JP2003119247A - Resin composition, soldering resist composition and their cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which excels in photosensitivity and developability, excels in the flexibility, soldering heat resistance, resistance to thermal deterioration, and resistance to electroless gold plating of a cured product, and is suited particularly in use as a soldering resist and an interlayer insulating layer. SOLUTION: The resin composition comprises (A) an oligomer to be obtained by reacting (a) an epoxy resin having at least two epoxy groups per molecule, (b) a compound having two hydroxy groups and one carboxy group per molecule, (c) a carboxy group-containing rubbery polymer, and (d) an unsaturated group-containing monobasic acid.

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 liquid resist ink or the like, and are particularly useful as a composition for printed wiring boards. 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 an electronic component is 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, as a solder resist ink used for such an application, a polyfunctional epoxy resin-based ink has been mainly used. The cured film obtained has good heat resistance but low flexibility. There was a problem. Therefore, such a solder resist ink is limited in its use to a rigid board that does not require flexibility (flexibility) of a cured film, and is widely used in recent years in flexible printed wiring boards (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 composed of 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.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to use a specific oligomer (A), which is excellent in curability (photosensitivity) even if the amount of photopolymerization initiator used is smaller than the conventional amount. It has excellent developability even if it is smaller than the acid value (mgKOH / g), and the cured film obtained by heat curing in the post-curing process is rich in flexibility, solder heat resistance, heat deterioration resistance, and electroless. It is an object of the present invention to provide an organic solvent- or alkali-developing type resin composition, particularly a resin composition suitable for a resist ink for flexible printed wiring boards, and a cured product thereof which form a film excellent in gold plating resistance, acid resistance and water resistance.

[0006]

The present inventors have found that, in order to solve the above problems, the above problems can be achieved by using a resin composition containing a specific oligomer (A). The present invention has been completed. That is, the present invention provides (1) one molecule of an epoxy resin (b) having at least two epoxy groups in one molecule of an oligomer (A) (a) obtained by reacting the following components (a) to (d): A resin composition containing a compound having two hydroxyl groups and one carboxyl group (c) a carboxyl group-containing rubbery polymer (d) an unsaturated group-containing monobasic acid therein, (2) Oligomer (A) obtained by reacting the following components (a) to (e) (a) Epoxy resin having at least two epoxy groups in one molecule (b) Two hydroxyl groups and one in one molecule A resin composition containing a compound (c) having a carboxyl group, a carboxyl group-containing rubbery polymer (d) an unsaturated group-containing monobasic acid (e) a polybasic acid anhydride, The weight average molecular weight of (A) is 1000 to 1. 0,00
The resin composition according to the above (1) or (2), which is 0,
(4) The acid value of the oligomer (A) is 1 to 300 mgKOH
/ G, the resin composition according to any one of the above (1) to (3), (5) the epoxy resin (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, and M is a hydrogen atom or a formula (G) below.

[Chemical 4]

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. ) Any one of the above (1) to (4), which is an epoxy resin represented by
(6) The resin composition according to the item (6), wherein the proportion of M in the formula (1) represented by the formula (G) is 70 to 90 mol%.
(7) Two hydroxyl groups and one hydroxyl group in one molecule
The compound (b) having one carboxyl group has 2 to 2 carbon atoms.
(6) The resin composition according to any one of (1) to (6), which is a dimethylol derivative of carboxylic acid.
The unsaturated group-containing monobasic acid (d) is one or more selected from (meth) acrylic acid and a maleimide group-containing monobasic acid, according to any one of the above (1) to (7). A resin composition, (9) the resin composition according to the above (2), wherein the polybasic acid anhydride (e) is a phthalic anhydride derivative, (10)
The above (1) to (9) containing a photopolymerization initiator (C)
The resin composition according to any one of (1) to (11), the resin composition according to any one of (1) to (11) including the thermosetting component (D), and (12) a thermosetting component. (D)
The resin composition according to the above (11), wherein is an epoxy resin, and (13) 1,4-as a curing accelerator for the epoxy resin.
(12) The resin composition according to (12) containing a dihydropyridine derivative, (14) above (1) containing a diluent (B).
To the resin composition according to any one of (13),
(15) A composition for a solder resist of a printed wiring board or an interlayer insulating layer, comprising the resin composition according to (14) above, (16) any one of (1) to (15) above
A cured product of the composition according to item (17), an article having the layer of the cured product according to (16) above, and (18) an article according to (17) above which is a printed wiring board.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the following, "parts" or "%" are based on mass unless otherwise specified. The resin composition of the present invention contains an oligomer (A). The molecular weight of the oligomer (A) used here is 1 as a weight average molecular weight.
000-100,000 is preferable, and the acid value is 1-3.
00 mg KOH / g is preferred.

