JP2001040174A - Resin composition, solder resist resin composition and hardened products therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. suitable for a solder resist and an interlayer insulating layer, a hardened product from which is excellent in resilience, soldering heat resistance, thermal degradation resistance and electroless gold plating resistance, and allows development in an org. solvent or in a dil. alkaline soln. SOLUTION: This resin compsn. comprises an unsatd. group-contg. polycarboxylic acid resin (A) which is a reaction product of an epoxy resin (a) having more than one epoxy group in one molecule, a monocarboxylic acid compd. (b) having an ethylenically unsatd. group and a polybasic acid anhydride (c-1), and a carboxyl group-contg. oligomer (B) obtd. by reacting a polyol compd. (d), a polybasic acid anhydride (c-2) having two acid anhydride groups in a molecule and an ethylenically unsatd. group-contg. polyhydroxy compd. (e).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a specific unsaturated group-containing polycarboxylic acid resin (A) and a urethane oligomer (B) and useful as a resin composition for printed wiring boards and its curing. About things. More specifically, solder resist for flexible printed wiring boards,
Excellent developability, useful as plating resist and interlayer electrical insulating material for multilayer printed wiring boards. The cured film has excellent adhesion, flexibility (flexibility), solder heat resistance, chemical resistance, gold plating resistance, etc. The present invention relates to a resin composition that gives an excellent cured product 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 the resulting cured film has a problem that heat resistance is good but flexibility is low. Was. Therefore, such a solder resist ink is used for a rigid board which does not require the flexibility (flexibility) of a cured film, and the use thereof is limited, and a flexible printed wiring board (FPC) which has been increasingly used in recent years is used.
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 developed a resin containing a specific unsaturated group-containing polycarboxylic acid resin (A) and a carboxyl group-containing oligomer (B). The present inventors have found that the above object can be achieved by using a composition, and have completed the present invention. That is, according to the present invention, (1) an epoxy resin (a) having two or more epoxy groups in one molecule, a monocarboxylic acid compound (b) having an ethylenically unsaturated group, and a polybasic acid anhydride ( c-1) and an unsaturated group-containing polycarboxylic acid resin (A) which is a reaction product with c-1), and a polyol compound (d) and a polybasic acid anhydride having two acid anhydride groups in a molecule (c-2). A) a resin composition containing a carboxyl group-containing oligomer (B) obtained by reacting an ethylenically unsaturated group-containing polyhydroxy compound (e);
(2) The resin composition according to (1), wherein the epoxy resin (a) having two or more epoxy groups in one molecule is an epoxy resin obtained by glycidylating a bisphenol type epoxy compound, and (3) a bisphenol type epoxy compound. Is the equation (1)

[0006]

Embedded image

(In the formula (1), X represents —CH ₂ — or —C
(CH ₃ ) ₂ −, and n is a number of 1 or more on average. The resin composition according to (2), which is an epoxy compound represented by (1), (4) any one of (1) to (3), wherein the epoxy resin (a) has an epoxy equivalent of 280 to 500 g / equivalent. The weight average molecular weight of the resin composition described in (5), (5) carboxyl group-containing oligomer (B) is 500 to
The resin composition according to any one of the above (1) to (5), wherein the acid value of the carboxyl group-containing oligomer (B) is 1 to 200 mgKOH / g. To (5); (7) the resin composition according to any one of (1) to (6), which comprises a reactive diluent (C); 8) The resin composition according to any one of the above (1) to (7), which contains a photopolymerization initiator (D);

(9) The resin composition according to any one of the above (1) to (8), which contains a thermosetting component (E), (10) a solder resist or a simple insulating layer for a printed wiring board A resin composition according to any one of the above (1) to (9), (11) a cured product of the resin composition according to any one of the above (1) to (10),
(12) An article having the cured product layer according to (11), and (13) an article according to (12), which is a printed wiring board.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention is a mixture of the above-mentioned unsaturated group-containing polycarboxylic acid resin (A) and the above-mentioned carboxy group-containing oligomer (B). The acid value (mg / KOH / g) of the unsaturated group-containing polycarboxylic acid resin (A) used here is preferably from 70 to 150, particularly preferably from 80 to 120. The molecular weight of the carboxyl group-containing oligomer (B) is 5 as a weight average molecular weight.
It is preferably from 100 to 100,000, and its acid value is from 1 to 100.
200 mg KOH / g is preferred.

