JPH04348124A - Unsaturated group-containing polycarboxylic acid resin, resin composition, solder resist resin composition and cured product using the same - Google Patents

Abstract

PURPOSE:To obtain the subject polycarboxylic acid resin excellent in developability, etc., without any tack on the resist surface after predrying by reacting a reaction product between an epoxy resin of a phenolated polybutadiene and (meth)acrylic acid with a polybasic carboxylic acid (anhydride). CONSTITUTION:An unsaturated group-containing polycarboxylic acid resin is obtained by reacting (A) a reaction product between an epoxy resin of a phenolated polybutadiene and (meth)acrylic acid with (B) a polybasic carboxylic acid (anhydride) such as maleic acid or tetrachlorophthalic acid. The aforementioned resin is capable of providing cured films excellent in adhesion, electrical insulating properties, solder heat and chemical resistance. Furthermore, a resin composition is preferably a resin composition containing the above- mentioned unsaturated group-containing polycarboxylic acid resin.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an unsaturated group-containing polycarboxylic acid resin, which is useful as a solder resist resin composition for printed wiring boards containing the resin, and which has no tack on the resist surface after pre-drying. The present invention relates to a resin composition that has excellent developability and whose cured film has excellent adhesion, electrical insulation, solder heat resistance, and chemical resistance, and a cured product thereof.

0002

BACKGROUND OF THE INVENTION In recent years, ultraviolet curable compositions have been widely used in various fields for reasons such as resource saving, energy saving, improved workability, and improved productivity. 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 these, solder resist inks were the first to transition to ultraviolet curable compositions.

0003

[Problems to be Solved by the Invention] Screen printing methods have often been used to form resist patterns on printed wiring boards. Phenomena such as bleed, smearing, or sagging occur, making 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 dry film type photoresists do not eliminate air bubbles during thermocompression bonding. There are problems such as easy formation, concerns about heat resistance and adhesion, and high price. On the other hand, currently commercially available liquid resists include those that use organic solvents as developing solutions and those that are developed with dilute alkaline aqueous solutions, but those that use organic solvents have problems in addition to air pollution. However, the solvent is expensive, and the cured product also has problems in solvent resistance and acid resistance. In addition, for those that can be developed with a dilute alkaline aqueous solution, when the negative film is brought into contact with the resist-coated surface after pre-drying, and the negative film is peeled off after exposure, the resist may not peel off easily from the resist-coated surface, or the resist may stick to the negative film. However, there are cases where the negative film cannot be reused, which is a problem.

0004

[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventors have found that there is no tack on the resin composition coated surface after pre-drying, and after contacting with a negative film and exposing it to light. A resin useful as a solder resist resin composition whose negative film can be easily peeled off, which can be developed with an alkaline aqueous solution, and whose cured film has excellent adhesion, electrical insulation, soldering heat resistance, chemical resistance, etc. We have succeeded in providing a composition and a cured product thereof. That is, the present invention provides (1
) An unsaturated group-containing polycarboxylic acid resin which is a reaction product of a phenolated polybutadiene epoxy resin and (meth)acrylic acid and a polybasic carboxylic acid or its anhydride. (2) A resin composition, especially a solder composition, characterized by containing the unsaturated group-containing polycarboxylic acid resin described in (1) above.
The present invention relates to a resist resin composition and (3) a cured product of the resin composition described in (2) above.

The unsaturated group-containing polycarboxylic acid resin of the present invention can be obtained by reacting an epoxy resin of phenolated polybutadiene with (meth)acrylic acid, and then reacting a polybasic carboxylic acid or its anhydride. can be obtained by Phenolized polybutadiene is composed of polybutadiene (preferably average molecular weight is 500 to 2000) and O
It is an addition reaction product of phenols which may be substituted with an alkyl group such as -cresol, for example, P-LPB.
(OH value 340, softening point 170°C), P-700-30
0 (OH value 333, softening point 130°C) [all manufactured by Nippon Petrochemical Co., Ltd., trade name, addition reaction product of polybutadiene and O-cresol], etc.
Such commercial products can be used as raw materials. The reaction between phenolated polybutadiene and epihalohydrin such as epichlorohydrin for synthesizing an epoxy resin of phenolated polybutadiene can be carried out by a known method.

