JPH10259218A - Active energy ray curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of providing a cured film low in water absorption and water resistance using inexpensive materials, by including a specific epoxy (meth)acrylate and a prescribed reactive diluent. SOLUTION: This composition comprises (A) 10-90wt.% of an epoxy (meth) acrylate which is obtained by mixing (i) a (hydrogenated) dimer acid with (ii) a diepoxide (e.g. a bisphenol A type epoxy resin) and (iii) (meth)acrylic acid in the ratio of <1molpt. of the component (i) and 0.4-1.2molpts. of the component (iii) based on 1molpt. of the component (ii) and reacting the mixture at 80-120 deg.C for 3-6 hours and has preferably 1,000-10,000 number-average molecular weight, (B) 10-90wt.% of a polyfunctional diluent (e.g. 1,9-nonanediol diacrylate) containing a >=3C alkylene group in the molecule, (C) 0-10wt.% of a reactive diluent except the component B and (D) 0-20wt.% of a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an active energy ray-curable resin composition. The active energy ray-curable resin composition of the present invention includes various plastics, papers, overcoating agents for electronic components, adhesives, binders for printing inks,
It can be used in various fields such as solder resist.

[0002]

2. Description of the Related Art Heretofore, as active energy ray-curable resin compositions, there have been known various active energy ray-curable resins such as unsaturated polyesters, epoxy acrylates and urethane acrylates in combination with a reactive diluent. And is used for protecting the surface of various substrates and imparting gloss.

However, since the active energy ray-curable resin composition contains a large amount of a hygroscopic (meth) acryloyl group, the cured film obtained has a high water absorption and is used in a field where water resistance is required. Has the disadvantage that it is not suitable. In particular, in the field of protective coating agents for electronic components used in personal computers and mobile phones, conventional active energy ray-curable resin compositions having poor water resistance are difficult to use.

To improve the water resistance of such an active energy ray-curable resin composition, urethane acrylates and ester acrylates having a polyolefin skeleton or a hydrogenated polybutadiene skeleton have been developed.
All of them use expensive raw materials, so there is one aspect that it is difficult to use.

[0005]

SUMMARY OF THE INVENTION The present invention aims to solve the above-mentioned problems. That is, an object of the present invention is to provide an active energy ray-curable resin composition that provides a cured film having low water absorption and excellent water resistance using an inexpensive material.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, as the active energy ray-curable resin, the following specific epoxy (meth)
The present inventors have found that an active energy ray-curable resin composition containing an acrylate and a specific reactive diluent can solve the above problem, and have completed the present invention.

That is, the present invention relates to (A) an epoxy (meth) acrylate obtained by reacting (hydrogenated) dimer acid, diepoxide and (meth) acrylic acid, and (B) a polyfunctional reactive diluent. The present invention relates to an active energy ray-curable resin composition contained therein.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy (meth) acrylate (A) in the present invention is an oligomer obtained by reacting (hydrogenated) dimer acid, diepoxide and (meth) acrylic acid.

(Hydrogenated) dimer acid means dimer acid and / or hydrogenated dimer acid. Note that dimer acid is a dimer of unsaturated fatty acid, and hydrogenated dimer acid is a compound obtained by hydrogenating an olefinic double bond of the dimer.

The diepoxide is not particularly limited as long as it has two epoxy groups in the molecule. For example, bisphenol A type epoxy resins obtained by reacting bisphenol A with epichlorohydrin, epoxy resins obtained by hydrogenating them, glycidyl ether type epoxy resins obtained by reacting epichlorohydrin with 1,6 hexanediol, polypropylene glycol, etc. can give. The diepoxide may be used alone or in combination of two or more. As commercially available diepoxy, for example, Epicoat 152, Epicoat 82
8, Epicoat 834, Epicoat 1001, Epicoat 1004 (all manufactured by Yuka Shell Epoxy Co., Ltd.), Denacol Ex-830, Denacol Ex-920, Denacol Ex-211, Denacol Ex-212, Denacol Ex-721 (all, Nagase Kasei Kogyo Co., Ltd.).

Further, (meth) acrylic acid means acrylic acid and / or methacrylic acid. In the present invention, (meta) has the same meaning hereinafter.

The proportions of the (hydrogenated) dimer acid, diepoxide and (meth) acrylic acid are not particularly limited, but usually the proportion of the diepoxide to the (hydrogenated) dimer acid is 1 mol part of the diepoxide (mol parts of the diepoxide). (Hydrogenated) is based on the molecular weight calculated from the epoxy equivalent), and is used within a range of less than 1 mol part of (hydrogenated) dimer acid. Preferably, the amount of the (hydrogenated) dimer acid is about 0.4 to 0.8 part by mol with respect to 1 part by mol of diepoxide. In order to sufficiently improve the water resistance of the active energy ray-curable resin composition, (water Addition) The lower limit of the amount of dimer acid used is more preferably 0.5 mol part. Further, the upper limit is more preferably 0.75 mol part. When the amount of (hydrogenated) dimer acid is 1 mol part or more, there is no hydroxyl group for reacting (meth) acrylic acid.

