JP2003048932A - Resin composition, solder-resist resin composition and cured materials thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin having excellent photosensitivity, providing a cured material with excellent flexibility, solder heat resistance, heat deterioration resistance, electroless plating resistance, developable with an organic solvent or a diluted alkali solution, especially suitable for a solder-resist and an interlayer insulating layer. SOLUTION: This resin composition comprises an oligomer (A) obtained by reacting an epoxy compound (a) containing at least two epoxy groups in one molecule with a carboxy group-containing rubber-like polymer (b), a maleamide group-containing monobasic acid (c) and a polybasic acid anhydride d) and a (meth)acryloyl group-containing monobasic acid (e) as arbitrary components and a diluent (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various coating materials, surface treatment materials, optical waveguide materials, laminated plates, adhesives, adhesive materials, printing inks, sealants, color resists (LC).
The present invention relates to a resin composition and a cured product thereof which can be used as a resin composition for a printed wiring board and can be used as a liquid resist ink and the like. More specifically, it is useful as a solder resist for a flexible printed wiring board, a plating resist, an interlayer electrical insulating material for a multilayer printed wiring board, has excellent developability, and its cured film has excellent adhesion, flexibility (flexibility), The present invention relates to a resin composition and a cured product thereof that give a cured product having excellent solder heat resistance, chemical resistance, gold plating resistance and the like.

[0002]

2. Description of the Related Art Unnecessary in a soldering process performed when a wiring (circuit) pattern formed on a substrate by a method such as screen printing is protected from an external environment or when electronic parts are surface-mounted on a printed wiring board. In order to prevent solder from adhering to such a portion, a protective layer called a cover coat or a solder mask is coated on the printed wiring board. Conventionally, a multifunctional epoxy resin-based one has been mainly used as a solder resist ink used for such an application, but the resulting cured film has a problem that it has good heat resistance but low flexibility. It was Therefore, such a solder resist ink is limited in its use of a rigid board in which flexibility (flexibility) of a cured film is not required, and has been frequently used in recent years in a flexible printed wiring board (FPC).
Is difficult to use.

Under the circumstances as described above, many proposals have recently been made as a resist ink 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 heat-drying solvent containing polyparabanic acid and a phenoxy resin as essential components. Type solder resist ink has been proposed.
However, since these solder resists form a resist pattern by screen printing, the line width of the screen is limited, and it is difficult to cope with fine image formation due to today's high density. . For this reason, in recent years, there has been proposed a photo-developing type as seen in JP-A-2-173949, JP-A-2-173750, JP-A-2-173775, etc., but still provides sufficient flexibility. It hasn't arrived yet.

[0004]

The object of the present invention is to use a specific oligomer (A) so that the photopolymerization initiator is not used, or the curability (photosensitivity) is improved even if the amount is smaller than the conventional amount. Excellent, it can be formed by exposure and development with organic solvents and dilute aqueous alkali solution, and the cured film obtained by heat curing in the post-curing process is rich in flexibility, solder heat resistance, heat deterioration resistance, and (EN) It is intended to provide a resin composition suitable for an organic solvent or alkali development type resist ink for flexible printed wiring boards, and a cured product thereof, which can form a film excellent in electrolytic gold plating resistance, acid resistance and water resistance.

[0005]

[Means for Solving the Problems] In order to solve the above problems, the present inventor has used the resin composition containing a specific oligomer (A) and a diluent (B) to solve the above problems. The inventors have found that the above can be achieved and completed the present invention. That is, according to the present invention,

(1) An epoxy compound (a) having at least two epoxy groups in one molecule, a carboxyl group-containing rubbery polymer (b), a maleimide group-containing monobasic acid (c), and an optional component Resin composition containing oligomer (A) obtained by reacting basic acid anhydride (d) with (meth) acryloyl group-containing monobasic acid (e) and diluent (B), (2), oligomer (A) The weight average molecular weight of (1) is 1,000 to 100,000, and the acid value of the resin composition (3) and oligomer (A) is 1 to 300 m.
The resin composition according to (1), which is gKOH / g, (4),
An epoxy compound (a) having at least two epoxy groups in one molecule is represented by the formula (1)

[0007]

[Chemical 3]

(In the formula (1), X is --CH ₂ -or --C
(CH ₃ ) ₂ −, m is an integer of 1 or more, M is a hydrogen atom or the following formula (G), and when m is larger than 1, at least one of M is the formula (G). The rest represent hydrogen atoms. )

