KR101394173B1 - Photosensitive hybrid resin with improved strength, hardness and adhesion, and curable composition comprising the same and cured product thereof - Google Patents

Abstract

The present invention relates to a photosensitive hybrid resin excellent in strength, hardness and adhesiveness, and an alkali developing curable composition containing the same and a cured product thereof. More particularly, the present invention relates to a photosensitive hybrid resin excellent in strength, hardness and adhesiveness, It is possible to form a cured film excellent in resistance, electroless gold plating resistance, flexural resistance, flexibility, electrical insulation and the like, so that an interlayer insulating layer of a resist or a multilayer wiring board used in a general printed wiring board or a flexible printed wiring board tape carrier package, And a photocurable or thermosetting composition capable of alkali development containing the same and a cured product thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive hybrid resin excellent in strength, hardness and adhesiveness, and a curable composition capable of alkali development containing the same, and a cured product thereof and a cured product thereof. [0002]

The present invention relates to a photosensitive hybrid resin excellent in strength, hardness and adhesiveness, and an alkali developing curable composition containing the same and a cured product thereof. More particularly, the present invention relates to a photosensitive hybrid resin excellent in strength, hardness and adhesiveness, It is possible to form a cured film excellent in resistance, electroless gold plating resistance, flexural resistance, flexibility, electrical insulation and the like, so that an interlayer insulating layer of a resist or a multilayer wiring board used in a general printed wiring board or a flexible printed wiring board tape carrier package, And a photocurable or thermosetting composition capable of alkali development containing the same and a cured product thereof.

Background Art [0002] In recent years, high performance of solder resists has been demanded in response to the increase in the density of printed wiring boards due to the thinning and shortening of electronic devices. In recent years, solder resist printed circuit boards and sealing resins have been used instead of IC packages (QFP (quad flat back package) and SOP (small outline package)) using lead frames and sealing resin IC packages have emerged. This new package has a structure in which a metal such as solder in the form of a ball is placed in an area on one side of a solder resist printed circuit board and the IC chip is directly connected with a wire bonding or a bump or the like and sealed with a sealing resin , BGA (Ball Grid Array), and CSP (Chip Scale Package). Such a package has a finer number of pins than the package of the same size, such as QFP, and is more easily downsized. Also, in mounting, a low defect rate is realized by the self-aligning effect of the ball-like solder, and the application is progressing rapidly.

However, in a commercially available printed circuit board on which an alkali developing type solder resist is applied, resistance to PCT (Pressure Cooker Test), which is a long-term reliability test of the package, deteriorates and peeling of the cured product occurs. Further, due to the moisture absorption of the solder resist, the moisture absorbed in the package during the reflow of the package is boiled, and cracks are generated in the solder resist film and its vicinity in the package. The problem of such hygroscopicity and long-term reliability is not limited to the case of the above-described mounting technique, but may be a solder resist of a general printed wiring board, a multilayer wiring board such as a solder resist used for manufacturing a flexible printed wiring board or a tape carrier package But also for the interlayer insulating layer and other functional coating compositions. As the electric industry and the semiconductor industry develop in recent years, further improvement of characteristics such as adhesion, heat resistance, toughness, flexibility, chemical resistance and the like are required.

Currently, some of general-purpose printed wiring boards and most solder resists for industrial printed wiring boards use liquid developing solder resists which are formed by irradiating ultraviolet rays and developing them to form an image and curing by heat or light irradiation. This is because a high- . Also, in consideration of environmental problems, an alkali developing type liquid solder resist using an alkaline aqueous solution as a developer is mainly used. Examples of the alkali developing type solder resist using an alkali aqueous solution include a photosensitive resin obtained by adding an acid anhydride to the reaction product of a novolak type epoxy compound and an unsaturated base acid disclosed in Japanese Patent Application Laid-Open (kokai) No. 61-243869 , A photopolymerization initiator, a diluent, and an epoxy compound; A photosensitive resin to which an acid anhydride is added to the reaction product of a novolac epoxy compound and an unsaturated-basic acid disclosed in JP-A-3-253093, a photopolymerization initiator, a diluent, a vinyltriazine or a vinyltriazine and a dicyandiamide And a melamine resin; (Meth) acrylic acid is added to an epoxy resin obtained by reacting epichlorohydrin with the reaction product of salicylaldehyde and monovalent phenol, as disclosed in JP-A-3-71137 and JP-A-3-250012 And a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or its anhydride, a photopolymerization initiator, an organic solvent, and the like.

However, these conventional photosensitive resins are disadvantageous in that they are easy to generate cracks due to heat shock because they have excellent heat resistance, but have large shrinkage upon curing, little elongation, and insufficient toughness.

The present invention has been made to solve the problems of the prior art as described above and it is an object of the present invention to provide a cured film excellent in strength, hardness, adhesion, solder heat resistance, moisture absorption resistance, PCT resistance, electroless gold plating resistance, flexural resistance, A photosensitive hybrid resin suitable for use as an interlayer insulating layer of a resist or a multilayer wiring board used in a general printed wiring board or a flexible printed wiring board tape carrier package and a composition for other functional coating, and a photosensitive hybrid resin containing the same, Or a thermosetting composition and a cured product thereof.

In order to accomplish the above object, the present invention provides a process for producing an unsaturated monocarboxylic acid, comprising reacting an alkylene oxide-adducted novolac phenolic resin (A) modified with an unsaturated monocarboxylic acid and a siloxane compound having at least one functional group selected from an unsaturated group and an alkylene oxide group (B) is combined with a polybasic acid anhydride (C) as a linking group, and has an acid value of 50 to 200 mg KOH / g.

