KR101168438B1 - Alkaline developable resin composition - Google Patents

Abstract

An epoxy adduct having a structure in which an unsaturated monobasic acid (B) and a compound (C) selected from a phenol compound, an alcohol compound, an amine compound and a carboxylic acid are added to the epoxy resin (A) represented by the following general formula (I). The alkali developable resin composition containing the reaction product obtained by esterifying the polybasic acid anhydride (D).

(In Formula, Cy is a C3-5 cycloalkyl group, X is H, C1-10 alkyl group, Y and Z are C1-C10 alkyl groups, n is 0-10, p is 0-5, r is 0. Indicates a number of 4).

Alkali, developability, photoinitiator, sensitivity, resolution, alkali resistance, epoxy resin

Description

Alkaline developable resin composition {ALKALINE DEVELOPABLE RESIN COMPOSITION}

The present invention relates to an alkali developable resin composition containing a specific compound having an ethylenically unsaturated bond, and an alkali developable photosensitive resin composition comprising a photopolymerization initiator in the alkali developable resin composition.

An alkali developable photosensitive resin composition contains the alkali developable resin composition containing a compound which has an ethylenically unsaturated bond, and a photoinitiator, and makes it polymerize-cure by irradiating an ultraviolet or electron beam to this alkali developable photosensitive resin composition. Therefore, it is used for photocurable inks, photosensitive printing plates, printed wiring boards, various photoresists, and the like. In recent years, with the progress of light and short and small functionalization of electronic equipment, the alkali developable photosensitive resin composition which can form a fine pattern with high precision is desired.

As this alkali developable resin composition and alkali developable photosensitive resin composition, the following patent document 1 proposes the photopolymerizable unsaturated compound and the alkali developable photosensitive resin composition containing the said compound. Moreover, the following patent document 2 has proposed the resin composition containing polycarboxylic acid resin, and the photosensitive resin composition containing the said resin composition. Moreover, the following radiation sensitive resin composition containing alkali-soluble unsaturated resin and the said resin is proposed by following patent document 3. However, these well-known alkali developable photosensitive resin compositions did not have sufficient sensitivity, and it was difficult to obtain an appropriate pattern shape and a fine pattern. Therefore, the alkali developable photosensitive resin composition which is excellent in transparency, adhesiveness, and alkali resistance and which can form a fine pattern with high precision was desired.

Patent Document 1: Japanese Patent No. 3148429

Patent Document 2: Japanese Unexamined Patent Publication No. 2003-107702

Patent Document 3: Japanese Unexamined Patent Publication No. 2003-89716

The problem to be solved is that there has been no alkali developable resin composition and alkali developable photosensitive resin composition which have sufficient sensitivity as described above and can obtain an appropriate pattern shape and a fine pattern.

Therefore, the objective of this invention is providing the alkali developable resin composition and alkali developable photosensitive resin composition which are excellent in a sensitivity, a resolution, transparency, adhesiveness, alkali resistance, etc., and can form a fine pattern with high precision.

The present invention has a structure in which a compound (C) selected from unsaturated monobasic acids (B) and phenol compounds, alcohol compounds, amine compounds and carboxylic acids is added to the epoxy resin (A) represented by the following general formula (I). It is an alkali developable resin composition containing the reaction product obtained by esterifying polybasic acid anhydride (D) with respect to the epoxy adduct, The said epoxy adduct is said unsaturated with respect to one epoxy group of the said epoxy resin (A). The carboxyl group of monobasic acid (B) is 0.1-1.0, the phenolic hydroxyl group, alcoholic hydroxyl group, amino group, or carboxyl group of said compound (C) is 0-0.9, and the said unsaturated monobasic acid (B) and said compound ( The sum total of C) is 0.1-1.0, and the esterification is the ratio which the acid anhydride structure of the said polybasic acid anhydride (D) becomes 0.1-1.0 with respect to one hydroxyl group of the said epoxy adduct. The said objective is achieved by providing the alkali developable resin composition performed at a rate.

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, Y and Z each independently represent 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, and the alkyl group, the alkoxy group and the alkenyl group are halogen It may be substituted by an atom, n represents the number of 0-10, p represents the number of 0-5, r represents the number of 0-4.)

Moreover, this invention achieves the said objective by providing the alkali developable photosensitive resin composition containing the said alkali developable resin composition and a photoinitiator.

EMBODIMENT OF THE INVENTION Hereinafter, the alkali developable resin composition and alkali developable photosensitive resin composition of this invention are demonstrated in detail based on preferable embodiment.

The alkali-developable resin composition of the present invention is a compound (C) selected from an unsaturated monobasic acid (B) and a phenol compound, an alcohol compound, an amine compound and a carboxylic acid in the epoxy resin (A) represented by the general formula (I). ) Is a phenolic hydroxyl group, alcoholic hydroxyl group, amino group or the like of the compound (C) in a ratio of 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid (B) with respect to one epoxy group of the epoxy resin (A). The polyaddition acid anhydride (D) is added to the epoxy addition product having a structure in which the sum of the components (B) and (C) is 0.1 to 1.0 while the proportion of carboxyl groups is from 0 to 0.9. It contains the reaction product obtained by esterifying in the ratio which an acid anhydride structure becomes 0.1-1.0 with respect to one hydroxyl group of water.

