JPH05178950A - Resin composition, solder resist resin composition and cured products thereof - Google Patents

Abstract

PURPOSE:To obtain a resin composition desirable for a solder resist by incorporating an unsaturated polycarboxylic acid resin of a specified composition. CONSTITUTION:An epoxy resin of the formula (wherein R1 and R2 are each a residue derived from a compound containing two or more phenolic hydroxyl groups; Z1 and Z2 are each 0, 1 or greater; M is glycidyl or hydrogen; and n is 1 or greater) is reacted with a (meth)acrylic acid in the presence of a catalyst (e.g. triethylamine) desirably in a diluent (e.g. methyl ethyl ketone). The obtained reaction product is reacted with a polybasic carboxylic acid or its anhydride (e.g. maleic anhydride) to produce an unsaturated polycarboxylic acid resin. This resin is used as an essential component to produce a solder resist resin composition.

Description

Detailed Description of the Invention

[0001]

The present invention is useful as a solder resist resin composition for printed wiring boards containing an unsaturated group-containing polycarboxylic acid resin and has excellent developability, and its cured film has excellent adhesion, solder heat resistance and resistance. The present invention relates to a resin composition excellent in chemical resistance, gold plating resistance, and electric insulation and a cured product thereof.

[0002]

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

[0003]

Although a screen printing method has been widely used as a method for forming a resist pattern on a printed wiring board, when such a screen printing method is used, in many cases, bleeding, bleeding, or bleeding during printing, or Causes a phenomenon such as sagging, which makes it impossible to cope with the recent increase in the density of 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 concern about heat resistance and adhesion, and it is expensive. On the other hand, currently available liquid resists are
There are those that use organic solvents as developers and those that develop with dilute aqueous alkali solutions. However, those that use organic solvents are not only a problem of air pollution, but also expensive solvents and solvent resistance of cured products. There is also a problem with acid resistance. Further, those developable with a dilute alkaline aqueous solution have problems such as whitening of the surface after solder heat resistance test with an aqueous flux of a cured product of a resist and insufficient gold plating resistance.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors of the present invention have shown that it is possible to develop with a dilute aqueous alkaline solution, the adhesion of the cured film, the solder heat resistance and the chemical resistance. The present invention succeeded in providing a resin composition which is excellent in properties and gold plating resistance and which is not particularly whitened after the solder heat resistance test with an aqueous flux and is particularly useful as a solder resist resin composition, and a cured product thereof.

That is, the present invention is as follows:

[0006]

[Chemical 2]

(In the formula, R ₁ and R ₂ are the same or different and each represents a residue in which a hydroxyl group of a compound having two or more phenolic hydroxyl groups is removed. Z ₁ and Z ₂ are the same or different and 0 or 1 The above integers are given, 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 glycidyl. Group, and when n is 2 or more, M is at least one is a glycidyl group.) Reaction of an epoxy resin represented by (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.

[2] A solder resist resin composition comprising the unsaturated group-containing polycarboxylic acid resin described in [1]. 3. A cured product of the resin composition according to item 1 or 2. It is about. Specific examples of the epoxy resin represented by the formula (1) used in the present invention include the formula (1)
Wherein R ₁ and R _{2 in the} above represent a residue in which a hydroxyl group of a compound having three or more phenolic hydroxyl groups is removed,

[0009]

[Chemical 3]

[0010]

[Chemical 4]

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[0020]

[Chemical 14]

(In the formula, P represents 0 or an integer of 1 or more.) R ₁ and R ₂ represent a residue in which a hydroxyl group of a compound having two phenolic hydroxyl groups is removed.

