JP4400926B2 - Photosensitive resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a photosensitive resin composition using a crystalline bisphenolfluorene epoxy compound as a curing agent and a cured product thereof. More specifically, it is useful as a solder resist for printed wiring boards, interlayer insulation materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, photosensitive optical waveguides, etc., developability, heat resistance, thermal stability The present invention relates to a resin composition that gives a cured product excellent in electrical insulation, adhesion, chemical resistance, plating resistance, and the like, and the cured product.

  A photosensitive resin composition using an epoxy carboxylate compound is excellent in balance of properties such as environmental, thermal and mechanical properties and adhesion to a substrate. For this reason, it has been used for a long time in the fields of paints, coatings, adhesives and the like. Recently, it has been used in a wide range of industrial fields such as electrical / electronic component manufacturing applications and printed circuit board manufacturing applications, and its application range is expanding. However, with the expansion of this application field, it has become necessary to further add high functions such as heat resistance and adhesion to photosensitive resin compositions using epoxycarboxylate compounds. Development of various photosensitive resin compositions has been promoted mainly for printed circuit board manufacturing applications.

  Printed wiring boards used in portable devices and other devices that are required to be smaller and lighter and improve communication speeds are becoming more accurate and denser, and as a result, the demand for solder resists is becoming higher. Although there is a need for substrate adhesion, high insulation, and electroless gold plating resistance while having heat resistance and thermal stability higher than conventional ones, currently commercially available solder resists are not sufficient for these. . For example, Patent Document 1 and Patent Document 2 include an epoxy resin obtained by glycidyl etherification of an alcoholic hydroxyl group of a compound obtained by adding an ethylene oxide chain to bisphenolfluorene, a resin composition containing the epoxy resin, and a cured product thereof. Is described. However, there is no description about the use as a photosensitive resin composition.

  Moreover, although the composition containing a bisphenol fluorene epoxy compound is described in patent document 3, there is no description as a structural component of the radical polymerization type photosensitive resin composition. Patent Document 4 and Patent Document 5 describe a crystalline epoxy resin having a bisphenolfluorene skeleton and a thermosetting composition used for a sealant containing the same, but for use as a photosensitive resin composition. There is no description.

JP-A-10-36485 Japanese Patent Laid-Open No. 10-45871 Japanese Patent No. 2820553 JP 2004-35762 A JP 2004-43333 A

As described above, currently available solder masks cannot sufficiently meet the demand for high performance required for printed wiring boards.
The object of the present invention is excellent in photosensitivity to active energy rays in order to cope with fine images that can correspond to a high-performance printed wiring board, and can be patterned by development with an aqueous alkaline solution, and obtained curing can be achieved. An object of the present invention is to provide a resin composition having a film satisfying various properties required for a solder mask and the like, and a cured product thereof.

In order to solve the above-mentioned problems, the present inventors have completed the present invention as a result of intensive studies.
That is, the present invention

1) A photosensitive resin composition containing an alkaline aqueous solution-soluble resin (A), a reactive crosslinking agent (B), a radical polymerization photopolymerization initiator (C) and a curing agent (D), wherein the curing agent (D) Is the following formula (1)

[Wherein n represents an average value of 0 to 3, R ¹ represents a hydrogen atom, a halogen atom, a C _{1 to} C ₄ lower alkyl group or a phenyl group, and R ² represents a hydrogen atom or a methyl group. . ]
A photosensitive resin composition which is a crystalline compound represented by:
2) The photosensitive resin composition according to 1) above, wherein the curing agent (D) is a crystalline compound in which n is 0 in formula (1), and R ¹ and R ² are hydrogen atoms;
3) An alkaline aqueous solution-soluble resin (A) reacts an epoxy compound (a) having two or more epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. The photosensitive resin composition as described in 1) or 2) above, which is a compound obtained by reacting the resulting epoxycarboxylate compound with a polybasic acid anhydride (c);

4) Hardened | cured material of the photosensitive resin composition of any one of said 1) -3);
5) A substrate having a layer of the cured product as described in 4) above;
6) An article having the substrate according to 5) above;
7) A method for producing a coating film, comprising the steps of applying the photosensitive resin composition according to any one of 1) to 3) above to a substrate, photocuring, developing treatment and heat treatment;
8) The production method according to 7) above, wherein the coating film is a solder mask for printed wiring boards, a solder mask for flexible printed wiring boards, an interlayer insulating film for multilayer printed wiring boards, or an optical waveguide;
About.

