JPH09241328A - Resin composition, resist ink resin composition and their cured products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which is developable with water, can give cured coating films excellent in adhesion, soldering-heat resistance, chemical resistance, gold plating resistance, etc., and is useful as a solder resist resin composition by mixing a specified copolymer with a diluent, a photopolymerization initiator and a curing component. SOLUTION: This composition comprises a (meth)acrylate resin [A] being a copolymer of 10-50 pts.wt. compound (e.g. glycidyl (meth)acrylate) having one epoxy group and one ethylenic unsaturation in the molecule with 50-90 pts.wt. acryloylmorpholine and/or a reaction product of this copolymer with (meth)acrylic acid, a diluent [B], a photopolymerization initiator [C] and a curing component [D] (e.g. epoxy resin). The mixing ratio among the respective components is desirably such that the composition comprises 10-90wt.% component A, 10-70wt.% component B, 0.5-20wt.% component C and 0.5-50wt.% component D.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent developability suitable for a solder resist resin composition for printed wiring boards, and its cured film has excellent adhesion, solder heat resistance, chemical resistance, gold plating resistance and the like. The present invention relates to a resin composition and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, ultraviolet ray curable compositions have been widely used in various fields for reasons such as resource saving, energy saving, workability improvement and productivity improvement. In the field of processing printed wiring boards, various inks such as solder resist inks and marking inks have been transferred from conventional thermosetting compositions to ultraviolet curable compositions for the same reason. Among them, the solder resist ink was quickly shifted to an ultraviolet curable composition.

[0003]

Although a screen printing method has been widely used as a method for forming a resist pattern on a printed wiring board, when such a screen printing method is used, in many cases, bleeding, bleeding, or bleeding during printing, or
Development such as sagging occurs, which makes it impossible to cope with the recent increase in density of printed wiring boards.

In order to solve these problems, a tri-film type photoresist and a liquid developable resist ink have been proposed and used, but in the case of a dry film type photoresist, air bubbles are generated during thermocompression bonding. Is likely to occur, there is a concern about heat resistance and adhesion, and there is a problem that it is expensive. On the other hand, liquid resists that are currently commercially available include those using an organic solvent as a developing solution and those developing with a dilute aqueous alkali solution, but those using an organic solvent have the problem of air pollution. In addition, the solvent is expensive, and the cured product has problems in solvent resistance and acid resistance.

Further, those which can be developed with a dilute alkaline aqueous solution have problems such as insufficient gold plating resistance.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors of the present invention have shown that the film can be developed with water, and the cured film has adhesion, solder heat resistance, chemical resistance,
We have succeeded in providing a resin composition useful as a solder resist resin composition excellent in gold plating resistance and the like and a cured product thereof.

That is, the present invention provides a compound (a) 1 having one epoxy group and one ethylenically unsaturated group in the molecule.
0 to 50 parts by weight and acryloylmorpholine (b) 50 to
(Meth) acrylate resin (A), diluent (B), photopolymerization initiator (C) and curing which are copolymers with 90 parts by weight and / or reaction products of the copolymers and (meth) acrylic acid The present invention relates to a resin composition containing the component (D), a resist ink resin composition, and a cured product thereof.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, 10 to 50 parts by weight of a compound (a) having one epoxy group and one ethylenically unsaturated group in the molecule and 50 to 90 parts by weight of acryloylmorpholine (b). A copolymer with and / or the above,
A (meth) acrylate resin (A) which is a reaction product of a copolymer and (meth) acrylic acid is used. Compound (a) having one epoxy group and one ethylenically unsaturated group in the molecule (for example, glycidyl (meth) acrylate,