According to another aspect of the present invention, there is provided a process for producing a phenolic resin, comprising: (1) an addition reaction of an alkylene oxide to a novolak type phenolic resin; (2) reacting the reaction product of step (1) with an unsaturated monocarboxylic acid; (3) reacting the reaction product of step (2) with a polybasic acid anhydride; And (4) reacting the reaction product of the step (3) with a siloxane compound having at least one functional group selected from an unsaturated group and an alkylene oxide group.

According to another aspect of the present invention, there is provided a curable composition capable of developing an alkali, which comprises the hybrid photosensitive resin, a polymerization initiator, and an epoxy resin.

According to another aspect of the present invention, there is provided a cured product obtained by photo-curing or thermosetting a curable composition capable of alkali development.

Since the hybrid photosensitive resin of the present invention has both a novolac-type resin structure and a siloxane structure and has an unsaturated group and a carboxyl group at the terminal of the side chain, the reactivity is improved and a high level of heat resistance and toughness are balanced with chain extension, Hardness and flexibility as well as a cured product having excellent water resistance and chemical resistance can be provided. In addition, due to the terminal carboxyl group, development with an aqueous alkali solution is also possible. Therefore, when a photocurable or thermosetting composition comprising the hybrid photosensitive resin of the present invention is used, it is possible to provide a photosensitive resin composition which is excellent in adhesion, solder heat resistance, moisture absorption resistance, PCT resistance, electroless gold plating resistance, bending resistance, endurance, flexibility, An excellent cured film having various properties can be formed at a low cost and with good productivity. Therefore, the hybrid photosensitive resin of the present invention is useful for the production of ultraviolet curing type printing inks which are cured using active energy rays, solder resists used in the production of printed wiring boards, etching resists, plating resists, interlayer insulating materials and tape carrier packages A resist for a flexible wiring board, a resist for a color filter, a composition for a functional coating, and the like.

Hereinafter, the present invention will be described in more detail.

1. Hybrid photosensitive resin

The hybrid photosensitive resin of the present invention comprises an alkylene oxide-addition novolak type phenol resin (A) modified with an unsaturated monocarboxylic acid and a siloxane compound (B) having at least one functional group selected from an unsaturated group and an alkylene oxide group (C) as a linking group and has an acid value of 50 to 200 mg KOH / g, more preferably 70 to 180 mg KOH / g. If the acid value of the hybrid photosensitive resin is less than 50 mg KOH / g, the solubility in an aqueous alkaline solution deteriorates, and development of a formed film becomes difficult. When the acid value exceeds 200 mg KOH / g, there is a problem that the acid is developed to the surface irrespective of exposure conditions.

(A) an alkylene oxide-addition novolak-type phenolic resin modified with an unsaturated monocarboxylic acid

The component (A) can be produced by subjecting a novolac phenolic resin to an addition reaction with an alkylene oxide, and then reacting the addition reaction product with an unsaturated monocarboxylic acid. Wherein each reaction can be carried out in the presence or absence of a solvent using a catalyst as described below.

The novolac phenolic resin is obtained by the condensation reaction of phenols and formaldehyde. Usually, this reaction is carried out in the presence of an acidic catalyst. Examples of the phenol in the novolak type phenol resin include phenol, cresol, ethyl phenol, propyl phenol, butyl phenol, hexyl phenol, octyl phenol, nonyl phenol, phenyl phenol and cumyl phenol.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyrane.

The addition ratio of the alkylene oxide to the novolak type phenol resin is preferably 0.3 to 10.0 moles of the alkylene oxide per 1 mole of the -OH group of the novolak type phenol resin. When the addition ratio of the alkylene oxide is less than this range, the photocurability of the hybrid photosensitive resin may become insufficient. Conversely, if the addition ratio exceeds the above range, the thermosetting property may become insufficient. More preferably, 1.0 to 5.0 moles of an alkylene oxide per 1 mole of -OH groups of the novolak type phenolic resin is used.

The reaction of adding an alkylene oxide to a novolac-type phenol resin can be carried out, for example, by reacting an alkali metal compound such as sodium hydroxide, a quaternary basic salt compound such as trimethylbenzylammonium hydroxide or tetramethylammonium hydroxide, In the presence of a mixture of a metal compound and a quaternary basic salt compound, for example, ethylene glycol monoethyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol mono Methyl ethyl ketone, methyl isobutyl ketone and the like, aromatic hydrocarbons such as toluene, xylene, and tetramethyl benzene, and the like, and organic solvents such as acetone, methyl ethyl ketone and methyl ethyl ketone, Or in a mixed solvent, And a pressure of 80 to 180 DEG C and an atmospheric pressure to 10 kg / cm < 2 >. Ketones and aromatic hydrocarbons may be used singly or as a mixture of two or more thereof.

The alkylene oxide-addition novolak-type phenol resin thus obtained is subjected to an esterification reaction with an unsaturated monocarboxylic acid.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,? -Cyanosinic acid,? -Styryl acrylic acid and? -Furfuryl acrylic acid, Can be mixed and used. Among them, it is preferable to use acrylic acid, methacrylic acid or a mixture thereof in terms of photoreactivity and cured product properties, in particular, heat resistance, hygroscopicity and electrical properties.