[0022]

[Chemical 15]

[0023]

[Chemical 16]

[0024]

[Chemical 17]

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[Chemical 18]

[0026]

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[0029]

[Chemical formula 22]

[0030]

[Chemical formula 23]

[0031]

[Chemical formula 24]

[0032]

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[0033]

[Chemical formula 26]

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[Chemical 27]

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[Chemical Formula 39]

[0047]

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[0050]

[Chemical 43]

[0051]

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[0061]

[Chemical 54]

Examples thereof include, but are not limited to: R ₁ and R ₂ in the formula (1) may include different ones. The epoxy resin of the formula (1) can be obtained, for example, by the formula (2)

[0063]

[Chemical 55]

(Wherein R ₁ , R ₂ and Z ₁ , Z ₂ and n
Represents the same meaning as in formula (1). It can be obtained by reacting the alcoholic hydroxyl group of the compound represented by (4) 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 compounds and ether compounds may be used in combination as the solvent. Unless dimethylsulfoxide or a quaternary ammonium salt is used, the reaction does not proceed sufficiently and a large amount of alkali metal hydroxide remains, which causes polymerization and makes it difficult to produce the epoxy resin of the present invention.

The amount of dimethyl sulfoxide used is determined by the formula (2)
It is preferably 5% by weight to 300% by weight with respect to the epoxy resin represented by. If it 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 reaction time is required. Not preferable.
300% by weight with respect to the epoxy resin represented by the formula (2)
If it exceeds, the effect of increasing the amount is almost eliminated, but the volume efficiency is deteriorated, which is not preferable.

Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride and the like. The amount used is 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 relative to 1 equivalent of hydroxyl group, the reaction between the alcoholic hydroxyl group of the epoxy resin represented by the formula (2) and epichlorohydrin is delayed, and a long-time reaction is required, which is not preferable. If the amount exceeds 50 g per 1 equivalent of hydroxyl groups, the effect of increasing the amount will be almost eliminated, but the cost will increase, which is not preferable.

The amount of epichlorohydrin used may be equivalent to or more than 1 equivalent of the alcoholic hydroxyl group to be epoxidized in the epoxy resin represented by the formula (2). However, if the amount exceeds 30 times the equivalent of the hydroxyl group, the effect of increasing the amount will almost disappear, and the volume efficiency will deteriorate, 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 preferred. The amount of the alkali metal hydroxide used may be approximately equivalent to 1 equivalent of the alcoholic hydroxyl group to be epoxidized in the epoxy resin represented by the formula (2). When all the alcoholic hydroxyl groups of the epoxy resin represented by the formula (2) are to be epoxidized, they may be used in excess, but if the amount exceeds 2 equivalents to 1 equivalent of the alcoholic hydroxyl groups, the polymer is slightly polymerized. Tends to happen. The alkali metal hydroxide may be solid or aqueous solution. When an aqueous solution is used, the reaction can be carried out during the reaction while distilling the water in the reaction system out of the reaction system under normal pressure or reduced pressure.

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

After completion of the reaction, excess epichlorohydrin and dimethylsulfoxide are distilled off under reduced pressure, and then the resin is dissolved in an organic solvent to carry out a dehydrohalogenation reaction with an alkali metal hydroxide. On the other hand, after completion of the reaction, the product is washed with water to separate the by-product salt and dimethylsulfoxide or quaternary ammonium salt, and the excess epichlorohydrin is distilled off from the oil layer under reduced pressure. The dehydrohalogenation reaction may be carried out. As the organic solvent, methyl isobutyl ketone, benzene, toluene, xylene, etc. 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 the reaction product (epoxy (meth) acrylate) of the epoxy resin and (meth) acrylic acid produced by the above method. It can be obtained by reacting.

In the reaction of the epoxy resin with the (meth) acrylic acid, the (meth) acrylic acid is reacted in a ratio of preferably about 0.8 to 1.5 equivalents relative to 1 equivalent of the epoxy groups 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, 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.) to accelerate the reaction, and the amount of the catalyst used is preferably based on the reaction raw material mixture. 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, metoquinone, hydroquinone, phenothiazine, etc.),
The amount used is preferably 0.0 with respect to the reaction raw material mixture.
1 to 1% by weight, particularly preferably 0.05 to 0.5% by weight
Is. The reaction temperature is preferably 60 to 150 ° C, particularly preferably 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 the above-mentioned epoxy (meth) acrylate and polybasic carboxylic acid or its anhydride (for example, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, head). It can be obtained by reacting with an acid or the like and an anhydride of these acids (esterification reaction of hydroxyl group in epoxy (meth) acrylate). In the reaction, the acid or the anhydride thereof, preferably 0.05 to 1.00 equivalent, is reacted with 1 equivalent of the hydroxyl group with respect to the hydroxyl group in the epoxy (meth) acrylate. The reaction temperature is 60 to 150 ° C, particularly preferably 80 to 100 ° C. The acid value (mgKOH / g) of the unsaturated group-containing polycarboxylic acid resin is preferably 30 to 150,
It is particularly preferably 50 to 120.

