JP3351556B2 - Resin composition, solder resist resin composition and cured product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is particularly useful as a solder resist resin composition for printed wiring boards containing an unsaturated group-containing carboxylic acid compound, has excellent developability, and has a cured film having excellent adhesion, electrical insulation, Solder heat resistance, gold plating resistance,
The present invention relates to a resin composition having excellent electrolytic corrosion resistance and chemical resistance, and a cured product thereof.

[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 been widely used as a method for forming a resist pattern on a printed wiring board. However, such a screen printing method often involves bleeding, bleeding, or bleeding during printing. A phenomenon such as sagging occurs, which makes it impossible to cope with recent high-density printed wiring boards. In order to solve these problems, dry film type photoresists and liquid developable resist inks have been proposed and used. However, in the case of dry film type photoresists, air bubbles are apt to be generated during thermocompression bonding, and heat resistance is high. There are also problems such as concerns about properties and adhesion, and high price. On the other hand, liquid resists that are currently commercially available include those that use an organic solvent as a developing solution and those that develop with a dilute aqueous alkaline solution, while those that use an organic solvent require expensive solvents in addition to the problem of air pollution. In addition, there are also problems with the solvent resistance and acid resistance of the cured product. Also, those which can be developed with a dilute alkaline aqueous solution are problematic in that the cured product has insufficient heat resistance, chemical resistance, gold plating resistance, and electrolytic corrosion 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, there is no tack on the surface of the resin composition coated with the pre-dried resin, and after the contact with a negative film and exposure. Solder resist with easy peeling of negative film, development with alkali aqueous solution, and excellent cured film adhesion, electrical insulation, gold plating resistance, solder heat resistance, electrolytic corrosion resistance, chemical resistance, etc. The present invention succeeded in providing a resin composition particularly useful as a resin composition and a cured product thereof.

That is, the present invention provides: Epoxy resin (a) represented by formula (1)

[0006]

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In the formula, Z is the formula (1A) or the formula (1B)

[0008]

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[0009]

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In the formulas (1A) and (1B), a plurality of Rs each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. , N each independently represent a number from 0 to 10, and m + n represents a number from 0 to 10. Also, Z
May be different for each structural unit or may be the same. And an unsaturated group-containing compound (b) represented by the formula (2)

[0011]

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Wherein R ₁ represents a hydrogen atom or a methyl group, and n is 0 or a number from 1 to 5. The reaction product is further reacted with a polybasic carboxylic acid or an anhydride thereof. And reacting 0.8 to 1.5 equivalents of the carboxyl group of the unsaturated group-containing compound (b) with respect to 1 equivalent of the epoxy group of the epoxy resin (a). ) And (b), the amount of the anhydride group of the polybasic carboxylic anhydride is from 0.05 to 1 equivalent of the hydroxyl group in the reaction product.
1. A resin composition, particularly a solder resist resin composition, comprising an unsaturated group-containing carboxylic acid compound which is a compound obtained by reacting 1.00 equivalent. It relates to a cured product of the resin composition according to the above 1.

The unsaturated group-containing carboxylic acid compound used in the present invention comprises a reaction product of an epoxy resin (a) represented by the formula (1) and an unsaturated group-containing compound (b) represented by the formula (2). It can be obtained by reacting a polybasic carboxylic acid or its anhydride.

The epoxy resin (a) represented by the formula (1)
Can be synthesized, for example, by the following method. That is,
Equation (3)

[0015]

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(Wherein Z has the same meaning as described above) and a compound represented by the formula (4)

[0017]

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(Wherein, Z has the same meaning as described above), and is reacted by an appropriate ratio in the presence of a catalyst. The compound represented by the formula (3) is represented by the formula (5)

[0019]

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(In the formula, X represents a naphthalene ring or a benzene ring. A plurality of Rs independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. ) And a compound of formula (6)

[0021]

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(Wherein, Y represents a naphthalene ring or a benzene ring. A plurality of Rs each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group.) Can be obtained by subjecting the compound represented by the formula to a dehydration condensation reaction in the presence of an acid catalyst.

The methylolated compound of the formula (5) and the compound of the formula (6) used as the raw materials are selected and used in combination so as to obtain the desired compound of the formula (3).

The methylol compound of the formula (5) is a known compound and can be synthesized, for example, by reacting a naphthol such as 2-naphthol or xylyl or phenol with formaldehyde in the presence of an alkali metal hydroxide. it can.

Examples of the methylol represented by the formula (5) include 1-methylol-2-naphthol 1-methylol-6-bromo-2-naphthol 2-methylol-4,6-dimethylphenol 4-methylol-2, 6-dimethylphenol 4-methylol-2,3,6-trimethylphenol 4-methylol-2,6-dibromophenol.

The compounds represented by the formula (6) include 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methyl-1-naphthol, phenol, o-cresol, m-cresol, p-naphthol Cresol, 2,4-
Xylenol, 2,6-xylenol, 3,5 xylenol, 2,3,6-trimethylphenol, 2,3,5
-Trimethylphenol, 2-t-butylphenol,
2,4-dichlorophenol, o-chlorophenol,
Examples include, but are not limited to, p-bromophenol, o-ethylphenol, p-ethylphenol, o-phenylphenol, p-phenylphenol, and the like. The amount of the naphthols or phenols of the formula (6) to be used is preferably 0.9 to 20 moles, particularly preferably 1 to 1 mole, per mole of the methylolated compound of the formula (5).
２2 mole times.

The acid catalyst used in the dehydration condensation reaction includes protonic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, boric acid trifluoride, boron trifluoride etherate, and the like.
In addition to Lewis acids such as zinc chloride and aluminum chloride, acetic acid,
Oxalic acid or the like can be used. Of these, hydrochloric acid,
Oxalic acid, p-toluenesulfonic acid, and the like are preferably used, and the amount of these acid catalysts used is preferably 0.01 to 0.2 times the mole of the methylol compound represented by the formula (5).

The dehydration-condensation reaction between the methylol compound of the formula (5) and the compound of the formula (6) in the presence of an acid catalyst is usually carried out at 10 to 100 ° C., preferably at 2 to 100 ° C.
Performed at 0-60 ° C. Further, the reaction time is usually 1 to 10
Can be selected within the time range. This reaction is preferably carried out in the presence of a suitable solvent such as water, methanol, methyl isobutyl ketone, and toluene. Although the amount of the solvent used is not particularly limited, it is usually used in an amount of 1 to 30 parts by weight per 1 part by weight of the methylol compound.