The oligomer (A) used in the present invention is an epoxy resin (a) containing at least two epoxy groups in one molecule and a compound having two hydroxyl groups and one carboxyl group in one molecule ( It is a product obtained by reacting b), a carboxyl group-containing rubbery polymer (c), an unsaturated group-containing monobasic acid (d), and a polybasic acid anhydride (e) as an optional component.

Specific examples of the epoxy resin (a) having at least two epoxy groups in one molecule used herein include novolac type epoxy resins (for example, phenol,
Those obtained by reacting novolaks obtained by reacting phenols such as cresol, halogenated phenols and alkylphenols with formaldehyde under an acidic catalyst with epichlorohydrin and / or methylepichlorohydrin. As commercially available products, Nippon Kayaku Co., Ltd. EOCN-103, EOCN-140S, EO
CN-1020, EOCN-1027, EPPN-20
1, BREN-S; DEN-43 manufactured by Dow Chemical Company
1, DEN-439; N manufactured by Dainippon Ink and Chemicals, Inc.
-730, N-770, N-865, N-665, N-
673, VH-4150, etc.), bisphenol type epoxy resin (for example, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, and the like obtained by reacting bisphenol with epichlorohydrin and / or methylepichlorohydrin; An epoxy resin represented by the general formula (1), which is obtained by reacting a diglycidyl ether of bisphenol A or bisphenol F with a condensate of the above bisphenol and epichlorohydrin and / or methylepichlorohydrin. Manufactured by Yuka Shell Co., Ltd. Epicoat 1004, Epicoat 100
2; DER-330, DER-33 manufactured by Dow Chemical Co.
7 etc.), trisphenol methane type epoxy resin (for example, those obtained by reacting trichlorophenol methane, tris cresol methane, etc. with epichlorohydrin and / or methyl epichlorohydrin. Commercially available products such as EPPN-501 and EPPN-502. ), Tris (2,3-epoxypropyl) isocyanurate, biphenyl diglycidyl ether, and others, Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd .; Epomic VG-3101 manufactured by Mitsui Petrochemical Industries, Ltd .; Mitsubishi Gas Chemical Co., Inc. ) TETRAD-X, TETRAD-C; alicyclic amino group-containing epoxy resins such as EPB-13 and EPB-27 manufactured by Nippon Soda Co., Ltd., copolymer type epoxy resins (for example, a copolymer of glycidyl methacrylate and styrene). ,
CP-50 manufactured by NOF CORPORATION, which is a copolymer of glycidyl methacrylate, styrene and methyl methacrylate
M, CP-50S, a copolymer of glycidyl methacrylate and cyclohexylmaleimide, etc.), or other epoxy resin having a special structure. Particularly preferable examples include the epoxy resin represented by the general formula (1). Among them, in the formula (1), the proportion in which M is a glycidyl group is preferably 70 to 90 mol%.

Next, examples of the compound (b) having two hydroxyl groups and one carboxyl group in the above molecule include dimethylol compound of carboxylic acid, and specific examples thereof include dimethylolpropionic acid, Dimethylol acetic acid,
Examples thereof include dimethylol compounds of carboxylic acids having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms such as dimethylol butyric acid, dimethylol valeric acid, and dimethylol caproic acid.

The structure of the carboxyl group-containing rubbery polymer (c) is not particularly limited, but for example, a conjugated diene vinyl monomer such as a butadiene-acrylic acid copolymer and an ethylenically unsaturated monomer. Copolymer with monobasic acid; Copolymer of conjugated diene vinyl monomer such as butadiene-acrylonitrile-acrylic acid copolymer, ethylenically unsaturated monobasic acid and other vinyl monomer; Examples thereof include carboxylic acid pendant conjugated diene vinyl polymers such as maleated polybutadiene represented by Formula 2, and rubber polymers having a carboxyl group at both ends of a linear polymer.