As described above, the unsaturated group-containing polycarboxylic acid resin (A) used in the present invention comprises, as described above, an epoxy resin (a) having two or more epoxy groups in one molecule and a monomer having an ethylenically unsaturated group. It is a reaction product of the carboxylic acid compound (b) and the polybasic acid anhydride (c-1).

The epoxy resin (a) having two or more epoxy groups in one molecule includes, for example, glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidylamines, epoxy resins and the like.

Examples of the glycidyl ethers include glycidylated epoxy compounds represented by the above general formula (1), bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, and cresol novolak epoxy resin. , Trisphenol methane type epoxy resin, brominated epoxy resin, biquilenol type epoxy resin, biphenol type epoxy resin and the like. Examples of the alicyclic epoxy resin include 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate And 1-epoxyethyl-3,4-epoxycyclohexane. Examples of glycidyl esters include diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, and the like.Examples of glycidylamines include tetraglycidyl diaminodiphenylmethane, and a heterocyclic epoxy resin. Examples thereof include triglycidyl isocyanurate and the like.

Among these epoxy resins (a) having two or more epoxy groups in one molecule, glycidyl ethers are preferable, and more preferably glycidylated epoxy compounds represented by the general formula (1). The epoxy equivalent is preferably 280 to 500 g / equivalent. In addition, n in general formula (1) is calculated from an epoxy equivalent.

The glycidylated product of the epoxy compound represented by the general formula (1) can be obtained by reacting an alcoholic hydroxyl group of the epoxy compound represented by 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-3050, N-7050: manufactured by Dainippon Ink and Chemicals, Inc.) ), DER series (DER-642U,
Bisphenol A type epoxy compounds such as DER-673MF: manufactured by Dow Chemical Co., Ltd., YDF series (YD
F-2004 and 2007: manufactured by Toto Kasei Co., Ltd.) and the like.

The reaction between the starting epoxy compound and the 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 to be used is approximately 1 to 1 equivalent of the alcohol hydroxyl group to be epoxidized of the compound represented by the formula (2).
Just use the equivalent. When the alcoholic hydroxyl group of the compound represented by the formula (2) is entirely epoxidized, it may be used in excess, but if it exceeds 2 equivalents to 1 equivalent of the alcoholic hydroxyl group, the polymer tends to be slightly polymerized. It is in.

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 dehalogenation reaction can be carried out with an alkali metal hydroxide.

Examples of the monocarboxylic acid compound (b) having an ethylenically unsaturated group include (meth) acrylic acid and acrylic acid dimer, and among them, (meth) acrylic acid is preferable.

The epoxy resin (a) is reacted with the monocarboxylic acid (b) 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 (b) 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 diluent (C), aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran; methyl ethyl ketone; Ketones such as methyl isobutyl ketone; butyl cellosolve acetate, carbitol acetate,
Glycol derivatives such as diethylene glycol dimethyl ether and propylene glycol monomethyl ether acetate; one or two kinds of solvents (C-1) such as alicyclic hydrocarbons such as cyclohexanone and cyclohexanol and petroleum solvents such as petroleum ether and petroleum naphtha The above may be added.

During or after the reaction, one or more of the following reactive diluents (C-2) can be used.

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

During the reaction, it is preferable to use a polymerization inhibitor 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, the polybasic acid anhydride (c-1) is reacted. The polybasic anhydride (c-1) is preferably a carboxylic anhydride, for example, succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyl-tetrahydrophthalic anhydride. Acid, 4-methyl-hexahydrophthalic anhydride and the like. The amount used is, per hydroxyl group equivalent to the hydroxyl group in the epoxy (meth) acrylate,
The polybasic acid anhydride is preferably 0.05 to 1.00.
The reaction is performed in equivalent amounts. The reaction temperature is from 60 to 150 ° C, particularly preferably from 80 to 100 ° C.