The dehydration-condensation reaction solution is repeatedly washed with water in the presence of an excess of a catalyst such as toluene or methyl isobutyl ketone until the inside of the system becomes neutral. Is removed to obtain a compound of the formula (3).

The epoxy resin of the formula (4) is obtained by reacting the compound of the formula (3) with epihalohydrin. The epihalohydrin used in this reaction includes epichlorohydrin, epibromhydrin, epiiodohydrin and the like, but epichlorohydrin, which is easily available industrially and is inexpensive, is preferable. This reaction can be carried out according to a conventionally known method for obtaining a polyglycidyl ether from a novolak-type phenol resin and epihalohydrin.

For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a mixture of the compound represented by (3) and excess epichlorohydrin,
Alternatively, the reaction is usually carried out at a temperature between 20 and 120 ° C. while adding. At this time, the alkali metal hydroxide may be used as an aqueous solution.In that case, the alkali metal hydroxide is continuously added, and water and epichlorohydrin are continuously reduced under reduced pressure or normal pressure from the reaction system. A method may be employed in which distilling is further performed, liquid separation is performed, water is removed, and epichlorohydrin is continuously returned to the reaction system.

In the above method, the amount of epichlorohydrin used is usually 1 to 20 mol, preferably 2 to 10 mol, per equivalent of the hydroxyl group (phenolic hydroxyl group) in the compound represented by the formula (3). is there. The amount of the alkali metal hydroxide to be used is generally 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol, per 1 equivalent of the hydroxyl group (phenolic hydroxyl group) in the compound of the formula (3). is there. In order to make the reaction proceed smoothly, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl sulfone, dimethyl sulfoxide, dimethylformamide,
It is preferable to add an aprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone. The amount of the aprotic polar solvent used is in the range of 5 to 200%, preferably 10 to 100%, based on the weight of epichlorohydrin. This production method using an aprotic polar solvent significantly improves the ease of reaction and the purity of the product, such as the concentration of hydrolyzable chlorine, as compared with the conventional method of adding alcohols such as methanol and ethanol. Be looked at. This reaction is usually carried out for 1 to 20 hours.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is used as a catalyst in a mixture of the compound represented by the formula (3) and an excess of epihalohydrin. ° C ~ 150
C., and a solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the resulting halohydrin ether. The glycidyl ether can also be obtained by ring closure. In this case, the amount of the quaternary ammonium salt used is in the range of 0.001 to 0.2 mol, preferably 0.05 to 0.1 mol per hydroxyl group of the compound of the formula (3) (1 equivalent of phenolic hydroxyl group). It is.

Usually, these reactants are washed with water or without water to remove excess epihalohydrin under heating and reduced pressure, and then dissolved again in a solvent such as toluene, methyl isobutyl ketone, and the like. An aqueous solution of an alkali metal hydroxide and an aprotic polar solvent such as dimethyl sulfoxide and dimethyl sulfone are added, and the reaction is performed again. In this case, the amount of the alkali metal hydroxide to be used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.1 mol, per equivalent of the hydroxyl group (phenolic hydroxyl group) in the compound of the formula (3) used. Is a mole. The reaction temperature is usually 50
The reaction time is usually 0.5 to 2 hours.

After the completion of the reaction, salts produced as by-products are removed by filtration, washing with water, etc., and the solvent such as toluene, methyl isobutyl ketone or the like is distilled off under reduced pressure under heating to remove the epoxy resin (4) containing less hydrolyzable halogen. Obtainable.

The epoxy resin represented by m = 0 in the formula (1) is obtained by combining one or more compounds represented by the formula (3) obtained by the above method with the compound represented by the formula (4). One or two represented
It can be obtained by reacting at least one kind of epoxy resin in an appropriate ratio in the presence of a catalyst. Further, it can be obtained by reacting the compound represented by the formula (3) with epihalohydrin at an appropriate ratio in the presence of an alkali metal hydroxide.

Examples of the catalyst used in the reaction of the compound of the formula (3) with the epoxy resin of the formula (4) include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; Examples include phosphine and trihexylphosphine. In this case, the amount of the catalyst used is usually 0.01 g to 10 g, preferably 0.1 to 6 g, per equivalent of the epoxy group of the epoxy resin of the formula (4).
Range.

The compound of the formula (3) is preferably used in an amount of 0.3 to 0.7 mol, particularly preferably 0.4 to 0.6 mol, per mol of the epoxy resin of the formula (4). The reaction is started by dissolving in a solvent such as methyl isobutyl ketone, toluene and xylene, and adding the above catalyst.

In this case, the reaction temperature is 70 to 105 ° C.
Is preferable, and a method of increasing the temperature stepwise is more preferable. A suitable reaction time is usually 2 to 15 hours, more preferably 4 to 10 hours.

Usually, these reactants are washed with water to remove the catalyst, and then the solvent is distilled off under reduced pressure under heating to obtain an epoxy resin represented by m = 0 in the formula (1).

The compound of the formula (3) is preferably used in an amount of 0.3 to 0.7 mol per 1 mol of the epoxy resin of the formula (4),
Particularly preferably, 0.4 to 0.6 mol is used, these are made compatible by heating, and the reaction is carried out by adding the above-mentioned catalyst. Epoxy resin can be obtained.

The reaction temperature in this case is 100 to 23.
0 ° C. is preferable, and the reaction time is 0.5 to 10
Time, more preferably 1 to 5 hours, is appropriate.

In the epoxy resin obtained by the above method, m is 0 in the formula (1). The alcohol hydroxyl group of this epoxy resin and epihalohydrin are converted to dimethyl sulfoxide or quaternary ammonium salt. Alternatively, epoxidation can be further performed by reacting in the coexistence of 1,3-dimethyl-2-imidazolidinone and an alkali metal hydroxide, and an epoxy resin in which m is not 0 in the formula (1) is used. Obtainable. Further, by adjusting the amount of the alkali metal hydroxide, it is possible to arbitrarily control the ratio between m and n in the formula (1). At this time, m / (m + n) is preferably 0.10 to 0.80,
Particularly preferably, it is 0.15 to 0.70, and m + n is preferably 0.1 to 10. At the time of the reaction, alcohols, aromatic hydrocarbons, ketones, cyclic or linear ether compounds and the like may be used in combination as a solvent. Dimethyl sulfoxide, quaternary ammonium salt, 1,3-
Dimethyl-2-imidazolidinone may be used in combination.

