JP2003268067A - Photosensitive resin, and photosensitive resin composition using the same, and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has excellent photosensitivity and gives cured products having excellent flexibility, gold-plating resistance, adhesiveness, pencil hardness, solvent resistance, acid resistance, heat resistance, and the like. <P>SOLUTION: This polyurethane compound (E) is characterized by being obtained by the reaction of the following compounds (A), (B), (C), and (D). The photosensitive resin composition comprises the polyurethane compound (E), a photopolymerization initiator (F), and a cross-linking agent (G). The compound (A): an epoxy carboxylate compound obtained by reacting an epoxy compound having two epoxy groups in the molecule with a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule. The compound (B): a diisocyanate compound. The compound (C): a diol compound having a carboxy group. (D): an epoxy compound having an ethylenically unsaturated group in the molecule. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyurethane compound (E), a photosensitive resin composition using the same, and a cured product thereof, and more specifically, a solder resist for a flexible printed wiring board, a plating resist, and a multilayer printed wiring. A resin composition and a cured product thereof, which are useful as an interlayer insulating film for plates, a photosensitive optical waveguide, etc., and give a cured product having excellent developability, electrical insulation, adhesion, solder heat resistance, chemical resistance, plating resistance, etc. Regarding things.

[0002]

2. Description of the Related Art Currently, solder resists for some consumer printed wiring boards and most industrial printed wiring boards are exposed to light and developed to form an image by heat treatment from the viewpoint of high accuracy and high density. Further, a liquid developing type solder resist which is finish-cured by light irradiation is used. Further, in consideration of environmental problems, an alkali developing type liquid solder resist using a dilute alkaline aqueous solution as a developing solution has become the mainstream. As an alkaline developing type solder resist using such a dilute aqueous alkaline solution, for example, in JP-A-61-243869, an acid anhydride is added to a reaction product of a novolac type epoxy resin and an unsaturated-basic acid. There is disclosed a solder resist composition comprising a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy resin. However, this composition is rigid and has no flexibility.

[0003]

A printed wiring board is a high-precision printed wiring board with the aim of reducing the size and weight of portable equipment and improving the communication speed.
Higher densities are required, and the demands on solder resists are becoming more and more sophisticated, and the performance that can withstand substrate adhesion, high insulation, and electroless gold plating is more flexible than conventional requirements. There is a demand, and the solder resists currently on the market cannot sufficiently meet these demands. The main object of the present invention is to provide a fine image capable of accommodating the high functionality of today's printed wiring boards with excellent photosensitivity to active energy rays, to form a pattern by development with a dilute alkaline aqueous solution, and to perform post-curing. To provide a resin composition suitable for a solder resist ink having a cured film obtained by thermosetting in a process having sufficient flexibility, a high insulating property, an adhesive property, and an excellent resistance to electroless gold plating, and a cured product thereof. is there.

[0004]

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

(1) Polyurethane compound (E), compound (A) obtained by reacting compound (A), compound (B), compound (C) and compound (D) shown below. ): Epoxycarboxylate compound compound (B) obtained by reacting an epoxy compound (a) having two epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule : Diisocyanate compound compound (C): diol compound compound (D) having a carboxyl group: epoxy compound (2) having an ethylenically unsaturated group in the molecule, the epoxy equivalent of the epoxy compound (a) is 100
The polyurethane compound (E) and (3) epoxy compound (a) described in (1) above, which has a weight ratio of up to 900 g / equivalent, is a phenyldiglycidyl ether compound, a bisphenol type epoxy compound, a hydrogenated bisphenol type epoxy compound,
One or more epoxies selected from halogenated bisphenol epoxy compounds, alicyclic diglycidyl ether compounds, aliphatic diglycidyl ether compounds, polysulfide diglycidyl ether compounds, biphenol epoxy compounds and bixylenol epoxy compounds The polyurethane compound (E) or (4) monocarboxylic acid compound (b) according to the above (1) or (2), which is a compound, is produced by reaction of (meth) acrylic acid or (meth) acrylic acid with ε-caprolactone. (1) which is one or more monocarboxylic acids selected from the group consisting of compounds and cinnamic acid.
Alternatively, the polyurethane compound (E) or (5) compound (B) according to any one of (3) may be used as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, or naphthalene diisocyanate. , One or more compounds selected from tridene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyan diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate. The polyurethane compound (E according to any one of the above items (1) to (4) , (6) a diol compound polyurethane compound according to any one of from the hydroxyl group of (C) is above (1) an alcoholic hydroxyl group (5) (E), is (7) an epoxy compound (D), glycidyl
((Meth) acrylate, glycidyl cinnamic acid, and one or more epoxy compounds selected from the monoacrylic oxides of epoxy compounds having two epoxy groups in the molecule (1) to (7) (7) The polyurethane compound (E) or (8) according to any one of (1) to (7), which is soluble in an alkaline aqueous solution. Solid content acid value is 30 to 150 mg · KOH / g, The polyurethane compound (E) according to the above (8), (10) The aqueous alkaline solution soluble polyurethane compound (E) according to the above (8) or (9) is contained. (11) a photopolymerization initiator (F), a cross-linking agent (G), and a curing component (H) as an optional component. object , (12) a cured product of the photosensitive resin composition according to (10) or (11), (13) a substrate having a layer of the cured product according to (12), (14) described in (13) above. (15) Epoxy 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 group in the molecule The method is characterized by reacting a carboxylate compound (A), a diisocyanate compound (B) and a diol compound (C) having a carboxyl group with an epoxy compound (D) having an ethylenically unsaturated group in the molecule. To provide a method for producing a polyurethane compound (E).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the following, (meth) acrylic acid means methacrylic acid or acrylic acid, and (meth) acrylate means methacrylate or acrylate. The polyurethane compound (E) of the present invention is characterized by being obtained by reacting the following compound (A), compound (B), compound (C), and compound (D).