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

The composition of the present invention further comprises epoxy compounds such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, tris (2,3-epoxypropyl) isocyanurate, and these epoxy compounds. Epoxy (meth) acrylates which are a reaction product of (meth) acrylic acid and / or the above-mentioned reactive simple substances can be contained. The amount of these used is preferably 0 to 100 parts by weight with respect to 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 its derivative, an imidazole compound, a triazine compound, a urea compound,
Aromatic amines, polyphenol compounds, cationic photopolymerization catalysts, etc.) 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 the method for curing the composition of the present invention to obtain a cured product, there are curing methods by electron beam, ultraviolet ray and heat, but it is preferable to cure by ultraviolet ray and, if necessary, heat. A photopolymerization initiator is used in the case of curing with ultraviolet rays. As the photopolymerization initiator, any known photopolymerization initiator can be used, but one having good storage stability after blending is desirable. Examples of such a photopolymerization initiator include benzoin, benzyl, benzoisomethyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 , 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl 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
Examples include ′ -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-dimethylamine benzoic acid ethyl ester, N, N-
Known and commonly used photosensitizers such as dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine can be used alone or in combination with two or more kinds.

A preferred combination is 2,4-diethylthioxanthone or 2-isopropylthioxanthone and N, N.
-Combination with dimethylaminobenzoic acid ethyl ester,
2-Methyl-1- [4- (methylthio) phenyl] -2
A combination of -morpholinopropan-1-one (Irgacure 907 manufactured by Ciba-Geigy) and 2,4-dimethylthioxanthone or 2-isopropylthioxanthone. The proportion of the photopolymerization initiator used is preferably 0 to 50 parts by weight, and 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 inorganic fillers such as talc, silica, alumina, barium sulfate, magnesium oxide and the like, and cyanine green, cyanine blue and the like as color pigments. Further, if necessary, hexamethoxymelamine, melamine resin such as hexabutoxymelamine, thixotropic agent such as Aerosil, silicone, fluorine-based polymer, leveling agent such as acrylic copolymer, defoaming agent, ultraviolet ray, absorber, An antioxidant, a polymerization inhibitor, etc. can also be added.

The composition of the present invention is obtained by blending the blending components preferably in the above proportions and uniformly mixing them with a roll mill or the like. The cured product of the composition of the present invention can be obtained by curing the composition in the following manner. That is, it can be cured with ultraviolet rays and, if necessary, with heat to obtain a cured product. When curing with heat, the heating temperature is 1
20 to 170 ° C. is preferable, and the heating time is preferably 30 minutes to 2 hours. When the composition of the present invention is used as a solder resist resin composition, for example, it is cured as follows,
Obtain a cured product. That is, the resin composition of the present invention is applied to a printed wiring board 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 or the like to form a coating film. 60-80 ° C
After drying with, contact the negative film directly with the coating film,
Next, after irradiating with ultraviolet rays, the unirradiated portion of the coating film is dissolved and removed with an alkaline aqueous solution such as a 0.5 to 2% sodium carbonate aqueous solution, a 0.5 to 1% caustic soda aqueous solution or a caustic potash aqueous solution, and then 120 to 170 A cured film can be obtained by heat 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 or a coating agent. 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, and the like, and solder heat resistance in an aqueous flux. Little whitening of the surface after the sexuality test.

