JPS62232427A - Novel epoxy acrylate of methacrylate resin composition and solder resist in composition - Google Patents

Abstract

PURPOSE:To obtain an UV-curable resin composition suitable for a solder resist ink excellent in heat resistance, moisture resistance, adhesion and electrical insulation, by using a reaction product of a specified epoxide with (meth)acrylic acid. CONSTITUTION:Epoxy (meth)acrylate comprising a reaction product of an epoxide obtained by reacting tricyclodecanedimethylol with epichlorohydrin, with (meth)acrylic acid. An UV-curable resin composition can be obtained by mixing said epoxy (meth)acrylate (A) with a (meth)acrylate monomer (B) and a photopolymerization initiator (C) as an optional component. The mixing ratio of the epoxide to the (meth)acrylic acid is preferably 0.5-2.0 by equivalent. Examples of the photopolymerization initiators (C) which can be particularly suitably used include 2-ethylanthraquinone and 2,4-diethylthioxane.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel epoxy (meth)acrylate and an ultraviolet curable resin composition using the same, particularly for use as a permanent protective film for printed wiring boards. The present invention relates to an ultraviolet curable resin composition suitable for use as a solder resist ink, which is cured by ultraviolet rays and has excellent heat resistance, moisture resistance, adhesion, and electrical insulation properties.

(Prior Art) In recent years, ultraviolet curable compositions have been widely used 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. Solder resist inks quickly transitioned to UV-curable compositions.

(Problems to be Solved by the Invention) However, there is a drawback that the adhesion to printed circuit boards and the required electrical properties, especially electrical insulation, are inferior to conventional hot air dry-curing inks. is the actual situation.

(Means for Solving the Problems) In order to solve the above problems, the present inventors have produced a new epoxy (meth)acrylate suitable for ultraviolet curable solder resist ink as a result of intensive research, and Using (meth)acrylate, we succeeded in providing an ultraviolet curable resin composition with excellent heat resistance, moisture resistance, adhesion, and electrical insulation. That is, the present invention provides (1) an epoxy (meth)acrylate comprising a reaction product of an epoxide obtained by reacting tricyclodecane dimethylol and epichlorohydrin and (meth)acrylic acid.

(2) Epoxy (meth)acrylate (A) consisting of a reaction product of an epoxide obtained by reacting tricyclodecane dimethylol and epichlorohydrin and (meth)acrylic acid, and (meth)acrylate monomer (B) and optional A resin composition comprising a photopolymerization initiator (C) as a component.

(3) Epoxy (meth)acrylate (A) and (meth)acrylate monomer CB) consisting of a reaction product of epoxidized product obtained by reacting tricyclodecane dimethylol and epichlorohydrin and (meth)acrylic acid
and a photopolymerization initiator (C) as an optional component.

It is related to.

Epoxy (meth)acrylate (A
) is obtained by reacting tricyclodecane dimethylol and epichlorohydrin, and is obtained by adding the epoxidized product and (meth)acrylic acid. Tricyclodecane dimethylol has a hydroxymethyl group of 3°8-. Di(hydroxymethyl)-tricifo- containing in the 3,9- or 4,8-position and having the following structural formula:
[:5,2,1.0)-decane and the like.

The reaction between tricyclodecane dimethylol and epichlorohydrin can be carried out by a known method. For example, 1 mole of tricyclodecane dimethylol and 2 moles of epichlorohydrin are heated at 40 to 100°C, preferably 40 to
It is obtained by reacting at 70°C.

In the reaction between epoxide and acrylic acid or methacrylic acid, the ratio of acrylic acid or methacrylic acid used per 1 chemical equivalent of epoxide is preferably 0.5 to 20 chemical equivalents, particularly preferably 0.9 to 1.1 chemical equivalent. It is equivalent. The reaction temperature is 70-130°C, especially 80-100°C.
is preferred.

The reaction can be accelerated using a catalyst.

Such catalysts are known catalysts such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, and triphenylstibine, and the amount used is preferably 0.05 to 20% based on the weight of the reaction solution, particularly Preferably it is used in an amount of 0.1 to 5%.

Next, specific compounds of the (meth)acrylate monomer (B) containing an acryloyl group or a methacryloyl group in the molecule include 2-hydroxyethyl (meth)acrylate, ethyl calpitol (meth)acrylate,
Tripropylene glycol di(meth)acrylate, neohentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, trimethylol bromine triacrylate, trimethylol bromine polypropoxy triacrylate, Tetrahydrofurfuryl (meth)acrylate, dicyclopentadieneoxyethyl (meth)acrylate, hydrogenated dicyclobenzidiene (meth)acrylate,
Isobornyl (meth)acrylate, dioxane glycol di(meth)acrylate (manufactured by Nippon Kayaku, KAYA
RAD R-604) and the like. Particularly preferred examples include 2-hydroxyethyl methacrylate, ethylcarpitol acrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolbrovane polyproboxytriacrylate, and hydrogenated dicyclopentadiene acrylate.