The carboxyl group-containing oligomer (B) used in the present invention comprises a polyol compound (d), a polybasic acid anhydride (c-2) having at least two acid anhydride groups in the molecule, and an ethylenically unsaturated compound. It can be obtained by reacting a saturated group-containing polyhydroxy compound (e).

Examples of the polyol compound (d) include alkyl polyols, polyester polyols, polyether polyols, acrylic polyols, polybutadiene polyols, 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, pentaerythritol and the like.

Examples of the polyester polyol include a condensation type polyester polyol, an addition-polymerized polyester polyol, and a polycarbonate polyol. As the condensation type polyester polyol, ethylene glycol, propylene glycol, diethylene 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.

Examples of the addition-polymerized polyester polyol include polycaprolactone having 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.

As other polyols, (meth) acryl polyol which is a copolymer of a hydroxyl group-containing (meth) acrylate and another (meth) acrylic ester, and a copolymer of butadiene having a hydroxyl group at a terminal. A homo- or copolymer having a polybutadiene polyol, a silicon-modified polyol, a phenolic polyol containing a phenol molecule in the molecule,
Epoxy polyols, flame-retardant polyols containing a phosphorus atom, a halogen atom, etc., and the like, having a molecular weight of 100 to 1
00,000 is preferred. These polyol compounds,
They can be used alone or in combination of two or more.

The polybasic anhydride (c-2) having two acid anhydride groups in the molecule is preferably a carboxylic anhydride, for example, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyl Tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride,
Examples thereof include butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate), which can be used alone or as a mixture of two or more.

Examples of the ethylenically unsaturated group-containing polyhydroxy compound (e) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and caprolactone-modified 2 -Hydroxyethyl (meth)
Examples thereof include (meth) acrylate-based polyhydroxy compounds such as acrylate, pentaerythritol tri (meth) acrylate, and glycerol diacrylate, which can be used alone or in combination of two or more.

The carboxyl group-containing oligomer (B) used in the present invention can be prepared, for example, as follows. First, the polyol compound (d) and 2 in the molecule
Reacting a polybasic acid anhydride (c-2) having two acid anhydride groups to prepare a terminal acid anhydride group-containing prepolymer,
Next, the ethylenically unsaturated group-containing polyhydroxy compound (e) is reacted.

The terminal acid anhydride group-containing prepolymer is obtained by reacting one equivalent of the hydroxyl group of the polyol compound (d) with one polybasic acid anhydride (c-2) having two acid anhydride groups in the molecule. The reaction is preferably performed in the range of 0.05 to 2.0 equivalents (as acid anhydride equivalents). The reaction temperature of this esterification reaction is 60
The reaction time is preferably 1 to 10 hours. or,
An amine compound such as triethylamine may be added as a reaction catalyst in an amount of 0.1 to 5%.

Then, the prepolymer containing a terminal acid anhydride group is preferably reacted with a polyhydroxy compound (e) containing an ethylenically unsaturated group to obtain a carboxyl group-containing oligomer (B). The amount of the hydroxyl group of the ethylenically unsaturated group-containing polyhydroxy compound (e) is 0.9 to 1.5 with respect to 1 equivalent of the acid anhydride group of the terminal acid anhydride group-containing prepolymer.
The reaction is preferably carried out in an equivalent amount, particularly preferably 1.0
~ 1.1 equivalents. The reaction temperature is usually from room temperature to 100
° C, preferably 50-90 ° C. In order to prevent gelation due to radical polymerization during this reaction, usually 50 to 2
It is preferable to add 2,000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, and p-benzoquinone. The reaction between these hydroxyl groups and isocyanate groups proceeds without a catalyst,
For example, triethylamine, dibutyltin laurate,
A catalyst such as dibutyltin diacetate may be added.
At the time of this reaction, the above-mentioned diluting solvent (C-1) or the following reactive diluent (C-2) may be added.

The amount of the components (A) and (B) contained in the resin composition of the present invention is 10 (A) + (B) in total.
The content of (A) is preferably 1 to 80% by weight, and particularly preferably 20 to 70% by weight.
99% by weight and (B) 1 to 99% by weight are preferred.