As long as the epoxy compound (a) having two or more epoxy groups in the molecule used for producing the polyurethane compound (E) of the present invention is a compound having two or more epoxy groups, its structure, The molecular weight is not particularly limited, but the epoxy equivalent is preferably 100 to 900 g / equivalent. When the epoxy equivalent is less than 100 g / equivalent, the molecular weight of the obtained polyurethane compound (E) may be small and film formation may be difficult or flexibility may not be sufficiently obtained, and the epoxy equivalent is 900.
If it exceeds g / equivalent, the introduction rate of the monocarboxylic acid (b) having an ethylenically unsaturated group may be low, and the photosensitivity may be lowered.

Specific examples of the epoxy compound (a) include:
For example, phenyl diglycidyl ether compounds such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether,
Bisphenol-A type epoxy resin, bisphenol-
F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,
Bisphenol type epoxy compounds such as epoxidized products of 1,1,3,3,3-hexafluoropropane, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, Hydrogenated bisphenol type epoxy compounds such as hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxidized product, brominated bisphenol-A type epoxy resin,
Halogenated bisphenol epoxy compounds such as brominated bisphenol-F epoxy resins, alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether compounds, 1,6-hexanediol diglycidyl ether, 1,4-butanediol Examples thereof include aliphatic diglycidyl ether compounds such as diglycidyl ether and diethylene glycol diglycidyl ether, polysulfide type diglycidyl ether compounds such as polysulfide diglycidyl ether, and biphenol type epoxy resin.

Commercially available products of these epoxy compounds are:
For example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 100
4 (all manufactured by Japan Epoxy Resin), Epomic R-140, Epomic R-301, Epomic R-3
04 (all manufactured by Mitsui Chemicals), DDR-331, DDR
-332, DDR-324 (all manufactured by Dow Chemical Co., Ltd.), Epicron 840, Epiclon 850 (all manufactured by Dainippon Ink) UVR-6410 (manufactured by Union Carbide), YD-8125 (manufactured by Toto Kasei Co., Ltd.), etc. Bisphenol-A type epoxy resin, UVR-6490 (manufactured by Union Carbide Co.), YDF-2001, YDF-2
004, YDF-8170 (all manufactured by Tohto Kasei Co., Ltd.),
Bisphenol-F type epoxy resins such as Epicron 830 and Epicron 835 (all manufactured by Dainippon Ink and Chemicals), H
BPA-DGD (Maruzen Petrochemical Co., Ltd.), Lycaredin HBD
− Hydrogenated bisphenols such as 100 (manufactured by Shin Nippon Rika) −
A type epoxy resin, DDR-513, DDR-514,
Brominated bisphenol-A type epoxy resin such as DDR-542 (all manufactured by Dow Chemical Co., Ltd.), Celoxide 2021 (manufactured by Daicel), Licaredin DMD-100
(Nippon Rika), DX-216 (Nagase Kasei) and other alicyclic epoxy resins, DD-503 (Asahi Denka), Rikaresin W-100 (Nippon Rika), DX-212, D
FL-DP-5, aliphatic diglycidyl ether compounds such as X-214 and DX-850 (both manufactured by Nagase Kasei)
0, polysulfide type diglycidyl ether compound such as FLDP-60 (all manufactured by Toraythiocol), YX
Biphenol-type epoxy compounds such as -4000 (manufactured by Japan Epoxy Resin).

Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule used for producing the polyurethane compound (E) of the present invention include acrylic acids, crotonic acid, α-cyanocinnamic acid, Examples include cinnamic acid or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, saturated or unsaturated dibasic acid anhydride, and one hydroxyl group in one molecule (meth).
Examples thereof include half-esters that are equimolar reaction products with acrylate derivatives, and half-esters that are equimolar reaction products with saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives. From the viewpoint of sensitivity when used as a product, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is particularly preferable.

As the diisocyanate compound (B) used for producing the polyurethane compound (E) of the present invention, any diisocyanate compound (B) can be used as long as it has two isocyanate groups in the molecule. Particularly excellent phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyan diisocyanate , N-acyl diisocyanate, trimethylhexamethylene diisocyanate or lysine diisocyanate Isocyanate is preferred.

The diol compound (C) having a carboxyl group used for producing the polyurethane compound (E) of the present invention is a diol compound having an alcoholic hydroxyl group or a phenolic hydroxyl group and a carboxyl group in the molecule at the same time. All of them can be used, but compounds having an alcoholic hydroxyl group, which are excellent in developability in an alkaline aqueous solution, are particularly preferable, and diol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferable compounds.

