JPWO2007032326A1 - Photosensitive resin composition and cured product thereof - Google Patents

Abstract

A photosensitive resin composition having excellent photosensitivity, excellent flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, and the like, and a cured product thereof. In a photosensitive resin composition comprising a photosensitive aqueous alkali-soluble resin (A), a reactive crosslinking agent (B), a photopolymerization initiator (C), and a curing agent (D), the curing agent (D) is Formula (1) [wherein n represents the number of repetitions. ] The photosensitive resin composition which is a 4,4'-form bisphenol F type epoxy resin represented by this. [Selection figure] None

Description

  The present invention uses a 4,4′-form bisphenol F-type epoxy resin having good molecular symmetry as a curing agent, and contains a photosensitive aqueous alkali-soluble resin, a reactive crosslinking agent, and a photopolymerization initiator. The present invention relates to a resin composition and a cured product thereof. More specifically, it is useful as a solder resist for printed wiring boards, an interlayer insulating material for multilayer printed wiring boards, a solder resist for flexible printed wiring boards, a dry film resist, a plating resist, a photosensitive optical waveguide, and the like. The present invention relates to a liquid or dry film type resin composition that gives a cured product excellent in thermal stability, electrical insulation, adhesion, chemical resistance, plating resistance, and the like, and the cured product.

  A photosensitive resin composition using a photosensitive epoxycarboxylate compound is environmentally friendly and has an excellent balance of various properties such as thermal and mechanical properties and adhesion to a substrate. For this reason, it is used in the fields of paints, coatings, adhesives, etc., and recently, it has been used in a wide range of industrial fields such as electrical / electronic component manufacturing applications and printed wiring board manufacturing applications. The range is expanding. On the other hand, with the expansion of this field of use, a photosensitive resin composition using a photosensitive epoxy carboxylate compound is required to have higher performance with respect to characteristics such as heat resistance and adhesion.

  For printed circuit boards, high precision and high density are required to reduce the size and weight of mobile communication devices and improve communication speed, and the requirements for solder resists used for them are further heat resistant and thermal stable. While maintaining the above, it has become increasingly sophisticated that it has excellent substrate adhesion, high insulation, and electroless gold plating resistance. However, it cannot be said that the existing solder resist sufficiently corresponds to these.

  Patent Document 1 describes a solder mask composition containing a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak type epoxy resin and an unsaturated monobasic acid. Heat resistance, adhesion, and plating resistance were not sufficient.

  Patent Document 2 describes a photopolymerizable resin composition containing a urethane-modified vinyl ester resin, and a cured product of this composition has flexibility, but has sufficient performance with respect to heat resistance and adhesion. There wasn't.

  Patent Document 3 describes a resin composition in which a hardly soluble fine particle epoxy resin is used as a curing agent, and a part thereof can be replaced with a soluble resin such as a bisphenol F type epoxy resin. Patent Document 4 exemplifies a bisphenol F type epoxy resin as a soluble epoxy resin.

  However, the bisphenol F type epoxy resin has a high solubility in a solvent, and the dissolved epoxy resin easily reacts with the acid-modified photosensitive resin, so that a residue remains during development.

  Patent Document 5 discloses a 4,4′-form bisphenol F-type epoxy resin having a good molecular symmetry, that is, a crystalline resin having a high content ratio of a compound in which n = 0 in the following formula (1). Are listed. However, since its melting point is as low as 50 to 70 ° C., it reacts with the acid-modified photosensitive resin during pre-baking (drying process before curing) that is usually performed during curing, and there is a disadvantage that a residue remains during development. It was. Patent Document 6 describes a 4,4′-form bisphenol F-type epoxy resin, but does not disclose use as a curing agent for a photosensitive alkaline aqueous solution-soluble resin.

JP-A 61-243869 JP-A-9-52925 Japanese Patent Publication No. 7-17737 JP 2000-109541 A JP-A-8-73563 WO2006 / 008984

  The object of the present invention is excellent in photosensitivity to active energy rays for printing fine images in response to high performance requirements for solder masks that can be used for the above-described high-performance printed wiring boards and the like. Easy pattern formation by development with alkaline aqueous solution, excellent in flexibility, adhesion, solder heat resistance, electroless gold plating resistance, etc. of cured products obtained by thermal curing in post-curing (post-cure) process. It is providing the resin composition which does not remain, and its hardened | cured material.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

  That is, the present invention

1) In the photosensitive resin composition containing the photosensitive aqueous alkali-soluble resin (A), the reactive crosslinking agent (B), the photopolymerization initiator (C) and the curing agent (D), the curing agent (D) is Formula (1)

［式中、ｎは繰り返し数を表す。］
で表される４，４’−体のビスフェノールＦ型エポキシ樹脂である感光性樹脂組成物；

[Wherein n represents the number of repetitions. ]
A photosensitive resin composition which is a 4,4′-form bisphenol F-type epoxy resin represented by:

2) The photosensitive resin composition according to 1) above, wherein n of the curing agent (D) is a positive number of 1 to 7, and the melting point thereof is a crystal of 80 to 150 ° C .;

3) Photosensitive alkaline aqueous solution-soluble resin (A) is a reaction between an epoxy compound (a) having two or more epoxy groups in the molecule and a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. The photosensitive resin composition according to 1) or 2) above, which is a reaction product of the resulting epoxycarboxylate compound and the polybasic acid anhydride (c);

4) A photosensitive alkaline aqueous solution-soluble resin (A) is obtained by reaction of an epoxy compound (d) having two epoxy groups in the molecule and a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. A reaction product of an epoxycarboxylate compound obtained with a diisocyanate compound (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diol compound (g) having no carboxyl group as an optional component, Or the photosensitive resin composition as described in said 1) or 2) which is a reaction product of the said reaction product and the polybasic acid anhydride (c) as an arbitrary component;

5) A cured product of the photosensitive resin composition according to any one of 1) to 4) above;
6) A substrate having a cured product layer described in 5) above;
7) An article having the base material described in 6) above;
About.

  Curing photosensitive aqueous alkali-soluble resin (A), reactive crosslinking agent (B), photopolymerization initiator (C), and 4,4'-form bisphenol F-type epoxy resin having a melting point of 80 to 150 ° C. The photosensitive resin composition of the present invention contained as an agent (D) is excellent in tackiness and photosensitivity, can be patterned by development with an alkaline aqueous solution, and is also used as a curing and post-curing (post-cure) process by active energy rays. The cured product obtained by thermosetting has excellent performance such as flexibility, solvent resistance, acid resistance, thermal stability, flexibility, adhesion, solder heat resistance, electroless gold plating resistance, etc. It is suitable for a photosensitive resin composition for printed wiring boards and a photosensitive resin composition for dry films.

  The photosensitive resin composition of the present invention comprises a photosensitive alkaline aqueous solution-soluble resin (A), a reactive crosslinking agent (B), a photopolymerization initiator (C) and the above formula (1) [where n is the number of repetitions. To express. A curing agent (D), which is a 4,4′-form bisphenol F-type epoxy resin represented by the formula:

  The photosensitive aqueous alkali-soluble resin is a resin that has an active group that is cured by active energy rays or the like and can be developed with an aqueous alkaline solution.