  The photosensitive resin composition using the crystalline curing agent of the present invention is less toxic, has excellent tackiness, photosensitivity (photosensitivity), thermal stability, and can be patterned by development with an alkaline aqueous solution that is environmentally friendly. A cured product obtained by curing the photosensitive resin composition sufficiently satisfies adhesion, pencil hardness, solvent resistance, acid resistance, solder heat resistance, electroless gold plating resistance, and the like. In particular, it is suitable as a photosensitive resin composition that can be used for solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists or photosensitive optical waveguide formation.

The photosensitive resin composition of the present invention comprises an alkali aqueous solution-soluble resin (A), a reactive crosslinking agent (B), a radical polymerization photopolymerization initiator (C), and the above formula (1) [where n is an average value. And R ¹ represents a hydrogen atom, a halogen atom, a C _{1 to} C ₄ lower alkyl group or a phenyl group, and R ² represents a hydrogen atom or a methyl group. ] As a hardening | curing agent (D), the crystalline compound represented by this is contained.

  Although it does not specifically limit as aqueous alkali solution-soluble resin (A) contained in the photosensitive resin composition of this invention, The epoxy compound (a) which has two or more epoxy groups in a molecule | numerator, and ethylenic unsaturated in a molecule | numerator A compound obtained by reacting a polybasic acid anhydride (c) with an epoxycarboxylate compound obtained by reacting a monocarboxylic acid compound (b) having a group is preferred. The epoxy compound (a) having two or more epoxy groups is preferably an epoxy compound (a) having an epoxy equivalent of 100 to 900 g / equivalent. When the epoxy equivalent is less than 100, the molecular weight of the resulting aqueous alkali-soluble resin (A) is small, and film formation may be difficult, or sufficient flexibility may not be obtained, and the epoxy equivalent exceeds 900. In this case, the introduction rate of the monocarboxylic acid compound (b) having an ethylenically unsaturated group may be lowered, and the photosensitivity may be lowered.

  Specific 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). Resin, bisphenol-F type epoxy resin, etc.), biphenol type epoxy resin, bisphenol-A novolac 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, Inc.), D.I. E. N438 (made by Dow Chemical Co.), Epicoat 154 (made by Yuka Shell Epoxy Co., Ltd.), EPPN-201, RE-306 (all made by Nippon Kayaku Co., Ltd.), etc. are mentioned.
Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR. -6650 (made by Union Carbide), ESCN-195 (made by Sumitomo Chemical Co., Ltd.), etc. are mentioned.

Examples of the trishydroxyphenylmethane type epoxy resin include, for example, EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co.), Epicoat E1032H60 (oil) Chemical Shell Epoxy Co., Ltd.).
Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

  Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (both made by oil-based shell epoxy), UVR-6410 (made by Union Carbide), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei Co., Ltd.), etc. Examples thereof include bisphenol-F type epoxy resin.

As a biphenol type epoxy resin, for example, biphenol type epoxy resin such as NC-3000, NC-3000-H (both manufactured by Nippon Kayaku Co., Ltd.), YX-4000 (manufactured by Yuka Shell Epoxy Co., Ltd.) Bixylenol type epoxy resin, YL-6121 (manufactured by Yuka Shell Epoxy Co., Ltd.), etc.
Examples of the bisphenol A novolac type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.), Epicoat E157S75 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like.

