JPS60199025A - Photo-setting resin composition - Google Patents

Abstract

PURPOSE:To provide a photo-setting resin composition having excellent adhesivity especially to the surface of metal and glass, and suitable as a coating agent, printing ink, adhesive, etc., by compounding specific components such as polyfunctional epoxy compound, dicyandiamide, a photo-polymerization initiator, etc. at specific ratios. CONSTITUTION:The objective composition can be produced by compouding (A) 100pts.wt. of a polyfunctional epoxy compound (e.g. bisphenol A epoxy resin) with (B) 100-300pts. preferably 20-200pts. of a compound having >=2 polymerizable unsaturated groups (e.g. ethylene glycol), (C) 0.3-15pts., preferably 0.5-10pts. of dicyandiamide, (D) 0.3-10pts., preferably 0.3-5pts. of a urea compound of formula (X and Y are H, Cl, Br, CH3, NO2, or OCH3; R1 and R2 are alkyl, alkenyl, aryl or aralkyl; R1 and R2 may together form a ring) (e.g. 3- phenyl-1-dimethylurea) and (E) preferably 0.5-20pts. of a photo-polymerization initiator (e.g. 4,4'-dimethyldiphenyl iodonium hexafluorophosphate, etc.).

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a photocurable resin composition, and more specifically,
The present invention relates to a photocurable resin composition suitable as a resin for forming thin film cured resin products such as printing materials, printing inks, and adhesives.

[Technical background of the invention and its problems]

In recent years, development of resins that are cured by radiation such as electron beams and light has been progressing in response to demands for pollution prevention and energy conservation.

However, conventional photocurable resin compositions have poor wettability to the coated object, and in order to increase the photocuring speed, the number of unsaturated groups in the photocurable prepolymer must be increased, or the ratio of polymerizable crosslinking agent must be increased. The crosslinking density was increased by increasing the crosslinking density. As a result, internal strains in the cured film remain unrelaxed, resulting in poor adhesion to objects and a very brittle coating film. Therefore, we use resin compositions with polar groups such as hydroxyl groups and carboxyl groups to improve wetting to the object to be coated, and add tilting agents such as dioctyl 7-talate to plasticize the cured film. At the same time, there are methods to increase adhesion, but none of these methods has yielded a photocurable resin composition with good adhesion.

[Purpose of the invention]

An object of the present invention is to provide a photocurable resin composition that has good adhesion to objects to be coated, particularly whole horse surfaces and glass surfaces, and is suitable for paints, printing inks, adhesives, and the like.

[Summary of the invention]

The photocurable resin composition of the present invention includes: (A) polyfunctional epoxy compound 100 parts by weight CB) compound having two or more polymerizable unsaturated groups in the molecule 10-3
00 parts by weight (C) Dicyandiamide 0.3 to 15 parts by weight CD) Following formula (1) (wherein, X and Y are -H, -CL, -Br.

-CR2, -No, -OCH, R1 and R1 represent an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and R3 and R8 may be combined to form a ring. ) A urea compound represented by: 0.3 to 10 parts by weight (K) of a photopolymerization initiator.

The present invention will be explained in more detail below.

The polyfunctional epoxy compound (A) in the present invention may be any compound as long as it has two or more epoxy groups in one molecule, and specific examples thereof include bisphenol Am epoxy resin; bisphenol F type epoxy resin; phenol novolac type epoxy resin; fatty m type epoxy resin; heterocyclic epoxy resin containing triglycidyl isocyanate, hydantoin epoxy, etc.; hydrogenated bisphenol human type epoxy resin; propylene glycol-diglycidyl ether, pentaeyl lysridol- Aliphatic epoxy resins such as polyglycidyl ethers; epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin; spiro ring-containing epoxy resins; O-allyl-phenol novolacized foods and epichlorohydrin Glycidyl ether type epoxy resin which is a reaction product of epichlorohydrin and a diallylbisphenol compound having an allyl group at the 0-position of each hydroxyl group of a bisphenol group, etc. , one or more selected from these can be used arbitrarily. Furthermore, in order to adjust workability and curing speed, monofunctional epoxy compounds such as phenyl glycidyl ether, butyl glycidyl ether, etc. may be used in combination.

Examples of the compound CB) having two or more polymerizable unsaturated groups in the molecule of the present invention include ethylene glycol, nato-2 ethylene glycol, 1,6-hextinediol, neopentyl glycol, and polyethylene glycol. Acrylic esters and methacrylic esters of alcohols; d such as maleic anhydride and fumaric acid;
β-unsaturated dibasic acid and polyhydric alcohol and/or part of the unsaturated acid is phthalic anhydride, in7thalic acid,
Examples include unsaturated polyesters obtained by substitution with saturated polybasic acids such as trimellitic acid and copolymerization. The blending amount is 10 to 300 parts by weight, preferably 20 to 20 parts by weight, per 100 parts by weight of the polyfunctional epoxy compound (A).
It is in the range of 0 parts by weight. Further, in order to adjust workability and curing speed, monofunctional monomer monomers such as acrylic esters, methacrylic esters, glycidyl methacrylate, etc. may be used in combination. The above compounds may be used alone or in a mixed system.