The epoxy compound (D) having an ethylenically unsaturated group in the molecule used for producing the polyurethane compound (E) of the present invention is an epoxy compound having an ethylenically unsaturated group. Although all can be used, glycidyl (meth) acrylate, glycidyl cinnamic acid, or a monoacrylic oxide of an epoxy compound having two epoxy groups in the molecule is preferable.

The polyurethane compound (E) of the present invention is produced by reacting the epoxy compound (a) with the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule (hereinafter referred to as the first reaction). The epoxycarboxylate compound (A) having an alcoholic hydroxyl group formed, the diisocyanate compound (B), and the diol compound (C) having a carboxyl group are reacted (hereinafter referred to as the second reaction), and this is reacted with an ethylenic compound in the molecule. It can be obtained by reacting an epoxy compound (D) having a saturated group (hereinafter referred to as the third reaction).

The first reaction is solvent-free or a solvent having no alcoholic hydroxyl group, specifically, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic carbonization such as benzene, toluene, xylene and tetramethylbenzene. Hydrogen ethers, 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, glu Esters such as dialkyl acid salts, dialkyl succinates and dialkyl adipates, cyclic esters such as γ-butyrolactone, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and further crosslinking agents described later. It can be carried out in a single or mixed organic solvent such as (G).

The proportion of the raw materials charged in this reaction is 80 to 120 equivalent% of the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, relative to 1 equivalent of the epoxy compound (a). preferable. If it deviates from this range, gelation may occur during the second reaction, or the thermal stability of the finally obtained polyurethane compound (E) may decrease.

During the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reactant. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst used include:
Examples thereof include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate and the like.
During the reaction, hydroquinone monomethyl ether, 2-
It is preferable to use a thermal polymerization inhibitor such as methylhydroquinone, hydroquinone, diphenylpicrylhydrazine or diphenylamine. In the first reaction, while appropriately sampling, the end point is when the acid value of the sample becomes 1 mg · KOH / g or less, preferably 0.5 mg · KOH / g or less.

In the second reaction, after the completion of the first reaction, the diol compound (C) having a carboxyl group is added to the reaction liquid (when the solvent is used, the solvent is usually used without removing the solvent), and the diisocyanate compound ( B) is a urethanization reaction in which B) is gradually added and reacted with the dispersion medium or solvent. The reaction can be performed without a catalyst, but a basic catalyst can also be used to accelerate the reaction, and the amount of the catalyst used is 10% by weight based on the reactant.
It is the following. The reaction temperature at this time is 40 to 120 ° C.
And the reaction time is preferably 5 to 60 hours. At this time, the above-mentioned solvent or thermal polymerization inhibitor may be used. The second reaction is 2250c in the infrared absorption spectrum of the sample, with appropriate sampling.
The end point is when the absorption around m ⁻¹ disappears.

The third reaction is an epoxy compound (D) having an ethylenically unsaturated group in its molecule in the reaction liquid (usually without removing the solvent when a solvent is used) after the completion of the second reaction. Is an epoxy acrylate reaction with the aforementioned diol compound (C) having a carboxyl group as a dispersion or a solution. The reaction can be carried out without a catalyst, but a basic catalyst can be used to accelerate the reaction, and the amount of the catalyst used is 10% by weight or less based on the reactant. The reaction temperature at this time is 4
0 to 120 ° C., and the reaction time is preferably 5 to
60 hours. At this time, the above-mentioned solvent or thermal polymerization inhibitor may be used.

During the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reactant. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst used include:
Examples thereof include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, zirconium octanoate and the like.

The charged amounts of the respective components are as follows: the charged equivalent of the compound (A) in the second reaction is x equivalent, the charged equivalent of the compound (B) is y equivalent, and the charged equivalent of the compound (C) is z equivalent. The equivalent ratio is preferably in the range of 5 ≧ (x + z) / y ≧ 1. When the value of (x + z) / y is less than 1, an isocyanate group remains at the terminal of the polyurethane compound (E) of the present invention, and the thermal stability is low and gelation may occur during storage, which is preferable. Absent. On the other hand, when this value exceeds 5, the molecular weight of the polyurethane compound (E) becomes low, which may cause problems of tackiness and low sensitivity.

The thus obtained polyurethane compound (E) of the present invention can be isolated by removing the solvent by a suitable method, but it is used as a photosensitive resin composition. In many cases, it can be used without removing the solvent. The polyurethane compound (E) of the present invention is usually soluble in an alkaline aqueous solution, but is also soluble in the above-mentioned solvents, and when used in a solder resist, a plating resist, etc., it can be developed with a solvent. is there. In addition, the solid acid value of the polyurethane compound (E) is 3
If it is less than 0 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and if patterning is performed,
There is a risk that it will remain as a residue or, in the worst case, patterning may not be possible. In addition, the solid acid value is 150 mgK
If it exceeds OH / g, the solubility in an alkaline aqueous solution becomes too high and the photocured pattern may peel off, which is not preferable.

