JP2002234932A - Epoxy carboxylate compound soluble in alkali aqueous solution photosensitive resin composition using the same and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, whose cured product has excellent adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance and the like. SOLUTION: An epoxy carboxylate compound (A) soluble in an alkali aqueous solution is a reaction product between an epoxy carboxylate to be obtained by reacting an epoxy compound (a) having two or more epoxy groups in the molecule, a monocarboxylic acid compound (b) having a heterocyclic structure in the molecule, and a monocarbyxlic acid compound (c) having an ethylenically unsaturated double bond in the molecule and a polybasic acid anhydride (d). The photosensitive resin composition uses this compound, and a cured product is obtained by curing the photosensitive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous alkali-soluble epoxy carboxylate compound, a photosensitive resin composition using the same, and a cured product thereof, and more particularly to a solder resist for a printed wiring board, a plating resist, and a multilayer print. Useful as an interlayer electrical insulating material for wiring boards, excellent in developability, its cured film has low water absorption and excellent electrical insulation, and has excellent adhesion, solder heat resistance, chemical resistance, gold plating resistance, etc. And a cured product thereof.

[0002]

2. Description of the Related Art At present, solder resists for some consumer printed wiring boards and most industrial printed wiring boards are exposed to light and then developed from the viewpoint of high precision and high density to form an image, and heat is applied. In addition, a liquid development type solder resist which is finally cured by light irradiation is used. Further, in consideration of environmental problems, a liquid solder resist of an alkali development type using a dilute alkali aqueous solution as a developing solution has become mainstream. For example, JP-A-61-243869 discloses an alkali-developable solder resist using a dilute alkali aqueous solution, in which an acid anhydride is added to a reaction product of a novolak-type epoxy resin and an unsaturated-basic acid. A solder resist composition comprising a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy resin is disclosed.

[0003]

However, printed wiring boards have become increasingly more precise and denser, and the requirements for solder resists have become more and more advanced. In addition, the electroless gold plating properties are required, and currently available solder resists cannot sufficiently meet these requirements. An object of the present invention is to provide a fine image capable of responding to the high performance of today's printed wiring boards, having excellent sensitivity to active energy rays, forming a pattern by developing with a dilute alkaline aqueous solution, and performing a post-curing (post-curing) process. It is an object of the present invention to provide a resin composition suitable for a solder resist ink having a cured film obtained by heat curing having high insulation properties, excellent adhesion, and excellent electroless gold plating resistance, and a cured product thereof.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies on an epoxy carboxylate compound soluble in an aqueous alkali solution, and have completed the present invention. That is, the present invention provides (1) an epoxy compound (a) having two or more epoxy groups in a molecule and a monocarboxylic acid compound (b) having a heterocyclic structure in a molecule.
And a reaction product of an epoxycarboxylate compound obtained by reacting a monocarboxylic acid compound (c) having an ethylenically unsaturated double bond in the molecule with a polybasic anhydride (d). Alkaline aqueous solution-soluble epoxy carboxylate compound (A), (2) an epoxy compound having two or more epoxy groups in a molecule (a)
Wherein the epoxy equivalent of (1) is an epoxy compound having an epoxy equivalent of 90 to 600 g / equivalent, and (3) a monocarboxylic acid compound having a heterocyclic structure in the molecule (b). Is a monocarboxylic acid compound having a furan ring structure or a tetrahydrofuran ring structure, the alkaline aqueous solution-soluble epoxy carboxylate compound (A) according to any one of (1) and (2), and (4) in the molecule. A monocarboxylic acid compound (c) having an ethylenically unsaturated double bond,
The alkali according to any one of (1) to (3), which is a monocarboxylic acid selected from (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid. The reaction amount of the aqueous solution-soluble epoxy carboxylate compound (A) and (5) the monocarboxylic acid compound (b) having a heterocyclic structure is 10 to 40 equivalent% with respect to 1 equivalent of the epoxy resin (a) (1). Or the aqueous alkali solution-soluble epoxy carboxylate compound (A) according to any one of (4) to (4), and (6) the polybasic acid anhydride (d) is succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydro Phthalic anhydride,
One or more (1) selected from the group consisting of itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride The aqueous alkali solution-soluble epoxy carboxylate compound (A) according to any one of (1) to (5);
The alkaline aqueous solution-soluble epoxy carboxylate compound (A) according to any one of (1) to (5), which is 150 mg · KOH / g, (8) (1) to (7)
An alkaline aqueous solution-soluble epoxy carboxylate compound (A), a photopolymerization initiator (B) according to any one of the above,
(9) (7) a photosensitive resin composition containing a crosslinking agent (C) and a curing component (D) as an optional component.
And (10) to provide a substrate having a layer of the cured product described in (9).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The alkaline aqueous solution-soluble epoxy carboxylate compound (A) of the present invention comprises an epoxy compound (a) having two or more epoxy groups in a molecule and a monocarboxylic acid having a heterocyclic structure in a molecule. Compound (b)
And a reaction product of an epoxycarboxylate compound obtained by reacting a monocarboxylic acid compound (c) having an ethylenically unsaturated double bond in the molecule with a polybasic anhydride (d). And

