JP3058747B2 - Resin composition, solder resist resin composition and cured product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention has excellent developability useful as a solder resist resin composition for a printed wiring board containing an unsaturated group-containing polycarboxylic acid resin, and its cured film has excellent adhesion, solder heat resistance, and heat resistance. The present invention relates to a resin composition having excellent chemical properties, gold plating resistance, and electrical insulation properties.

[0002]

2. Description of the Related Art In recent years, ultraviolet curable compositions have been frequently 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]

A screen printing method has often been used as a method for forming a resist pattern on a printed wiring board. However, such a screen printing method often causes bleeding, bleeding, or bleeding during printing. Causes a phenomenon such as sagging, which makes it impossible to cope with recent high-density printed wiring boards. To solve these problems, dry film type photoresists and liquid developable resist inks have been proposed and used, but in the case of dry film type photoresists, bubbles are generated during thermocompression bonding. It is easy to use, there is a concern about heat resistance and adhesion, and there are problems such as high price. On the other hand, liquid resists currently on the market are:
Some use an organic solvent as a developer, and some develop with a dilute aqueous alkaline solution. However, those using an organic solvent are expensive in addition to the problem of air pollution. There is also a problem with acid resistance. Further, those which can be developed with a dilute alkaline aqueous solution have problems such as whitening of the surface after a solder heat resistance test with an aqueous flux of a cured resist and insufficient gold plating resistance.

[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, they can be developed with a dilute alkaline aqueous solution, and the adhesiveness of the cured film, solder heat resistance, chemical resistance The present invention has succeeded in providing a resin composition which is excellent in heat resistance, gold plating resistance and the like, does not cause surface whitening after a solder heat resistance test with an aqueous flux, and is particularly useful as a solder resist resin composition.

That is, the present invention provides:

[0006]

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(Wherein R ₁ and R ₂ are the same or different and each represents a residue of a compound having two or more phenolic hydroxyl groups from which the hydroxyl group has been removed. Z ₁ and Z ₂ are the same or different and are 0 or 1 And the sum of Z ₁ and Z ₂ is 1 or more, M is a glycidyl group or a hydrogen atom, and n is an integer of 1 or more, provided that when n is 1, M is always glycidyl. Is a group, and when n is 2 or more, at least one of M is a glycidyl group.) A reaction between a reactant of (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof A resin composition comprising an unsaturated group-containing polycarboxylic acid resin as a product.

[0008] (2) A solder resist resin composition comprising the unsaturated group-containing polycarboxylic acid resin according to (1). It is about. Specific examples of the epoxy resin represented by the formula (1) used in the present invention include, for example, a residue obtained by removing a hydroxyl group of a compound having three or more phenolic hydroxyl groups in R 1 and R 2 in the formula (1). The expression

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[0021] (wherein, P is 0 or 1 or more represents an integer.) As an indication of R ₁ and R ₂ hydroxyl group is removed residue of a compound having two phenolic hydroxyl groups of the formula

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The following are examples, but the present invention is not limited to these. Further, R ₁ and R ₂ in the formula (1) may include different values. The epoxy resin of the formula (1) is, for example, a compound of the formula (2)

[0063]

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(Wherein R ₁ , R ₂ and Z ₁ , Z ₂ and n
Has the same meaning as in formula (1). )) Can be obtained by reacting an alcoholic hydroxyl group with epichlorohydrin. The reaction between the alcoholic hydroxyl group of the epoxy resin represented by the formula (2) and epichlorohydrin can be carried out in the presence of an alkali metal hydroxide, for example, by using dimethyl sulfoxide or a quaternary ammonium salt. At that time, alcohols, aromatic hydrocarbons, ketones, cyclic and ether compounds, etc. may be used in combination as a solvent. Unless dimethyl sulfoxide or a quaternary ammonium salt is used, the reaction does not proceed sufficiently, and a large amount of alkali metal hydroxide remains, causing polymerization and it is difficult to produce the epoxy resin of the present invention.

