JP2001316436A - Resin composition, solder resist resin composition and their cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which gives a cured produce excellent in flexibilyty, soldering heat resistance, heat deterioration resistance and electroless gold plating resistance and is developable with an organic solvent or a dilute alkaline solution and suitable for a solder resist and an interlayer insulating layer. SOLUTION: The resin composition comprises an oligomer (A) which is a reaction product of a terminal anhydride or isocyanate group-containing imide compound (c), which is a reaction produce of a tetracarboxylic dianhydride (a) with a polyisocyanate compound (b), with a (meth)acrylate (d) bearing at least one hydroxyl group in one molecule, and a diluent (B) such as γ- butyrolactone or the like. The amounts of the components (A) and (B) contained in the resin composition are such that the total of the components (A) and (B) accounts for 10-90 wt.% in the composition and that the ratio of the components (A) and (B) employed is 10-90 wt.% for the component (A) and 10-90 wt.% for the component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition containing the specific oligomer (A) of the present invention and a diluent (B) and useful as a resin composition for printed wiring boards, and a cured product thereof. More specifically, it is useful as a solder resist for a flexible printed wiring board, a plating resist, and an interlayer electrical insulating material for a multilayer printed wiring board. It has excellent developability, and its cured film has adhesiveness, flexibility (flexibility), The present invention relates to a resin composition that gives a cured product excellent in solder heat resistance, chemical resistance, gold plating resistance, and the like, and a cured product thereof.

[0002]

2. Description of the Related Art A wiring (circuit) pattern formed on a substrate by screen printing or the like is not required in a soldering process performed when protecting a wiring (circuit) pattern from an external environment or mounting electronic components on a printed wiring board. In order to protect solder from adhering to any part, a protective layer called a cover coat or a solder mask is coated on a printed wiring board. Heretofore, as a solder resist ink used for such an application, a polyfunctional epoxy resin-based ink has been mainly used, but there is a problem that a cured film obtained has good heat resistance but low flexibility. . Therefore, such a solder resist ink is used for a rigid board in which the flexibility (flexibility) of a cured film is not required, and is applied to a flexible printed wiring board (FPC) which has been increasingly used in recent years. Is difficult to use.

Under the circumstances described above, many proposals have recently been made as resist inks having flexibility. For example, JP-A-2-269166 discloses a thermosetting solder resist ink comprising polyparabanic acid, an epoxy resin and a polar solvent, and JP-A-6-41485 discloses a thermal drying method comprising polyparabanic acid and a phenoxy resin as essential components. Molded solder resist inks have been proposed.
However, since these solder resists form a resist pattern by screen printing, it is difficult to respond to fine image formation associated with today's high density, for example, the line width of the screen is limited. . For this reason, in recent years, there has been proposed a photo-developing type as disclosed in JP-A-2-173949, JP-A-2-173750, JP-A-2-173951, and the like, but still has sufficient flexibility. It has not been done yet.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fine image capable of coping with the high density of today's printed circuits, having excellent sensitivity to active energy rays, exposure and organic solvents, water or diluted alkaline aqueous solutions. The cured film obtained by heat-curing in a post-curing (post-curing) step is rich in flexibility, and has excellent solder heat resistance, heat deterioration resistance, electroless gold plating resistance, acid resistance, and water resistance. It is an object of the present invention to provide a resin composition suitable for an organic solvent, water or alkali developing type resist ink for a flexible printed wiring board which forms an excellent film, and a cured product thereof.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have solved the above problem by using a resin composition containing a specific oligomer (A) and a diluent (B). Have been achieved, and the present invention has been completed. That is, the present invention relates to (1) a terminal acid anhydride group-containing or isocyanate group-containing imide compound (c) which is a reaction product of a tetracarboxylic dianhydride (a) and a polyisocyanate compound (b), and A resin composition comprising an oligomer (A), which is a reactant of (meth) acrylate (d) having one hydroxyl group, and a diluent (B), (2) two or more in one molecule Unsaturated group-containing polycarboxylic acid resin (C) which is a reaction product of an epoxy resin having an epoxy group (e), a monocarboxylic acid compound having an ethylenically unsaturated group (f), and a polybasic acid anhydride (g) (3) The epoxy resin (e) having two or more epoxy groups in one molecule is represented by the formula (1):

[0006]

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(In the formula (1), X is -CH2- or -C
(CH3) 2-, n is an integer of 1 or more, and M represents a hydrogen atom or the following formula (G).

[0008]

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(Where n is 1, M represents the formula (G), and the remainder represents a hydrogen atom.) The resin composition according to item (2), which is an epoxy resin (e) represented by the formula (2): (4) The resin composition according to any one of (1) to (3), which contains a photopolymerization initiator (D), and (5) which contains a thermosetting component (E). (6) The resin composition according to any one of (1) to (5), which is used for a solder resist or an interlayer insulating layer of a printed wiring board, 7) a cured product of the resin composition according to any one of (1) to (6), (8)
(9) The article having the cured product layer according to (7), and (9) the article according to (8), which is a printed wiring board.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention is a mixture of an oligomer (A) and a diluent (B). The molecular weight of the oligomer (A) used here is preferably from 500 to 100,000 as a weight average molecular weight, and its acid value is preferably from 0 to 300 mgKOH / g.