Structural formula 1

[0016]

[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

[0019]

[Chemical 6]

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

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

Structural formula 3

[Chemical 7]

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

Structural formula 4

[0025]

[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

[0028]

[Chemical 9]

(Here, h represents the average number of repeating units and is an integer of 1 or more.) The conjugated diene vinyl polymer used in the carboxyl group-containing rubber polymer is exemplified above. A polymer derived from isoprene, chloroprene or the like may be used instead of the polymer derived from butadiene. Examples of the ethylenically unsaturated monobasic acid that can be copolymerized with the conjugated diene vinyl monomer include (meth) acrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethylmalate, monopropyl. Malate, monobutyl maleate, mono (2-ethylhexyl)
Examples thereof include malate and sorbic acid, and of these, (meth) acrylic acid is preferable. Further, as the other vinyl monomer, 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 unsaturated group-containing monobasic acid (d) include (meth) acrylic acid, a dimer of acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, Examples include unsaturated monocarboxylic acids such as α-cyanocinnamic acid and cinnamic acid. Furthermore, a reaction product of a saturated or unsaturated dibasic acid anhydride and (meth) acrylates having one hydroxyl group in one molecule, and a reaction of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound object,
Examples thereof include a half ester which is a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound, and these can be obtained by reacting the former and the latter in equimolar amounts. Here, as the saturated or unsaturated dibasic acid anhydride,
For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylentmethylenetetrahydrophthalic anhydride, etc. Can be mentioned. Further, as the (meth) acrylates, for example,
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate,
1 such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, (meth) acrylate of phenylglycidyl ether
(Meth) acrylates having one hydroxyl group in the molecule can be mentioned. Examples of the saturated or unsaturated dibasic acid include succinic acid, maleic acid, adipic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid and fumaric acid. Examples of unsaturated group-containing monoglycidyl compounds include glycidyl (meth) acrylate,

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

And the like. Further, examples of the unsaturated group-containing monobasic acid (d) other than the above include maleimide group-containing monobasic acid. As an example of the maleimide group-containing monobasic acid, firstly,

[0037]

[Chemical 14]

As shown by the formula (1), a known technique [for example,
DH Rich et al. "Journal
Of Medical Chemistry (Journal o
f Medical Chemistry) "18th
Vol. 1004-1010 (1975)], compound (d-1), secondly, hydroxyl group-containing maleimide compound () and compound having one acid anhydride group in the molecule. Half ester compound with () (d-
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-aminocapric acid, 15-aminopentadecanoic acid, 2-aminopalmitic acid, 16-aminopalmitic acid and the like can be mentioned, but not limited thereto.

Specific examples of the hydroxyl group-containing maleimide compound () include reaction formulas

[0040]

[Chemical 15]

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

[0042]

[Chemical 16]

As shown in (1), a molecule which can be synthesized from maleic anhydride and a primary amino alcohol by using a known technique (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 can be mentioned, but the invention is not limited thereto.

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

The half ester compound (d-2) is
It can be obtained by reacting one chemical equivalent of the hydroxyl group in the hydroxyl-containing maleimide compound () with about 1 chemical equivalent of the 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 preferable unsaturated group-containing monobasic acid (d) include acrylic acid and maleimidocaproic acid. Examples of the polybasic acid anhydride (e) 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 derivatives such as phthalic anhydride.

Specific examples of the oligomer (A) include the first
To (a), (b) component, (c) component and (d) component are reacted to obtain an oligomer (A-), and secondly, (a) component, (b) component and (c) An oligomer (A-) obtained by reacting the component with the component (d) and then reacting with the component (e) can be exemplified.

The reaction ratio of each component is 0.3 to 1.1 equivalents of carboxyl groups in the total amount of components (b) + (c) + (d) with respect to 1 equivalent of epoxy groups in component (a). Is preferably reacted, particularly preferably 0.9 to 1.05 equivalent. When the total amount of carboxyl groups in the components (b) + (c) + (d) is 1 equivalent, the usage ratio of each component is
The component (b) is preferably 0.05 to 0.5 equivalents, particularly preferably 0.1 to 0.3 equivalents, and the component (c) is
0.005-0.3 equivalents are preferable, 0.01-0.2 equivalents are especially preferable, and (d) component is 0.2-
0.945 equivalent, particularly preferably 0.5 to 0.8
It is 9 equivalents. The components (e) are (a), (b) and (c).
And 0 to 1 equivalent of hydroxyl group in the reaction product of component (d)
It is preferable to react 1 equivalent.

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

During the reaction, a polymerization inhibitor may be used for the purpose of preventing polymerization. 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%. The reaction temperature is preferably 70 to 120 ° C., and the reaction time is preferably 5 to 40 hours.