  Examples of the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition include an epoxy compound (a) having two or more epoxy groups in the molecule and an ethylenically unsaturated group in the molecule. The reaction product of the epoxycarboxylate compound obtained by reaction of the monocarboxylic acid compound (b) it has and the polybasic acid anhydride (c) is mentioned.

  The epoxy compound (a) shown in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. By having two or more epoxy groups, a plurality of ethylenically unsaturated groups can be introduced in one molecule when reacted with the monocarboxylic acid compound (b). By setting the epoxy equivalent to 100 g / equivalent or more, the molecular weight is increased, the film formability is improved, and the flexibility is improved. Moreover, since the introduction amount of an ethylenically unsaturated group increases by making an epoxy equivalent 900g / equivalent or less, the sensitivity with respect to hardening improves. The number of epoxy groups in one molecule is preferably 2 or more and 50 or less. More preferably, the number is 3 to 20. If it is this range, the fall of the sclerosis | hardenability by the reduction | decrease of the cure site | part which is anxious when there are few epoxy groups, the viscosity increase accompanying the high molecular weight raise | generated about when it is many can be prevented.

  Examples of the epoxy compound (a) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol type epoxy resins (bisphenol-A type epoxy resins). Bisphenol-F type epoxy resin, etc.), biphenol type epoxy resin, bisphenol-A novolak type epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and the like.

  Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink & Chemicals), D.I. E. N438 (manufactured by Dow Chemical Co., Ltd.), Epicoat 154 (manufactured by Yuka Shell Epoxy), EPPN-201, RE-306 (all by Nippon Kayaku) and the like.

  Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku), and UVR-6650 (Union Carbide). Product), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the trishydroxyphenylmethane type epoxy resin include, for example, EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku), TACTIX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (oilized shell epoxy) Manufactured) and the like.

  Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink and Chemicals), TACTIX-556 (manufactured by Dow Chemical Company), and the like.

  Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical), RE-310S (manufactured by Nippon Kayaku), YD-8125 (manufactured by Tohto Kasei), UVR-6490 (manufactured by Union Carbide), YDF- And bisphenol-F type epoxy resin such as 8170 (manufactured by Tohto Kasei Co., Ltd.).

  In addition, polyfunctional bisphenol A type epoxy resins such as NER-1202, NER-1302, and NER-1504 (manufactured by Nippon Kayaku), NER-7403, and NER-7604 (manufactured by Nippon Kayaku) ) And the like.

  Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H (both made by Nippon Kayaku), bixylenol type epoxy resins such as YX-4000 (made by Yuka Shell Epoxy), and YL. -6121 (product made from oil-ized shell epoxy) etc. are mentioned.

  Examples of the bisphenol-A novolac type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink and Chemicals), Epicoat E157S75 (manufactured by Yuka Shell Epoxy), and the like.

  Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku) and EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.).

  Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries).

  Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries).

  As the epoxy compound (a), phenol novolac type epoxy resins, cresol novolac type epoxy resins, polyfunctional bisphenol type epoxy resins, and biphenol type epoxy resins are particularly preferably used. These can provide a photosensitive resin composition excellent in various properties such as heat resistance, mechanical strength, and chemical resistance, especially when a permanent resist material such as a solder resist is taken into consideration.

  Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule include acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated dibasic acid and an unsaturated group. The reaction material with a monoglycidyl compound is mentioned. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, reaction products of (meth) acrylic acid and lactones (for example, ε-caprolactone, etc.), saturated or Half esters, saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, which are equimolar reactants of unsaturated dibasic acid anhydrides and (meth) acrylate derivatives having one hydroxyl group per molecule The reaction product of (meth) acrylic acid, (meth) acrylic acid and ε-caprolactone in terms of sensitivity when a photosensitive resin composition is used. Or cinnamic acid is particularly preferred.

  The polybasic acid anhydride (c) is a compound having one or more acid anhydride structures in the molecule. For example, succinic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerin bis (anhydrotrimellitate) monoacetate, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3 ′ , 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) pro 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydride And 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione. Of these, succinic acid and tetrahydrophthalic anhydride are preferred. These are generally industrially available, and can provide a photosensitive resin composition having a relatively low price and excellent developability.

  As described above, the photosensitive aqueous alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention is composed of an epoxy compound (a) having two or more epoxy groups in the molecule and an ethylenic molecule in the molecule. Reaction of an epoxy carboxylate compound having an alcoholic hydroxyl group obtained by a reaction of a monocarboxylic acid compound (b) having an unsaturated group (hereinafter referred to as a first reaction) with a polybasic acid anhydride (c) (hereinafter referred to as a “basic acid anhydride”). The second reaction).

  The first reaction is a solvent-free or solvent having no alcoholic hydroxyl group, for example, ketones such as acetone, ethylmethylketone, cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, tetramethylbenzene, ethylene glycol Glycol ethers such as dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate , Carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate (eg Dimethyl glutarate, etc.), dialkyl succinate (eg, dimethyl succinate, etc.), esters such as dialkyl adipate (eg, dimethyl adipate, etc.), cyclic esters such as γ-butyrolactone, petroleum ether, petroleum naphtha, The reaction is carried out with a petroleum solvent such as hydrogenated petroleum naphtha or solvent naphtha, or a single or mixed solvent such as a reactive crosslinking agent (B) described later.

  The raw material charge ratio in this first reaction is such that the carboxyl group of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is 0.8 per equivalent of the epoxy group of the epoxy compound (a). A range of -1.2 equivalents is preferred. Within this range, there are few epoxy groups remaining as unreacted or monocarboxylic acid (b) remaining as an excess, so that the storage stability of the resin (A) over time, thermal stability, production Time stability is improved.

  In the first reaction, it is preferable to use a catalyst to promote the reaction. When the catalyst is used, the amount used is about 0.1 to 10% by weight with respect to the reaction product.

  Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, zirconium octoate and the like.

  The reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.

  In the first reaction, a thermal polymerization inhibitor may be used. As the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 2,6- Examples include di-t-butyl-p-cresol.

  The first reaction has an end point when the acid value of the sample is 1 mg · KOH / g or less, preferably 0.5 mg · KOH / g or less, while appropriately sampling.

  In the present invention, the solid content acid value is the amount (mg) of potassium hydroxide required to neutralize the acidity of the carboxylic acid in 1 g of the resin, and the acid value is 1 g of the solution containing the resin. It is the amount (mg) of potassium hydroxide necessary for the sum, and is measured by a normal neutralization titration method according to JIS K0070. If the concentration of the resin in the solution is known, the solid content acid value can be calculated from the acid value of the solution.

  The second reaction is an esterification reaction in which the polybasic acid anhydride (c) is added to the reaction solution and reacted after completion of the first reaction. The second reaction may be performed after separating the product of the first reaction, or the second reaction may be performed subsequently without separating the product of the first reaction. When a solvent is used for the second reaction, a solvent similar to the solvent that can be used for the first reaction can be used.

  The second reaction can be carried out without a catalyst, but a basic catalyst (for example, pyridine, triethylamine, benzyldimethylamine, triethylammonium hydroxide, dimethylaminopyridine, etc.) can be used to accelerate the reaction. When the catalyst is used, the amount used may be 10% by weight or less based on the reaction product.