The epoxy compound having two or more epoxy groups in the molecule used for producing the aqueous alkaline solution-soluble epoxy carboxylate compound (A) of the present invention can be used as long as it satisfies this condition. However, it is particularly desirable that the epoxy compound (a) has an epoxy equivalent of 90 to 600 g / equivalent. If the epoxy equivalent is less than 90, the molecular weight of the epoxy carboxylate compound (A) may be small, making film formation difficult,
On the other hand, when the epoxy equivalent exceeds 600, the introduction rate of the monocarboxylic acid (c) having an ethylenically unsaturated double bond may decrease, and the photosensitivity may decrease.

Specific examples of epoxy compounds having two or more epoxy groups in the molecule include phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, and dicyclopentadiene phenol type epoxy resin. Resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin,
Bisphenol-A novolak type epoxy resin, naphthalene skeleton-containing epoxy resin, heterocyclic epoxy resin and the like can be mentioned.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG. N438 (manufactured by Dow Chemical Company), Epicoat 154 (Yukaka Epoxy Co., Ltd.)
And RE-306 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, and EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (manufactured by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.).

As the trishydroxyphenylmethane type epoxy resin, for example, EPPN-503, EPPN-
502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.),
TACTIX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (manufactured by Yuka Shell Epoxy)
And the like. Examples of the dicyclopentadiene phenol-type epoxy resin include, for example, Epicron EXA-720
0 (manufactured by Dainippon Ink and Chemicals, Inc.), TACTIX-
556 (manufactured by Dow Chemical Company).

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.C. E. FIG. Bisphenol-A type epoxy resin such as R-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Toto Kasei), UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei)
And bisphenol-F type epoxy resins.

Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000P and NC-3000S (produced by Nippon Kayaku Co., Ltd.), and YX-4.
000 (manufactured by Yuka Shell Epoxy), YL-6121 (manufactured by Yuka Shell Epoxy), and the like. Examples of the bisphenol A novolak type epoxy resin include, for example, Epicron N-8
80 (manufactured by Dainippon Ink and Chemicals, Inc.), Epicoat E
157S75 (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.) and EXA-
4750 (manufactured by Dainippon Ink and Chemicals, Inc.). As the alicyclic epoxy resin, for example, EHPE-
3150 (manufactured by Daicel Chemical Industries, Ltd.). As the heterocyclic epoxy resin, for example, TEPI
C, TEPIC-L, TEPIC-H, TEPIC-S
(All manufactured by Nissan Chemical Industries, Ltd.).

The monocarboxylic acid compound (b) having a heterocyclic structure in the molecule used for producing the aqueous alkaline solution-soluble epoxy carboxylate compound (A) of the present invention should be used as long as it satisfies the above conditions. Examples thereof include monocarboxylic acid compounds having a heterocyclic structure containing one or more oxygen atoms, nitrogen atoms and / or sulfur atoms in the molecule, and particularly having a furan ring structure or a tetrahydrofuran ring structure in the molecule. It is preferably a monocarboxylic acid compound. It is known that a furan ring or a tetrahydrofuran ring structure is particularly effective in improving the adhesion of a coating film by being hydrogen-bonded to a substrate surface such as a metal surface or a glass surface due to the polarity of the structure itself. .

Specific examples of the monocarboxylic acid compound (b) having a heterocyclic structure include, for example, 2-furancarboxylic acid, 3-furancarboxylic acid, 3- (2-furyl) acrylic acid, and tetrahydrofuran-2-carboxylic acid. Acids and their derivatives;

Examples of the monocarboxylic acid compound (c) having an ethylenically unsaturated double bond in the molecule used for producing the aqueous alkaline solution-soluble epoxy carboxylate compound (A) of the present invention include acrylic acids and crotonic acid. , Α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples of the acrylic acids include (meth) acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, a saturated or unsaturated dibasic anhydride and a (meth) acrylate derivative having one hydroxyl group in one molecule And half-esters which are equimolar reactants, and half-esters which are equimolar reactants of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative. From the viewpoint of the sensitivity when the reaction is performed, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone or cinnamic acid is particularly preferred.