[Chemical 4] The resin composition according to any one of (1) to (3), which is an epoxy resin represented by: (5), and any of (1) to (4) containing a photopolymerization initiator (C). (6), the resin composition according to any one of (1) to (5) containing a thermosetting component (D), (7), a printed wiring board Any one of (1) to (6) for a solder resist or an interlayer insulating layer
(8), a cured product of the resin composition according to any one of (1) to (7), (9),
An article having the layer of the cured product according to (8), (10), and an article according to (11) 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 an oligomer (A) and a diluent (B). The oligomer (A) used here has a weight average molecular weight of preferably 1,000 to 100,000 and an acid value of preferably 1 to 300 mgKOH / g.

The oligomer (A) used in the present invention comprises an epoxy compound (a) having at least two epoxy groups in one molecule, a carboxyl group-containing rubbery polymer (b), and a maleimide group-containing monobasic acid (c). ) And a polybasic acid anhydride (d) as an optional component and a (meth) acryloyl group-containing monobasic acid (e).

Specific examples of the epoxy compound (a) having at least two epoxy groups in one molecule used herein include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, and , A bisphenol type epoxy resin such as an epoxy resin represented by the general formula (1); phenol.
Novolac type epoxy resins such as novolac type epoxy resins and cresol novolac type epoxy resins; trisphenolmethane type epoxy resins; dicyclopentadiene modified novolac type epoxy resins; naphthalene modified epoxy resins; 3,4-epoxy-6-methylcyclohexylmethyl Alicyclic epoxy resins such as -3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; Phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester,
Glycidyl esters such as dimer acid glycidyl ester; heterocyclic epoxy resins such as triglycidyl isocyanurate; GMA (glycidyl methacrylate) copolymers and various fluorine atom-containing epoxy resins, and the like. Among them, flexibility, The epoxy resin represented by the general formula (1) is preferable because it has an excellent balance of various properties such as solder heat resistance and plating resistance.

The structure of the carboxyl group-containing rubbery polymer (b) is not particularly limited, but for example, an ethylenically unsaturated monobasic acid such as polybutadiene-acrylic acid copolymer and a conjugated diene can be used. Copolymer with vinyl monomer; polybutadiene-acrylonitrile-
Copolymers of ethylenically unsaturated monobasic acids such as acrylic acid copolymers, conjugated diene vinyl monomers and other vinyl monomers; carboxylic acids such as maleated polybutadiene represented by the following structural formula 1 or structural formula 2. Examples thereof include a pendant conjugated diene-based vinyl polymer, or a linear polymer having a carboxyl group at both ends of the molecule.

Structural formula 1

[0014]

[Chemical 5]

(Here, n and l represent the average number of repeating units, and each is an integer of 1 or more.)

Structural formula 2

[0017]

[Chemical 6]

(Here, a, b and c represent the average number of repeating units, each being an integer of 1 or more.)

Examples of the latter rubber-like polymer having a carboxyl group at both terminals of the linear polymer include, for example, a carboxyl group at both terminals of a molecule such as polybutadienedicarboxylic acid represented by the following structural formula 3. A diene vinyl polymer having: butadiene represented by the following structural formula 4
Acrylonitrile copolymer is a copolymer of an ethylenically unsaturated monobasic acid such as a polymer having a carboxyl group at both ends of the molecule and a conjugated diene vinyl monomer, and a polymer having a carboxyl group at both ends of the molecule (for example, , Molecular weight 3500, bound acrylonitrile 27% by weight, carboxyl group 1.9 / molecule HYCAR CTBN 1300 ×
13 [B. F. Good rich chemical
Manufactured by K.K.); and a half ester of a conjugated diene vinyl monomer such as a copolymer of polybutadiene glycol represented by the following structural formula 5 and maleic anhydride, and an acid anhydride.

Structural formula 3

[0021]

[Chemical 7]

(Here, e represents the average number of repeating units and is an integer of 1 or more.)

Structural formula 4

[0024]

[Chemical 8]

(Here, f and g represent the average number of repeating units, and each is an integer of 1 or more.)

Structural formula 5

[0027]

[Chemical 9]

(Here, h represents the average number of repeating units and is an integer of 1 or more.)