The amount of dimethylsulfoxide or 1,3-dimethyl-2-imidazolidinone used is expressed by the formula (1) (m =
5) to 300% by weight based on the epoxy resin represented by
% By weight is preferred.

Examples of the quaternary ammonium salt include tetramethylammonium chloride and tetramethylammonium bromide.
= 0) alcoholic hydroxyl group 1 of the epoxy resin represented by
Usually, 0.3 to 50 g is preferable for the equivalent.

The epihalohydrin used in this reaction includes epichlorohydrin, epibromohydrin, epiiodohydrin and the like, and epichlorohydrin which is easily available industrially and is inexpensive is preferable. The amount used is preferably at least 1 equivalent to 1 equivalent of the alcoholic hydroxyl group of the epoxy resin represented by the formula (1) (m = 0).

As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide and the like can be used, but sodium hydroxide is preferable. The amount of the alkali metal hydroxide used may be 1 to 1.5 times equivalent to 1 equivalent of the hydroxyl group to be epoxidized of the epoxy resin represented by the formula (1) (m = 0). 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 in the reaction system out of the reaction system under normal pressure or reduced pressure during the reaction.

The reaction temperature is preferably from 30 to 100 ° C. After completion of the reaction, excess epihalohydrin and solvents are recovered by distillation under reduced pressure, then the resin is dissolved in an organic solvent, and the dehydrohalogenation reaction can be performed with an alkali metal hydroxide. On the other hand, after the completion of the reaction, by-separation with water to separate by-product salts and solvents, and to recover excess epihalohydrin and solvents from the oil layer by distillation under reduced pressure, dissolve the resin in an organic solvent, and use an alkali metal hydroxide. A dehydrohalogenation reaction may be performed. 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. Thus, an epoxy resin represented by the formula (1) and m is not 0 is obtained.

Specific examples of the unsaturated group-containing compound (b) represented by the formula (2) include acrylic acid and methacrylic acid.

[0050]

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[0051]

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And the like.

The reaction between the epoxy resin (a) represented by the formula (1) and the unsaturated group-containing compound (b) represented by the formula (2) is preferably performed with respect to one equivalent of the epoxy group of the epoxy compound. (Meth) acrylic acid is reacted at a ratio of about 0.8 to 1.5 equivalents, particularly preferably about 0.9 to 1.1 equivalents,
Solvents such as butyl cellosolve acetate, methyl ethyl ketone, ethyl cellosolve acetate, carbitol acetate, isopropyl cellosolve acetate, diethylene glycol dimethyl ether, and solvent naphtha as a diluent at the time of the reaction, or carbyl (meth) acrylate, phenoxyethyl (meth) acrylate, pentaerythritol tetra (meta) It is preferable to use reactive monomers such as acrylate, trimethylolpropane tri (meth) acrylate tris (hydroxyethyl) isocyanurate tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate. To further promote the reaction, a catalyst (eg, triethylamine,
Benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, triphenylphosphine, etc.), and the amount of the catalyst to be used is preferably 0.1 to 10% by weight, particularly preferably 0.1 to 10% by weight, based on the reaction mixture. 0.3 to 5% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (e.g., methoquinone, hydroquinone, phenothiazine, etc.), and the amount used is preferably 0.01 to 1% by weight based on the reaction raw material mixture. Particularly preferably 0.05
~ 0.5% by weight. The reaction temperature is preferably 60-1.
The temperature is 50 ° C, particularly preferably 80 to 120 ° C. The reaction time is preferably from 5 to 60 hours, particularly preferably from 10 to 60 hours.
50 hours.

Next, a reaction product of the epoxy resin (a) and the unsaturated group-containing compound (b) and a polybasic carboxylic acid or its anhydride (for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, Reaction with hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, etc., and anhydrides of these acids) The acid or anhydride thereof is preferably used in an amount of 0.05 to 1.0 per equivalent of hydroxyl group relative to the hydroxyl group in the reaction product of the epoxy resin (a) and the unsaturated group-containing compound (b).
Allow 0 equivalents to react. The reaction temperature is preferably 60 to 150
° C, particularly preferably 80 to 100 ° C. The acid value (mg / KOH / g) of the unsaturated group-containing carboxylic acid compound is 30 to 250.
Is preferred, and particularly preferably 50 to 150. The amount of the unsaturated group-containing carboxylic acid compound contained in the resin composition or the solder resist resin composition (hereinafter, collectively referred to as “composition”) of the present invention is preferably from 10 to 90% by weight, more preferably from 20 to 90% by weight in the composition. 80% by weight is preferred.

The composition of the present invention further comprises a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol type epoxy resin, a tris (2,3-
Epoxy compounds such as (epoxypropyl) isocyanurate, epoxy (meth) acrylates which are a reaction product of these epoxy compounds and (meth) acrylic acid, and / or the above-mentioned 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,
Triazine compounds, urea compounds, 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, the amount of the epoxy resin is 1
0.5 to 50 parts by weight per 100 parts by weight is preferred.

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, ultraviolet light and heat.
It is preferable to cure with ultraviolet rays and, if necessary, with heat. When curing with ultraviolet light, it is preferable to use a photopolymerization initiator. 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 benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1- Dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinol-
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,
Examples include 4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone and the like. These can be used alone or in combination of two or more. Further, such a photopolymerization initiator is N, N-
Known or conventional photosensitizers such as dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine can be used alone or in combination of two or more. Preferred combinations are 2,4-diethylthioxysanton and 2
-Combination of isopropylthioxanthone and N, N-dimethylaminobenzoic acid ethyl ester, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, Ciba-Geigy) and 2,4-diethylthioxanthone or 2-
And a combination with 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 carboxylic acid compound.

The composition of the present invention may further contain an inorganic filler (eg, talc, silica, alumina, barium sulfate, magnesium oxide, etc.) and a coloring pigment (eg, cyanine green, cyanine blue, etc.). If necessary, hexamethoxy melamine, melamine resin such as hexabutoxy melamine, thixotropic agents such as Aerosil,
Leveling agents such as silicone, fluoropolymers and acrylic copolymers, defoamers, ultraviolet rays, absorbers, antioxidants,
A polymerization inhibitor or the like can be added.