  The reaction temperature is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

  In addition, the acid anhydride addition step, which is the second reaction, has the point that the acid value of the reaction product is within the range of plus or minus 10% of the acid value set according to the intended use while sampling appropriately. The end point.

  The photosensitive aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention includes an epoxy compound (d) having two epoxy groups in the molecule and an ethylenically unsaturated group in the molecule. An epoxycarboxylate compound obtained by the reaction of a monocarboxylic acid compound (b) having a diisocyanate compound (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a carboxyl group as an optional component. The reaction product of the diol compound (g) which is not used and the polybasic acid anhydride (c) as an optional component can also be used.

  The epoxy compound (d) shown in the present invention is a compound having two epoxy groups in one molecule. When it has more than two epoxy groups, it reacts with the monocarboxylic acid compound (b) and then reacts with the diisocyanate compound (e) to act as a polyol having more than two hydroxyl groups in one molecule. Cause gelation. The epoxy compound (d) is preferably a compound having an epoxy equivalent of 100 to 900 g / equivalent. When the epoxy equivalent is 100 g / equivalent or more, it is possible to prevent a decrease in film formability due to a decrease in the molecular weight of the resulting photosensitive alkaline aqueous solution-soluble resin (A). Moreover, the toughness of the coating film is improved. On the other hand, when the epoxy equivalent is 900 g / equivalent or less, the introduction rate of the monocarboxylic acid compound (b) having an ethylenically unsaturated group into the photosensitive alkaline aqueous solution-soluble resin (A) is increased, and the photosensitivity can be improved. .

  Examples of the epoxy compound (d) include phenyl diglycidyl ether compounds such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, and bisphenol-S. Type epoxy resin, bisphenol type epoxy compound such as epoxidized product of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, hydrogenated bisphenol-A type epoxy resin , Hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy Hydrogenated bispheno Type epoxy compound, brominated bisphenol-A type epoxy resin, halogenated bisphenol type epoxy compound such as brominated bisphenol-F type epoxy resin, alicyclic diglycidyl ether compound such as cyclohexanedimethanol diglycidyl ether compound, 1, 6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, aliphatic diglycidyl ether compounds such as diethylene glycol diglycidyl ether, polysulfide type diglycidyl ether compounds such as polysulfide diglycidyl ether, biphenol type epoxy resins, etc. Can be mentioned.

  These epoxy compounds are also commercially available. For example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004 (all manufactured by Japan Epoxy Resin), Epomic R-140, Epomic R-301, Epomic R-304 ( All are manufactured by Mitsui Chemicals, Inc., DER-331, DER-332, DER-324 (all manufactured by Dow Chemical Company), Epicron 840, Epicron 850 (all manufactured by Dainippon Ink), UVR-6410 (manufactured by Union Carbide). ), RE-310S (manufactured by Nippon Kayaku), YD-8125 (manufactured by Tohto Kasei), etc., bisphenol-A type epoxy resin, UVR-6490 (manufactured by Union Carbide), YDF-2001, YDF-2004, YDF-8170 (Both manufactured by Toto Kasei) Bisphenol-F type epoxy resins such as Epicron 830 and Epicron 835 (both manufactured by Dainippon Ink), hydrogenated bisphenol-A types such as HBPA-DGE (manufactured by Maruzen Petrochemicals), Rica Resin HBE-100 (manufactured by Shin Nippon Chemical) Epoxy resin, brominated bisphenol-A type epoxy resin such as DER-513, DER-514, and DER-542 (all manufactured by Dow Chemical Co.), Celoxide 2021 (manufactured by Daicel), Rica Resin DME-100 (manufactured by Shin Nippon Rika) ), Alicyclic epoxy resins such as EX-216 (manufactured by Nagase Kasei), ED-503 (manufactured by Asahi Denka), Rica Resin W-100 (manufactured by Shin Nippon Rika), EX-212, EX-214, EX-850 ( Aliphatic diglycidyl ether compounds such as Nagase Kasei), FLEP-50, FLEP-60 Both east Thiokol Co.) polysulfide type diglycidyl ether compounds such as, YX-4000 (manufactured by Japan Epoxy Resins) biphenol type epoxy compounds such like. Among them, the mononuclear content is preferably a bisphenol-A type epoxy resin. These can provide a photosensitive resin composition excellent in various properties such as heat resistance, mechanical strength, and chemical resistance, especially when a permanent resist material such as a solder resist is taken into consideration.

  The diisocyanate compound (e) used in the production of the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention is particularly limited as long as it is a compound having two isocyanate groups in the molecule. Instead, a plurality of diisocyanate compounds may be mixed and used.

  Examples of the diisocyanate compound (e) include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridenic diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, Examples include lensulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane or norbornane diisocyanate methyl. Among these, when an aliphatic diisocyanate such as isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate is used, a soluble resin (A) having good flexibility can be obtained.

  The carboxylic acid compound (f) having two hydroxyl groups in the molecule used for the production of the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention includes an alcoholic hydroxyl group in the molecule. Or it is not specifically limited if it is a compound which has a total of two phenolic hydroxyl groups and a carboxyl group, The carboxylic acid compound which has two alcoholic hydroxyl groups which are excellent in alkaline aqueous solution developability is especially preferable, For example, dimethylol propionic acid And compounds such as dimethylolbutanoic acid.

  A diol compound (g) having no carboxyl group may be used for the production of the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention. The diol compound (g) is not particularly limited as long as it is an aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms and does not have a carboxyl group. These are used as optional components according to the purpose, and are used according to the required properties of the materials used. For example, aliphatic hydrocarbon diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, tricyclo Alicyclic hydrocarbon diols such as decanedimethanol and adamantane dimethanol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol, polyester diols such as polycaprolactone diol, polyhexanediol hydrocarbon, Polycarbonate diols such as polycyclohexanedimethanol carbonate, spiroglycol, dioxane glyco Heterocyclic diols, both-end hydroxyl-modified polybutadiene polymer, both-end hydroxyl-modified polybutadiene-acrylonitrile copolymer, both-end hydroxyl-modified styrene-acrylonitrile copolymer, both-end hydroxyl-modified polyethylene, both-end hydroxyl-modified polypropylene And terminal hydroxyl group-modified copolymers. Of these, alicyclic hydrocarbon diols, polyalkylene glycols, polyester diols, and heterocyclic diols are preferred. These are generally industrially available, and can provide a photosensitive resin composition having relatively low cost and excellent developability and flexibility.

  As described above, the photosensitive alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention comprises an epoxy compound (d) having two epoxy groups in the molecule and an ethylenic non-soluble resin in the molecule. An epoxy carboxylate compound having an alcoholic hydroxyl group obtained by a reaction of a monocarboxylic acid compound (b) having a saturated group (hereinafter referred to as a third reaction), a diisocyanate compound (e), and two hydroxyl groups in the molecule. It is separately produced by a urethanization reaction (hereinafter referred to as a fourth reaction) with the carboxylic acid compound (f) it has. The fourth reaction may be carried out by adding a diol compound (g) having no carboxyl group as an optional component.

  After the fourth reaction, an optional component polybasic acid anhydride (c) may be added and reacted.