Dicyandiamide, which is the third essential component used in the present invention, is in the range of 0.3 to 15 parts by weight, preferably 05 to 10 parts by weight, based on 100 parts by weight of the polyfunctional epoxy compound (A). If it is outside the above range, desired curing speed and adhesive properties cannot be obtained.

The urea compound (D) in the present invention is represented by the above formula (1), and specific examples thereof include 3-phenyl-1-dimethylurea, 3-P-chlorophenyl-1,t-dimethylurea,
3-P-bromphenyl-1,1-dimethylurea, 3
-P-ayucyl-1,1-dimethylurine 13-phenyl-
Examples include 1,1-cyfuropentamethyleneurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 13-phenyl-1,1-dibutylurea, and the blending amount is determined based on the polyfunctional epoxy resin. The amount is in the range of 0.1 to 10 parts by weight, preferably 05 to 5 parts by weight, per 100 parts by weight of compound (A). If it exceeds the above range, desired curing speed and adhesive properties cannot be obtained.

The photopolymerization initiator (E) in the present invention is a compound that generates a Lewis acid upon irradiation with light, such as aromatic iodonic cation, aromatic sulfonium cation, aromatic ammonium cation and BF, -, PF, - , S
Any salt may be used as long as it is a salt with an anion represented by bF, "-, 80Ct, -, 5bCt-, etc., and specific examples include 4,4' dimethyl diphenyliodonium hexafluorophosphate, trifluorophosphate, etc. Examples include phenylsulfonium hexafluorophosphate and diphenyliodonium hexafluorophosphate, which are used alone or in a mixed system.In addition, as the photopolymerization initiator (E), U.S. Pat. No. 3,708,296
Various known compounds such as aryl diazonium salts of Lewis acids disclosed in No. 1, et al. can also be used. The blending amount is usually 0.5 to 20 parts by weight per 100 parts by weight of the polyfunctional epoxy resin compound [:A].

In the present invention, various additives may be added depending on the application of paint, printing ink, adhesive, etc., within a range that does not impede the object of the present invention. Such additives include finely powdered silica as a thixotropic agent, fluorine surfactants as leveling agents, silicon compounds as antifoaming agents; talc and calcium carbonate as extender pigments; titanium white as pigments for coloring. Phthalocyanine blue, carbon black; r-glycidoxyglobyltrimethoxysilane, vinyltriethoxysilane, etc. can be used as a silane coupling agent.

As a curing method, the coating film applied to the object to be coated is irradiated with active energy rays to be cured.

Although ultraviolet rays, electron beams, etc. can be used as active energy rays, a curing method using ultraviolet irradiation is advantageous due to its curing speed, price, etc.

In the present invention, the ultraviolet light mainly consists of light in the wavelength range of 150 to 450 nm, and is a chemical lamp.

Irradiation is performed using a high-pressure mercury lamp, metal helide lamp, xenon lamp, etc.

[Embodiments of the invention]

Bisphenol A epoxy resin with an epoxy equivalent of 500, bisphenol F epoxy resin with an epoxy equivalent of 170, glycidyl methacrylate), 1,6-hexanediol diacrylate, dicyandiamide, 3-P
-Chlorophenyl-1,1-dimethylurea°, diphenyliodonium hexafluorophosphate, and benzophenone were thoroughly mixed in the parts by weight shown in Table 1, and then kneaded with a three-roll roll to form the compositions of the present invention (Examples 1 to 3). 3) and comparative example compositions (comparative examples 1 and 2) were prepared.

The photocurable resin compositions obtained in the above Examples and Comparative Examples were applied to a film thickness of 20μ on an iron plate, an aluminum plate, or a glass plate.
Using a W high-pressure mercury lamp, irradiation was performed for 60 seconds from a distance of 6.5 cML below the lamp for curing. Cross-cut the cured coating film into 1 cfn pieces with a width of 1 cm using a cutter, apply cellophane tape and peel off at once.
We conducted an adhesion test to determine the number of squares remaining.
Test results of 2-1 were obtained.

〔Effect of the invention〕

The photocurable resin composition of the present invention has excellent adhesion, which is particularly required for paints, printing inks, adhesives, etc., and the industrial value of the present invention is extremely large.

(Margin below) Table-1

Claims (1)

[Claims] (A) Polyfunctional epoxy compound 100 parts by weight CB) Compound having two or more polymerizable saturated groups in the molecule 10-
300 parts by weight (C) Dicyandiamide 0.3 to 15 parts by weight [03 formula (11 (wherein, X and Y are -H, -CL, -Br. -C) i+s, -NOI, -0CHs, R1 and R1 represents an alkyl group, alkenyl group, aryl group, or aralkyl group, and R1 and R2 may combine to form a ring.) 0.3 to 10 parts by weight of a urea compound (E) Photopolymerization A photocurable resin composition comprising an initiator.