JP3436788B2 - Resin composition, resist ink composition and cured product thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is particularly useful as a resist ink composition for printed wiring boards, and has heat resistance, moisture resistance, and
The present invention relates to a resin composition and a cured product thereof that give a cured product having excellent adhesion and electrical insulation.

[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 printed wiring board processing, various inks such as solder resist inks and marking inks have been shifting from conventional thermosetting compositions to ultraviolet curable compositions for the same reason. Among them, the solder resist ink quickly moved to an ultraviolet curable composition.

[0003]

However, the adhesion to the printed circuit board, the required heat resistance, the electrical characteristics,
In particular, the fact is that the electrical insulating property is inferior to that of the conventional hot air drying and curing type ink.

[0004]

Means for Solving the Problems As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a resist ink composition having excellent adhesion, solder heat resistance, moisture resistance and electric insulation of the cured film. It has succeeded in providing a resin composition which is particularly useful as a product.

That is, the present invention is a resin composition characterized by containing a reaction product (A) of an epoxy resin (a) represented by the formula (1) and a monocarboxylic acid compound useful with an unsaturated group (b). , A resist ink composition and a cured product thereof.

[0006]

[Chemical 4]

(However, in the formula, R is

[0008]

[Chemical 5]

Or

[0010]

[Chemical 7]

N is a number from 1 to 10. )

The reactant (A) used in the present invention can be obtained by reacting the epoxy resin (a) represented by the formula (1) with the unsaturated group-containing monocarboxylic acid (b). Epoxy resin (a) represented by the formula (1)
As a specific example, for example, Mitsubishi Gas Chemical Co., Ltd. having a meta-xylene skeleton, product name, TETRAD-G (epoxy equivalent 270, softening point 80 ° C., molecular weight about 1000),
Product name, TETRAD-H (epoxy equivalent 265, softening point 86 ° C., molecular weight about 1000) and the like can be mentioned.

Next, specific examples of the unsaturated group-containing monocarboxylic acid compound (b) include, for example, acrylic acid, a dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacryl. Acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, saturated or unsaturated dibasic acid anhydrides, and half-esters which are reaction products of (meth) acrylates having one hydroxyl group in one molecule (specifically, Specifically, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride Saturated and unsaturated dibasic acid anhydrides such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate Over DOO, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate,
1) such as pentaerythritol tri (meth) acrylate and phenylglycidyl ether (meth) acrylate
Half-esters obtained by reacting equimolar amounts of (meth) acrylates having one hydroxyl group in the molecule. ) And a half-ester which is a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound, (specifically, succinic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid) Or unsaturated dibasic acids such as itaconic acid, fumaric acid and glycidyl (meth) acrylate

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10]

[0017]

[Chemical 11]

Half ester etc. obtained by reacting an unsaturated group-containing monoglycidyl compound such as the above at an equimolar ratio can be used alone or in combination. Particularly preferred is acrylic acid.

In the reaction of the epoxy resin (a) represented by the formula (1) with the unsaturated group-containing monocarboxylic acid compound (b), the unsaturated group-containing monocarboxylic acid compound is contained with respect to 1 equivalent of the epoxy group of the epoxy resin. The monocarboxylic acid compound is reacted preferably in a ratio of about 0.3 to 1.5 equivalents.

During the reaction, solvents such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether and solvent naphtha are used as diluents.
Alternatively, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl).
It is preferable to use reactive monomers such as isocyanurate tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Further, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.) in order to accelerate the reaction, and the amount of the catalyst used is based on the reaction raw material mixture. And preferably 0.1 to 10
%, 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, methoquinone, hydroquinone, phenothiazine, etc.), and the amount thereof is preferably 0.01 to the reaction raw material mixture. It is 1% by weight, particularly preferably 0.05 to 0.5% by weight. The reaction temperature is preferably 60 to 150 ° C., particularly preferably 80 to 12
It is 0 ° C. The reaction time is preferably 5 to 60 hours,
Particularly preferably, it is 10 to 50 hours.

The amount of the reaction product (A) contained in the composition of the present invention is preferably 5 to 90% by weight, and particularly preferably 10 to 10% by weight.
80% by weight is preferred.

The composition of the present invention further comprises epoxy compounds such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, tris (2,3-epoxypropyl) isocyanurate, and these epoxy compounds. It is possible to include a reaction product of the (meth) acrylic acid with the compound and / or the above-mentioned diluent. The amount of these used is the reaction product (A) 10
0 to 500 parts by weight is preferable with respect to 0 parts by weight.

When the above epoxy compound is used,
Epoxy resin curing agents (for example, dicyandiamide and its derivatives, imidazole compounds, triazine compounds, urea compounds, aromatic amines, polyphenol compounds and cationic photopolymerization catalysts) can be used alone or in combination of two or more. When using an epoxy resin curing agent,
The amount used was 0.1% by weight per 100 parts by weight of the epoxy compound.
5 to 50 parts by weight is preferable.