  The third reaction is a solventless or solvent having no alcoholic hydroxyl group, for example, ketones such as acetone, ethylmethylketone, cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, tetramethylbenzene, ethylene glycol, etc. Glycol ethers such as dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate , Carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate (for example, Dimethyl rutarate), esters such as dialkyl succinate (eg dimethyl succinate), dialkyl adipate (eg dimethyl adipate, etc.), cyclic esters such as γ-butyrolactone, petroleum ether, petroleum naphtha, water It is carried out with a petroleum solvent such as petroleum naphtha or solvent naphtha, or a single or mixed solvent such as a reactive crosslinking agent (B) described later.

  The raw material charge ratio in this third reaction is such that the carboxyl group of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is 0.8 per equivalent of the epoxy group of the epoxy compound (d). A range of -1.2 equivalents is preferred. Within this range, there are few epoxy groups remaining as unreacted or monocarboxylic acid (b) remaining as an excess, so that the storage stability of the resin (A) over time, thermal stability, production Time stability is improved.

  In the third reaction, it is preferable to use a catalyst in order to promote the reaction. When the catalyst is used, the amount used is about 0.1 to 10% by weight with respect to the reaction product.

  Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, zirconium octoate and the like.

  The reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.

  In the third reaction, a thermal polymerization inhibitor may be used, and as the thermal polymerization inhibitor, for example, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 2, Examples include 6-di-t-butyl-p-cresol.

  In the third step of the epoxycarboxylate reaction, the sample has an acid value (conforming to JIS K5601-2-1: 1999) of 1 mg · KOH / g or less, preferably 0.5 mg · KOH / The time when g or less is reached is the end point.

  In the fourth reaction, after completion of the third reaction, a carboxylic acid compound (f) having two hydroxyl groups in the molecule and a diol compound (g) having no carboxyl group as an optional component are added to the reaction solution. This is a urethanization reaction in which a dispersion or solution is added and the diisocyanate compound (e) is gradually added and reacted. The fourth reaction may be performed after the product of the third reaction is separated, or the fourth reaction may be performed continuously without separating the product of the third reaction.

  The fourth reaction can be performed without a catalyst, but a basic catalyst can be used to promote the reaction, and examples of the catalyst include the same catalysts as those used in the second reaction. When the catalyst is used, the amount used may be 10% by weight or less based on the reaction product.

  The reaction temperature is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

  At this time, the above-mentioned solvent or thermal polymerization inhibitor may be used.

The urethanization step as the fourth reaction is performed when the reduction of the peak area in the vicinity of 2250 cm ⁻¹ derived from the isocyanate group reaches a specified amount by an infrared absorption spectrum measurement method while appropriately sampling, or JIS K1556: A titration method shown in 1968 or the like can be applied. Among these, the latter method is more preferable. Specifically, the end point is preferably a point where the isocyanate group content calculated from the actual charging ratio falls within a range of 2%.

  In addition, when the polybasic acid anhydride (c) is reacted as an optional component, it may be reacted in the same manner as the second reaction after the fourth reaction.

  The charged amount of the carboxylic acid compound (f) having two hydroxyl groups in the molecule or the polybasic acid anhydride (c) as an optional component is such that the solid content acid value of the photosensitive alkaline aqueous solution-soluble resin (A) is 50 to 50. It is preferable to add a calculated amount of 150 mg · KOH / g. If the solid content acid value is 50 mg · KOH / g or more, good solubility in an alkaline aqueous solution is exhibited, and if the solid content acid value is 150 mg · KOH / g or less, it is excessively dissolved during patterning during development. It is possible to prevent the patterning property from being deteriorated.

  The amount of diisocyanate compound (e) charged is: (number of moles of epoxy carboxylate compound formed in the third reaction + number of moles of carboxylic acid compound (f) having two hydroxyl groups in the molecule + diol as an optional component) The ratio of (number of moles of compound (g)) / (number of moles of diisocyanate compound (e)) is preferably in the range of 1-5. If this ratio is 1 or more, the isocyanate group remaining after the completion of the reaction does not remain, so that deterioration of storage stability due to crosslinking of the isocyanate group can be prevented. Further, when this ratio is 5 or less, the molecular weight becomes large, so that it is possible to prevent deterioration of tackiness and sensitivity.

  The content ratio of the photosensitive alkaline aqueous solution-soluble resin (A) in the photosensitive resin composition of the present invention is usually 15 to 70% by weight, preferably 100% by weight when the solid content of the photosensitive resin composition is 100% by weight, preferably Is 20 to 60% by weight.

  The photosensitive alkaline aqueous solution-soluble resin (A) of the present invention thus obtained can be made solid by removing it with an appropriate method when a solvent is used.

  The reactive crosslinking agent (B) contained in the active energy ray-curable resin composition of the present invention is reactive when the photosensitive resin composition is cured, as in the alkaline aqueous solution-soluble resin (A) of the present invention. Is a general term for those forming a cross-linked structure. These are used for imparting physical properties before and after curing according to the purpose of use.

  Specific examples of the reactive crosslinking agent (B) that can be used include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds that are sensitive to both. . Among these, it is preferable to select a radical reaction type crosslinking agent because the aqueous alkali solution-soluble resin (A) of the present invention has an acidic group. This is because the crosslinking reaction proceeds with the cation derived from (A).

  Examples of radical reaction type acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, alkyl (meth) acrylates such as lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene Alkylene glycol mono (meth) acrylates such as glycol (meth) acrylate monomethyl ether, aromatic (meth) acrylates such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) Examples thereof include cycloaliphatic (meth) acrylates such as acrylate, and heterocyclic-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate.

  Polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate and other alkylene diol (meth) acrylates Glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, alkylene glycol di (meth) acrylate such as polypropylene glycol di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, Aromatic (meth) acrylates such as bisphenol di (meth) acrylate, cycloaliphatic (meth) acrylates such as hydrogenated bisphenol ethylene oxide (meth) acrylate , Heterocycle-containing (meth) acrylates such as tris (meth) acryloyloxyethyl isocyanurate, other epoxy acrylates such as adipic acid epoxy di (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, alkyl polyol (meth) acrylates such as triethylolpropane tri (meth) acrylate, ethylene such as dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethylolpropane tri (meth) acrylate Di (meth) acrylates of ε-caprolactone adducts of hydroxybivalic acid neopent glycol, such as (meth) acrylates of oxide adducts or propylene oxide adducts Rate, polyol caprolactone modified (meth) acrylates of poly (meth) acrylate of a reaction product of dipentaerythritol and ε- caprolactone.

  Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Besides the above, as the reactive crosslinking agent (B), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate , Acryloylmorpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compounds Half-esters that are reaction products of acid anhydrides (eg succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.), polyethylene glycol di (meth) acrylate, tripropylene glycol di (Meta) Acrelay , Trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate (ethylene oxide modified trimethylolpropane triacrylate), glycerin polypropoxytri (meth) acrylate, hydroxybivalate neopent glycol ε -Caprolactone adduct di (meth) acrylate (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly ( (Meth) acrylate, dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl compounds (eg, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycidyl ether) Diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane Examples include epoxy (meth) acrylate, which is a reaction product of polyethoxypolyglycidyl ether and the like and (meth) acrylic acid.