The use ratio of the unsaturated monocarboxylic acid to the alkylene oxide-added novolak type phenolic resin is preferably 0.2 to 5.0 moles of the unsaturated monocarboxylic acid per 1 mole of the alkylene oxide group of the alkylene oxide-addition novolak type phenol resin . If the ratio of the unsaturated monocarboxylic acid is less than this range, there may be a problem that the density of the curing due to the light is lowered due to the lack of the unsaturated group. Conversely, if the ratio exceeds the above range, There may be a problem in the reliability evaluation in the case of the above. More preferably, 0.5 to 2.0 moles of an unsaturated monocarboxylic acid per 1 mole of alkylene oxide groups of the alkylene oxide-addition novolac phenolic resin is used.

In the esterification reaction of the alkylene oxide-addition novolac-type phenolic resin and the unsaturated monocarboxylic acid, the reaction temperature is preferably 50 to 150 ° C. There are no particular restrictions on the pressure conditions, and the reaction can be carried out under either reduced pressure, atmospheric pressure or pressurized conditions. Examples of the reaction solvent include n-hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, trichloroethane, tetrachlorethylene, methyl chloroform, diisopropyl ether, ethyleneglycol monoethyl ether acetate, ethylene glycol monobutyl ether Acetate, diethylene glycol monoethyl acetate, diethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and the like. These solvents may be used alone or in admixture of two or more. As the esterification catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin and the like can be suitably used. The esterification reaction is preferably carried out in the presence of a polymerization inhibitor, and examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like.

(B) a siloxane compound having at least one functional group selected from an unsaturated group and an alkylene oxide group

Examples of the component (B) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and mixtures thereof, and a single polymer or a copolymer of two or more thereof may be used .

The component (B) is preferably used in an amount of 1.0 to 5.0 mols of the component (B) per 1 mol of the carboxylic acid group of the polybasic acid anhydride (C) described later. When the amount of the component (B) used is less than this range, improvement in properties such as hardness and adhesion may be insufficient. Conversely, if the amount exceeds the above range, compatibility and shelf life may become insufficient. More preferably, 1.0 to 1.5 moles of the component (B) per 1 mole of the carboxylic acid group of the polybasic acid anhydride (C) is used.

 (C) a polybasic acid anhydride

Examples of the component (C) include anhydride tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, anhydrous nadic acid, anhydrous 3,6-endomethylenetetrahydrophthalic acid, anhydrous methylendomethylene tetrahydro Alicyclic dibasic acid anhydrides such as phthalic acid and anhydrous tetrabromophthalic acid; Aliphatic or aromatic dibasic acid anhydrides such as succinic anhydride, maleic anhydride, itaconic anhydride, anhydrous octenyl succinic acid, anhydrous pentadodecenyl succinic acid, and maleic anhydride; Or biphenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, anhydrous pyromellitic acid, benzophenonetetracarboxylic acid dianhydride And aliphatic or aromatic tetrabasic acid dianhydrides such as water. One of these may be used singly or a mixture of two or more of them may be used. Alicyclic dibasic anhydride is particularly preferable.

The hybrid photosensitive resin of the present invention has a hybrid structure in which the components (A) and (B) are combined using the present component (C) as a linking group.

The reaction of coupling the component (A) with the component (C) is usually carried out at 50 to 150 ° C in the presence or absence of an organic solvent as introduced herein, in the presence of a polymerization inhibitor such as hydroquinone or oxygen . In this case, if necessary, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, phosphorus compounds such as triphenylphosphine Etc. may be added as a catalyst.

The reaction ratio of the component (A) to the component (C) is preferably 0.01 to 0.1 mole of the component (A) per 1 mole of the carboxylic acid group of the component (C). If the relative reaction ratio of the component (A) is less than this range, there may be a problem that the reactivity is lacked due to the lack of a catalyst for activating the reaction. If the ratio exceeds this range, unintended other reactants are produced There may be a problem. More preferably, 0.03 to 0.06 mole of component (A) per mole of carboxylic acid group of component (C) is used. From the viewpoint of the acid value, the component (C) is used in such an amount that the acid value of the final resultant hybrid photosensitive resin is 50 to 200 mg KOH / g, more preferably 70 to 180 mg KOH / g.

The linkage between component (B) and component (C) is usually accomplished by coupling component (B) to the remaining carboxylic acid groups of component (C) linked to component (A). This reaction is usually carried out at 50 to 150 DEG C under a nitrogen atmosphere in the presence or absence of an organic solvent as introduced herein. At this time, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like may be added as catalysts, if necessary.

As described above, the reaction ratio of the component (B) to the component (C) is preferably 0.05 to 2.0 moles of the component (B) per mole of the carboxylic acid group of the component (C). When the amount of the component (B) used is less than this range, improvement in properties such as hardness and adhesion may be insufficient. Conversely, if the amount exceeds the above range, compatibility and shelf life may become insufficient. More preferably, 1.0 to 1.5 moles of the component (B) per 1 mole of the carboxylic acid group of the component (C) is used. From the viewpoint of the acid value, the component (B) is used in such an amount that the acid value of the final resultant hybrid photosensitive resin is 50 to 200 mg KOH / g, more preferably 70 to 180 mg KOH / g.

