JP2002338652A - Aqueous alkaline solution-soluble urethane forming epoxycarboxylate compound, photosensitive resin composition using the same and its hardened material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having an excellent photosensitivity, and enabling production of a hardened material being excellent in flexibility, adhesivity, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, or the like. SOLUTION: An aqueous alkaline solution-soluble urethane forming epoxycarboxylate compound (D) comprises reacting a compound (A) being an epoxycarboxylate compound (A) comprising reacting an epoxy compound (a) having two epoxy groups in a molecule and a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond, a compound (B) being an carboxylic acid compound having two hydroxyl groups, and a compound (C) being a diisocyanate compound (C). The photosensitive resin composition comprises using the compound (D), and a hardened material comprises hardening the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a urethanized epoxy carboxylate compound (D) soluble in an aqueous alkali solution.
And a photosensitive resin composition using the same and a cured product thereof, and more particularly, useful as a solder resist for a flexible printed wiring board, a plating resist, an interlayer insulating film for a multilayer printed wiring board, etc. ,
The present invention relates to a resin composition that gives a cured product having excellent adhesion, solder heat resistance, chemical resistance, plating resistance, and the like, 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]

SUMMARY OF THE INVENTION Printed wiring boards are intended to reduce the size and weight of portable devices and to improve communication speeds.
With the demand for higher density, the demand for solder resists has also become increasingly sophisticated, and the ability to withstand substrate adhesion, high insulation, and electroless gold plating while maintaining more flexibility than conventional requirements. These requirements have not been met, 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 sufficient flexibility, high insulation properties, 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

(1) Alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) obtained by reacting compound (A), compound (B) and compound (C) shown below: Compound (A) ): An epoxy carboxylate compound obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule. B): Carboxylic acid compound having two hydroxyl groups in the molecule (B) Compound (C): diisocyanate compound.

(2) The epoxy compound (a) having two epoxy groups in the molecule has an epoxy equivalent of 150 to 9
An alkali aqueous solution-soluble urethanized epoxy carboxylate compound (D) according to (1), which is an epoxy compound of 00 g / equivalent, and (3) an epoxy compound (a) having two epoxy groups in a molecule is phenyldiglycidyl. Ether compounds, bisphenol type epoxy compounds, hydrogenated bisphenol type epoxy compounds, halogenated bisphenol type epoxy compounds, alicyclic diglycidyl ether compounds, aliphatic diglycidyl ether compounds, polysulfide type diglycidyl ether compounds, or biphenol type epoxy compounds An alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) according to any one of (1) and (2), which is an epoxy compound selected from the group consisting of: (4) an ethylenically unsaturated double bond in the molecule; Have Monocarboxylic acid compound (b) is,
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. Aqueous solution-soluble urethanized epoxy carboxylate compounds (D), (5) The carboxylic acid compound (B) having two hydroxyl groups in the molecule is dimethylolpropionic acid or dimethylolbutanoic acid (1) to (4). Wherein the urethanized epoxy carboxylate compound (D) and the (6) diisocyanate compound (C) are phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and diphenylmethane diisocyanate. , Naphthalenedi seaweed Diisocyanate compounds (1) to (5) which are selected from anate, triden diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, allylene sulfone ether diisocyanate, allylsilane diisocyanate, N-acyl diisocyanate or lysine diisocyanate. An aqueous alkaline solution-soluble urethanized epoxy carboxylate compound (D) according to any one of the above,
(7) The acid value of the solid content is 50 to 150 mg · KOH / g.
The alkaline aqueous solution according to any one of (1) to (6), wherein the urethanized epoxy carboxylate compound (D) is soluble in an aqueous alkaline solution according to any one of (1) to (6). Soluble urethane epoxycarboxylate compound (D), photopolymerization initiator (E),
(9) a photosensitive resin composition comprising a crosslinking agent (F) and a curing component (G) as an optional component;
(10) a cured product of the photosensitive resin composition according to (8),
A substrate having a layer of the cured product according to (9), (11)
An object of the present invention is to provide an article having the substrate according to (10).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) of the present invention is characterized by being obtained by reacting the above compounds (A), (B) and (C). I do.