  The addition ratio of these reactive crosslinking agents (B) is usually 2 to 40% by weight, preferably 5 to 30% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

  The photopolymerization initiator (C) used in the present invention is preferably a radical photoinitiator. For example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 -Dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Acetophenones such as propan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthio Thioxanthones such as sandone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethyl Benzophenones such as aminobenzophenone; known general radical photoinitiators such as phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Is mentioned.

  The addition ratio of the photopolymerization initiator (C) is usually 1 to 30% by weight, preferably 2 to 25% by weight when the solid content of the photosensitive resin composition is 100% by weight. In addition, the photopolymerization initiator (C) can be used alone or as a mixture of two or more thereof. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N- It may be used in combination with a reaction accelerator such as a benzoic acid derivative such as dimethylaminobenzoic acid isoamyl ester. The addition amount of these reaction accelerators is preferably 100% by weight or less with respect to the photopolymerization initiator (C).

  The curing agent (D) contained in the photosensitive resin composition of the present invention is the above formula (1) [wherein n represents the number of repetitions. ] 4,4'-form bisphenol F type epoxy resin having good molecular symmetry. The curing agent (D) forms a cured coating film having stronger chemical resistance and the like by post-curing that reacts with the carboxy group remaining in the resin coating film after photocuring by heating.

  The 4,4′-form bisphenol F-type epoxy resin having good molecular symmetry represented by the formula (1) has liquid crystallinity.

  The melting point of the curing agent (D) is usually 70 to 150 ° C, preferably 80 to 150 ° C. Moreover, the epoxy equivalent is 250-2000 g / equivalent normally, Preferably it is 300-1000 g / equivalent.

  The epoxy resin used as the curing agent (D) represented by the above formula (1) contained in the photosensitive resin composition of the present invention is, for example, the following formula (2):

で表されるフェノール系化合物を原料とする。該化合物は融点が１６３℃前後の結晶であり、例えば、商品名ｐ，ｐ’−ＢＰＦ（本州化学製；純度＞９９％）として市販されている。該フェノール系化合物とエピハロヒドリンとをアルカリ金属水酸化物の存在下で反応させて低分子量のエポキシ樹脂を得、更にこの化合物と式（２）で表されるフェノール系化合物と反応させ、得られた反応混合物から結晶を析出させることにより感光性樹脂組成物に含有する硬化剤（Ｄ）としてのエポキシ樹脂を得ることができる。

A phenol compound represented by the formula is used as a raw material. The compound is a crystal having a melting point of around 163 ° C., and is commercially available, for example, under the trade name p, p′-BPF (manufactured by Honshu Chemical; purity> 99%). The phenolic compound and epihalohydrin were reacted in the presence of an alkali metal hydroxide to obtain a low molecular weight epoxy resin, which was further reacted with the phenolic compound represented by the formula (2). By precipitating crystals from the reaction mixture, an epoxy resin as a curing agent (D) contained in the photosensitive resin composition can be obtained.

  As the epihalohydrin, epichlorohydrin or epibromohydrin can be used, and the amount used is usually 2 to 15 mol, preferably 3 to 1 mol of the phenolic hydroxyl group of the phenolic compound represented by the formula (2). 12 moles.

  Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, which can be used as a solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added to the reaction system and at the same time under reduced pressure or normally. A method of distilling water and epihalohydrin under pressure, separating the solution and removing water, and returning the epihalohydrin continuously to the reaction system can be preferably used.

  The usage-amount of the alkali metal hydroxide in the said reaction is 0.9-1.2 mol normally with respect to 1 mol of hydroxyl groups of this phenol type compound represented by Formula (2), Preferably it is 0.95-1. 15 moles.

  The reaction temperature is usually 20 to 110 ° C, preferably 25 to 100 ° C. The reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.

  Addition of alcohols such as methanol, ethanol, propanol and butanol, or aprotic polar solvents such as dimethyl sulfoxide and dimethyl sulfone to the above reaction is preferable in order to facilitate the reaction.

  When using alcohol, the amount of its use is 3-30 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 5-20 weight%.

  When an aprotic polar solvent is used, the amount used is usually 10 to 150% by weight, preferably 15 to 120% by weight, based on the amount of epihalohydrin.

  In addition, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added as a catalyst to a solution in which epihalohydrin and the phenolic compound of formula (2) are dissolved. Add a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product obtained by reacting for 0.5 to 8 hours and react at 20 to 100 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure). The method may be used.

  Next, after the epoxidation reaction liquid obtained is washed with water or without being washed with water, excess epihalohydrin, solvent, and the like are removed under reduced pressure by heating to obtain a low molecular weight epoxy resin.

  Furthermore, the obtained epoxy resin is dissolved in toluene, methyl isobutyl ketone, and the like, and an aqueous solution of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to ensure ring closure, so that hydrolyzable halogen can be removed. Less epoxy resin can be used. In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of a phenol type compound, Preferably it is 0.05-0.2 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the ring-closing reaction, the produced salt is removed by filtration or water washing, and the solvent is removed under reduced pressure by heating to obtain a low molecular weight epoxy resin. The epoxy equivalent of the epoxy resin is usually about 160 to 200 g / equivalent.

  In the present invention, the term “epoxy equivalent” means the same as a commonly used meaning, and means the mass of an epoxy compound containing 1 g equivalent of an epoxy group, which is expressed in units of g / equivalent, and is usually a method described in JIS K 7236. Measured by

  The low molecular weight epoxy resin thus obtained is subjected to a condensation reaction with the phenol compound represented by the formula (2), and the polymer contains n = 1 or more in the formula (1) without losing crystallinity. The ratio can be increased. The charging ratio between the epoxy resin and the compound represented by formula (2) is generally 0.05 to 0.95 mol, preferably 0.05 to 0.95 mol of the phenolic hydroxyl group of the compound of formula (2) with respect to 1 mol of the epoxy group of the epoxy resin. Is preferably in a ratio of 0.1 to 0.9 mol.

  The use of a catalyst is preferred to promote the reaction. Examples of the catalyst include benzyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, quaternary phosphonium salts such as ethyltriphenylphosphonium iodide, triphenylphosphine, tetramethylammonium chloride, sodium hydroxide, A potassium hydroxide etc. are mentioned.

  The usage-amount of this catalyst is 0.01-10 weight part normally with respect to 1 mol of epoxy groups of an epoxy resin, Preferably it is 0.05-5 weight part.

  Of the above catalysts, quaternary phosphonium salts are preferred because they easily give a linear epoxy resin, and since these salts are water-soluble, they can be easily removed by washing with water after the reaction.

  In this reaction, it is preferable to use a solvent in order to control the reaction temperature. Examples of the solvent include cyclopentanone, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide and the like. The amount used is usually about 5 to 150% by weight, preferably about 10 to 100% by weight, based on the total weight of the epoxy resin and the phenolic compound represented by formula (2).

  The reaction temperature is usually 60 to 180 ° C, preferably 70 to 160 ° C. The progress of the reaction can be followed by GPC (gel permeation chromatography) or the like, and is performed until the phenolic compound represented by the formula (2) is no longer detected. The reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.

  After completion of the reaction, the reaction solution may be cooled as it is to crystallize the desired epoxy resin and collected by filtration, but it is cooled by adding a poor solvent for the desired epoxy resin (a solvent with low solubility of epoxy resin). Is preferred.