The proportion of the carboxyl groups of the unsaturated monobasic acid (B) is preferably 0.4 to 1.0 with respect to one epoxy group of the epoxy resin (A), and the phenolic hydroxyl group, alcoholic hydroxyl group, amino group or the like of the compound (C) Preferably the ratio of carboxyl groups is 0-0.6 piece, and the sum of (B) component and (C) component becomes like this. Preferably it is 0.4-1.0 piece. Moreover, the ratio of the acid anhydride structure of polybasic acid anhydride (D) with respect to one hydroxyl group of the said epoxy adduct is preferably 0.4-1.0 piece.

Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy in the general formula (I) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like. The alkyl group having 1 to 10 carbon atoms represented by Y and Z may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, amyl, isoamyl, tertiary amyl, hexyl, heptyl , Octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, etc. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propyloxy, butyloxy, methoxyethyl, ethoxyethyl, Propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, allyl, butenyl, propenyl, and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Since the epoxy resin (A) used for preparation of the alkali developable resin composition of this invention is excellent in adhesiveness to the base material of hardened | cured material, alkali resistance, workability, strength, etc. by having a triaryl monocycloalkylmethane skeleton, In the development removal of the uncured portion, it is considered that a clear image can be formed with high accuracy even with a fine pattern. As an epoxy resin (A), Cy is a cyclohexyl group in the said General formula (I); X is a phenyl group; p and r are 0; It is preferable that n is 0-5, especially 0-1.

As specific examples of the epoxy resin (A) represented by the general formula (I), compounds of the following compounds No. 1 to No. 9 may be mentioned. However, this invention is not restrict | limited at all by the following compounds.

After adding (B) component and (C) component as needed to (A) component contained in the alkali developable resin composition of this invention, the reaction product obtained by esterifying (D) component is the following, for example: It can manufacture by the method shown by the reaction formula of General formula (11).

First, to the epoxy resin (1) which is (A) component, unsaturated monobasic acid (2) which is (B) component, and (3) the phenolic compound etc. which are (C) component as needed, are added, and the compound which is an epoxy adduct ( The resin composition containing 4) is obtained. Subsequently, the compound (4) is made to react with the polybasic acid anhydride (5) which is (D) component, and esterification is performed, and the resin composition containing the compound (6) which is a target reaction product is obtained. Furthermore, the resin composition containing the compound (8) can be obtained by making the compound (6) react with the epoxy compound (7) which is (E) component arbitrarily.

The method of obtaining the compound (4) which is an epoxy adduct shown by the said [Formula 11] is not limited to the said method, For example, when n in compound (4) is 0, it is the following [formula 12] As shown in the scheme, compound (4) can also be obtained by reacting a monoepoxy compound containing bisphenol (9) and glycidyl methacrylate (10).

As unsaturated monobasic acid (B) used in order to obtain the alkali developable resin composition of this invention, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate? And hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, and the like.

As a phenolic compound which can be used as a compound (C) used in order to obtain the alkali developable resin composition of this invention, For example, phenol, chlorophenol, cresol, ethylphenol, propylphenol, cumylphenol, a tertiary butyl compound Phenol, tertiary amyl phenol, hexyl phenol, octyl phenol, isooctyl phenol, tertiary octyl phenol, nonyl phenol, dodecyl phenol, octadecyl phenol, 2,4-dize-3 butylphenol, 2,5-dize-3 butylphenol , 3,5-dije3butylphenol, 2,4,6-tribromophenol, 4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, terpene phenol, naphthol, etc. are mentioned.

Alcohol compounds that can be used as the compound (C) used to obtain the alkali developable resin composition of the present invention include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol and sec-butyl alcohol. , 2-pentyl alcohol, 3-pentyl alcohol, 2-hexyl alcohol, 3-hexyl alcohol, 2-heptyl alcohol, 3-heptyl alcohol, 4-heptyl alcohol, 2- octyl alcohol, 3- octyl alcohol, 4- octyl alcohol , tert-butyl alcohol, 2-methylbutan-2-ol, 2-methylpentan-2-ol, 2-methylhexan-2-ol, 2-methylheptan-2-ol and the like.

As an amine compound which can be used as a compound (C) used in order to obtain the alkali developable resin composition of this invention, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octyl Amine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, morpholine, piperidine and the like.

Examples of the carboxylic acid that can be used as the compound (C) used to obtain the alkali developable resin composition of the present invention include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, lactic acid, butyric acid, octylic acid and lauric acid. And aliphatic, aromatic or alicyclic monocarboxylic acids such as linoleic acid, ricinolic acid, benzoic acid, toluic acid, cinnamic acid, phenylacetic acid and cyclohexanecarboxylic acid.