In the present invention, a diluent (C) may be used. As the diluent (C), the above-mentioned solvents (C-1) and organic solvents having a hydroxyl group in the molecule, for example, methanol,
(C1-C4) primary alcohols such as ethanol and propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl Examples thereof include alkylene glycol mono (C1 to C2) alkyl ethers such as ether and dipropylene glycol monoethyl ether, and the following reactive diluent (C-2).

Examples of the reactive diluent (C-2) include carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, acrylol morpholine, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxytri ( (Meth) acrylates not containing a hydroxyl group, such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-
Hydroxy-3-phenylpropyl (meth) acrylate, pentaerythritol tri (meth) acrylate,
Various (meth) acrylates such as hydroxyl group-containing (meth) acrylates such as glycerol di (meth) acrylate and dipentaerythritol penta (meth) acrylate are exemplified.

Of these reactive diluents (C-2),
The (meth) acrylates containing no hydroxyl group can be used during the reaction of the components (A) and (B), and the (meth) acrylates containing a hydroxyl group can be added and used after the completion of the reaction. The amount of the reactive diluent (C-2) used is 20 to 300 parts by weight based on 100 parts by weight of the components (A) and (B).
A suitable amount is 30 parts by weight, preferably 30 to 250 parts by weight.

In the present invention, a photopolymerization initiator (D) may be used. The photopolymerization initiator (D) is used when the resin composition of the present invention is cured by ultraviolet irradiation. The amount used is the total weight of the components (A), (B) and (C) 1
0 to 20 parts by weight, preferably 0.5 to 100 parts by weight
The ratio is preferably 20 to 20 parts by weight, more preferably 2 to 15 parts by weight.

Examples of the photopolymerization initiator (D) include benzoins such as benzoin, benzoin methyl ether, benzoin 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
Acetophenones such as -methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthoxine, 2-isopropylthioxanthone and 2-chlorothioxanthone Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and 2,4,6-trimethylbenzoyldiphenylphos Fin oxide are listed.

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

In the present invention, it is preferable to use a thermosetting component (E) as a curing system component in addition to the above-described components.
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 functional group capable of thermosetting with the unsaturated group-containing polycarboxylic acid resin (A) and the oligomer (B) in the molecule. Although not limited, examples thereof include an epoxy resin, a melamine compound, a urea compound, an oxazoline compound, and a phenol compound.

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 epoxy resin. Glycidyl ethers such as resins and biphenol type epoxy resins; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxy Alicyclic epoxy resins such as cyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, diglycidyl tetrahydrophthalate, Glycidyl esters such as mer acid glycidyl ester; glycidyl amine such as tetraglycidyl diaminodiphenylmethane; 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.

Examples of the phenol compound include phenol, cresol, chilenol, catechol, resorcin, hydroquinone, pyrogallol, resol and the like.

Of these thermosetting components (E), epoxy resins are particularly preferred because of their excellent reactivity with the carboxyl groups in the components (A) and (B) and good adhesion to copper.

The preferable range of the use amount of the thermosetting component (E) is that the functional group of the thermosetting component (E) is usually 0 per carboxyl group in the components (A) and (B). .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 (B). Is preferred. Examples of the curing accelerator for the epoxy resin include 2-methylimidazole, 2-ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole, and 1-cyanoethyl-2-. Imidazole compounds such as undecyl imidazole; melamine, guanamine, acetoguanamine, benzoguanamine, ethyldiaminotriazine, 2,4-diaminotriazine, 2,4-diamino-6-tolyltriazine, 2,4-diamino-6-xylyl Triazine derivatives such as triazine; tertiary amines such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine and m-aminophenol; polyphenols and the like. These curing accelerators can be used alone or in combination.