As described above, the oligomer (A) used in the present invention is a imide compound having a terminal acid anhydride group or an isocyanate group, which is a reaction product of a tetracarboxylic dianhydride (a) and a polyisocyanate compound (b). (C) and 1
It is a reactant of (meth) acrylate (d) having at least one hydroxyl group in the molecule. More specifically, for example, the anhydride group of the tetracarboxylic dianhydride (a) and the isocyanate group of the polyisocyanate compound (b) are subjected to a decarboxylation reaction to perform a terminal acid anhydride group or a terminal isocyanate group-containing imide compound (c Get) Next, the imide compound (c)
By reacting (meth) acrylate (d) having at least one hydroxyl group in one molecule with an anhydride group or an isocyanate group. The tetracarboxylic dianhydride (a) is, for example, a general (2)

[0012]

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(Wherein, R1 is 4 of 2-30 carbon atoms)
Represents a valent organic group. )) Or its derivative and the like. Specific examples are not particularly limited, for example, pyromellitic acid, 3,
3 ′, 4,4′-benzophenonetetracarboxylic acid,
3,3 ′, 4,4′-biphenyltetracarboxylic acid,
2,3 ′, 3,4′-biphenyltetracarboxylic acid,
2,3 ′, 4,4′-biphenyltetracarboxylic acid,
3,3 ′, 4,4′-diphenylethertetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid,
2,3,6,7-naphthalenetetracarboxylic acid, 1,
4,5,8-naphthalenetetracarboxylic acid, 3,3 ′,
4,4'-diphenylsulfonetetracarboxylic acid, m-
Terphenyl-3,3 ', 4,4'-tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,
2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis [4'-
(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4 ′-(2,3- or 3 , 4-
Dicarboxyphenoxy) phenyl] propane, 2,
3,6,7-anthracenetetracarboxylic acid, 1,2,2
7,8-phenanthrenetetracarboxylic acid, 4,4′-
Dianhydride of aromatic tetracarboxylic acid such as bis (2,3-dicarboxyphenoxy) diphenylmethaneethylene glycol bis (anhydrotrimellitate), the following general formula (3)

[0014]

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(Wherein R5 and R6 are monovalent hydrocarbon groups, preferably C1-10 hydrocarbon groups, more preferably C1-5 alkyl groups or C6-10 aryl groups. (Phenyl group, tolyl group, naphthyl group), which may be the same or different, and liter is an integer of 1 or more), an aromatic tetracarboxylic dianhydride, cyclobutenetetracarboxylic acid, Aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, and 3,4,9,10-pesolenetetracarboxylic acid; Alternatively, they are used in combination of two or more. Specific examples of the polyisocyanate compound (b) include, for example, 2,4- and / or 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, hydrogenated MD
I, lysine isocyanate, organic polyisocyanate such as triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, a triple of these organic polyisocyanates, or a terminal isocyanate product which is a reaction product of these organic polyisocyanates and polyol Is mentioned. Specific examples of the polyol include, for example, alkyl polyol, polyester polyol, polyether polyol, acrylic polyol, polybutadiene polyol, perfluoroalkyl polyol, perfluoropolyether polyol, rubber-modified polyol, polysiloxane polyol, and phenolic. Polyols and / or flame-retardant polyols.

Examples of the alkyl polyol include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, trimethylolpropane, and pentaerythritol.

Examples of the polyester polyol include a condensation type polyester polyol, an addition polymerization polyester polyol, and a polycarbonate polyol. As the condensation type polyester polyol, ethylene glycol, propylene glycol, ethylene glycol,
1,4-butanediol, neopentyl glycol,
Diol compounds such as 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,4-hexanedimethanol, dimer acid diol, and polyethylene glycol, and adipic acid, isophthalic acid, and terephthalic acid It is obtained by a condensation reaction with an organic polybasic acid such as acid or sebacic acid, and has a molecular weight of 100 to 100,00.
0 is preferred.

The addition-polymerized polyester polyol includes polycaprolactone, and has a molecular weight of 100 to 100.
100,000 is preferred. Polycarbonate polyol is synthesized by direct phosgenation of polyol, transesterification with diphenyl carbonate, and the like, and preferably has a molecular weight of 100 to 100,000.

As the polyether polyol, PEG
, PPG-based, and PTG-based polyols. P
The EG-based polyol is obtained by subjecting ethylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and preferably has a molecular weight of 100 to 100,000. PP
The G-based polyol is obtained by subjecting propylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and preferably has a molecular weight of 100 to 100,000. PT
The G-based polyol is synthesized by cationic polymerization of tetrahydrofuran, and preferably has a molecular weight of 100 to 100,000.

Examples of the polyether polyol other than the above-mentioned polyether polyol include an ethylene oxide adduct or a propylene oxide adduct of bisphenol A, and the molecular weight is preferably 100 to 100,000.

Other polyols include (meth) acryl polyol, which is a copolymer of a hydroxyl group-containing (meth) acrylate and another (meth) acrylate, and a copolymer of butadiene with a hydroxyl group at a terminal. Polybutadiene polyol, a phenolic polyol containing a phenol molecule in the molecule, an epoxy polyol, a flame-retardant polyol containing a phosphorus atom, a halogen atom and the like, and a molecular weight of 100 to 100, 000 is preferred.
These polyol compounds are preferably diol compounds, and can be used alone or in combination of two or more. For example, 0.5 to 0.9 equivalents of the isocyanate group of the polyisocyanate compound (b) is subjected to a decarboxylation reaction with respect to 1 equivalent of the anhydride group of the tetracarboxylic dianhydride (a) to form a terminal acid anhydride. Substance group-containing imide compound (c-1) can be obtained. On the other hand, the isocyanate group-containing imide compound (c-2) is subjected to a decarboxylation reaction of 1.1 to 2.0 equivalents of the isocyanate group of the component (b) with respect to 1 equivalent of the anhydride group of the component (a). Obtainable. The reaction temperature is usually from 80 to 200C, preferably from 90 to 130C. The reaction time is 5 to 30 hours. During the reaction, use of a basic compound, for example, a tertiary amine such as tributylamine, triethylamine, benzyldimethylamine, N, N-dimethylaminobenzene, triphenylphosphine, triphenylstibine, etc., to promote the reaction is preferred. Preferably. The amount used is preferably 0.05 to 5% by weight in the reaction mixture. or,
It is preferable to use organic solvents.