For example, phenolated polybutadiene and epihalohydrin in an excess molar amount relative to the hydroxyl equivalent of the phenolated polybutadiene are combined with a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, triethylammonium chloride, or The reaction is carried out in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. When a quaternary ammonium salt or the like is used, the reaction stops at the stage of the ring-opening addition reaction, so the alkali metal hydroxide is then added to carry out the ring-closing reaction. In addition, when the alkali metal hydroxide is added and reacted from the beginning, the ring-opening addition reaction and the ring-closing reaction are performed at once. The proportion of epihalohydrin used is generally 1 to 50 mol, preferably 3 to 15 mol, per 1 hydroxyl equivalent of the phenolated polybutadiene. The amount of alkali metal hydroxide used is usually 0.8 to 1.0 per hydroxyl equivalent of the phenolated polybutadiene.
5 mol, preferably in the range of 0.9 to 1.3 mol,
When using a quaternary ammonium salt, the amount used is:
Usually 0.001 to 1 mol, preferably 0.005 to 0.5 mol per hydroxyl equivalent of phenolated polybutadiene.
It is in the molar range. The reaction temperature is usually 30 to 130°C,
Preferably it is 40-120°C. Reaction time is usually 5
~30 hours. Furthermore, the reaction can be allowed to proceed while removing water produced in the reaction from the reaction system. After the reaction is completed, by-produced salts are removed by water washing, filtration, etc., and excess epihalohydrin is distilled off, thereby obtaining a phenolated polybutadiene epoxy resin.

In the reaction between the epoxy resin of phenolated polybutadiene and (meth)acrylic acid, the amount of (meth)acrylic acid is preferably about 0.8 to 1.5 chemical equivalents per chemical equivalent of the epoxy group of the epoxy resin. The reaction is carried out in equivalent ratios, particularly preferably about 0.9 to 1.1 chemical equivalents. During the reaction, solvents such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, solvent naphtha, or carbitol (meth)acrylate can be used as a diluent. , phenoxyethyl (meth)acrylate, pentaerythritol tetra(meth)
Acrylate, trimethylolpropane tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, dipentaerythritol
It is preferable to use reactive monomers such as polyhexa(meth)acrylate and polypentaerythritol poly(meth)acrylate. Further, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.) to promote the reaction, and the amount of the catalyst to be used is preferably determined based on the reaction raw material mixture. teeth,
It is 0.1 to 10% by weight, particularly preferably 0.3 to 5% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, phenothiazine, etc.), and the amount used is preferably 0.01 to 1 weight per weight of the reaction raw material mixture. %, particularly preferably 0.05 to 0.5% by weight. The reaction temperature is preferably 60 to 150°C, particularly preferably 80 to 150°C.
The temperature is 120°C. Further, the reaction time is preferably 5 to 60 hours, particularly preferably 10 to 50 hours.

Next, the obtained reaction product of the phenolated polybutadiene epoxy resin and (meth)acrylic acid is reacted with a polybasic carboxylic acid or its anhydride. Specific examples of polybasic carboxylic acids or their anhydrides include:
Examples include maleic acid, succinic acid, phthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyromellitic acid, and their anhydrides. It will be done.

The reaction between the reaction product of the epoxy resin of phenolated polybutadiene and (meth)acrylic acid and the polybasic carboxylic acid or its anhydride is the reaction between the epoxy resin of phenolated polybutadiene and (meth)acrylic acid. This is an esterification reaction between the hydroxyl group in the reaction product with the above acid or its anhydride. The reaction temperature is preferably 60 to 150°C, particularly preferably 80 to 120°C. The reaction time is preferably 1 to 30 hours, particularly preferably 5 to 20 hours. When carrying out this reaction, the reaction product obtained by reacting the epoxy resin of phenolated polybutadiene and (meth)acrylic acid as described above can be used as it is as a raw material for this esterification reaction. Acid value (mg) of esterification reaction product [unsaturated group-containing polycarboxylic acid resin]
KOH/g) is preferably in the range of 30 to 150 mgKOH/g. As is clear from the above synthesis method, the unsaturated group-containing polycarboxylic acid resin of the present invention has the following structural moieties pendantly attached to the basic skeleton of phenolated polybutadiene.