As the photopolymerization initiator for the component CC), any known photopolymerization initiator can be used, but it is desirable that the photopolymerization initiator has good storage stability after being blended. As such photopolymerization initiators,
For example, benzoin alkyl ethers such as benzoin ethyl ether and benzoin isobutyl ether, 2
．． 2-jethoxyacetophenone, 4'-phenoxy-
Acetophenone such as 2,2-dichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 4
Propiophenones such as '-isopropyl-2-hydroxy-2-methylpropiophenone, anthraquinones such as benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone and 2-ethylanthraquinone, 2-chloroanthraquinone, 2- Examples include thioxanthone photopolymerization initiators such as chlorothioxanthone and 2,4-diethylthioxanthone. One or more of these photopolymerization initiators (C) can be used as a mixture in any proportion. Particularly preferred photopolymerization initiators include 2-ethylanthraquinone and 2,4-diethylthioxanthone.

In the resin composition and solder resist ink composition (hereinafter collectively referred to as "composition") of the present invention, the photopolymerization initiator (C) may be mixed in advance, but it may be mixed before using the composition. It may also be used as

The amount of component (A) used in the composition of the present invention is preferably 10 to 70% by weight, particularly preferably 15 to 5% by weight of the composition.
0% by weight is desirable. If the amount of component (A) is less than 10% by weight, curability, hardness, moisture resistance, and heat resistance will be reduced, and if it is more than 70% by weight, printability and heat-resistant adhesion during solder immersion will be reduced.

The amount of component (B) is preferably 25 to 85% by weight, particularly preferably 40 to 80% by weight of the composition.

When component (C) is contained, the amount thereof is preferably 0.5 to 15% by weight, particularly preferably 1 to 8% by weight of the composition.
It is.

The resin composition of the present invention is particularly useful as a solder resist ink composition, but can also be used as a groove material for compact discs, a coating agent for optical fibers, and the like.

The composition of the present invention is easily cured by irradiation with electron beams or ultraviolet rays. This curing can be performed by a conventional method.

The solder resist ink composition of the present invention is printed by a screen printing method or an offset printing method, but
In order to improve printability in that case, extender pigments such as talc, calcium carbonate, alumina, barium sulfate, mica, leveling agents, coloring pigments, thixotropic agents, thickeners, chelating agents, etc. are added to the composition of the present invention. You can add it.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. Note that parts in the examples are parts by weight.

[Example of production of epoxidized product of tricyclodecane dimethylol]

Production Example 1 In a three-part reactor equipped with a stirrer, a thermometer, and a temperature control device, tricyclodecanedimethylol [3°8-di(hydroxymethyl)-IJcyclo[5,2,1,o] was added.
]-decane] 588 parts, BF3/ethyl ether 1.4
After raising the temperature to the liquid temperature of 55°C, 555 parts of epichlorohydrin was gradually added dropwise over about 6 hours.
The mixture was stirred at 0°C for 1 hour, and then 800 parts of a 30% aqueous sodium hydroxide solution was added dropwise over about 4 hours. 60 minutes after completion of dripping
After stirring for 1 hour at ℃, the aqueous layer was separated, washed with 500 parts of water and 1000 parts of methyl isobutyl ketone, and the solvent methyl isobutyl ketone was distilled under reduced pressure to obtain a pale yellow epoxide. 865 copies were obtained. This material has the following physical properties.

Epoxy equivalent 187 Viscosity (25°0.) 1800
Cps specific gravity (25°(:,) 1
．． 138 Example 1 374 parts of the epoxide obtained in Production Example 1, 137 parts of acrylic acid, 0.26 parts of methoquinone, and triphenylstipine were placed in a reactor equipped with a stirrer, a thermometer, a temperature controller, and a condenser. 3.7 parts were charged, and the reaction was carried out while maintaining the liquid temperature at 90 to 95°C until the acid value (■KOH/g) became 1 or less to obtain epoxy acrylate. This product has the following properties.

Color Phase (APIIA) s.

Acid value (mgKOH/g) 0.5 viscosity
The absorption frequency of the obtained product was measured by high-resolution nuclear magnetic resonance (NMR) at 490° C. (25° C., Polse) and the results are shown below.

Absorption frequency (Hz) 1 2498.046 2 1972.656 3 1927.734 4 1195.312 5 1156.250 6 1140.625 7 1130.859 8 1105.468 9 1078.125 10 1044.921 11 1031.25012
1003.906 13 990.234 14 931.640 Absorption frequency (Hz) 15 738.281 16 685.546 17 677.734 18 673.828 19 662.109 20 625.000 21 609.375 22 597.656 23 593.750 24 525.390 25 511.718 26 490.234 27 468.750 28 427.734 29 371.093 30 0,000 In the above measurement, tetramethylsilane was used as a reference substance and 'H, 13C -1-1 coupling measurements were performed, and the final +3c D couple showed the same 13 constant results.