As the polybasic acid anhydride (d) used for producing the alkali aqueous solution-soluble epoxy carboxylate compound (A) of the present invention, any compound having an acid anhydride structure in the molecule can be used. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, and 3-, which are excellent in alkali aqueous solution developability, heat resistance, hydrolysis resistance, etc.
Methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride is particularly preferred.

The alkaline aqueous solution-soluble epoxy carboxylate compound (A) of the present invention is produced by the above-mentioned epoxy compound (a), a monocarboxylic acid compound (b) having a heterocyclic structure in the molecule, and an ethylenically unsaturated compound in the molecule. After reacting with the monocarboxylic acid compound (c) having a saturated double bond (hereinafter referred to as a first reaction), the above-mentioned polybasic anhydride (d) is half-esterified with the resulting alcoholic hydroxyl group ( Hereinafter, referred to as a second reaction).

In the first reaction, no solvent or a solvent having no alcoholic hydroxyl group, for example, ketones such as acetone, ethyl methyl ketone and cyclohexanone, benzene, toluene, xylene, tetramethylbenzene and the like are used. Aromatic hydrocarbons, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, glycol ethers such as triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve Acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, glue Esters such as dialkyl oxalate, dialkyl succinate and dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and further crosslinking agents described below It can be obtained by reacting in a single or mixed organic solvent such as (C).

The reaction amount (hereinafter referred to as x) of the monocarboxylic acid compound (b) having a heterocyclic structure in the molecule is as follows.
10 to 40 equivalent% to 1 equivalent of the epoxy resin (a),
The monocarboxylic acid compound (c) having an ethylenically unsaturated double bond in the molecule is preferably (100-x) equivalent% based on 1 equivalent of the epoxy resin (a).
When x is less than 10 equivalent%, the adhesion of the coating film may be insufficient, and when x exceeds 40 equivalent%, the introduced amount of ethylenically unsaturated double bond becomes low, and Is undesirably reduced or the crosslink density may be reduced.

At the time of the reaction, a catalyst is preferably used to promote the reaction, and the amount of the catalyst is 0.1 to 10% by weight based on the weight of the reaction product. At that time, the reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine,
Triphenylstibine, methyltriphenylstibine,
Chromium octoate, zirconium octoate and the like can be mentioned.

The second reaction is obtained by, after the completion of the first reaction, adding the above-mentioned polybasic acid anhydride (d) to the reaction solution and further reacting. At that time, the reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.
The polybasic acid anhydride (d) may be added in an amount such that the solid acid value of the aqueous alkali carboxylate compound (A) of the present invention is 50 to 150 mg · KOH / g.
It is preferable to add a calculated value such that When the acid value of the solid content is less than 50 mg · KOH / g, the solubility in an aqueous alkali solution is insufficient, and when patterning is performed, there is a possibility that it will remain as a residue, or in the worst case, patterning may not be possible. In addition, the solid content acid value is 150
If the amount exceeds mg · KOH / g, the solubility in an aqueous alkali solution becomes too high, and the photocured pattern may undesirably peel off.

The photosensitive resin composition of the present invention contains the above-described alkaline aqueous solution-soluble epoxy carboxylate compound (A), a photopolymerization initiator (B), a crosslinking agent (C), and a curing component (D) as optional components. It is characterized by doing.

Specific examples of the photopolymerization initiator (B) used in the photosensitive resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and 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-hydroxynclohexyl phenyl ketone,
2-methyl-1- [4- (methylthio) phenyl] -2
Acetophenones such as morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-
Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide;
Benzophenones such as 4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. As the proportion of these additives, the solid content of the photosensitive resin composition is 100% by weight.
The content is 1 to 30% by weight, preferably 2 to 25% by weight.

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine, ethyl N, N-dimethylaminobenzoate, N, N-dimethylaminobenzoate It can be used in combination with an accelerator such as a benzoic acid derivative such as acid isoamyl ester.
The amount of these accelerators to be added may be the photopolymerization initiator (B)
Is preferably 100% or less.