[0080]

EXAMPLES The present invention will be described in more detail below with reference to examples. In addition, the part in a synthesis example and an Example is a weight part. (Synthesis Example of Epoxy Resin) Synthesis Example 1 R ₁ and R ₂ in Formula (2) are

[0081]

[Chemical 56]

In the polyglycidyl ether of tris (hydroxyphenyl) methane, the average value of n in formula (2) is 0.78, the epoxy equivalent is 205, the content of hydrolyzable chlorine is 0.071%, and the softening point is 71. After dissolving 199 parts of an epoxy resin (epoxy resin (e)) having a melt viscosity of 3.6 poises at 0 ° C. in 370 parts of epichlorohydrin, 6 parts of tetramethylammonium chloride was added at 70 ° C. with stirring, and then, 48% NaOH 30
Parts were added dropwise over 100 minutes. 3 more at 70 ℃ after dropping
A time reaction was performed. After the reaction was completed, 200 parts of water was added and the mixture was washed with water. After oil-water separation, most of the epichlorohydrin was distilled off from the oil layer under reduced pressure, and then methyl isobutyl ketone 45
Dissolve it in 0 parts, add 5 parts of 30% NaOH, and add 70 parts.
The reaction was carried out at 0 ° C for 1 hour. After the reaction was completed, the product 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 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 0.78 alcoholic hydroxyl groups in the formula (2) are epoxidized.

Synthesis Example 2 199 parts of the epoxy resin (e) used in Synthesis Example 1 was replaced with 370 parts of epichlorohydrin and 185% of dimethyl sulfoxide.
Parts, and then stirred at 70 ° C. with 98.5% NaOH.
10.6 parts was added over 100 minutes. 7 more after addition
The reaction was carried out at 0 ° C for 3 hours. Then, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was 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 reaction was completed, the product 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.
07%, softening point 71.0 ° C, melt viscosity (150 ° C) 3.
197 parts of 5-poise epoxy resin (b) was obtained. When the obtained epoxy resin (b) is calculated from the epoxy equivalent, about 0.52 of 0.78 alcoholic hydroxyl groups in the formula (2) are epoxidized.

Synthesis Example 3 R ₁ and R ₂ in the formula (2) are

[0085]

[Chemical 57]

In the epoxy resin which is, the average value of n in the formula (2) is 1.46, the epoxy equivalent is 308, the content of hydrolyzable chlorine is 0.107%, the softening point is 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 poises was used. 82.0 ° C, melt viscosity (150
C.) 187 parts of an epoxy resin (c) having a poise of 11.0 was obtained. The obtained epoxy resin (c) has an alcoholic hydroxyl group of 1.46 when calculated from the epoxy equivalent in the formula (2).
Most of the pieces are epoxidized.

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

[0088]

[Chemical 58]

In the cresol novolac epoxy resin of the formula (p is 0 or an integer of 1 or more), the average value of n in the formula (2) is 0.38, and 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
Epoxy equivalent 19 in the same manner as in Synthesis Example 2 except that 240 parts of 0.5 poise of epoxy resin (g) was used.
0, hydrolyzable chlorine content 0.034%, softening point 43.
241 parts of an epoxy resin (d) having a melt viscosity (150 ° C.) of 0.5 poise and a temperature of 5 ° C. were obtained. Obtained epoxy resin (d)
When calculated from the epoxy equivalent, about 0.33 of 0.38 alcoholic hydroxyl groups in the formula (2) are epoxidized.