The composition of the present invention can be obtained by blending the blended components, preferably in the above-mentioned ratios, and uniformly mixing with a roll mill or the like. When the composition of the present invention is cured by heat, the heating temperature is preferably 120 to 170 ° C., and the heating time is 30.
Minutes to 2 hours are preferred. When the composition of the present invention is used as a solder resist resin composition, for example, the composition is cured as follows to obtain a cured product. In other words, screen printing, spraying, roll coating, electrostatic coating,
Usually 10 to 10 by a method such as a curtain flow coating method.
After coating the resin composition of the present invention with a film thickness of 0 μm and drying the coating film usually at 60 to 80 ° C., the negative film is brought into direct contact with the coating film, and then irradiated with ultraviolet light, and then further irradiated with 0.5 to 0.5 μm.
The unirradiated portion of the coating is dissolved and removed with an aqueous alkali solution such as a 2% aqueous sodium carbonate solution or a 0.5% to 1% aqueous caustic soda solution or an aqueous caustic potassium solution, and then heat-cured at 120 to 170 ° C. for usually 30 minutes to 1 hour. By doing so, a cured film is obtained.

The composition of the present invention is particularly useful as a solder resist resin composition.
It is also useful as a printing ink or coating agent. The resin composition containing the unsaturated group-containing carboxylic acid compound of the present invention has developability, hardness of a cured product, solder heat resistance, acid resistance, alkali resistance, solvent resistance, insulation resistance, electrolytic corrosion resistance and plating resistance. It is excellent in such points.

EXAMPLES The present invention will be described more specifically with reference to the following examples. The softening point in the synthesis examples and JIS K2425
The value obtained by (ring and ball method) is the hydroxyl equivalent, the epoxy equivalent is g
/ Eq. In addition, the water-absorbing base in dioxane,
It is the amount of chlorine (titrated) generated when decomposed with 1N-KOH-ethanol for 30 minutes under reflux.

Synthesis Example 1 (1) Synthesis of naphthol methylol compound In a flask equipped with a thermometer, a cooling tube, a dropping funnel, and a stirrer, 288 parts by weight of 2-naphthol (2 mol), 400 parts by weight of a 20% by weight aqueous sodium hydroxide solution A part (2 mol) was charged and the inside of the system was heated to 40 ° C. and reacted for 1 hour. Next, the inside of the system was cooled to 5 ° C., and granular paraformaldehyde (purity 9
2%) 68 parts by weight (2.1 mol) were added and reacted at 5 ° C. for 4 hours.

After completion of the reaction, 126 parts by weight of acetic acid (99% pure) was neutralized by dropping while paying attention to heat generation. Then, after adding 1000 parts by weight of methyl isobutyl ketone, washing with water is repeated to remove excess formaldehyde, and the formula (4)
(Where X represents a naphthalene ring, and R represents all hydrogen atoms), and a solution (reaction mixture) (A) containing a 2-naphthol methyl roll product represented by the formula (A) was obtained.

(2) Synthesis of naphthol resin corresponding to formula (3) 576 parts by weight (4 mol) of 1-naphthol was charged into this reaction mixture (A), and the system was made a homogeneous phase. After further adding 5 parts by weight of p-toluenesulfonic acid, the reaction was carried out at 30 ° C. for 2 hours and then at 50 ° C. for 1 hour. After the completion of the reaction, the reaction mixture was transferred to a separating funnel and repeatedly washed with water to return to neutral. Thereafter, methyl isobutyl ketone and 1-
The naphthol was removed to obtain 570 parts by weight of the naphthol resin (B). The obtained naphthol resin (B) had an ICI viscosity at 150 ° C. of 1.7 ps, a softening point of 82 ° C. and a hydroxyl equivalent of 151.

The naphthol resin (B) was subjected to GPC analysis using tetrahydrofuran as a solvent, and a main peak component considered to be binuclear having two naphthol rings was collected and analyzed by mass spectrum (FAB-MS). As a result, since M ⁺ 300 was obtained, it was confirmed that the main peak component was a binuclear body represented by the following formula (7).

[0064]

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(3) Synthesis of Epoxy Resin Corresponding to Formula (4) To 155 parts by weight of the naphthol resin (B) obtained in (2), 555 parts by weight (6 mol) of epichlorohydrin and 140 parts by weight of dimethyl sulfoxide were added and dissolved. Thereafter, the mixture was heated to 40 ° C., and 42 parts by weight (1.04 mol) of flake sodium hydroxide (99% pure) was added over 100 minutes, and then further at 50 ° C. for 2 hours and at 70 ° C. for 1 hour. Reacted.
Then, after washing was repeatedly returned to neutral, excess epichlorohydrin was distilled off from the oil layer under reduced pressure by heating using a rotary evaporator, and 500 parts by weight of methyl isobutyl ketone was added to the residue and dissolved.

Further, the solution of methyl isobutyl ketone was heated to 70 ° C., 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was allowed to react for 1 hour. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure, and the epoxy resin (C) 190
Parts by weight were obtained. 150 ° C of the obtained epoxy resin (C)
Has an ICI viscosity of 0.9 ps and a softening point of 70.5
° C, epoxy equivalent 212, hydrolyzable chlorine 250
ppm.

The epoxy resin (C) was subjected to a GPC analysis, and a main peak considered to be a binuclear substance was collected and analyzed by mass spectrum (FAB-MS).
⁺ By 412 has been obtained, the main peak component was confirmed to be a binuclear represented by the following formula (8).

[0068]

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(4) Synthesis of epoxy resin in which m in formula (1) is 0: 60 parts by weight of naphthol resin (B) obtained in (2) above and epoxy resin (3) obtained in (3) C) 170 parts by weight were dissolved in 115 parts by weight of methyl isobutyl ketone, and 2 g of tetramethylammonium chloride was further added to add 1 part by weight.
The reaction was performed at 10 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and the catalyst was removed by washing with water. Thereafter, methyl isobutyl ketone was distilled off from the oil layer under reduced pressure by heating using a rotary evaporator to obtain 209 parts by weight of an epoxy resin (D). The obtained epoxy resin (D) represented by the following formula (9) at 150 ° C.
Is 10 ps, the softening point is 96 ° C., the epoxy equivalent is 624, and when calculated from the epoxy equivalent, the formula (9)

[0070]

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(Where W ₁ is the formula (10)

[0072]

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Is shown. )), N represents 2, 3.

