JP4878876B2 - Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition - Google Patents

Description

  The present invention relates to an epoxy resin having a specific structure, an alkali-developable resin composition containing a specific photopolymerizable unsaturated compound having an ethylenically unsaturated bond added to the epoxy resin, and the alkali-developable resin composition. The present invention relates to an alkali-developable photosensitive resin composition containing a photopolymerization initiator.

  The alkali-developable photosensitive resin composition contains an alkali-developable resin composition containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this alkali-developable photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, it is used for photo-curable inks, photosensitive printing plates, printed wiring plates, various photoresists, and the like. Yes. In recent years, with the progress of miniaturization and high functionality of electronic devices, an alkali-developable photosensitive resin composition capable of forming a fine pattern with high accuracy is desired.

  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 sensitivity and adhesion, and it has been difficult to obtain an appropriate pattern shape and fine pattern. Therefore, an alkali-developable photosensitive resin composition that is excellent in sensitivity 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 alkali-developable resin composition that has excellent sensitivity and adhesiveness and can obtain an appropriate pattern shape and fine pattern.

  Accordingly, an object of the present invention is to provide an alkali-developable resin composition and an alkali-developable photosensitive resin composition that are excellent in sensitivity, resolution, developability, adhesion, and the like and can form a fine pattern with high accuracy. .

In the present invention , a polyhydroxy aromatic compound (excluding a bisphenol compound represented by the following general formula (II)) is added to the epoxy compound represented by the following general formula (I) and the epoxy group of the epoxy compound . By providing an epoxy resin (A) having a structure obtained by alternately copolymerizing at a ratio of 0.1 to 1.0 hydroxyl groups of the polyhydroxy aromatic compound, 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).)

Further, the present invention is the above epoxy resin (A), the unsaturated monobasic acid (B), with respect to one epoxy group of the epoxy resin (A), the carboxyl group of the unsaturated monobasic acid (B) Is added to the epoxy adduct having a ratio of 0.1 to 1.0 to the polybasic acid anhydride (C) with respect to one hydroxyl group of the epoxy adduct. The photopolymerizable unsaturated compound (X) having a structure obtained by esterification at a ratio of 0.1 to 1.0 acid anhydride structures of the product (C) is contained in the solvent. The above object is achieved by providing an alkali-developable resin composition.

Further, the present invention is the above epoxy resin (A), the unsaturated monobasic acid (B), with respect to one epoxy group of the epoxy resin (A), the carboxyl group of the unsaturated monobasic acid (B) Is added to the epoxy adduct having a ratio of 0.1 to 1.0 to the polybasic acid anhydride (C) with respect to one hydroxyl group of the epoxy adduct. The reaction product having a structure obtained by esterifying the product (C) with an acid anhydride structure in a ratio of 0.1 to 1.0 is further added with the epoxy compound (D) to the hydroxyl group of the epoxy adduct. The photopolymerizable unsaturated compound (Y) having a structure obtained by adding 0.1 to 1.0 epoxy groups of the epoxy compound (D) in one solvent is contained in the solvent. By providing an alkali-developable resin composition characterized in that It is those that have achieved the target.

Further, the present invention is the above epoxy resin (A), the unsaturated monobasic acid (B), with respect to one epoxy group of the epoxy resin (A), the carboxyl group of the unsaturated monobasic acid (B) Is added to the epoxy adduct having a ratio of 0.1 to 1.0 to the polybasic acid anhydride (C) with respect to one hydroxyl group of the epoxy adduct. To the reaction product having a structure obtained by esterifying the product (C) at a ratio of 0.1 to 1.0 acid anhydride structures , the epoxy compound (D) is converted to the hydroxyl group 1 of the epoxy adduct. The epoxy compound (D) is added at a ratio of 0.1 to 1.0 epoxy group , and the polybasic acid anhydride (E) is added to one hydroxyl group of the epoxy adduct. , d in a ratio acid anhydride structure polybasic acid anhydride (E) is 0.1 to 1.0 or By providing an alkali developable resin composition photopolymerizable unsaturated compound having a structure obtained by etherification with (Z), characterized in that it contains in the solvent is obtained by achieving the above object.

  This invention achieves the said objective by providing the alkali developable photosensitive resin composition characterized by making the said alkali developable resin composition contain a photoinitiator (F).