The amount of dimethyl sulfoxide used is determined by the formula (2)
Is preferably 5% by weight to 300% by weight with respect to the epoxy resin represented by the formula: When the content is 5% by weight or less with respect to the epoxy resin represented by the formula (2), the reaction between the alcoholic hydroxyl group of the epoxy resin represented by the formula (2) and epichlorohydrin becomes slow, so that a long-time reaction is required. Not preferred.
300% by weight based on the epoxy resin represented by the formula (2)
When it exceeds, the effect of increasing the amount is almost negligible, but the volumetric efficiency becomes poor, which is not preferable.

Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride. The amount of the quaternary ammonium salt is based on 1 equivalent of the alcoholic hydroxyl group of the epoxy resin represented by the formula (2). 0.3-5
0 g is preferred. If the amount is less than 0.3 g per 1 equivalent of the hydroxyl group, the reaction between the alcoholic hydroxyl group of the epoxy resin represented by the formula (2) and epichlorohydrin becomes slow, and a long-time reaction is required, which is not preferable. If it exceeds 50 g with respect to 1 equivalent of hydroxyl group, the effect of increasing the amount is almost negligible, but the cost increases, which is not preferable.

The epichlorohydrin may be used in an amount of at least one equivalent to one equivalent of the alcoholic hydroxyl group to be epoxidized in the epoxy resin represented by the formula (2). However, if the equivalent is more than 30 equivalents to 1 equivalent of the hydroxyl group, the effect of increasing the amount is almost negligible, but the volumetric efficiency deteriorates, which is not preferable.

As the alkali metal hydroxide, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, but caustic soda is preferable. The amount of the alkali metal hydroxide used may be approximately equivalent to 1 equivalent of the alcoholic hydroxyl group to be epoxidized of the epoxy resin represented by the formula (2). When the total amount of the alcoholic hydroxyl groups of the epoxy resin represented by the formula (2) is epoxidized, it may be used in excess, but if it exceeds 2 equivalents with respect to 1 equivalent of the alcoholic hydroxyl groups, the polymer becomes slightly polymerized. Tends to happen. The alkali metal hydroxide may be a solid or an aqueous solution. When an aqueous solution is used, the reaction can be carried out while distilling water out of the reaction system under normal pressure and reduced pressure during the reaction.

The reaction temperature is preferably from 30 to 100 ° C. When the reaction temperature is lower than 30 ° C., the reaction becomes slow and a long-time reaction is required. If the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable.

After completion of the reaction, excess epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and then the resin is dissolved in an organic solvent and a dehydrohalogenation reaction can be performed with an alkali metal hydroxide. On the other hand, after completion of the reaction, the product is washed with water and separated to separate a by-product salt and dimethyl sulfoxide or a quaternary ammonium salt. Excess epichlorohydrin is distilled off from the oil layer under reduced pressure, and then the resin is dissolved in an organic solvent to prepare an alkali metal hydroxide. To carry out a dehydrohalogenation reaction. As the organic solvent, methyl isobutyl ketone, benzene, toluene, xylene and the like can be used,
Methyl isobutyl ketone is preferred. They can be used alone or in a mixed system. The unsaturated group-containing polycarboxylic acid resin used in the present invention is obtained by adding a polybasic carboxylic acid or an anhydride thereof to a reaction product (epoxy (meth) acrylate) of the epoxy resin produced by the above method and (meth) acrylic acid. It can be obtained by reacting.

In the reaction between the epoxy resin and (meth) acrylic acid, (meth) acrylic acid is reacted at a ratio of preferably about 0.8 to 1.5 equivalents to 1 equivalent of the epoxy group of the epoxy resin. . During the reaction, as a diluent, solvents such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, and solvent naphtha, or carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, pentaerythritol tetra ( Reactive monomers such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polypentaerythritol poly (meth) acrylate It is preferable to use a class or the like. Further, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.) in order to promote the reaction, and the amount of the catalyst used is preferably based on the reaction raw material mixture. It is 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, phenothiazine and the like),
The amount used is preferably 0.0
1 to 1% by weight, particularly preferably 0.05 to 0.5% by weight
It is. The reaction temperature is preferably from 60 to 150 ° C, particularly preferably from 80 to 120 ° C. The reaction time is preferably 5 to 60 hours, particularly preferably 10 to 50 hours.