Examples of the polybasic acid anhydride (D) used to obtain the alkali developable resin composition of the present invention include succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and 2,2'-3,3'-benzophenonetetracarb. Main acid anhydride, 3,3'-4,4'- benzophenone tetracarboxylic anhydride, ethylene glycol bis anhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride, methyl tetrahydro phthalic anhydride, tetrahydro phthalic anhydride , Nadic acid anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- Anhydrides such as 1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride, dodecenyl anhydrous succinic acid, and methylhymic anhydride, 3,3 ', 4,4'-biphenyltetracar Main dianhydride, 3,3'4,4'-diphenylte Trasulfonic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, methylhexahydro The dianhydrides, such as phthalic anhydride, are mentioned, Among these, a diacid anhydride or a combination of a diacid anhydride and a monoacid anhydride is preferable.

In this invention, the said epoxy compound (E) is used for acid value adjustment, It can be used in order to improve the developability of the alkali developable resin composition of this invention. As an epoxy compound, 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, dodec Silglycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, pro Pargyl (propargyl) glycidyl ether, p-methoxyethylglycidyl ether, phenylglycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether , 2-methylcresylglycidyl ether, 4-fur Nylphenylglycidyl ether, benzylglycidyl ether, p-cumylphenylglycidyl ether, tritylglycidyl ether, 2,3-epoxypropylmethacrylate, epoxidized soybean oil, epoxidized linseed oil ), Glycidyl butyrate, vinyl cyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene Oxide, following compound No. 10, No. 11, etc. are mentioned.

It is preferable that the acid value of solid content of the alkali developable resin composition of this invention is 60-120 mgKOH / g, and it is preferable to select the usage-amount of an epoxy compound (E) so that the said acid value may be satisfied.

The alkali developable composition of this invention can further be made into the alkali developable photosensitive resin composition by adding a photoinitiator.

The alkali developable resin composition and the alkali developable photosensitive resin composition of the present invention are usually solvents capable of dissolving or dispersing the components, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, chloroform, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol It is used as a phase composition. In the solution composition, the content of the solvent is preferably 30 to 90% by weight, particularly 40 to 70% by weight.

The content of the reaction product obtained by adding (B) component and (C) component as needed to (A) component, then esterifying (D) component, and reacting (E) component as needed, said content of the said solution phase 1 to 70 weight%, especially 3 to 30 weight% are preferable in a composition.

As said photoinitiator used for the alkali developable photosensitive resin composition of this invention, it is possible to use a conventionally well-known compound, For example, benzophenone, phenyl biphenyl ketone, 1-hydroxy-1- Benzoylcyclohexane, benzyl, benzyl-di-methylketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morphoryl-2- (4 ' -Methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxycyxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl Sulfide, benzoinbutyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane Methyl benzoyl formate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyloyl) carbazole, 2 -Methyl-1- [4- ( Tylthio) phenyl] -2-morpholinopropane-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. 12, No. 13, etc. are mentioned.

(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', and R ₃ represents R, OR, COR, SR or NRR ', and R and R' represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, of which an alkyl group And the alkylene moiety of the aralkyl group may be interrupted by one or more selected from unsaturated bonds, ether bonds, thioether bonds, and ester bonds, and R and R 'may together form a ring, and n is 0 ~ 5)

Wherein X ₁ , R ₁ , R ₂ , R ₃ , R and R 'are the same as those of Compound No. 12, X ₁ ' represents a halogen atom or an alkyl group, and Z represents an oxygen atom or a sulfur atom. , m and n 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 ', respectively, and R ₄ represents a diol residue or dithiol residue.)

In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator is 0 to 30% by weight, particularly 0.5 to 5% by weight, based on the solution-phase composition in which a solvent is added to the alkali-develotable resin composition of the present invention. % Is preferred.

The alkali developable resin composition and alkali developable photosensitive resin composition of this invention can use together the monomer which has an unsaturated bond, a chain transfer agent, surfactant, etc. together.

As a monomer which has the said unsaturated bond, 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-hexanedioldiacrylate, trimethylolpropanetriacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, Butyl methacrylate, cyclohexyl methacrylate, trimethylol propane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and the like. .

Examples of the chain transfer agent include thioglycolic acid, thio apple 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-mercapto Ethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenylether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1 Mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercapto Mercaptoification, such as benzothiazole, mercaptoacetic acid, trimethylol propane tris (3-mercapto propionate), and pentaerythritol tetrakis (3-mercaptopropionate) A disulfide compound obtained by oxidizing a compound and the said mercapto compound, an iodide alkyl compound, such as iodide acetic acid, iodine propionic acid, 2-iodine ethanol, 2-iodine ethanesulfonic acid, and 3-iodine propanesulfonic acid, etc. are mentioned.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carbonates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, higher amine halide salts and quaternary substances. Cationic surfactants such as ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and nonionic surfactants such as fatty acid monoglycerides, surfactants such as amphoteric surfactants, and silicone surfactants can be used. You may use in combination.