0010

(In the formula, R represents H or CH3, and X represents a residue of a polybasic carboxylic acid.) The resin composition or solder resist resin composition of the present invention (hereinafter collectively referred to as the "composition") The amount of the unsaturated group-containing polycarboxylic acid resin contained in the composition is preferably 10 to 90% by weight, particularly preferably 20 to 80% by weight. The composition of the present invention further includes epoxy resin compounds such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, tris(2,3-epoxypropyl) isocyanurate, etc. Epoxy (meth) which is a reaction product of epoxy compound and (meth)acrylic acid
Acrylates and/or the above-mentioned reactive monomers can be included. The amount used is 0 to 10 parts by weight per 100 parts by weight of the unsaturated group-containing polycarboxylic acid resin.
0 parts by weight is preferred. When using the above-mentioned epoxy compound, 1 epoxy resin curing agent (for example, dicyandiamide and its derivatives, imidazole compound, triazine compound, urea compound, aromatic amine, polyphenol compound, photocationic polymerization catalyst, etc.) It can be used as a species or as a mixture of two or more. When using an epoxy resin curing agent, the amount used is preferably 0.5 to 50 parts by weight per 100 parts by weight of the epoxy compound.

Methods for curing the composition of the present invention to obtain a cured product include curing methods using electron beams, ultraviolet rays, and heat, and it is preferable to cure with ultraviolet rays and, if necessary, with heat. When curing with ultraviolet light, a photoinitiator is used. As the photopolymerization initiator, any known photopolymerization initiator can be used, but it is desirable that the photopolymerization initiator has good storage stability after being blended. Examples of such photopolymerization initiators include benzoyl, benzyl, benzoin methyl ether, benzone insopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -phenylacetophenone 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[
4-(Methylthio)phenyl]-2-morpholino-propan-1-one, N,N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2- Amylanthraquinone, 2-
Aminoanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethylketanol, benzophenone, methylbenzophenone, 4,
Examples include 4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, and Michler's ketone. These can be used alone or in combination of two or more. Furthermore, such photopolymerization initiators include N,N-dimethylaminobenzoic acid ethyl ester,
N,N-dimethylaminobenzoic acid isoamyl ester,
Known and commonly used photosensitizers such as triethanolamine and triethylamine can be used alone or in combination with two or more.

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
-morpholino-propan-1-one (Ciba Geigy)
A combination of 2,4-diethylthioxanthone, 2,4-isopropylthioxanthone, and 2,4-diethylthioxanthone. The usage ratio of the photopolymerization initiator is 0 to 100 parts by weight of the unsaturated group-containing polycarboxylic acid resin as described above.
50 parts by weight is preferred, particularly preferably 4-35 parts by weight. The composition of the present invention further includes inorganic fillers such as talc, silica, alumina, barium sulfate, magnesium oxide, etc. and coloring pigments such as cyanine green,
Cyanine blue etc. can be added. Also, furthermore,
If necessary, melamine resins such as hexamethoxymelamine and hexabutoxymelamine, thixotropic agents such as Aerosil, leveling agents such as silicone, fluorine-based polymers, and aryl copolymers, antifoaming agents, ultraviolet rays, and absorbers. ,
Antioxidants, polymerization inhibitors, etc. can also be added. The composition of the present invention can be obtained by blending the ingredients preferably in the above-mentioned proportions and uniformly mixing them using a roll mill or the like.

[0014] The composition of the present invention is preferably one that is cured by ultraviolet rays and, if necessary, by heat to form a cured product. When curing by heat, the heating temperature is preferably 120 to 170°C, and the heating time is 30 minutes to 2 hours is sufficient. When the composition of the present invention is used as a solder resist resin composition, it is cured, for example, as follows to obtain a cured product. That is, the film of the present invention is coated on a printed wiring board with a film thickness of 10 to 100 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, or a curtain flow coating method. After applying the composition and drying the coating film at 60 to 80°C, a negative film is brought into direct contact with the coating film, then ultraviolet rays are irradiated, and 0.5 to 2% Na2CO3 aqueous solution or 0.5% Na2CO3 aqueous solution or 0.5%
After dissolving and removing the unirradiated parts of the coating film with a ~1% aqueous caustic soda solution or aqueous alkaline solution such as a caustic potash aqueous solution,
A cured film is obtained by heating and curing at 20 to 170°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, printing ink, coating agent, etc. The resin composition containing the novel unsaturated group-containing polycarboxylic acid resin of the present invention is excellent in developability, hardness of cured product, soldering heat resistance, acid resistance, alkali resistance, solvent resistance, insulation resistance, etc. ing.