Specific examples of the crosslinking agent (C) used in the photosensitive resin composition of the present invention include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butane Diol mono (meth) acrylate, carbitol (meth) acrylate, acryloyl morpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol A half ester which is a reaction product of an acid anhydride of a monocarboxylic acid compound (such as mono (meth) acrylate) and a polycarboxylic acid compound (eg, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) Polyethylene glycol di (meth) acrylate, Ripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxy tri (meth) acrylate, ε-caprolactone of neopenglycol hydroxyvivalate Di (meth) acrylate of adduct (for example, KAY manufactured by Nippon Kayaku Co., Ltd.)
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono or polyglycidyl Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Epoxy (meth) which is a reaction product of (meth) acrylic acid with hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. Acrylate and the like can be mentioned. The proportion of these additives is, assuming that the solid content of the photosensitive resin composition is 100% by weight, 2 to 40% by weight,
Preferably, it is 5 to 30% by weight.

The curing component (D) as an optional component used in the photosensitive resin composition of the present invention includes, for example, an epoxy compound and an oxazine compound. Curing component (D)
Is particularly preferably used when a carboxyl group remaining in the resin coating film after photocuring reacts by heating to obtain a cured coating film having stronger chemical resistance.

Specific examples of the epoxy compound used for the curing component (D) include phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol- Examples include A-type epoxy resin, bisphenol-F-type epoxy resin, biphenol-type epoxy resin, bisphenol-A novolak-type epoxy resin, epoxy resin containing naphthalene skeleton, and heterocyclic epoxy resin.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.); E. FIG. N438 (manufactured by Dow Chemical Company), Epicoat 154 (Yukaka Epoxy Co., Ltd.)
And RE-306 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolak type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), EOCN-102S, and EOCN-103.
S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (manufactured by Union Carbide), ESCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.).

As the trishydroxyphenylmethane type epoxy resin, for example, EPPN-503, EPPN-
502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.),
TACTIX-742 (manufactured by Dow Chemical Company), Epicoat E1032H60 (manufactured by Yuka Shell Epoxy)
And the like. Examples of the dicyclopentadiene phenol-type epoxy resin include, for example, Epicron EXA-720
0 (manufactured by Dainippon Ink and Chemicals, Inc.), TACTIX-
556 (manufactured by Dow Chemical Company).

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy), UVR-6410 (manufactured by Union Carbide), D.C. E. FIG. Bisphenol-A type epoxy resin such as R-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Toto Kasei), UVR-6490 (manufactured by Union Carbide), YDF-8170 (manufactured by Toto Kasei)
And bisphenol-F type epoxy resins.

Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000P and NC-3000S (produced by Nippon Kayaku Co., Ltd.), and YX-4.
000 (manufactured by Yuka Shell Epoxy), YL-6121 (manufactured by Yuka Shell Epoxy), and the like. Examples of the bisphenol A novolak type epoxy resin include, for example, Epicron N-8
80 (manufactured by Dainippon Ink and Chemicals, Inc.), Epicoat E
157S75 (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.) and EXA-
4750 (manufactured by Dainippon Ink and Chemicals, Inc.). As the alicyclic epoxy resin, for example, EHPE-
3150 (manufactured by Daicel Chemical Industries, Ltd.). As the heterocyclic epoxy resin, for example, TEPI
C, TEPIC-L, TEPIC-H, TEPIC-S
(All manufactured by Nissan Chemical Industries, Ltd.).

Specific examples of the oxazine compound used for the curing component (D) include, for example, Bm-type benzoxazine, Pa-type benzoxazine, and Ba-type benzoxazine (all manufactured by Shikoku Chemical Industry Co., Ltd.). Is mentioned.

The addition ratio of the curing component (D) is 200 equivalents calculated from the acid value and the solid content of the epoxy carboxylate compound soluble in an aqueous alkali solution of the present invention.
% Is preferred. If this amount exceeds 200%, the developability of the photosensitive resin composition of the present invention may be significantly reduced, which is not preferable.

If necessary, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, fillers such as aluminum hydroxide, aluminum oxide, silica and clay, and thixotropic addition of aerosil and the like. Agents; coloring agents such as phthalocyanine blue, phthalocyanine green, and titanium oxide; silicone, fluorine-based leveling agents and defoamers; and polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether are added for the purpose of enhancing various performances of the composition. I can do it.