Specific examples of the organic solvents include γ-butyrolactone, γ-valerolactone, γ-caprolactone,
lactones such as γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone; dioxane;
Ethers such as 1,2-dimethoxymethane, diethylene glycol dimethyl ether (or diethyl, dipropyl, dibutyl ether) and tetraethylene glycol dimethyl ether (or diethyl, dipropyl, dibutyl ether); carbonates such as ethylene carbonate and propylene carbonate; methyl ethyl ketone, methyl Ketones such as isobutyl ketone, cyclohexanone and acetophenone; phenols such as phenol, cresol and xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate; hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane , N-methylpyrrolidone, nitrogen-containing polar solvents such as dimethylformamide and the like can be used. .

Specific examples of (meth) acrylate (d) having at least one hydroxyl group in one molecule include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di ( (Meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate,

(Meth) acrylate (d-1) having one hydroxyl group in one molecule such as pentaerythritol tri (meth) acrylate, dipentaerythritol benzyl (meth) acrylate and two (Meth) acrylate (d-2) having a hydroxyl group can be exemplified.

(Meth) having two hydroxyl groups in one molecule
Specific examples of the acrylate (d-2) include, for example, 1
Epoxy di (meth) acrylate, which is a reaction product of an epoxy resin having two epoxy groups in a molecule and acrylic acid or methacrylic acid, may be mentioned. Specific examples of the epoxy resin having two epoxy groups in one molecule include, for example, bisphenol A diglycidyl ether,
Aromatic diglycidyl ethers such as bisphenol F diglycidyl ether, bixylenol diglycidyl ether, biphenol diglycidyl ether, full orange phenol diglycidyl ether; polyethylene glycol diglycidyl ether, polypropylene glycidyl ether, 1,6-hexanediol di Aliphatic diglycidyl ethers such as glycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and tricyclodecane dimethanol diglycidyl ether 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate;
Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, diglycidyl tetrahydrophthalate; Glycidyl esters such as glycidyl diadate can be mentioned.

The reaction between the terminal acid anhydride group-containing imide compound (c-1) and the (meth) acrylate (d) having at least one hydroxyl group in one molecule is carried out by the anhydride of the component (c-1). The hydroxyl group of the component (d) is 0.9 with respect to 1 equivalent of the group.
To 2.5 equivalents, particularly preferably 1.0 to 2.
Use 0 equivalents. The reaction temperature is preferably 60 to 150 ° C, and the reaction time is preferably 1 to 10 hours.

The reaction between the imide compound having a terminal isocyanate group (c-2) and the component (d) is carried out in such a manner that one equivalent of the isocyanate group of the component (c-2) is equivalent to 0.9 to 2 hydroxyl groups of the component (d). 0.5 equivalent is preferred, particularly preferably 1.0 equivalent.
Use ~ 2.0 equivalents. The reaction temperature is preferably 60 to 100 ° C, and the reaction time is preferably 5 to 30 hours.

In the present invention, a diluent (B) is used. Specific examples of the diluent (B) include the above-mentioned organic solvents, butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, and tetraethylene glycol. Alcohols such as monomethyl (or monoethyl) ether; mixtures of dimethyl succinate, dimethyl glutarate and dimethyl adipate; organic solvents (B-1) such as solvent naphtha; carbitol (meth) acrylate; phenoxyethyl (meth) acrylate , Acryloylmorpholine, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth)
Reactive diluents (B-2) such as acrylate, dipentaerythritol penta and hexa (meth) acrylate.

The amount of the components (A) and (B) contained in the resin composition of the present invention is 10 (A) + (B) in total in the composition.
The content of (A) is preferably 10 to 90% by weight, and particularly preferably 20 to 80% by weight.
90% by weight and (B) 10 to 90% by weight are preferred.

In the present invention, the unsaturated group-containing polycarboxylic acid resin (C) may be used. As described above, the unsaturated group-containing polycarboxylic acid resin (C) comprises an epoxy resin (e) having two or more epoxy groups in one molecule and a monocarboxylic acid compound (f) having an ethylenically unsaturated group. It is a reaction product with a polybasic acid anhydride (g).

Examples of the epoxy resin (e) having two or more epoxy groups in one molecule include the epoxy resin represented by the general formula (1), the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, and the phenol Glycidyl ethers such as novolak type epoxy resin, cresol / novolak type epoxy resin, trisphenolmethane type epoxy resin, brominated epoxy resin, biquilenol type epoxy resin and biphenol type epoxy resin; 3,4-epoxy-6-methylcyclohexyl Alicyclic compounds such as methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; glycidylamines such as tetraglycidyl diaminodiphenylmethane; and heterocyclic epoxy resins such as triglycidyl isocyanurate. However, an epoxy resin represented by the general formula (1) is preferred.
In addition, n in general formula (1) is calculated from an epoxy equivalent.

The epoxy resin (e) can be obtained by reacting an alcoholic hydroxyl group of the starting epoxy compound in which M is a hydrogen atom in the general formula (1) with an epihalohydrin such as epichlorohydrin. Raw material epoxy compounds are commercially available, for example, Epicoat series (Epicoat 1009, 1031: manufactured by Yuka Shell Epoxy Co., Ltd.) and Epicron series (Epiclon N-3).
050, N-7050: Dainippon Ink and Chemicals, Inc.
DER series (DER-642U, DER-6)
73MF: Bisphenol A type epoxy resin such as Dow Chemical Co., Ltd., YDF series (YDF-200
4, 2007: manufactured by Toto Kasei Co., Ltd.) and the like.