[0015]

[Examples] The present invention will be specifically explained below using examples. Note that parts in the examples are parts by weight. Example 1 Phenolized polybutadiene (manufactured by Nippon Petrochemical Co., Ltd.,
P-LPB, OH equivalent 340, softening point 170°C) 340
After dissolving 1 part in 740 parts of epichlorohydrin, 60 parts of
87.5 parts of a 48% NaOH aqueous solution was added dropwise at 5 hours. During dropping, the reaction temperature was 60°C and the pressure was 100 to 150 mmH.
Under the conditions of g, produced water and water from the aqueous sodium hydroxide solution were continuously removed from the reaction system by azeotropy with epichlorohydrin, and epichlorohydrin was returned to the system. Next, after recovering excess unreacted epichlorohydrin under reduced pressure, 760 parts of methyl isobutyl ketone was added and uniformly dissolved, and further 13.4 parts of a 30% NaOH aqueous solution was added.
It was made to react at 70-75 degreeC for 1 hour. After the reaction is complete, 30 liters of water
After adding 0 parts and washing with water, oil and water were separated and methyl isobutyl ketone was distilled and recovered from the oil layer to obtain 390 parts of an epoxy resin having an epoxy equivalent of 448 and a softening point of 155°C. Next, 448 parts of the epoxy resin obtained above, 68 parts of acrylic acid, 0.3 parts of methylhydroquinone, and 3 parts of triphenylstibine were added.
．． 7 parts of carbitol acetate, 155 parts of carbitol acetate, and 66.8 parts of solvent naphtha were added thereto, and the mixture was heated to 95°C and reacted for 40 hours. Then tetrahydrophthalic anhydride 144
．． 4 parts, 153.5 parts of carbitol acetate, and 66.2 parts of solvent naphtha were charged and reacted at 90°C for 24 hours to obtain unsaturated group-containing polycarboxylic acid resin (A-1) 10
Obtained 93 copies. The acid value (in the components excluding the solvent) of the obtained product was 80 mgKOH/g, and the viscosity (25
℃, poise) 230.

Example 2 93.1 parts of maleic anhydride was used in place of tetrahydrophthalic anhydride in Example 1, and carbitol acetate was used in place of 93.1 parts of maleic anhydride.
153.5 parts to 130 parts, and 66.5 parts of solvent naphtha.
The reaction was carried out in the same manner as in Example 1, except that 2 parts were changed to 56.2 parts, and unsaturated group-containing polycarboxylic acid resin (A-2) 1
010 copies were obtained. The acid value (in the components excluding the solvent) of the obtained product was 89 mgKOH/g, and the viscosity (
25°C, poise) 190.

Example 3 The phenolated polybutadiene in Example 1 was changed to P-700-300 (OH equivalent: 333, softening point: 130°C) manufactured by Nippon Petrochemical Co., Ltd., and the amount used was increased to 333 parts. Except for the above, 380 parts of an epoxy resin having an epoxy equivalent of 476 and a softening point of 98.4° C. was obtained in the same manner as in Example 1. Next, 476 parts of the epoxy resin obtained above, 68 parts of acrylic acid, 0.3 parts of methylhydroquinone, 3.9 parts of triphenylstibine, 163 parts of carbitol acetate and 70 parts of solvent naphtha were added, and the temperature was raised to 95°C. The mixture was warmed and reacted for 40 hours. Next, 133.2 parts of phthalic anhydride, 153 parts of carbitol acetate, and 85 parts of solvent naphtha.
．． 5 parts were charged and reacted at 90°C for 24 hours to obtain 1128 parts of unsaturated group-containing polycarboxylic acid resin (A-3). Acid value of the obtained product (in components excluding solvent)
is 75mgKOH/g, viscosity (25℃, poise)
It was 200.