As described above, according to one embodiment of the present invention, the hybrid photosensitive resin of the present invention comprises (1) an addition reaction of an alkylene oxide to a novolak type phenolic resin; (2) reacting the reaction product of step (1) with an unsaturated monocarboxylic acid; (3) reacting the reaction product of step (2) with a polybasic acid anhydride; And (4) reacting the reaction product of the step (3) with a siloxane compound having at least one functional group selected from an unsaturated group and an alkylene oxide group. The resultant component (A) of the step (2) is obtained and is connected to the component (C) in the step (3), and the remaining carboxylic acid And the component (B) is connected to the group. The reaction conditions for each step are as described above.

The hybrid photosensitive resin of the present invention is obtained by forming a main chain having excellent flexibility and elongation by chain extension formed by adding an alkylene oxide to a novolak type phenolic resin and forming a main chain having excellent flexibility and elongation by addition of an alkylene oxide to the terminal- Unsaturated monocarboxylic acid is added and a polybasic acid anhydride is added so that the unsaturated group or carboxyl group is not present on the same side chain and is located at the end of each side chain. Therefore, it has excellent reactivity, high heat resistance and toughness, And exhibits excellent alkali developability due to the presence of a carboxylic acid and also has a hydrophilic secondary -OH group having low reactivity such as a conventional acid anhydride modified epoxy acrylate resin, it is possible to provide a cured product rich in water resistance and chemical resistance . As well as good adhesion to various substrates by end-OH groups present in the side chain, additional unsaturated groups introduced into the chain extension by the siloxane compound, and -OH groups present in the siloxane compound. In addition, unsaturated groups and / or alkylene oxide groups are additionally introduced due to the introduction of the siloxane compound, thereby increasing the degree of curing. As a result, the heat resistance and toughness of the resist using the conventional photosensitive resin can be exerted (resin- As the C-Si-bond structure is introduced, the strength of the coating is also enhanced. Therefore, when the hybrid photosensitive resin of the present invention is used in a curable composition, it can exhibit excellent alkali developability and curability, and can exhibit excellent adhesiveness, solder heat resistance, moisture absorption resistance, PCT resistance, electroless gold plating It is possible to obtain a cured product having excellent resistance to bending, bending resistance, flexibility, warpage and electrical insulation.

2. Curable composition capable of alkali development

According to the present invention, there is also provided a photocurable or thermosetting composition capable of developing an alkali, which comprises the hybrid photosensitive resin, a polymerization initiator and an epoxy resin.

Examples of the polymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- Amino acetophenones such as on, N, N-dimethylaminoacetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Organic peroxides such as benzoyl peroxide and cumene peroxide; Thiol compounds such as 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; Organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, and tribromomethylphenyl sulfone; Benzophenones such as benzophenone and 4,4'-bisdiethylaminobenzophenone, or xanthones; And a photopolymerization initiator such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide can be used. These may be used alone or as a mixture of two or more. Further, photoinitiators such as N, N-dimethylaminobenzoate ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine, May be further added. Further, a titanocene compound such as CGI-784 (Ciba Specialty Chemicals) having absorption in the visible light region and the like can be added to promote the photoreaction. A particularly preferred photopolymerization initiator is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- Butane-1-one and the like, but not limited thereto, and it is not limited to photopolymerization initiators and photoinitiators, as long as it absorbs light in the ultraviolet or visible region to radically polymerize unsaturated groups such as (meth) acryl groups , Which may be used singly or in combination. The amount of the polymerization initiator to be used is preferably 0.5 to 25 parts by weight, more preferably 3.0 to 15 parts by weight based on 100 parts by weight of the hybrid photosensitive resin. If the amount of the polymerization initiator to be used is too small, there may be a problem of inhibiting the photo-curing. On the other hand, if the amount is too large, the storage stability of the product may be problematic.