[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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And the like. ) And acryloylmorpholine (b) are polymerized to obtain a copolymer. The polymerization reaction is preferably carried out in an organic solvent or water. Examples of the organic solvent include methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, solvent naphtha, propylene glycol monomethyl ether acetate and the like. Examples of the radical polymerization initiator used for producing the copolymer of the present invention include m-diisopropylbenzene monohydroperoxide, t-butyl hydroperoxide, diisopropylcyclohexyl hydroperoxide, trimethylcyclohexyl hydroperoxide and cumene. Hydroperoxide, dicumyl peroxide, t-hexyl-α-
Cumyl peroxide, n-butyl-2-ethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, succinic acid peroxide, t-butylperoxypivalate, dit-butylperoxyazelate, mono-t- Butyl peroxysuccinic acid, t-hexyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyisoamyl carbonate, 1,1-bis (t-
Hexylperoxy) cyclohexane, organic peroxides such as methyl ethyl ketone peroxide, or 2,2'-
Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2 ' -Azobis (2-methylpropionitrile), 1,1'-azobis (cyclohexane-1-
Carbonitrile), 2-phenylazo-4-methoxy-
2,4-Dimethylvaleronitrile, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dibasic acid, 2,2'-azobis [2- (2-imidazoline-
2-yl) propane] dibasic acid, 2,2'-azobis [trimethylpentane], 4,4'-azobis (4-cyanovaleric acid and other azo initiators, potassium persulfate, ammonium persulfate and the like are preferred. The polymerization temperature is preferably 0 to 160 ° C., particularly 20 to 140 ° C.
Is preferred. The reaction time is preferably 1 to 20 hours, particularly preferably 3 to 10 hours. The proportions of the component (a) and the component (b) used are 10 to 50 parts by weight of the component (a) and the component 5 of the component (b).
0 to 90 parts by weight. When the amount of the component (a) is 50 parts by weight or more, the solubility of the copolymer in water becomes insufficient,
When the amount of the component (a) is 10 parts by weight or less, the curability by ultraviolet rays becomes insufficient.

A (meth) acrylate resin can be obtained by reacting the copolymer thus obtained with (meth) acrylic acid. (Meth) acrylic acid 0.8 to 1.3 per 1 equivalent of epoxy group in the copolymer
It is preferable to react in an equivalent amount, and particularly preferably 0.9 to 1.1 equivalent amount. Further, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) in order to accelerate the reaction, and the amount of the catalyst used depends on the reaction raw material mixture. On the other hand, preferably 0.1 to 10% by weight, particularly preferably,
0.3 to 5% by weight.

In order to prevent the polymerization during the reaction, it is preferable to use a polymerization inhibitor (eg, methquinone, hydroquinone, phenothiazine, etc.), and the amount thereof is preferably 0.01 to the reaction raw material mixture. ~ 1% by weight,
It is particularly preferably 0.05 to 0.5% by weight. The reaction temperature is preferably 60 to 150 ° C., particularly preferably 80.
~ 120 ° C. The reaction time is preferably 5 to 60 hours, particularly preferably 10 to 50 hours.

The average molecular weight of the copolymer and / or (meth) acrylate resin (A) thus obtained is 1
000 to 300000 is preferable, and 5000 to 10 is particularly preferable.
0000 is preferred. (A) included in the composition of the present invention
The amount of the component is preferably 10 to 90% by weight, and particularly preferably 20 to 90% by weight in the composition.

In the present invention, the diluent (B) is used. Specific examples of the diluent (B) include, for example, methyl ethyl ketone, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, carbitol acetate, diethylene glycol, diethylene glycol dimethyl ether, Solvents such as propylene glycol monomethyl ether acetate, solvent naphtha, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra ( Mention may be made of reactive monomers such as (meth) acrylate, dipentaerythritol penta and hexa (meth) acrylate. The amount of the component (B) contained in the composition of the present invention is preferably 10 to 70% by weight, more preferably 20 to 50% by weight in the composition. Specific examples of the photopolymerization initiator (C) include, for example, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholino-propan-1-one, 2,4
-Diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 4- (p-methylphenylthio) benzophenone, 2-ethyneanthraquinone, benzophenone, 4,4'-bisdiethylaminobenzophenone and the like can be mentioned. These can be used alone or in combination of two or more.