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like.
Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.).
Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule include acrylic acids, crotonic acid, α-cyanocinnamic acid, and cinnamic acid.
Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydride, and (meth) acrylate having one hydroxyl group in one molecule. Half-esters which are equimolar reactants with derivatives, reaction products of (meth) acrylic acid and ε-caprolactone, saturated or unsaturated dibasic acids and unsaturated group-containing monoglycidyl compounds (for example, monoglycidyl (meta And half-esters which are equimolar reaction products with acrylate derivatives).
The monocarboxylic acid compound (b) having an ethylenically unsaturated group includes (meth) acrylic acid, (meth) acrylic acid and ε-caprolactone in terms of photosensitivity when the photosensitive resin composition of the present invention is used. Especially preferred are the reaction products of

  As the polybasic acid anhydride (c) used for producing the alkaline aqueous solution-soluble resin (A) of the present invention, any polybasic acid anhydride (c) may be used as long as it has one or more acid anhydride structures in the molecule. Specifically, for example, succinic anhydride, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, 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′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ester Tertetracarboxylic dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane, 5- (2 , 5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) ) -Naphtho [1,2-c] furan-1,3-dione is selected from one or more polybasic acid anhydrides.

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

  Examples of the reactive crosslinking agent (B) contained in the photosensitive resin composition of the present invention include (meth) acrylates. Specifically, for example, 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) ) Acrylates, 1,4-butanediol mono (meth) acrylates) and polybasic acid anhydrides (eg succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) Half-esters, polyethylene glycol di (me ) Acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, and ε- of hydroxypentaline neopentyl glycol Di (meth) acrylate of caprolactone adduct (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetra (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone Poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl compounds (eg butyl glycidyl ether, phenyl glycidyl ether, polyethylene Glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylol Propane polyethoxypolyglycidyl ether and the like) and epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid.

  The content of the reactive crosslinking agent (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 radical polymerization type photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention is not particularly limited as long as radicals are generated by active energy rays. Specifically, for example, benzoin, benzoin methyl ether, Benzoins such as benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one , Acetophenones such as 1-hydroxy cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tert-butyl Antra Anthraquinones such as non, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal Benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide and the like.

  The content ratio of the radical polymerization type 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.

  These photopolymerization initiators (C) can be used alone or in admixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, It can be used in combination with an accelerator such as a benzoic acid derivative such as N, N-dimethylaminobenzoic acid isoamyl ester. When these accelerators are added, the addition amount is preferably 100% or less with respect to the radical polymerization type 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 an average value of 0 to 3, R ¹ represents a hydrogen atom, a halogen atom, C _1. a lower alkyl group or a phenyl group -C _4, R ² represents a hydrogen atom or a methyl group. ] The crystalline compound represented by this.
In the formula (1) in the curing agent (D), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and examples of the C _{1 to} C ₄ lower alkyl group include a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group can be mentioned.
Furthermore, a crystalline compound in which n is 0, and R ¹ and R ² are hydrogen atoms can be taken out as described in the examples below. For example, thermal stability, tackiness, etc. can be obtained by using the compound. The characteristics are improved in terms of surface, which is preferable.
The curing agent (D) reacts by heating with the carboxyl group remaining in the resin coating film after the photosensitive resin composition of the present invention is cured with active energy rays, and further has a stronger chemical resistance. A membrane can be obtained.

  The epoxy equivalent of the curing agent (D) is in the range of 100 to 800 g / eq, more preferably in the range of 150 to 500 g / eq, and the melting point is preferably in the range of 70 to 200 ° C, and is preferably in the range of 90 to 170 ° C. A range is particularly preferred.

As a content rate of a hardening | curing agent (D), the quantity of 200% or less of the equivalent of a carboxyl group calculated from the solid content acid value of alkali aqueous solution-soluble resin (A) and its usage-amount is preferable.
When this amount exceeds 200%, the developability of the photosensitive resin composition of the present invention may be remarkably lowered, which is not preferable.