The alkali developable resin composition and the alkali developable photosensitive resin composition of the present invention may further improve the properties of the cured product by using a thermoplastic organic polymer. Examples of the thermoplastic organic polymers include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, and (meth) acrylic acid-methylmetha. Acrylate copolymers, polyvinyl butyral, cellulose esters, polyacrylamides, saturated polyesters, and the like.

In addition, the alkali developable resin composition and the alkali developable photosensitive resin composition of the present invention, if necessary, anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine ( thermal polymerization inhibitors such as phenothiazine); Plasticizers; Adhesion promoters; Fillers; Antifoam; General additives, such as a leveling agent, can be added.

The alkali developable photosensitive resin composition of the present invention can be applied to supporting substrates such as metals, papers, plastics, and the like by known means such as roll coaters, curtain coaters, various types of printing, and immersion. In addition, it is also possible to transfer onto another support gas once it is carried out on a support gas such as a film, and there is no limitation on the application method.

The alkali developable photosensitive resin composition of this invention can be used for various uses, such as a photocurable paint, a photocurable adhesive agent, a printing plate, and a photoresist for a printed wiring board, There is no restriction | limiting in particular in the use.

Moreover, as a light source of the active light used when hardening the alkali developable photosensitive resin composition of this invention, what emits light of wavelength 300-450 nm can be used, For example, ultra-high pressure mercury, mercury vapor arc, carbon arc ( carbon arc, xenon arc, etc. may be used.

<Examples>

Hereinafter, although an Example etc. are given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

Example 1 Preparation of Alkaline Developable Resin Composition No. 1

<Step 1> Preparation of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane

70.5 g of biphenylcyclohexyl ketone, 200.7 g of phenol, and 10.15 g of thioacetic acid were added, and 40.0 g of trifluoromethanesulfonic acid was added dropwise at 18 degrees over 20 minutes. After 18 hours of reaction at 17-19 ° C, 500 g of water was added to stop the reaction, 500 g of toluene was added, and the organic layer was washed with water until pH 3-4, and the organic layer was separated. Toluene, water and excess phenol were distilled off. Toluene was added to the residue, and the precipitated solid was collected by filtration and dispersed and washed with toluene to obtain 59.2 g (yield 51%) of pale yellow crystals. The melting point of the pale yellow crystal was 239.5 degrees, and it was confirmed that the pale yellow crystal was the target product.

<Step 2> Preparation of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane

57.5 g of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane and 195.8 g of epichlorohydrin obtained in Step 1 were added thereto, and benzyl 0.602 g of triethylammonium chloride was added and the mixture was stirred at 64 degrees for 18 hours. Then, it heated up to 54 degreeC, 43.0 g of 24weight% sodium hydroxide aqueous solution was dripped, and it stirred for 30 minutes. Epichlorohydrin and water were removed, 216 g of methyl isobutyl ketone was added, the mixture was washed with water, and then 2.2 g of 24% by weight sodium hydroxide was added dropwise. After stirring at 80 ° C for 2 hours, the mixture was cooled to room temperature, neutralized with 3% by weight aqueous sodium monophosphate solution, and washed with water. The solvent was distilled off to obtain 57 g (yield 79%) of a yellow solid (melting point 64.2 degrees, epoxy equivalent 282, n = 0.04). It was confirmed that the yellow crystal was the target product.

<Step 3> Production of alkali developable resin composition No. 1

43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (hereinafter also referred to as compound (a)) obtained in step 2, acrylic acid (hereinafter 11 g, 2,6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added thereto. It stirred for 16 hours. After cooling to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate and 9.4 g of biphenyltetracarboxylic dianhydride (hereinafter also referred to as compound (d-1)) were added, followed by stirring at 120 ° C for 8 hours. . Furthermore, 6.0 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound (d-2)) was added, and 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, 11 degrees at 40 degrees After stirring for hours, 29 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain an alkali developable resin composition No. 1 serving as a target as a propylene glycol-1-monomethyl ether-2-acetate solution (Mw = 4000). , Mn = 2100, acid value (solid content) 85 mgKOH / g).

In addition, the reaction product which alkali-developable resin composition No.1 contains about one hydroxyl group of the epoxy adduct of the structure which added the compound (b) which is (B) component to the compound (a) which is (A) component, The acid anhydride structures of the compound (d-1) and the compound (d-2) as the component (D) were esterified with the epoxy adduct, the compound (d-1) and the compound (d-2) at a ratio of 0.68. Obtained. Moreover, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in 1.0 ratio with respect to one epoxy group of compound (a).