The resin composition of the present invention may further contain a diluent (B). Specific examples of the diluent (B) include, for example, the above-mentioned solvents, butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol chorumonomethyl (or monoethyl).
Organic solvents (B-1) such as ethers, alcohols such as triethylene glycol monomethyl (or monoethyl) ether and tetraethylene glycol monomethyl (or monoethyl) ether, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate , Acryloylmorpholine, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate
Examples thereof include reactive diluents (B-2) such as acrylate, pentaerythritol tetra (meth) 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 (A) + (B) in total of 1 in the composition.
0 to 90% is preferable, 20 to 80% is particularly preferable,
Further, the use ratio of (A) and (B) is 10 to 90 for (A).
%, (B) is preferably 10 to 90%, and (B) / (A)
It is particularly preferable that the mass ratio of is about 5 to 15%.

The resin composition of the present invention may further contain a photopolymerization initiator (C). Examples of the photopolymerization initiator (C) 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-methyl-1-phenylpropane-1
-One, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
Acetophenones such as (methylthio) phenyl] -2-morpholino-propan-1-one; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2
Anthraquinones such as chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, Benzophenones such as 4,4-bismethylaminobenzophenone; 2,4,6-
Trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned. 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-.
It can also be used in combination with a promoter such as a benzoic acid derivative such as dimethylaminobenzoic acid ethyl ester and N, N-dimethylaminobenzoic acid isoamyl ester.

The content of the photopolymerization initiator (C) is 0.5 to 20 relative to 100 parts by mass of the total amount of the components (A) and (B).
Parts, preferably 2 to 15 parts, particularly preferably 2 to 5 parts.

In the present invention, it is preferable that a thermosetting component (D) is further contained as a curing component in each of the above-mentioned components, and by containing this, a printed wiring board excellent in solder heat resistance and electric characteristics is contained. It can be used as a material. The thermosetting component (D) used in the present invention is not particularly limited as long as it has a functional group capable of thermosetting with the oligomer (A) in the molecule, and examples thereof include epoxy resin, melamine compound and urea. Examples thereof include compounds, oxazoline compounds, and phenol compounds. 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 Buri 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. 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 and 2,4. -Diphenyloxazoline and the like. As the phenol compound, for example,
Examples thereof include phenol, cresol, chylenol, catechol, resorcin, hydroquinone, pyrogallol, and resole.

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. 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.

The preferred 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, it is 1.0 to 1.5 because it has excellent solder heat resistance and electrical characteristics when it is used as a printed wiring board.
The equivalent ratio is preferable.

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.

Further, 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, a fluorine-based leveling agent, an antifoaming agent, a polymerization inhibitor such as hydroquinone and hydroquinone monomethyl ether, and the like can be added for the purpose of improving various properties of the composition.

The above-mentioned component (D) may be mixed in the resin composition in advance, but it is preferable to use it by mixing it before coating it on the printed circuit board. In that case,
A main component solution mainly composed of the component (A), a part or all of the component (B) and an epoxy curing accelerator, and the main component (D), and a part of the component (B). Alternatively, it is preferable to mix and use two liquids of a curing agent solution in which all the components are mixed.

The resin composition of the present invention uses, for example, a polymer film (for example, a film made of polyethylene terephthalate, polypropylene, polyethylene, etc.) as a support, and the resin composition is laminated thereon to form a diluent (B).
A photosensitive film can also be obtained by evaporating the organic solvent (B-1) used as.

The resin composition (liquid or film form) 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 a sealant, a paint and a coating. It can also be used as an agent or an adhesive.

The cured product of the present invention is obtained by curing the above resin composition of the present invention by irradiation with energy rays such as ultraviolet rays. Curing by irradiation with energy rays such as ultraviolet rays can be carried out by a conventional method. For example, when irradiating with ultraviolet rays, an ultraviolet ray generator such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (excimer laser, etc.) may be used. The cured product of the resin composition of the present invention is 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 film thickness of this cured product layer is 0.5 to 160 μm.
m is preferable, and about 1 to 60 μm is particularly preferable.

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 in a state where the film is not in contact), 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, tetrahydrofuran and the like. 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 and the alkaline aqueous solution, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amids 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.

[0068]

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.