Further, in the present invention, the above-mentioned unsaturated group-containing polycarboxylic acid resin (A), carboxy group-containing oligomer (B), diluent (C), photopolymerization initiator (D) and thermosetting component (E) ), And if necessary, various additives,
For example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay,
A thixotropic agent such as Aerosil; a coloring agent such as phthalocyanine blue, phthalocyanine green, and titanium oxide; a silicone, a fluorine-based leveling agent and an antifoaming agent; and a polymerization inhibitor such as hydroquinone and hydroquinone monomethyl ether. It can be added for the purpose of enhancing.

The above-mentioned component (E) may be mixed in advance with the resin composition, 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 (B) 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.

The resin composition of the present invention is useful in a liquid state 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 as a paint,
It can also be used as a coating agent, adhesive or the like. Furthermore,
If necessary, the composition of the present invention can be used in the form of a film by applying to a substrate such as a polyester film and removing the organic solvent.

The cured product of the present invention is obtained by curing the above-mentioned resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Examples of the active energy rays include ultraviolet rays, electron beams, and X-rays. When irradiating ultraviolet rays, the irradiation amount is 10 to 10000 mJ / cm ² , and when irradiating an electron beam, the irradiation amount is 0.1 to 100 Mrad. preferable.
Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method. For example, when irradiating ultraviolet rays, an ultraviolet ray generating device such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and an ultraviolet light emitting laser (such as an excimer laser) may be used.

The cured product of the resin composition of the present invention is used for an electric / electronic component such as a printed board as a permanent resist or an interlayer insulating material for a build-up method. The thickness of the cured product layer is about 0.5 to 160 μm,
It is preferably about μm.

The printed wiring board of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, the present invention is applied to a substrate for printed wiring with a film thickness of 5 to 160 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain coating method. Is applied, and the coating film is dried at a temperature of 60 to 110 ° C., preferably 60 to 100 ° C., whereby 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 irradiated with ultraviolet light at an intensity of about 10 to 2000 mJ / cm ^2. The unexposed portion is developed using a developing solution described later, for example, by spraying, rocking immersion, brushing, scrubbing, or the like. Then, if necessary, further irradiate ultraviolet rays, then 100 to 200 ° C., preferably 140 to 18
By performing heat treatment at a temperature of 0 ° C., excellent flexibility, heat resistance, solvent resistance, acid resistance, adhesiveness,
A printed wiring board having a permanent protective film satisfying various characteristics such as electric characteristics can be obtained.

Examples of the organic solvent used for 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; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; and petroleum solvents such as petroleum ether and petroleum naphtha And the like, water, and an aqueous alkali solution include aqueous alkali solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines. 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.

[0061]

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.

Synthesis Example 1 (Synthesis Example of Unsaturated Group-Containing Polycarboxylic Acid Resin (A)) In the general formula (1), X is —CH ₂ —, and the average degree of polymerization n is bisphenol F of 6.2. 380 type epoxy compound (epoxy equivalent 950 g / eq, softening point 85 ° C)
And 925 parts of epichlorohydrin were dissolved in 462.5 parts of dimethyl sulfoxide.
60.9 parts (1.5 mol) of 8.5% NaOH were 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 distilled and recovered from the oil layer under reduced pressure.
Then, dimethyl sulfoxide was distilled off, the reaction product containing by-product salts was dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH was added, followed by reaction at 70 ° C. for 1 hour. After the completion of the reaction, the resultant was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer, and the epoxy equivalent was 310 g / eq and the softening point was 69 ° C.
The epoxy resin (a) was obtained. When the obtained epoxy resin (a) was calculated from the epoxy equivalent, about 5 of the 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy compound were epoxidized.

310 parts of this epoxy resin (a) and 251 parts of carbitol acetate were charged, and heated and stirred at 90 ° C. to dissolve. The obtained solution was cooled to 60 ° C., and 60 parts of acrylic acid and dimer acid (acid value (mg KOH / g)
= 196) 97 parts, methylhydroquinone 0.8 parts and triphenylphosphine 2.5 parts were added, heated and dissolved at 80 ° C, reacted at 98 ° C for 35 hours, and the acid value was 0.5 mgK.
An epoxy acrylate having OH / g and a solid content of 65% was obtained. Then, the epoxy acrylate 718.5
Parts, succinic anhydride 100 parts, carbitol acetate 5
4 parts were charged and reacted at 90 ° C. for 6 hours.
An unsaturated group-containing polycarboxylic acid resin (A-1) having 9 mgKOH / g and a solid content of 65% was obtained.