The above-mentioned hardening component (D) may be previously mixed with the resin composition, but it is preferable to use the hardening component (D) by mixing it before applying it to a printed wiring board. That is, the two-component type of the main component solution containing the component (A) as a main component and an epoxy curing accelerator and the like and the curing agent solution containing the component (D) as a main component are mixed. It is preferable to use a mixture.

The photosensitive resin composition of the present invention can also be used as a support, for example, as a photosensitive film coated on a polymer film (for example, a film made of polyethylene terephthalate, polypropylene, polyethylene or the like).

The photosensitive resin composition (liquid or film form) of the present invention is useful as an insulating material between layers of electronic parts, as a resist ink such as a solder resist for a printed circuit board, as well as a printing ink and a triad. It can also be used as an agent, paint, coating agent, adhesive and the like.

The cured product of the present invention is obtained by curing the above-mentioned resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. For example, when irradiating ultraviolet rays, an ultraviolet ray generating device such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and 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 an electric / electronic component such as a printed board as a permanent resist or an interlayer insulating material for a build-up method. The thickness of this cured product layer is 0.5 to 160 μm.
m, preferably about 1 to 60 μm.

The printed wiring board of the present invention can be obtained, for example, as follows. That is, when using a liquid resin composition, the printed wiring board, screen printing method, spray method, roll coating method, electrostatic coating method, preferably a film thickness of 5 to 160 μm by a method such as curtain coating method. The composition of the present invention is applied, and the coating film is usually applied to 60 to 11
By drying at a temperature of 0 ° C., preferably 60 to 100 ° C., a tack-free coating film can be formed. afterwards,
A photomask on which an exposure pattern such as a negative film is formed is brought into direct contact with the coating film (or placed on the coating film in a non-contact state), and ultraviolet rays are usually applied at 10 to 2000 mJ / cm 2.
Irradiation is carried out with a moderate intensity, and the unexposed portion is developed by using a developing solution described later, for example, by spraying, rocking immersion, brushing, scrubbing, or the like. Then, if necessary, further irradiate ultraviolet rays, and then heat-treat at a temperature of usually 100 to 200 ° C., preferably 140 to 180 ° C., so as to have excellent electric insulation after the wet heat test and to have excellent electroless gold plating property. A printed wiring board having a permanent protective film that is excellent and satisfies various properties such as heat resistance, solvent resistance, acid resistance, and adhesion is obtained.

Examples of the aqueous alkali solution used for the development include aqueous solutions of inorganic alkalis such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate and potassium phosphate. An aqueous organic alkali solution such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.

[0042]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Example 1 In a 2 L flask equipped with a stirrer and a reflux tube, as an epoxy compound (a) having two or more epoxy groups in a molecule, NER-7000 (manufactured by Nippon Kayaku Co., Ltd.) Bisphenol-F type epoxy resin, epoxy equivalent: 30
(0.72 g / equivalent) as 376.9 g of a monocarboxylic acid compound (b) having a heterocyclic structure in the molecule,
28.1 furancarboxylic acid (molecular weight: 112.08)
g, acrylic acid (molecular weight: 7) as a monocarboxylic acid compound (c) having an ethylenically unsaturated double bond in the molecule;
2.06) and propylene glycol monomethyl ether acetate (hereinafter referred to as PGM) as a reaction solvent.
EA) as a thermal polymerization inhibitor
0.32 g of methylhydroquinone and 1.9 g of triphenylphosphine as a reaction catalyst were charged, and 98 ° C.
The reaction was continued until the acid value of the reaction solution became 2 mg · KOH / g or less. Next, tetrahydrophthalic anhydride (molecular weight: 1) was added to the reaction mixture as polybasic anhydride (d).
522.7), 172.7 g, and PGMEA 190.9 g
g, 0.50 g of 2-methylhydroquinone, 9
The reaction was carried out at a temperature of 5 ° C. for 5 hours to obtain a resin liquid containing 65% by weight of an alkali aqueous solution-soluble epoxy carboxylate compound of the present invention. When the solid content acid value was measured, it was 100
mg · KOH / g. This resin solution is designated as A-1.