The photosensitive resin composition of the present invention comprises the polyurethane compound (E) of the present invention, a photopolymerization initiator (F), a cross-linking agent (G), and a curing component (H) as an optional component. And The content ratio of the above-mentioned polyurethane compound (E) used in the photosensitive resin composition of the present invention is usually 15 to 70% by weight, preferably 100% by weight when the solid content of the photosensitive resin composition is 100% by weight, 20 to 60% by weight. In the photosensitive resin composition of the present invention, the components other than the solid content are the solvents used when preparing the polyurethane compound (E) (a similar solvent may be added to adjust the viscosity of the resin composition). Is.

Specific examples of the photopolymerization initiator (F) 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
-Acetophenones such as hydroxyquinohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-
Anthraquinones such as ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2
Thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone;
Examples thereof include phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. The addition ratio of these is usually 1 to 30% by weight, preferably 2 to 25% by weight, when the solid content of the photosensitive resin composition is 100% by weight.
Is.

These can be used alone or as a mixture of two or more kinds, and further, tertiary amines such as triethanolamine and methyldiethanolamine, ethyl N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid. It can be used in combination with a promoter such as a benzoic acid derivative such as acid isoamyl ester.
These promoters are added to the photopolymerization initiator (F) in an amount of 10
If necessary, an amount of 0% by weight or less is added.

Specific examples of the crosslinking agent (G) used in the photosensitive resin composition of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 1,4-butanediol mono. (Meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono ( (Meth) acrylate etc.) and acid anhydrides of polycarboxylic acid compounds (for example, succinic acid-free, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.), half ester, polyethylene glycol Di (meth) acrylate, tripro Addition of ε-caprolactone to renglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, and hydroxypentavalene neopentene glycol. Di (meth) acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., KAY
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 compound. (For example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether and (meth) acrylic Epoxy (meth) acrylate, which is a reaction product of an acid, and the like can be mentioned. The addition ratio of these is usually 2 to 40% by weight when the solid content of the photosensitive resin composition is 100% by weight,
It is preferably 5 to 30% by weight.

Examples of the curing component (H) used as an optional component in the photosensitive resin composition of the present invention include epoxy compounds and oxazine compounds. The curing component (H) is particularly preferably used in the case of reacting with the carboxyl groups remaining in the resin coating film after photocuring by heating to obtain a cured coating film having stronger chemical resistance.

Specific examples of the epoxy compound as the curing component (H) include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A.
Type epoxy resin, bisphenol-F type epoxy resin,
Examples thereof include biphenol type epoxy resin, bisphenol-A novolak type epoxy resin, naphthalene skeleton-containing epoxy resin, and heterocyclic epoxy resin.

Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink and Chemicals, Inc.), D.I. D. N438 (manufactured by Dow Chemical Co.), Epicoat 154 (Yukaka Shell Epoxy Co., Ltd.)
Manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink and Chemicals, Inc.), DOCN-102S, DOCN-103.
S, DOCN-104S (Nippon Kayaku Co., Ltd.), UVR
-6650 (made by Union Carbide), DSCN-1
95 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the trishydroxyphenylmethane type epoxy resin include DPPN-503 and DPPN-
502H, DPPN-501H (manufactured by Nippon Kayaku Co., Ltd.),
TACTIX-742 (manufactured by Dow Chemical Co.), Epicoat D1032H60 (manufactured by Yuka Shell Epoxy Co., Ltd.)
Etc. Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon DXA-720.
0 (manufactured by Dainippon Ink and Chemicals, Inc.), TACTIX-
556 (manufactured by Dow Chemical Co.) and the like.

As the bisphenol type epoxy resin,
For example, Epicoat 828, Epicoat 1001 (made by Yuka Shell Epoxy), UVR-6410 (made by Union Carbide), D.I. D. R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.) and other bisphenol-A type epoxy resins, UVR-6490 (manufactured by Union Carbide Co.), YDF-8170 (manufactured by Toto Kasei Co., Ltd.)
And other bisphenol-F type epoxy resins.

As the biphenol type epoxy resin, for example, biphenol type epoxy resins such as NC-3000P, NC-3000S (manufactured by Nippon Kayaku Co., Ltd.), YX-4.
000 (produced by Yuka Shell Epoxy Co., Ltd.) and bixylenol type epoxy resin, YL-6121 (produced by Yuka Shell Epoxy Co., Ltd.) and the like. Examples of the bisphenol A novolac type epoxy resin include Epiclon N-8.
80 (manufactured by Dainippon Ink and Chemicals, Inc.), Epicoat D
157S75 (produced by Yuka Shell Epoxy Co., Ltd.) and the like.

As the naphthalene skeleton-containing epoxy resin, for example, NC-7000 (manufactured by Nippon Kayaku Co., Ltd.), DXA-
4750 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like. Examples of the alicyclic epoxy resin include DHPD-
3150 (manufactured by Daicel Chemical Industries, Ltd.) and the like. Examples of the heterocyclic epoxy resin include TDPI
C, TDPIC-L, TDPIC-H, TDPIC-S
(Both manufactured by Nissan Chemical Industries, Ltd.) and the like.

Specific examples of the oxazine compound as the curing component (H) include, for example, Bm type benzoxazine,
Examples thereof include Pa type benzoxazine and Ba type benzoxazine (both manufactured by Shikoku Chemicals Co., Ltd.).