Example 2 Preparation of Alkaline Developable Resin Composition No. 2

43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 11 g of acrylic acid (compound (b)), 2, 0.05 g of 6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate and 16 g of biphenyltetracarboxylic dianhydride (compound (d-1)) were added, followed by stirring at 120 degrees for 8 hours. Furthermore, after adding 0.7 g of tetrahydrophthalic anhydride (compound (d-2)) and stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, 29 g of propylene glycol-1-monomethyl ether-2-acetates were added, and alkali developing resin composition No. 2 which is a target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution (Mw = 8100, Mn = 2900, acid value (solid content) 89 mgKOH / g).

In addition, the reaction product which alkali-developable resin composition No.2 contains per one hydroxyl group of the epoxy adduct of the structure which added the compound (b) which is (B) component to the compound (a) which is (A) component, The acid anhydride structures of the compound (d-1) and the compound (d-2) as the component (D) were esterified with the epoxy adduct, the compound (d-1) and the compound (d-2) at a ratio of 0.74. Obtained. Moreover, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in 1.0 ratio with respect to one epoxy group of compound (a).

Example 3 Preparation of Alkaline Developable Resin Composition No. 3

43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 11 g of acrylic acid (compound (b)), 2, 0.05 g of 6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. Cool to room temperature, add 35 g of propylene glycol-1-monomethyl ether-2-acetate, 16 g of biphenyltetracarboxylic dianhydride (compound (d-1)), and 39 mg of tetra-n-butylammonium bromide, and add 120 degrees. After stirring for 4 hours at 100 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, 29 g of propylene glycol-1-monomethyl ether-2-acetate was added to As a 1-monomethyl ether-2-acetate solution, alkali developing resin composition No. 3 which is a target object was obtained (Mw = 8600, Mn = 3000, acid value (solid content) 87 mgKOH / g).

In addition, the reaction product which alkali-developable resin composition No. 3 contains per one hydroxyl group of the epoxy adduct of the structure which added the compound (b) which is (B) component to the compound (a) which is (A) component, The acid anhydride structure of the compound (d-1) which is (D) component is obtained by esterifying an epoxy adduct and a compound (d-1) in 0.71 ratio. Moreover, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in 1.0 ratio with respect to one epoxy group of compound (a).

Example 4 Preparation of Alkaline Developable Resin Composition No. 4

43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 11 g of acrylic acid (compound (b)), 2.6- 0.05 g of di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate and 10 g of biphenyltetracarboxylic dianhydride (compound (d-1)) were added, followed by stirring at 120 degrees for 8 hours. Furthermore, 6 g of tetrahydrophthalic anhydride (compound (d-2)) was added, and after stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, 6.3 g of silglycidyl ether (compound (e)) was added, and it stirred at 120 degreeC for 10 hours. It cooled to 50 degree | times, 29 g of propylene glycol-1-monomethyl ether-2-acetates were added, and the alkali developable resin composition No. 4 which is a target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution ( Mw = 4700, Mn = 2500, acid value (solid content) 45 mgKOH / g).

In addition, the reaction product which alkali-developable resin composition No. 4 contains per one hydroxyl group of the epoxy adduct of the structure which added the compound (b) which is (B) component to the compound (a) which is (A) component, The acid anhydride structures of the compound (d-1) and the compound (d-2) as the component (D) were esterified by the epoxy adduct with the compound (d-1) and the compound (d-2) at a ratio of 0.7. It is a structure obtained by esterifying 0.36 of the carboxyl groups derived from what was obtained and also an acid anhydride structure with the compound (e) which is (E) component. In addition, the said epoxy adduct has a structure which the carboxyl group of compound (b) added in one ratio with respect to one epoxy group of compound (a).

Example 5 Preparation of Alkaline Developable Resin Composition No. 5

43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), phenol (hereinafter also referred to as compound (c)) 5.7 g and 25 g of propylene glycol-1-monomethyl ether-2-acetate were added and heated to 115 degrees. 0.2 g of triphenylphosphine was added, and it stirred at 120 degree | times for 4 hours, 50 g of propylene glycol-1-monomethyl ether- 2-acetate was added, and it cooled to 50 degree | times. 48 mg of 2,6-di-tert-butyl-p-cresol, 0.49 g of benzyltriethylammonium bromide, and 6.6 g of acrylic acid (compound (b)) were added, stirred at 120 ° C for 5 hours, and cooled to 50 ° C. . 10.27 g of biphenyl tetracarboxylic dianhydride (compound (d-1)) were added, and it stirred at 120 degree | times for 8 hours. 6.23 g of tetrahydrophthalic anhydride (compound (d-2)) was added, followed by stirring at 120 degrees for 4 hours, 100 degrees for 3 hours, 80 degrees for 4 hours, 60 degrees for 6 hours, and 40 degrees for 11 hours. It cooled to 50 degree | times, 58.3 g of propylene glycol-1-monomethyl ether- 2-acetates were added, and the alkali developable resin composition No. 5 which is a target object was obtained as a propylene glycol-1- monomethyl ether- 2-acetate solution. (Mw = 4300, Mn = 2200, acid value (solid content) 87 mgKOH / g).