(5) Synthesis of epoxy resin in which m is greater than 0 in the formula (1) The epoxy resin obtained in the above (4) was placed in a flask equipped with a thermometer, a cooling tube, a dropping funnel and a stirrer. 20 resin (D)
7 parts by weight, 308 parts by weight of epichlorohydrin were charged,
After heating to 70 ° C with stirring to make the system uniform, 4
The mixture was cooled to 0 ° C., and 1.7 g of tetramethylammonium chloride was added while maintaining the temperature. Next, 12 parts by weight of the flaky sodium hydroxide was divided into 10 portions to obtain 1 portion.
It was added every 0 minutes, and then reacted at 40 ° C. for 4 hours.
Subsequently, washing with hot water was repeated, and excess epichlorohydrin was distilled off from the oil layer under reduced pressure by heating using a rotary evaporator, and 200 parts by weight of methyl isobutyl ketone was added to the residue and dissolved. Further, the solution of methyl isobutyl ketone was heated to 70 ° C., and 5 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. After reacting for 1.5 hours, washing with water was repeated. The methyl isobutyl ketone was distilled off to obtain a solid epoxy resin (E) at room temperature. The obtained epoxy resin (E) has a softening point of 91.5 ° C and ICI at 150 ° C.
The viscosity was 9.3 ps and the epoxy equivalent was 405.
Also, when calculated from the epoxy equivalent, about 1.1 of the alcoholic hydroxyl groups present on average 2.3 per molecule in the epoxy resin (D) obtained in (4) were epoxidized. I understood that. (M / (m + n) =
0.48). Therefore, the epoxy resin (E) is represented by the formula (1)
, Z represents the equation (10), m = 1.1, n = 1.
2 epoxy resin.

Synthesis Example 2 (1) Synthesis of Phenol Methylol Compound 122 parts by weight (1 mol) of 2,4-xylenol was placed in a flask equipped with a thermometer, a cooling tube, a dropping funnel, and a stirrer.
50 parts by weight of a 40% by weight aqueous sodium hydroxide solution was charged, and the inside of the system was heated to 40 ° C. Next, 34 parts by weight (1.05 mol) of granular paraformaldehyde (purity 92%) was added and reacted at 50 ° C. for 4 hours. After the reaction is completed,
After cooling to ℃, 63 parts by weight of acetic acid (99% pure) was neutralized by dropping while paying attention to heat generation. Next, after adding 500 parts by weight of methyl isobutyl ketone, washing with water was repeated to remove excess formaldehyde to obtain a solution (reaction mixture) (F) containing 2-methylol 4,6-dimethylphenol.

(2) Synthesis of Naphthol Resin Corresponding to Formula (3) 288 parts by weight (2 mol) of 1-naphthol was charged into this reaction mixture (F), and the system was made a homogeneous phase. Further, after adding 2 parts by weight of p-toluenesulfonic acid, the mixture was reacted at 30 ° C. for 2 hours and then at 50 ° C. for 1 hour. After the completion of the reaction, the reaction mixture was transferred to a separating funnel and repeatedly washed with water to return to neutral. Thereafter, methyl isobutyl ketone and 1-
The naphthol was removed to obtain 256 parts by weight of the naphthol resin (G). The obtained naphthol resin (G) had an ICI viscosity at 150 ° C. of 0.2 ps, a softening point of 60 ° C., and a hydroxyl equivalent of 140.

The naphthol resin (G) was subjected to a GPC analysis using tetrahydrofuran as a solvent, and a main peak component considered to be a binuclear body having one naphthol ring and one benzene ring was fractionated to obtain a mass spectrum (FAB). −
Analysis by MS) gave M ⁺ 278, confirming that the main peak component was a binuclear compound represented by the following formula (11).

[0078]

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(3) Synthesis of Epoxy Resin Corresponding to Formula (4) To 140 parts by weight of the naphthol resin (G) obtained in (2), 555 parts by weight (6 mol) of epichlorohydrin and 140 parts by weight of dimethyl sulfoxide were added and dissolved. Thereafter, the mixture was heated to 50 ° C., and 42 parts by weight (1.04 mol) of sodium flake (99% pure) was added over 100 minutes, and then further at 60 ° C. for 2 hours and at 70 ° C. for 1 hour. Reacted.
Then, after washing was repeatedly returned to neutral, excess epichlorohydrin was distilled off from the oil layer under reduced pressure by heating using a rotary evaporator, and 500 parts by weight of methyl isobutyl ketone was added to the residue and dissolved.

Further, the solution of methyl isobutyl ketone was heated to 70 ° C., and 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. After reacting for 1 hour, washing with water was repeated to make the solution neutral. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure, and the epoxy resin (H) 186 was removed.
Parts by weight were obtained. 150 ° C of the obtained epoxy resin (H)
Is 0.1 ps and epoxy equivalent is 20 ps.
It was 2.

The epoxy resin (G) was subjected to a GPC analysis to disperse a main peak considered to be a binuclear substance, and analyzed by mass spectrum (FAB-MS).
⁺ By 390 has been obtained, the main peak component was confirmed to be a binuclear represented by the following formula (12).

[0082]

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(4) Synthesis of Epoxy Resin in which m is 0 in Formula (1) 56 parts by weight of naphthol resin (G) obtained in (2) and epoxy resin (G) obtained in (3) H) 162 parts by weight were dissolved in 66 parts by weight of methyl isobutyl ketone, and 1 g of tetramethylammonium chloride was added thereto to obtain 11
The reaction was performed at 0 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and the catalyst was removed by washing with water. Thereafter, methyl isobutyl ketone was distilled off from the oil layer using a rotary evaporator under heating and reduced pressure to remove the epoxy resin (I) 21
0 parts by weight were obtained. ICI at 150 ° C. of the epoxy resin (I) represented by the formula (13) thus obtained.
The viscosity is 5.1 ps, the softening point is 95.6 ° C., the epoxy equivalent is 596, and when calculated from the epoxy equivalent, the formula (13) is obtained.

[0084]

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(Where W ₂ is represented by the formula (14)

[0086]

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FIG. )), N represents 2,4.

