JP3534527B2 - Epoxy acrylate resin and its use - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy acrylate resin, a curable resin composition containing the resin, and a cured product thereof. The resin can be used as a solder resist composition, an insulating paint, an adhesive, a printing ink, a coating agent and the like, and is particularly useful as a solder resist composition.

[0002]

2. Description of the Related Art UV curable resins are the resins that most meet the demands of the times such as low pollution, resource saving, high performance, and added functionality. Among these, epoxy acrylate resin It has attracted attention because it has various advantages such as chemical resistance, high heat resistance, high hardness, and high adhesiveness. In the printed wiring board processing field, various inks such as solder resist inks and marking inks are shifting from thermosetting resins to UV curable resins. Among them, solder resist inks are among the fastest to become UV curable resins. And moved. A screen printing method is often used as a method for forming a resist pattern on a printed wiring board. However, when this method is used, the accuracy of the obtained resist pattern decreases due to phenomena such as bleeding, bleeding, and sagging during printing. However, it has become impossible to cope with the recent increase in the density of printed wiring boards.

In order to solve these problems, dry film type photoresists and liquid-developable resist inks have been proposed. However, in the case of a dry film type photoresist, bubbles are easily generated during thermocompression bonding, and there are problems in heat resistance and adhesion. Further, when a liquid resist is used, an organic solvent or a dilute alkaline aqueous solution is used as a developing solution. When an organic solvent is used, the solvent resistance and acid resistance of the cured product remain uncertain, and air pollution. Such problems may occur. On the other hand, in a resin composition of a type developed with a dilute alkaline aqueous solution, for example, a phenol novolac type epoxy acrylate resin or a bisphenol A epoxy acrylate resin, or a reaction product of these epoxy acrylate resin and a divalent acid anhydride is known. (For example, JP-A-61-1
243869, Japanese Patent Publication No. 56-40329, etc.). However, when these known epoxy acrylate resins or acid modified products thereof are used, for example, as a resin composition for a solder resist, the hardness, moisture resistance, heat resistance, chemical resistance, gold plating resistance of the obtained cured film, In addition to insufficient electrolytic corrosion resistance, the unirradiated portion has insufficient solubility in a dilute alkaline aqueous solution (hereinafter referred to as developability).

[0004]

The object of the present invention is to solve the above-mentioned problems and to provide a cured film having excellent hardness, moisture resistance, heat resistance, chemical resistance, gold plating resistance, electrolytic corrosion resistance, and the like.
And to provide a resin and a curable resin composition having excellent developability.

[0005]

The present inventors have arrived at the present invention as a result of extensive studies on the above problems. That is, the present invention relates to an epoxy acrylate resin represented by the general formula (1) (chemical formula 3), and is selected from an epoxy resin represented by the general formula (2) (chemical formula 4) and acrylic acid and methacrylic acid. It relates to an epoxy acrylate resin obtained from at least one kind.

[0006]

[Chemical 3] (In the formula, R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an alkoxy group which may have a substituent, a nitro group or a halogen atom, and R 1 ₂ represents a hydrogen atom or a methyl group, and m is 1 to 3.
Represents an integer, and n represents an integer of 0 to 10).

[0007]

[Chemical 4] (In the formula, R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an alkoxy group which may have a substituent, a nitro group or a halogen atom, and m Represents an integer of 1 to 3, and n represents an integer of 0 to 10)

Furthermore, the present invention further comprises an epoxy acrylate resin obtained from the epoxy resin represented by the general formula (2) and at least one selected from acrylic acid and methacrylic acid, and a carboxylic acid or an anhydride thereof. The present invention relates to an acid-modified epoxy acrylate resin obtained by reaction. The present invention also relates to a curable resin composition containing the epoxy acrylate resin or the acid-modified epoxy acrylate resin, a solder resist composition, and a cured product obtained by curing these compositions.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the compound represented by the general formula (1) or (2),
R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an alkoxy group which may have a substituent, a nitro group or a halogen atom, and preferably a hydrogen atom A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, a nitro group or a halogen atom. Represent Among these, R ₁
Is more preferably a hydrogen atom, an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, an unsubstituted linear or branched alkoxy group having 1 to 10 carbon atoms, or a chlorine atom. Is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
It is an isobutyl group, a tert-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group or a chlorine atom. Particularly preferably, R ₁ is a hydrogen atom or a methyl group.