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

  Hereinafter, the epoxy resin, the alkali-developable resin composition and the alkali-developable photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.

Epoxy resin (A) of the present invention, the epoxy compound represented by the general formula (I), polyhydroxy aromatic compound (excluding bisphenol compound represented by the general formula (II).), It can be obtained by alternately copolymerizing one epoxy group of the epoxy compound at a ratio of 0.1 to 1.0 hydroxyl groups of the polyhydroxy aromatic compound .

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 with 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 epoxy resin (A) of the present invention has a triarylmonocycloalkylmethane skeleton as the epoxy compound represented by the above general formula (I) used for the preparation thereof, thereby allowing the cured product to adhere to a substrate, Since processability, 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 compound, in 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.

The epoxy resin (A) of the present invention can be produced, for example, by a method represented by the following reaction formula [Chemical Formula 12].
That is, the epoxy compound (1) and the polyhydroxy aromatic compound (2) are alternately copolymerized to obtain the epoxy resin (3) as the component (A). The copolymerization reaction of epoxy compound (1) and polyhydroxy aromatic compound (2) can be carried out according to a conventional method, the polyhydroxy aromatic compound with respect to one epoxy group d epoxy compound (1) (2 hydroxyl groups from 0.1 to 1.0 amino), good Mashiku uses the amount of the epoxy compound satisfying 0.2 to 0.8 amino ratio (1) and polyhydroxy aromatic compound (2), 50 The reaction is carried out at ˜150 ° C. for 2 to 15 hours.
The epoxy resin (A) of the present invention preferably has at least two epoxy groups. In the following [Chemical Formula 12], n in the epoxy resin (3) as the component (A) is 0-10. Is preferred.

  The epoxy resin (A) of the present invention is a paint or adhesive for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc. in addition to the alkali developable resin described later; Tape, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive for adhesive flooring; processing of art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, impregnated paper, etc. Paper: Fiber processing agents such as natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers, etc., fraying prevention agents, processing agents, etc .; building materials such as sealing materials, cement admixtures, waterproofing materials; electronic and electrical It can be used for a wide range of applications such as device sealants.

In the alkali-developable resin composition of the present invention, the unsaturated monobasic acid (B) is added to the epoxy resin (A), and the unsaturated monobasic acid (B) is added to one epoxy group of the epoxy resin (A). ) To the epoxy adduct having a structure in which the carboxyl group is added at a ratio of 0.1 to 1.0, the polybasic acid anhydride (C) is acid-anhydrated to one hydroxyl group of the epoxy adduct. If necessary, the epoxy compound (D) may be added at a ratio of 0.1 to 1.0 in the physical structure, and 0.1 to 1.0 epoxy group for one hydroxyl group of the epoxy adduct. And then, if necessary, the polybasic acid anhydride (E) is added at a ratio such that the acid anhydride structure is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct. It contains a photopolymerizable unsaturated compound having a structure obtained by esterification.
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) The ratio of the epoxy groups 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. .

The polybasic acid anhydride (C) is esterified to the epoxy adduct having a structure in which the unsaturated monobasic acid (B) is added to the epoxy resin (A) contained in the alkali-developable resin composition of the present invention. Photopolymerizable unsaturated compound (X) having a structure obtained by forming a photopolymerizable compound, and photopolymerizable compound having a structure obtained by further adding an epoxy compound (D) to the photopolymerizable unsaturated compound (X) Unsaturated compound (Y), and photopolymerizable unsaturated compound (Z) having a structure obtained by esterifying polybasic acid anhydride (E) to photopolymerizable unsaturated compound (Y), For example, it can be produced by a method represented by the following reaction formula [Chemical 13].
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 addition reaction of the unsaturated monobasic acid (B) to the epoxy resin (A) can be carried out according to a conventional method, but is preferably reacted 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 polybasic acid anhydride (C) can be carried out 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 epoxy compound (D) can be carried out according to a conventional method, but the reaction is preferably carried out at 30 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 polybasic acid anhydride (E) can be carried out according to a conventional method, but the reaction is preferably carried out at 50 to 150 ° C. for 3 to 10 hours.

  The unsaturated monobasic acid (B) used for obtaining the alkali-developable resin composition of the present invention is used for improving 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 or more And polyfunctional (meth) acrylates having a (meth) acryloyl group.