Further, such a photopolymerization initiator is a known radical photopolymerization accelerator such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine. They can be used alone or in combination with two or more kinds. A preferred combination is 2,4-diethylthioxanthone or 2-isopropylthioxanthone and N, N-.
Combination with dimethylaminobenzoic acid ethyl ester, 2
-Methyl-2- [4- (methylthio) phenyl] -2-
A combination of morpholino-propan-1-one (Irgacure 907, manufactured by Ciba Geigy) and 2,4-diethylthioxanthone or 2-isopropylthioxanthone is used. Further, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, 4,4'-bis [bisphenylsulfonio] phenyl sulfide bishexafluoroantimonate, 4,4 Examples thereof include photocationic polymerization initiators such as ′ -bis [bisphenylsulfonio] phenylsulfide bishexafluorophosphate and Optomer SP-170 (photocationic polymerization initiator manufactured by Asahi Denka Co., Ltd.).

The proportion of the photopolymerization initiator used is preferably 0.5 to 20 parts by weight in the composition of the present invention.

Examples of the curing component (D) include bisphenol A type epoxy resin, biphenyl diglycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin, tris (2,3-epoxypropyl) isocyanurate, and other epoxy resins. Resins, and alkoxylated melamines such as hexamethoxymelamine and hexabutoxymelamine can be used. When using an epoxy resin, an epoxy resin curing agent (for example,
Cydiandiamide and its derivatives, imidazole compounds, triazine compounds, melamine, urea compounds, benzoguanamide, aromatic amines, polyphenol compounds,
Acid anhydrides and the like) can be used alone or in combination of two or more. When an epoxy resin curing agent is used, the amount used is 0.5 to 5 per 100 parts by weight of the epoxy resin.
0 parts by weight is preferred.

The proportion of the curing component (D) used in the composition of the present invention is preferably 0.5 to 50% by weight, particularly 5 to 20%.
% By weight is preferred.

The composition of the present invention may further contain inorganic fillers such as talc, silica, alumina, barium sulfate, magnesium oxide and the like, and cyanine green, cyanine blue and the like as color pigments. Further, if necessary, a thixotropic agent such as Aerosil, a leveling agent such as silicone, a fluoropolymer, an acrylic copolymer, a defoaming agent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, etc. may be added. it can.

The composition of the present invention can be obtained by blending the blending components preferably in the above proportions and uniformly mixing them with a roll mill or the like. The cured product of the composition of the present invention can be obtained by curing the composition in the following manner. That is, it can be cured with ultraviolet rays and, if necessary, with heat to obtain a cured product. When curing with heat, the heating temperature is preferably 120 to 170 ° C., and the heating time is preferably 30 minutes to 2 hours.

When the composition of the present invention is used as a resist ink composition, it is cured as follows to obtain a cured product. That is, the screen printing method on the printed wiring board,
The resin composition of the present invention is applied in a film thickness of, for example, 10 to 100 μm by a method such as a spray method, a roll coating method, an electrostatic coating method, or a curtain flow coating method, and a coating film having a thickness of 60 to 80 is applied.
After drying at 0 ° C, the negative film is brought into direct contact with the coating film and then irradiated with ultraviolet rays, and further water, 0.5-2% sodium carbonate aqueous solution, 0.5-1% caustic soda aqueous solution, caustic potash aqueous solution, etc. After the unirradiated portion of the coating film is dissolved and removed with an alkaline aqueous solution, a cured film is obtained by heat curing at 120 to 170 ° C. for 30 minutes to 1 hour.

Although the composition of the present invention is useful as a liquid resist ink resin composition, it is also suitable as an insulating paint, a protective film for a color filter, a printing ink, a lens, an adhesive or a coating agent. is there. The resin composition of the present invention is excellent in developability and hardness of a cured product, solder heat resistance, acid resistance, alkali resistance, gold plating resistance and the like.

[0027]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Parts in Synthesis Examples and Examples are parts by weight. (Synthesis example of copolymer (A))

Synthesis Example 1 50 parts of glycidyl methacrylate, 50 parts of acryloylmorpholine, 66.7 parts of propylene glycol monomethyl ether acetate, and 0.19 parts of perbutyl ND (organic peroxide manufactured by NOF CORPORATION) were charged to 55 ° C. After heating, the temperature was maintained for 6 hours to carry out a polymerization reaction. The average molecular weight of the obtained copolymer (A-1) was about 15,000, and the epoxy equivalent of the solid content was 285.