Specific examples of the epoxy resin include Epicote 828, Epicote 834, Epicote 1001, Epicote 1004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 840, Epiclon 850 manufactured by Dainippon Ink and Chemicals, YD-013, YD-127, and YD-128 manufactured by Dow Chemical Co., Ltd., DER317, DER (trade name, 331, D.E.R. 661, D.E.R. Bisphenol A type epoxy resins such as Sumi-epoxy ESA-011, ESA-014, ELA-115 and ELA-128 (all trade names) available from Sumitomo Chemical Co., Ltd.; Epikote YL 903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152, Epiclon 165 manufactured by Dainippon Ink and Chemicals, Inc., Ebine, YDB-400, YDB-500 manufactured by Dotogasei Co., DER542, a product of Sumitomo Chemical Co., Ltd., Sumi-epoxy ESB-400 and ESB-700 (all trade names) available from Sumitomo Chemical Co., Epicolon N-770 manufactured by Dainippon Ink and Chemicals, Inc .; Epiclon N-770, Epiclon N-770 manufactured by Dainippon Ink and Chemicals, Inc., Epikote 152, Epikote 154 manufactured by Nippon Epoxy Resin Co., Ltd., DEN431 and DEN438 manufactured by Dow Chemicals, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, and EPPN-201 manufactured by Nippon Kayaku Co., Novolak-type epoxy resins such as Sumi-epoxy ESCN-195X and ESCN-220 (all trade names) available from Sumitomo Chemical Co., Ltd.; Epiclon 830 manufactured by Dainippon Ink and Chemicals, Inc., Epikote 807 manufactured by Japan Epoxy Resin Co., Ltd., bisphenol F (trade name) manufactured by Eto Grapes, YDF-170, YDF-175 and YDF- Type epoxy resin; A hydrogenated bisphenol A type epoxy resin such as Eugene or ST-2004, ST-2007 and ST-3000 (all trade names) manufactured by Tokto Kasei Co., Ltd.; Epikote 604 manufactured by Japan Epoxy Resin Co., Ltd., Eginite YH-434 manufactured by Tokto Kasei Co., Ltd. and Sumi-epoxy ELM-120 (all trade names) available from Sumitomo Chemical Co., Epoxy resin; Alicyclic epoxy resins such as Celloxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd.; A trihydroxyphenylmethane type epoxy resin such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., EPPN-501 and EPPN-502 (all trade names) manufactured by Nihon Kayaku Co., A bicyclylene type or biphenol type epoxy resin such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Japan Epoxy Resin Co., Ltd., or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 (product of Nihon Kayaku Co., Ltd.), EPX-30 (product of Asahi Denka Kogyo Co., Ltd.) and EXA-1514 (product name of product of Dainippon Ink and Chemicals, Inc.); Bisphenol A novolak type epoxy resins such as Epikote 157S (all trade names) manufactured by Japan Epoxy Resins Co., Ltd.; Tetraphenylol ethane type epoxy resin such as Epikote YL-931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; A heterocyclic epoxy resin such as TEP1C (trade name) manufactured by Nissan Chemical Industries, Ltd.; Diglycidyl phthalate resins such as Blenda DGT (trade name) available from Nippon Shokubai Co., Ltd.; Tetraglycidylcylenol ethane resins such as ZX-1063 (trade name) manufactured by Tokto Kasei Co., Ltd.; Epoxy resins including naphthalene groups such as ESN-190, ESN-360, and HP-4032, EXA-4750 and EXA-4700 (all trade names) manufactured by Dainippon Ink and Chemicals, Incorporated; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H (all trade names) manufactured by Dainippon Ink and Chemicals, Incorporated; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M (all trade names) manufactured by Japan KK; And epoxy resin of cyclohexylmaleimide and glycidyl methacrylate. However, the epoxy resin is not limited to these. These epoxy resins may be used alone or in combination of two or more. Of these, biphenol-type or bicyclylene-type epoxy resins or mixtures thereof are particularly preferred.

The epoxy resin as described above is thermally cured to improve properties such as adhesion and heat resistance of the resist. The amount thereof is preferably 10 to 70 parts by weight, more preferably 15 to 60 parts by weight, based on 100 parts by weight of the hybrid photosensitive resin. If the amount of the epoxy resin used is less than the above range, the hygroscopicity of the cured film becomes high, the PCT resistance tends to be lowered, and the solder heat resistance and the internal electrolytic plating property are also likely to be lowered. On the other hand, if it exceeds the above range, the developability of the coating film and the electrolytic gold plating property of the cured film may be deteriorated and the PCT resistance may also be lowered.

The curable composition of the present invention may further comprise a photosensitive (meth) acrylate compound to improve the photoreactivity of the composition. As the photosensitive (meth) acrylate compound, a liquid, solid or semi-solid photosensitive (meth) acrylate compound having at least one (meth) acryl group in one molecule at room temperature can be used. The photosensitive (meth) acrylate compound in a liquid state at room temperature serves to adjust the composition to a viscosity suitable for various coating methods or to help solubility in an aqueous alkali solution, in addition to improving the photoreactivity of the composition. Examples of the photosensitive (meth) acrylate compound include acrylates containing -OH groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate Ryu; Water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; Polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; Acrylates of alkylene oxides (e.g., ethylene oxide, propylene oxide, etc.) adducts of polyfunctional alcohols (e.g., trimethylol propane, water added bisphenol A and the like) or polyhydric phenols (e.g., bisphenol A, biphenol and the like); A polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modification of an acrylate containing an -OH group; Epoxy acrylates such as bisphenol A diglycidyl ether, water-added bisphenol A, diglycidyl ether or (meth) acrylic acid adduct of phenol novolak epoxy resin, methacrylates corresponding to the acrylates, and the like These may be used alone or in combination of two or more. Among them, a polyfunctional (meth) acrylate compound having at least two (meth) acryl groups in one molecule is preferable.

When the photosensitive (meth) acrylate compound is used, the amount of the photosensitive (meth) acrylate compound used is preferably 50 parts by weight or less (for example, 1 to 50 parts by weight) based on 100 parts by weight of the hybrid photosensitive resin. If the amount of the photosensitive (meth) acrylate compound to be used is too large, drying of the coating film is not easy, and the properties of the coating film tend to deteriorate.

The curable composition of the present invention may further contain, in addition to the above-described photosensitive components, an acid anhydride to the reaction product of other carboxyl group-containing photosensitive resin such as a novolak type and / or bisphenol type epoxy compound and an unsaturated- A photosensitive resin and the like may be further included.

The curable composition of the present invention may further comprise an organic solvent to dissolve the hybrid photosensitive resin or the photosensitive (meth) acrylate compound, and to adjust the composition to a viscosity suitable for the application method. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; But are not limited to, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate And the like; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents may be used alone or in a mixture of two or more. The amount of the organic solvent to be used may be appropriately selected depending on the application method.