Next, the unsaturated group-containing polycarboxylic acid resin is obtained by mixing the epoxy (meth) acrylate with a polybasic carboxylic acid or an anhydride thereof (for example, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, (An esterification reaction of a hydroxyl group in an epoxy (meth) acrylate). In the reaction, the acid or its anhydride, preferably 0.05 to 1.00 equivalent, is reacted per equivalent of the hydroxyl group with respect to the hydroxyl group in the epoxy (meth) acrylate. The reaction temperature is from 60 to 150 ° C, particularly preferably from 80 to 100 ° C. The acid value (mgKOH / g) of the unsaturated group-containing polycarboxylic acid resin is preferably from 30 to 150,
Particularly preferably, it is 50 to 120.

The amount of the unsaturated group-containing polycarboxylic acid resin contained in the composition of the present invention is preferably from 10 to 90% by weight, particularly preferably from 20 to 80% by weight in the composition.

The composition of the present invention further comprises an epoxy compound such as a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol type epoxy resin, tris (2,3-epoxypropyl) isocyanurate and the like. Epoxy (meth) acrylates, which are reactants of (meth) acrylic acid, and / or the aforementioned reactive simple substances can be contained. These are preferably used in an amount of 0 to 100 parts by weight based on 100 parts by weight of the unsaturated group-containing polycarboxylic acid resin.
When the epoxy compound is used, an epoxy resin curing agent (for example, dicyandiamide and a derivative thereof, an imidazole compound, a triazine compound, a urea compound,
Aromatic amines, polyphenol compounds, and cationic photopolymerization catalysts) can be used alone or in combination of two or more. When an epoxy resin curing agent is used, its amount is preferably 0.5 to 50 parts by weight per 100 parts by weight of the epoxy compound.

As a method of curing the composition of the present invention to obtain a cured product, there is a curing method using an electron beam, an ultraviolet ray, and heat, but it is preferable to cure with an ultraviolet ray and, if necessary, with heat. When curing with ultraviolet light, a photopolymerization initiator is used. As the photopolymerization initiator, any known photopolymerization initiator can be used, but one having good storage stability after blending is desirable. Examples of such photopolymerization initiators include benzoin, benzyl, benzoisomethyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, , 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 can be used alone or in combination of two or more. Further, such photopolymerization initiators include N,
N-dimethylamine benzoic acid ethyl ester, N, N-
Known or conventional photosensitizers such as dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine can be used alone or in combination with two or more kinds.

Preferred combinations are 2,4-diethylthioxanthone or 2-isopropylthioxanthone and N, N
-Combination with dimethylaminobenzoic acid ethyl ester,
2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholinopropan-1-one (Circa Geigy, Irgacure 907) in combination with 2,4-dimethylthioxanthone or 2-isopropylthioxanthone. The use ratio of the photopolymerization initiator is preferably 0 to 50 parts by weight, particularly preferably 4 to 35 parts by weight, per 100 parts by weight of the unsaturated group-containing polycarboxylic acid resin.

The composition of the present invention may further contain an inorganic filler such as talc, silica, alumina, barium sulfate, magnesium oxide and the like, and a coloring pigment such as cyanine green and cyanine blue. Further, if necessary, hexamethoxy melamine, melamine resin such as hexabutoxy melamine, thixotropic agent such as Aerosil, silicone, fluorine-based polymer, leveling agent such as acrylic copolymer, defoaming agent, ultraviolet ray, absorbent, An antioxidant, a polymerization inhibitor and the like can be added.

The composition of the present invention can be obtained by blending the blending components preferably in the ratio described above and uniformly mixing them by a roll mill or the like. The composition of the present invention is cured according to a conventional method as follows to obtain a cured product. That is, it can be cured by ultraviolet rays and, if necessary, by heat to obtain a cured product. When curing with heat, the heating temperature is 1
The temperature is preferably from 20 to 170C, and the heating time is preferably from 30 minutes to 2 hours. When using the composition of the present invention as a solder resist resin composition, for example, cured as follows,
Obtain a cured product. That is, the resin composition of the present invention is applied to a printed wiring board in a 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, a curtain flow coating method, and the like. 60-80 ° C
After drying, the negative film is brought into direct contact with the coating,
Next, ultraviolet rays are irradiated, and the unirradiated portion of the coating film is dissolved and removed with an alkaline aqueous solution such as a 0.5 to 2% aqueous sodium carbonate solution or a 0.5 to 1% aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. A cured film is obtained by heating and curing at 30 ° C. for 30 minutes to 1 hour.