(5) Synthesis of epoxy resin in which m is greater than 0 in formula (1) The epoxy resin obtained in (4) was placed in a flask equipped with a thermometer, a cooling tube, a dropping funnel and a stirrer. 100 parts by weight of (I) and 296 parts by weight of epichlorohydrin were charged and heated to 70 ° C. while stirring to form a homogeneous phase in the system.
C., and while maintaining this temperature, 1.7 g of tetramethylammonium chloride was added. Then, 8.1 parts by weight of the flaky sodium hydroxide was divided into 10 portions and added to 1 portion.
It was added every 0 minutes, and then reacted at 40 ° C. for 4 hours.
Subsequently, washing with hot water was repeated, and excess epichlorohydrin was distilled off from the oil layer under reduced pressure by heating using a rotary evaporator, and 200 parts by weight of methyl isobutyl ketone was added to the residue and dissolved. Further, the solution of methyl isobutyl ketone was heated to 70 ° C., and 5 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. After reacting for 1.5 hours, washing with water was repeated. Methyl isobutyl ketone was distilled off to obtain an epoxy resin (J) of the present invention which was solid at room temperature. The softening point of the obtained epoxy resin (J) was 87.6 ° C, the ICI viscosity at 150 ° C was 4.5 ps, and the epoxy equivalent was 325. Also, when calculated from the epoxy equivalent, the epoxy resin (I) obtained in (4) has an average of 2.
It was found that out of four alcoholic hydroxyl groups, about two were epoxidized. (M / m + n = 0.
83). Accordingly, the epoxy resin (J) is an epoxy resin in which Z in the formula (I) represents the formula (14), and m = 2 and n = 0.4.

Synthesis Example 3 (1) Synthesis of naphthol resin corresponding to formula (3) Reaction mixture (A) obtained by a method similar to (1) of Example 1
488 parts by weight (4 mol) of 2,6-xylenol were added to the mixture, and the inside of the system was made a homogeneous phase. After further adding 4 parts by weight of p-toluenesulfonic acid, the reaction was carried out at 30 ° C. for 1 hour and then at 70 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel and repeatedly washed with water to return to neutral. Thereafter, 2,6-xylenol was removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 513 parts by weight of a light brown, crystalline naphthol resin (K) at room temperature. The melting point of the obtained naphthol resin (K) was 163 ° C., and the hydroxyl equivalent was 139.

The naphthol resin (K) was subjected to a GPC analysis using tetrahydrofuran as a solvent, and a main peak component considered to be a binuclear body having one naphthol ring and one benzene ring was fractionated to obtain a mass spectrum (FAB −
As a result of analysis by (MS), M ⁺ 278 was obtained, and it was confirmed that the main peak component was a binuclear compound represented by the following formula (15).

[0091]

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(2) Synthesis of epoxy resin corresponding to formula (4) Using 420 parts by weight of naphthol resin (K) obtained in (1), 1665 parts by weight (18 mol) of epichlorohydrin, 420 parts by weight of dimethyl sulfoxide , And the mixture was heated to 50 ° C., and 42 parts by weight (1.04 mol) of flaky sodium hydroxide (99% pure) was added over 100 minutes, and then further added at 70 ° C. for 2 hours at 60 ° C. For 1 hour. Then, after returning to neutral by repeatedly washing with water,
The excess epichlorohydrin was distilled off from the oil layer using a rotary evaporator under heating and reduced pressure, and 15
00 parts by weight of methyl isobutyl ketone was added and dissolved.

Further, the solution of methyl isobutyl ketone was heated to 70 ° C., 30 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. Then, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain an epoxy resin (L) 545.
Parts by weight were obtained. 150 ° C of the obtained epoxy resin (L)
Is 0.2 ps and the epoxy equivalent is 19 ps.
It was 5.

The epoxy resin (L) was subjected to a GPC analysis, and a main peak considered to be a binuclear substance was collected and analyzed by mass spectrum (FAB-MS).
⁺ By obtained at 390, the main peak component was confirmed to be a binuclear represented by the following formula (16).

[0095]

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(3) Synthesis of epoxy resin in which m is 0 in formula (1) 112 parts by weight of naphthol resin (K) obtained in the above (1) and epoxy resin (2) obtained in (2) L) 324 parts by weight were dissolved in 132 parts by weight of methyl isobutyl ketone, and 2 g of tetramethylammonium chloride was further added and reacted at 110 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and the catalyst was removed by washing with water. Thereafter, methyl isobutyl ketone was distilled off from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 425 parts by weight of an epoxy resin (M). The epoxy resin (M) thus obtained represented by the formula (17) has an ICI viscosity at 150 ° C. of 4.6 ps, a softening point of 87.2 ° C., an epoxy equivalent of 552, and an epoxy equivalent of 552. Equation (17)

[0097]

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(Where W ₃ is the formula (18)

Embedded image

Is shown. )), N represents 2.1.

(4) Synthesis of epoxy resin in which m is greater than 0 in formula (1) The epoxy resin obtained in (3) was placed in a flask equipped with a thermometer, a cooling tube, a dropping funnel, and a stirrer. After 200 parts by weight of (M) and 560 parts by weight of epichlorohydrin were charged, the mixture was heated to 70 ° C. with stirring to form a homogeneous phase in the system.
C., and while maintaining this temperature, 1.9 g of tetramethylammonium chloride was added. Then, 6.2 parts by weight of the flaky sodium hydroxide was divided into 10 portions and added to 1 portion.
It was added every 0 minutes, and then reacted at 40 ° C. for 4 hours.
Subsequently, washing with hot water was repeated, and excess epichlorohydrin was distilled off from the oil layer under reduced pressure by heating using a rotary evaporator, and 400 parts by weight of methyl isobutyl ketone was added to the residue and dissolved. Further, the solution of methyl isobutyl ketone was heated to 70 ° C., and 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. After reacting for 1.5 hours, washing with water was repeated. Methyl isobutyl ketone was distilled off to obtain a solid epoxy resin (N) at room temperature. The obtained epoxy resin (N) has a softening point of 80.1 ° C and an IC at 150 ° C.
The I viscosity was 4.0 ps and the epoxy equivalent was 387.
Further, when calculated from the epoxy equivalent, about 0.7 of the alcoholic hydroxyl groups present on average 2.1 per molecule in the epoxy resin (M) obtained in (3) were epoxidized. (M / (m + n) =
0.33). Therefore, the epoxy resin (N) is represented by the formula (1)
, Z represents the expression (18), m = 0.7, n = 1.
4 is an epoxy resin.