Specific examples of R ₁ include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group,
4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclohexylmethyl group, cyclohexylethyl group, tetrahydrofurfuryl group, 2
-Methoxyethyl group, 2-ethoxyethyl group, 2-n-
Butoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-
n-butoxypropyl group, 3-n-hexyloxypropyl group, 2-methoxyethoxyethyl group, 2-ethoxyethoxyethyl group, 2-phenoxymethyl group, 2-phenoxyethoxyethyl group, chloromethyl group, 2-chloroethyl group , 3-chloropropyl group, 2,2,2-trichloroethyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group , N
-Hexyloxy group, 2-ethylhexyloxy group, n
-Octyloxy group, n-decyloxy group, n-dodecyloxy group, n-tetradecyloxy group, n-octadecyloxy group, cyclopentyloxy group, cyclohexyloxy group, 4-tert-butylcyclohexyloxy group, cycloheptyloxy group , Cyclooctyloxy group, cyclohexylmethyloxy group, cyclohexylethyloxy group, 2-methoxyethyloxy group, 2-ethoxyethyloxy group, 2-n-butoxyethyloxy group, 3-methoxypropyloxy group, 3-ethoxypropyl An oxy group, a 3-n-propoxypropyloxy group,
3-n-butoxypropyloxy group, 3-n-hexyloxypropyloxy group, 2-methoxyethoxyethyloxy group, 2-phenoxymethyloxy group, 2-phenoxyethoxyethyloxy group, chloromethyloxy group,
Examples thereof include 2-chloroethyloxy group, 3-chloropropyloxy group, 2,2,2-trichloroethyloxy group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. In the general formula (1), R ₂ represents a hydrogen atom or a methyl group. Moreover, in General formula (1) or General formula (2), m is an integer of 1-3, n represents the integer of 0-10.

The epoxy acrylate resin represented by the general formula (1) is preferably prepared according to a method known per se, for example, a method described in JP-B-44-31472 and JP-B-45-1465. Manufactured. That is, typically, it can be produced, for example, by reacting an epoxy resin represented by the general formula (2) with acrylic acid, methacrylic acid, or a mixture of both. The epoxy resin represented by the general formula (2) is disclosed in, for example, JP-A-63 / 1988.
It is manufactured by the method described in JP-A-150270. That is, 6,6'-dihydroxy-3,3,3 ', 3'
-Tetramethyl-1,1'-spirobiindane and epihalohydrin can be produced by a method of reacting them in the presence of a dehydrohalogenating agent. When the epoxy acrylate resin represented by the general formula (1) of the present invention is produced, the amount of acrylic acid, methacrylic acid or a mixture of both of them is not particularly limited with respect to the epoxy resin represented by the general formula (2). Although not limited thereto, preferably, 0.1 to 1 chemical equivalent of the epoxy group of the epoxy resin composition is 0.1 to 0.1% of acrylic acid, methacrylic acid or a mixture of both.
It is 5 chemical equivalents, and preferably 0.3 to 3 chemical equivalents.

It is preferable to add a diluent during the reaction. Examples of the diluent include butyl cellosolve acetate, ethyl cellosolve acetate, methyl ethyl ketone, carbitol acetate, isopropyl cellosolve acetate, diethylene glycol dimethyl ether, solvent naphtha and the like. Organic solvent or styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate , Tris (hydroxyethyl) isocyanurate tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Further, it is preferable to use a catalyst for the purpose of promoting the reaction. Specific examples of preferred catalysts include:
For example, triethylamine, benzyldimethylamine,
N, N-dimethylbenzylamine, dimethylaniline,
Examples thereof include methyltriethylammonium chloride, triethylbenzylammonium chloride, benzyltrimethylammonium hydroxide, triphenylstibine, triphenylphosphine, potassium hydroxide and the like. The amount of the catalyst used is preferably 0.1 to 10% by weight, more preferably 0.3, based on the reaction raw material mixture.
~ 5% by weight. It is also preferable to use a polymerization inhibitor in order to prevent polymerization during the reaction.
Examples of preferable polymerization inhibitors include metoquinone, hydroquinone, phenothiazine and the like. At this time, the amount of the polymerization inhibitor used is based on the raw material mixture.
Preferably 0.01-3%, more preferably 0.0
5 to 1%.