  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 for obtaining the alkali-developable resin composition of the present invention increases the acid value of the alkali-developable resin composition to improve the pattern shape, developability and development speed. For example, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2′-3,3′-benzophenonetetracarboxylic anhydride, 3,3 '-4,4'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride , Nadic acid anhydride, methyl nadic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydro Hydrophthalic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride An acid, an anhydrous methyl hymic acid, etc. are mentioned. Among these, succinic anhydride, trimellitic anhydride, and hexahydrophthalic anhydride are preferable.

As an epoxy compound (D) used in order to obtain the alkali developable 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 KM 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.) Manufactured), 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 obtaining the alkali-developable resin composition of the present invention, those mentioned as the polybasic acid anhydride (C) can be used.
An epoxy compound (D) is further added to the photopolymerizable unsaturated compound having a structure obtained by reacting each component of (A) to (E), and then the polybasic acid anhydride (E) is esterified. In addition, the epoxy compound (D) may be further added to the photopolymerizable unsaturated compound having a structure obtained by reacting the components (A) to (E). A lactone compound may be esterified instead of the basic acid anhydride (E).

  The content of the photopolymerizable unsaturated compound (X), (Y) or (Z) having a structure obtained by reacting each component of (A) to (E) is the alkali of the present invention. In the developable resin composition, 1 to 70% by mass, particularly 3 to 30% by mass is preferable, and the acid value of the solid content is preferably 35 to 120 mg / KOH, particularly 50 to 110 mg / KOH.

The alkali-developable resin composition of the present invention, in addition to the photopolymerizable unsaturated compound, Ru is contained solvent. For example, when making content of a photopolymerizable unsaturated compound into said preferable range, a solvent can be used for remainder other than a 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 from (A)-(E) component.

The alkali-developable resin composition of the present invention is mainly mixed with a photopolymerization initiator (F) and a solvent and used as an alkali-developable photosensitive resin composition.
Below, the said alkali-developable photosensitive resin composition (henceforth the alkali-developable photosensitive resin composition of this invention) is demonstrated based on preferable embodiment.

The alkali-developable photosensitive resin composition of the present invention comprises at least a photopolymerization initiator (F) and a solvent in the alkali-developable resin composition of the present invention containing the photopolymerizable unsaturated compound. It is.
In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerizable unsaturated compound is 50 to 90 in terms of the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. % By mass, particularly 60 to 80% by mass is preferred.

  As the photopolymerization initiator (F), 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-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl Anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butylbenzene Nzoyltrichloromethane, 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 alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator (F) is 0 with respect to the solution-like composition obtained by adding a solvent to the alkali-developable resin composition of the present invention. .1 to 30% by mass, particularly 0.5 to 5% by mass is preferable.

The solvent contained in the 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 ketone Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; acetic acid Ester solvents such as methyl, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, etc. Cellsolv solvent; alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; BTX solvent such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane, etc. Aliphatic hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc. Paraffinic solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, Acetonitrile, disulfide Arsenide, 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 alkali-developable photosensitive resin composition of the present invention, the content of the solvent is such that the total solid content in the alkali-developable photosensitive resin composition is 5 to 40% by mass, particularly 15 to 30% by mass. It is good to adjust.

  The alkali-developable resin composition and the alkali-developable 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, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Lithol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate and the like.
In the alkali-developable photosensitive resin composition of the present invention, the content of the monomer having an unsaturated bond is 0.01% in the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. -20% by mass, particularly 0.1-10% by mass is preferred.

  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.

  The properties of the cured product can be improved by further using a thermoplastic organic polymer in the alkali-developable resin composition and the alkali-developable photosensitive resin composition of the present invention. 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 alkali-developable photosensitive resin composition of the present invention includes, if necessary, thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filler. Conventional additives such as an antifoaming agent, a dispersant, a leveling agent, and a silane coupling agent can be added.

  The alkali-developable photosensitive resin composition of the present invention is applied onto a support substrate such as metal, paper, plastic, etc. by a known means such as a roll coater, curtain coater, various printing, and 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 alkali-developable photosensitive resin composition of the present invention is mainly mixed with the solvent and the photopolymerization initiator and used as an alkali-developable photosensitive resin composition. There is no restriction | limiting in particular in the use, It can use for various uses, such as a photocurable coating material, a photocurable adhesive agent, a printing plate, a photoresist for printed wiring boards.