The addition ratio of the curing component (H) is preferably 200% or less of the equivalent calculated from the acid value of the solid content of the polyurethane compound of the present invention and the amount used. This amount is 2
If it exceeds 00%, the developability of the photosensitive resin composition of the present invention may be significantly lowered, which is not preferable. When the curing component (H) is an epoxy resin, melamine, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole,
Epoxy curing accelerators such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and the like can be used in combination, but as will be described below, the components (E) and (H) are 2 It is preferable to use it separately in a liquid.

If necessary, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, and other fillers, and thixotropy such as aerosil are provided. Agents; phthalocyanine blue, phthalocyanine green, colorants such as titanium oxide, silicone, fluorine-based leveling agents and defoaming agents; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether are added for the purpose of enhancing various properties of the composition. You can

The above-mentioned curing component (H) may be mixed with the above resin composition in advance, but it may be mixed and used before being applied to the printed wiring board. That is, the above-mentioned (E) component is the main component solution containing the epoxy curing accelerator and the like as the main component solution, and the curing agent solution containing the curing component (H) as the main component. It is preferable to use them as a mixture.

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

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

The cured product of the present invention is obtained by curing the above resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing can be carried out by an ordinary method by irradiation with energy rays such as ultraviolet rays. For example, when irradiating with ultraviolet rays, an ultraviolet ray generator such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (excimer laser, etc.) may be used.

The cured product of the resin composition of the present invention is, for example, a resist film, an interlayer insulating material for a build-up method, or a base material for electric / electronic / optical parts such as a printed circuit board, an optoelectronic board or an optical board as an optical waveguide. Used as. Examples of the article of the present invention using these base materials include computers, home appliances, mobile devices, and the like. The film thickness of this cured product layer is about 0.5 to 160 μm, and 1 to 100 μm.
A degree is preferable.

A printed wiring board using the photosensitive resin composition of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, the present invention can be applied to a printed wiring board by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc., in a film thickness of 5 to 160 μm. The coating film can be formed by applying the composition of (1) and drying the coating film at a temperature of usually 50 to 110 ° C, preferably 60 to 100 ° C. Thereafter, the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays at an intensity of about 10 to 2000 mJ / cm ² through a photomask on which an exposure pattern such as a negative film is formed, and the unexposed portion is developed as described below. Development is performed by using a liquid, for example, by spraying, rocking dipping, brushing, scrubbing, or the like. Thereafter, if necessary, further irradiation with ultraviolet rays is carried out, and then usually 100 to 200 ° C., preferably 1
By heat treatment at a temperature of 40 to 180 ° C., excellent gold plating properties, heat resistance, solvent resistance, acid resistance, adhesion,
A printed wiring board having a permanent protective film satisfying various characteristics such as flexibility can be obtained.

As the alkaline aqueous solution used for the above-mentioned development, an inorganic alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, or the like can be used. Organic alkaline aqueous solutions such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine and the like can be used.

[0044]

The present invention will be described in more detail with reference to the following 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, RE-310S (bifunctional bisphenol-A manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy compound (a) having two or more epoxy groups in the molecule. Type epoxy resin, epoxy equivalent: 184.0g
/ Equivalent) 368.0 g, 141.24 g of acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and hydroquinone monomethyl ether 1 as a thermal polymerization inhibitor. .02
and triphenylphosphine as a reaction catalyst.
Charged 53 g, the acid value of the reaction solution was 0.5 m at a temperature of 98 ° C.
Epoxycarboxylate compound (A) (theoretical molecular weight: 509.2)
4) was obtained. Then, to this reaction solution were added 684.17 g of carbitol acetate as a reaction solvent, 0.977 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 303.74 g of dimethylolpropionic acid as a diol compound (C) having a carboxyl group. The temperature was raised to 45 ° C. 457.61 g of trimethylhexamethylene diisocyanate (molecular weight: 210.27) as a diisocyanate compound (B) was added to this solution at a reaction temperature of 50 ° C.
The solution was gradually added so as not to exceed the value. After the dropping, the temperature is raised to 80 ° C. and the infrared absorption spectrum measurement method is used.
The reaction was carried out for 6 hours until the absorption around 2250 cm ^-1 disappeared. In this solution, as an epoxy compound (D) having an ethylenically unsaturated group in the molecule, 53.53 g of glycidyl methacrylate (molecular weight: 142.15), carbitol acetate 28.82 g, and a thermal polymerization inhibitor of 2-
1.02 g of methylhydroquinone and 5.09 g of triphenylphosphine as a reaction catalyst were added. After the addition, the temperature was raised to 95 ° C. and the reaction was performed for 6 hours to obtain a resin solution containing 65% by weight of the polyurethane compound (E) of the present invention (this solution is referred to as E-1). When the acid value was measured, it was 51.56 mg · KOH / g (solid content acid value: 79.
32 mg · KOH / g).