(Synthesis Example of Oligomer (A)) Synthesis Example 1 In the above general formula (1), X is —CH 2 —, M is a hydrogen atom, and average degree of polymerization m is bisphenol F of 6.2.
-Type epoxy resin (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 98.5% NaOH 60.9 g (1.5 mol) at 70 ° C. under stirring. Was added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the reaction was completed, 250 g of water was added and the mixture was washed with water. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered from the oil layer under reduced pressure, and then dimethyl sulfoxide was distilled off,
The reaction product containing by-product salt is treated with methyl isobutyl ketone 75
Dissolve it in 0 g, add 10 g of 30% NaOH, and add
The reaction was carried out at 0 ° C for 1 hour. After completion of the reaction, 2 with 200 g of water
After washing with water and separating oil and water, methyl isobutyl ketone is distilled and recovered from the oil layer to obtain an epoxy equivalent of 310 g / eq.
An epoxy resin (a-1) having a softening point of 69 ° C. 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) 310 g and dimethylolpropionic acid 20.1 g
And molecular weight 3500, bound acrylonitrile 27%, carboxyl group 1.91 / molecule HYCAR CTBN1
300 × 13 [B. F. Goodrich Chemi
52.5 g, acrylic acid 43.4 g, maleimidocaproic acid 44.2 g (the number of epoxy groups: the total number of carboxyl groups = 1: 0.98), 2.0 g of triphenylphosphine and 0.3 g of methylhydroquinone. And carbitol acetate 238.4g were charged, and at 35 ° C about 35
The reaction was carried out for a time to obtain an oligomer (A-1). The solid content of the product is 65%, and the weight average molecular weight of the solid is about 65.
00 (according to GPC method), solid content acid value is 1.5 mg KO
It was H / g.

Synthesis Example 2 681.1 g of the oligomer (A-1) obtained in Synthesis Example 1
And 53.2 g of tetrahydrophthalic anhydride and 35.0 g of succinic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1: 0.7
0) and 52.2 g of carbitol acetate are reacted at 90 ° C. for about 10 hours, and the solid content has an acid value of 72 mgKOH /
g, solid content weight average molecular weight of about 9000 (according to GPC method), solid content of 65% product (oligomer (A--
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, methyl hydroquinone 0.3 g and carbitol acetate 206.4 g were charged and reacted at 98 ° C. for 35 hours, then tetrahydrophthalic anhydride 43.1 g, succinic anhydride 28.4 g and carbitol acetate 38.
5 g was charged and reacted at 90 ° C. for about 10 hours to obtain a product having an acid value of solid content of 72 mgKOH / g, a weight average molecular weight of solid content of about 7,000 (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.
UV irradiation with an integrated exposure dose of / cm ² and development with γ-butyrolactone (Example 1), 1.0 wt% Na ₂ CO ₃ aqueous solution (Examples 2, 3 and Comparative Examples 1 to 3), and 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 substrate 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.

[0073]

[Table 1]

[0074]

[Table 2]

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-morpholinopropan-1-one. * 3: Kayakyu DETX-S: manufactured by Nippon Kayaku Co., Ltd.,
Photopolymerization initiator, 2,4-diethylthioxanthone. * 4: YX-4000: Bipheninol type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. * 5; DEN-438: Phenol novolac type 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) A 21-step step tablet (manufactured by Stoffer Co., Ltd.) is brought into close contact with the coating film after photosensitivity drying and irradiation with ultraviolet rays having an integrated light amount of 600 mJ / cm ² is performed. Next, γ-butyrolactone (Example 1) and a 1% aqueous sodium carbonate solution (Examples 2, 3 and Comparative Examples 1 to 3) remained for 60 seconds under a spray pressure of 2.0 kg / cm ² without being developed. Check the number of steps on the coating. The following criteria were used. ○ ・ ・ ・ ・ 6 or more steps. △ ... 4 to 5 steps. × ... 3 steps or less. (2) Developability The coating film was dried at 80 ° C. for 90 minutes and sprayed with 30 ° C. γ-butyrolactone (Example 1), 1% sodium carbonate aqueous solution (Examples 2, 3, Comparative Examples 1 to 3). The developability by development was evaluated. ○ ・ ・ ・ ・ No residue visually. △ ・ ・ ・ ・ Some residue was visually observed. × ・ ・ ・ ・ There are many residues visually. (3) Solder heat resistance test A rosin-based flux was applied to a 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) Judgment was made in a state where the flexible test substrate was bent 180 degrees. ○ ・ ・ ・ ・ No cracks. △ ・ ・ ・ ・ Slightly cracked. × ・ ・ ・ ・ The bent film was cracked and the cured film was peeled off. (5) Thermal deterioration resistance test After the 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 After the test substrate was plated with gold as described below, it was judged in the state when it was peeled off with a Sellotape (registered trademark) adhesive tape. ○ ・ ・ ・ ・ No abnormality. △ ・ ・ ・ ・ Somewhat peeled off. × ・ ・ ・ ・ No peeling.