The epoxy compound (a) having two or more epoxy groups in the molecule used for producing the aqueous alkali-soluble urethanized epoxy carboxylate compound (D) of the present invention has an epoxy equivalent of 150 to 90, in particular.
Desirably, the epoxy compound (a) is 0 g / equivalent. When the epoxy equivalent is less than 150, the molecular weight of the obtained urethane-containing epoxy carboxylate compound (D) is small, and there is a possibility that film formation may be difficult or sufficient flexibility may not be obtained, and when the epoxy equivalent exceeds 900. In addition, the introduction rate of the monocarboxylic acid (b) having an ethylenically unsaturated double bond may decrease, and the photosensitivity may decrease.

Specific examples of epoxy compounds having two epoxy groups in the molecule include, for example, phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol-A type epoxy resin. Bisphenol-type epoxy resin, bisphenol-S type epoxy resin, bisphenol type epoxy resin such as epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3 , 3,
Hydrogenated bisphenol type epoxy compounds such as 3-hexafluoropropane epoxy compound, halogenated bisphenol type epoxy compounds such as brominated bisphenol-A type epoxy resin, brominated bisphenol-F type epoxy resin, cyclohexane dimethanol diglycidyl ether compound Alicyclic diglycidyl ether compounds such as
1,6-hexanediol diglycidyl ether, 1,
Examples thereof include aliphatic diglycidyl ether compounds such as 4-butanediol diglycidyl ether and diethylene glycol diglycidyl ether; polysulfide-type diglycidyl ether compounds such as polysulfide diglycidyl ether; and biphenol-type epoxy resins.

[0010] Commercial products of these epoxy compounds include:
For example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 100
4 (all made by Japan Epoxy Resin), EPOMIC R-140, EPOMIC R-301, EPOMIC R-3
04 (all made by Mitsui Chemicals), DER-331, DER
-332, DER-324 (all manufactured by Dow Chemical Co.), Epicron 840, Epicron 850 (all manufactured by Dainippon Ink), UVR-6410 (Union Carbide), YD-8125 (Toto Kasei) and the like. Bisphenol-A type epoxy resin, UVR-6490 (manufactured by Union Carbide), YDF-2001, YDF-2
004, YDF-8170 (all manufactured by Toto Kasei)
Bisphenol-F type epoxy resins such as Epicron 830 and Epicron 835 (both manufactured by Dainippon Ink), H
BPA-DGE (Maruzen Petrochemical), Rica Resin HBE
Hydrogenated bisphenol such as -100 (manufactured by Nippon Rika)
A type epoxy resin, DER-513, DER-514,
Brominated bisphenol-A type epoxy resin such as DER-542 (both manufactured by Dow Chemical Company), celloxide 2021 (manufactured by Daicel), and Rica Resin DME-100
(Nippon Rika), EX-216 (Nagase Kasei) and other alicyclic epoxy resins, ED-503 (Asahi Denka), Rica Resin W-100 (Nippon Rika), EX-212, E
Aliphatic diglycidyl ether compounds such as X-214 and EX-850 (both manufactured by Nagase Kasei), FLEP-5
0, polysulfide-type diglycidyl ether compounds such as FLEP-60 (all manufactured by Toray Thiokol), YX
-4000 (manufactured by Japan Epoxy Resin) and the like.

The monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule used for producing the aqueous alkali solution-soluble urethanized epoxy carboxylate compound (D) of the present invention includes, for example, acrylic acid 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. The acrylic acids include, for example, (meth) acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, saturated or unsaturated dibasic anhydride, and one hydroxyl group in one molecule (meth)
Half-esters which are an equimolar reactant of an acrylate derivative and half-esters which are an equimolar reactant of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative, and the like. From the viewpoint of the sensitivity when the product is used, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone or cinnamic acid is particularly preferred.

The carboxylic acid compound (B) having two hydroxyl groups in the molecule used for producing the aqueous alkaline solution-soluble urethanized epoxy carboxylate compound (D) of the present invention includes alcoholic hydroxyl groups and / or
Alternatively, any compound having both a phenolic hydroxyl group and a carboxyl group can be used, but dimethylolpropionic acid or dimethylolbutanoic acid, which is particularly excellent in developability with an aqueous alkaline solution, is preferred.

As the diisocyanate compound (C) used for producing the aqueous alkali solution-soluble urethanized epoxy carboxylate compound (D) of the present invention, any diisocyanate compound having two isocyanate groups in the molecule can be used. Phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate
Naphthalene diisocyanate, triden diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, allylene sulfone ether diisocyanate, allylsilane diisocyanate, N-acyl diisocyanate, or lysine diisocyanate are preferred.