  Moreover, as the light source of the active light used when curing the alkali-developable photosensitive resin composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury Steam 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%.
Examples 1 to 8 are the production of an epoxy resin, the production of a photopolymerizable unsaturated compound, and an alkali developable resin composition No. 1 containing the photopolymerizable unsaturated compound. 1-No. Comparative Examples 1 to 4 show the production of a comparative epoxy resin, the production of a comparative photopolymerizable unsaturated compound, and a comparative alkali developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. 9-No. 12 preparations are shown. Examples 9 to 16 are alkali-developable resin composition Nos. Obtained in Examples 1 to 8. 1-No. 8 is mixed with a photopolymerization initiator and a solvent to obtain an alkali-developable photosensitive resin composition No. 1-No. In Comparative Examples 5 to 8, Comparative Alkali Developable Resin Composition Nos. 1 to 4 obtained in Comparative Examples 1 to 4 were prepared. 9-No. 12 is mixed with a photopolymerization initiator and a solvent, and a comparative alkali-developable photosensitive resin composition No. 9-No. 12 preparations are shown.

[Example 1] Production of epoxy resin, production of photopolymerizable unsaturated compound, and alkali-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.

[Example 2] Production of epoxy resin, 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. The photopolymerizable unsaturated compound contained in 2 is an epoxy resin a-2, which is an (A) component obtained by alternately copolymerizing an epoxy compound 1 and a polyhydroxy aromatic compound 2, 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.

[Example 3] Production of epoxy resin, production of photopolymerizable unsaturated compound, and alkali-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. The photopolymerizable unsaturated compound 3 contains the epoxy resin a-3, which is the component (A) obtained by alternately copolymerizing the epoxy compound 1 and the polyhydroxy aromatic compound 3, and the 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.

[Example 4] Production of epoxy resin, production of photopolymerizable unsaturated compound, and alkali-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. The photopolymerizable unsaturated compound 4 contains the epoxy resin a-4, which is the component (A) obtained by alternately copolymerizing the epoxy compound 1 and the polyhydroxy aromatic compound 1, with 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 0.75, 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.

[Example 5] Production of epoxy resin, production of 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. The photopolymerizable unsaturated compound contained in 5 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 0.75, 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.

[Example 6] Production of epoxy resin, production of photopolymerizable unsaturated compound, and alkali 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. The photopolymerizable unsaturated compound contained in 6 is an epoxy resin a-6, which is obtained by alternately copolymerizing the epoxy compound 1 and the polyhydroxy aromatic compound 3, 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). -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.

[Example 7] Production of epoxy resin, production of photopolymerizable unsaturated compound, and alkali-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, which is obtained by alternately copolymerizing the epoxy compound 1 and the polyhydroxy aromatic compound 5, and the (B) component. 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.

[Example 8] Production of epoxy resin, production of photopolymerizable unsaturated compound, and alkali 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 Example 1] Production of a comparative epoxy resin, 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 Example 2] Production of comparative epoxy resin, production of 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 Example 3] Production of comparative epoxy resin, production of 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 Example 4] Production of comparative epoxy resin, production of comparative photopolymerizable unsaturated compound, and comparative alkaline developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of 12 733 g of resorcinol diglycidyl ether (epoxy equivalent 122), 165 g of resorcinol, 9.6 g of tetrabutylammonium acetate and 599 g of propylene glycol-1-monomethyl ether-2-acetate 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 9 to 16 (Preparation of alkali-developable photosensitive resin compositions No. 1 to No. 8 containing alkali-developable resin compositions No. 1 to No. 8 obtained in Examples 1 to 8, respectively) ) And Comparative Examples 5 to 8 (Comparative Alkali Developable Photosensitive Resin Compositions No. 9 to No. 9 respectively containing Comparative Alkali Developable Resin Composition Nos. 9 to 12 obtained in Comparative Examples 1 to 4). 12 preparation)]
Alkali-developable resin composition No. obtained in Examples 1-8. Comparative alkali-developable resin composition Nos. 1-8 and Comparative Examples 1-4 obtained in Comparative Examples 1-4. 6.3 g of trimethylolpropane triacrylate, 2.1 g of benzophenone and 78 g of propylene glycol-1-monomethyl ether-2-acetate were added to 44 g of 9-12, respectively, and the alkali-developable photosensitive resin composition Item No. 1-No. 8 and comparative alkali-developable photosensitive resin composition No. 9-No. 12 was obtained.

