Specifically, γ-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried well, and then the above-mentioned colored alkali development type photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds. Dried. After pre-baking at 70 ° C. for 20 minutes, a 5% polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, developed by immersing in a 2.5% sodium carbonate solution at 25 ° C. for 30 seconds, and washed thoroughly with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The following evaluation was performed about the obtained pattern. The results are shown in [Table 1].

<Resolution>
At the time of exposure and development, A is good pattern formation even if the line width is 10 μm or less, B is good pattern formation if the line width is 10 to 15 μm, and good pattern formation is required unless the line width is 15 μm or more. What was not made was evaluated as C.
<Developability>
Judgment was made based on the presence or absence of a development residue remaining between 15 μm line and space lines obtained by development. A sample in which no residue was observed was marked with ◯, and a sample in which a residue was identified was marked with ×.
<Adhesion>
Observe the peeling of the pattern obtained by development visually, ○ if the pattern peeling was not observed at all, △ if the pattern peeling was partially observed, what the pattern peeling was observed on the entire surface X.

Moreover, the pattern shape was evaluated according to the following method.
Specifically, the colored alkali-developable photosensitive resin composition was spin-coated (600 rpm, 7 seconds) on a glass substrate, air-dried for 10 minutes, and then heated on a hot plate at 90 ° C. for 2 minutes. Next, using a mask with a pixel size of 30 μm × 100 μm, using a super-high pressure mercury lamp as a light source, exposing it to light, developing it with a 2.5% aqueous sodium carbonate solution, thoroughly washing it with water, and baking it at 230 ° C. for 30 minutes. Fixed. The pattern shape was observed about the obtained pattern using the scanning electron microscope (SEM). A pattern having a forward taper was indicated by ◯, a pattern having a vertical shape by Δ, and a pattern having an overhang (reverse taper) by ×. The results are shown in [Table 1].

  In addition, the colored alkali development type photosensitive resin composition Nos. Obtained in Examples 1 to 8 were used. 1-No. When a color filter was produced according to a conventional method using 8, a good color filter was obtained.

The colored alkali-developable photosensitive resin compositions of Examples 1 to 8 were excellent in resolution, developability and adhesion, and had a good pattern shape.
On the other hand, the comparatively colored alkali development type photosensitive resin composition No. 9 and no. No. 10 had good pattern shape with excellent adhesion, but the resolution was lowered, and it could not be formed unless the line width was 15 μm or more, and the developability was not good. In addition, comparative colored alkali-developable photosensitive resin composition Nos. 11 and no. Although No. 12 was excellent in resolution and developability, the adhesion was poor and the pattern shape was not good.
In addition, the color filter using the colored alkali development type photosensitive resin composition of the present invention was satisfactory for practical use.

Claims (6)

An epoxy resin having a structure in which an epoxy compound represented by the following general formula (I) and a polyhydroxy aromatic compound (excluding a bisphenol compound represented by the following general formula (II)) are alternately copolymerized (A ), A photopolymerizable unsaturated compound (X) having a structure obtained by esterifying a polybasic acid anhydride (C) to an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to A colored alkali-developable photosensitive resin composition, which further comprises a photopolymerization initiator (F) and a colorant (G) in an alkali-developable resin composition containing

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a hydrogen atom, a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms, and the phenyl group and the carbon number 3 -10 cycloalkyl group may be substituted by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and Y and Z are each independently a carbon atom. An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom, wherein the alkyl group, the alkoxy group, and the alkenyl group are substituted with a halogen atom; And p represents a number from 0 to 4, and r represents a number from 0 to 4.)

(In the formula, Cy, X, Y, Z, p and r are the same as those in the general formula (I).)   2. The colored alkali developing photosensitive resin composition according to claim 1, wherein in the general formula (I), Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0. 3.   Reaction product obtained by esterifying a polybasic acid anhydride (C) to an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to the epoxy resin (A) according to claim 1 or 2. In addition, an alkali-developable resin composition containing a photopolymerizable unsaturated compound (Y) having a structure obtained by adding an epoxy compound (D) to the product, a photopolymerization initiator (F) and a colorant ( A colored alkali-developable photosensitive resin composition comprising G).   Reaction product obtained by esterifying a polybasic acid anhydride (C) to an epoxy adduct having a structure in which an unsaturated monobasic acid (B) is added to the epoxy resin (A) according to claim 1 or 2. An alkali-developable resin composition containing a photopolymerizable unsaturated compound (Z) having a structure obtained by adding an epoxy compound (D) to the product and subsequently esterifying the polybasic acid anhydride (E) A colored alkali-developable photosensitive resin composition, which further contains a photopolymerization initiator (F) and a colorant (G).   Content of the said photopolymerizable unsaturated compound (X), (Y) or (Z) is 1-70 mass% in the said colored alkali development type photosensitive resin composition, The said photoinitiator (F ) Is 0.1 to 30% by mass in the colored alkali-developable photosensitive resin composition, and the content of the colorant (G) is from the colored alkali-developable photosensitive resin composition. The colored alkali-developable photosensitive resin composition according to claim 1, wherein the content is 0.5 to 70% by mass in the total solid content excluding the solvent.   A color filter using the colored alkali development type photosensitive resin composition according to claim 1.