The production of the urethanized epoxy carboxylate compound (D) soluble in an aqueous alkali solution of the present invention comprises the above-mentioned epoxy compound (a) and a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule. (Hereinafter referred to as the first reaction), an epoxy carboxylate compound (A) in which an alcoholic hydroxyl group is generated, and
Carboxylic acid compound having two hydroxyl groups in the molecule (B)
By a urethanation reaction (hereinafter referred to as a second reaction) with a diisocyanate compound (C).

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, tetramethyl benzene 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 carried out in a single or mixed organic solvent such as (F).

In the reaction, the raw materials are charged at a ratio of 80 to 80 equivalents per equivalent of the epoxy compound (a) as the monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule. It is preferably 120 equivalent%. If the ratio is outside this range, gelation may occur during the second reaction, or the thermal stability of the finally obtained aqueous alkaline solution-soluble urethanized epoxy carboxylate compound (D) may be lowered, which is not preferable. .

At the time of the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst to be used is 0.1 to 10% by weight based on the reaction product. At that time, the reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst used include:
Examples include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like.

In the second reaction, after the completion of the first reaction, the above-mentioned carboxylic acid compound (B) having two hydroxyl groups in the molecule is added to the reaction solution to form a dispersion or a solution. This is a urethanization reaction in which the diisocyanate compound (C) is gradually added and reacted. Although the reaction can be carried out without a catalyst, a catalyst can be used to promote the reaction.
-10% by weight. The reaction temperature at this time is 40-
120 ° C. and the reaction time is preferably 5-60
Time.

In terms of the charged amount of each component, the carboxylic acid compound (B) having two hydroxyl groups in the molecule has an acid value of the solid content of the alkali aqueous solution-soluble urethanized epoxy carboxylate compound (D) of the present invention of 50. ~ 150m
g · KOH / g, and the diisocyanate compound (C) is (moles of compound (A) + moles of compound (B)) / (moles of compound C) as 1 It is preferable to charge so as to be in the range of 5 to 5. If this value is less than 1, an isocyanate group will remain at the terminal of the alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) of the present invention, and the gel is likely to gel during storage due to low thermal stability. It is not preferable.
When this value exceeds 5, the molecular weight of the urethanized epoxy carboxylate compound soluble in an aqueous alkali solution (D) becomes low, which may cause a problem of tackiness and a problem of low sensitivity. In addition, the acid value of the solid content is 50 mg · KO.
When it is less than H / 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 performed. On the other hand, if the acid value of the solid content exceeds 150 mg · KOH / g, the solubility in an aqueous alkali solution becomes too high, and the photocured pattern may be undesirably separated.

The photosensitive resin composition of the present invention comprises the above-mentioned alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D), a photopolymerization initiator (E), a crosslinking agent (F),
It is characterized by containing a curing component (G) as an optional component.

The content ratio of the above-mentioned alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) used in the photosensitive resin composition of the present invention is as follows when the solid content of the photosensitive resin composition is 100% by weight. Usually 15 ~
70% by weight, preferably 20 to 60% by weight.

Specific examples of the photopolymerization initiator (E) 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; and 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.
And usually 1 to 30% by weight, preferably 2 to 2% by weight.
5% by weight.

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, 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 (E)
Is preferably 100% or less.

Specific examples of the crosslinking agent (F) 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 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 optional curing component (G) used in the photosensitive resin composition of the present invention includes, for example, an epoxy compound and an oxazine compound. Curing component (G)
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 (G) 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.).

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503 and EPPN-503.
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 (G) 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 (G) is 200 equivalents of the solid content of the epoxy carboxylate compound soluble in an aqueous alkali solution of the present invention calculated from the acid value and the amount used.
% 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, clay, etc., and thixotropic addition such as aerosil. Agents; coloring agents such as phthalocyanine blue, phthalocyanine green, and titanium oxide; silicones; fluorine-based leveling agents and defoamers; and polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether are added for the purpose of enhancing the performance of the composition. I can do it.

The above-mentioned hardening component (G) may be mixed with the resin composition in advance, but may also be used before being applied to the 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, etc.).