The reaction between the starting epoxy compound and epihalohydrin is preferably carried out in the presence of dimethyl sulfoxide.
Done. The epihalohydrin may be used in an amount of 1 equivalent or more based on 1 equivalent of the alcoholic hydroxyl group in the raw material epoxy compound. However, when the amount exceeds 15 equivalents to 1 equivalent of the alcoholic hydroxyl group, the effect of increasing the amount is almost negligible, but the volumetric efficiency deteriorates.

In carrying out the reaction, an alkali metal hydroxide is used. As the alkali metal hydroxide, for example, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, but caustic soda is preferable. The amount of the alkali metal hydroxide used is determined based on the M
Is approximately 1 equivalent to 1 equivalent of an alcohol hydroxyl group to be epoxidized in a raw material epoxy compound in which is a hydrogen atom. When the total amount of the alcoholic hydroxyl groups of the raw material epoxy compound in which M of the compound represented by the formula (1) is a hydrogen atom is epoxidized, it may be used in excess, but 2 equivalents to 1 equivalent of the alcoholic hydroxyl group may be used. If it exceeds, the polymer tends to be slightly polymerized.

The reaction temperature is preferably from 30 to 100 ° C.
When the reaction temperature is lower than 30 ° C., the reaction becomes slow and a long-time reaction is required. If the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable.

After completion of the reaction, excess epihalohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and then the resulting resin is dissolved in an organic solvent and a dehydrohalogenation reaction can be carried out with an alkali metal hydroxide.

The monocarboxylic acid compound (f) having an ethylenically unsaturated group includes, for example, (meth) acrylic acid, acrylic acid dimer, etc., and among them, (mechanical) acrylic acid is preferable.

The epoxy resin (e) is reacted with the monocarboxylic acid (f) having an ethylenically unsaturated group to obtain an epoxy (meth) acrylate compound. It is preferable to react 0.3 to 1.2 equivalents of the total amount of the carboxyl group of the component (f) to 1 equivalent of the epoxy group of the epoxy resin, and particularly preferably 0.9 to 1.05 equivalent. .

During or after the reaction, as a diluting solvent, aromatic hydrocarbons such as toluene and xylene; ethyl acetate;
Esters such as butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; cyclohexanone And one or more solvents such as alicyclic hydrocarbons such as cyclohexanol and petroleum solvents such as petroleum ether and petroleum naphtha.

During or after the reaction, one or more of the above-mentioned reactive diluents (B-2) can be used.

Further, it is preferable to use a catalyst for accelerating the reaction. Examples of the catalyst include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, triphenylphosphine and the like. The amount used is preferably from 0.1 to 10% by weight, particularly preferably from 0.3 to 5% by weight, based on the reaction raw material mixture.

During the reaction, it is preferable to use a polymerization inhibitor in order to prevent polymerization of the ethylenically unsaturated group. Examples of the polymerization inhibitor include methoquinone, hydroquinone, methylhydroquinone, phenothiazine and the like. The amount used is preferably from 0.01 to 1% by weight, particularly preferably from 0.05 to 1% by weight, based on the reaction raw material mixture.
0.5% by weight. The reaction temperature is from 60 to 150 ° C, particularly preferably from 80 to 120 ° C. The reaction time is preferably 5 to 60 hours.

Next, a polybasic acid anhydride (g) is reacted. Examples of the polybasic acid anhydride (g) include succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyl-
Examples include tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride and the like. The amount of the polybasic anhydride to be used is preferably 0.1 to 1 equivalent of the hydroxyl group in the epoxy (meth) acrylate.
The reaction is carried out in an amount of from 0.5 to 1.00 equivalent. The reaction temperature is 60 to 1
The temperature is 50 ° C, particularly preferably 80 to 100 ° C.

The amount of the component (A) + (B) component 1
0 to 300 parts by weight, preferably 3
A ratio of 0 to 200 parts by weight is appropriate.

In the present invention, a photopolymerization initiator (D) may be used. Examples of the photopolymerization initiator (D) include benzoins such as benzoin, benzoin methyl ether, bemesoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone,
1,1-dichloroacetophenone, 2-hydroxy-2
Such as -methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylkent, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Acetophenones; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylbutylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; and 2,4-diethylthioxanthkin, 2-isopropylthioxanthone and 2-chlorothioxanthone Thioxanthones; Ketals such as acetophenone dimethyl ketal and benzylmethyl ketal; Benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and 2,4,6-trimethylbenzoyldiphenylphosph In'okisaido, and the like.

These can be used alone or as a mixture of two or more kinds. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid It can be used in combination with an accelerator such as a benzoic acid derivative such as isoamyl ester.

The amount of the photopolymerization initiator (D) is usually 0.5 to 20 parts by weight, preferably 100 parts by weight of the total weight of the components (A), (B) and (C). A ratio of 2 to 15 parts by weight is preferable.

In the present invention, it is preferable to use a thermosetting component (E) as a curing system component in addition to the components described above.
By using this, a material for a printed wiring board having excellent solder heat resistance and electrical characteristics can be obtained. The thermosetting component (E) used in the present invention is not particularly limited as long as it has a urethane oligomer (A), an unsaturated group-containing polycarboxylic acid resin (C) and a thermosetting functional group in the molecule. Although not limited thereto, examples thereof include an epoxy resin, a melamine compound, a urea compound, an oxazoline compound, and a compound containing a dihydrobenzoxazine ring. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin, brominated epoxy resin, and biquilenol type. Glycidyl ethers such as epoxy resins and biphenol type epoxy resins; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4- Alicyclic epoxy resins such as epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, diglycidyl tetrahydrophthalate, dimer Glycidyl amines such as tetraglycidyl diaminodiphenylmethane; glycidyl esters such as glycidyl ester and heterocyclic epoxy resins such as triglycidyl isocyanurate. Among them, an epoxy resin having a melting point of 50 ° C. or more is preferable because a tack-free photopolymerizable film can be formed after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin. Examples of the urea compound include urea and urea resins which are polycondensates of urea and formalin.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline,
2,4-diphenyloxazoline and the like.