  Furthermore, various additives as necessary, for example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, thixotropic agent such as aerosil, etc .; phthalocyanine Coloring agents such as blue, phthalocyanine green and titanium oxide, silicone, fluorine leveling agents and antifoaming agents; thermosetting catalysts such as melamine; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether enhance the performance of the composition. It can be added for the purpose.

  In addition, said hardening | curing agent (D) may be previously mixed with the resin composition, and can also be mixed and used before application | coating to a printed wiring board etc. That is, it is blended into a two-pack type of a main agent solution mainly composed of the component (A) and an epoxy curing accelerator and the like and a curing agent solution mainly composed of the curing agent (D), and these are mixed in use. May be used. Furthermore, you may use the solvent mentioned later suitably as needed.

  The alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin composition of the present invention includes, for example, an epoxy compound (a) having two or more epoxy groups in the molecule and an ethylenically unsaturated group in the molecule. Reaction of the alcoholic hydroxyl group of the epoxycarboxylate compound obtained by the reaction with the monocarboxylic acid compound (b) having (hereinafter referred to as the first reaction) and the polybasic acid anhydride (c) (hereinafter referred to as the second reaction) ).

  The first reaction is a solvent-free or solvent having no hydroxyl group, specifically, for example, ketones such as acetone, ethyl methyl ketone and cyclohexanone, and aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene. , Glycol ethers such as ethylene glycol 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, Succinic acid Esters such as dialkyl and dialkyl adipates, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and the reactive crosslinking agent (B) described above It can carry out in the single or mixed organic compound chosen from.

  The raw material charge ratio in this reaction is preferably 80 to 120 equivalent% of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule with respect to 1 equivalent of the epoxy group of the epoxy compound (a). When deviating from this range, gelation may occur during the second reaction, or the thermal stability of the finally obtained aqueous alkali-soluble resin (A) may be lowered.

In the reaction, it is preferable to use a catalyst for promoting the reaction. When the catalyst is used, the amount used is about 0.1 to 10% by weight based on the total weight of the reaction raw materials. The reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.
Specific examples of the catalyst include triethylamine, benzyldimethylamine, dimethylaminopyridine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, Examples thereof include chromium octoate and zirconium octoate.

Moreover, as a thermal polymerization inhibitor, use of hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 2,6-di-tert-butyl-p-cresol and the like is preferable.
The first reaction has an end point when the acid value of the sample is 1 mg · KOH / g or less, preferably 0.5 mgKOH / g or less, with appropriate 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 a solution containing the resin. It is the amount (mg) of potassium hydroxide required to neutralize 1 g, 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 for reaction after completion of the first reaction. Although the reaction can be carried out without a catalyst, a basic catalyst can be used to promote the reaction. When the catalyst is used, the amount used is preferably 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.
The basic catalyst is not particularly limited as long as it does not react with the polybasic acid anhydride (c).

  As the charged amount of the polybasic acid anhydride (c), it is preferable to add a calculated amount such that the solid content acid value of the alkaline aqueous solution-soluble resin (A) is 50 to 150 mg · KOH / g. When the solid content acid value is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and the resin composition remains as a residue during the developing operation, and in the worst case, the development cannot be performed. Moreover, when the solid content acid value exceeds 150 mg · KOH / g, the solubility in an alkaline aqueous solution becomes too high, and problems such as peeling of the cured resist may occur.

The alkaline aqueous solution-soluble resin (A) of the present invention thus obtained can be isolated by removing it by an appropriate method when a solvent is used in the reaction.
The alkaline aqueous solution-soluble resin (A) contained in the photosensitive resin of the present invention is soluble in an alkaline aqueous solution, but it is also soluble in the above-mentioned solvent, and when used in a solder resist, a plating resist, etc. It is also possible to develop.