Synthetic Example 2 30 parts of glycidyl methacrylate, 70 parts of acryloylmorpholine, 66.7 parts of propylene glyceryl monomethyl acetate and perbutyl PV (manufactured by NOF Corporation)
0.19 parts of organic peroxide) was charged and heated to 65 ° C.,
The temperature was maintained for 6 hours to carry out the polymerization reaction. The average molecular weight of the obtained copolymer (A-2) was about 30,000, and the epoxy equivalent of the solid content was 474. (Synthesis Example of (Meth) Acrylate Resin (A)) Synthesis Example 3 790 parts of the photopolymer (A-2) obtained in Synthesis Example 2, 72 parts of acrylic acid, 0.5 part of metoquinone, 48 parts of propylene glycol monomethyl acetate. And 2.7 parts of triphenylphosphine were charged, heated to 95 ° C. and reacted for 32 hours. The acid value (mgKOH / g) of the reaction solution became 1.0 or less, so the reaction was terminated and the (meth) acrylate resin (A-3) was obtained. The average molecular weight of the (meth) acrylate resin (A-3) was 22,000.

Examples 1 to 3 and Comparative Examples 1 and 2 The compositions were blended according to the blending composition (numerical values are parts by weight) shown in Table 1 and kneaded with a three-roll mill to prepare. A copper-clad polyimide film substrate (copper thickness / 12 μm / polyimide film thickness / 25 μm) which is patterned by screen printing to have a thickness of 20 to 30 μm using a 100-mesh polyester screen
m), and the coated film is dried with a hot air drier at 80 ° C. for 30 minutes. Then, a negative film having a resist pattern was brought into close contact with the coating film, and ultraviolet rays were irradiated (exposure amount 500 mJ / cm ² ) using an ultraviolet ray exposure device (Oak Seisakusho, model HMW-680GW). 6 with water (temperature 30 ° C)
Development was carried out for 0 seconds with a spray pressure of 2.0 kg / cm ² , and the unexposed portion was dissolved and removed. The developability of the obtained product was evaluated as described below. Then, heat curing was performed for 40 minutes in a hot air dryer at 150 ° C., and the test piece having the cured film obtained was tested for developability, adhesion, pencil hardness, whitening agent, heat resistance, and gold plating resistance as described below. The test was conducted. Table 1 shows the results. The test method and evaluation method are as follows. (Developability) The following evaluation criteria were used.

◯ ··· During development, ink was completely removed and development was possible. Δ: There is a slight residue during development. X ...- Some areas are not developed during development.

(Adhesiveness) According to JIS K5400,
100 pieces of 1 mm squares were made on the test piece, and a peeling test was performed using cellophane tape. The peeling state of the first eye was observed and evaluated according to the following criteria.・ ・ ・: 100/100 with no peeling. Δ: 50/100 to 90/100. ×: 0/100 to 50/100.

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

(Heat Resistance) According to the test method of JIS K6481, dipping the test piece in a solder bath at 260 ° C. for 10 seconds is 1
The change in appearance was evaluated by repeating 0 or 4 times. (Post-flux resistance) The immersion for 10 seconds was performed 10 times, and the change in appearance was evaluated. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling, and solder dip in the cured film Note) Post-flux used: JS-64P (Yamaei) Made by Kagaku Co., Ltd.

(Flux resistance for levelers) Immersion was carried out 4 times for 10 seconds to evaluate the change in appearance. ○ ・ ・ ・ No change in appearance △ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling and solder dipping of the cured film Note) Leveler flux used: SSF-832
(Manufactured by Sanei Chemical Co.,

(Whitening resistance) Flux (Ronco CF-
430, YOSHIKAWA CHEMICAL Co., Ltd.
Was applied to a cured film, immersed in a solder bath at 260 ° C. for 5 seconds, and then immersed in hot water at 100 ° C. for 30 minutes to evaluate the change in appearance. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ Slight whitening observed × ・ ・ ・ ・ Whitening observed over the entire surface