The amount of (meth) acrylic acid to be used is usually preferably 0.4 to 1.2 mol parts per mol part of diepoxide, the lower limit being 0.5 mol part and the upper limit being 1. mol part. 0 mole parts is more preferred.

The production of (A) epoxy (meth) acrylate is carried out by using (hydrogenated) dimer acid, diepoxide and (meth)
A method in which acrylic acid is charged at the same time, a method in which (hydrogenated) dimer acid and diepoxide are reacted and then (meth) acrylic acid is charged and reacted can be employed. The reaction temperature is usually 8
The temperature is about 0 to 120 ° C, preferably 110 ° C or more. The reaction time is usually about 3 to 6 hours. In addition,
Upon the reaction, a polymerization inhibitor such as hydroquinone monomethyl ether may be added.

The epoxy (meth) acrylate (A) thus obtained preferably has a number average molecular weight of about 1,000 to 10,000.

In the present invention, in order to improve the water resistance of the active energy ray-curable resin composition, (B) a polyfunctional reactive compound having an alkylene group having 3 or more carbon atoms in the molecule is used as a reactive diluent. Use diluent. Examples of the polyfunctional reactive diluent (B) include neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, tripropylene glycol, butylethylpropanediol, bisphenol A, and trimethylolpropane. (Meth) acrylate obtained by reacting a polyhydric alcohol such as pentaerythritol with (meth) acrylic acid, or (meth) acrylic acid obtained by reacting a modified alkylene oxide of the polyhydric alcohol with (meth) acrylic acid ( (Meth) acrylate and the like. Particularly, as the (B) polyfunctional reactive diluent of the present invention, among the above-mentioned examples, those using a polyhydric alcohol having an alkylene group having 5 or more carbon atoms in the molecule are preferred because of their excellent water resistance. preferable.

The active energy ray-curable resin composition of the present invention comprises (A) an epoxy (meth) acrylate and (B) a polyfunctional reactive diluent having an alkylene group having 3 or more carbon atoms in the molecule. It contains. The use ratio is usually 10 to 90% by weight of the component (B) with respect to 10 to 90% by weight of the component (A). In order to sufficiently improve the physical properties (particularly water resistance) of the cured film, the lower limit of the component (A) is preferably 30% by weight, and the upper limit is preferably 80% by weight in consideration of coatability. preferable. On the other hand, the lower limit of the component (B) is preferably 20% by weight, and the upper limit is preferably 70% by weight.

The active energy ray-curable resin composition of the present invention may contain (C) a reactive diluent other than the component (B). (C) Reactive diluents other than the component (B) include vinyl acetate, styrene, vinyltoluene, N-vinylformamide, N-vinylpyrrolidone,
Monofunctional reactive diluents such as acryloylmorpholine, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, and methoxytriethylene glycol acrylate; and bifunctional reactive diluents such as triethylene glycol divinyl ether and polyethylene glycol di (meth) acrylate Diluents. (C) The amount of the reactive diluent other than the component (B) used is 0 to 10% by weight. When it is more than 10% by weight, it is difficult to satisfy water resistance.

When the active energy ray-curable resin composition of the present invention is cured with ultraviolet rays, a photopolymerization initiator is used as needed, and is unnecessary when cured with an electron beam. As the photopolymerization initiator, various known ones can be used without any limitation, for example, Darocure 1173,
Irgacure 651, Irgacure 184, Irgacure 907 (all manufactured by Ciba-Geigy), benzophenone, o-benzoyl benzoic acid methyl ester, p-
Examples thereof include dimethylaminobenzoate, p-dimethylacetophenone, thioxanthone, and alkylthioxanthone. The used amount of the photopolymerization initiator is 0 to 20% by weight, preferably 2 to 12% by weight in the active energy ray-curable resin composition.

Further, additives such as a slip agent, a leveling agent and an antifoaming agent can be used in the active energy ray-curable resin composition of the present invention. The amount used is about 0 to 10% by weight in the active energy ray-curable resin composition.

The viscosity of the thus obtained active energy ray-curable resin composition of the present invention at the time of application varies depending on the use in which the composition is used, and may be appropriately determined in consideration of coating film performance, coating film leveling, and the like. It is determined. In adjusting the viscosity, it is optional to add an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the composition and does not attack the substrate to which the composition is applied, and examples thereof include ethyl acetate and toluene. The amount of the organic solvent used is arbitrary, and is appropriately determined for various uses.