The curable composition of the present invention may also preferably contain a curing catalyst in order to improve the thermosetting property. Examples of the curing catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; And phosphorus compounds such as triphenylphosphine, etc. These may be used alone or in admixture of two or more. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4 MHZ (imidazole compound), U-CAT3 503X, U (Bicyclic amidine compounds and salts thereof), and the like, but are not particularly limited thereto, and examples thereof include a curing catalyst for epoxy resin, a curing catalyst for epoxy resin, , Or can accelerate the reaction between the epoxy group and the carboxyl group. Preferably, in combination with the above-mentioned curing catalyst, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino- S-triazine derivatives such as cyclohexyl-S-triazine and isocyanuric acid adducts may also be used. The curing catalyst may be contained in the composition in a usual amount, for example, 0.1 to 20 parts by weight, preferably 0.5 to 15.0 parts by weight based on 100 parts by weight of the hybrid photosensitive resin.

The curable composition of the present invention may further contain additives such as barium sulfate, barium titanate, silicon oxide powder, fine particle silicon oxide, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, Aluminum, aluminum hydroxide, mica, and the like, may be included alone or in combination of two or more. These are used for the purpose of suppressing the curing shrinkage of the coating film and improving the properties such as adhesion and hardness. The amount of the inorganic filler used is generally 10 to 300 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the hybrid photosensitive resin.

The composition of the present invention may further contain a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, hydroquinone, hydroquinone monomethyl ether, t Known thickening agents such as butylcatechol, pyrogallol and phenothiazine, known thickeners such as fine silica, bentonite and montmorillonite, antifoaming agents and / or leveling agents such as silicone, fluorine and high molecular weight, , Thiazole-based, and triazole-based silane coupling agents, and the like.

There is no particular limitation on the method for producing the curable composition of the present invention, and a known method and apparatus for manufacturing a photosensitive resin composition can be used as is or modified appropriately. Also, there is no particular limitation on the method of using the curable composition of the present invention, and the known coating / drying method and apparatus for photosensitive resin composition may be used as it is or modified appropriately. For example, after mixing the above-mentioned components in the composition ratio described above, the mixture is diluted with an organic solvent to adjust the viscosity to a suitable viscosity for the application method, and this is applied to a printed wiring board on which circuits are formed, Spray coating or roll coating. Then, the organic solvent contained in the composition is volatilized and dried at a temperature of, for example, about 60 to 100 ° C to form a tacky-free coating film .

3. The cured product of the curable composition

According to another aspect of the present invention, there is provided a cured product obtained by photo-curing or thermosetting a curable composition capable of alkali development.

For example, as described above, the curable composition of the present invention is coated on a substrate and dried to form a coating film. Then, an active energy ray such as a laser beam is directly irradiated onto the coating film as a pattern, or through a photomask Alternatively, the composition may be photocured by exposing the coating film to an active energy ray, and the unexposed portion may be developed with a dilute aqueous alkaline solution to form a resist pattern. Alternatively, it may be heat-cured, irradiated with active energy rays or cured by heating, or cured by heating, and finally cured (cured) by active energy ray irradiation. The cured product thus obtained is excellent in adhesion, solder heat resistance, moisture absorption resistance, PCT resistance, electroless gold plating resistance, flex resistance, bending resistance, flexibility, warpage, electrical insulation and the like.

As the aqueous alkali solution, aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. As an irradiation light source for light curing, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp or a metal halide lamp can be used, and other laser beams can be used as an active energy ray.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited to these examples.

[Example]

≪ Preparation of Hybrid Photosensitive Resin &

Synthesis Example 1

(1) A novolak type cresol resin (PSF-2803, equivalent of -OH group = 109 g / cm < 3 >) was added to an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introducing device, (mass ratio = 2/1) were charged, and the inside of the reactor was replaced by nitrogen atmosphere while stirring. Subsequently, the temperature was raised to 150 占 폚, and 8 kg / Cm < 2 >, 60 g of propylene oxide was slowly added dropwise. The reaction was continued for about 4 hours and then cooled to room temperature. 3.3 g of 36% hydrochloric acid aqueous solution was added to this reaction solution, followed by mixing to neutralize the sodium hydroxide. This neutralization reaction product was diluted with toluene, washed three times, and the solvent was removed through an evaporator to obtain an alkylene oxide-adducted novolak type cresol resin having a hydroxyl equivalent of 167 g / eq. This was an average of 1 mole of alkylene oxide per equivalent of phenolic-OH group.

(2) To a reactor equipped with a stirrer, a thermometer and an air blowing tube, 122 g of the obtained alkylene oxide-added novolac cresol resin, 34 g of acrylic acid, 3.0 g of p-toluenesulfonic acid, 0.05 g of hydroquinone monomethyl ether and 100 g of toluene And the mixture was reacted at 110 DEG C for 6 hours while blowing air and stirring. After the water produced by the reaction started to flow out as an azeotropic mixture with toluene, the reaction was continued for another 5 hours and then cooled to room temperature. The resulting reaction solution was washed with an aqueous 5% sodium chloride solution, toluene was distilled off through an evaporator, and diethylene glycol monoethyl ether acetate was added thereto to obtain an alkylene oxide-adducted novolak type cresol resin solution (solid content 60%).

(3) 170 g of the acrylic acid-modified alkylene oxide-adducted novolak type cresol resin solution, 0.05 g of hydroquinone monomethyl ether and 0.2 g of pyridine were charged into a reactor equipped with a stirrer, a reflux condenser and a condenser, After heating to 캜, 23 g of anhydrous tetrahydrophthalic acid was added and reacted for 6 hours, followed by cooling and extraction. The solid content of the carboxyl group-containing photosensitive resin thus obtained was 64% and the acid value was 67 mg KOH / g.