(Gold resistance) Gold was plated for 30 minutes at a current density of 1 A / dm ² using Autoronex CI (plating solution) manufactured by Celllex Co., Ltd., and then a peeling test of the coating film was carried out with cellophane tape. It was The criteria are as follows. ○ ・ ・ ・ ・ It does not come off at all. △ ・ ・ ・ ・ Slightly peeled off × ・ ・ ・ ・ ・ ・ Peeled over the entire surface

[0038]

[Table 1] Table 1 Examples Comparative Examples 1 2 3 * 8 12 Product (A-1) 116.7 16.7 Product (A-2) 16.7 Product (A-3) 116.7 116.7 116.7 116.7 KAYARAD DPHA * 15 5 5 5 Propylene glycol monomethyl acetate 10 10 15 10 10 EPPN-201 * 2 15 30 TEPIC-S * 3 5 Irgacure 907 * 4 7 7 7 7 KAYACURE DETX-S * 5 3 3 3 3 3 Optomer SP-170 * 7 7 Melamine 3 3 3 3 3 3 Dicyandiamide 1 1 1 1 1 Flotacyanin green (pigment) 2 2 2 2 2 KS-603 (antifoaming agent) * 6 2 2 2 2 2 Barium sulfate 30 30 30 30 30 Silica dioxide 20 20 20 20 20 20 Developability ○ ○ ○ ○ ○ Adhesion ○ ○ ○ ○ ○ Pencil hardness 7H 6H 8H 4H 4H Heat resistance (post blacks resistance) ○ ○ ○ × × Error flux resistance) ○ ○ ○ × × whitening resistance ○ △ ○ × × gold-plating properties ○ ○ ○ × ×

Note * 1 KAYARAD DPHA: Nippon Kayaku Co., Ltd.
Manufactured by dipentaerythritol penta and hexaacrylate. * 2 EPPN-201: Nippon Kayaku Co., Ltd., phenol novolac type epoxy resin, softening point 65 ° C * 3 TEPIC-S: Nissan Chemical Co., Ltd., tris (2,3-epoxypropyl) isocyanurate, melting point 95-125 ° C * 4 Irgacure 907: manufactured by Ciba Geigy,
Photopolymerization initiator * 5 KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator * 6 KS-603: manufactured by Shin-Etsu Chemical Co., Ltd., defoamer * 7 Optomer SP-170: Asahi Denka Kogyo (stock)
Production, photo-cationic polymerization initiator * 8 In Example 3, after irradiation with ultraviolet rays (500 mJ / cm ² ), 10
After heating at 0 ° C. for 5 minutes, development was performed with water, and thereafter, the same procedure was performed.

From the evaluation results in Table 1, the composition of the present invention is
It is apparent that it can be developed with water and is excellent in hardness, heat resistance, adhesion, whitening resistance, and gold plating resistance.

[0041]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is exposed to ultraviolet rays selectively through a film having a pattern formed thereon, and develops the unexposed portion to form a solder resist pattern. The obtained cured product has adhesion, solder heat resistance, chemical resistance,
It has excellent resistance to gold plating and is suitable for solder resist ink compositions.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C09D 4/06 PDS C09D 4/06 PDS 11/00 PTE 11/00 PTE 133/14 PPHY 133/14 PFY G03F 7/027 515 G03F 7/027 515 7/038 503 7/038 503 H05K 3/28 H05K 3/28 D // C08G 59/17 NHG C08G 59/17 NHG

Claims (3)

[Claims] 1. A copolymer of 10 to 50 parts by weight of a compound (a) having one epoxy group and one ethylenically unsaturated group in the molecule and 50 to 90 parts by weight of an acryloylmorpholine (b). And / or containing a (meth) acrylate resin (A) which is a reaction product of the copolymer and (meth) acrylic acid, a diluent (B), a photopolymerization initiator (C) and a curing component (D). A characteristic resin composition. 2. A copolymer of 10 to 50 parts by weight of a compound (a) having one epoxy group and one ethylenically unsaturated group in the molecule and 50 to 90 parts by weight of an acryloylmorpholine (b), and And / or containing a (meth) acrylate resin (A) which is a reaction product of the copolymer and (meth) acrylic acid, a diluent (B), a photopolymerization initiator (C) and a curing component (D). A characteristic resist ink resin composition. 3. A cured product of the resin composition according to claim 1.