JPH11231522A - Solder photoresist ink composition and printed circuit board using that composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solder photoresist ink compsn. which can be developed with a diluted alkaline aq. soln. and the hardened coating film of which has excellent durability against a pressure cooker, and to provide a printed circuit board which uses this compsn. SOLUTION: This compsn. contains a UV-curing resin. a modified silicone having functional groups, a diluent, a photopolymn. initiator and a thermosetting resin. The modified silicone has <=4000 double bond equlv. having acryloyl groups or methacryloyl groups, or <=5000 epoxy equiv. having glycidyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solder photoresist ink composition and a printed wiring board. More specifically, the present invention relates to a solder photoresist ink composition which can be developed with a dilute alkaline aqueous solution and has a cured coating film having excellent resistance to pressure and cooker, and a printed wiring board using the composition.

[0002]

2. Description of the Related Art In recent years, in the field of processing printed wiring boards, photocurable compositions have been widely used as solder resist inks, and liquid solder photoresist ink compositions have been used as a type thereof. Is coming. For example, Japanese Unexamined Patent Publication (Kokai) No. 61-243869 discloses a reaction liquid of a novolak-type epoxy compound and an unsaturated monocarboxylic acid with a polybasic acid anhydride as an alkali developing liquid solder photoresist ink composition. A liquid solder photoresist ink composition comprising an active energy ray-curable resin obtained by the above method, a photopolymerization initiator and a diluent has been proposed. Printed wiring boards manufactured using such a liquid solder photoresist ink composition have excellent heat resistance, but are resistant to prolonged exposure to high temperature and high humidity conditions, so-called pressure cooker. There is a problem that resistance is poor. For this reason, it can be developed with a dilute alkaline aqueous solution,
In addition, there is a need for a solder photoresist ink composition that provides a cured coating film having excellent resistance to pressure and cooker, and a printed wiring board having excellent pressure and cooker resistance that can be easily manufactured.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a solder photoresist ink composition which can be developed with a dilute aqueous alkaline solution and has a cured coating film having excellent resistance to pressure and cooker, and a printed wiring using the composition. The purpose is to provide a substrate.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a conventional resin containing an ultraviolet curable resin, a diluent, a photopolymerization initiator and a thermosetting resin has been obtained. It was found that by adding a modified silicone having a functional group to the solder photoresist ink composition of (1), the pressure cooker resistance can be significantly improved without impairing the solder heat resistance and adhesion of the cured coating film. The present invention has been completed based on this finding. That is, the present invention provides (1) a solder photoresist ink composition comprising: an ultraviolet curable resin, a modified silicone having a functional group, a diluent, a photopolymerization initiator, and a thermosetting resin. (1) The modified silicone having a functional group is a modified silicone having an acryloyl group or a methacryloyl group and having a double bond equivalent of 4,000 or less, or a modified silicone having a glycidyl group having an epoxy equivalent of 5,000 or less. (3) The solder photoresist ink composition according to the above (1) or (2), wherein the content of the modified silicone having a functional group is 1 to 20% by weight. And (4) Section (1), (2) or
(3) A printed wiring board using the solder photoresist ink composition described in (3). Further, as a preferred embodiment of the present invention, (5) the ultraviolet-curable resin is obtained by adding a dibasic anhydride to a reaction product of an epoxy resin having two or more epoxy groups in a molecule and an unsaturated monocarboxylic acid Is a resin obtained by reacting
(1) The solder photoresist ink composition according to (1),
(6) The solder photoresist ink composition according to (1), wherein the content of the ultraviolet curable resin is 25 to 55% by weight, (7) The (1), wherein the diluent is a photopolymerizable monomer. (8) The solder photoresist ink composition according to (1), wherein the content of the diluent is 1 to 20% by weight, and (9) the content of the photopolymerization initiator is 1 (1) the solder photoresist ink composition according to (1), wherein the thermosetting resin is a cresol novolac type epoxy resin; and ,
(11) The solder photoresist ink composition according to (1), wherein the content of the thermosetting resin is 2 to 20% by weight.
Can be mentioned.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The solder photoresist ink composition of the present invention contains an ultraviolet curable resin, a modified silicone having a functional group, a diluent, a photopolymerization initiator, and a thermosetting resin. The ultraviolet-curable resin used in the composition of the present invention is not particularly limited, but a dibasic acid anhydride is added to a reaction product of an epoxy resin having two or more epoxy groups in a molecule and an unsaturated monocarboxylic acid. The ultraviolet-curable resin obtained by reacting is preferably used. In the first reaction, a hydroxyl group is formed by an addition reaction between the epoxy group of the epoxy resin and the carboxyl group of the unsaturated monocarboxylic acid, and in the second reaction, esterification between the hydroxyl group and the dibasic acid anhydride is performed. A reaction occurs. Examples of the epoxy resin having two epoxy groups in the molecule include Nippon Kayaku Co., Ltd. EPPN-
201, a phenol novolak type epoxy resin such as YDPN-638 manufactured by Toto Kasei Co., Ltd .;
OCN-1020, EOCN-103S, Sumitomo Chemical Co., Ltd.
Cresol novolac type epoxy resin such as ESCN-220, manufactured by Yuka Shell Epoxy Co., Ltd.
001, Bisphenol A type epoxy resin such as Epicoat 1002, Epototo YDF-2 manufactured by Toto Kasei Co., Ltd.
And bisphenol F type epoxy resins such as 001. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and vinyl acetic acid. Among these, acrylic acid can be preferably used in that it has good reactivity with an epoxy group and the resulting resin has excellent photocurability.