  The crystalline epoxy compound represented by the above formula (1) as the curing agent (D) contained in the photosensitive resin composition of the present invention is, for example, a compound of the following formula (2) such as epichlorohydrin. It can be obtained by dissolving in epihalohydrin, removing the solvent and epihalohydrin as necessary after reaction in the presence of an alkali metal hydroxide, and then adding an organic solvent to precipitate crystals of the desired epoxy resin.

［式中、ｎ、Ｒ^１、Ｒ^２は前記と同じ意味を示す。］
式（２）の化合物は、公知の合成法またはそれに準じた方法にて製造することもでき、あるいは、市販されている場合、その化合物を使用することもできる。

[Wherein, n, R ¹ and R ² have the same meaning as described above. ]
The compound of the formula (2) can be produced by a known synthesis method or a method analogous thereto, or when it is commercially available, the compound can be used.

  In the above reaction, an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and continuously under reduced pressure or normal pressure. A method of distilling water and epihalohydrin, separating the distilling portion to remove water, and continuously returning epihalohydrin to the reaction system may be used. Examples of the alkali metal hydroxide that can be used include alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide.

  The amount of epihalohydrin used in this reaction is 0.8 to 12 molar equivalents, preferably 0.9 to 11 molar equivalents, relative to 1 equivalent of the phenolic or alcoholic hydroxyl group of the compound represented by the above formula (2). is there. At this time, in order to increase the solubility of the compound and allow the reaction to proceed smoothly, an alcohol such as methanol, ethanol, propanol or butanol, or an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide is added to react. It is preferable to carry out.

  When alcohols are used, the amount used is usually 2 to 50% by weight, preferably 4 to 40% by weight, based on the amount of epihalohydrin, and usually 5 to 100% by weight when an aprotic polar solvent is used. , Preferably 10 to 90% by weight.

  Further, the reaction of the compound represented by the formula (2) with epihalohydrin is carried out by adding a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like to the mixture as a catalyst. A solid or aqueous solution of an alkali metal hydroxide is added to the chlorohydrin etherified compound of the formula (2) obtained by reacting at 150 ° C. for 0.5 to 8 hours, and reacted at 20 to 120 ° C. for 1 to 10 hours. And dehydrohalogenation (ring closure).

  In this case, the usage-amount of a quaternary ammonium salt is 0.1-10 weight part with respect to 100 weight part of compounds represented by Formula (2).

  Next, after washing the reaction product of the epoxidation reaction with water, the epihalohydrin and the solvent are removed under reduced pressure by heating, and after adding the following organic solvent into the resulting molten reaction product, the crystalline compound is returned to room temperature. Precipitates. Examples of the organic solvent that can be used include methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, and xylene. The amount of these organic solvents used for crystallization is usually 50 to 400% by weight, preferably 100 to 300% by weight, based on the weight of the reactant residue.

  After sufficient crystals have precipitated, the crystals are filtered using a normal pressure or vacuum filter. In order to obtain crystals with higher purity, it is preferable to perform further washing with the above organic solvent or alcohols such as methanol and ethanol.

The photosensitive resin composition of the present invention contains the alkali aqueous solution-soluble resin (A), the reactive crosslinking agent (B), the radical polymerization type photopolymerization initiator (C), and the curing agent (D).
As a solvent in the case of using the photosensitive resin composition of the present invention as a solution, the solvent used in the synthesis of the alkali aqueous solution-soluble resin (A) may be used as it is, or the solvent used in the reaction. The solvents exemplified as above may be used separately or mixed.

  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.

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.
An optical waveguide is a special electronic component that confines light by creating a portion having a refractive index slightly higher than the surroundings on the surface of the substrate or just below the substrate surface, and performs multiplexing / demultiplexing and switching of the light. Specific examples of the components include optical multiplexing circuits, frequency filters, optical switches, and optical interconnection components that are useful in the fields of communication and optical information processing.