Synthesis Example of Unsaturated Group-Containing Carboxylic Acid Compound Synthesis Example 4 624 parts of the epoxy resin (D) (epoxy equivalent: 624, softening point: 96 ° C.) obtained in Synthesis Example 1, 72 parts of acrylic acid,
1.4 parts of methylhydroquinone, 4.5 parts of triphenylphosphine and 565 parts of carbitol acetate were added, and the mixture was heated to 100 ° C. and reacted for 30 hours to obtain an acrylic acid reactant of the epoxy resin (D) (reaction mixture) The acid value (mgKOH / g) was 1.0. Then, 152 parts of tetrahydrophthalic anhydride was further charged and reacted at 95 ° C. for 20 hours, and the solid component had an acid value (mgKOH / g) of 66 and a viscosity of 462. A poison (25 ° C.) unsaturated group-containing carboxylic acid compound (product a) was obtained.

Synthesis Example 5 405 parts of the epoxy resin (E) obtained in Synthesis Example 1 (epoxy equivalent: 405, softening point: 91.5 ° C.), acrylic acid 72
Part, methylhydroquinone 1.0 part, triphenylphosphine 3.2 parts and carbitol acetate 420.7
The resulting mixture was heated to 100 ° C. and reacted for 30 hours to obtain an acrylic acid reactant of the epoxy resin (E) (acid value was 1.
1). Next, hexahydrophthalic anhydride 1
54 parts were charged and reacted at 95 ° C. for 20 hours to obtain an unsaturated group-containing carboxylic acid compound (product b) having an acid value (mg KOH / g) of 89.5 and a viscosity of 410 poise (25 ° C.) for 20 hours. .

Synthesis Example 6 The epoxy resin (I) obtained in Synthesis Example 2 (epoxy equivalent: 59)
6, softening point 95.6 ° C) 596 parts, acrylic acid 72 parts,
1.1 parts of methylhydroquinone, 4.2 parts of triphenylphosphine and 510.7 parts of carbitol acetate were added, and the mixture was heated to 100 ° C. and reacted for 30 hours to obtain an acrylic acid reactant of the epoxy resin (I) ( The acid value was 1.2.) Then, 98 parts of maleic anhydride was further charged and 9
The reaction was performed at 5 ° C for 20 hours, and the acid value (mgKOH / g) of the solid was 7
An unsaturated group-containing carboxylic acid compound having a viscosity of 4.0 and a viscosity of 435 poise (25 ° C.) (product C) was obtained.

Synthesis Example 7 The epoxy resin (J) obtained in Synthesis Example 2 (epoxy equivalent 32
5, softening point 87.6 ° C) 325 parts, β-acryloyloxypropionic acid 144 parts, methylhydroquinone 0.
88 parts, 3.2 parts of triphenylphosphine and 414 parts of carbitol acetate were added, and the mixture was heated to 100 ° C. and reacted for 30 hours to obtain a β-acryloyloxypropionic acid reaction product of the epoxy resin (J). Next, 152 parts of tetrahydrophthalic anhydride was further charged and reacted at 95 ° C. for 20 hours, and the solid component had an acid value (mgKOH / g) of 91.6 and a viscosity of 35.
A 3-poise (25 ° C.) unsaturated carboxylic acid (product d) was obtained.

Synthesis Example 8 The epoxy resin (M) obtained in Synthesis Example 3 (epoxy equivalent 55
2, softening point 87.2 ° C) 552 parts, acrylic acid 72 parts,
1.1 parts of methylhydroquinone, 3.98 parts of triphenylphosphine and 482.7 parts of carbitol acetate were added, and the mixture was heated to 100 ° C and reacted for 30 hours. Next, 100 parts of succinic anhydride was further charged and reacted at 95 ° C. for 20 hours, and the solid component had an acid value (mg KOH / g) of 78.7 and a viscosity of 3
A 98-poise (25 ° C.) unsaturated group-containing carboxylic acid compound (product e) was obtained.

Synthesis Example 9 The epoxy resin (N) obtained in Synthesis Example 3 (epoxy equivalent 38
7, softening point 80.1 ° C) 387 parts, methacrylic acid 82
, 0.9 parts of methylhydroquinone, 3.2 parts of triphenylphosphine and 414 parts of carbitol acetate, and the mixture was heated to 100 ° C and reacted for 30 hours. Then, a further 152 parts of tetrahydrophthalic anhydride were added to 95 parts.
Reaction at 20 ° C. for 20 hours, acid value of solid component (mgKOH / g)
6 to obtain a carboxylic acid compound having an unsaturated group (product F) having a viscosity of 254 poise (25 ° C.).

Examples 1 to 5 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 applied to the entire surface of a copper through-hole printed circuit board by a screen printing method so that the film thickness after drying is 15 to 25 μm, and after preliminarily drying the coating film at 70 ° C. for 15 minutes, the rear surface is similarly applied. , 70 ° C, 25
Pre-dried for minutes. Next, the solder mask pattern film was brought into contact with the coating surface, and 500 m long using a metal halide lamp double-sided simultaneous exposure apparatus (manufactured by Oak Co., HMW680).
Exposure was performed with a light amount of J / cm ^{2, and} the unirradiated portion of the coating film was sprayed with a 1.0 wt% aqueous sodium carbonate solution at a spray pressure of 2.5 kg / cm ² ,
The solution was developed at a liquid temperature of 25 ° C. for 60 seconds and dissolved and removed. The (developability) of the obtained product was evaluated as described below. After that, heat curing at 150 ° C for 60 minutes with a hot air dryer,
Regarding the test piece having the obtained cured film, as described later, (cured film hardness), (solder heat resistance), (acid resistance), (alkali resistance), (solvent resistance), (gold plating resistance), (electrolytic corrosion resistance) (Insulation resistance) and (insulation resistance).

Table 2 shows the results. Test Method and Evaluation Method (Developability) The developability was visually determined with a magnifying glass. ○ ・ ・ ・ ・ Completely developed △ ・ ・ ・ ・ Some parts are not developed thin × ・ ・ ・ ・ ・ ・ Many parts are not developed (Hardened film hardness) The hardness of the hardened film is measured according to JIS K5400 did. (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 to evaluate the change in appearance. (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 (Yamaei (Flux resistance for leveler) Ten times of immersion for 10 seconds was performed four times 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.)