As the conjugated diene vinyl monomer used in the carboxyl group-containing rubbery polymer (b), butadiene, isoprene, chloroprene, etc. may be used in addition to the butadiene used in the above-mentioned exemplified polymers. Good. Further, the ethylenically unsaturated monobasic acid that can be copolymerized with the conjugated diene-based vinyl monomer is not limited to those listed as the above exemplified polymers, and examples thereof include (meth) acrylic acid, crotonic acid, and cinnamic acid. , Acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl) malate, sorbic acid, etc., among which (meth) acrylic acid is preferred. The other vinyl monomers are not limited to the above exemplified compounds, and include acrylic acid, methacrylic acid, acrylonitrile,
Styrene, vinyltoluene or the like can be used.

The number of carboxyl groups in the obtained rubber-like polymer is not particularly limited, but the number of carboxyl groups in the molecule is 1 to 5 on average, more preferably 1.5 to. It is desirable to be in the range of 3.

Specific examples of the maleimide group-containing monobasic acid (c) are as follows.

[0032]

[Chemical 10]

As shown by the formula (1), a known technique [for example, D.
DH Rich et al. "Journal
Of Medical Chemistry (Journal o
f Medical Chemistry) "18th
Vol. 1004-1010 (1975)], secondly, a compound (c-1), secondly, a hydroxyl group-containing maleimide compound () and a compound having one acid anhydride group in the molecule. Half ester compound with () (c-
2) etc. can be mentioned.

Examples of the primary aminocarboxylic acid include asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, α-methylphenylalanine, lysine, leucine. , Cycloleucine, 3-aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid,
6-aminocaproic acid, 7-aminoheptanoic acid, 2-aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 2-aminocapric acid, 9-aminocaprin Acid, 1
5-aminopentadecanoic acid, 2-aminopalmitic acid,
Examples thereof include 16-aminopalmitic acid, but are not limited thereto.

The above-mentioned maleimide compound containing a hydroxyl group ()
As a concrete example of

[0036]

[Chemical 11]

As shown by the following formula, from maleimide and formaldehyde, or the reaction formula

[0038]

[Chemical 12]

As shown in, in a molecule which can be synthesized from maleic anhydride and a primary amino alcohol using known techniques (see, for example, US Pat. No. 2,526,517, JP-A-2-268155). Examples thereof include compounds having one maleimide group and one hydroxyl group.

Examples of the primary amino alcohols include 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol and 2-amino-.
2-methyl-1-propanol, 2-amino-3-phenyl-1-propanol, 4 amino-1-butanol,
2-amino-1-butanol, 2-amino-3-methyl-1-butanol, 2-amino-4-methylthio-1-
Butanol, 2-amino-1-pentanol, (1-aminocyclopentane) methanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 2- (2
-Aminoethoxy) ethanol and the like,
It is not limited to this.

Examples of the compound () having one acid anhydride group in the molecule include maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride,
Examples thereof include tetrahydrophthalic anhydride and methyl-hexahydrophthalic anhydride.

The above half ester compound (c-2)
Can be obtained by reacting one chemical equivalent of the hydroxyl group in the maleimide compound containing a hydroxyl group () with about 1 chemical equivalent of an anhydride group in the compound having one acid anhydride group in the molecule. . The reaction temperature is preferably 60 to 100 ° C., and the reaction time is preferably 1 to 10 hours. If necessary, an organic solvent may be used during the reaction.

Examples of the polybasic acid anhydride (d) as an optional component include maleic anhydride, succinic anhydride,
Examples thereof include itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride and phthalic anhydride.

Examples of the (meth) acryloyl group-containing monobasic acid (e) as an optional component include (meth) acrylic acid and (meth) acrylic acid dimer.

The type of the oligomer (A) which is a reaction product of the combination of the components (a) to (e) is as follows.
Firstly, an oligomer (A-1) obtained by reacting a component (a), a component (b) and a component (c), and secondly,
An oligomer (A-2) obtained by reacting the component (a), the component (b), the component (c), and the component (e), and thirdly,
The oligomer (A-) obtained by reacting the component (a), the component (b) and the component (c) and then the component (d).
3) and 4thly, the oligomer (A-4) etc. which are obtained by reacting a component (a), a component (b), a component (c) and a component (e) and then a component (d) are mentioned. be able to.