In the present invention, the amounts of the epoxy resin having two or more epoxy groups in the molecule and the unsaturated monocarboxylic acid are preferably substantially equivalent. If the epoxy resin is in excess, unreacted epoxy groups remain, causing undesired reactions during subsequent reactions,
Gelation of the resin may occur. When the amount of the unsaturated monocarboxylic acid is excessive, unreacted carboxyl groups remain and a low-molecular-weight substance is contained in the resin, so that the properties of the cured product may be deteriorated.
The reaction temperature between the epoxy resin and the unsaturated monocarboxylic acid is 1
The temperature is preferably from 00 to 120 ° C. Reaction temperature 12
If the temperature exceeds 0 ° C., the unsaturated monocarboxylic acid may undergo thermal polymerization and gelate during the reaction. During the reaction of the epoxy resin and the unsaturated monocarboxylic acid, as a solvent,
Aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; petroleum solvents such as petroleum ether and petroleum naphtha; cellosolves such as cellosolve and butyl cellosolve; carbitol and butyl carbitol Carbitols, such as
Acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate and the like can be used. Among these, petroleum solvents and acetates can be suitably used. The amount of these solvents used in the reaction between the epoxy resin and the unsaturated monocarboxylic acid is preferably 30 to 50% by weight based on the total weight of the reaction system.

Next, in a second reaction, a reaction product of the epoxy resin and the unsaturated monocarboxylic acid is reacted with a dibasic acid anhydride. Examples of dibasic acid anhydrides include, for example, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride,
Examples thereof include hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, and methylbutenyltetrahydrophthalic anhydride. Among them, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride can be suitably used. The dibasic acid anhydride reacts with a hydroxyl group of a reaction product of the epoxy resin and the unsaturated monocarboxylic acid to form an ester bond and a free carboxyl group. The amount of the dibasic acid anhydride to be reacted is preferably 0.4 to 1 mol per 1 mol of the hydroxyl group of the reaction product of the epoxy resin and the unsaturated monocarboxylic acid. When the amount of the dibasic acid anhydride to be reacted is less than 0.4 mol per 1 mol of the hydroxyl group of the reaction product of the epoxy resin and the unsaturated monocarboxylic acid, the dilute alkali developability may decrease. When the amount of the dibasic acid anhydride to be reacted exceeds 1 mol per 1 mol of the hydroxyl group of the reaction product of the epoxy resin and the unsaturated monocarboxylic acid, the unreacted dibasic anhydride becomes an ultraviolet curable resin. Remains in solution,
It may adversely affect the subsequent reaction steps. The dibasic acid anhydride reacts with the reaction product of the epoxy resin and the unsaturated monocarboxylic acid. If the reaction product of the epoxy resin and the unsaturated monocarboxylic acid is present as a solution in a solvent, dibasic acid anhydride is added to this solution,
The reaction can be advanced by heating and dissolving.
The reaction temperature is preferably from 70 to 100 ° C. The ultraviolet curable resin thus obtained preferably has an acid value of the resin of 40 to 150 mgKOH / g. The acid value of the resulting ultraviolet-curable resin can be easily adjusted by appropriately selecting the amount of the dibasic acid anhydride that reacts. In the composition of the present invention, the content of the ultraviolet curable resin is preferably 25 to 55% by weight,
More preferably, it is 30 to 45% by weight.