Example 2 In a 2 L flask equipped with a stirrer and a reflux tube, RE-310S (bifunctional bisphenol-A manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy compound (a) having two or more epoxy groups in the molecule. Type epoxy resin, epoxy equivalent: 184.0g
/ Equivalent) of 368.0 g, methacrylic acid (molecular weight: 86.09) of 168.74 g as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and hydroquinone monomethyl ether of 1 as a thermal polymerization inhibitor. .0
7 g and 1.61 g of triphenylphosphine as a reaction catalyst were charged, and the acid value of the reaction solution was 0.8 at a temperature of 98 ° C.
Epoxycarboxylate compound (A) (theoretical molecular weight: 536.
74) was obtained. Next, 738.15 g of carbitol acetate as a reaction solvent, 1.05 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and dimethylolpropionic acid as a diol compound (C) having a carboxyl group were added to the reaction solution as a reaction solvent. 1) to 393.2
4 g was added and the temperature was raised to 45 ° C. To this solution, 440.87 g of hexamethylene diisocyanate (molecular weight: 168.20) as a diisocyanate compound (B) was gradually added dropwise so that the reaction temperature did not exceed 50 ° C. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption around 2250 cm ⁻¹ disappeared by the infrared absorption spectrum measurement method. Glycidyl methacrylate (molecular weight: 142.15) 115.51 as an epoxy compound (D) having an ethylenically unsaturated group in the molecule in this solution
g, carbitol acetate 62.20 g, 2-methylhydroquinone as a thermal polymerization inhibitor 1.14 g, and triphenylphosphine 5.72 g as a reaction catalyst. After the addition, the temperature was raised to 95 ° C. and the reaction was performed for 6 hours to obtain a resin solution containing 65% by weight of the polyurethane compound (E) of the present invention (this solution is referred to as E-2). When the acid value was measured, it was 52.00 mg · KOH / g (solid content acid value: 80.00 mg · KOH / g).

Example 3 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 the molecule, YX-8000 (2 manufactured by Japan Epoxy Resin) was used.
404.1 g of functional hydrogenated bisphenol-A type epoxy resin, epoxy equivalent: 202.06 g / equivalent, acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. ) To 14
4.1 g, 1.10 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor and 1.61 g of triphenylphosphine as a reaction catalyst were charged, and the acid value of the reaction solution at a temperature of 98 ° C. was 0.5 mg · KOH / g or less. The reaction was continued until it became an epoxycarboxylate compound (A) (theoretical molecular weight: 548.2). Then, to this reaction solution, 754.76 g of methyl ethyl ketone as a reaction solvent, 4.31 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor, and dimethylolpropionic acid (molecular weight: 13 as a diol compound (C) having a carboxyl group).
335.08 g of 4.1) was added and the temperature was raised to 45 ° C.
Isophorone diisocyanate (molecular weight: 222.3) 518.
42 g was gradually added dropwise so that the reaction temperature did not exceed 50 ° C. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption around 2250 cm ⁻¹ disappeared by the infrared absorption spectrum measurement method. Glycidyl methacrylate (molecular weight: 142.1) was added to this solution as an epoxy compound (D) having an ethylenically unsaturated group in the molecule.
5) 59.06 g, methyl ethyl ketone 31.80
g, 1.12 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 5.62 g of triphenylphosphine as a reaction catalyst. After the addition, the temperature was raised to 95 ° C. and the reaction was carried out for 6 hours to obtain a resin solution containing 65% by weight of the polyurethane compound (E) of the present invention.
-3). When the acid value was measured, it was 52.00 mg.
・ KOH / g (Solid content acid value: 80.00 mg ・ KOH /
g).

Examples 4, 5 (E-1) and (E-) obtained in Example 1 and Example 2
2) was further used, and the components shown in Table 1 were mixed at the blending ratio (weight ratio) shown in Table 1 and kneaded with a three-roll mill to obtain a photosensitive resin composition of the present invention. This was applied to a printed board by screen printing so that the dry film thickness was 15 to 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 30 minutes.
It was dried for a minute. Then, ultraviolet rays were irradiated through a mask on which a circuit pattern was drawn, using an ultraviolet exposure device (Model HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.). After that, spray development was performed with a 1 wt% sodium carbonate aqueous solution to remove the resin in the portion not irradiated with ultraviolet rays. After washing with water and drying, the printed board was subjected to a heat curing reaction for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured film. About the obtained cured product,
Various tests as described below were performed. The results are shown in Table 2.
Shown in. The test method and evaluation method are as follows.

(Tackiness) The dried film applied to the substrate was rubbed with absorbent cotton to evaluate the tackiness of the film. The evaluation criteria are as follows. ○ ・ ・ ・ ・ The absorbent cotton does not stick. × ・ ・ ・ ・ The cotton lint sticks to the film.

(Developability) The following evaluation criteria were used. ○ ... ・ Ink was completely removed during development and development was possible. X ...- Some areas are not developed during development.

(Resolution) A 50 μm negative pattern is brought into close contact with the dried coating film and exposed to ultraviolet rays with an integrated light amount of 200 mJ / cm ² . Next, it is developed with a 1 wt% sodium carbonate aqueous 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. × ... Peeling or jagged pattern edges.