  Further, this reaction was performed in a poor solvent of the target epoxy resin, and after cooling, a good solvent (a solvent having high solubility of the target epoxy resin) such as N, N-dimethylformamide and dimethyl sulfoxide was added. The epoxy resin represented by the above formula (1) obtained by dissolving the crystals once and adding a poor solvent thereto is preferable because the temperature range showing its liquid crystallinity becomes wider.

  Examples of the poor solvent include methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, methanol, ethanol, water and the like. The amount of the poor solvent used is usually about 50 to 400% by weight, preferably about 100 to 300% by weight, based on the total weight of the epoxy resin and the compound represented by formula (2).

  By separating the precipitated crystals by filtration and drying, an epoxy resin contained in the photosensitive resin composition of the present invention and used as a curing agent (D) can be obtained.

  The epoxy resin is represented by the above formula (1), n represents the number of repetitions, and the average value is usually a positive number of 0 to 7, preferably 1 to 7, and a positive number of 3 to 5 is particularly preferable. The content ratio of compounds with different n can be determined by HPLC using a GPC column, and the average value of n can also be determined therefrom.

  As measurement conditions, an eluent in which the epoxy resin is completely dissolved is used, and the column is suitable for the eluent, and it is desirable that n = 0 and n = 1 be separable.

  The epoxy resin obtained by the above reaction preferably has a compound content of n = 0 of 25% or less (area% by GPC, the same shall apply hereinafter), particularly preferably 20% or less, and particularly preferably Is 5% or less. When the content ratio of the compound with n = 0 exceeds 25%, the melting start temperature is broad and low, and the developability is poor.

  On the other hand, the temperature range showing liquid crystallinity may be wider when a low molecular weight compound is present, for example, in an amount of about 8 to 15%. do it.

  When the epoxy resin represented by the formula (1) is measured by DSC (differential thermal analyzer), many endothermic peaks are observed at two or more locations. The peaks may overlap, which indicates that the epoxy resin has liquid crystallinity. Although the correlation between the liquid crystal property and the thermal stability and excellent developability of the photosensitive resin composition in the present invention is not clear at present, since it is a substance showing a liquid crystal state, it is in the epoxy resin system. Unlike the usual liquid epoxy resin, the existence state in is considered to be able to achieve both excellent thermal stability and developability. Furthermore, it is possible to specify the temperature range in which the epoxy resin exhibits optical anisotropy by observing while raising the temperature using a polarizing microscope, and the temperature range is around 80 to 160 ° C. The epoxy resin exhibits liquid crystallinity over such a wide temperature range.

  Among the epoxy resins represented by the formula (1), an epoxy resin with n = 0 also exhibits liquid crystallinity, but the epoxy resin is usually liquid at room temperature or crystalline with a melting point of 40 ° C. or less and exhibits liquid crystallinity. The temperature range shown is very narrow.

  The addition ratio of the curing agent (D) in the photosensitive resin composition of the present invention is preferably an amount of 200% or less of the equivalent calculated from the solid content acid value of the photosensitive alkaline aqueous solution-soluble resin (A) and the amount used. . In addition, since the melting start temperature can be made high if the compound of n = 0 is 25 weight% or less, developability and the storage stability as a resin composition can be improved. That is, the addition ratio of the curing agent (D) contained in the alkaline aqueous solution-soluble photosensitive resin composition can vary in relation to the composition of the composition and the acid value of the photosensitive alkaline aqueous solution-soluble resin (A), When the solid content of the aqueous alkaline resin-soluble photosensitive resin composition is 100% by weight, it is about 3 to 30% by weight.

  Furthermore, the photosensitive resin composition of the present invention includes various additives as required, such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay and the like. The composition includes a filler, a thixotropic agent such as Aerosil, a colorant such as phthalocyanine blue, phthalocyanine green, and titanium oxide, a leveling agent or antifoaming agent such as silicone or a fluorine-based agent, or a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether. It can be added for the purpose of enhancing various performances.

  The photosensitive resin composition of the present invention contains the photosensitive aqueous alkali-soluble resin (A), the reactive crosslinking agent (B), the photopolymerization initiator (C), and the curing agent (D).

  The photosensitive alkaline aqueous solution-soluble resin (A) of the present invention is usually soluble in an alkaline aqueous solution, but is also soluble in the solvent used in the above production, and when used for a solder resist, a plating resist, etc. It is also possible to develop with these solvents.

  When the photosensitive resin composition of the present invention is used as a liquid resist, the curing agent (D) may be mixed in advance in the resin composition, but it is mixed before application to the printed wiring board. Can also be used. That is, by mixing into a two-pack type of a main agent solution mainly composed of the above-mentioned photosensitive alkaline aqueous solution-soluble resin (A) component and a curing agent solution mainly composed of the curing agent (D), and mixing them in use. And such use is preferred.

  The photosensitive resin composition of the present invention can also be used as a dry film resist having a structure in which a resin composition is sandwiched between a support film and a protective film.

  When used as a dry film type resist, the above-mentioned photosensitive alkaline aqueous solution-soluble resin (A), reactive crosslinking agent (B), photopolymerization initiator (C), curing agent (D), filler, additive, etc. Is used as a photosensitive layer, and the photosensitive layer is sandwiched between a support layer and a protective layer to obtain a dry film. In use, the protective layer is peeled off, laminated on the substrate, exposed to light, and the support layer is peeled off for development.

  The preparation of the dry film is specifically performed as follows, but is not limited thereto.

  Add the alkali water-soluble resin solution (A), the reactive crosslinking agent (B), the photopolymerization initiator (C), the curing agent (D), the thermosetting catalyst and the concentration adjusting solvent, and knead uniformly with a bead mill. Disperse to obtain a resist resin composition.

  Next, the film is uniformly applied to a support film such as a polyethylene terephthalate film by a roll coating method, and is passed through a hot air drying furnace having a temperature sufficient to volatilize the solvent used, for example, a temperature of 70 ° C. and an air volume. A resin layer having a thickness of 30 μm is formed, and a protective film such as a polyethylene film is attached on the resin layer to obtain a dry film. For example, the obtained dry film is applied to a printed circuit board such as a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll, and a resin layer is applied to the entire surface of the substrate while peeling off the protective film. . The attaching process is preferably performed in a vacuum. Ultraviolet rays are irradiated through a mask on which a circuit pattern is drawn using an ultraviolet exposure device. Spray development is performed with an alkaline aqueous solution such as a 1% sodium carbonate aqueous solution, the resin not exposed to ultraviolet rays is removed, washed and dried, and the printed circuit board is heated and cured with a hot air drier to obtain a cured film.

  The photosensitive resin composition (liquid or film-like) of the present invention is useful as a resist material such as an insulating material between electronic components, an optical waveguide connecting optical components, a solder resist for printed circuit boards, and a coverlay. In addition, it can also be used as a color filter, printing ink, sealant, paint, coating agent, adhesive and the like.

  A cured product obtained by curing the photosensitive resin composition of the present invention by irradiation with active energy rays such as ultraviolet rays is also included in the present invention. Curing by irradiation with active energy rays such as ultraviolet rays can be performed by a conventional method. For example, in the case of irradiating ultraviolet rays, an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used.