The reaction ratio of each component is such that 0.3 to 1.1 equivalents of carboxyl groups in the total amount of (b) + (c) + (e) components to 1 equivalent of epoxy groups in the component (a). Are preferably reacted, and particularly preferably 0.95 to 1.05
It is equivalent. When the total amount of carboxyl groups in the components (b) + (c) + (e) is 1 equivalent, the usage ratio of each component is
The component (b) is preferably 0.005-0.3 equivalents, particularly preferably 0.01-0.2 equivalents, and the component (c) is preferably 0.05-0.995 equivalents, particularly preferably , 0.1-0.99 equivalent, and the component (e) is 0-
0.945 equivalent is preferable, and 0 to 0.
89 equivalents. The anhydride group in the component (d) is preferably reacted in an amount of 0 to 1 equivalent with respect to 1 equivalent of the hydroxyl group in the reaction product of the components (a), (b), (c) and (e).

The oligomerization reaction is carried out without solvent or with solvents, for example, ketones such as acetone, ethylmethylketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene; ethylene glycol dimethyl ether and ethylene. Glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether,
Glycol ethers such as triethylene glycol dimethyl ether; ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. Preferred are cyclic esters such as γ-butyrolactone; petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha.

During the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reactant. Specific examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate, zirconium octanoate and the like.

A polymerization inhibitor may be used for the purpose of preventing polymerization during the reaction. Specific examples of the polymerization inhibitor include P-methoxyphenol, hydroquinone, methylhydroquinone, phenothiazine and the like. The amount of the polymerization inhibitor used is 0.05 with respect to the reaction product.
~ 3% by weight.

The reaction temperature is preferably 70 to 120 ° C,
The reaction time is preferably 5 to 40 hours.

In the present invention, the diluent (B) is used. Specific examples of the diluent (B) include the above solvents, butanol, octyl alcohol, ethylene glycol,
Organic solvents (B-1) and carbitol (meth) such as alcohols such as glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, and tetraethylene glycol monomethyl (or monoethyl) ether Reactions of acrylate, phenoxyethyl (meth) acrylate, acryloylmorpholine, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta and hexa (meth) acrylate Examples thereof include a sex diluent (B-2).

The amount of the components (A) and (B) contained in the resin composition of the present invention is (A) + (B) in total 10 in the composition.
Is preferably 90 to 90% by weight, particularly preferably 20 to 80% by weight, and the ratio of (A) and (B) used is 10% for (A).
˜90% by weight, and (B) is preferably 10 to 90% by weight.

In the present invention, the photopolymerization initiator (C) may be used. Examples of the photopolymerization initiator (C) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone,
1,1-dichloroacetophenone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Acetophenones; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, and other anthraquinones; 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and other thioxanthones. Kinds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphos Fin oxide are listed.

These can be used alone or as a mixture of two or more kinds, and 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 a promoter such as a benzoic acid derivative such as acid isoamyl ester.

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

In the present invention, it is preferable to use a thermosetting component (D) as a curing system component in each of the above components,
By using this, a printed wiring board material having excellent solder heat resistance and electrical characteristics can be obtained. The thermosetting component (D) used in the present invention may be any one having a functional group capable of thermosetting with the oligomer (A) in the molecule,
Although not particularly specified, examples thereof include an epoxy resin, a melamine compound, a urea compound, an oxazoline compound, and a phenol compound. 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, biquinolen type. Glycidyl ethers such as epoxy resin and biphenol type epoxy resin; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4- Alicyclic epoxy resins such as epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer Glycidyl amines such as tetraglycidyl diaminodiphenylmethane; glycidyl esters such as glycidyl ester and heterocyclic epoxy resins such as triglycidyl isocyanurate.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensation product of melamine and formalin. Examples of the urea compound include urea and a urea resin which is a polycondensation product of urea and formalin.

As the oxazoline compound, 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 can be mentioned.

Examples of the phenol compound include phenol, cresol, chylenol, catechol, resorcin, hydroquinone, pyrogallol and resole. Of these, an epoxy resin having a melting point of 50 ° C. or higher is preferable because it can form a photopolymer film without tack after drying.

Among these thermosetting components (D), epoxy resins are preferable because they are particularly excellent in reactivity with the carboxyl group in the component (A) and have good adhesion to copper.