Although the reaction temperature varies depending on the catalyst, the reaction between the epoxy resin represented by the general formula (2) and acrylic acid or methacrylic acid proceeds, and the raw materials, reaction intermediates and products are thermally polymerized. A temperature that does not occur is preferable, more preferably 60 ° C to 150 ° C, particularly 80 ° C to 1
A reaction temperature of 30 ° C. is preferred. The reaction time depends on the reaction temperature, but it is preferably 2 to 80 hours, more preferably 3 to 50 hours. After completion of the reaction, excess (meth) acrylic acid, diluent and the like may be removed by a method such as distillation, or these may be used without removal.

Next, the acid-modified epoxy acrylate resin of the present invention will be described. The acid-modified epoxy acrylate resin of the present invention is a carboxylic acid or its anhydride obtained by using the epoxy acrylate resin obtained from the epoxy resin represented by the general formula (2) and at least one selected from acrylic acid and methacrylic acid. It is produced by reacting with. The carboxylic acid is a monovalent or polyvalent carboxylic acid, preferably a monovalent or polyvalent aliphatic carboxylic acid, or a monovalent or polyvalent aromatic carboxylic acid, more preferably a monovalent or divalent carboxylic acid. It is a valent aliphatic carboxylic acid or a monovalent or divalent aromatic carboxylic acid.

As the carboxylic acid or its anhydride,
For example, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, myristylic acid, cyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, methoxyacetic acid, phenoxyacetic acid, Phenylacetic acid, acrylic acid, methacrylic acid, benzoic acid, 4-methylbenzoic acid, 4-te
rt-Butylbenzoic acid, 3-methoxybenzoic acid, 2,4
-Dimethylbenzoic acid, 4-biphenylcarboxylic acid, 1-
Naphthoic acid, 2-naphthoic acid, maleic acid, succinic acid,
Itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyrrolic acid, benzophenonetetracarboxylic acid, etc. and these An acid anhydride can be mentioned. The amount of these carboxylic acids or their anhydrides used is 0.01 to 1.2 chemical equivalents, preferably 0.05 to 1.0 chemical equivalents, per 1 chemical equivalent of the hydroxyl group in the epoxy acrylate resin. Is.

If desired, various known esterification catalysts, the above-mentioned diluents and the like may be further added during the reaction. The reaction temperature is not particularly limited, but is preferably a temperature at which the raw material epoxy acrylate resin or the like does not undergo thermal polymerization, preferably 50 ° C to 180 ° C, and particularly preferably 80 ° C to 150 ° C. The reaction time depends on the reaction temperature, but is preferably 30 minutes to 80 hours, more preferably 1 to 50 hours.

The acid-modified epoxy acrylate resin of the present invention can be separated by a known method such as distillation after the reaction. The acid-modified epoxy acrylate resin of the present invention may contain an epoxy group in the molecule. That is, as described above, by adjusting the amount of acrylic acid, methacrylic acid, or a mixture of both to the epoxy resin to a desired amount within the above range, unreacted epoxy groups are contained in the resulting epoxy acrylate resin. An acid-modified epoxy acrylate resin containing an epoxy group can be obtained by allowing it to remain and further acid-modifying it.
In the acid-modified epoxy acrylate resin, for example,
When the content of epoxy groups increases, that is, when the content of (meth) acryloyl groups decreases, the sensitivity (photocurability) to ultraviolet rays tends to decrease, but the thermosetting property increases and heat curing It is possible to exhibit effects such as excellent film properties afterwards, and it is safe to contain an epoxy group in a range that does not impair the desired effects of the present invention. The acid value of the acid-modified epoxy acrylate resin can be appropriately adjusted according to the application, but is preferably 20 to 300 mg / KOHg, more preferably 30 to 250 mg / KOHg, and particularly preferably Is 50 to 150 mg / KOHg.

Next, the curable resin composition of the present invention will be described in detail. The curable resin composition is characterized by containing either the epoxy acrylate resin or the acid-modified epoxy acrylate resin of the present invention described above, and a known resin, light and / or thermal polymerization initiation described later. It is also possible to add agents and the like. In addition to this, the curable resin may be further composed of an inorganic filler, a color pigment, or the like, if desired. As the epoxy acrylate resin or the acid-modified epoxy acrylate resin of the present invention, the reaction product may be used as it is. In the curable resin composition of the present invention, the amount of the epoxy acrylate resin of the present invention contained in the composition is preferably 10 to 90% by weight, more preferably 20 to 80% by weight.