As a specific example of the dihydrobenzoxazine ring-containing compound, for example, a mixture of 1 equivalent of a hydroxyl group of a compound having a phenolic hydroxyl group and about 1 equivalent of an anomi group of a primary amine is heated to 70 ° C. or more.
~ 5 mol, 70-110 ° C, preferably
The reaction is carried out at 90-100 ° C for 20-120 minutes.
It can be synthesized by drying under reduced pressure at a temperature of 0 ° C. or lower. It is preferable that all the phenolic hydroxyl groups of the compound having a phenolic hydroxyl group react with the primary amine and formaldehyde to form a dihydrobenzoxazine ring. The compound having a phenolic hydroxyl group is not particularly limited, and bisphenol A,
Bisphenol F, biphenol, trisphenol,
Examples thereof include compounds such as tetraphenol and phenol resins. Examples of the phenol resin include phenol or monovalent phenol compounds such as alkylphenols such as xylenol, t-butylphenol and octylphenol, resorcinol, bisphenol A
Novolak resin or resol resin obtained by reacting a phenol compound such as a polyhydric phenol compound with formaldehyde, a phenol-modified xylene resin, a melamine phenol resin, a polybutadiene-modified phenol resin, etc. And methylamine, cyclohexylamine, aniline, substituted aniline and the like. Formaldehyde is
It may be used in the form of formalin or polyformaldehyde.

The dihydrobenzoxazine ring-containing compound can be prepared by a known method (for example, DE 2217099).
No., H, Ishida, J .; Polym. Sci. , P
artA32, 1121 (1994), etc.).

Among these thermosetting components (E), epoxy resins and dihydrobenzos are particularly preferred because of their excellent reactivity with carboxyl groups in components (A) and (C) and good adhesion to copper. Oxazine ring-containing compounds are preferred.

The preferred range of the amount of the thermosetting component (E) used is generally such that the functional group of the thermosetting component (E) is 0 per carboxyl group in the components (A) and (C). .2
It is a ratio that becomes 3.0 equivalents. Among them, 1.0 is preferred because of its excellent soldering heat resistance and electrical characteristics when it is made into a printed wiring board.
A ratio of up to 1.5 equivalents is preferred.

When an epoxy resin is used as the thermosetting component (E), a curing accelerator for the epoxy resin is used to accelerate the reaction with the carboxyl groups in the components (A) and (C). Is preferred. Specific examples of the curing accelerator for the epoxy resin include 2-methylimidazole, 2-ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 1-methylimidazole.
Imidazole compounds such as cyanoethyl-2-ethylimidazole and 1-cyanoethyl-2-undecylimidazole; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4-
Triazine derivatives such as diaminotriazine, 2,4-diamino-6-tolyltriazine, 2,4-diamino-6-xylyltriazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine, m-aminophenol And the like; tertiary amines; polyphenols and the like. These curing accelerators can be used alone or in combination.

Further, in the present invention, the above-mentioned oligomer (A), diluent (B), unsaturated group-containing polycarboxylic acid resin (C), photopolymerization initiator (D) and thermosetting component (E)
In addition, if necessary, various additives, for example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, and thixotropic agents such as aerosil Adding colorants 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 for the purpose of enhancing the performance of the composition. Can be done.

The above component (E) may be mixed with the resin composition in advance, but it is preferable to use the component (E) before mixing it on a printed circuit board. That is, the two-component type of the main component solution mainly composed of the components (A) and (C) and the epoxy curing accelerator and the like, and the curing agent solution mainly composed of the component (E), When used, it is preferable to mix them.

In the resin composition of the present invention, as a support, for example, an organic solvent (B) used as a diluent (B) on a polymer film (for example, a film composed of polyethylene terephthalate, polypropylene, polyethylene, etc.) -1) can be evaporated and laminated to use as a photosensitive film.

The resin composition (liquid or film form) of the present invention is useful as an insulating material between layers of an electronic component, as a resist ink such as a solder resist for a printed circuit board, and in addition to a triad, a paint, and a coating. It can also be used as an agent, adhesive or the like. The cured product of the present invention is obtained by curing the above-described 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, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp,
An ultraviolet generator such as a xenon lamp or an ultraviolet light emitting laser (such as an excimer laser) may be used. The cured product of the resin composition of the present invention can be used as an interlayer insulating material for a permanent resist or a build-up method, for example, as an electric or conductive material such as a printed circuit board.
Used for electronic components. The thickness of the cured product layer is 0.5 to
It is about 160 μm, 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 printed wiring board is usually coated with a film having a 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 the invention and drying the coating at a temperature of 60 to 110 ° C, preferably 60 to 100 ° C,
A tack-free 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, development is performed by spraying, rocking immersion, brushing, scrubbing, or the like. Then, if necessary, further irradiate ultraviolet rays, and then heat-treat at a temperature of usually 100 to 200 ° C., preferably 140 to 180 ° C., so that the resist film has excellent flexibility, heat resistance and solvent resistance. Thus, a printed wiring board having a permanent protective film that satisfies various properties such as acid resistance, adhesion, and electrical properties can be obtained.

Examples of the organic solvent used in the development include halogens such as trichloroethane, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; 1,4-dioxane and tetrahydrofuran. Ethers of methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; lactones such as γ-butyrolactone; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, dimethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; Solvents such as petroleum solvents such as petroleum ether and petroleum naphtha,
As the water and the aqueous alkali solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used. Further, as an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can be used as the active light for exposure.