A suitable range of the amount of the thermosetting component (D) used is usually 0.2 to 3 functional groups of the thermosetting component (D) per one carboxyl group in the component (A). The ratio is 0.0 equivalent. Above all, a ratio of 1.0 to 1.5 equivalents is preferable from the viewpoint of excellent solder heat resistance and electric characteristics when used as a printed wiring board.

When an epoxy resin is used as the thermosetting component (D), it is preferable to use a curing accelerator for the epoxy resin in order to accelerate the reaction with the carboxyl group in the component (A). Examples of the curing accelerator for the epoxy resin include imidazole compounds such as 2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole; melamine, guanamine, acetoguanamine, benzoguanamine, 2, Triazine derivatives such as 4-diaminotriazine and 2,4-diamino-6-tolyltriazine;
Examples include tertiary amines such as triethanolamine, pyridine, and m-dimethylaminophenol; polyphenols and the like. In addition, a substance that itself changes into a curing accelerator upon irradiation with radiation such as ultraviolet rays, for example, 1-
Ethyl-3,5-dimethoxycarbonyl-4- (2-nitrophenyl) -1,4-dihydropyridine, 1,2,
6-trimethyl-3,5-dimethoxycarbonyl-4-
(2-nitrophenyl) -1,4-dihydropyridine,
2,6-Dimethyl-3,5-diacetyl-4- (2-nitrophenyl) -1,4-dihydropyridine, 1-carboxyethyl-3,5-dimethoxycarbonyl-4-
A 1,4-dihydropyridine derivative such as (2-nitrophenyl) -1,4-dihydropyridine can also be preferably used. These curing accelerators can be used alone or in combination.

Furthermore, in the present invention, in addition to the above-mentioned oligomer (A), diluent (B), photopolymerization initiator (C) and thermosetting component (D), if necessary, various additives, for example, Fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, thixotropic agents such as Aerosil; phthalocyanine blue, phthalocyanine green, coloring agents such as titanium oxide, Silicone, fluorine-based leveling agents and defoaming agents; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be added for the purpose of improving various properties of the composition.

The component (D) as described above may be mixed in advance with the resin composition, but it is preferable to use it by mixing it before coating it on the printed circuit board. In this case, the above-mentioned (A) component is the main component solution containing the epoxy curing accelerator and the like as the main component solution, and the (D) component is the main component solution containing the two-component type, and these are mixed before use. It is preferable to mix and use.

The resin composition of the present invention is used as a support, for example, on a polymer film (for example, a film made of polyethylene terephthalate, polypropylene, polyethylene or the like) as an organic solvent (B-) used as a diluent (B). It can also be used as a photosensitive film by evaporating 1) and laminating it.

The resin composition (liquid or film) of the present invention is useful as an insulating material between layers of electronic parts and as a resist ink such as a solder resist for a printed circuit board, as well as an antistatic agent, a paint, a coating. It can also be used as an agent or an adhesive. The cured product of the present invention is one obtained by curing the above 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 carried out by a conventional method. For example, when irradiating with ultraviolet rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp,
An ultraviolet generator such as a xenon lamp or an ultraviolet light emitting laser (excimer laser etc.) may be used. The cured product of the resin composition of the present invention can be used as an electrical insulating material such as a printed circuit board as a permanent resist or an interlayer insulating material for a build-up method.
Used for electronic parts. The film thickness of this 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 present invention can be applied to a printed wiring board by a method such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc., in a film thickness of 5 to 160 μm. By applying the composition of (1) and drying the coating film at a temperature of usually 60 to 110 ° C, preferably 60 to 100 ° C,
A tack-free coating film can be formed. After that, 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 without contacting the film), and ultraviolet rays are usually irradiated at an intensity of about 10 to 2000 mJ / cm ^2. Then, using an unexposed portion with a developer described later,
For example, development is performed by spraying, rocking dipping, brushing, scrubbing, or the like. Thereafter, if necessary, further irradiation with ultraviolet rays is performed, and then heat treatment is usually performed at a temperature of 100 to 200 ° C., preferably 140 to 180 ° C., whereby excellent flexibility is achieved, and the heat resistance and solvent resistance of the resist film are excellent. A printed wiring board having a permanent protective film satisfying various properties such as acid resistance, adhesion, and electrical properties 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; methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; lactones such as γ-butyrolactone; 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 ether. , Petroleum solvents such as petroleum naphtha,
As the water or alkaline aqueous solution, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used. A low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable as an irradiation light source for photocuring. In addition, a laser beam or the like can be used as the active light for exposure.