(Synthesis Example of Polycarboxylic Acid Resin Containing Unsaturated Group) Synthesis Example 5 189 parts of the epoxy resin (a) obtained in Synthesis Example 1, 68.5 parts of acrylic acid, 0.5 part of methquinone, triphenylphosphine 1.4 parts and 139 parts of carbitol acetate were charged, the temperature was raised to 95 ° C, the reaction was carried out at 95 ° C, and when the acid value (mgKOH / g) of the reaction solution became 1.0 or less (about 35 hours). Cool to 60 ° C., then 101.3 parts tetrahydrophthalic anhydride and 54. carbitol acetate.
Charge 5 parts, raise the temperature to 90 ° C., and carry out the reaction until the acid value becomes 104 (solid content acid value (mgKOH / g excluding solvent) and unsaturated group-containing polycarboxylic acid resin (Product A) The viscosity of product A (25 ° C., poise) 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 is raised to 95 ° C, the reaction is carried out at 95 ° C, and when the acid value (mgKOH / g) of the reaction solution becomes 1.0 or less (about 35 hours), it is cooled to 60 ° C, and then 70 parts of maleic anhydride and 38 parts of carbitol acetate was charged, the temperature was raised to 90 ° C., and the reaction was carried out until the acid value became 120 (solid type acid value excluding the solvent) to give an unsaturated group-containing polycarboxylic acid resin (Product B). Obtained. Viscosity of product B (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., the reaction was carried out at 95 ° C., and when the acid value (mgKOH / g) of the reaction solution became 1.0 or less (about 35 hours), it was cooled to 60 ° C., and then phthalic anhydride 103.
Charge 6 parts and 55.8 parts carbitol acetate,
The temperature was raised to 90 ° C., and the reaction was carried out until the acid value reached 110 (solid type acid value excluding the solvent) to obtain an unsaturated group-containing polycarboxylic acid resin (Product C). Viscosity of product C (25 ° C,
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 methoquinone, 1.5 parts of triphenylphosphine and 14 parts of carbitol acetate.
Charge 6.2 parts, raise the temperature to 95 ° C, carry out the reaction at 95 ° C, and the acid value (mgKOH / g) of the reaction solution is 1.0 or less (about 35 hours)
When cooled to 60 ° C, 121.6 parts of hexahydrophthalic anhydride and 6 parts of carbitol acetate are added.
After charging 5.5 parts, the temperature was raised to 90 ° C and the acid value was 114.
The reaction was carried out until (solid acid value excluding solvent), and an unsaturated group-containing polycarboxylic acid resin (Product D) was obtained. The viscosity of product D (25 ° C., poise) was 230 poise.

Examples 1 to 4 and Comparative Examples 1 and 2 The solder resist resin composition (ink) was blended according to the blending composition (numerical values are parts by weight) shown in Table 1 and kneaded with a three-roll mill. By screen printing this
The entire surface is coated on a copper through-hole printed wiring board so that the film thickness after drying is 15 to 25 μm, and the coating film is 70 ° C.
After predrying for 15 minutes, apply the back surface in the same manner,
Pre-dried at 25 ° C for 25 minutes. Next, a solder mask pattern film is brought into contact with the surface of the coating film, and exposed at a light amount of 500 mJ / cm ² using a metal halide lamp double-sided simultaneous exposure device (HMW680 manufactured by Oak Co.) and coated with a 1.0 wt% sodium carbonate aqueous solution. Spray pressure 2.5kg on the unirradiated part of the membrane
Development was carried out for 60 seconds at a liquid temperature of 25 ° C./cm ² , and the solution was removed by dissolution. The (developability) of the obtained product was evaluated as described below. Then, the test piece having a cured film obtained by heat-curing at 150 ° C. for 60 minutes with a hot-air dryer is as described below (cured film hardness), (solder heat resistance), (whitening resistance), (acid resistance). Property), (alkali resistance), (solvent resistance),
(Gold resistance) and (insulation resistance) tests were conducted.

The results are shown in Table 2. The test method and evaluation method are as follows. (Developability) The developability was visually evaluated with a magnifying glass. ○: Completely developed △: Thinly undeveloped part ×: Very undeveloped part (hardened film hardness) The hardness of the hardened film is JISK5400 It measured according to it. (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 10 times or 4 times to evaluate the change in appearance. (Post-flux resistance) Dipping was performed 10 times for 10 seconds to evaluate the change in appearance. ○ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ ・ Floating, peeling, and solder dip in the cured film Note) Post flux used: JS-64P (Manufactured by Yamaei Chemical Co., Ltd.) (Flux resistance for levelers) Dipped for 10 seconds 4 times to evaluate changes in appearance. ○: No change in appearance △: Discoloration of cured film is observed ×: Floating, peeling, or solder subside of cured film Note) Used flux for leveler: SSF- 832
(Manufactured by Sanei 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 the change in appearance. ○ ・ ・ ・ No change in appearance △ ・ ・ ・ ・ ・ Slight whitening is observed × ・ ・ ・ ・ ・ Whitening is observed on the entire surface (acid resistance) The test piece is immersed in a 10 vol% sulfuric acid aqueous solution at 25 ° C. for 15 After dipping for a minute, the appearance of the cured film was visually changed. Regarding 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, slight peeling of cured film ×: Lifting of cured film The peeling test showed a large amount of peeling (alkali resistance). The test piece was immersed in a 10 wt% sodium hydroxide aqueous solution at 25 ° C. for 15 minutes, and the same test as the acid resistance test was conducted for evaluation.