In addition, the reaction product which alkali-developable resin composition No. 5 contains has the structure which added the compound (b) and the compound (c) which are (C) component to the compound (a) which is (A) component. The acid anhydride structure of the compound (d-1) and the compound (d-2) which are (D) component is 0.73 with respect to one hydroxyl group of an epoxy adduct which has, Epoxy adduct, a compound (d-1), and a compound It is obtained by esterifying (d-2). In addition, the said epoxy adduct has 0.6 carboxyl groups of compound (b), 0.4 phenolic hydroxyl groups of compound (c), and compound (b) and compound (c) of 1 epoxy group of compound (a). The sum has a structure added at a ratio of 1.0.

Example 6 Preparation of Alkaline Developable Resin Composition No. 6

43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane (compound (a)), 7.1 g of phenol (compound (c)) and propylene 25 g of glycol-1-monomethylether-2-acetate were added and heated to 115 degrees. 0.2 g of triphenylphosphine was added, and it stirred at 120 degree | times for 4 hours, 50 g of propylene glycol-1-monomethyl ether- 2-acetate was added, and it cooled to 50 degree | times. 48 mg of 2,6-di-tert-butyl-p-cresol, 0.49 g of benzyltriethylammonium bromide and 5.5 g of acrylic acid (compound (b)) were added, stirred at 120 ° C for 5 hours, and cooled to 50 ° C. . 10.27 g of biphenyl tetracarboxylic dianhydride (compound (d-1)) were added, and it stirred at 120 degree | times for 8 hours. 6.23 g of tetrahydrophthalic anhydride (compound (d-2)) was added, followed by stirring at 120 degrees for 4 hours, 100 degrees for 3 hours, 80 degrees for 4 hours, 60 degrees for 6 hours, and 40 degrees for 11 hours. It cooled to 50 degree | times, 58.3 g of propylene glycol-1-monomethyl ether- 2-acetates were added, and the alkali developable resin composition No. 6 which is a target object was obtained as a propylene glycol-1- monomethyl ether- 2-acetate solution. (Mw = 4400, Mn = 2230, acid value (solid content) 86 mgKOH / g).

In addition, the reaction product which alkali-developable resin composition No.6 contains has the structure which added the compound (b) and the compound (c) which are (C) component to the compound (a) which is (A) component. With respect to one hydroxyl group of an epoxy adduct which has, the acid anhydride structure of compound (d-1) and compound (d-2) which are (D) component is 0.7 ratio, and an epoxy adduct, a compound (d-1), and a compound It is obtained by esterifying (d-2). In addition, the said epoxy adduct has 0.5 carboxyl groups of the compound (b), 0.5 phenolic hydroxyl groups of the compound (c), and compound (b) and the compound (c) of one epoxy group of the compound (a). The sum has a structure added at a ratio of 1.0.

Example 7 Preparation of Alkaline Developable Photosensitive Resin Composition No. 1

To 14 g of alkali developable resin composition No. 1 obtained in Example 1, 5.9 g of trimethylol propane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was added. No. 1 was obtained.

Example 8 Preparation of Alkali-developable Photosensitive Resin Composition No. 2

To 14 g of alkali developable resin composition No. 2 obtained in Example 2, 5.9 g of trimethylol propane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was stirred. No.2 was obtained.

Example 9 Preparation of Alkali-developable Photosensitive Resin Composition No. 3

To 12 g of alkali developable resin composition No. 1 obtained in Example 1, 8.1 g of dipentaerythritol hexaacrylate, 1.9 g of benzophenone, 47 g of ethyl cellosolve, and 31 g of cyclohexanone were added thereto, followed by stirring and alkali. No. 3 was obtained for the developable photosensitive resin composition.

Example 10 Preparation of Alkali Developable Photosensitive Resin Composition No. 4

To 7.2 g of alkali developable resin composition No. 1 obtained in Example 1, 4.3 g of trimethylolpropane triacrylate and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane 1.5 g of -1-membered and 87 g of ethyl cellosolve were added and stirred well to obtain an alkali developable photosensitive resin composition No. 4.

Example 11 Manufacture of alkali developable photosensitive resin composition No. 5

To 20 g of alkali developable resin composition No. 1 obtained in Example 1, 8.7 g of trimethylolpropane triacrylate, 4.6 g of an acrylic copolymer, and 2-methyl-1- [4- (methylthio) phenyl] -2 1.7 g of morpholino propane-1-one and 65 g of ethyl cellosolve were added and stirred well to obtain an alkali developable photosensitive resin composition No. 5.

In addition, the acrylic copolymer, 20 parts by weight of methacrylic acid, 15 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of methyl methacrylate and 55 parts by weight of butyl methacrylate are dissolved in 300 parts by weight of ethyl cellosolve, It was obtained by adding 0.75 parts by weight of azobisisobutylnitrile in a nitrogen atmosphere and reacting at 70 degrees for 5 hours.