[0069]

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 of Oligomer (A)) Synthesis Example 1. In the general formula (1), X is -CH.
_2- , M is a hydrogen atom, bisphenol F type epoxy resin having an average degree of polymerization n of 6.2 (epoxy equivalent: 950 g
/ Eq, softening point 85 ° C.) 380 g and epichlorohydrin 925 g were dissolved in dimethyl sulfoxide 462.5 g, and then stirred at 70 ° C. at 98.5% NaOH 60.9.
g (1.5 mol) was added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the reaction is complete, water 2
50 g was added and washed with water. After oil-water separation, most of dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, then dimethyl sulfoxide was distilled off, and a reaction product containing a by-product salt was dissolved in 750 g of methyl isobutyl ketone. 30% NaOH 1
0 g was added and reacted at 70 ° C. for 1 hour. After the reaction,
After washing twice with 200 g of water and separating oil and water, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin having an epoxy equivalent of 310 g / eq and a softening point of 69 ° C. (a-
1) was obtained. The obtained epoxy resin (a-1) was epoxidized from about 6.2 of 6.2 alcoholic hydroxyl groups in the starting bisphenol F type epoxy resin calculated from the epoxy equivalent. The obtained epoxy resin (a-1) 310g and molecular weight 350
0, bound acrylonitrile 27% by weight, HYCAR CTBN 1300 × 13 with 1.9 carboxyl groups / molecule
[B. F. 52.5 g, manufactured by Goodrich Chemical Company, 63.3 g of maleimidocaproic acid, 47.9 g of acrylic acid (the number of epoxy groups: the number of total carboxyl groups = 1: 0.99) and triphenylphosphine.2.
1 g and 0.3 g of P-methoxyphenol were reacted in 256.4 g of carbitol acetate to give an oligomer (A-
2-1) was obtained. The solid content of the product was 65%, the weight average molecular weight of the solid content was about 7,000 (according to GPC method), and the acid value of the solid content was 1.0 mgKOH / g.

Synthesis Example 2 732.5 g of oligomer (A-2-1) obtained in Synthesis Example 1
And tetrahydrophthalic anhydride 67.7 g and succinic anhydride 44.6 g (number of hydroxyl groups: number of acid anhydride groups = 1: 0.8
9) and 60.5 g of carbitol acetate are reacted at 90 ° C. for about 10 hours to give an acid value of solid content of 86 mgKOH /
g, the weight average molecular weight of the solid content is about 10,000 (according to the GPC method), and the product (oligomer (A-4
-1)) was obtained.

Synthesis Example 3 (Synthesis Example of Oligomer for Comparative Example) 310 g of the epoxy resin (a-1) obtained in Synthesis Example 1, 71.3 g of acrylic acid, and 1.75 of triphenylphosphine.
g, P-methoxyphenol 0.3 g and carbitol acetate 206.4 g were charged and reacted at 98 ° C. for 35 hours, then tetrahydrophthalic anhydride 54.5 g, succinic anhydride 35.9 g and carbitol acetate 4
8.7 g was charged and reacted at 90 ° C. for about 10 hours to obtain a product having an acid value of solid content of 86 mgKOH / g, a weight average molecular weight of solid content of about 7500 (by GPC method), and a solid content of 65%. .

Examples 1 to 3 and Comparative Examples 1 to 3 The resist compositions of the present invention were prepared by blending, dissolving and kneading according to the blending composition shown in Table 1. Next, the prepared resist composition is applied to a printed circuit board (imido film laminated with copper foil) by screen printing, and the temperature is set to 80 ° C.
And dried for 20 minutes. Then, a negative film is applied to this substrate, and 600 mJ is obtained by using an exposure machine according to a predetermined pattern.
1.0 wt% by irradiating ultraviolet rays with an integrated exposure amount of / cm ²
After development with an aqueous Na ₂ CO ₃ solution (Examples 2 and 3, Comparative Examples 1 to 3) and γ-butyrolactone (Example 1), a further 15
A test substrate was prepared by heat curing at 0 ° C. for 60 minutes. The photosensitive performance of the obtained resist composition was evaluated. The obtained test board was evaluated for its developability, solder heat resistance, flexibility, heat deterioration resistance, and electroless gold plating resistance. The results are shown in Table 2. The evaluation method and evaluation criteria are shown below.