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 printed circuit boards, as well as printing inks and triads. 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, 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 the 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 a liquid resin composition is used, the present invention is applied to a substrate for printed wiring with a film thickness of 5 to 160 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain coating method. By applying the composition of, and drying the coating film at a mixing degree of usually 60 ~ 110 ℃, preferably 60 ~ 100 ℃,
A coating film can be formed. Thereafter, 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 light is usually irradiated at an intensity of about 10 to 2000 mJ / cm ^2. Then, the unexposed portion using a developer described below, for example, spray,
Develop by rocking immersion, brushing, scrubbing, etc. Then, if necessary, further irradiate ultraviolet rays, then usually at 100 to 200 ° C, preferably 140 to 180 ° C.
By performing the heat treatment at a temperature of ° C., a printed wiring board having a permanent protective film which is excellent in gold plating property and satisfies various properties such as heat resistance, solvent resistance, acid resistance, adhesion, and flexibility can be obtained.

Examples of the alkaline aqueous solution used for the development include an inorganic alkaline aqueous solution 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.

[0041]

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, EP-807 (bifunctional bisphenol-F type manufactured by Mitsui Chemicals, Inc.) was used. 340.0 g of epoxy resin, epoxy equivalent: 170 g / equivalent), 144.1 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule, heat 0.24 g of 2-methylhydroquinone as a polymerization inhibitor and 1.45 g of triphenylphosphine as a reaction catalyst
The acid value of the reaction solution is 0.5 mg · K at 98 ° C.
The reaction was carried out until OH / g or less, to obtain an epoxy carboxylate compound (A) (theoretical molecular weight: 484.1). Next, 360.2 g of carbitol acetate was used as a reaction solvent in this reaction solution, and 2,2-bis (dimethylol) -propionic acid (molecular weight: 134.25 g) was used as the carboxylic acid compound (B) having two hydroxyl groups in the molecule. 16)
Was added, and 0.60 g of 2-methylhydroquinone was added as a thermal polymerization inhibitor, and the temperature was raised to 60 ° C. This solution was added to isophorone diisocyanate (molecular weight: 222.
3) 222.3 g was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After the completion of the dropwise addition, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption near 2250 Kaiser disappeared by the infrared absorption spectrum measurement method, and 70% by weight of the alkali aqueous solution-soluble urethanized epoxy carboxylate compound of the present invention was obtained. A resin solution was obtained (this solution was designated as D-1). When the acid value of the solid content was measured, it was 6
It was 6 mg · KOH / g.

Example 2 In a 2 L flask equipped with a stirrer and a reflux tube, Epicoat 828 manufactured by Japan Epoxy Resin was used as an epoxy compound (a) having two or more epoxy groups in a molecule.
(Bifunctional bisphenol-A type epoxy resin, epoxy equivalent: 183 g / equivalent) as acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule. ) To 14
4.1 g, 0.26 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 1.56 g of triphenylphosphine as a reaction catalyst, and at a temperature of 98 ° C., the acid value of the reaction solution is 0.5 mg · KOH / g. The reaction was continued until the temperature became as follows, to obtain an epoxy carboxylate compound (A) (theoretical molecular weight: 510.1). Next, 296.9 g of carbitol acetate was used as a reaction solvent in this reaction solution, and 2,2-bis (dimethylol) -propionic acid (molecular weight: 134.25 g) was used as the carboxylic acid compound (B) having two hydroxyl groups in the molecule. 16), 182.6 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 50 ° C.
Temperature. A solution prepared by dissolving 205.5 g of tolylene diisocyanate (molecular weight: 174.2) in 88.0 g of carbitol acetate was added to this solution at a reaction temperature of 55.
The solution was gradually dropped so as not to exceed ° C. After the completion of the dropwise addition, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption near 2250 Kaiser disappeared by the infrared absorption spectrum measurement method, and 70% by weight of the alkali aqueous solution-soluble urethanized epoxy carboxylate compound of the present invention was obtained. A resin solution was obtained (this solution was designated as D-2). When the acid value of the solid content was measured, it was 85 mg · KOH / g.