Synthesis Example 2 (Synthesis example of carboxyl group-containing oligomer (B)) In a round bottom flask equipped with a stirring device and a condenser, polytetramethylene glycol (hydroxyl value: 129 mg KO) was added.
H / g, molecular weight; 870) 1740 g, pyromellitic anhydride (acid value; 1011 mg KOH / g) 654 g, carbitol acetate 599 g and triethylamine 7.
2 g, and reacted at 85 ° C. for 10 hours to obtain a terminal acid anhydride group-containing prepolymer (acid value of solid; 187.5 mgK
OH / g). Next, 232 g of 2-hydroxyethyl acrylate, 1.6 g of p-methoxyphenol and 58 g of carbitol acetate were charged, and 10 g at 85 ° C.
Reaction time, the acid value of the solid is 102 mgKOH / g,
A carboxyl group-containing oligomer (B-1) diluted with 20% by weight of carbitol acetate having a weight average molecular weight of about 3500 (by the GPL method) was obtained.

Examples 1 to 12, Comparative Examples 1 to 4 (A-1), (B-
1) were mixed in the mixing ratio shown in Table 1, and then the photopolymerization initiator (D) (Irgacure 90, manufactured by Ciba-Geigy)
7: 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholinopropan-1-one 10 parts and diethylthioxanthone 1.2 parts), a reactive diluent (C) (manufactured by Nippon Kayaku Co., Ltd., KAYARDADDPHA;
16 parts of dipentaerythritol penta-hexaacrylate mixture), 10 parts of filler (fine silica), 1.2 parts of epoxy curing accelerator (melamine), silicone defoamer (KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.0 parts were blended in the combinations shown in Table 1, and kneaded using a three-roll mill to prepare main ingredients (blended components ((XA-1) to (XA-3), and (XX-1)). On the other hand, the thermosetting component (E) (epoxy resin) was used as a curing agent in the proportions shown in Table 2. (Compounding components (H-1) to (H-4).) Solder resist compositions were prepared by mixing and combining the combinations shown in Tables 3-1 to 3-4.

Table 1 Ingredients Main ingredients XA-1 XA-2 XA-3 XX-1 A-1 108 123 131 154 B-1 37.5 25 18.7

Table 2 Ingredients (parts by weight) H-1 H-2 H-3 H-4 Epicoat 1001 * 16630 YR-528 * 2 20 YX-4000 * 3 30 DEN-438 * 430

Note) * 1: Epicoat 1001: manufactured by Yuka Shell Epoxy Co., Ltd.
Bisphenol A epoxy resin (containing carbitol acetate, solid content concentration 75%) * 2; YR-528: manufactured by Toto Kasei Co., Ltd., rubber-modified epoxy resin * 3; YX-4000: manufactured by Yuka Shell Epoxy, bisphenol type Epoxy resin * 4; DEN-438: Dow Chemical Company, phenol novolak epoxy resin

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 3 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, and developed with an organic solvent or a 1 wt% Na ₂ CO ₃ aqueous solution. A test substrate was prepared by heat curing at 150 ° C. for 50 minutes. 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 3-1 shows the results.
It is shown in Table 3-4. 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) Thermal degradation resistance: After leaving the test substrate at 125 ° C. for 5 days, it was judged 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: The gold plating was performed on the test substrate as described below, and 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: The test substrate was subjected to an acidic degreasing solution 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.