Comparative Example 1 Production of alkali developable resin composition No. 7

184 g of bisphenol fluorene type epoxy resin (epoxy equivalent 231), 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and propylene glycol-1-monomethyl ether-2- 23 g of acetate was added and stirred for 16 hours at 120 degrees. After cooling to room temperature, 59 g of propylene glycol-1-monomethyl ether-2-acetate 35 g nonphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 degrees for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added and after stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, propylene glycol-1-monomethyl ether was added. 90 g of -2-acetate was added, and alkali developing resin composition No. 7 of the target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH) / g).

[Comparative Example 2] Preparation of alkali developable resin composition No. 8

154 g of bisphenol-A epoxy resin (epoxy equivalent 190), 59 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and propylene glycol-1-monomethyl ether-2-acetate 23 g was added and stirred for 16 hours at 120 degrees. After cooling to room temperature, 365 g of propylene glycol-1-monomethyl ether-2-acetate, 67 g of non-phthalic anhydride, and 0.24 g of tetra-n-butylammonium bromide were added, and 4 hours at 120 ° C and 3 hours at 100 ° C After stirring for 4 hours in the figure, 6 hours at 60 degrees, and 11 hours at 40 degrees, 90 g of propylene glycol-1-monomethyl ether-2-acetate was added thereto as a propylene glycol-1-monomethyl ether-2-acetate solution. Alkali-developable resin composition No. 8 of the target product was obtained (Mw = 7500, Mn = 2100, acid value (solid content) 91 mgKOH / g).

[Comparative Example 3] Preparation of alkali developable resin composition No. 9

<Step 1> Preparation of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) ethane

75 g of phenol and 50 g of 4-acetylbiphenyl were dissolved by heating at 60 ° C, and 5 g of 3-mercaptopropionic acid was added and stirred, and the hydrogen chloride gas was blown for 24 hours, followed by 72 hours of reaction. After washing with hot water at 70 degrees, the evaporate was distilled off by heating to 180 degrees under reduced pressure. Xylene was added to the residue to cool, the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 65 g (yield 68%) of pale yellow crystals. The melting point of the pale yellow crystals was 184 degrees, and the pale yellow crystals were identified as targets.

 <Step 2> Preparation of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) ethane

37 g of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) ethane and 149.5 g of epichlorohydrin obtained in Step 1 were added, and 0.45 g of benzyltriethylammonium chloride was added. It stirred for 18 hours at 64 degree. Then, it heated up to 54 degreeC, 32.6 g of 24weight% sodium hydroxide aqueous solution was dripped, and it stirred for 30 minutes. Epichlorohydrin and water were distilled off, and 140 g of methyl isobutyl ketone was added, washed with water, and 1.7 g of 24 wt% sodium hydroxide was added dropwise thereto. After stirring at 80 ° C for 2 hours, the mixture was cooled to room temperature, neutralized with 3% by weight aqueous sodium monophosphate solution, and washed with water. The solvent was distilled off and 38.7 g (yield 80%) of yellow viscous liquids were obtained (epoxy equivalent 248, n = 0.04). It was confirmed that the yellow viscous liquid was the target product.

<Step 3> Alkali-developable resin composition No. 9 production

49.6 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) ethane, 14.4 g of acrylic acid, 2,6-di-tert-butyl-p-cresol, 0.05 g, tetra 0.14 g of butylammonium acetate and 27.4 g of propylene glycol-1-monomethyl ether-2-acetate were added thereto, and the mixture was stirred at 120 degrees for 16 hours. After cooling to room temperature, 41.5 g of propylene glycol-1-monomethyl ether-2-acetate and 12.4 g of biphenyltetracarboxylic dianhydride were added, followed by stirring at 120 degrees for 8 hours. In addition, 7.9 g of tetrahydrophthalic anhydride was added, and after stirring for 4 hours at 120 degrees, 3 hours at 100 degrees, 4 hours at 80 degrees, 6 hours at 60 degrees, and 11 hours at 40 degrees, propylene glycol-1-monomethyl ether was added. The 2-acetate 34g was added, and alkali developing resin composition No. 9 of the target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution (Mw = 3700, Mn = 1900, acid value (solid content) 93 mgKOH /). g).

[Comparative Example 4] Production of alkali developable photosensitive resin composition No. 6

To 14 g of alkali developable resin composition No. 7 obtained in Comparative Example 1, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition was stirred. No.6 was obtained.

[Comparative Example 5] Production of alkali developable photosensitive resin composition No. 7

To 14 g of alkali developable resin composition No. 8 obtained in Comparative Example 2, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 7 was obtained.

[Comparative Example 6] Production of alkali developable photosensitive resin composition No. 8

To 14 g of alkali developable resin composition No. 9 obtained in Comparative Example 3, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No.8 was obtained.