The alkali-developable photosensitive resin composition No. prepared in Examples 9-16 above. 1-No. 8 and comparative alkali-developable photosensitive resin composition No. 1 prepared in Comparative Examples 5-8. 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 alkali-developable photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds and dried. I let you. 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.
That is, the 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.

The alkali-developable photosensitive resin compositions of Examples 9 to 16 were excellent in resolution, developability and adhesion, and had good pattern shapes.
On the other hand, the alkali-developable photosensitive resin compositions of Comparative Examples 5 to 6 have excellent adhesion and good pattern shape, but the resolution is lowered and the line width of 15 μm or more cannot be formed. The sex was not too good. Moreover, although the alkali developable photosensitive resin composition of Comparative Examples 7-8 was excellent in the resolution and developability, adhesiveness was bad and the pattern shape was also not favorable.

Claims (7)

A polyhydroxy aromatic compound (excluding a bisphenol compound represented by the following general formula (II)) is added to the epoxy compound represented by the following general formula (I) with respect to one epoxy group of the epoxy compound . An epoxy resin (A) having a structure obtained by alternating copolymerization at a ratio of 0.1 to 1.0 hydroxyl groups of the polyhydroxy aromatic compound .

(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).)   The epoxy resin (A) 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. To claim 1 or 2, wherein the epoxy resin (A), the unsaturated monobasic acid (B), with respect to one epoxy group of the epoxy resin (A), the carboxyl group of the unsaturated monobasic acid (B) Is added to the epoxy adduct having a ratio of 0.1 to 1.0 to the polybasic acid anhydride (C) with respect to one hydroxyl group of the epoxy adduct. The photopolymerizable unsaturated compound (X) having a structure obtained by esterification at a ratio of 0.1 to 1.0 acid anhydride structures of the product (C) is contained in the solvent. An alkali-developable resin composition. To claim 1 or 2, wherein the epoxy resin (A), the unsaturated monobasic acid (B), with respect to one epoxy group of the epoxy resin (A), the carboxyl group of the unsaturated monobasic acid (B) Is added to the epoxy adduct having a ratio of 0.1 to 1.0 to the polybasic acid anhydride (C) with respect to one hydroxyl group of the epoxy adduct. The reaction product having a structure obtained by esterifying the product (C) with an acid anhydride structure in a ratio of 0.1 to 1.0 is further added with the epoxy compound (D) to the hydroxyl group of the epoxy adduct. The photopolymerizable unsaturated compound (Y) having a structure obtained by adding 0.1 to 1.0 epoxy groups of the epoxy compound (D) in one solvent is contained in the solvent. An alkali-developable resin composition characterized by that. To claim 1 or 2, wherein the epoxy resin (A), the unsaturated monobasic acid (B), with respect to one epoxy group of the epoxy resin (A), the carboxyl group of the unsaturated monobasic acid (B) Is added to the epoxy adduct having a ratio of 0.1 to 1.0 to the polybasic acid anhydride (C) with respect to one hydroxyl group of the epoxy adduct. To the reaction product having a structure obtained by esterifying the product (C) at a ratio of 0.1 to 1.0 acid anhydride structures , the epoxy compound (D) is converted to the hydroxyl group 1 of the epoxy adduct. The epoxy compound (D) is added at a ratio of 0.1 to 1.0 epoxy group , and the polybasic acid anhydride (E) is added to one hydroxyl group of the epoxy adduct. , d in a ratio acid anhydride structure polybasic acid anhydride (E) is 0.1 to 1.0 or Alkali developable resin composition photopolymerizable unsaturated compound (Z), characterized in that it contains in a solvent having a structure obtained by etherification. Alkali developable resin composition according to any one of claims 3-5 in which the content of the photopolymerizable unsaturated compound, characterized in that 1 to 70 wt%. Alkali developable photosensitive resin composition characterized by the inclusion photopolymerization initiator (F) to the alkali-developable resin composition according to any one of claims 3-6.