The modified silicone having a functional group used in the present invention is not particularly limited, and examples thereof include a modified silicone having an acryloyl group or a methacryloyl group which is a radical polymerizable double bond and a modified silicone having a glycidyl group. Can be. The position of the functional group possessed by the modified silicone may be either terminal, one terminal or a side chain, and the functional group may be directly bonded to silicon of the main chain or may be bonded to the main chain via an oxyalkylene group. It may be bonded to silicon. A modified silicone having a methacryloyl group at one end can be obtained by an equilibration reaction between a siloxane oligomer obtained by hydrolysis of methacryloxypropylmethyldimethoxysilane and a cyclic siloxane in the presence of an acidic catalyst. A modified silicone having methacryloyl groups at both ends can be obtained by an equilibration reaction between bis (methacryloxypropyl) tetramethyldisiloxane and cyclic siloxane in the presence of an acidic catalyst. The modified silicone having a glycidyl group can be obtained by performing an addition reaction of dimethylpolysiloxane having a -SiH group with allyl glycidyl ether in the presence of a platinum catalyst. The double bond equivalent of the modified silicone having an acryloyl group or a methacryloyl group is preferably 4,000 or less, and is preferably 500 to 3,50.
More preferably, it is 0. The epoxy equivalent of the modified silicone having a glycidyl group is preferably 5,000 or less, more preferably 500 to 4,000. One of these modified silicones can be used alone, or two or more can be used in combination. In the composition of the present invention, the content of the modified silicone having a functional group is preferably from 1 to 20% by weight, more preferably from 3 to 10% by weight.

The diluent used in the present invention is not particularly limited, and may be a conventionally used photopolymerizable monomer or oligomer which functions as a diluent and improves photocurability. Examples of the photopolymerizable monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methoxytetraethylene glycol acrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, and tripropylene glycol. Acrylates such as diacrylate and polypropylene glycol diacrylate; polyhydric acrylates of polyhydric alcohols such as trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol; ethylene oxide or propylene oxide addition of these polyhydric alcohols Polyhydric acrylates, 2-hydroxyethyl methacrylate, Methacrylates such as hydroxypropyl methacrylate, methoxytetraethylene glycol methacrylate, polyethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and polypropylene glycol dimethacrylate; trimethylolpropane; Pentaerythritol,
Examples include polyhydric methacrylates of polyhydric alcohols such as ditrimethylolpropane and dipentaerythritol, and polyhydric methacrylates of ethylene oxide or propylene oxide adducts of these polyhydric alcohols. In the composition of the present invention, the content of the diluent is preferably 1 to 20% by weight.

The photopolymerization initiator used in the present invention is not particularly limited. Examples thereof include benzoins such as benzoin and benzoin methyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2. -Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, N, N-dimethylaminoacetophenone,
Acetophenones such as -methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one;
Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-
Thioxanthones such as diisopropylthioxanthone and 2-isopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone,
Benzophenones such as 4'-dichlorobenzophenone and 4,4'-bisdiethylaminobenzophenone can be mentioned. One of these photopolymerization initiators can be used alone, or two or more can be used in combination. Among them, 2-methyl-1
Preferred are combinations of acetophenones and thioxanthones, such as a combination of-[4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2,4-diethylthioxanthone. In the composition of the present invention, the content of the photopolymerization initiator is preferably from 1 to 20% by weight, more preferably from 1.5 to 10% by weight.

The thermosetting resin used in the present invention is not particularly limited. For example, Epicoat 1007, Epicoat 1009, Epicoat 1031, manufactured by Yuka Shell Epoxy Co., Ltd.
DER-642U, DER-67 manufactured by Dow Chemical Co., Ltd.
Bisphenol A epoxy resin such as 3MF, bisphenol F epoxy resin such as YDF-2004 and YDF-2007 manufactured by Toto Kasei Co., Ltd., and E manufactured by Nippon Kayaku
Phenol novolak type epoxy resin such as PPN-201, EOCN-102S, EOCN manufactured by Nippon Kayaku Co., Ltd.
Cresol novolak type epoxy resins such as -103S and EOCN-1020 can be exemplified. Among them, cresol novolak type epoxy resins such as EOCN-103S and EOCN-1020 are preferable.
In the composition of the present invention, the content of the thermosetting resin is 2 to
It is preferably 20% by weight, more preferably 4 to 15% by weight. The solder photoresist ink composition of the present invention may further contain a known inorganic filler such as barium sulfate, barium titanate, silicon oxide, and amorphous silica. The content of the inorganic filler is preferably from 0 to 50% by weight, and more preferably from 5 to 30% by weight. In the composition of the present invention, if necessary, phthalocyanine green, phthalocyanine blue, iodine green, crystal violet, coloring pigments such as titanium oxide, silicone-based, known additives such as fluorine-based antifoaming agent and the like Can be done.