Example 3 In a 3 L flask equipped with a stirrer and a reflux tube, an epoxy compound (a) having two or more epoxy groups in a molecule was prepared by using Flep-60 (a bifunctional polysulfide type epoxy manufactured by Toray Thiokol Co., Ltd.). Resin, epoxy equivalent: 288
g / equivalent) of 576 g, 144.1 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule, and 2-methylhydroquinone as a thermal polymerization inhibitor Was charged, and the acid value of the reaction solution was 0.5 mg · KOH at a temperature of 98 ° C.
/ G or less to obtain an epoxy carboxylate compound (A) (theoretical molecular weight: 720.1). Next, 622.9 g of carbitol acetate was used as a reaction solvent in this reaction solution, and 2,2-bis (dimethylol) -propionic acid (molecular weight: 134.25 g) was used as the carboxylic acid compound (B) having two hydroxyl groups in the molecule. 16) to 27
8.0 g and 1.04 g of 2-methylhydroquinone as a thermal polymerization inhibitor were added, and the temperature was raised to 60 ° C. To this solution is added isophorone diisocyanate (molecular weight: 222.3) 4
55.3 g was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After the completion of the dropwise addition, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption near 2250 Kaiser disappeared by the infrared absorption spectrum measurement method, and 70% by weight of the alkali aqueous solution-soluble urethanized epoxy carboxylate compound of the present invention was obtained. A resin solution containing D-
3). When the solid acid value was measured, it was 80 mg
KOH / g.

Comparative Resin Synthesis In a 1 L flask equipped with a stirrer and a reflux tube, 220 g of Nippon Kayaku EOCN-104S (polyfunctional cresol novolak type epoxy resin, epoxy equivalent: 220 g / equivalent), and acrylic acid to 72. 1 g, 125.2 g of carbitol acetate as a reaction solvent, 0.21 g of 2-methylhydroquinone as a thermal polymerization inhibitor and 1.25 g of triphenylphosphine as a reaction catalyst were added, and the mixture was reacted at a temperature of 98 ° C. for 24 hours. I let it. Next, 105.7 g of licacid TH (tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika), 45.3 g of carbitol acetate, and 0.2 ml of 2-methylhydroquinone were added to the reaction solution.
28 g was added and reacted at a temperature of 95 ° C. for 4 hours to obtain a comparative resin having a solid content of 70% and an acid value of 98 mg · KOH / g of solid content.

Examples 4 to 6, Comparative Example 1 (D-1), (D-2) obtained in Examples 1 to 3,
(D-3) and a comparative resin were mixed at the compounding ratio shown in Table 1,
If necessary, the mixture was kneaded with a three-roll mill to obtain a photosensitive resin composition of the present invention. This was applied to a printed circuit board by a screen printing method so that the dry film thickness became 15 to 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes. Next, ultraviolet light was irradiated through a mask on which a circuit pattern was drawn using an ultraviolet light exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW). 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 was heated and cured by a hot air dryer at 150 ° C. for 60 minutes to obtain a cured film. For the obtained cured product, as described below, photosensitivity, surface gloss, substrate warpage, flexibility, adhesion, pencil hardness,
Tests for solvent resistance, acid resistance, heat resistance, and gold plating resistance were performed. 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

(Flexibility) The cured film is bent at 180 ° C. and observed. The following criteria were used: ○ ・ ・ ・ ・ ・ ・ No cracks on film surface × ・ ・ ・ ・ ・ ・ Film surface cracks

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

(Pencil hardness) Evaluation was made 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 Cellotape (R), 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 using Cellotape (R) was performed 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) The test piece was coated with rosin-based plaque and immersed in a solder bath at 260 ° C. for 5 seconds. This was defined as one cycle, and three cycles were repeated. After being allowed to cool to room temperature, a peeling test was performed using Cellotape (R), 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; 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 (available from Meltex, 15 vol% of Aurolectroles UP and 3 vol% of gold potassium cyanide, pH 6), electroless gold plating, washing with water, and further heating with 60 ° C. warm 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, and after confirming that there was no abnormality in the appearance, a peeling test was performed using Cellotape (R).
Evaluation was made 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 shock resistance) A test piece was subjected to -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 Comparative example Note 4 5 6 1 Resin solution D-1 43.14 D-2 43.14 D-3 43.14 43.14 Crosslinking agent (F) DPCA-60 * 1 7.05 7.05 DPHA * 2 7.05 7.05 Photopolymerization initiator (E) Irgacure 907 * 3 7.05 7.05 7.05 7.05 DETX-S * 4 0.70 0.70 0.70 0.70 Curing component (G) YX-4000 * 5 12.08 12.08 12.08 12.08 Thermosetting catalyst Melamine 1.01 1.01 1.01 1.01 Filler Barium sulfate 15.00 15.00 15.00 15.00 Phthalocyanine blue 0.50 0.50 0.50 0.50 Additive BYK-354 * 6 0.70 0.70 0.70 0.70 KS-66 * 7 0.70 0.70 0.70 0.70 Solvent CA 12.06 12.06 12.06 12.06