  The cured product of the present invention is obtained by curing the above resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing can be performed by conventional methods by irradiation with energy rays such as ultraviolet rays. 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 resin composition of the present invention is used for, for example, a resist film, an interlayer insulating material for a build-up method, or an optical waveguide for an electric / electronic / optical base material such as a printed board, an optoelectronic board or an optical board. . Specific examples of these include articles such as computers, home appliances, and portable devices.
The thickness of the cured product layer is about 0.5 to 160 μm, and preferably about 1 to 100 μm.

As an example, the production of a printed wiring board using the photosensitive resin of the present invention will be briefly described. A liquid resin composition (solution) is applied to a printed wiring board with a film thickness of 0.5 to 160 μm by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or the like. The coating film is usually dried at a temperature of 50 to 110 ° C, preferably 60 to 100 ° C. Thereafter, an active energy ray such as ultraviolet rays is irradiated to the coating film directly or indirectly through a photomask in which an exposure pattern such as a negative film is formed, usually at an intensity of about 10 to 2000 mJ / cm ² , and the unexposed portion is described later. Using the liquid, development is performed, for example, by spraying, rocking immersion, brushing, scrubbing, or the like.
If necessary, it is further irradiated with ultraviolet rays and then heat-treated at a temperature of usually 100 to 200 ° C., preferably 140 to 180 ° C., so that it has excellent resistance to gold plating, thermal stability, heat resistance, solvent resistance, and acid resistance. A printed wiring board having a permanent protective film satisfying various properties such as property and adhesion can be obtained.

  Examples of the alkaline aqueous solution used for the 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 tetramethylammonium hydroxide. Organic alkali aqueous solutions such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can 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 (Nippon Kayaku Co., Ltd. polyfunctional cresol novolak type epoxy resin as an epoxy compound (a) having two or more epoxy groups in the molecule in a 3 L flask equipped with a stirrer and a reflux tube; Epoxy equivalent: 215.0 g / equivalent) 860.0 g, 288.3 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, as a reaction solvent Charge 492.1 g of carbitol acetate, 4.921 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and 4.921 g of triphenylphosphine as a reaction catalyst, and react at 98 ° C. Was reacted until the acid value became 0.5 mg · KOH / g or less to obtain an epoxycarboxylate compound.
Next, 169.8 g of carbitol acetate as a reaction solvent was added to this reaction solution, 201.6 g of tetrahydrophthalic anhydride was added as a polybasic acid anhydride (c), and the mixture was reacted at 95 ° C. for 4 hours to be soluble in an aqueous alkali solution. A resin solution containing 67% by weight of the resin (A) 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
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 87.5 g of BPFL (bisphenolfluorene manufactured by JFE Chemical Co.) represented by the following formula (3), 370 g of epichlorohydrin, and 26 g of methanol while purging with nitrogen gas. Under stirring, the temperature was raised to the reflux temperature and dissolved. Next, 20 g of flaky sodium hydroxide was added in portions over 100 minutes, and then further reacted at reflux temperature for 1 hour. After completion of the reaction, 150 g of water was added and washed to remove the generated salt and the like, and then excess epichlorohydrin and the like were distilled off under reduced pressure by heating using a rotary evaporator, and 231 g of the residue was stirred. Of methyl isobutyl ketone was added and cooled to room temperature. The precipitated crystals are separated using a vacuum filter, further washed with 300 g of methyl isobutyl ketone and 300 g of methanol, and dried to obtain 71 g of white crystals having the structure of the following formula (4). (This crystal is designated as D-1.) The crystalline compound had an epoxy equivalent of 236 g / eq, a melting point of 153 ° C., and a melt viscosity at 200 ° C. of 0.01 Pa · s. The epoxy equivalent and melt viscosity were measured by a known and commonly used method.