The curable resin composition of the present invention comprises, in addition to the above-mentioned epoxy acrylate resin of the present invention, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol type epoxy resin, tris (2,3-epoxypropyl). ) Epoxy compounds such as isocyanurate, epoxy (meth) acrylates and polyester acrylates which are reaction products of these epoxy compounds with (meth) acrylic acid, and prepolymers or polymerizable monomers such as the aforementioned reactive monomers. It may be contained. The amount of these used is preferably 20 with respect to 100 parts by weight of the epoxy acrylate resin of the present invention.
It is 0 part by weight or less, and more preferably 100 parts by weight or less. When an epoxy compound is used, an epoxy resin curing agent can be used, and examples of the epoxy resin curing agent include dicyandiamide and its derivatives, imidazole compounds, triazine compounds, urea compounds, aromatic amines, polyphenol compounds, Photocationic polymerization catalysts can be mentioned. The amount of the epoxy resin curing agent used is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the epoxy compound. Of course, you may use together 2 or more types of the epoxy acrylate resin of this invention.

As the photopolymerization initiator, various known photopolymerization initiators can be used. Preferred photopolymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether,
Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-
Hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert- Butyl anthraquinone,
1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,
Examples include 4'-bisdiethylaminobenzophenone and Michler's ketone. These can be used alone or in combination of two or more. The amount of the photopolymerization initiator used is preferably 0 to 50 parts by weight, and more preferably 4 to 10 parts by weight with respect to 100 parts by weight of the epoxy acrylate resin or the acid-modified epoxy acrylate resin of the present invention.
35 parts by weight.

Furthermore, the simultaneous use of one or more of these photopolymerization initiators and known photosensitizers
It is preferable. Examples of the photosensitizer include:
N, N-dimethylaminobenzoic acid ethyl ester, N,
Examples include N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. A preferable combination of the photopolymerization initiator and the photosensitizer is 2,4-diethylthioxanthone or 2-
As a combination of isopropylthioxanthone and N, N-dimethylaminobenzoic acid ethyl ester, and a preferable combination of the above photopolymerization initiators, 2-
Examples thereof include a combination of methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one and 2,4-diethylthioxanthone or 2-isopropylthioxanthone.

The radical polymerization initiator used in the thermal polymerization is not particularly limited. Examples of preferred radical polymerization initiators include known benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, tert-butyl peroxypivalate, and other peroxides. And azo compounds such as azobisisobutyronitrile. The amount of the thermal polymerization initiator used is preferably 0 to 50 parts by weight, and more preferably 0.01 to 35 parts by weight, based on 100 parts by weight of the epoxy acrylate resin of the present invention.

Further, in producing the curable resin composition of the present invention, if necessary, an inorganic filler (eg talc, silica, alumina, barium sulfate, magnesium oxide etc.), a thixotropic agent (eg Aerogel). Etc.), melamine resin (eg hexamethoxymelamine, hexabutoxymelamine etc.), leveling agent (eg silicone, fluoropolymer, acrylic copolymer etc.), color pigment (eg cyanine green, cyanine blue etc.), eraser It is also possible to add a foaming agent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a flow control agent and the like. The curable resin composition thus obtained is useful for various applications such as solder resist compositions, insulating coatings, adhesives, printing inks, coating agents, etc., but particularly good performance as a solder resist composition. Have. When the curable resin composition of the present invention is used as a solder resist composition, various compounds that can be used in the curable resin composition can be added.

The cured product of the present invention can be obtained by curing the curable resin composition of the present invention obtained by the above-mentioned method according to a known method, for example, a curing method using electron beams, ultraviolet rays and heat. Preferably, it is a method of producing a cured product by curing it with ultraviolet rays and then further thermally curing it if necessary. When performing thermosetting, the heating temperature is preferably 80 ° C to 180 ° C, more preferably 120 ° C.
It is ℃ -170 ℃. The heating time is usually 5 minutes to 20 hours, preferably 10 minutes to 10 hours, and more preferably 30 minutes to 2 hours, although it depends on the heating temperature.