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 JER: bifunctional biphenyl skeleton epoxy resin * 6 Big Chemie: leveling agent * 7 Shin-Etsu Chemical: antifoaming agent

[0063]

As is clear 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. 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.

[0065]

The urethanized epoxy carboxylate compound soluble in an aqueous alkali solution, the photosensitive resin composition using the same, and the cured product thereof are excellent in photosensitivity in the formation of a coating film by being exposed and cured by ultraviolet rays, and can be obtained. The cured product has satisfactory flexibility, adhesion, 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. ing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/18 H05K 3/18 D 5E346 3/28 3/28 D 3/46 3/46 T (72) Inventor Minoru Yokoshima 4-6-32 Inodai, Toride-shi, Ibaraki Pref. BA09 CA04 CA22 CB03 CB08 CC03 DA01 DB04 DK02 DK08 FE03 HA07 HC03 HC12 HC17 HC61 HC71 HC73 JA02 RA14 5E314 AA32 AA38 CC07 DD07 FF06 GG14 5E343 CC63 DD01 ER12 ER18 5E346 AA12 CC08 CC09 DD03 HH13

Claims (11)

[Claims] An alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) obtained by reacting the following compounds (A), (B) and (C): Compound (A) : An epoxy carboxylate compound obtained by reacting an epoxy compound (a) having two epoxy groups in a molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in a molecule, a compound (B) ): Carboxylic acid compound having two hydroxyl groups in the molecule. Compound (C): diisocyanate compound. 2. The epoxy compound (a) having two epoxy groups in the molecule has an epoxy equivalent of 150 to 900 g /
The alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) according to claim 1, which is an equivalent amount of an epoxy compound. 3. An epoxy compound (a) having two epoxy groups in a molecule is a phenyldiglycidyl ether compound, a bisphenol type epoxy compound, a hydrogenated bisphenol type epoxy compound, a halogenated bisphenol type epoxy compound, an alicyclic compound. Diglycidyl ether compound,
The alkaline aqueous solution-soluble urethanized epoxy according to any one of claims 1 and 2, wherein the epoxy compound is an epoxy compound selected from an aliphatic diglycidyl ether compound, a polysulfide type diglycidyl ether compound, and a biphenol type epoxy compound. Carboxylate compound (D). 4. A monocarboxylic acid compound (b) having an ethylenically unsaturated double bond in the molecule, comprising (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid. The alkaline aqueous solution-soluble urethanized epoxy carboxylate compound (D) according to any one of claims 1 to 3, which is a monocarboxylic acid selected from the group consisting of: 5. The aqueous alkali solution according to claim 1, wherein the carboxylic acid compound (B) having two hydroxyl groups in the molecule is dimethylolpropionic acid or dimethylolbutanoic acid. Soluble urethane epoxy carboxylate compound (D). 6. A diisocyanate compound (C) comprising: phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate,
A diisocyanate compound selected from naphthalene diisocyanate, triden diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, allylene sulfone ether diisocyanate, allylsilane diisocyanate, N-acyl diisocyanate, or lysine diisocyanate. Item 5
The urethanized epoxy carboxylate compound (D) soluble in an aqueous alkali solution according to any one of the above. 7. The solid content acid value is from 50 to 150 mg · KOH.
The urethanized epoxy carboxylate compound (D) soluble in an aqueous alkali solution according to any one of claims 1 to 6, wherein 8. An aqueous alkaline solution-soluble urethanized epoxy carboxylate compound (D), a photopolymerization initiator (E), a cross-linking agent (F) and an optional component according to any one of claims 1 to 7. A photosensitive resin composition comprising a curing component (G). 9. A cured product of the photosensitive resin composition according to claim 8. 10. A substrate having the layer of the cured product according to claim 9. 11. An article having the substrate according to claim 10.