Examples 1 and 2
Using the alkaline aqueous solution-soluble resin (A-1) obtained in Synthesis Example 1 and the crystalline curing agent (D-1) obtained in Synthesis Example 2, other compounds shown in Table 1 were mixed at the blending ratio. The photosensitive resin composition of the present invention was obtained by kneading with a three-roll mill. This is applied to a printed circuit board by a screen printing method so that the dry film thickness is 15 to 25 μm, and the coating film is applied with a hot air dryer at 80 ° C. for 40 minutes, 50 minutes, 60 minutes, and 70 minutes. Let dry for hours. Subsequently, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin in the non-ultraviolet irradiated area. After washing with water and drying, the printed circuit board was heat-cured for 60 minutes with a hot air dryer at 150 ° C. to obtain a cured film. About the obtained hardened | cured material, the photosensitivity, surface glossiness, adhesiveness, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold-plating resistance test were done as mentioned later. The results are shown in Table 2.

Comparative Example Alkaline aqueous solution-soluble resin (A-1), ESF-300 (non-crystalline biphenylfluorene type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) obtained in Synthesis Example 1; epoxy equivalent 246 g / equivalent, softening point 76 (° C.) was used as a curing agent, and the other compounds shown in Table 1 were mixed at the blending ratio and kneaded with a three-roll mill to obtain the photosensitive resin composition of the present invention. This is applied to a printed circuit board by a screen printing method so that the dry film thickness is 15 to 25 μm, and the coating film is applied with a hot air dryer at 80 ° C. for 40 minutes, 50 minutes, 60 minutes, and 70 minutes. Let dry for hours. Subsequently, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW). Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin in the non-ultraviolet irradiated area. After washing with water and drying, the printed circuit board was heat-cured for 60 minutes with a hot air dryer at 150 ° C. to obtain a cured film. About the obtained hardened | cured material, the photosensitivity, surface glossiness, adhesiveness, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold-plating resistance test were done as mentioned later. The results are shown in Table 2.

Table 1
Examples Comparative examples
Note 1 2
Resin solution A-1 51.80 51.80 51.80
Reactive crosslinking agent (B)
DPHA * 1 3.38 3.38
HX-220 * 2 3.38
Radical polymerization type photopolymerization initiator (C)
Irgacure 907 * 3 4.50 4.50 4.50
DETX-S * 4 0.45 0.45 0.45
Curing agent (D)
Curing agent (D-1) 17.62 17.62
ESF-300 * 5 17.62
Additives Melamine * 6 1.00 1.00 1.00
Barium sulfate * 7 15.15 15.15 15.15
Phthalocyanine blue 0.45 0.45 0.45
BYK-354 * 8 0.39 0.39 0.39
KS-66 * 9 0.39 0.39 0.39
Solvent CA * 10 4.87 4.87 4.87

* 1 Dipentaerythritol polyacrylate; Nippon Kayaku Co., Ltd. * 2 ε-caprolactone-modified hydroxypivalate neopentyl glycol diacrylate; Nippon Kayaku Co., Ltd. * 3 2-Methyl- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one; manufactured by Vantico * 4 2,4-diethylthioxanthone; manufactured by Nippon Kayaku Co., Ltd. * 5 ESF-300; manufactured by Nippon Steel Chemical Co., Ltd.

* 6 Thermosetting catalyst * 7 Filler * 8 Leveling agent; manufactured by BYK Chemie * 9 Defoamer; manufactured by Shin-Etsu Chemical Co., Ltd. * 10 Carbitol acetate (solvent)

In addition, the test method and evaluation method of Table 2 are as follows.
(Tackiness) Absorbent cotton was rubbed on the dried film applied to the substrate, and the tackiness of the film was evaluated.
○: Absorbent cotton is not attached.
× ··· Absorbent cotton lint sticks to the membrane.

(Thermal stability) The developability when the drying time at 80 ° C. was 40 minutes, 50 minutes, 60 minutes and 70 minutes was evaluated, and the following evaluation criteria were used.
○: The ink was completely removed during development and development was possible.
× ··· Some parts are not developed during development.

(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:
○ The pattern edge is a straight line and is resolved.
X: Peeling or pattern edges are jagged.