  The cured product of the photosensitive resin composition of the present invention is used, for example, as a resist film, an interlayer insulating material for a build-up method, or an optical waveguide as an electric / electronic / optical base material such as a printed board, an optoelectronic board, or an optical board. Is done. Specific examples of articles having these base materials include computers, home appliances, and portable devices. These substrates and articles are also included in the present invention.

  The thickness of the cured product layer is about 0.5 to 160 μm, preferably about 1 to 100 μm.

Shown for use in printed wiring boards, for example, by using a liquid resin composition on a printed wiring board by methods such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc. The photosensitive resin composition of this invention is apply | coated with the film thickness of 5-160 micrometers, and a coating film is formed by drying (prebaking) at the temperature of 50-110 degreeC normally, Preferably it is 60-100 degreeC. Then, a developer that irradiates the coating film directly or indirectly with an active energy ray such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm ² through a photomask having an exposure pattern such as a negative film, and describes an unexposed portion later. For example, development is performed by spraying, rocking dipping, brushing, scrubbing, or the like. Thereafter, if necessary, further irradiation with ultraviolet rays is performed, and then heat treatment is usually performed at a temperature of 100 to 200 ° C., preferably 140 to 180 ° C., thereby being excellent in gold plating resistance, heat resistance, solvent resistance, and acid resistance. A printed wiring board having a permanent protective film having excellent properties such as properties, adhesion, and flexibility can be obtained.

  Examples of the alkaline aqueous solution used for development include inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, and tetramethyl hydroxide. Organic alkaline aqueous solutions such as ammonium, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.

  As described above, an organic solvent can also be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example.

Synthesis example 1
EOCN-103S (polyfunctional cresol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy compound (a) having two or more epoxy groups in a molecule in a 3 L flask equipped with a stirrer and a reflux tube: 210.0 g / equivalent) is 860.0 g, 288.3 g of acrylic acid (molecular weight: 72.06) is used as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and carbitol acetate is used as the reaction solvent. Was charged with 4.921 g of 2,6-di-t-butyl-p-cresol as a thermal polymerization inhibitor and 4.921 g of triphenylphosphine as a reaction catalyst, and the acid value of the reaction solution at a temperature of 98 ° C. Was reacted until 0.5 mg · KOH / g or less, to obtain an epoxycarboxylate compound.

  Next, 169.8 g of carbitol acetate as a reaction solvent and 201.6 g of tetrahydrophthalic anhydride as a polybasic acid anhydride (c) were charged into this reaction solution, and reacted at 95 ° C. for 4 hours to obtain a photosensitive alkaline aqueous solution-soluble resin. (A) A resin solution containing 67% by weight was obtained (this solution is referred to as A-1). When the acid value was measured, it was 69.4 mg · KOH / g (solid content acid value: 103.6 mg · KOH / g).

Synthesis example 2
As an epoxy compound (d) having two epoxy groups in a molecule in a 3 L flask equipped with a stirrer and a reflux tube, Nippon Kayaku RE-310S (bifunctional bisphenol-A type epoxy resin, epoxy equivalent: (184.0 g / equivalent)) 368.0 g, 141.2 g of acrylic acid (molecular weight: 72.06) as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and hydroquinone monomethyl as the thermal polymerization inhibitor 1.02 g of ether and 1.53 g of triphenylphosphine as a reaction catalyst were charged and reacted at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mg · KOH / g or less, and an epoxycarboxylate compound (theoretical molecular weight) : 509.2).

Next, 755.5 g of carbitol acetate as a reaction solvent, 268.3 g of dimethylolpropionic acid (molecular weight: 134.16) as a carboxylic acid compound (f) having two hydroxyl groups in the molecule, 1.08 g of 2-methylhydroquinone as a polymerization inhibitor and 140.3 g of spiroglycol (molecular weight: 304.38) as an arbitrary diol compound (g) were added, and the temperature was raised to 45 ° C. To this solution, 485.2 g of trimethylhexamethylene diisocyanate (molecular weight: 210.27) was gradually added dropwise as a diisocyanate compound (e) so that the reaction temperature did not exceed 65 ° C. After completion of the dropwise addition, the temperature is raised to 80 ° C., and the mixture is reacted for 6 hours until absorption near 2250 cm ⁻¹ disappears by infrared absorption spectrum measurement, and contains 65% by weight of the photosensitive aqueous alkali-soluble resin (A) of the present invention. A resin solution was obtained (this solution is referred to as A-2). When the acid value was measured, it was 52.0 mg · KOH / g (solid content acid value: 80.0 mg · KOH / g).

Synthesis example 3
A phenol compound represented by the above formula (2) (trade name p, p′-BPF; manufactured by Honshu Chemical Co., Ltd.) 100 while purging a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer with nitrogen purge. 370 parts of epichlorohydrin and 26 parts of methanol were added to the part, and the temperature was raised to 65-70 ° C. with stirring and dissolved completely. Then, 40.4 parts of flaky sodium hydroxide was added in portions over 100 minutes under reflux conditions. did. Thereafter, heating was further performed at 70 ° C. for 1 hour. Subsequently, 150 parts of water was added and washed twice, and excess epichlorohydrin and the like were removed from the oil layer under heating and reduced pressure. 312 parts of methyl isobutyl ketone was added to the residue and dissolved, and 10 parts of 30% aqueous sodium hydroxide solution was added at 70 ° C. and reacted for 1 hour. After the reaction, washing with water was performed three times, and methyl isobutyl ketone was distilled off under reduced pressure by heating to obtain 150 parts of an epoxy resin represented by the formula (1). The epoxy equivalent of the obtained epoxy resin was 170 g / equivalent, the viscosity at 25 ° C. was 850 mP · s (E-type viscometer; the same applies hereinafter), and the total chlorine content was 1100 ppm.

  85 parts of the resulting epoxy resin, 25 parts of the compound represented by the formula (2) and 55 parts of cyclopentanone were added and dissolved under stirring, and 0.09 part of triphenylphosphine was added. After reacting under reflux for 4 hours and confirming that the compound represented by formula (2) completely disappeared by GPC, stirring was continued and the reaction was continued for a total of 6 hours, followed by cooling to 80 ° C. and methyl isobutyl ketone 220 Part was added to precipitate crystals. The crystals were filtered and dried to obtain 85 parts of white powdery crystalline epoxy resin (D-1). It was 127 degreeC when melting | fusing point of the obtained epoxy resin (D-1) was measured with DSC (differential thermal analyzer). The amount of n = 0 in the formula (1) measured by GPC was 2.6 area%, and the epoxy equivalent was 697 g / equivalent. The number of repetitions n was 2.3 as an average value.

In addition, the measurement of GPC was implemented according to the following conditions.
Equipment: TOSOH HLC-8220 GPC
Eluent: Tetrahydrofuran column: TOSOH TSKgel SuperHZM-N × 1, TSKgel SuperHZ1000 × 2, in-line flow rate: 0.3 ml / min Temperature: 40 ° C.
Detector: Differential refractometer

Examples 1 and 2 and Comparative Example 1
(A-1), (A-2) and (D-1) obtained in Synthesis Example 1, Synthesis Example 2 and Synthesis Example 3 and Japan Epoxy Resin Epicoat 4003P were mixed at the blending ratio shown in Table 1. As necessary, the mixture was kneaded with a three-roll mill to obtain a photosensitive resin composition.