The composition of the present invention is particularly useful as a solder resist resin composition, but is also useful as an insulating paint, a printing ink, an adhesive, a coating agent and the like. The resin composition containing the unsaturated group-containing polycarboxylic acid resin of the present invention is excellent in developability and hardness of a cured product, solder heat resistance, acid resistance, alkali resistance, gold plating resistance, etc., and heat resistance in an aqueous flux. Less whitening of surface after performance test.

[0080]

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 Epoxy Resin) Synthesis Example 1 R ₁ and R ₂ in Formula (2) are

[0081]

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In the polyglycidyl ether of tris (hydroxyphenyl) methane, the average value of n in the formula (2) is 0.78, the epoxy equivalent is 205, the hydrolyzable chlorine content is 0.071%, and the softening point is 71. After dissolving 199 parts of an epoxy resin (epoxy resin (e)) having a melt viscosity (150 ° C.) and 3.6 poise in 370 parts of epichlorohydrin, 6 parts of tetramethylammonium chloride is added at 70 ° C. with stirring, and then 48% NaOH 30
Was added dropwise over 100 minutes. After dropping, it is 3
A time reaction was performed. After completion of the reaction, 200 parts of water was added and washed with water. After oil-water separation, most of epichlorohydrin was distilled off from the oil layer under reduced pressure, and then methyl isobutyl ketone 45
0 parts, and further added 5 parts of 30% NaOH to add 70%
The reaction was carried out at a temperature of 1 hour. After the completion of the reaction, the resultant was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone is distilled and recovered from the oil layer, and an epoxy resin having an epoxy equivalent of 189, a hydrolyzable chlorine content of 0.071%, a softening point of 71.0 ° C., and a melt viscosity (150 ° C.) of 3.6 poise. (A) 19
5 parts were obtained. When the obtained epoxy resin (a) is calculated from the epoxy equivalent, about 0.46 of the 0.78 alcoholic hydroxyl groups in the formula (2) are epoxidized.

Synthesis Example 2 Epoxy resin (e) used in Synthesis Example 1 (199 parts) was replaced with 370 parts of epichlorohydrin and 185 parts of dimethyl sulfoxide.
And 98.5% NaOH at 70 ° C. with stirring.
10.6 parts were added over 100 minutes. 7 more after addition
The reaction was performed at 0 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and the reaction product containing by-product salt and dimethyl sulfoxide is dissolved in 450 parts of methyl isobutyl ketone,
Further, 5 parts of 30% NaOH was added and reacted at 70 ° C. for 1 hour. After the completion of the reaction, the resultant was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy equivalent of 187 and a hydrolyzable chlorine content of 0.1.
07%, softening point 71.0 ° C, melt viscosity (150 ° C)
197 parts of a 5-poise epoxy resin (b) were obtained. When the obtained epoxy resin (b) is calculated from the epoxy equivalent, about 0.52 of the 0.78 alcoholic hydroxyl groups in the formula (2) are epoxidized.

Synthesis Example 3 R ₁ and R ₂ in Formula (2)

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The average value of n in the formula (2) is 1.46, epoxy equivalent 308, hydrolyzable chlorine content 0.107%, softening point 88.0 ° C.
Epoxy equivalent 241, hydrolyzable chlorine content 0.074%, softening point in the same manner as in Synthesis Example 1 except that 188 parts of an epoxy resin (epoxy resin (f)) having a melt viscosity (150 ° C.) of 16 poise was used. 82.0 ° C, melt viscosity (150
C.) 187 parts of 11.0 poise epoxy resin (c) were obtained. When the obtained epoxy resin (c) is calculated from the epoxy equivalent, the alcoholic hydroxyl group 1.46 in the formula (2) is obtained.
Most of the pieces are epoxidized.