Example 2 In a 2 L flask equipped with a stirrer and a reflux tube, EOCN-104S (cresol novolak, manufactured by Nippon Kayaku Co., Ltd.) was used as an epoxy compound (a) having two or more epoxy groups in the molecule. Epoxy resin, epoxy equivalent: 220
g / equivalent) as a monocarboxylic acid compound (b) having a heterocyclic structure in the molecule, 52.8 g of 2-furancarboxylic acid (molecular weight: 112.08), and ethylenically unsaturated in the molecule. Acrylic acid (molecular weight: 72.06) as the monocarboxylic acid compound (c) having a double bond
79.2 g, 159.1 g of carbitol acetate (hereinafter referred to as CA) as a reaction solvent, 0.32 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 1.9 g of triphenylphosphine as a reaction catalyst, At a temperature of 98 ° C., the acid value of the reaction solution is 2 mg · KOH /
g. Then, as a polybasic acid anhydride (d), 172.7 g of tetrahydrophthalic anhydride (molecular weight: 152.15) and 19% of CA were added to the reaction solution.
0.9 g and 0.50 g of 2-methylhydroquinone were charged and reacted at a temperature of 95 ° C. for 5 hours to obtain a resin solution containing 65% by weight of an alkaline aqueous solution-soluble epoxy carboxylate compound of the present invention. When the solid content acid value was measured,
It was 105 mg · KOH / g. A-
Let it be 2.

Example 3 In a 2 L flask equipped with a stirrer and a reflux tube, Nippon Kayaku Co., Ltd. EPPN-503 (trishydroxy) was used as an epoxy compound (a) having two or more epoxy groups in the molecule. 348.2 g of a phenylmethane type epoxy resin, epoxy equivalent: 182 g / equivalent), and a monocarboxylic acid compound (b) having a heterocyclic structure in the molecule, 2
-Furancarboxylic acid (molecular weight: 112.08) to 64.
3 g of acrylic acid (molecular weight: 7) as a monocarboxylic acid compound (c) having an ethylenically unsaturated double bond in the molecule.
2.06) as a reaction solvent and 16
9.7 g, 0.34 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 2.0 g of triphenylphosphine as a reaction catalyst, and at 98 ° C., the acid value of the reaction solution is 2 mg · KOH / g or less. The reaction was continued until
Then, tetrahydrophthalic anhydride (molecular weight: 152.15) was added to the reaction mixture as polybasic anhydride (d).
1.0 g, 180.3 g of CA, and 0.50 g of 2-methylhydroquinone were charged and reacted at a temperature of 95 ° C. for 5 hours to obtain a resin solution containing an alkali aqueous solution-soluble epoxy carboxylate compound of 65% by weight of the present invention. . When the acid value of the solid content was measured, it was 105 mg · KOH / g. This resin solution is designated as A-3.

Examples 4 to 6 (A-1), (A-2) and (A-3) obtained in Examples 1 to 3 were mixed in the mixing ratio shown in Table 1, and if necessary, 3 The mixture was kneaded with the present roll mill to obtain the photosensitive resin composition of the present invention. This was screen-printed to a dry film thickness of 1
The coating was applied to a printed board so as to have a thickness of 5 to 25 μm, and the coating was dried with a hot air drier at 80 ° C. for 30 minutes. Next, UV exposure equipment (Oak Manufacturing Co., Ltd., model HMW
-680 GW) and irradiated with ultraviolet light through a mask on which a circuit pattern was drawn. Thereafter, spray development was performed with a 1% aqueous solution of sodium carbonate to remove the resin in the unirradiated portion of the ultraviolet rays. After washing and drying, the printed circuit board is
And a heating and curing reaction was performed for 60 minutes using a hot-air dryer to obtain a cured film.
The obtained cured product was tested for photosensitivity, surface gloss, substrate warpage, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, and gold plating resistance as described below. Table 2 shows the results. In addition, the test method and the evaluation method are as follows.

(Developability) The following evaluation criteria were used.・: At the time of development, the ink was completely removed and development was possible. ×: Some parts are not developed during development.

(Resolution) A 50 μm negative pattern is adhered to the dried coating film, and the coated film is irradiated with ultraviolet rays having an integrated light amount of 200 mJ / cm ² . Next, it is developed 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) A step tablet (manufactured by Kodak Co., Ltd.) was brought into close contact with the dried coating film, and the integrated light amount was 50
Irradiation exposure with ultraviolet rays of 0 mJ / cm ² is performed. Next, the film is developed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm @ 2, and the number of steps of the coating film left undeveloped is confirmed.