[0062]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples. In the following, “parts” means “parts by weight” unless otherwise specified.

(Terminal acid anhydride group-containing imide compound (c-
Synthesis Example of 1)) Synthesis Example 1 1764 g of γ-butyrolactone, 1230 g (3 mol) of ethylene glycol bis (anhydrotrimellitate)
After charging 9.0 g of tributylamine and the mixture, the temperature was raised to 98 ° C., and while maintaining the temperature at 95 to 100 ° C., 524 g (2 mol) of 4,4′-dicyclohexylmethane-diisocyanate was added little by little in about 5 hours. After the addition, the reaction was continued at 98 ° C. for about 15 hours. After the isocyanate concentration became 0.1% by weight or less, the mixture was cooled to room temperature, and the solid content acid value (mgK
OH / g) 128, nonvolatile content 50%, terminal acid anhydride group-containing imide compound (c-1-1) was obtained.

Synthesis Example 2 After charging 896.3 g of γ-butyrolactone, 436 g (2 mol) of pyromellitic anhydride and 4.0 g of tributylamine, the temperature was raised to 98 ° C., and while maintaining the temperature at 95 to 100 ° C., 1, 455 g (1 mol) of a reaction product of 2 mol of 6-hexamethylene diisocyanate and 1 mol of 3-methyl-1,5-pentanediol were added in small portions over about 5 hours. After the addition, the reaction was continued at 98 ° C. for about 15 hours. After the isocyanate concentration became 0.1% by weight or less, the mixture was cooled to room temperature, and the solid content acid value (mg KOH / g) 250, nonvolatile content 50%,
An imide compound (c-1-2) containing a terminal acid anhydride group was obtained.

(Synthesis Example of (meth) acrylate (d) Having Two Hydroxyl Groups in One Molecule) Synthesis Example 3 Bisphenol A diglycidyl ether (trade name: YD-8125, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 17)
5) 350 g, acrylic acid 144.1 g, P-methoxyphenol 0.24 g and triphenylphosphine 1.
0 g, heated to 98 ° C. and reacted for about 30 hours,
The process was terminated when the acid value (mgKOH / g) became 1.0 or less, and an epoxy acrylate (d-1) of bisphenol A diglycidyl ether was obtained.

(Synthesis Example of Oligomer (A)) Synthesis Example 4 The terminal acid anhydride group-containing imide compound (c-
1-1) 3528.5 g, 255.2 g of 2-hydroxyethyl acrylate, g of P-methoxyphenol and g of carbitol acetate were charged.
The reaction was carried out for 0 hour, and the reaction was terminated when the acid anhydride group disappeared. The weight average molecular weight of the product is about 3000 (GPC
), The acid value of the solids 56.2 (mg KOH / g),
An oligomer (A-1) having a nonvolatile content of 50% was obtained.

Synthesis Example 5 The terminal anhydride-containing imide compound obtained in Synthesis Example 2 (c-
1-2) 3585.2 g, 1486 g of the epoxy acrylate (d-1) obtained in Synthesis Example 3 and 1486 g of carbitol acetate were charged, and reacted at 90 ° C. for about 10 hours.
The reaction was terminated when the acid anhydride group disappeared. An oligomer (A-2) having a weight average molecular weight of about 5000 (by GPC), an acid value of solids of 69 (mgKOH / g) and a nonvolatile content of 50% was obtained.

(Synthesis Example of Dihydrobenzoxazine Ring-Containing Compound (E)) Synthesis Example 6 <Synthesis of Phenol Volak Resin> Phenol 190
g, 100 g of formalin (37% aqueous solution) and 0.4 g of oxalic acid, and reacted at a reflux temperature for about 6 hours. Subsequently, the internal pressure was reduced, and then unreacted phenol and condensed water were removed. The obtained resin had a softening point of 84 ° C. and a 3 to polynuclear / binuclear ratio: 82/18 (peak area ratio by GPC).

<Introduction of Dihydrobenzoxazine Ring> 170 g of phenol novolak resin synthesized as described above
(Corresponding to 1.6 moles of hydroxyl groups) to 140 g (1.6
Mol) and dissolved at 80 ° C. to prepare a uniform mixed solution. This mixed solution was heated to 90 ° C formalin 25.
It was added to 9 g in 30 minutes. After completion of the addition, the mixture was maintained at the reflux temperature for 3 hours, and then reduced under reduced pressure at 100 ° C. for about 2 hours to remove the condensed water. Synthesized. Excess aniline and formalin were removed during drying, and the yield of this compound was 300 g. This indicates that, among the hydroxyl groups of the phenol novolak resin, 1.4 moles reacted and dihydrobenzoxazine was cyclized.

Synthesis Example 7 Bisphenol A 91.2 (0.4 mol), 37% formalin 130 g (1.6 mol), P-anisidine
250 ml of 5 g (0.8 mol) toluene was charged and reacted at 80 ° C. for 5 hours with stirring. After allowing the reaction product to stand and separating the aqueous layer, the organic layer was washed twice with 2 liters of water. Thereafter, the aqueous layer was separated, and toluene was distilled off under reduced pressure to obtain 200 g of a yellow solid. By recrystallizing the reaction product from ascent, a melting point of 15% was obtained.
At 0.8 ° C., the compound was a compound (E-2) having a dihydrobenzoxazine ring represented by the following structural formula.