Synthesis Example 4 R ₁ and R ₂ in the formula (2) are

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In the cresol novolak epoxy resin represented by the formula (where p represents 0 or an integer of 1 or more), the average value of n in the formula (2) is 0.38, the average p in the above formula is 2.2, Epoxy equivalent 199, hydrolyzable chlorine content 0.035%, softening point 45.0 ° C, melt viscosity (1
50 ° C.) An epoxy equivalent of 19 was obtained in the same manner as in Synthesis Example 2 except that 240 parts of a 0.5 poise epoxy resin (g) was used.
0, hydrolyzable chlorine content 0.034%, softening point
241 parts of an epoxy resin (d) having a melt viscosity (150 ° C.) of 0.5 poise at 5 ° C. was obtained. The obtained epoxy resin (d)
When calculated from the epoxy equivalent, about 0.33 of the 0.38 alcoholic hydroxyl groups in the formula (2) are epoxidized.

(Synthesis Example of Unsaturated Group-Containing Polycarboxylic Acid Resin) Synthesis Example 5 189 parts of epoxy resin (a) obtained in Synthesis Example 1, 68.5 parts of acrylic acid, 0.5 part of methoquinone, triphenylphosphine Charge 1.4 parts and 139 parts of carbitol acetate, raise the temperature to 95 ° C., perform the reaction at 95 ° C., and when the acid value (mgKOH / g) of the reaction solution becomes 1.0 or less (about 35 hours). Cool to 60 ° C., then 101.3 parts of tetrahydrophthalic anhydride and carbitol acetate.
5 parts were charged, the temperature was raised to 90 ° C., and the reaction was conducted until the acid value reached 104 (solid KOH / g excluding the solvent) (product A). The viscosity (25 ° C., poise) of the product A was 330 poise.

Synthesis Example 6 197 parts of the epoxy resin (b) obtained in Synthesis Example 2, 68.5 parts of acrylic acid, 0.7 part of methquinone, 1.5 parts of triphenylphosphine and 143 parts of carbitol acetate 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 solution was cooled to 60 ° C., and then 70 parts of maleic anhydride and 38 parts of carbitol acetate were charged, the temperature was raised to 90 ° C., and the reaction was carried out until the acid value reached 120 (solid acid value excluding the solvent) to obtain an unsaturated group-containing polycarboxylic acid resin (Product B). Obtained. Product B viscosity (25 ° C, poise)
Was 290 poise.

Synthesis Example 7 187 parts of the epoxy resin (c) obtained in Synthesis Example 3, 68.5 parts of acrylic acid, 0.4 part of methquinone, 1.4 parts of triphenylphosphine and 138 parts of carbitol acetate 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 solution was cooled to 60 ° C, and then phthalic anhydride.
6 parts and 55.8 parts of carbitol acetate were charged,
The temperature was raised to 90 ° C., and the reaction was carried out until the acid value reached 110 (solid acid value excluding the solvent) to obtain an unsaturated group-containing polycarboxylic acid resin (product C). Viscosity of product C (25 ° C,
Poise) It was 430 poise.

Synthesis Example 8 190 parts of the epoxy resin (d) obtained in Synthesis Example 4, 81.8 parts of methacrylic acid, 0.4 part of methquinone, 1.5 parts of triphenylphosphine and carbitol acetate 14
6.2 parts were charged, heated to 95 ° C., and reacted at 95 ° C., and the acid value (mg KOH / g) of the reaction solution was 1.0 or less (about 35 hours).
Is cooled to 60 ° C. and then 121.6 parts of hexahydrophthalic anhydride and carbitol acetate 6
5.5 parts were charged, the temperature was raised to 90 ° C., and the acid value was 114.
The reaction was carried out until the solid content acid value (excluding the solvent) was obtained to obtain an unsaturated group-containing polycarboxylic acid resin (Product D). The viscosity of the product D (25 ° C., poise) was 230 poise.