(Solvent resistance) A test piece was put in dichloromethane.
It was immersed at 5 ° C. for 30 minutes, and the change in appearance was observed. ○ ・ ・ ・ No change in appearance △ ・ ・ ・ Swelling and permeation (Gold plating resistance) Autolex C manufactured by Celllex
I (plating liquid) is used, and the current density of 1 A / dm ² is 3
After performing gold plating for 0 minutes, a peeling test of the coating film was performed with a cellophane tape. The judgment criteria are as follows. ○: No peeling at all △: Very slight peeling ×: Peeling on the entire surface (Insulation resistance) Measure the initial insulation resistance using a test piece In addition, according to the test method of IPC-SM-840B (IPC class III), moisture absorption after 7 days and insulation resistance after electrolytic corrosion were measured.

Table 1 Actual 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 KAYARAD 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 * 8 3 2 2 2 2 3 Dicyandiamide 5 5 5 5 (Epoxy resin curing agent) 2-Ethyl-4-methylimidazole 2 2 2 2 (Epoxy resin curing agent) Phthalocyanine green (Pigment) 2 2 2 2 2 2 KS-603 (antifoaming agent) 2 2 2 2 2 2 Hexamethoxymelamine 10 10 Tarks 60 60 40 60 40 60

Note * 1 KAYARAD R-5027: Nippon Kayaku Co., Ltd.
Made of phenol novolac type epoxy acrylate and dibasic acid anhydride reaction product, butyl cellosolve acetate 4
Product containing 0% by weight, acid value 68.5 (mgKOH / g) * 2 KAYARAD R-5089: Nippon Kayaku Co., Ltd.
Made of bisphenol A type epoxy acrylate and dibasic acid anhydride reaction product, carbitol acetate 40% by weight
Contained products, acid value 63 (mgKOH / g) * 3 KAYARAD R-2058: Nippon Kayaku Co., Ltd.
Made of phenol novolac type epoxy acrylate, containing 30% by weight of butyl cellosolve acetate. * 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 novolac type epoxy resin, Softening point 65 ° C * 6 KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.
Dipentaerythritol, polyacrylate * 7 Irgacure 907: Ciba Geigy, photopolymerization initiator * 8 KAYACURE DETX: Nippon Kayaku Co., Ltd.
Photopolymerization initiator * 9 KS-603: Shin-Etsu Chemical Co., Ltd., defoamer

Table 2 Actual Example Comparative Example 1 2 3 4 1 2 Image quality ○ ○ ○ ○ ○ ○ Hardened product hardness 8H 8H 7H 8H 8H 4H Solder heat resistance Post flux resistance ○ ○ ○ ○ ○ ○ Flux resistance for levelers ○ ○ ○ ○ ○ ○ 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 From the evaluation results in Table 2, a cured product of the resin composition of the present invention Is
It is clear that it has excellent hardness, whitening resistance, acid resistance, alkali resistance, solvent resistance, and gold plating resistance.

[0101]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is resistant to a developer in an exposed portion in the formation of a solder resist pattern by developing an unexposed portion selectively exposed to ultraviolet rays through a patterned film. The resulting cured product has excellent 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. ⁵ Identification code Internal reference number FI Technical display location G03F 7/038 501 503 H05K 3/28 C 7511-4E

Claims (3)

[Claims] 1. A formula (1): (In the formula, R ₁ and R ₂ are the same or different and represent a residue in which a hydroxyl group of a compound having two or more phenolic hydroxyl groups is removed. Z ₁ and Z ₂ are the same or different and are an integer of 0 or 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
Indicates the above integer. 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. And an unsaturated group-containing polycarboxylic acid resin which is a reaction product of a polybasic carboxylic acid or an anhydride thereof with a reaction product of an epoxy resin and (meth) acrylic acid represented by .. 2. A solder resist resin composition comprising the unsaturated group-containing polycarboxylic acid resin according to claim 1. 3. A cured product of the resin composition according to claim 1 or 2.