This was applied to a printed circuit board by screen printing so that the dry film thickness was 15 to 25 μm, and dried for 30 minutes with an 80 ° C. hot air drier. Next, ultraviolet rays (500 mJ / cm ² ) are irradiated through a mask on which a circuit pattern is drawn using an ultraviolet exposure apparatus (Oak Seisakusho, model HMW-680GW), and then spray development is performed with a 1% sodium carbonate aqueous solution. The resin in the irradiated part was removed. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction with a hot air dryer at 150 ° C. for 60 minutes to obtain a cured film.

Epicoat 4003P was measured by HPLC according to the following conditions.
Instrument: TOSOH 8020 Series Eluent: Acetonitrile: Water = 7: 3 → 10: 0 Gradient column: TOSOH TSKgel ODS-80TM
Flow rate: 0.8 ml / min Temperature: 40 ° C
Detector: UV detector (254 nm)

  About composition or cured product, tackiness, developability, resolution, photosensitivity, surface gloss, substrate warp, flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, resistance The test of PCT property and thermal shock resistance was conducted. The results are shown in Table 2. The test method and evaluation method are as follows.

(Tackiness) Absorbent cotton was rubbed on the dried film applied to the substrate, and the tackiness of the film was evaluated.
○ ··················································…

(Developability) The following evaluation criteria were used.
○ ············································································································································

(Resolution) A negative pattern of 50 μm is brought into intimate contact with the dried coating film and irradiated with ultraviolet rays having an integrated light quantity of 200 mJ / cm ² . Next, development is performed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the transfer pattern is observed with a microscope. The following criteria were used:
○ ··· Pattern edge is straight and resolved × ··· Peeled or jagged pattern edge

(Photosensitivity) Step tablet 21 (manufactured by Kodak Co., Ltd.) is brought into close contact with the dried coating film and irradiated with ultraviolet rays with an integrated light amount of 500 mJ / cm ² . Next, development is performed with a 1% sodium carbonate aqueous solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the number of stages of the coating film remaining without development is confirmed.

(Surface gloss) The dried coating film is exposed to 500 mJ / cm ² of ultraviolet rays. Next, development is performed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the dried cured film is observed. The following criteria were used:
○ ・ ・ ・ ・ No cloudiness is seen at all × ・ ・ ・ ・ Slight cloudiness is seen

(Substrate sled) The following criteria were used.
○ ········································································· •

(Flexibility) The cured film is bent and observed at 180 degrees. The following criteria were used:
○ ···· No crack on the film surface × ··· The film surface breaks

(Adhesiveness) According to JIS K5400, 100 test pieces having 1 mm diameters were made on a test piece, and a peeling test was performed using cello tape (registered trademark). The peeled state of the goblet was observed and evaluated according to the following criteria.
○ ···········································

  (Pencil hardness) Evaluation was performed according to JIS K5400.

(Solvent resistance) The test piece is immersed in isopropyl alcohol at room temperature for 30 minutes. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film and there is no swelling or peeling × ·········

(Acid resistance) The test piece is immersed in a 10% hydrochloric acid aqueous solution at room temperature for 30 minutes. After confirming that there was no abnormality in the external appearance, a peeling test with cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film and there is no swelling or peeling × ········

(Heat resistance) A rosin-based plax was applied to a test piece and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as 1 cycle and repeated 3 cycles. After being allowed to cool to room temperature, a peeling test with Cellotape (registered trademark) was conducted, and the following criteria were evaluated.
○ ··· No abnormalities in the appearance of the coating film and no blistering or peeling × ······

(Gold plating resistance) The test substrate was immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 vol% aqueous solution of Metex L-5B) for 3 minutes, washed with water, and then in a 14.4 wt% ammonium persulfate aqueous solution at room temperature. The test substrate was immersed for 3 minutes and then washed with water. Further, the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and then washed with water. This substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, Melplate Ni-865M 20 vol). After being immersed in a 20% aqueous solution, pH 4.6) for 20 minutes and nickel-plated, it was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water. Next, the test substrate was immersed for 10 minutes in a gold plating solution at 95 ° C. (Meltex, aqueous solution of Aurolectroles UP 15 vol% and 3 vol% potassium cyanide, pH 6), subjected to electroless gold plating, washed with water, It was immersed in warm water at 60 ° C. for 3 minutes, washed with water and dried. Cellotape (registered trademark) was adhered to the obtained electroless gold plating evaluation substrate, and the state when peeled was observed.
○ ···· No abnormality at all ····· Slightly peeled

(PCT resistance) After leaving the test substrate in water at 121 ° C. and 2 atm for 96 hours, it was confirmed that there was no abnormality in appearance, a peeling test was performed with cello tape (registered trademark), and evaluation was performed according to the following criteria.
○ ··· There is no abnormality in the appearance of the coating film and there is no swelling or peeling × ········

(Thermal shock resistance) A thermal history with one cycle of −55 ° C./30 minutes and 125 ° C./30 minutes was added to the test piece, and after 1000 cycles, the test piece was observed with a microscope and evaluated according to the following criteria.
○ ·················································· /

  As is clear from the above results, the photosensitive resin composition of the present invention using the photosensitive alkaline aqueous solution-soluble resin and the curing agent represented by the formula (1) has no tackiness and high sensitivity, and its cured film. Is excellent in soldering heat resistance, chemical resistance, gold plating resistance, etc., and does not generate cracks on the surface of the cured product and exhibits excellent flexibility. In the resin composition of the present invention, no residue is generated, the developability is excellent, and the residue is generated in the resin composition of the comparative example using a bisphenol F type resin having a low 4-4 ′ bisphenol F content as a curing agent. Therefore, it is clear that the developability is inferior.

Claims (7)

In the photosensitive resin composition containing the photosensitive alkaline aqueous solution-soluble resin (A), the reactive crosslinking agent (B), the photopolymerization initiator (C) and the curing agent (D), the curing agent (D) is represented by the formula ( 1)

[Wherein n represents the number of repetitions. ]
A photosensitive resin composition which is a 4,4′-form bisphenol F-type epoxy resin represented by the formula:   The photosensitive resin composition according to claim 1, wherein n of the curing agent (D) is a positive number of 1 to 7, and the melting point thereof is a crystal of 80 to 150 ° C.   A photosensitive alkaline aqueous solution-soluble resin (A) is obtained by a reaction between an epoxy compound (a) having two or more epoxy groups in the molecule and a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. The photosensitive resin composition according to claim 1, which is a reaction product of an epoxycarboxylate compound and a polybasic acid anhydride (c).   Epoxy obtained by reaction of photosensitive aqueous alkali-soluble resin (A) by reaction of epoxy compound (d) having two epoxy groups in the molecule and monocarboxylic acid compound (b) having ethylenically unsaturated groups in the molecule Reaction product of carboxylate compound and diisocyanate compound (e), carboxylic acid compound (f) having two hydroxyl groups in the molecule, and diol compound (g) having no carboxyl group as an optional component, or The photosensitive resin composition according to claim 1 or 2, which is a reaction product of a reaction product and a polybasic acid anhydride (c) as an optional component.   Hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-4.   The base material which has a layer of the hardened | cured material of Claim 5.   An article comprising the substrate according to claim 6.