(Surface gloss) 500 mJ
/ Cm ² UV irradiation. Next, it is developed with a 1% aqueous solution of sodium carbonate for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the cured film after drying is observed. The following criteria were used: ○ ・ ・ ・ ・ ・ ・ No fogging observed ×× ・ ・ ・ Slight fogging observed

(Substrate Warpage) The following criteria were used. ○ ・ ・ ・ ・ ・ ・ No warp is seen on the substrate △ ・ ・ ・ ・ Very little substrate is warped × ・ ・ ・ ・ ・ ・ A warp is seen on the substrate

(Adhesion) According to JIS K5400,
100 test pieces were made with 1 mm-thick squares, and a peeling test was performed using Cellotape (registered trademark). The state of peeling was evaluated by the following criteria. 〇 ・ ・ ・ ・ ・ ・ No peeling × ・ ・ ・ ・ ・ ・ Peel off

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

(Solvent Resistance) A test piece is immersed in isopropyl alcohol at room temperature for 30 minutes. After confirming that there was no abnormality in the appearance, a peeling test was carried out using cellophane tape and evaluated according to the following criteria. ○ ・ ・ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no blistering or peeling × ・ ・ ・ ・ Pattern with blistering or peeling

(Acid Resistance) A test piece is immersed in a 10% hydrochloric acid aqueous solution at room temperature for 30 minutes. After confirming that there is no abnormality in the appearance,
A peeling test was performed using cellotape and evaluated according to the following criteria. ○ ・ ・ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no blistering or peeling × ・ ・ ・ ・ Body with blistering or peeling

(Heat resistance) A rosin-based plaque was applied to a test piece and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as one cycle, and three cycles were repeated. After allowing to cool to room temperature, a peeling test was performed using cellophane tape, and evaluated according to the following criteria. 〇: No abnormalities in the appearance of the coating film and no blistering or peeling ×: ・ ・ ・ Films with blistering or peeling

(Gold Plating Resistance) A test substrate was treated with an acidic degreasing solution (Mexex L-5, manufactured by Nippon McDermitt) at 30 ° C.
B in a 20 vol% aqueous solution), washed with water, then immersed in a 14.4 wt% aqueous ammonium persulfate solution at room temperature for 3 minutes, washed with water, and further placed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute. After immersion for a minute, it was washed with water.
Next, this substrate was immersed in a 30 ° C. catalyst solution (manufactured by Meltex, a 10 vol% aqueous solution of a metal plate activator 350) for 7 minutes, washed with water, and washed at 85 ° C. with a nickel plating solution (manufactured by Meltex, Melplate Ni-). 865M 2
After immersing in a 0 vol% aqueous solution (pH 4.6) for 20 minutes and performing nickel plating, the substrate was immersed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute and washed with water. Next, the test substrate is
Immersion for 10 minutes in a gold plating solution (manufactured by Meltex, an aqueous solution of 15 vol% of Aurolectroles UP and 3 vol% of gold potassium cyanide, pH 6), electroless gold plating was performed, followed by washing with water and 60 ° C. hot water. Dipped for minutes, washed with water and dried. A cellophane adhesive tape was adhered to the obtained electroless gold-plated evaluation substrate, and the state when peeled off was observed. ：: No abnormality at all. X: Some peeling was observed.

(PCT Resistance) The test substrate was 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 was carried out using cellophane tape and evaluated according to the following criteria. ○ ・ ・ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no blistering or peeling × ・ ・ ・ ・ Body with blistering or peeling

(Thermal shock resistance) Test pieces were tested at -55 ° C / 30
Min, 125 ° C / 30 min as one cycle, heat history was added, and after 1000 cycles, the specimen was observed under a microscope,
Evaluation was made according to the following criteria. ○ ・ ・ ・ ・ ・ ・ No cracks in the coating ×× ・ ・ ・ Cracks in the coating

Table 1 Example Note 4 56 Resin solution A-1 47.73 A-2 39.98 A-3 39.98 Crosslinking agent (C) DPCA-60 * 1 7.76 DPHA * 2 7.50 7.50 Photopolymerization initiator (B) Irgacure 907 * 3 6.38 3.75 3.75 DETX-S * 4 0.64 0.38 0.38 Curing component (D) NC-3000S * 5 14.93 YX-4000 * 6 3.75 TEPIC * 7 3.75 EOCN-1020 * 8 9.00 Thermosetting catalyst Melamine 1.01 1.13 1.13 Filler sulfuric acid Barium 17.62 12.56 Spherical silica 12.97 8.25 Talc 0.75 12.56 Phthalocyanine blue 0.74 0.64 0.64 Additive BYK-354 * 9 0.74 0.75 0.75 KS-66 * 10 0.74 0.75 0.75 Solvent PGMEA 6.36 CA 11.00 11.00