Examples 1 to 4 and Comparative Examples 1 and 2 Solder resist resin compositions (inks) were blended according to the blending compositions shown in Table 1 (the numerical values are parts by weight) and kneaded with a three-roll mill. This is screen-printed
Apply the whole surface to the copper through-hole printed wiring board so that the film thickness after drying becomes 15 to 25 μm, and apply the coating film at 70 ° C.
After pre-drying for 15 minutes, the back surface was similarly applied,
Pre-dried at 25 ° C for 25 minutes. Next, a solder mask pattern film was brought into contact with the coating film surface, exposed to light at 500 mJ / cm ² using a metal halide lamp double-sided simultaneous exposure apparatus (manufactured by Oak Co., HMW680), and coated with a 1.0 wt% aqueous sodium carbonate solution. 2.5 kg spray pressure on unirradiated part of film
The solution was developed at a liquid temperature of 25 ° C./cm ² for 60 seconds and dissolved and removed. The obtained (developability) was evaluated as described below. Thereafter, heat curing was performed at 150 ° C. for 60 minutes using a hot air drier, and the test piece having the obtained cured film was cured (hardened film hardness), (solder heat resistance), (whitening resistance), and (acid resistance) as described below. ), (Alkali resistance), (solvent resistance),
(Gold plating resistance) and (insulation resistance) were tested.

Table 2 shows the results. In addition, the test method and the evaluation method are as follows. (Developability) The developability was visually determined with a magnifying glass. ○ ・ ・ ・ ・ ・ ・ Completely developed △ △ ・ ・ ・ ・ Some parts that are not developed ×× ・ ・ ・ ・ ・ Parts which are not developed considerably (Curing film hardness) The hardness of the cured film is reduced to JISK5400. It measured according to. (Solder heat resistance) According to the test method of JISC6481,
The test piece was immersed in a solder bath at 260 ° C. for 10 seconds for 10 times or 4 times, and the change in appearance was evaluated. (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 dipping of the cured film Note) Post flux used: JS-64P (Manufactured by Yamaei Chemical Co., Ltd.) (Flux resistance for leveler) Four seconds of immersion for 10 seconds were performed to evaluate changes 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 Yamaei Chemical Co., Ltd.)

(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 changes in appearance. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ ・ Some whitening is observed × ・ ・ ・ ・ ・ Whitening is observed on the whole surface (acid resistance) Then, the cured film was visually observed for change in appearance. For the adhesion, 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, but slight peeling of cured film ×: Floating of cured film The test piece that was largely peeled off in the peeling test (alkali resistance) was immersed in a 10 wt% aqueous sodium hydroxide solution at 25 ° C. for 15 minutes, and the same test as the acid resistance test was performed to evaluate.

(Solvent resistance)
It was immersed at 5 ° C. for 30 minutes, and the appearance change was observed. ○ ・ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ ・ Swelled and permeated (gold plating resistance), manufactured by Celllex, Autolonex C
I (plating solution) at a current density of 1 A / dm ²
After gold plating for 0 minutes, a peeling test of the coating film was performed using a cellophane tape. The criteria are as follows. ○ ・ ・ ・ ・ No peeling at all △ ・ ・ ・ ・ ・ Slight peeling ×× ・ ・ ・ ・ Peeling is observed on the entire surface (Insulation resistance) Measure the initial insulation resistance using the test piece Further, according to the test method of IPC-SM-840B (IPC class III), the moisture absorption after 7 days and the insulation resistance after electrolytic corrosion were measured.

Table 1 Example Comparative Example 1 2 3 4 1 2 Product A 107.7 70 Product B 107.7 Product C 107.7 Product D 37.7 KAYARAD R-5027 * 1 116.7 KAYARAD R-5089 * 2 116.7 〃 R- 2058 * 3 20 20 20 20 20 20 TEPIC-S * 4 30 30 30 EPPN-201 * 5 30 KAYARD DPHA * 6 14 8 5 14 5 14 Carbitol acetate 10 10 10 10 10 10 Irgacure 907 * 7 12 8 8 8 8 12 KAYACURE DETX * 83 22 22 23 Dicyandiamide 55 55 (Epoxy resin curing agent) 2-Ethyl-4-methylimidazole 22 22 (Epoxy resin curing agent) Phthalocyanine green (Pigment) 22 22 22 22 KS-603 (Antifoaming agent) 22 22 22 Hexamethoxymelamine 10 10 Talk 60 60 40 60 40 60