(Photosensitivity) A step tablet 21 steps (manufactured by Kodak Co., Ltd.) was brought into close contact with the dried coating film to obtain an integrated light amount of 50.
It is exposed to ultraviolet light of 0 mJ / cm ² . Next, it is developed with a 1% sodium carbonate aqueous solution 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 on the coating film after drying
Irradiate and expose with ultraviolet rays of / cm ² . Then, it is developed with a 1% sodium carbonate aqueous solution 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 cloudiness is observed × ・ ・ ・ ・ Slight cloudiness is observed

(Substrate Warpage) The following criteria were used. ○ ・ ・ ・ ・ No warpage on the substrate △ ・ ・ ・ ・ Slightly warped substrate × ・ ・ ・ ・ Warp of the substrate can be seen

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

(Adhesiveness) According to JIS K5400,
100 1 mm squares were made on the test piece, and a peeling test was performed using Cellotape (R). The peeling state of the first eye was observed and evaluated according to the following criteria. ○ ・ ・ ・ ・ No peeling × ・ ・ ・ ・ Peeling

(Pencil hardness) The pencil hardness was evaluated according to JIS K5400.

(Solvent resistance) The test piece is immersed in isopropyl alcohol for 30 minutes at room temperature. 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. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Acid resistance) The test piece is immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there is no abnormal appearance,
A peeling test using Cellotape (R) was performed and evaluated according to the following criteria. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Heat resistance) A rosin-based plaque was applied to the test piece and immersed in a solder bath at 260 ° C for 5 seconds. This was set as one cycle and repeated for three cycles. After allowing to cool to room temperature, a peeling test using Cellotape (R) was performed and evaluated according to the following criteria. 〇 ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Gold plating resistance) A test substrate was treated with an acidic degreasing solution (MDtDx L-5, manufactured by Nippon McDermitt) at 30 ° C.
(20 vol% aqueous solution of B) for 3 minutes, then washed with water, then immersed in 14.4 wt% ammonium persulfate aqueous solution for 3 minutes at room temperature, and then washed with water, and further test substrate was immersed in 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute. After dipping for a minute, it was washed with water.
Next, this substrate was immersed in a catalyst solution at 30 ° C (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and a nickel plating solution at 85 ° C (Meltex Ni-Melplate Ni- 2 of 865M
It was dipped in a 0 vol% aqueous solution, pH 4.6) for 20 minutes to perform nickel plating, and then dipped in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water. Then, the test board is
Immersing in a gold plating solution at ℃ (Meltex, an aqueous solution of 15% by volume of Aurolectroles UP and 3% by volume of potassium gold cyanide, pH 6) for 10 minutes to perform electroless gold plating, followed by rinsing with water and further heating with hot water at 60 ° C. It was soaked for a minute, washed with water and dried. A cellophane adhesive tape was attached to the obtained electroless gold-plated evaluation substrate, and the state of peeling was observed. ◯: No abnormality. X: Some peeling was observed.

(PCT resistance) After the test substrate was left in water at 121 ° C. and 2 atm for 96 hours, it was confirmed that there was no abnormality in appearance, and then a peeling test was performed using Cellotape (R).
The following criteria evaluated. ○ ・ ・ ・ ・ The appearance of the coating film is not abnormal and there is no blistering or peeling × ・ ・ ・ ・ The coating has blistering or peeling

(Thermal shock resistance) The test piece was tested at -55 ° C / 30.
Min, 125 ° C./30 minutes as one cycle, a thermal history is added, and after 1000 cycles, the test piece is observed under a microscope.
The following criteria evaluated. ○ ・ ・ ・ ・ No cracks in the coating film × ・ ・ ・ ・ ・ ・ Cracks in the coating film

[0064] Table 1                                       Example Note 45 Resin solution   E-1 51.80   E-2 51.80 Cross-linking agent (G)   DPCA * 1 3.38   HX-220 * 2 3.38 Photopolymerization initiator (F)   Irgacure 907 * 3 4.50 4.50   DDTX-S * 4 0.45 0.45 Curing component (H)   YX-4000 * 5 17.62 17.62 Epoxy resin curing accelerator   Melamine 1.00 1.00 filler   Barium sulfate 15.15 15.15 Colorant   Phthalocyanine blue 0.45 0.45 Additive   BYK-354 * 6 0.39 0.39   KS-66 * 7 0.39 0.39 solvent   CA * 8 4.87 4.87

Note * 1 Nippon Kayaku: ε-caprolactone modified dipentaerythritol hexaacrylate * 2 Nippon Kayaku: ε-caprolactone modified hydroxypivalic acid neopentyl glycol diacrylate * 3 Vantico: 2-methyl- (4 -(Methylthio) phenyl) -2-morpholino-1-propane * 4 Nippon Kayaku: 2,4-diethylthioxanthone * 5 JDR: Bifunctional bixylenol type epoxy resin * 6 BYK Chemie: Leveling agent * 7 Shin-Etsu Chemical Product: Defoamer * 8 Carbitol acetate

Table 2 Example 45 Evaluation item Tackiness ○ ○ Developability ○ ○ Resolution ○ ○ Light sensitivity 12 11 Surface gloss ○ ○ Substrate sled ○ △ Flexibility ○ ○ Adhesion ○ ○ Pencil hardness 4H 5H Solvent resistance ○ ○ Acid resistance ○ ○ Heat resistance ○ ○ Gold plating resistance ○ ○ PCT resistance ○ ○ Thermal shock resistance ○ ○

Example 6 54.44 g of the resin solution (E-3) obtained in Example 3,
As a cross-linking agent (G), HX-220 (trade name: bifunctional acrylate resin manufactured by Nippon Kayaku) 3.54 g, and as a photopolymerization initiator (F), Irgacure 907 (trade name: photopolymerization initiator manufactured by Bantico) 4.72g and Kayacure D
DTX-S (trade name: photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd.) was used.
47 g, YX-8000 (trade name: Japan Epoxy Resin, bifunctional hydrogenated bisphenol-A type epoxy resin, epoxy equivalent: 202.06) as a curing component (H)
g / equivalent) of 14.83 g, melamine of 1.05 g as a thermosetting catalyst and methyl ethyl ketone of 20.95 g as a concentration-adjusting solvent were added, and the mixture was kneaded and uniformly dispersed in a bead mill to obtain a photosensitive resin composition of the present invention. .