Table 3-1 Example 1-234 (X) Component XA-1 XA-1 XA-1 XA-1 (H) Component H-1 H-2 H-3 H-4 Developability ○ ○ ○ ○ Solder heat resistance ○ ○ ○ ○ Flexibility ○ ○ ○ ○ Heat deterioration ○ ○ ○ ○ Electroless gold plating resistance ○ ○ ○ ○

Table 3-2 Example 5 678 (X) Component XA-2 XA-2 XA-2 XA-2 (H) Component H-1 H-2 H-3 H-4 Developability ○ ○ ○ ○ Solder heat resistance ○ ○ ○ ○ Flexibility ○ ○ ○ ○ Heat deterioration ○ ○ ○ ○ Electroless gold plating resistance ○ ○ ○ ○

Table 3-3 Example 9 10 11 12 (X) Component XA-3 XA-3 XA-3 XA-3 (H) Component H-1 H-2 H-3 H-4 Developability ○ ○ ○ ○ Solder heat resistance ○ ○ ○ ○ Flexibility ○ ○ ○ ○ Heat deterioration ○ ○ ○ ○ Electroless gold plating resistance ○ ○ ○ ○

Table 3-4 Comparative Example 1 2 3 4 (X) Component XX-1 XX-1 XX-1 XX-1 (H) Component H-1 H-2 H-3 H-4 Developability ○ ○ ○ ○ Solder heat resistance ○ ○ ○ ○ Flexibility △ △ × × Heat deterioration △ △ × × Electroless gold plating resistance ○ ○ ○ ○

As is evident from the results shown in Tables 3-1 to 3-4, the resin composition of the present invention exhibits good alkali developability, and also has solder heat resistance, flexibility, heat deterioration resistance, and Provides a cured film with excellent electrolytic gold plating properties.

[0081]

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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 502 G03F 7/027 502 515 515 7/028 7/028 F term (reference) 2H025 AA00 AA10 AB15 AC01 AD01 BC14 BC34 BC43 BC74 BC81 BC85 BC92 CA01 CA27 CA35 CC03 CC17 CC20 FA03 FA15 FA29 FA39 FA43 4J002 BG07X BL01X CC16Y CC18Y CD01Y CD02Y CD04Y CD05Y CD06Y CD12Y CD19W CD19X CF27X CH05X CP03X EC036 EE026 EG030 EG030 GQ01 4J027 AA01 AA03 AC02 AC03 AC04 AC06 AE02 AE03 AE04 AE05 AE07 AF04 AJ08 BA07 BA08 BA19 BA23 BA24 BA26 BA27 BA28 CA10 CA29 CB10 CD06 CD10

Claims (13)

[Claims] 1. An epoxy resin (a) having two or more epoxy groups in one molecule, a monocarboxylic acid compound (b) having an ethylenically unsaturated group, and a polybasic anhydride (c-1). Unsaturated group-containing polycarboxylic acid resin (A) as a reactant
And a carboxyl obtained by reacting a polyol compound (d) with a polybasic acid anhydride (c-2) having two acid anhydride groups in a molecule and an ethylenically unsaturated group-containing polyhydroxy compound (e). A resin composition containing a group-containing oligomer (B). 2. The resin composition according to claim 1, wherein the epoxy resin (a) having two or more epoxy groups in one molecule is an epoxy resin obtained by glycidylating a bisphenol type epoxy compound. 3. A bisphenol type epoxy compound represented by the formula (1): ## STR1 ## (2) In the formula (1), X is —CH ₂ — or —C (CH ₃ ) ₂ —, and n is an average number of 1 or more. The resin composition as described in the above. 4. An epoxy resin (a) having an epoxy equivalent of 28
The resin composition according to any one of claims 1 to 3, wherein the amount is from 0 to 500 g / equivalent. 5. The resin composition according to claim 1, wherein the carboxyl group-containing oligomer (B) has a weight average molecular weight of 500 to 100,000. 6. The carboxyl group-containing oligomer (B) has an acid value of 1 to 200 mg KOH / g.
The resin composition according to any one of the above. 7. The method according to claim 1, which comprises a diluent (C).
The resin composition according to any one of the above. 8. The resin composition according to claim 1, further comprising a photopolymerization initiator (D). 9. The resin composition according to claim 1, further comprising a thermosetting component (E). 10. The printed wiring board according to claim 1, which is used for a solder resist or an interlayer insulating layer.
Item 14. The resin composition according to Item. 11. A cured product of the resin composition according to any one of claims 1 to 10. 12. An article having the cured product layer according to claim 11. 13. The article according to claim 12, which is a printed wiring board.