The method for preparing the solder photoresist ink composition of the present invention is not particularly limited. Examples thereof include an ultraviolet curable resin, a modified silicone having a functional group, a diluent, a photopolymerization initiator, a thermosetting resin, All or a part of the additives to be contained according to, uniformly mixed with a kneading machine such as a roll mill, and, if there is any remaining component, obtained by adding the remaining component to the mixture by the kneading machine Can be. The method for producing the printed wiring board of the present invention is not particularly limited. For example, the solder photoresist ink composition of the present invention is applied on the entire surface of a substrate by a screen printing method, a roll coater method, a spray method, a curtain coater method, or the like. Then, after drying at 70 to 90 ° C. to remove the tackiness (tack) on the surface, unnecessary portions are masked with a photomask or the like, and light curing can be performed.
After photo-curing, the unexposed portion is dissolved using a dilute alkaline aqueous solution, and further heat-cured at 130 to 170 ° C. to obtain a cured solder resist coating film. There is no particular limitation on the irradiation light source for photocuring, and a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, or the like can be used.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, solder heat resistance, adhesion, and pressure cooker resistance were evaluated by the following methods. (1) Solder heat resistance The solder photoresist ink composition is applied to the entire surface of a copper foil substrate in a thickness of 15 to 20 μm by a screen printing method, and temporarily dried at 80 ° C. for 20 minutes using a hot air circulation type drying furnace. After that, apply a photomask for pattern formation and irradiate with ultraviolet rays 500 mJ / cm ² by a 3 kW metal halide lamp,
Perform light curing. Next, after removing the uncured portion of the coating film using a 1% by weight aqueous solution of sodium carbonate as a developing solution,
Heat curing is performed at 150 ° C. for 30 minutes using a hot air circulation type drying furnace. A rosin-based flux is applied to the copper foil substrate coated with the resist ink and floated in a solder bath at 260 ° C. for 15 seconds so that the resist coating comes into contact with the solder. The resist coating film is checked for damage such as peeling or swelling, and this cycle is repeated every 15 seconds until the resist coating film is damaged. The solder heat resistance is evaluated based on the number of integrations up to the cycle before the resist coating film is damaged. A: The resist coating film is not damaged up to 4 cycles. ：: The resist coating film is damaged in the fourth cycle. Δ: The resist coating film is damaged in the third cycle. X: The resist coating film is damaged in 2 cycles or less. (2) Adhesion The copper photoresist substrate is coated with the solder photoresist ink composition in the same manner as the sample for evaluating solder heat resistance. On the copper foil substrate coated with this resist ink, 100 grids with a gap of 1 mm were made according to JIS K 5400 8.5.2.
A peeling test is performed using a cellophane adhesive tape, and the number is evaluated by the number of eyes that do not cause peeling. ◎: No peeling occurred at 100/100. ：: 71/100 to 99/100. Δ: 51/100 to 70/100. ×: 0/100 to 50/100. (3) Pressure / Cooker Resistance Test A copper photoresist substrate is coated with a solder photoresist ink composition in the same manner as the sample for evaluating solder heat resistance. After leaving the copper foil substrate coated with this resist ink in a container maintained at 127 ° C., 2 atm, and 100% relative humidity for 40 hours, the appearance of the substrate surface is visually observed and evaluated. A: Floating, peeling and whitening are not observed on the coating film. Δ: Floating, peeling, and whitening are observed on a part of the coating film. X: Floating, peeling, and whitening are observed on the entire surface of the coating film. Synthesis Example 1 (Synthesis of UV-curable resin) In a separable flask having a capacity of 500 ml, 143.4 g of ethyl carbitol acetate and a cresol novolak type epoxy resin [EOCN-103S, manufactured by Nippon Kayaku Co., Ltd.
Epoxy equivalent 214] 199.2 g, acrylic acid 67.1
g, and heated to 110 ° C. while stirring.
The reaction was continued for 20 hours while maintaining 10 ° C. Thereafter, the reaction product was cooled to room temperature, 23.3 g of succinic anhydride, 35.4 g of tetrahydrophthalic anhydride and 31.6 g of ethyl carbitol acetate were added, and the temperature was raised to 90 ° C.
The mixture was reacted at a temperature of 3 ° C. for 3 hours to obtain a solution of an ultraviolet curable resin having an acid value of 80 mgKOH / g. Synthesis Example 2 (Synthesis of UV curable resin) In a separable flask having a capacity of 500 ml, 144.3 g of ethyl carbitol acetate and a bisphenol A type epoxy resin [Epicoat 10 manufactured by Yuka Shell Epoxy Co., Ltd.
After adding 232.2 g and 35.9 g of acrylic acid, the temperature was raised to 110 ° C. with stirring, and the reaction was continued for 20 hours while maintaining 110 ° C. The reaction was then cooled to room temperature and succinic anhydride 19.9
g, 35.8 g of tetrahydrophthalic anhydride and 30.7 g of ethyl carbitol acetate, heated to 90 ° C. and reacted at 90 ° C. for 3 hours to obtain a solution of an ultraviolet curable resin having an acid value of 75 mg KOH / g. I got Example 1 20.0 g of the ultraviolet curable resin solution synthesized in Synthesis Example 1,
1.0 g of dipentaerythritol hexaacrylate,
Photopolymerization initiator [Irgacure 90, manufactured by Ciba-Geigy Corporation]
7] 2.0 g, barium sulfate 6.0 g, defoamer [Nichika Chemical