Table 1 Example 1 2 3 (A) component Oligomer (A-2-1) 154 obtained in Synthesis Example 1 Oligomer (A-4-1) 154 154 obtained in Synthesis Example 2 Obtained in Synthesis Example 3 Oligomer (B) component KAYARAD DPHA ^{* 1} 16 16 16 Carbitol acetate (C) component Irgacure 907 ^{* 2} 4 2 2 Kayacure DETX-S ^{* 3} 0.48 0.24 0.24 (D) component YX-4000 ^{* 4} 30 30 DEN- 438 ^{* 5} 30 Others Fine powder silica (filler) 10 10 10 Melamine (epoxy curing accelerator) 1.2 1.2 1.2 KS-66 (antifoaming agent) ^{* 6} 1.0 1.0 1.0 Comparative Example 1 2 3 (A) component Synthetic Example 1 Obtained Oligomer (A-2-1) Oligomer obtained in Synthesis Example 2 (A-4-1) Oligomer obtained in Synthesis Example 3 154 154 154 (B) Component KAYARAD DPHA ^{* 1} 16 16 16 Carbitol acetate (C ) Ingredient Irgacure 907 ^{* 2} 10 10 3 Kayacure DETX-S ^{* 3} 1.2 1.2 0.36 (D) Ingredient YX-4000 ^{* 4} 30 30 DEN-438 ^{* 5} 30 Others Fine silica (filler) 10 10 10 Melamine (accelerating epoxy curing) Agent) 1.2 1.2 1.2 KS-66 (anti-foaming agent) ^{* 6} 1.0 1.0 1.0

Note) * 1: KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.
Mixture of dipentaerythritol penta and hexaacrylate. * 2; Irgacure 907: Ciba Specialty Chemicals, photopolymerization initiator, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholino-propan-1-one. * 3: Kayakyu DETX-S: manufactured by Nippon Kayaku Co., Ltd.,
Photopolymerization initiator, 2,4-diethylthioxanthone. * 4; YX-4000: Bisphenol type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. * 5; DEN-438: Phenol novolac epoxy resin manufactured by Dow Chemical Company. * 6; KS-66: A silicone defoamer manufactured by Shin-Etsu Chemical Co., Ltd.

Evaluation Method and Evaluation Criteria (1) Photosensitivity: Step tablets 2 on the coating film after drying.
Adhesion of 1-stage (made by Stoffer Co., Ltd.) and integrated light amount 600mJ
Irradiate and expose with ultraviolet rays of / cm ² . Next, the number of steps of the coating film left without being developed with a spray pressure of 2.0 kg / cm ² for 60 seconds with a 1% sodium carbonate aqueous solution is confirmed. The following criteria were used. ○ ・ ・ ・ ・ 6 or more steps. △ ... 4 to 5 steps. × ... 3 steps or less. (2) Developability: The coating film is dried at 80 ° C. for 60 minutes and then 3
The developability by spray development with 0 ° C. γ-butyrolactone (Example 1) and 1% sodium carbonate aqueous solution (Examples 2 and 3, Comparative Examples 1 to 3) was evaluated. ○ ・ ・ ・ ・ No residue visually. × ・ ・ ・ ・ There is a residue visually.

(3) Solder heat resistance: A rosin-based flux was applied to a test substrate, dipped in molten solder at 260 ° C. for 10 seconds, and then peeled with a cellophane adhesive tape to determine the state of a cured film. ○ ・ ・ ・ ・ No abnormality. × ・ ・ ・ ・ Peeled.

(4) Flexibility: Judgment was made in a state where the test substrate was bent 180 degrees. ○ ・ ・ ・ ・ No cracks. △ ・ ・ ・ ・ Slightly cracked. × ・ ・ ・ ・ The bent film was cracked and the cured film was peeled off.

(5) Heat deterioration resistance: After the test substrate was left at 125 ° C. for 5 days, it was judged in the state of 180 ° solid bending. ○ ・ ・ ・ ・ No cracks. △ ・ ・ ・ ・ Slightly cracked. × ・ ・ ・ ・ The bent film was cracked and the cured film was peeled off.

(6) Electroless gold plating resistance: The test substrate was plated with gold as described below, and then judged by the state when the test substrate was peeled off with a cellophane tape ^(R) adhesive tape. ○ ・ ・ ・ ・ No abnormality. △ ・ ・ ・ ・ Somewhat peeled off. × ・ ・ ・ ・ No peeling.