Evaluation of obtained alkali developable photosensitive resin composition No. 1-8 was performed as follows.

That is, after spin-coating r-glycidoxy propylmethylethoxysilane on a board | substrate and spin-drying well, the said alkali developable photosensitive resin composition Nos. 1-7 were spin-coated (1300 r.pm, 50 second), and dried. . After prebaking at 70 degrees for 20 minutes, a 5% by weight solution of polyvinyl alcohol was coated to form an oxygen barrier film. After 20 minutes of drying at 70 degrees, a predetermined mask was used, and after exposure using an ultrahigh pressure mercury lamp as a light source, the solution was immersed in a 2.5 wt% sodium carbonate solution for 25 seconds for 30 seconds, and washed well with water. After washing with water, baking was carried out at 230 degrees for 1 hour to fix the pattern. The following evaluation was performed about the obtained pattern. The results are shown in Table 1.

<Sensitivity>

At the time of exposure, the exposure amount that is a roneun, 100mJ / cm ² was sufficient to 100mJ / cm ² was sufficient that the exposure at 200mJ / cm ² by b.

<Resolution>

At the time of exposure development, it was A that was able to form a pattern satisfactorily even at a line width of 10 micrometers or less, and that which was able to form a pattern satisfactorily as long as 10 to 30 micrometers of line width was good. What was not possible was evaluated by C.

<Adhesiveness>

According to the test method of JIS D 0202, a crosscut was put into the grid | coated film, and the peeling test was done with the cellophane tape, and the state of peeling of a grid was visually evaluated. (Circle) and the thing in which peeling was recognized were made into what the peeling was not recognized at all.

<Alkali resistance>

The coated film after the heat treatment was a) 5% by weight NaOHaq. 24 h, b) 4 wt% KOHaq. 10 minutes at 50 ° C., c) 1 wt.% NaOHaq. It was immersed in the conditions of 5 minutes at 80 degreeC, and the appearance after immersion was evaluated visually. (Circle) and the thing in which the moxibustion of the resist was seen or the peeling of the resist was recognized as x that there was no external appearance change and there was no peeling of the resist at all.

Alkali-developable photosensitive resin composition Sensitivity resolution Adhesiveness Alkali resistance No. 1 (Example 7) a A ○ ○ No.2 (Example 8) a A ○ ○ No.3 (Example 9) a A ○ ○ No.4 (Example 10) a A ○ ○ No. 5 (Example 11) a A ○ ○ No.6 (Comparative Example 4) b C × × No.7 (Comparative Example 5) b C × × No.8 (Comparative Example 6) b C × ×

The alkali developable photosensitive resin composition of Examples 7-11 was highly sensitive and excellent in the resolution, and the obtained coating film was the thing excellent in adhesiveness with the board | substrate, and alkali resistance.

On the other hand, since the alkali developable photosensitive resin composition of Comparative Examples 4-6 has a low sensitivity, it has no choice but to increase the exposure dose, and the resolution is lowered and cannot be formed unless the line width is 30 µm or more. The adhesiveness and alkali resistance of were also undesirable.

The alkali developable photosensitive resin composition of this invention is excellent in transparency, adhesiveness, alkali resistance, etc., and can form a fine pattern with high precision.

Claims (4)

About the epoxy adduct which has a structure which added the compound (C) chosen from unsaturated monobasic acid (B) and a phenolic compound, an alcohol compound, an amine compound, and a carboxylic acid to the epoxy resin (A) shown by following General formula (1), An alkali developable resin composition containing a reaction product obtained by esterifying a polybasic acid anhydride (D), The said epoxy adduct is 0.1-1.0 carboxyl groups of the said unsaturated monobasic acid (B) with respect to one epoxy group of the said epoxy resin (A), The phenolic hydroxyl group, alcoholic hydroxyl group, and amino group of the said compound (C) Or having 0 to 0.9 carboxyl groups, and having a structure in which the sum of the unsaturated monobasic acids (B) and the compound (C) is added at a rate of 0.1 to 1.0, The said esterification is performed in the ratio which the acid anhydride structure of the said polybasic acid anhydride (D) becomes 0.1-1.0 with respect to one hydroxyl group of the said epoxy adduct. The alkali developable resin composition characterized by the above-mentioned. [Formula 1]

(In the formula, Cy represents a cycloalkyl group having 3 to 10 carbon atoms, X represents a phenyl group or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, Y and Z each independently represent 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, and the alkyl group, the alkoxy group and the alkenyl group are halogen It may be substituted by an atom, n represents the number of 0-10, p represents the number of 0-5, r represents the number of 0-4.) The alkali developable resin composition according to claim 1, wherein the reaction product is further reacted with an epoxy compound (E). The alkali developable resin composition according to claim 1, wherein in the formula (1), Cy is a cyclohexyl group, X is a phenyl group, and p and r are 0. An alkali developable photosensitive resin composition containing the alkali developable resin composition and photoinitiator as described in any one of Claims 1-3.