As a method for curing the composition of the present invention to obtain a cured product, there are curing methods by electron beam, ultraviolet ray and heat, but it is preferable to cure by ultraviolet ray and, if necessary, heat. A photopolymerization initiator is used in the case of curing with ultraviolet rays. As the photopolymerization initiator, any known photopolymerization initiator can be used, but one having good storage stability after blending is desirable.

Examples of such a photopolymerization initiator include, for example,
Benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, N, N
-Dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4
-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone,
4,4'-bisdiethylaminobenzophenone, Michler's ketone and the like can be mentioned. These may be used alone or in combination of two or more.

Further, together with a photopolymerization initiator, known conventional photosensitizers such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine are used alone. Alternatively, it can be used in combination with two or more kinds. A preferable combination is 2,4-diethylthioxanthone or 2-isopropylthioxanthone and N, N-dimethylamine benzoic acid ethyl ester, 2-methyl-2-.
[4- (Methylthio) phenyl] -2-morpholinopropan-1-one (Ciba-Gaikygie Co., Irgacure 907) and 2,4-diethylthioxanthone or 2
-Isopropylthioxanthone combination and the like.

The proportion of the photopolymerization initiator used is preferably 0 to 50 parts by weight, particularly preferably 4 to 35 parts by weight, per 100 parts by weight of the reaction product (A).

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 can be added to the composition of the present invention. Further, if necessary, hexamethoxymelamine, melamine resin such as hexabutoxymelamine, thixotropic agent such as Aerosil, silicone, fluorine-based polymer, leveling agent such as acrylic copolymer, defoaming agent, ultraviolet absorber, Antioxidants, polymerization inhibitors and the like can be added.

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 according to a conventional method as follows. That is, it can be cured with ultraviolet rays and, if necessary, with heat to obtain a cured product. When cured with heat,
The heating temperature is preferably 120 to 170 ° C., and the heating time is 3
0 minutes to 2 hours is preferable.

The resin composition of the present invention is particularly useful as a solder resist resin composition, but is also useful as a printing ink, an overprint varnish for paper, a paint, an adhesive, and the like.

When the composition of the present invention is used as a solder resist resin composition, for example, it is cured as follows,
Obtain a cured product. That is, the resin composition of the present invention is applied to a printed wiring board with a film thickness of 10 to 100 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method and a curtain flow coating method (if necessary). After drying the coating film at 60 to 80 ° C., the negative film is brought into direct contact with the coating film. Then, the film is irradiated with ultraviolet rays (if necessary, the unexposed portion of the coating film is dissolved and removed with an organic solvent). After that, it is heated and cured at 120 to 170 ° C. for 30 minutes to 1 hour.) A cured film is obtained. The resin composition containing the reaction product (A) of the present invention is excellent in hardness, solder heat resistance, moisture resistance, electrical insulation and adhesion of the cured product.

[0034]

EXAMPLES The present invention will be described in more detail below with reference to examples. The parts in the synthesis examples are parts by weight. Synthesis Example of Reactant (A) Synthesis Example 1 Solid epoxy resin having a metaxylene skeleton (TETRAD-G, manufactured by Mitsubishi Gas Chemical Co., Inc., epoxy equivalent 2)
70, softening point 80 ° C., average molecular weight 1000) 270 parts,
Acrylic acid 68.5 parts, methoquinone 0.5 part, triphenylphosphine 2.3 parts and hydroxypivalic acid neopentyl glycol diacrylate 338.5 parts were charged, the temperature was raised to 95 ° C, and the reaction was carried out at 95 ° C. When the acid value (mgKOH / g) of the reaction solution became 1.0 or less (about 35 hours), the reaction was terminated to obtain a reaction product (A-1). Reaction product (A-
The viscosity of 1) (25 ° C.) was 530 poise.

Synthesis Example 2 Solid epoxy resin having a metaxylene skeleton (TETRAD-H, manufactured by Mitsubishi Gas Chemical Co., Inc., epoxy equivalent 2)
65, softening point 86 ° C., average molecular weight 1000) 265 parts,
Charge 68.5 parts of acrylic acid, 0.8 parts of methquinone, 3.6 parts of triphenylphosphine, 102.5 parts of trimethylolpropane triacrylate and 265 parts of phenoxyethyl acrylate, raise the temperature to 95 ° C., and heat at 95 ° C. The reaction was performed, and when the acid value of the reaction solution became 1.0 or less (about 35 hours), the reaction was terminated to obtain a reaction product (A-2). The viscosity (25 ° C.) of the reaction product (A-2) was 410 poise.

Synthesis Example 3 Solid epoxy resin having a meta-xylene skeleton (manufactured by Mitsubishi Gas Chemical Co., Inc., TETRAD-G, epoxy equivalent 2
70, softening point 80 ° C., average molecular weight 1000) 270 parts,
81.8 parts of methacrylic acid, 0.9 part of methoquinone, 4.0 parts of triphenylphosphine and 352 parts of carbitol acrylate were charged, the temperature was raised to 95 ° C, the reaction was carried out at 95 ° C, and the acid value of the reaction solution was 1 When it was below 0.0 (about 35 hours), the reaction was terminated to obtain a reaction product (A-3). The viscosity (25 ° C.) of the reaction product (A-3) was 395 poise.