Example 2゜The epoxide compound 3 obtained in Production Example 1 was added to the reaction apparatus of Example 1.
74 parts, methacrylic acid 163.4 parts, methoquinone 0.2
7 parts, methyltriethylammonium chloride 1.9
While keeping the liquid temperature at 90-95℃, adjust the acid value (
The reaction is carried out until KOI-1/g) becomes 1 or less,
Epoxy methacrylate was obtained. This product has the following properties.

Hue CAPHA) 140 acid
Value (II1gKOH/g) 0.9 viscosity
degree (25℃, Po1se) 435 parts M
Absorption frequency (Hz) 1 2513.671 2 2048.828 3 1890.625 4 1142.578 5 1111.328 6 1082.031 M Absorption frequency (Hz) 7 1033.203 8 992.187 9 679 0,000 Example 3 27 parts of the epoxy acrylate obtained in Example 1, 14 parts of methylolpropane triacrylate, 17 parts of hydroxypivalic acid neopentyl glycol diacrylate (manufactured by Nippon Kayaku ■, KAYARADMANDA), 2-
10 parts of hydroxyethyl methacrylate, 0.6 parts of cyanine green, 1 part of Modaflow (leveling agent manufactured by Monsanto), 30 parts of talc, and Irgacure 65
Add 3 parts of 1 (manufactured by Ciba Geigy, photopolymerization initiator) and 50
After uniformly mixing at ~80°C, the mixture was thoroughly kneaded with three rolls (manufactured by Bengami Seisakusho) and printed on a screen with 20 mm vertically and 30 mm horizontally (by screen printing using a screen with turns). , printed on copper foil of a printed wiring board and cured with ultraviolet rays, the pencil hardness of the cured film is 3H.

No blistering or flaking occurred during humidification treatment at 40°C, 90% RH for 4 hours, and solder immersion at 260°C for 20 seconds immediately after immersion in 80°C hot water for 1 hour. Also, the insulation resistance is 1. , l×10 Ω.

Example 4゜40 parts of epoxy acrylate obtained in Example 1, dioxane glycol diacrylate (manufactured by Nippon Kayaku ■, KAYA
RAD R-604) 11 parts, hydrogenated dicyclopentadiene acrylate (manufactured by Hitachi Chemical, FA-513A)
10 parts, 7 parts of carpitol acrylate, 0.6 parts of cyanine green, 1 part of Modaflow (leveling agent manufactured by Monsanto), 30 parts of talc, and Ar65
1 was added, kneaded, printed, and cured in the same manner as in Example 1. The pencil hardness of the cured coating was 4I-[, 40°C90%.
No blistering or peeling occurred during humidification treatment at RH for 4 hours and immersion in 260°C for 20 seconds immediately after immersion in warm water at 80°C for 1 hour. Also, the insulation resistance is 1.5X10
It was Ω.

Example 5 20 parts of epoxy methacrylate obtained in Example 2, 24 parts of trimethylolpropane triacrylate, 10 parts of 2-hydroxypropyl methacrylate, 14 parts of dicyclopentadieneoxyethyl acrylate, 0.6 part of cyanine green, Modaflow ( After adding 1 part of Monsando Co. ff leveling agent), 30 parts of talc, and 3 parts of 2-ethyl anthraquinone, the mixture was kneaded, printed, and cured in the same manner as in Example 1. The pencil hardness of the cured film was 3H140°C90. %
No blistering or peeling occurred during humidification treatment at RH for 4 hours and solder immersion at 260°C for 20 seconds immediately after immersion in 80°C warm water for 1 hour. Also, the insulation resistance is 1.2X10
It was Ω.

Comparative Example 1゜In place of the epoxy acrylate used in Example 4, phenol novolac type epoxy resin (Shell Chemical ■
The cured film was cured in the same manner as in Example 4 except that an adduct of Epicoat 154) manufactured by Co., Ltd. and acrylic acid was used, and the pencil hardness of the cured film was 4I-1. Humidification treatment for 14 hours at 40°C and 90% R1. and 260 immediately after immersion in 80°C hot water for 1 hour.
Blistering and peeling occurred during solder immersion for 20 seconds. Further, the insulation resistance was 3.0×10 Ω.

(Effects of the Invention) The UV-curable resin composition using the epoxy (merry) acrylate of the present invention has excellent heat resistance, moisture resistance, adhesion, and electrical insulation, and is particularly suitable for UV-curable solder resist ink. Suitable.

Claims (3)

[Claims] (1) Epoxy (meth)acrylic acid and an epoxide obtained by reacting tricyclodecane dimethylol and epichlorohydrin (
Meta) acrylate. (2) Epoxy (meth)acrylate (A) consisting of a reaction product of an epoxide obtained by reacting tricyclodecane dimethylol and epichlorohydrin and (meth)acrylic acid, and (meth)acrylate monomer (B) and optional A resin composition comprising a photopolymerization initiator (C) as a component. (3) Epoxy (meth)acrylate (A) and (meth)acrylate monomer (B) consisting of a reaction product of epoxidized food obtained by reacting tricyclodecane dimethylol and epichlorohydrin and (meth)acrylic acid. A solder resist ink composition comprising a photopolymerization initiator (C) as an optional component.