Note * 1 Nippon Kayaku: ε-caprolactone-modified dipentaerythritol hexaacrylate * 2 Nippon Kayaku: trimethylolpropane triacrylate * 3 Vantico: 2-methyl- (4- (methylthio) phenyl)- 2-morpholino-1-propane * 4 Nippon Kayaku: 2,4-diethylthioxanthone * 5 Nippon Kayaku: Multifunctional biphenyl skeleton epoxy resin * 6 JER: Bifunctional biphenyl skeleton epoxy resin * 7 Nissan Chemical: Tris glycidyl isocyanurate * 8 Nippon Kayaku: Cresol novolak epoxy resin * 9 Big Chemie: Leveling agent * 10 Shin-Etsu Chemical: Antifoaming agent

[0062]

As is evident from the results in Table 2, the photosensitive resin composition of the present invention has high sensitivity, and its cured film has excellent solder heat resistance, chemical resistance, gold plating resistance, etc., and has a cured product surface. It is clear that the photosensitive resin composition for printed circuit boards has no cracks and does not warp even when a thinned substrate is used.

[0064]

The alkaline aqueous solution-soluble epoxy carboxylate compound of the present invention and the photosensitive resin composition using the same are excellent in photosensitivity in the formation of a coating film by being exposed and cured by ultraviolet rays, and the resulting cured product is obtained. Has satisfactory adhesiveness, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, etc., and is particularly suitable for a photosensitive resin composition for printed wiring boards.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/46 H05K 3/46 TF term (Reference) 2H025 AA01 AA04 AA06 AA10 AA14 AA20 AB15 AC01 AD01 BC32 BC42 BC74 CA01 CA27 CA34 CC20 FA03 FA17 4J036 AA01 CA19 CA21 CA22 DA01 HA02 JA08 5E314 AA27 AA32 CC01 CC15 DD07 GG11 GG14 5E343 CC43 CC63 CC67 ER12 ER16 ER18 GG03 5E346 AA12 CC09 DD02 DD03 HH11 HH13

Claims (10)

[Claims] 1. An epoxy compound (a) having two or more epoxy groups in a molecule, a monocarboxylic acid compound (b) having a heterocyclic structure in a molecule, and an ethylenically unsaturated double bond in a molecule. An alkaline aqueous solution-soluble epoxy carboxylate compound (A), which is a reaction product of an epoxy carboxylate compound obtained by reacting a monocarboxylic acid compound (c) with a polybasic acid anhydride (d). 2. The epoxy compound (a) having two or more epoxy groups in the molecule has an epoxy equivalent of 90 to 600 g.
The alkaline aqueous solution-soluble epoxy carboxylate compound (A) according to claim 1, wherein the epoxy carboxylate compound is (a) / equivalent of an epoxy compound. 3. The monocarboxylic acid compound having a heterocyclic structure in the molecule (b) is a monocarboxylic acid compound having a furan ring structure or a tetrahydrofuran ring structure. The aqueous alkali-soluble epoxy carboxylate compound (A) described in (1). 4. A monocarboxylic acid compound (c) having an ethylenically unsaturated double bond in the molecule is selected from the group consisting of (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid. The aqueous alkali-soluble epoxycarboxylate compound (A) according to any one of claims 1 to 3, which is a monocarboxylic acid selected from the group consisting of: 5. The method according to claim 1, wherein the reaction amount of the monocarboxylic acid compound (b) having a heterocyclic structure is 10 to 40 equivalent% with respect to 1 equivalent of the epoxy resin (a). The aqueous alkaline solution-soluble epoxy carboxylate compound (A) according to the above item. 6. The polybasic anhydride (d) comprises succinic anhydride,
From the group of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride One or more selected ones of claim 1
The alkaline aqueous solution-soluble epoxy carboxylate compound (A) according to any one of claims 5 to 5. 7. The solid content acid value is from 50 to 150 mg · KOH.
The alkaline aqueous solution-soluble epoxy carboxylate compound (A) according to any one of claims 1 to 5, wherein 8. An alkaline aqueous solution-soluble epoxy carboxylate compound (A), a photopolymerization initiator (B), a crosslinking agent (C) and a curing component as an optional component according to any one of claims 1 to 7. A photosensitive resin composition comprising (D). 9. A cured product of the photosensitive resin composition according to claim 7. 10. A substrate having the layer of the cured product according to claim 9.