Examples 1 to 4 and Comparative Examples 1 and 2 The solder resist resin composition (ink) was blended according to the blending composition (numerical values are parts by weight) shown in Table 1 and kneaded with a three-roll mill. The film thickness is 1 by the screen printing method.
It was applied to a copper through-hole printed wiring board so as to have a thickness of 5 to 25 μm, and ultraviolet rays were irradiated using a high pressure mercury lamp (2 KW, 80 W / cm) to cure the coating film to obtain a test piece. Using this test piece, the cured film hardness, acid resistance, alkali resistance, solder heat resistance, and insulation resistance were tested as described below. The results are shown in Table 2.

The test method and evaluation method are as follows. (Hardness of cured film) The hardness of the cured film was measured according to JIS K5400. (Solder heat resistance) 2 according to JIS6481 test method
Dip the test piece in a solder bath at 60 ° C for 10 seconds 10 times or 4
The test was repeated and the change in appearance was evaluated. (Post-flux resistance) Immersion was performed 10 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 dip in the cured film Note) Post-flux used: JS-64P (San-ei) (Chemical Co., Ltd.)

(Flux resistance for levelers) Immersion was performed 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 dip in the cured film Note) Flux for leveler used: SSF-832
(Manufactured by Sanei Chemical Co., Ltd.)

(Acid resistance) The test piece was immersed in a 10 vol% sulfuric acid aqueous solution at 25 ° C. for 15 minutes, and the appearance of the cured film was visually observed. For the adhesiveness, a peeling test using a cellophane tape was performed on the solder pattern portion to determine the peeled state of the resist. ○ ──── No change in appearance, no peeling of cured film △ ──── No change in appearance, slight peeling of cured film × ──── Peeling test causes large peeling

(Alkali resistance) The test piece was immersed in a 10 wt% sodium hydroxide aqueous solution at 25 ° C for 15 minutes, and the same test as the acid resistance test was carried out for evaluation.

(Insulation Resistance) The initial insulation resistance was measured using a test piece, and the insulation resistance after the test was measured according to the test method of IPC-SM-840B.

[0043]

Table 1 Table 1 Example Comparative Example 1 2 3 4 12 Reaction product (A-1) 40 25 Reaction product (A-2) 40 30 25 Reaction product (A-3) 20 KAYARAD R-011 * 1 40 KAYARAD R-190 * 2 50 2-hydroxyethyl methacrylate 10 10 10 10 KAYARAD R-604 * 3 10 30 30 trimethylolpropane triacrylate 30 40 20 30 carbitol acrylate 20 10 20 10 20 10 2-ethylanthraquinone (light Polymerization initiator) 3.5 3.5 3.5 3.5 3.5 3.5 Phthalocyanine green (pigment) 1.5 1.5 1.5 1.5 1.5 1.5 Talc 50 50 50 50 50 50 Modaflow * 4 1.5 1.5 1.5 1.5 1.5 1.5 Hardened film hardness 5H 6H 6H 5H 5H 4H Solder heat resistance Post Flux resistance ○ ○ ○ ○ ○ △ Flux resistance for levelers ○ ○ ○ ○ △ × Acid resistance ○ ○ ○ ○ × × Alkali resistance ○ ○ ○ ○ △ ○ Insulation resistance (Ω) Initial value (× 10 ¹³ ) 5.5 5.4 5.7 5.5 2.5 1.1 After test (× 10 ¹² ) 3.4 3.6 3.8 3.5 0.3 0.5

Note) * 1 KAYARAD R-01
1: A product obtained by reacting acrylic acid with a phenol novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd. It contains trimethylolpropane acrylate as a diluent. * 2 KAYARAD R-190: Nippon Kayaku Co., Ltd.
Made by reacting acrylic acid with bisphenol A type epoxy resin. It contains diethylene glycol dimethacrylate as a diluent. * 3 KAYARAD R-604: Nippon Kayaku Co., Ltd.
Made by bifunctional acrylate monomer. * 4 Modaflow: Leveling agent manufactured by Monsanto

From Table 1, it is clear that the cured product of the resin composition of the present invention is excellent in hardness, solder heat resistance, acid resistance, alkali resistance and electric insulation.

[0046]

EFFECTS OF THE INVENTION The resin composition of the present invention is excellent in hardness, solder heat resistance, chemical resistance and electric insulation, and is particularly suitable for a solder resist resin composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-7-224143 (JP, A) JP-A-6-1907 (JP, A) JP-A-1-142547 (JP, A) JP-A-61- 59447 (JP, A) JP 4-355450 (JP, A) JP 7-238142 (JP, A) JP 5-117350 (JP, A) JP 5-214048 (JP, A) Japanese Patent Publication No. 35-13847 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/16-59/17 C08F 299/02 G03F 7/027 515

Claims (3)

(57) [Claims] 1. An epoxy resin (a) represented by the formula (1): (However, in the formula, R is Or [Chemical 3] And n is a number from 1 to 10. And an unsaturated group-containing monocarboxylic acid compound (b) as a reaction product (A). 2. A resist ink composition comprising the reaction product (A) according to claim 1. 3. A cured product of the composition according to claim 1.