0.3 g of Formrex SOL-30 manufactured by K.K. and 0.5 g of phthalocyanine green pigment paste were kneaded by a roll mill, and cresol novolak type epoxy resin [EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.] was added thereto. 2.3 g of a solution diluted to 65% by weight with ethyl carbitol acetate and 2.0 g of a modified silicone having a glycidyl group having an epoxy equivalent of 3,000 were added and mixed to obtain a solder photoresist ink composition. The coating film obtained by curing this solder photoresist ink composition did not cause damage to the resist coating film up to 4 cycles in the solder heat resistance test, and was 100/100 in the adhesion test.
No peeling occurred, and no floating, peeling, and whitening were observed in the coating film under the conditions of pressure and cooker resistance. Example 2 20.0 g of the ultraviolet-curable resin solution synthesized in Synthesis Example 1,
1.0 g of dipentaerythritol hexaacrylate,
Photopolymerization initiator [Irgacure 90, manufactured by Ciba-Geigy Corporation]
7] 2.0 g, barium sulfate 6.0 g, defoamer [Nichika Chemical
0.3 g of Formrex SOL-30 manufactured by K.K. and 0.5 g of phthalocyanine green pigment paste were kneaded by a roll mill, and cresol novolak type epoxy resin [EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.] was added thereto. 2.3 g of a solution diluted to 65% by weight with ethyl carbitol acetate and 2.0 g of a modified silicone having a methacryloyl group having a double bond equivalent of 2,700 were added and mixed to obtain a solder photoresist ink composition. The coating film obtained by curing the solder photoresist ink composition,
In the solder heat resistance test, the resist coating film was damaged in the fourth cycle, and in the adhesion test, 100/100
No peeling occurred, and no floating, peeling, and whitening were observed in the coating film under the conditions of pressure and cooker resistance. Example 3 20.0 g of the ultraviolet-curable resin solution synthesized in Synthesis Example 2,
1.0 g of dipentaerythritol hexaacrylate,
Photopolymerization initiator [Irgacure 90, manufactured by Ciba-Geigy Corporation]
7] 2.0 g, barium sulfate 6.0 g, defoamer [Nichika Chemical
0.3 g of Formrex SOL-30 manufactured by K.K. and 0.5 g of phthalocyanine green pigment paste were kneaded by a roll mill, and cresol novolak type epoxy resin [EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.] was added to ethyl acetate. Solution diluted to 65% by weight with carbitol acetate 2.
3 g and 2.0 g of a modified silicone having a glycidyl group having an epoxy equivalent of 3,000 were added and mixed to obtain a solder photoresist ink composition. The coating film obtained by curing this solder photoresist ink composition does not cause damage to the resist coating film up to 4 cycles in the solder heat resistance test, and does not peel at 100/100 in the adhesion test, Under pressure-cooker resistance conditions, no floating, peeling or whitening was observed on the coating film. Example 4 20.0 g of the ultraviolet-curable resin solution synthesized in Synthesis Example 2,
1.0 g of dipentaerythritol hexaacrylate,
Photopolymerization initiator [Irgacure 90, manufactured by Ciba-Geigy Corporation]
7] 2.0 g, barium sulfate 6.0 g, defoamer [Nichika Chemical
0.3 g of Formrex SOL-30 manufactured by K.K. and 0.5 g of phthalocyanine green pigment paste were kneaded by a roll mill, and cresol novolak type epoxy resin [EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.] was added to ethyl acetate. Solution diluted to 65% by weight with carbitol acetate 2.
3 g and 2.0 g of a modified silicone having a methacryloyl group having a double bond equivalent of 2,700 were added and mixed to obtain a solder photoresist ink composition. The coating film obtained by curing the solder photoresist ink composition was damaged in the resist coating at the fourth cycle in the solder heat resistance test, and did not peel off at 100/100 in the adhesion test, Under pressure-cooker resistance conditions, no floating, peeling or whitening was observed on the coating film. Comparative Example 1 20.0 g of the ultraviolet-curable resin solution synthesized in Synthesis Example 1,
1.0 g of dipentaerythritol hexaacrylate,
Photopolymerization initiator [Irgacure 90, manufactured by Ciba-Geigy Corporation]
7] 2.0 g, barium sulfate 6.0 g, defoamer [Nichika Chemical
0.3 g of Formrex SOL-30 manufactured by K.K. and 0.5 g of phthalocyanine green pigment paste were kneaded by a roll mill, and cresol novolak type epoxy resin [EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.] was added thereto. 2.3 g of a solution diluted to 65% by weight with ethyl carbitol acetate was added and mixed to obtain a solder photoresist ink composition. The coating film obtained by curing this solder photoresist ink composition did not damage the resist coating film until 4 cycles in the solder heat resistance test, and did not peel off at 100/100 in the adhesion test. However, under the conditions of resistance to pressure and cooker, floating, peeling, and whitening were observed on the entire surface of the coating film. Comparative Example 2 20.0 g of the ultraviolet-curable resin solution synthesized in Synthesis Example 2,
1.0 g of dipentaerythritol hexaacrylate,
Photopolymerization initiator [Irgacure 90, manufactured by Ciba-Geigy Corporation]
7] 2.0 g, barium sulfate 6.0 g, defoamer [Nichika Chemical
0.3 g of Formrex SOL-30 manufactured by K.K. and 0.5 g of phthalocyanine green pigment paste were kneaded by a roll mill, and cresol novolak type epoxy resin [EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.] was added thereto. 2.3 g of a solution diluted to 65% by weight with ethyl carbitol acetate was added and mixed to obtain a solder photoresist ink composition. The coating film obtained by curing the solder photoresist ink composition was damaged in the fourth cycle in the solder heat resistance test, and did not peel off at 100/100 in the adhesion test. However, under the conditions of resistance to pressure and cooker, floating, peeling, and whitening were observed on the entire surface of the coating film. Examples 1-4
Table 1 shows the results of Comparative Examples 1 and 2.