(Acid Resistance) A test piece was immersed in a 10 vol% sulfuric acid aqueous solution at 25 ° C. for 15 minutes, and the appearance change of the cured film was visually observed. The adhesiveness was determined by conducting a peeling test using a cellophane tape on the solder pattern portion to determine the resist peeling state. ○ ・ ・ ・ ・ ・ ・ No change in appearance and no peeling of cured film △ ・ ・ ・ ・ No change in appearance but slight peeling of cured film × ・ ・ ・ ・ ・ ・ Floating of cured film observed in peeling test A test piece having large peeling (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) The test piece was immersed in dichloromethane at 25 ° C for 30 minutes, and the appearance change was observed. ○ ・ ・ ・ ・ ・ ・ No change in appearance × ・ ・ ・ ・ ・ ・ Swelling and infiltration (gold plating resistance) Using a test piece, using Cellulex Autronex CI (plating solution) .0A /
After gold plating for 30 minutes at a current density of dm ² , a peeling test of the coating film was carried out using a cellophane tape. The criteria are as follows. ○ ・ ・ ・ ・ ・ ・ No peeling × ・ ・ ・ ・ Part or all of the coating film peeled

(Electrolytic corrosion resistance)
° C, 100% RH, 2 atm, 30 hours, applied voltage 100
Inspection of discoloration and surface condition after standing under the condition of V was performed. ○ ・ ・ ・ ・ ・ ・ No discoloration or abnormal surface condition on either + or-side × ・ ・ ・ ・ ・ ・ No discoloration or abnormal surface condition on either + or-side (Insulation resistance) Measure the insulation resistance,
Also, the test method of IPC-SM-840B (IPC class II
According to I), the moisture absorption after 7 days and the insulation resistance after electrodeposition were measured.

[0111]

Table 1 Example 1 Comparative Example 1 2 3 4 5 1 2 Product A 116.7 Product B 116.7 Product C 116.7 Product D 116.7 Product E 70 Product F 46.7 KAYARAD R-5027 * 1 116.7 KAYARAD R-5089 * 2 116.7 KAYARAD R-2058 * 3 20 20 20 20 20 20 20 TEPIC-S * 4 15 10 15 15 EPPN-201 * 55 KAYARAD DPHA * 6 3 5 5 3 3 5 5 Irgacure 907 * 7 12 12 12 12 12 12 12 KAYACURE DETX * 82 22 22 22 22 Carbitol acetate 20 20 20 20 20 10 10 Dicyandiamide (Epoxy resin curing agent) 5.5 5 5 Phthalocyanine green (Pigment) 2 2 2 2 2 2 2 KS-603 (antifoaming agent) * 9 2 2 2 2 2 2 2 KAYARAD SPGDA * 10 10 10 10 Talc 60 60 60 60 60 60 60

Note * 1 KAYARAD R-5027: manufactured by Nippon Kayaku Co., Ltd. A reaction product of phenol novolak type epoxy acrylate and dibasic acid anhydride, a product containing 40% by weight of butyl cellosolve acetate, an acid value of 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
* 3 KAYARAD R-2058: Nippon Kayaku Co., Ltd. phenol novolak type epoxy acrylate, butyl cellosolve acetate 30% by weight containing product * 4 TEPIC-S: Nissan Chemical Co., Ltd. Tris (2,3-epoxypropyl) isocyanurate, melting point 95-125 ° C * 5 EPPN-201: Nippon Kayaku Co., Ltd. phenol novolak type epoxy resin, softening point 65 ° C * 6 KAYARAD DPHA: Nippon Kayaku (stock)
Dipentaerythritol, polyacrylate * 7 Irgacure 907: photopolymerization initiator manufactured by Ciba-Geigy * 8 KAYACURE DETX: photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd. * 9 KS-603: Shin-Etsu Chemical Co., Ltd. Defoamer * 10 KAYARAD SPGDA: Spiroglycol diacrylate, Nippon Kayaku Co., Ltd., melting point 12
0-125 ° C

[0113]

Table 2 Example 2 Comparative Example 1 2 3 4 5 12 2 Developability ○ ○ ○ ○ ○ ○ ○ Hardened film hardness 7H 8H 8H 9H 8H 8H 8H Soldering heat resistance Post flux resistance ○ ○ ○ ○ ○ ○ ○ Leveler ○ ○ ○ ○ ○ ○ ○ Acid resistance ○ ○ ○ ○ ○ × × Alkali resistance ○ ○ ○ ○ ○ △ ○ Solvent resistance ○ ○ ○ ○ ○ △ △ Gold plating resistance ○ ○ ○ ○ ○ × × Electrolytic corrosion resistance ○ ○ ○ ○ ○ × × Insulation resistance (Ω) Initial value (× 10 ¹³ ) 7.1 4.5 6.2 5.1 5.7 4.1 2.7 Value after test (× 10 ¹² ) 8.5 7.3 15 9.5 9 4.5 4.1

As is clear from Table 2, the cured product of the resin composition of the present invention is excellent in pencil hardness, solder heat resistance, chemical resistance, gold plating resistance, electrolytic corrosion resistance, electrical insulation and the like.

[0115]

The resin composition of the present invention has a resistance to a developing solution in an exposed portion in forming a solder resist pattern by selectively developing an unexposed portion exposed to ultraviolet light through a film on which a pattern is formed. The obtained cured product is excellent in pencil hardness, solder heat resistance, chemical resistance, gold plating resistance, electrolytic corrosion resistance, electrical insulation, and the like, and is particularly suitable as a solder resist resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 59/14-59/17 H05K 3/28

Claims (3)

(57) [Claims] An epoxy resin (a) represented by the formula (1): ＺIn the formula, Z is the formula (1A) or the formula (1B) Embedded image (In the formulas (1A) and (1B), a plurality of R
Are each independently a hydrogen atom, a halogen atom,
And represents an alkyl group or an aryl group. ),
m and n each independently represent a number from 0 to 10, and
m + n represents a number from 0 to 10. Further, Z may be different for each structural unit or may be the same. And an unsaturated group-containing compound (b) represented by the formula (2): (Wherein, R ₁ represents a hydrogen atom or a methyl group, and n represents 0
Or a number from 1 to 5. A) a compound obtained by further reacting the reaction product of the above) with a polybasic carboxylic acid or an anhydride thereof, wherein the compound is a compound containing an unsaturated group (b) with respect to one equivalent of the epoxy group of the epoxy resin (a). ) Of 0.8 to 1.5 equivalents of the carboxyl group, and then the component (a)
And a compound obtained by reacting 0.05 to 1.00 equivalent of an anhydride group of a polybasic carboxylic acid anhydride with 1 equivalent of a hydroxyl group in the reaction product of (b). A resin composition comprising a carboxylic acid compound. 2. A solder resist resin composition comprising the carboxylic acid compound having an unsaturated group according to claim 1. 3. A cured product of the resin composition according to claim 1 or 2.