When the epoxy acrylate resin of the present invention is used as a solder resist composition, for example, a cured product can be obtained by the following method. That is,
Screen printing method, spray method,
The epoxy acrylate resin of the present invention is applied in a film thickness of 10 to 100 μm by a method such as a roll coating method, an electrostatic coating method, and a curtain flow coating method, and the coating film is preferably
It is dried at room temperature to 100 ° C, more preferably 60 ° C to 80 ° C. A solder mask pattern film is directly contacted with the coating film, followed by irradiation with ultraviolet rays, and a further 0.1.
The unirradiated portion of the coating film is dissolved and removed with an alkaline aqueous solution such as a 5 to 2% sodium carbonate aqueous solution, a 0.5 to 1% caustic soda aqueous solution, or a caustic potash aqueous solution. Furthermore, the heating temperature is preferably 80 ° C to 180 ° C, more preferably
At 120 ° C to 170 ° C, the heating time is preferably 10
A cured film can be produced by heat curing for 10 minutes to 10 hours, more preferably 30 minutes to 2 hours.

[0027]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these production examples and examples. Reference Production Example: Epoxy Resin Production Method In a reaction vessel, 6,6′-dihydroxy-3,3,3 ′,
3'-Tetramethyl-1,1'-spirobiindane 15
Charged with 4 g and epichlorohydrin 463 g, 95
The temperature is raised to ℃ to dissolve. 110 g of 40% aqueous sodium hydroxide solution was added dropwise to this over 3 hours, and the temperature was 90 to 100 ° C.
And stirred for 2 hours. After cooling this, 200 ml of methyl ethyl ketone was charged, and washing with water was repeated until chloride and a slight excess of sodium hydroxide were removed. The solvent and epichlorohydrin were distilled off from the organic layer under reduced pressure to obtain 211 g of an epoxy resin represented by the following formula (3) (formula 5). Yield 89%. As a result of analysis by liquid chromatography, the composition was 86% for n = 0, 8% for n = 1, and 6% for n ≧ 2 (Area%, the same applies hereinafter). The epoxy equivalent was 238 g / eq and the softening point was 50 ° C.

[0028]

[Chemical 5]

Production Example 1 In a reaction vessel, the epoxy resin represented by the above formula (3) obtained by the method described in the above Reference Production Example [n = 0; 86%,
n = 1; 8%, n ≧ 2; 6%, epoxy equivalent 238 g /
eq] 238 g, acrylic acid 72 g, triethylamine 0.9 g, hydroquinone 0.1 g and styrene 31 g as a diluent, and while blowing air at 80 ° C.
The mixture was stirred for 1 hour at 130 ° C. for 3 hours to obtain 327 g of wax-like epoxy acrylate resin. This compound has an acid value (mgKOH / g) of 3.0 and an ICI viscosity of 1.
It was 8 poise (100 ° C.). In addition, as a result of analyzing the obtained epoxy acrylate resin by liquid chromatography, the composition of the epoxy acrylate resin represented by the following formula (1-i) (Chemical formula 6) was such that n = 0 was 86% and n =
1 was 8%, and n ≧ 2 was 6% (Area%), which were almost in agreement with the composition of the raw material epoxy resin within an error range.

[0030]

[Chemical 6]

Production Example 2 An epoxy resin represented by the above formula (3) [n = 0; obtained by a method similar to the method described in Reference Production Example, was placed in a reaction vessel.
84%, n = 1; 7%, n ≧ 2; 9%, epoxy equivalent 2
45 g / eq] 245 g, acrylic acid 144 g, triethylamine 1.2 g, hydroquinone 0.2 g and styrene 39 g as a diluent were charged, and the mixture was stirred at 80 ° C. for 1 hour and at 130 ° C. for 3 hours while blowing air. Then, excess acrylic acid was distilled off to obtain 344 g of wax-like epoxy acrylate resin. Acid value of this product (m
gKOH / g) was 24.4 and the ICI viscosity was 21.0 poise (100 ° C.).

Production Example 3 An epoxy resin represented by the following formula (4) (Chemical formula 7) obtained in the same manner as in the Reference Production Example in a reaction vessel [n = 0; 81%, n = 1; 14%, n ≧ 2; 5%, epoxy equivalent 285 g / eq] 285 g, acrylic acid 72
g, triethylamine 0.9 g, hydroquinone 0.1
g and 31 g of 1,6-hexanediol diacrylate as a diluent and 80 ° C. while blowing air.
The mixture was stirred for 1 hour at 130 ° C. for 3 hours to obtain 327 g of wax-like epoxy acrylate resin. This product has an acid value (mgKOH / g) of 6.7 and an ICI viscosity of 1.
It was 9.6 poise (100 ° C.).