[0014]

[Table 1]

As shown in Table 1, the solder photoresist ink compositions of Examples 1 to 4 containing the modified silicone having a methacryloyl group or the modified silicone having a glycidyl group were cured on a copper foil substrate. The obtained coating film has good solder heat resistance and adhesiveness, and also has excellent pressure cooker resistance. On the other hand, the coating film obtained by curing the solder photoresist ink compositions of Comparative Examples 1 and 2 containing no modified silicone having a functional group on a copper foil substrate has good solder heat resistance and adhesion. However, the resistance to pressure cooker is remarkably inferior.

[0016]

By coating with the solder photoresist ink composition of the present invention, it is possible to obtain a printed wiring board which is excellent in solder heat resistance, adhesion and pressure / cooker resistance.

Claims (4)

[Claims] 1. A solder photoresist ink composition comprising an ultraviolet curable resin, a modified silicone having a functional group, a diluent, a photopolymerization initiator and a thermosetting resin. 2. The modified silicone having a functional group is a modified silicone having an acryloyl group or a methacryloyl group having a double bond equivalent of 4,000 or less, or a modified silicone having a glycidyl group having an epoxy equivalent of 5,000 or less. Item 2. A solder photoresist ink composition according to Item 1. 3. The solder photoresist ink composition according to claim 1, wherein the content of the modified silicone having a functional group is 1 to 20% by weight. 4. A printed wiring board using the solder photoresist ink composition according to claim 1, 2 or 3.