[0071]

Embedded image

(Unsaturated group-containing polycarboxylic acid resin (C)
Synthesis Example 8) Synthesis Example 8 In the above general formula (1), X is -CH2-, M is a hydrogen atom, and the average polymerization degree n is 6.2.
After dissolving 380 parts of an epoxy compound of the type (epoxy equivalent: 950 g / eq, softening point: 85 ° C.) and 925 parts of epichlorohydrin in 462.5 parts of dimethyl sulfoxide, 60.9 parts of 98.5% NaOH (70%) was stirred at 70 ° C. (0.5 mol) was added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the completion of the reaction, 250 parts of water was added and washed. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation under reduced pressure from the oil layer, and then dimethyl sulfoxide was distilled off.
The reaction product containing by-produced salt is treated with methyl isobutyl ketone 75
0 parts, and further add 10 parts of 30% NaOH,
The reaction was performed at 0 ° C. for 1 hour. After the reaction is completed, add 2 parts with 200 parts of water.
Washing was performed once. After oil-water separation, methyl isobutyl ketone was recovered by distillation from the oil layer, and the epoxy equivalent was 310 g / e.
q, an epoxy resin (e) having a softening point of 69 ° C. was obtained. When the obtained epoxy resin (e) was calculated from the epoxy equivalent, about 5 out of 6.2 alcoholic hydroxyl groups in the starting bisphenol F type epoxy compound were epoxidized. This epoxy resin (e) 3
Charge 10 parts and 251 parts of carbitol acetate,
The mixture was heated and stirred at 90 ° C. and dissolved. 60 ° C.
Cooled to 60 parts of acrylic acid, dimer acid (acid value (m
gKOH / g) = 196) 97 parts, methylhydroquinone 0.8 parts and triphenylphosphine 2.5 parts were added,
The mixture was heated and dissolved at 80 ° C. and reacted at 98 ° C. for 35 hours to obtain an epoxy acrylate having an acid value of 0.5 mg KOH / g and a solid content of 65%. Next, 718.5 parts of this epoxy acrylate, 100 parts of succinic anhydride, and 54 parts of carbitol acetate were charged and reacted at 90 ° C. for 6 hours.
An unsaturated group-containing polycarboxylic acid resin (C-1) having a solid content acid value of 99 mgKOH / g and a solid content of 65% was obtained.

Examples 1 to 4 and Comparative Example 1 A compound was mixed and mixed according to the compounding composition shown in Table 1 and kneaded using a three-roll mill to prepare a solder resist composition. Table 1 Example Comparative Example 1 2 3 4 4 1 Oligomer (A-1) obtained in Synthesis Example 4 100 50 Oligomer (A-2) obtained in Synthesis Example 5 200 200 50 Unsaturated group-containing obtained in Synthesis Example 8 Polycarboxylic acid resin (C-1) 77 77 154 Dihydrobenzoxazine ring-containing compound (E-1) 30 obtained in Synthesis Example 6 Dihydrobenzoxazine ring-containing compound (E-2) 30 obtained in Synthesis Example 7 30 EPPN-201 * 1 30 40 Kayacure DETX-S * 2 1.2 1.2 1.2 1.2 1.2 1.2 KAYARAD DPHA * 3 16 16 16 16 16 16 Silica (fine powder) 10 10 10 10 10 Melamine 1. 2 1.2 Cyanine green (pigment) 1.5 1.5 1.5 1.5 1.5 1.5 KS-66 * 4 1.0 1.0 1.0 1.0 1.0 1.0 Irgacure 907 5 10 10 10 10 10 Carbitol acetate 10 10 7.5 Developability ○ ○ ハ ○ Solder heat resistance ○ ○ ○ ○ Flexibility ○ ○ ○ × × Heat deterioration 劣化 ○ ○ × 無 Electroless gold plating resistance ○ ○ ○ ○ ○

Note) * 1 EPPN-201: Nippon Kayaku Co., Ltd., phenol novolak type epoxy resin, softening point 67
C * 2 Kayacure-DETX-S: manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator 2,4-getylthioxanthone * 3 KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.
Dipentaerythritol penta and hexaacrylate mixture

* 4 KS-66: Shin-Etsu Chemical Co., Ltd.
* Silicone defoamer * Irgacure-907: Ciba-Geigy Co., Ltd., photopolymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one

Evaluation method: Each of the obtained resist compositions was evaluated as follows. That is, the resist compositions of Examples and Comparative Examples shown in Table 1 were applied to a printed circuit board (a laminate of an imide film and a copper foil) by screen printing, and dried at 80 ° C. for 20 minutes. Thereafter, a negative film is applied to the substrate, irradiated with ultraviolet rays at an integrated exposure amount of 500 mJ / cm 2 using an exposure machine according to a predetermined pattern, developed with an organic solvent or a 1 wt% aqueous solution of Na 2 CO 2, and further developed at 150 ° C. for 50 minutes. A test substrate was prepared by heat curing. With respect to the obtained test substrate, characteristics such as alkali developability, solder heat resistance, flexibility, heat deterioration resistance, and electroless gold plating resistance were evaluated. Table 1 shows the results. The evaluation method and evaluation criteria are as follows.

(1) Developability: The coating film was dried at 80 ° C. for 60 minutes, and the developability by spray development with a 1% aqueous sodium carbonate solution at 30 ° C. was evaluated.・: No residue is visually observed. ×: There is a residue visually.

(2) Solder heat resistance: A rosin-based flux was applied to a test substrate, immersed in molten solder at 260 ° C. for 10 seconds, and then evaluated by the state of the cured film when peeled off with a cellophane adhesive tape. ○ ・ ・ ・ ・ ・ ・ No abnormality. ×: There is peeling.

(3) Flexibility: Judgment was made in a state where the test substrate was folded at 180 degrees. ○ ・ ・ ・ ・ No crack. △ ・ ・ ・ ・ Slight cracks. C: Cracks were formed in the bent portion and the cured film was separated.