[0033]

[Chemical 7]

Production Example 4 In a reaction vessel, an epoxy resin represented by the above formula (3) obtained by the method described in Reference Production Example [n = 0; 86%, n =
1; 8%, n ≧ 2; 6%, epoxy equivalent 238 g / e
q] 238 g, acrylic acid 72 g, triethylamine 0.9 g, hydroquinone 0.1 g, and styrene 31 g as a diluent are charged, and while blowing air,
The mixture was stirred at 80 ° C. for 1 hour and then at 130 ° C. for 3 hours to obtain 327 g of a waxy reaction product. Further this reaction product 32
Add 130g of maleic anhydride to 7g, and add 10g at 100 ℃.
After reacting for a time, 412 g of acid-modified epoxy ester resin
Got The acid value (mgKOH / g) of this product is 104.
3. The ICI viscosity was 8 poise (100 ° C.).

Production Example 5 An epoxy resin represented by the above formula (3) [n = 0; 8] obtained in the same manner as in the Reference Production Example was placed in a reaction vessel.
4%, n = 1; 7%, n ≧ 2; 9%, epoxy equivalent 24
5 g / eq] 245 g, acrylic acid 144 g, triethylamine 1.2 g, metoquinone 0.2 g, and styrene 50 g as a diluent were charged, and the mixture was stirred at 80 ° C. for 1 hour and at 130 ° C. for 3 hours while blowing air. Then, excess acrylic acid and styrene were distilled off to obtain 344 g of a waxy reaction product. Next, 120 g of tetrahydromaleic anhydride and 80 g of carbitol acetate were added to this reaction product and reacted at 90 ° C. for 20 hours to obtain 498 g of an acid-modified epoxy acrylate resin. This had an acid value (mgKOH / g) of 98.4 and an ICI viscosity of 17 poise (100 ° C.).

Production Example 6 An epoxy resin composition represented by the above formula (4) obtained in the same manner as that described in Reference Production Example in a reaction vessel [n =
0; 81%, n = 1; 14%, n ≧ 2; 5%, epoxy equivalent 285 g / eq] 285 g, acrylic acid 72 g, triethylamine 0.9 g, hydroquinone 0.1 g, and 1,6-hexane as a diluent. Charge 31 g of diol diacrylate and stir at 80 ° C. for 1 hour and then at 130 ° C. for 3 hours while blowing air into the reaction product 327.
g was obtained. Next, trimellitic anhydride 19 was added to the reaction product.
0 g was added and the mixture was reacted at 90 ° C. for 20 hours to obtain 511 g of an acid-modified epoxy acrylate resin. This had an acid value (mgKOH / g) of 112.1 and an ICI viscosity of 24 poise (100 ° C.).

Production Example 7 365 g of an acid-modified epoxy acrylate resin was obtained in the same manner as in Production Example 4, except that 36 g of acrylic acid was used instead of 72 g of acrylic acid. The acid value (mgKOH / g) of this product is 51.5, I
The CI viscosity was 79 poise (100 ° C.).

Production Example 8 Acid modification according to the method of Production Example 4 except that 54 g of acrylic acid was used instead of 72 g of acrylic acid and 150 g of maleic anhydride was used instead of 130 g of maleic anhydride in Production Example 4. Epoxy acrylate resin 39
1 g was obtained. The acid value (mgKOH / g) of this product is 7
4.3, ICI viscosity was 55 poise (100 ° C.).

Production Example 9 Acid modification according to the method of Production Example 4 except that 54 g of acrylic acid was used instead of 72 g of acrylic acid and 110 g of acetic anhydride was used instead of 130 g of maleic anhydride in Production Example 4. Epoxy acrylate resin 350g
Got However, the ICI viscosity is 52 poise (100
℃).

Examples 1 to 9 Using the epoxy acrylate resins obtained in Production Examples 1 to 9 and the various materials shown in Table 1 (Tables 1 and 2), the compounding composition (numerical values shown in Table 1 Is a part by weight) and kneaded with a roll mill to prepare a solder resist composition (ink).
Was produced. Using this solder resist composition (ink), a resist-coated substrate was obtained according to the method for producing a resist-coated substrate described below, and evaluated by the following evaluation methods. The results are shown in Table 2 (Tables 3 and 4). .