Electroless Gold Plating Method The test substrate was immersed in an acidic degreasing solution (Metedex L-5B, 20 vol% aqueous solution of Methex L-5B, manufactured by Nippon MacDermid Co., Ltd.) at 30 ° C. for 3 minutes to be degreased, and then immersed in running water for 3 minutes. Washed with water. Next, the test substrate is immersed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes to perform soft etching,
Then, it was immersed 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 on which the catalyst was applied was heated to 85 ° C.
20 vol% aqueous nickel plating solution (PH4.
6) was immersed for 20 minutes for 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. Then, the test substrate was dipped in a gold plating solution at 95 ° C. (manufactured by Meltex Co., an aqueous solution of 15% by volume of Aulectroless UP and 3% by volume of potassium gold cyanide, PH6).
After immersion for 0 minutes to carry out electroless gold plating, it was immersed in running water for 3 minutes and washed with water, and immersed in warm water at 60 ° C. for 3 minutes and washed with hot water. After thoroughly washing with water, drain the water, dry,
A test substrate plated with electroless gold was obtained.

[0078]

[Table 3]

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 shows good developability. A cured film having excellent solder heat resistance, flexibility, heat deterioration resistance, and electroless gold plating is provided.

[0080]

According to the present invention, the amount of the photopolymerization initiator used is at least sufficient curability, the developability is excellent, and the flexibility, solder heat resistance, heat deterioration resistance and electroless gold plating resistance of the cured product are improved. 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.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J027 AE02 AE07 CB10 CC05 CD08                 4J036 AA01 AD01 AD08 CA20 CA22                       CD04 DA01 DB02 DB16 FB05                       HA02 JA01                 5E314 AA27 AA32 DD07 FF06 FF19                       GG10 GG14

Claims (18)

[Claims] 1. An oligomer (A) obtained by reacting the following components (a) to (d): (a) Epoxy resin having at least two epoxy groups in one molecule (b) Two in one molecule 1. A resin composition comprising the compound (c) having a hydroxyl group and one carboxyl group (c), a carboxyl group-containing rubber-like polymer (d), and an unsaturated group-containing monobasic acid. 2. An oligomer (A) obtained by reacting the following components (a) to (e): (a) Epoxy resin having at least two epoxy groups in one molecule (b) Two in one molecule A resin composition containing the compound (c) having a hydroxyl group and one carboxyl group, (c) a carboxyl group-containing rubbery polymer (d) an unsaturated group-containing monobasic acid (e) a polybasic acid anhydride . 3. The weight average molecular weight of the oligomer (A) is 10.
The resin composition according to claim 1 or 2, which is 00 to 100,000. 4. The acid value of the oligomer (A) is 1 to 300 mg.
The resin composition according to any one of claims 1 to 3, which is KOH / g. 5. An epoxy resin (a) having at least two epoxy groups in one molecule is represented by the formula (1): In 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. [Chemical 2] (However, when m is 1, M represents the formula (G), and when m is greater than 1, at least one M represents the formula (G),
The rest represent hydrogen atoms. The resin composition according to any one of claims 1 to 4, which is an epoxy resin represented by the formula (4). 6. The resin composition according to claim 5, wherein the ratio of M in the formula (1) to the formula (G) is 70 to 90 mol%. 7. The compound (b) having two hydroxyl groups and one carboxyl group in one molecule is a dimethylol compound of a carboxylic acid having 2 to 6 carbon atoms. The resin composition described. 8. The unsaturated group-containing monobasic acid (d) is selected from (meth) acrylic acid and maleimide group-containing monobasic acid.
The resin composition according to any one of claims 1 to 7, which is one kind or two or more kinds. 9. The resin composition according to claim 2, wherein the polybasic acid anhydride (e) is a phthalic anhydride derivative. 10. The method according to claim 1, further comprising a photopolymerization initiator (C).
The resin composition according to any one of items 1 to 9. 11. The resin composition according to claim 1, which contains a thermosetting component (D). 12. The resin composition according to claim 11, wherein the thermosetting component (D) is an epoxy resin. 13. 1,4 as a curing accelerator for epoxy resin
-The resin composition according to claim 12, which contains a dihydropyridine derivative. 14. The resin composition according to claim 1, which contains a diluent (B). 15. The resin composition according to claim 14,
A composition for a solder resist or an interlayer insulating layer of a printed wiring board. 16. A cured product of the composition according to any one of claims 1 to 15. 17. An article having a layer of the cured product according to claim 16. 18. The article according to claim 17, which is a printed wiring board.