(4) 150 g of the above-prepared carboxyl group-containing photosensitive resin and 20 g of a homopolymerizable siloxane compound of 3-methacryloxypropyltrimethoxysilane were placed in a reactor equipped with a stirrer and reacted at 60 ° C for about 4 hours while replacing the atmosphere with nitrogen atmosphere After cooling to room temperature, the mixture was extracted to prepare a hybrid photosensitive resin (A-1) (solid content: 66%, acid value: 90 mg KOH / g).

Synthesis Example 2

Except that 20 g of the homopolymerizable siloxane compound of 3-glycidoxypropyltrimethoxysilane was used in place of 20 g of the homopolymerizable siloxane compound of 3-methacryloxypropyltrimethoxysilane in the step (4) of Synthesis Example 1 , A hybrid photosensitive resin (A-2) was prepared in the same manner as in Synthesis Example 1 (solid content: 66%, acid value: 80 mg KOH / g).

Synthesis Example 3

In the step (4) of Synthesis Example 1, the copolymerization of 3-methacryloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane instead of 20 g of the homopolymerizable siloxane compound of 3-methacryloxypropyltrimethoxysilane (A-3) (solid content: 65%, acid value: 95 mg KOH / g) was prepared in the same manner as in Synthesis Example 1, except that 20 g of the siloxane compound of the formula (1) was used.

Photosensitive resin Comparative Example 1

A photosensitive resin containing a carboxyl group having a solid content of 64% and an acid value of 67 mg KOH / g, which was obtained as a result of the step (3) of Synthesis Example 1, was used as the photosensitive resin (B-1) of Comparative Example 1.

Photosensitive resin Comparative Example 2

220 g of cresol novolak type epoxy resin (Epiclon N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 220 g / eq.) Was placed in a reactor equipped with a stirrer, a reflux condenser and a condenser, and 220 g of carbitol acetate And then dissolved by heating. Then, 0.46 g of hydroquinone as a polymerization inhibitor and 1.38 g of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 DEG C, and 72 g of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 占 폚, and 106 g of tetrahydrophthalic anhydride was added and reacted for 8 hours, followed by cooling and extraction. The prepared photosensitive resin having a carboxyl group (solid content: 64%, acid value: 97 mg KOH / g) was used as the photosensitive resin (B-2) of Comparative Example 2.

Photosensitive resin Comparative Example 3

Except that 220 g of EPICOLON N-695 as cresol novolak type epoxy resin was used instead of 220 g of ECON-104S (epoxy equivalent weight of 220 g / eq., Available from Nippon Kayaku Co., Ltd.) A hybrid photosensitive resin was prepared (solid content: 64%, acid value: 97 mg KOH / g) and used as the photosensitive resin (B-3) of Comparative Composition Example 3.

≪ Preparation of curable composition >

Curable compositions were prepared using the photosensitive resins obtained in Synthesis Examples 1 to 3 and Photosensitive Resins Comparative Examples 1 to 3. The ingredients and the contents shown in Table 1 below were combined and dispersed through a three-roll mill to obtain a curable composition. The properties shown in the following Table 2 were measured or evaluated for each composition by the following methods, and the results are shown in Table 2.

(1) Glass transition temperature, elastic modulus, tensile strength and elongation

The curable composition was applied to a pre-washed and dried Teflon plate by a screen printing method and dried at 80 DEG C for 30 minutes by a hot air circulating dryer. This was cooled to room temperature, exposed to light at an exposure dose of 400 mJ, and cured at 150 캜 for 60 minutes in a hot air circulating dryer. After curing, the sample was cooled to room temperature, and the cured film hardened from the Teflon plate was peeled off and used as a sample for evaluation. The glass transition temperature of the evaluation sample was measured by TMA (Thermal Mechanical Analysis). The elastic modulus, tensile strength and elongation of the sample for evaluation were measured by a tensile compression tester (manufactured by Shimadzu Corporation).

(2) Insertability and flexibility

The curable composition was applied to a pre-washed and dried Kapton substrate (thickness = 25 mu m) by screen printing, and dried at 80 DEG C for 30 minutes in a hot air circulating dryer. This was cooled to room temperature, exposed to light at an exposure dose of 400 mJ, cured at 150 ° C for 60 minutes in a hot-air circulating drier, and then peeled off from the cured film and used as a sample for evaluation of bending resistance and flexibility.

The bending resistance was evaluated by observing whether or not a crack occurred in the cured film after bending the cured film outwardly at 180 degrees and evaluating the following criteria:

?: No cracks; ?: Slight cracks; X: significant cracks

Flexibility is determined by placing one edge of a film type specimen produced by processing the cured film with a width of 10 mm and a length of 90 mm on the electronic balance and bending the other edge so that the maximum The load was evaluated as the repulsive force based on the following criteria:

?: Less than 10 g; DELTA: 10 g to less than 30 g; ×: 30 g or more

(3) Absorption rate

The curable composition was applied to a glass plate which had been previously weighed by a screen printing method and dried in a hot air circulating dryer at 80 DEG C for 30 minutes. This was cooled to room temperature, exposed to light at an exposure amount of 400 mJ, and cured at 150 DEG C for 60 minutes in a hot-air circulating dryer to obtain an evaluation sample.

After the sample for evaluation was cooled to room temperature, the weight was measured. Subsequently, the sample for evaluation was treated with a PCT apparatus (TABAI ESPEC HAST SYSTEM TPC-412 MD) at 121 占 폚 and 100% RH for 24 hours. After the weight of the sample for evaluation was measured, The moisture absorption rate of the cured product was determined by the following equation.