Comparative Examples 1 to 3 A solder resist composition (ink) was prepared in the same manner as in Examples using the following resin compositions conventionally used and various materials shown in Table 1, and Evaluation was made in the same manner as above, and the results are shown in Table 2. Comparative Example 1: KAYARAD R-5027: manufactured by Nippon Kayaku Co., Ltd., a reaction product of a phenol novolac type epoxy acrylate and a dibasic acid anhydride, a product containing 40% by weight of butylcellosolev acetate, an acid value (mgKOH / g 68.5 Comparative Example 2: KAYARAD R-5089: manufactured by Nippon Kayaku Co., Ltd., reaction product of bisphenol A type epoxy acrylate and dibasic acid anhydride, carbitol acetate 40% by weight content, acid value (mgKOH / G) 63 Comparative Example 3: KAYARAD R-114: Bisphenol A type epoxy acrylate manufactured by Nippon Kayaku Co., Ltd.

[Production Method of Resist-Coated Substrate] The solder resist composition (ink) is applied to the entire surface of the copper through-hole printed wiring board by screen printing so that the film thickness after drying is 15 to 25 μm. 70 ° C, 1
Pre-dried for 5 minutes. The solder resist composition was applied to the back surface in the same manner as above, and predried at 70 ° C. for 25 minutes. Next, a solder mask pattern film is brought into contact with the coated surface, and a metal halide lamp double-side simultaneous exposure device (HMW680 manufactured by Oak Manufacturing Co., Ltd.) is used to perform 500.
It is exposed to light of nJ / cm ² , and then the unirradiated part of the coating film is developed with a 1.0 wt% sodium carbonate aqueous solution at a spray pressure of 2.5 Kg / cm ² and a liquid temperature of 25 ° C. for 60 seconds to remove it by dissolution. did. The developability of the obtained resist-coated substrate before curing was evaluated as described below. After that, it is heated and cured at 150 ° C. for 60 minutes in a hot air drier, and the resist coated substrate having the obtained cured film is cured film hardness (pencil hardness), moisture resistance, solder heat resistance, acid resistance as described below. , Alkali resistance, solvent resistance, gold plating resistance and electrolytic corrosion resistance were tested.

[Evaluation Method of Resist Coated Substrate] Using the resist coated substrate manufactured by the above method, the characteristics of the resist material were measured by the following methods. (1) Developability: Using the resist-coated substrate before curing, the developability was visually evaluated with a magnifying glass. ○: Completely developed △: Thinly undeveloped part ×: Significantly undeveloped part (2) Hardened film hardness: The pencil hardness of the hardened film was measured using a resist-coated substrate having a hardened film. It was measured according to JIS-K-5400. (3) Moisture resistance: Using a resist-coated substrate having a cured film, the appearance change of the cured film was visually observed after boiling for 2 hours in boiling water at 100 ° C. ◯: No change in appearance Δ: Swelling is observed in a part of the cured film X: Swelling or deformation is observed in a considerable part of the cured film (4) Soldering heat resistance: Using a resist coated substrate having a cured film, JISC6481 According to 260 ° C solder bath [J
S-64P: manufactured by Sanei Chemical Co., Ltd.] was immersed in the test piece for 10 seconds 10 times, and the change in appearance was visually observed. ◯: No change in appearance Δ: Discoloration is observed in a part of the cured film ×: Floating and peeling are observed in a considerable part of the cured film, and solder submerged (5) Acid resistance: Specimen 25 in 10 vol% sulfuric acid aqueous solution
After dipping at 15 ° C. for 15 minutes, the appearance change of the cured film was visually observed. ◯: No change in appearance Δ: Part of the cured film peels off ×: Floating is seen in a considerable part of the cured film, and the cured film peels off easily

(6) Alkali resistance test: 10 w of test piece
It was immersed in a t% sodium hydroxide aqueous solution at 25 ° C. for 15 minutes, and the appearance change of the cured film was visually observed. ◯: No change in appearance Δ: Part of the cured film peels off ×: Floating is seen in a considerable part of the cured film, and the cured film easily peels off (7) Solvent resistance: Test piece in dichloromethane at 25 ° C,
After dipping for 30 minutes, the appearance change of the cured film was visually observed. ○: No appearance change Δ: Swelling is observed in a part of the cured film ×: Swelling and solvent penetration are observed in a considerable part of the cured film (8 ) Gold plating resistance: A test piece was gold-plated for 30 minutes at a current density of 1.0 A / dm ² by using Autoronex CI (plating solution) manufactured by Celllex Co., and then an adhesive tape (Cellotape: Sekisui Chemical Co., Ltd.) The peeling test was performed by the company), and it was visually observed. ◯: No peeling at all Δ: Part of the cured film peeled off ×: Most of the cured film peeled off (9) Electrolytic corrosion resistance: 120 ° C., 100% R test piece
After being left under conditions of H, 2 atm, and applied voltage of 100 V for 30 hours, discoloration and surface change were visually observed. ◯: No discoloration or surface change observed on either + side or − side Δ: Slight discoloration on either + side or − side ×: Discoloration on both + side and − side And those in which surface abnormality is observed The above evaluation was performed using the solder resist composition having the composition shown in Table 1.