Electroless gold plating method: A test substrate was treated with an acidic degreasing solution at 30 ° C. (made by Nippon MacDermid Co., Ltd., Metex).
L-5B 20% by volume aqueous solution) for 3 minutes for degreasing, and then for 3 minutes under running water for washing. Next, the test substrate was immersed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 days.
It was soaked for 1 minute, soft-etched, then soaked in running water for 3 minutes and washed with water. Then, the test substrate was immersed in a catalyst liquid (Meltex Co., Ltd., 10 vol% aqueous solution of metal plate activator 350) at 30 ° C. for 7 minutes to apply a catalyst, and then immersed in running water for 3 minutes and washed with water. . The test substrate to which the catalyst had been applied was immersed in a 20 Vol% aqueous solution (PH 4.6) of a nickel plating solution at 85 ° C. for 20 minutes to perform electroless nickel plating. After immersing the test substrate 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 gold plating solution at 95 ° C. (manufactured by Meltex Co., Ltd., Ourollectroless UP15 Vol% and potassium cyanide 3 V).
After immersing in an ol% aqueous solution, PH6) for 20 minutes to perform electroless gold plating, it was immersed in running water for 3 minutes and washed with water, and was immersed in warm water at 60 ° C. for 3 minutes and washed with hot water. After thoroughly washing with water, the water was drained and dried to obtain a test substrate plated with electroless gold.

[0081]

As is clear from the results shown in Table 2, the resin composition of the present invention has sufficient photosensitivity even when the amount of the photopolymerization initiator used is small, and exhibits good developability. It provides a cured film having excellent solder heat resistance, flexibility, heat deterioration resistance, and electroless gold plating.

[0083]

According to the present invention, the amount of the photopolymerization initiator used is at least sufficient curability, and the cured product is excellent in flexibility, solder heat resistance, heat deterioration resistance, and electroless gold plating resistance. Development with a solution was possible, and a resin composition suitable for a solder resist and an interlayer insulating layer was obtained. This resin composition is suitable for a solder resist and an interlayer insulating layer of a printed wiring board, especially a flexible printed wiring board.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/46 H05K 3/46 TF term (reference) 4J027 AE02 AE03 AE04 AE05 AE09 BA01 BA07 BA13 BA26 BA28 CA10 CA25 CA29 CB10 CC02 CC05 CD08 CD10 4J036 AB17 AC02 AD07 AD08 AF06 AH00 AJ08 AK11 CA03 CA20 CA21 CD04 DB06 DC05 DC40 DC45 EA03 EA04 EA09 HA02 JA08 JA10 5E314 AA27 AA32 CC07 DD07 FF06 FF19 GG10 GG14 5E346 AA12 CC13 CC10 CC52 CC10 CC10H

Claims (10)

[Claims] 1. An epoxy compound (a) having at least two epoxy groups in one molecule, a carboxyl group-containing rubbery polymer (b), a maleimide group-containing monobasic acid (c), and a polybasic acid as an optional component. A resin composition containing an oligomer (A) obtained by reacting an anhydride (d) with a (meth) acryloyl group-containing monobasic acid (e) and a diluent (B). 2. The weight average molecular weight of the oligomer (A) is 10.
The resin composition according to claim 1, which is from 00 to 100,000. 3. The acid value of the oligomer (A) is 1 to 300 mg.
The resin composition according to claim 1, which is KOH / g. 4. An epoxy compound (a) having at least two epoxy groups in one molecule is represented by the formula (1): (In the formula (1), X is —CH ₂ — or —C (CH ₃ ) ₂ —, m is an integer of 1 or more, and M is a hydrogen atom or a formula (G) below. ] However, when m is 1, M represents the formula (G), and when m is larger than 1, at least one M represents the formula (G) and the rest represent hydrogen atoms. The resin composition according to any one of claims 1 to 3, which is an epoxy resin represented by the formula (4). 5. The resin composition according to claim 1, which contains a photopolymerization initiator (C). 6. The resin composition according to claim 1, which contains a thermosetting component (D). 7. The resin composition according to claim 1, which is for a solder resist of a printed wiring board or for an interlayer insulating layer. 8. A cured product of the resin composition according to claim 1. 9. An article having a layer of the cured product according to claim 8. 10. The article according to claim 9, which is a printed wiring board.