[Moisture absorption rate = {(W2-W1) / (W1-Wg)} 100]

W1 is the measured weight before the PCT treatment of the sample for evaluation, W2 is the measured weight after the PCT treatment of the sample for evaluation, and Wg is the weight of the glass plate.

(4) Pencil Hardness

The curable composition was applied to a glass plate by a screen printing method and dried in a hot air circulating dryer at 80 DEG C for 30 minutes. This was cooled to room temperature, exposed to light at an exposure amount of 400 mJ, and cured at 150 DEG C for 60 minutes in a hot-air circulating dryer to obtain an evaluation sample. The pencil hardness of the cured film of the evaluation sample was measured according to JIS K 5400.

(5) Acid resistance, alkali resistance and heat resistance

The curable composition was applied to the printed circuit board which had been washed and dried in advance by screen printing, and dried in a hot air circulating dryer at 80 DEG C for 30 minutes. This was cooled to room temperature, exposed to light at an exposure amount of 400 mJ, and cured at 150 DEG C for 60 minutes in a hot-air circulating dryer to obtain an evaluation sample.

The acid resistance was evaluated comprehensively according to the following criteria in terms of the state of the cured film and the adhesiveness after immersing the evaluation sample in a 10% sulfuric acid aqueous solution at 20 占 폚 for 30 minutes:

○: No change; ?: Very slight change; X: Bubbles or swelling and dropping occurred in the cured film

The alkali resistance was evaluated comprehensively according to the same criteria as in the above acid resistance evaluation standard, after the sample for evaluation was immersed in a 10% aqueous solution of sodium hydroxide at 20 DEG C for 30 minutes.

In the heat resistance test, the sample for evaluation was left in a hot-air circulating drier at 150 ° C for 24 hours, and 10 × 10 checkerboards were made according to JIS K 5600-5-6, peeled with tape, The number of checkered eyes was evaluated as follows:

○: No damage; ?: 1 to 30 damage; X: More than 31 damage

[Table 1] (Unit: parts by weight)

[Table 2]

As can be seen from the results shown in Table 2, the cured product obtained from the curable composition containing the hybrid photosensitive resin of the present invention had a glass transition temperature higher than that of the comparative cured product and superior toughness (elastic modulus and tensile strength) (Stretchability or bending resistance, flexibility), moisture absorption rate, hardness and the like were also excellent. In addition, it exhibited satisfactory properties in terms of chemical resistance and heat resistance.

Claims (16)

(A) and a siloxane compound (B), which are modified with an unsaturated monocarboxylic acid, are bonded to each other with a polybasic acid anhydride (C) as a linking group and have a structure of 50 to 200 mg KOH / g,
Wherein the siloxane compound (B) is selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) -Ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and mixtures thereof, and a single polymer or a copolymer of two or more thereof ,
Hybrid photosensitive resin. The hybrid photosensitive resin according to claim 1, wherein the alkylene oxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran and tetrahydropyran. The hybrid photosensitive resin according to claim 1, wherein the addition ratio of the alkylene oxide to the novolak type phenol resin is 0.3 to 10.0 moles of an alkylene oxide per 1 mole of the -OH group of the novolak type phenol resin. The composition according to claim 1, wherein the unsaturated monocarboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,? -Cyanosinic acid,? -Styryl acrylic acid and? Hybrid photosensitive resin. delete The hybrid photosensitive resin according to claim 1, wherein the polybasic acid anhydride (C) is at least one selected from alicyclic dibasic acid anhydrides, aliphatic or aromatic dibasic acid anhydrides, and aliphatic or aromatic tetrabasic acid dianhydrides. (1) subjecting a novolak type phenolic resin to an addition reaction with an alkylene oxide;
(2) reacting the reaction product of step (1) with an unsaturated monocarboxylic acid;
(3) reacting the reaction product of step (2) with a polybasic acid anhydride; And
(4) reacting the reaction product of step (3) with a siloxane compound,
Wherein the siloxane compound is selected from the group consisting of 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and mixtures thereof, and a single polymer thereof, or a copolymer of two or more thereof.
A method for producing a hybrid photosensitive resin. The method for producing a hybrid photosensitive resin according to claim 7, wherein the alkylene oxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran and tetrahydropyran. The method for producing a hybrid photosensitive resin according to claim 7, wherein the addition ratio of the alkylene oxide to the novolak type phenol resin is 0.3 to 10.0 moles of an alkylene oxide per 1 mole of the -OH group of the novolak type phenol resin. The composition according to claim 7, wherein the unsaturated monocarboxylic acid is at least one selected from acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,? -Cyanosinic acid,? -Styryl acrylic acid and? A method for producing a hybrid photosensitive resin. The method for producing a hybrid photosensitive resin according to claim 7, wherein the polybasic acid anhydride is at least one selected from alicyclic dibasic acid anhydride, aliphatic or aromatic dibasic acid anhydride, and aliphatic or aromatic tetrabasic acid dianhydride. delete A curable composition capable of developing an alkali, which comprises the hybrid photosensitive resin according to any one of claims 1 to 4, a polymerization initiator and an epoxy resin. The curable composition according to claim 13, which further comprises a photosensitive (meth) acrylate compound. 14. The curable composition according to claim 13, which further comprises a curing catalyst. A cured product obtained by photocuring or thermosetting the curable composition capable of alkali development of claim 13.