Note * 1 KAYARAD R-5027: Nippon Kayaku Co., Ltd.
Reaction product of phenol novolak type epoxy acrylate and dibasic acid anhydride, butyl cellosolve acetate 4
0% by weight content, acid value 68.5 (mgKOH / g) * 2 KAYARAD R-5089: Nippon Kayaku Co., Ltd.
Reaction product of bisphenol A type epoxy acrylate and dibasic acid anhydride, carbitol acetate 40% by weight
Contained products, acid value 63 (mgKOH / g) * 3 KAYARAD R-2058: Nippon Kayaku Co., Ltd.
Phenol novolak type epoxy acrylate, butyl cellosolve acetate containing 30% by weight. * 4 TEPIC-S: manufactured by Nissan Chemical Co., Ltd., tris (2,3-epoxypropyl) isocyanurate, melting point: 95 to 125 [deg.] C. * 5 EPPN-201: manufactured by Nippon Kayaku Co., Ltd., phenol novolak epoxy resin, Softening point 65 ° C * 6 KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.
Dipentaerythritol, polyacrylate * 7 Irgacure 907: manufactured by Ciba-Geigy, photopolymerization initiator * 8 KAYACURE DETX: Nippon Kayaku Co., Ltd.
* 9 KS-603: Shin-Etsu Chemical Co., Ltd., antifoaming agent

Table 2 Example Comparative example 1 2 3 4 1 2 Image quality ○ ○ ○ ○ ○ ○ Hardened material hardness 8H 8H 7H 8H 8H 4H Solder heat resistance Post flux resistance ○ ○ ○ ○ ○ ○ Leveler flux resistance ○ ○ ○ ○ ○ ○ Whitening resistance ○ ○ ○ ○ × × Acid resistance ○ ○ ○ ○ × × Alkali resistance ○ ○ ○ ○ △ ○ Solvent resistance ○ ○ ○ ○ △ △ Gold plating resistance ○ ○ ○ ○ △ × Insulation resistance (Ω) Initial value (× 10 ¹³ ) 5.1 4.5 2.1 4.3 3.5 2.6 Value after test (× 10 ¹² ) 3.7 5.3 3.7 5.7 5.1 4.3 Based on the evaluation results in Table 2, the cured product of the resin composition of the present invention was obtained. Is
It is clear that it has excellent hardness, whitening resistance, acid resistance, alkali resistance, solvent resistance, and gold plating resistance.

[0101]

The resin composition of the present invention is resistant to a developing solution in an exposed portion in the formation of a solder resist pattern by selectively developing an unexposed portion exposed to ultraviolet light through a patterned film. The cured product obtained is excellent in adhesion, electrical insulation, solder heat resistance, gold plating resistance, and chemical resistance, and is particularly suitable as a solder resist resin composition.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03F 7/038 501 G03F 7/038 501 503 503 H05K 3/28 H05K 3/28 C (56) References JP-A-2-97513 (JP, A) JP-A-5-32746 (JP, A) JP-A-5-32745 (JP, A) JP-A-5-32924 (JP, A) JP-A-63-312375 (JP, A) JP-A-1-203424 (JP, A) JP-A-49-2601 (JP, A) JP-A-4-270714 (JP, A) JP-A-4-33910 (JP, A) JP-A-3-131616 ( JP, A) JP-A-54-137088 (JP, A) JP-A-64-14224 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08G 59/00-59/72 C08L 1/00-101/14 C09D 1/00-201/10 G03F 7/00-7/115 H05K 3/00-3/46

Claims (2)

(57) [Claims] (1) Formula (1) (In the formula, R ₁ and R ₂ are the same or different and each represents a residue of a compound having two or more phenolic hydroxyl groups from which the hydroxyl group has been removed. Z ₁ and Z ₂ are the same or different and are 0 or an integer of 1 or more. And the sum of Z ₁ and Z ₂ is 1 or more, M is a glycidyl group or a hydrogen atom, and n is 1
The following integers are shown. However, when n is 1, M is always a glycidyl group, and when n is 2 or more, at least one M is a glycidyl group. A resin composition comprising an unsaturated group-containing polycarboxylic acid resin which is a reaction product of a reaction product of an epoxy resin represented by the formula (I) and (meth) acrylic acid with a polybasic carboxylic acid or an anhydride thereof. . 2. A solder resist resin composition comprising the unsaturated group-containing polycarboxylic acid resin according to claim 1.