(4) Heat Deterioration Resistance: The test substrate was left standing at 125 ° C. for 5 days, and then evaluated in a state of 180 ° solid bending. ○ ・ ・ ・ ・ No crack. △ ・ ・ ・ ・ Slight cracks. C: Cracks were formed in the bent portion and the cured film was separated.

(5) Electroless Gold Plating Resistance: After the test substrate was plated with gold as described below, the state was determined by peeling off with a cellophane adhesive tape. ○ ・ ・ ・ ・ No abnormality. Δ: Some peeling was observed. ×: No peeling.

Electroless gold plating method: A test substrate was acid-degreased at 30 ° C. (Metex, manufactured by Nippon MacDermid Co., Ltd.).
L-5B (20 Vol /% aqueous solution) for 3 minutes to degrease, then dipped in running water for 3 minutes and washed with water. Next, the test substrate is immersed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes, soft-etched, and then placed in running water for 3 minutes.
It was immersed for minutes and washed with water. After the test substrate was immersed in a 10 Vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was immersed in a 30 ° C. catalyst solution (10 vol% aqueous solution of a metal plate activator 350, manufactured by Meltex Co., Ltd.) for 7 minutes to give a catalyst, and then immersed in running water for 3 minutes and washed with water. . The test substrate to which the catalyst was applied was immersed in a 20 vol% aqueous solution of a nickel plating solution at 85 ° C., pH 4.6) for 20 minutes to perform electroless nickel plating. After the test substrate was immersed in a 10 Vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was subjected to a 95 ° C. gold plating solution (manufactured by Meltex Co., Ltd., Aulectroless UP15Vol% and potassium cyanide 3V).
immersed in running water for 3 minutes, washed with hot water at 60 ° C. for 3 minutes, and washed with hot water. After sufficient washing with water, the water was thoroughly removed, dried, and a test board electrolessly gold-plated was obtained. As is clear from the results shown in Table 1, the resin composition of the present invention shows good alkali developability, and is a cured film excellent in solder heat resistance, flexibility, heat deterioration resistance and electroless gold plating property. give.

[0083]

According to the present invention, the cured product is excellent in flexibility, solder heat resistance, heat deterioration resistance, and electroless gold plating resistance, can be developed with an organic solvent or a dilute alkali solution, and is used for a solder resist and an interlayer insulating layer. Thus, a resin composition suitable for was obtained. This resin composition is suitable for a solder resist and an interlayer insulating layer of a printed wiring board, particularly a flexible printed wiring board.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01B 3/30 H01B 3/30 D 5E314 M 5E346 3/40 3/40 C 5G305 H05K 3/28 H05K 3 / 28 D 3/46 3/46 TF term (reference) 2H025 AA10 AB15 BC62 BC64 BC74 BC85 CA00 CC03 CC17 CC20 4J011 QB18 QB19 QB20 QB22 RA11 SA02 SA03 SA12 SA14 SA15 SA16 SA17 SA19 SA20 SA22 SA25 SA28 SA32 SA34 SA38 SA54 SA59 SA59 SA63 SA64 UA01 VA01 WA01 WA02 WA06 4J027 AD05 AE02 AE03 AE04 AE05 AE07 AJ08 CA10 CA14 CA16 CA18 CA25 CA28 CA29 CA32 CA34 CA36 CB10 CC05 CD08 CD09 CD10 4J036 AA01 AA05 AC02 AC03 AC10 AC11 AC12 JA01 CA07 4J043 PA02 PA18 PB09 PB15 QB58 RA35 SA11 SA12 SB01 TA22 TA47 TB01 UA022 UA041 UA121 UA122 UA131 UA132 UA141 UA222 UA261 UA262 U A362 UA391 UB011 UB012 UB022 UB122 UB132 UB152 UB211 UB281 UB292 UB352 UB381 VA062 VA102 WA02 XA14 XA16 XA17 XA19 XB02 XB03 XB16 XB19 YB06 YB08 YB21 YB22 ZA46 ZB01 ZB02 ZB03 A50 ZB03 AB30 ZB03 ZB03 A50 EE13 EE20 HH11 HH18 5G305 AA06 AA11 AA14 AB17 AB24 AB31 AB34 AB36 BA09 CA07 CA15 CA21 CD12

Claims (9)

[Claims] 1. A terminal acid anhydride group or an isocyanate group-containing imide compound (c) which is a reaction product of a tetracarboxylic dianhydride (a) and a polyisocyanate compound (b) and at least one hydroxyl group in one molecule. A resin composition comprising an oligomer (A) which is a reaction product of a (meth) acrylate (d) having the following and a diluent (B). 2. A reaction product of an epoxy resin (e) having two or more epoxy groups in one molecule, a monocarboxylic acid compound (f) having an ethylenically unsaturated group, and a polybasic anhydride (g). The resin composition according to claim 1, which comprises an unsaturated group-containing polycarboxylic acid resin (C). 3. An epoxy resin (e) having two or more epoxy groups in one molecule is represented by the formula (1): ## STR1 ## (In the formula (1), X is -CH2- or -C (CH3) 2-
And n is an integer of 1 or more, and M represents a hydrogen atom or the following formula (G). Embedded image However, when n is 1, M indicates the formula (G), and when n is greater than 1, at least one of M indicates the formula (G) and the rest indicate a hydrogen atom. (E) an epoxy resin represented by
The resin composition according to claim 2, which is 4. Item 1 containing a photopolymerization initiator (D)
4. The resin composition according to any one of items 3 to 3. 5. The resin composition according to claim 1, further comprising a thermosetting component (E). 6. The resin composition according to claim 1, which is used for a solder resist or an interlayer insulating layer of a printed wiring board. 7. A cured product of the resin composition according to any one of claims 1 to 6. 8. An article having the cured product layer according to claim 7. 9. The article according to claim 8, which is a printed wiring board.