Example 4 476 parts of the epoxy resin obtained in Example 3, 8 parts of methacrylic acid
2.5 parts of methylhydroquinone, 0.3 parts of triphenylstibine, 167 parts of carbitol acetate, and 72 parts of solvent naphtha were added, and the mixture was heated to 95°C and reacted for 40 hours. Next, 146.3 parts of hexahydrophthalic anhydride, 162 parts of carbitol acetate, and 69 parts of solvent naphtha were charged and reacted at 90°C for 24 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-4) 11
Obtained 55 copies. The acid value (in the components excluding the solvent) of the obtained product was 75 mgKOH/g, and the viscosity (2
5°C, poise) 210.

Examples 5 to 8, Comparative Examples 1 to 2 Solder resist resin compositions (ink) according to the formulation shown in Table 1.
were blended and kneaded in a three-roll mill. Scree this
The coating was applied to the entire surface of the copper through-hole printed circuit board using the printing method so that the film thickness after drying was 15 to 25 μm. After pre-drying the coating film at 70°C for 15 minutes, the back surface was also coated in the same way. It was printed and pre-dried at 70°C for 25 minutes. Next, a solder mask pattern film was brought into contact with the coating surface, and a "solder mask pattern removability" test, which will be described later, was conducted. Next, the solder mask pattern film was brought into contact with the coated film surface, exposed to light at a light intensity of 500 mJ/cm2 using a metal halide lamp double-sided simultaneous exposure device (manufactured by Oak Corporation, HNW680), and 1.0 wt% carbonate sodium chloride was applied. - Spray the unirradiated areas of the coating film with an aqueous solution at a pressure of 2.5 kg/cm2 and a liquid temperature of 25
It was developed at ℃ for 60 seconds and dissolved and removed. The developability of the obtained product was evaluated as described below. after that,
Heat curing was performed at 150°C for 60 minutes in a hot air dryer, and the test pieces with the obtained cured film were tested for cured film hardness, soldering heat resistance, acid resistance, alkali resistance, solvent resistance, and insulation resistance as described below. I did this.

[0020] The results are shown in Table 2. Test method and evaluation method ``Solder mask pattern peelability'' After cooling for 10 minutes, the solder mask pattern was peeled off from the coating film and its condition was evaluated. ◎──No abnormality is observed when peeling○──
Items that make a slight crunching sound when peeling △ -- Items that make a noticeable crunching noise when peeling × -- Items that cause ink to adhere to the solder mask pattern when peeling

Developability Developability was visually judged using a magnifying glass. ○---Completely developed △---Thin areas that were not developed ×---Significant areas that were not developed Cured film hardness The hardness of the cured film was measured according to JIS K5400.

Soldering 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, and changes in appearance were evaluated. (Post-flux resistance) Dipping for 10 seconds was performed 10 times, and changes in appearance were evaluated. ○---No change in appearance △---Discoloration of cured film is observed ×---Lifting, peeling, and soldering of cured film Note) Post flux used: JS-64P (manufactured by Sanei Chemical Co., Ltd.) (Flux resistance for leveler) Dipping for 10 seconds was performed four times, and changes in appearance were evaluated. ○---No change in appearance △---Discoloration of cured film is observed ×---Lifting, peeling, and solder burrowing of cured film Note) Leveler flux used: SSF-832 (Sanei Chemical Co., Ltd.) made)

The acid resistance test piece was immersed in a 10 vol % sulfuric acid aqueous solution at 25° C. for 15 minutes, and changes in the appearance of the cured film were visually observed. Adhesion was determined by performing a peeling test on the solder pattern using cellophane tape to determine the peeling state of the resist. ○──No change in appearance, no peeling of cured film△──
There is no change in appearance, but there is slight peeling of the cured film×──
If lifting of the cured film is observed and peeling is large in the peeling test, the alkali-resistant test piece was placed in a 10 wt% sodium hydroxide aqueous solution at 25°C.
It was immersed for 15 minutes and evaluated by conducting a test similar to the acid resistance test.

[0024] Solvent resistance test pieces were immersed in dichloromethane at 25°C for 30 minutes, and changes in appearance were observed. ○---No change in appearance ×---Swelling and penetration Measure the initial insulation resistance using an insulation resistance test piece, and
- Insulation resistance such as moisture absorption and electric contact after 7 days was measured according to the SM-840B test method (IPC class III).