[0045]

[Table 1]

[0046]

[Table 2]

KAYARAD R-5027: manufactured by Nippon Kayaku Co., Ltd.
Reaction product of phenol novolac type epoxy acrylate and dibasic acid anhydride, butyl cellosolve acetate 40
Weight% contained product, acid value (mgKOH / g) 68.5 KAYARAD R-5089: Nippon Kayaku Co., Ltd., reaction product of bisphenol A type epoxy acrylate and dibasic acid anhydride, carbitol acetate 40 weight % Content, acid value (mgKOH / g) 63 ・ KAYARAD R-114: Nippon Kayaku Co., Ltd., bisphenol A type epoxy acrylate ・ KAYARAD R-2058: Nippon Kayaku Co., Ltd., phenol novolac type epoxy acrylate , Butyl cellosolve acetate 30% by weight-TEPIC-S: Nissan Chemical Co., Ltd., tris (2,3-epoxypropyl) isocyanurate, melting point 95-125
℃ ・ EPPN-201: Nippon Kayaku Co., Ltd., phenol novolac type epoxy resin, softening point 65 ℃ ・ KAYARAD DPHA: Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate ・ CAR-Ac: carbitol acetate ・Irgacure-907: Irgacure-907, manufactured by Ciba Geigy, photopolymerization initiator DIAMID (curing agent): dicyandiamide, epoxy resin curing agent, Pc-green (pigment): phthalocyanine green, KS-603: Shin-Etsu Chemical ( Defoamer manufactured by K.K. Co., Ltd. Table 2 shows the evaluation results of Examples 1 to 9 and Comparative Examples 1 to 3 described above.

[0048]

[Table 3]

[0049]

[Table 4]

As is clear from Table 2, when either the epoxy acrylate resin or the acid-modified epoxy acrylate resin of the present invention is used as a solder resist composition, a conventionally known epoxy acrylate resin is used. Hardened film hardness (pencil hardness), moisture resistance, acid resistance, alkali resistance, solvent resistance, gold plating resistance and galvanic corrosion resistance are superior to those in the case of using materials, and developability is comparable. .

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, the developability is excellent, and the cured film is excellent in various properties (cured film hardness, moisture resistance, acid resistance, alkali resistance, solvent resistance, gold plating resistance and electrolytic corrosion resistance). An epoxy acrylate resin, an acid-modified epoxy acrylate resin, and a curable resin composition containing these resins can be provided. The curable resin is very useful as a composition for solder resist.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-63-150270 (JP, A) JP-A-61-195112 (JP, A) JP-A-8-217852 (JP, A) JP-A-8- 92231 (JP, A) JP-A 5-32746 (JP, A) JP-A 63-312375 (JP, A) JP-A 6-93221 (JP, A) JP-A 1-230620 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 59/14-59/17 C08F 299/02 G03F 7/027 515

Claims (6)

(57) [Claims] 1. An epoxy acrylate resin represented by the general formula (1) (chemical formula 1). [Chemical 1] (In the formula, R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an alkoxy group which may have a substituent, a nitro group or a halogen atom, and R 1 ₂ represents a hydrogen atom or a methyl group, and m is 1 to 3.
Represents an integer, and n represents an integer of 0 to 10). 2. An epoxy resin represented by the general formula (2) (chemical formula 2), and (In the formula, R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an alkoxy group which may have a substituent, a nitro group or a halogen atom, and m Represents an integer of 1 to 3 and n represents an integer of 0 to 10) An epoxy acrylate resin obtained from at least one selected from acrylic acid and methacrylic acid. 3. An acid-modified epoxy acrylate resin obtained by reacting the epoxy acrylate resin according to claim 2 with a carboxylic acid or an anhydride thereof. 4. A curable resin composition containing the epoxy acrylate resin according to claim 1. 5. A solder resist composition containing the epoxy acrylate resin according to claim 1. 6. A cured product obtained by curing the composition according to claim 4 or 5.