The composition obtained was subjected to a roll coating method,
It is evenly applied to a polyethylene terephthalate film to be a support film, passed through a hot air drying oven at a temperature of 70 ° C. to form a resin layer having a thickness of 30 μm, and then a polyethylene film to be a protective film is attached onto the resin layer, A dry film was obtained. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm / polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C. while the protective film was peeled off, and the resin layer was attached to the entire surface of the substrate.

Next, ultraviolet rays were irradiated (irradiation amount 500 mJ / m ² ) using an ultraviolet reduction projection exposure apparatus equipped with a negative mask having an optical waveguide pattern. After irradiation,
The support film was peeled from the resin and developed with a 0.25 wt% tetramethylammonium aqueous solution for 30 seconds to dissolve and remove the unirradiated portion. After washing with water and drying, the printed board was subjected to a heat curing reaction for 30 minutes in a hot air dryer at 150 ° C. to obtain a cured film. The obtained cured product had good transparency and a pattern of 50 μm was resolved.

As is clear from the above results, the polyurethane compound of the present invention and the photosensitive resin composition using the same have no tackiness and high sensitivity, and the cured film thereof has solder heat resistance and chemical resistance. A photosensitive resin composition for a printed circuit board, which has excellent resistance to gold plating, does not cause cracks on the surface of the cured product, and has less warpage even when a thin film substrate is used.

[0071]

INDUSTRIAL APPLICABILITY The polyurethane compound of the present invention and the photosensitive resin composition using the same have excellent photosensitivity in the formation of a coating film by exposure and curing with ultraviolet rays, and the obtained cured product has flexibility and Gold plating resistance, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, etc. are also sufficiently satisfied, and in particular, a photosensitive resin composition for printed wiring boards and a photosensitive resin composition for forming an optical waveguide. Suitable for

Claims (15)

[Claims] 1. A polyurethane compound (E) obtained by reacting a compound (A), a compound (B), a compound (C) and a compound (D) shown below. Compound (A): Epoxycarboxylate compound 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 group in the molecule (B): diisocyanate compound compound (C): diol compound compound having a carboxyl group (D): epoxy compound having an ethylenically unsaturated group in the molecule 2. The epoxy equivalent of the epoxy compound (a) is
The polyurethane compound (E) according to claim 1, which has an amount of 100 to 900 g / equivalent. 3. The epoxy compound (a) is a phenyl diglycidyl ether compound, a bisphenol type epoxy compound, a hydrogenated bisphenol type epoxy compound, a halogenated bisphenol type epoxy compound, an alicyclic diglycidyl ether compound, an aliphatic diglycidyl ether. Compound, polysulfide type diglycidyl ether compound,
The polyurethane compound (E) according to claim 1 or 2, which is one or more epoxy compounds selected from a biphenol type epoxy compound and a bixylenol type epoxy compound. 4. The monocarboxylic acid compound (b) is (meth)
4. One or more monocarboxylic acids selected from acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, and cinnamic acid. Polyurethane compound (E). 5. The compound (B) is phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate,
1 selected from diphenylmethane diisocyanate, naphthalene diisocyanate, tridene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl cyan diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate The polyurethane compound (E) according to any one of claims 1 to 4, which is one or more kinds of compounds. 6. The polyurethane compound (E) according to any one of claims 1 to 5, wherein the hydroxyl group of the compound (C) is an alcoholic hydroxyl group. 7. The compound (D) is one or more selected from glycidyl ((meth) acrylate, glycidyl cinnamic acid, and a monoacrylic oxide of an epoxy compound having two epoxy groups in the molecule. 7. The polyurethane compound (E) according to any one of claims 1 to 6, which is the epoxy compound of. 8. The polyurethane compound (E) according to any one of claims 1 to 7, which is soluble in an alkaline aqueous solution. 9. The acid value of solid content is 30 to 150 mg.KOH
/ G, The polyurethane compound (E) according to claim 8. 10. A photosensitive resin composition containing the alkaline aqueous solution-soluble polyurethane compound (E) according to claim 8 or 9. 11. The photosensitive resin composition according to claim 10, which contains a photopolymerization initiator (F), a cross-linking agent (G), and a curing component (H) as an optional component. 12. A cured product of the photosensitive resin composition according to claim 10. 13. A substrate having a layer of the cured product according to claim 12. 14. An article having the substrate according to claim 13. 15. An epoxycarboxylate 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 group in the molecule ( A polyurethane compound characterized by reacting A), a diisocyanate compound (B) and a diol compound (C) having a carboxyl group, and then reacting an epoxy compound (D) having an ethylenically unsaturated group in the molecule. The manufacturing method of (E).