[0025]
Table 1
Example
Comparative example

5 6 7
8 1 2 Unsaturated group-containing polycarboxylic acid resin obtained in Example 1 (A-1)
116.7 76.
7 Unsaturated group-containing polycarboxylic acid resin obtained in Example 2 (A-2)
116.7 Unsaturated group-containing polycarboxylic acid resin obtained in Example 3 (A-3)
116.7 Unsaturated group-containing polycarboxylic acid resin obtained in Example 4 (A-4)
40
KAYARAD R-5027*(1)

116.7 R
-5089*(2)
116
．． 7 〃 R-2058*(
3) 20 20 20
20 20 20 TEPIC
-S*(4)
30
30 EPPN-201
*(5)
30KAYARAD DPHA*(6)
5 14 8 5
5 14 Carbitol acetate
10
24 10 Irgacure-907 *(7)
8 12 8 8
8 12 KAYACURE DETX*(
8) 2 3 2
2 2 3 Dicyandiamide (epoxy resin curing agent)
5 5
5 Phthalocyanine green (pigment) 2 2 2
2 2 2 KS-603(
Antifoaming agent) *(9) 2
2 2 2 2
2 Hexamethoxymelamine
10 10
10 talc
40 60
60 40 40 60

[0026]
Table 2
Example Comparative example
5 6 7 8
1 2 Solder mask pattern film Peelability ◎
◎ ◎ ◎ △
△ Developability ○
○ ○ ○
○ ○ Cured film hardness 8H
8H 8H 7H
8H 4H soldering heat resistance Post flux resistance ○ ○
○ ○ ○
○ Flux resistance for leveler ○
○ ○ ○ ○
○ Acid resistance ○
○ ○ ○
× × Alkali resistance ○
○ ○ ○ △
○ Solvent resistance ○
○ ○ ○
△ △ Insulation resistance (Ω) Initial value 1.5x
10142.0x10142.7x10141.0x1
0143.5x10132.6x1013 Value after test 3.3x10134.5x
10132.5x10133.6x10135.1x1
0124.3x1012

Note *(1) KAYARAD R-5027: Nippon Kayaku (
Co., Ltd., reaction product of phenol novolac type epoxy acrylate and dibasic acid anhydride, butyl cellosolve acetate
Product containing 40% by weight, acid value 68.5 (mgKOH/g)
*(2) KAYARAD R-5089: Nippon Kayaku (
Co., Ltd., reaction product of bisphenol A type epoxy acrylate and dibasic acid anhydride, product containing 40% by weight of carbitol acetate, acid value 63 (mgKOH/g) * (3) KA
YARAD R-2058: manufactured by Nippon Kayaku Co., Ltd., phenol novolac type epoxy acrylate, containing 30% by weight of butyl cellosolve acetate. *(4) TEPIC-S: manufactured by Nissan Chemical Co., Ltd., Tris (
2,3-epoxypropyl) isocyanurate, melting point 9
5-125℃

*(5) EPPN-201: Nippon Kayaku Co., Ltd., phenol novolac type epoxy resin, softening point 6
5℃ *(6) KAYARAD DPHA: Nippon Kayaku Co., Ltd.
manufactured by Dipentaerythritol polyacrylate * (
7) Irgacure-907: manufactured by Ciba Geigy, photopolymerization initiator * (8) KAYACURE DETX: manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator * (9) KS-603: Shin-Etsu Chemical Co., Ltd. antifoaming agent

[0029]

Effects of the Invention The resin composition of the present invention uses a novel unsaturated group-containing polycarboxylic acid resin, and allows selective exposure to ultraviolet light through a patterned film to develop unexposed areas. As a result, when forming a solder resist pattern, the patterned film has excellent peelability from the paint film, and has resistance to developer in the exposed area, and the resulting cured product has excellent adhesion and electrical properties. insulation,
It has excellent solder heat resistance, chemical resistance, etc., and is suitable as a solder resist resin composition.

Claims (4)

[Claims] 1. An unsaturated group-containing polycarboxylic acid resin which is a reaction product of a phenolated polybutadiene epoxy resin, (meth)acrylic acid, and a polybasic carboxylic acid or its anhydride. 2. A resin composition comprising the unsaturated group-containing polycarboxylic acid resin according to claim 1. 3. A solder resist resin composition comprising the unsaturated group-containing polycarboxylic acid resin according to claim 1. 4. A cured product of the resin composition according to claim 2 or 3. 0001