(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% sodium carbonate aqueous 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 observed.

(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.
〇 ・ ・ ・ ・ No peeling.
× ···· peeled off.

  (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 abnormality in the appearance of the coating film, and no swelling or peeling.
× ·············································································

(Gold plating resistance) The test substrate was immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 volume% aqueous solution of Metex L-5B) at 30 ° C. for 3 minutes, washed with water, and then a 14.4 wt% ammonium persulfate aqueous solution. The test substrate was immersed for 3 minutes at room temperature and then washed with water. Further, the test substrate was immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute at room temperature and then washed with water. Next, the substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 volume% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex Melplate Ni- After immersing in 865M 20 volume% aqueous solution, pH 4.6) for 20 minutes and performing nickel plating, it was immersed in 10 volume% sulfuric acid aqueous solution for 1 minute at room temperature and washed with water. Next, the test substrate is immersed in a gold plating solution at 95 ° C. (Meltex, an aqueous solution of 15% by volume of Aurolectroles UP and 3% by volume of potassium cyanide, pH 6) for 10 minutes, subjected to electroless gold plating, and then washed with water. Further, 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 off.

(PCT resistance) The test substrate is left in water at 121 ° C. and 2 atm for 96 hours. 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 shock resistance) The test piece was subjected to thermal history with -55 ° C / 30 minutes and 125 ° C / 30 minutes as one cycle, and after 1000 cycles, the test piece was observed with a microscope and evaluated according to the following criteria.
○ ········ No cracks in the coating film.
× ··············································································

Table 2
Example 1 Example 2 Comparative Example Evaluation Item Tackiness ○ ○ ×
Thermal stability 40 minutes ○ ○ ○
50 minutes ○ ○ ○
60 minutes ○ ○ ×
70 minutes ○ ○ ×
Resolution ○ ○ ○
Light sensitivity 8 7 5
Surface gloss ○ ○ ○
Adhesiveness ○ ○ ○
Pencil hardness 8H 8H 6H
Solvent resistance ○ ○ ×
Acid resistance ○ ○ ×
Heat resistance ○ ○ ○
Gold plating resistance ○ ○ ○
PCT resistance ○ ○ ×
Thermal shock resistance ○ ○ ○

As is clear from the above results, the photosensitive resin composition and the cured product using the alkaline aqueous solution-soluble resin of the present invention and the crystalline curing agent represented by the formula (1) have high resolution, surface gloss, adhesion , Pencil hardness, heat resistance, gold plating resistance, thermal shock resistance, solvent resistance, acid resistance, PCT resistance, tackiness, photosensitivity, good photosensitivity, 60 at 80 ° C The heat stability evaluated from the developability when dried for 70 minutes is also good.

Claims (6)

An epoxy carboxylate compound obtained by reacting an epoxy compound (a) having two or more epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule is added to a polybasic acid. Photosensitive resin composition containing alkaline aqueous resin (A) obtained by reacting anhydride (c) , reactive crosslinking agent (B), radical polymerization photopolymerization initiator (C) and curing agent (D) In the product, the curing agent (D) is represented by the following formula (1):

[In formula, n shows 0-3 by an average value. ]
In crystalline and is printed circuit board solder resist of a compound represented by the interlayer insulating material for multilayer printed wiring boards, flexible printed circuit board solder resist, the plating resist or a photosensitive resin composition for use in the photosensitive optical waveguide. The photosensitive resin composition according to claim 1, wherein the curing agent (D) is a crystal of a compound in which n is 0 in formula (1). Hardened | cured material of the photosensitive resin composition of Claim 1 or 2 . The base material which has the layer of the hardened | cured material of Claim 3 . An article comprising the substrate according to claim 4 . A method for producing a coating film, comprising the steps of applying the photosensitive resin composition according to claim 1 or 2 to a substrate, photocuring, developing treatment and heat treatment.