[0022]

The cured film of the active energy ray-curable resin composition of the present invention has a low water absorption and is excellent in water resistance and moisture resistance. It is also excellent in cured films such as curability and hardness.

[0023]

EXAMPLES The present invention will be described below in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, in each example, all parts and% are based on weight unless otherwise specified.

Production Example 1 A reaction apparatus equipped with a stirrer, a cooler and a thermometer was charged with hydrogenated dimer acid (EMPOL1004, manufactured by Henkel, acid number 19).
4) 117.3 parts, 153.6 parts of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy, Epicoat 828, epoxy equivalent 189), 153.6 parts, acrylic acid 29.1
Parts, hydroquinone monomethyl ether (0.3 parts) and triphenylphosphine (1.2 parts).
For 4 hours to obtain epoxy acrylate A.

Production Example 2 Hydrogenated dimer acid (EMPOL1004, acid value 194) manufactured by Henkel Co., Ltd. was 125.7 in the same reactor as in Production Example 1.
Parts, 1,6-hexanediol diglycidyl ether (Denacol Ex212, manufactured by Nagase Kasei Kogyo Co., Ltd., epoxy equivalent 150) 143.1 parts, acrylic acid 31.2
Parts, hydroquinone monomethyl ether (0.3 parts) and triphenylphosphine (1.2 parts).
For 6 hours to obtain epoxy acrylate B.

Production Example 3 In Production Example 1, dimer acid (EMPOL 1061, manufactured by Henkel, acid value 194) was used instead of hydrogenated dimer acid.
The same procedure as in Production Example 1 was carried out, except that the epoxy acrylate C was used.

Production Example 4 A bisphenol A epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828,
Epoxy equivalent 189) 217.6 parts, acrylic acid
After charging 4 parts, 0.3 part of hydroquinone monomethyl ether and 1.2 parts of triphenylphosphine, 110 parts
Reaction was performed at 4 ° C. for 4 hours to obtain epoxy acrylate D.

Example 1 (Preparation of an active energy ray-curable resin composition) 70 parts of the epoxy acrylate A obtained in Production Example 1, 1, 9
A varnish was prepared by mixing 30 parts of nonanediol diacrylate and 3 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy).

Examples 2 to 8 and Comparative Examples 1 to 3 In Example 1, the types or amounts of the epoxy acrylates A to D or the reactive diluents obtained in Production Examples 1 to 4 are shown in Table 1. A varnish was prepared in the same manner as in Example 1 except that the varnish was changed.

Comparative Example 4 A varnish was prepared in the same manner as in Example 1 except that urethane acrylate (Arakawa Chemical Industries, Ltd., beam set 551B) was used instead of epoxy acrylate A.

(1) Curability test The varnishes obtained in the above Examples and Comparative Examples were applied on a glass plate using a 3 mil applicator, and a high-pressure mercury lamp 80 W
/ Cm1 light, irradiation distance 10cm, belt speed 20m
The curability (mj) was measured while changing the irradiation dose under the condition of / min.

(2) Water Resistance The cured film obtained in the curing test (irradiation dose: 200 mj) was immersed in deionized water at 25 ° C. for 24 hours, and the water absorption was calculated from the formula (I). Water absorption (%) = {(W1−W0) / W0} × 100 (I) W0 is the weight (g) of the initial cured film, and W1 is the weight (g) of the cured film after 24 hours.

(3) Pencil hardness The pencil hardness of the cured film obtained in the curability test (irradiation dose: 200 mj) was measured based on JIS K-5400.

[0034]

[Table 1]

In Table 1, the abbreviations indicate NDDA: 1,9-nonanediol diacrylate, 3PGA: tripropylene glycol diacrylate, 6EGA: polyethylene glycol diacrylate, ACMO: acryloylmorpholine.

Claims (2)

[Claims] 1. An epoxy (meth) acrylate obtained by reacting (A) (hydrogenated) dimer acid, diepoxide and (meth) acrylic acid, and (B) a poly (alkylene group having an alkylene group having 3 or more carbon atoms in the molecule). An active energy ray-curable resin composition comprising a functional reactive diluent. 2. (A) 10 to 90% by weight of an epoxy (meth) acrylate obtained by reacting (hydrogenated) dimer acid, diepoxide and (meth) acrylic acid, and (B) a polyfunctional reactive diluent. 10 to 90% by weight, (C) 0 to 10% by weight of a reactive diluent other than (B) and (D) 0 to 20% by weight of a photopolymerization initiator and / or 0 to 10% by weight of an additive. The active energy ray-curable resin composition according to claim 1, comprising: