JPS6017295B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition that significantly improves the abrasion resistance, hot water resistance, surface hardness, heat resistance, solvent resistance, chemical resistance, etc. of plastic surfaces.

Among the plastics currently used, acrylic and methacrylic resins have excellent mechanical properties and are aesthetically pleasing, but they have poor abrasion resistance, surface hardness, and It is inferior in heat resistance or chemical resistance.Diethylene glycol pisallyl carbonate resin is a resin that has relatively excellent wear resistance, but the wear resistance and surface hardness of this resin are not necessarily sufficient for practical use. Therefore, various methods have been studied to improve the surface hardness of acrylic and methacrylic resins.

For example, in Japanese Patent Publication No. 35-17847, monomers such as diethylene or triethylene glycol dimethacrylate or alkanediol dimethacrylate having 3 to 6 carbon atoms are added inside the mold to improve surface hardness. A method is described in which Western-type polymerization of methyl methacrylate is performed after coating in the form of a film to improve surface hardness. Samurai Ko No. 37-9827 discloses that after coating a crosslinking monomer such as acrylic methacrylate or ethylene dimethacrylate and a polymerization catalyst on a mold, it is brought into close contact with a base resin previously manufactured in the same shape. A method of improving surface hardness by heating was introduced in Samurai Seki 47-26419 by mixing a hydrolyzate of alkyl silicate such as butyl silicate and an English polymer of pinyltriethoxysilane and vinyl acetate in a solvent. A method is described in which a liquid prepared by the above method is applied to a methacrylic resin plate and cured by heating. In addition, Japanese Patent Publication No. 45-34707 describes a composition containing an epoxy group-containing alkoxysilane, which includes a polymer of a hydroxyalkyl ester of a vinyl unsaturated carboxylic acid and 3 to 30% of the total composition. 30% of the aminoplast, the epoxy-containing alkoxysilane was added o.c. to the total composition. A method is described in which the addition of 5 to 10% is applied to a metal plate and then thermally cured. ．． However, Special Publications No. 35-17847 and No. 37-9
The method described in No. 827 has the disadvantage that curing takes a long time, and the abrasion resistance is not sufficient.

The coating strength obtained by the method described in Japanese Patent Publication No. 45-34707 has drawbacks such as lack of transparency and low surface hardness, so it is used for coating plastic products to increase surface hardness and resistance. It is not possible to expect the development of abrasive properties. Furthermore, the method described in JP-A-47-2641Y has a fatal drawback in terms of heat resistance. In other words, when applied to the surface of polymethyl methacrylate,
When a cured film is heated to 80° C. or higher for just a few minutes, a wrinkling phenomenon immediately appears on the surface and the optical properties of the resin are lost. Furthermore, this cured film cannot be applied thinly to all resins, and is unsuitable for polycarbonate resins, for example. On the other hand, cured films applied to plastic surfaces generally have poor hot water resistance compared to acrylic, methacrylic resins, polycarbonate, and diethylene glycol pisaryl carbonate resins, so the adhesion of the coating deteriorates over time. There is no doubt that wear resistance and aesthetics will deteriorate. For this reason, some methods of improving the water resistance of cured films have been studied. For example, Samurai Seki 49
-10703 P' This is a method for improving hot water resistance and abrasion resistance by coating a hydrolyzed product of vinylsilane and mercabutosilane on a methacrylic resin plate.
No. 17528 describes the hydrolysis products of acryloxysilane and mercaptoxysilane as unsaturated polyester resins.
A method for coating RP plates to improve hot water resistance and abrasion resistance is described. However, the method described in Samurai Kai No. 49-110703 and Japanese Patent Kokai No. 49-117528 causes cracks to form in the paint film after being immersed in 6000°C hot water for just a few minutes, resulting in poor adhesion and durability. It has the fatal disadvantage of reduced wear resistance. In order to improve the above-mentioned drawbacks, the inventors of the present invention have repeatedly studied the coating of silicon-containing polymers on plastic substrates, and have found that they have excellent hot water resistance, abrasion resistance, surface hardness, heat resistance, weather resistance, We have completed a curable resin composition suitable for forming a film on the surface of plastic substrates with excellent chemical properties and adhesion to plastic substrates. The curable resin composition according to the present invention contains 10 to 20 parts by weight of at least one aminosilane compound selected from the group represented by the general formula, and at least one epoxy group selected from the group represented by the general formula. 10 to 5 parts by weight of the vinyl compound or polymer thereof and 10 to 9 parts by weight of at least one polymerizable vinyl monomer selected from the group represented by the general formula, and 10 to 9 parts by weight of the polymer thereof in the presence of a suitable solvent. Obtained by the following reaction: However, in the above general formula, R is a straight chain or branched alkyl group having 6 or less carbon atoms; R2 is a straight chain or branched alkyl group having 4 or less carbon atoms; R3 is OR2 or or a straight chain or branched alkyl group having 4 or less carbon atoms: R4 is a mirror or branched alkylene group having 6 or less carbon atoms, R5 is hydrogen, and 1 carbon atom or less.
0 or less straight chain or branched alkyl group, cyclohexyl group, benzyl group, tolyl group, aminoalkyl group, or hydroxyalkyl group; R6 is a straight chain or branched lower alkyl group; R7 is ethylene or propylene group; R8 is hydrogen or lower Alkyl group: R9 is an alkylene group having 6 or less carbon atoms;

As one of the aminosiphne compounds that are raw ingredients of the composition of the present invention, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltripropoxysilane, aminomethyltributoxysilane, aminoethyltrimethoxysilane, and aminoethyltrimethoxysilane are used. , aminoethyltripropoxysilane, aminoethyltributoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltriproboxysilane, aminopropyltributoxysilane, N-aminomethyl-aminomethyltrimethoxysilane, N-aminomethyl- Aminomethyltriethoxysilane, N-aminomethyl-aminomethyltripropoxysilane, N-aminomethyl-aminomethyltributoxysilane, N1B-aminoethyl-8-aminoethyltrimethoxysilane, N18-aminoethyl-8-aminoethyltri Ethoxysilane, N-aminoethyl-B-aminoethyltripropoxysilane, N-aminoethyl-moaminoethyltriptoxysilane, N-y-aminopropyl-y-aminopropyltrimethoxysilane, N-y-aminopropyl- y-aminopropyltriethoxysilane, Ny-aminof.

Lopyl-y-ami/propyltripropoxysilane, N
-amino/propyl-y-aminopropyltributoxysilane, N-aminomethyl-6-aminoethyltrimethoxysilane, N-aminoethyl-8-aminoethyltributoxysilane, N-aminomethyl-y-aminopropyltrimethoxysilane, N -Aminomethyl-aminopropyltributoxysilane, N-8-aminoethyl-aminomethyltrimethoxysilane, N-8-aminoethyl-aminomethyltributoxysilane, N-aminomethyl-y-aminopropyltrimethoxysilane, N -aminomethyl-y-aminopropyltributoxysilane,
Ny-aminopropyl-aminomethyltrimethoxysilane, Ny-aminopropyl-aminomethyltributoxysilane, Ny-amino/propyl-6-aminoethyltrimethoxysilane, Ny-aminopropyl B -aminoethyltributoxysilane, N-8-aminoethyl-y-aminopropyltrimethoxysilane, N-8-aminoethyl-y-aminopropyltributoxysilane and the like. The epoxy group-containing vinyl compound which is one of the raw material components of the composition of the present invention is allyl glycidyl phenol, methallyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate. Examples of the polymerizable pinyl monomer compound, which is one of the raw material components of the composition of the present invention, include methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pendyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, hexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate , isobutyl acrylate, til, pendyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, lauryl acrylate, acrylic acid, vinyl acetate, vinyl propionate,
Vinyl butyrate, vinyltoluene, styrene, methacrylic acid, neobentyl glycol dimethacrylate, neobentyl glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate -tetraethylene glycol diacrylate, hexanediol diacrylate, hexanediol dimethacrylate, bentanediol diacrylate, bentanediol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, Hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, tripropylene Glycol monoacrylate, tripropylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monoacrylate
Methacrylate, tetrapropylene glycol monoacrylate, tetrapropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate,
Ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, ethoxydipropylene glycol acrylate, ethoxydipropylene glycol methacrylate, propoxydiethylene glycol acrylate, propoxydiethylene glycol methacrylate, propoxydipropylene glycol acrylate, propoxydipropylene glycol methacrylate, butoxydiethylene glycol acrylate, butoxydiethylene glycol methacrylate , butoxydipropylene glycol acrylate, butoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxytripropylene glycol acrylate, methoxytripropylene glycol methacrylate, ethoxytriethylene glycol acrylate, ethoxytriethylene glycol acrylate Ethylene glycol methacrylate, ethoxytripropylene glycol acrylate, ethoxytripropylene glycol methacrylate, propoxytriethylene glycol acrylate,
Propoxytriethylene glycol methacrylate, propoxytripropylene glycol acrylate, propoxytripropylene glycol methacrylate, butoxytriethylene glycol acrylate, butoxytriethylene glycol methacrylate, butoxytripropylene glycol acrylate, butoxytripropylene glycol methacrylate, methoxytetraethylene glycol acrylate, Methoxytetraethylene glycol methacrylate, methoxytetrapropylene glycol acrylate, methoxytetraph.

Ropylene glycol methacrylate, ethoxytetraethylene glycol acrylate, ethoxytetraethylene glycol methacrylate, ethoxytetrapropylene glycol acrylate, ethoxytetrapropylene glycol methacrylate, propoxytetraethylene glycol acrylate, propoxytetraethylene glycol methacrylate, propoxytetrapropylene glycol acrylate, propoxy Tetrapropylene glycol methacrylate, ptoxytetraethylene glycol acrylate, butoxytetraethylene glycol methacrylate, butoxytetrapropylene glycol acrylate, butoxytetrapropylene glycol methacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypolypropylene glycol acrylate, Methoxypolypropylene glycol methacrylate,
Ethoxypolyethylene glycol acrylate, ethoxypolyethylene glycol methacrylate, ethoxypolypropylene glycol acrylate, ethoxypolypropylene glycol methacrylate, propoxypolyethylene glycol acrylate, propoxypolyethylene glycol methacrylate, propoxypolypropylene glycol acrylate, propoxypolypropylene glycol methacrylate, poxypolyethylene glycol acrylate, butoxypolyethylene Examples include glycol methacrylate, butoxypolypropylene glycol acrylate, and butoxypolypropylene glycol methacrylate. The composition of the present invention may be produced by mixing the raw material components at once and polymerizing or copolymerizing the polymerizable vinyl monomer to a desired degree using a radical polymerization initiator or ionizing radiation, or It can also be produced by first polymerizing or copolymerizing a polymerizable pinyl monomer to a desired degree and then adding and mixing an aminosilane compound and a solvent.

The composition of the present invention produced as described above can be used, for example. Using a solvent such as loform, acetone, methyl ethyl ketone, etc., it is possible to adjust the viscosity to an appropriate value according to the coating method. Depending on the shape of the base resin and the purpose of use, the coating method can be arbitrarily selected from brush coating, spray coating, dipping coating, etc. Alternatively, it can be applied directly to the fin steel, heated and partially coated. Alternatively, after curing the entire material, the monomer serving as the base material may be polymerized by method. It is also possible to apply the resin directly to the mold, bring it into close contact with a previously produced plastic base resin, and heat it to bond it, forming a cured film on the surface. For curing of the primer applied to the plastic substrate in this way, any temperature in the range of 30q○ to 200oo can be selected, but preferably 60q○ to 15
The curing reaction can be allowed to proceed for several minutes to several hours at 0q○.

By coating and curing the curable resin composition of the present invention on a plastic substrate, it is possible to improve the abrasion resistance, surface hardness, heat resistance, weather resistance, etc. of the plastic substrate. In particular, even when the composition of the present invention is applied to transparent plastic substrates such as polycarbonate (polycarbonate, polyethylene glycol bisallyl carbonate), the transparency can be improved without eroding or whitening the substrate. Performance tests of cured films using the compositions of the present invention were evaluated according to the following.

Abrasion resistance (scratching strength) After lightly rubbing the coating with #0000 steel wool, rub it once again, and then grade the degree of scratches on the coating into four ranks: A': No scratches at all. do not have.

A: Up to 10 scratches will occur.

B: 10 or more scratches are present, but the gloss is still maintained.

C: Loss of luster due to countless scratches. Adhesion to the substrate: Peel test, i.e., with a razor blade on the coating.
Make a 10M hard cut that reaches the base material of 1 square millimeter, stick cellophane tape on top of it, and
The number of coatings remaining when the film was strongly peeled off was determined.

When there are no chicks, it is displayed as 100/100. Hereinafter, the present invention will be explained more specifically based on Examples.

Note that "parts" used in the examples are by weight unless otherwise specified. Example 1 10 parts by weight of N-8-aminoethyl-8-aminoethyltrimethoxysilane, 5 parts by weight of glycidyl methacrylate, and 1 part by weight of hydroxypropyl acrylate, p
- After mixing 15 parts by weight of dioxane, 6 parts by weight of cobalt
It was irradiated with y-rays of 0 and 1 at a dose rate of 5×1 R/hr for 2 hours at room temperature.

This solution was applied to a transparent plastic material and cured by heating. The cured film obtained was colorless and transparent in all cases, and had a 60%
No change in appearance was observed even after hot water treatment. The results obtained are shown in Table-1. Table 1 Example 2 After mixing 2 parts by weight of glycidyl methacrylate, 1 part by weight of hydroxyethyl methacrylate, and 10 parts by weight of methyl alcohol,
Irradiation was performed at room temperature for 2 hours at a dose rate of 1 piR/hr.

After adding 4 parts by weight of N-8-aminoalkyl-8*-aminoethyltrimethoxysilane to this solution, it was applied onto a transparent material and cured by heating. The obtained cured films were colorless and transparent in all cases, and no change in appearance was observed even after treatment with hot water at 60 qo. The results obtained are shown in Table-2. Table 2 Example 3 After mixing parts by weight of allyl glycidyl ether 2, 5 parts by weight of hydroxyethyl methacrylate, parts by weight of hydroxyethyl acrylate 1 and 2 parts by weight of penzoyl peroxide, 80q0 and a superfluous solution were prepared. The viscosity was increased to 150-20 p.

A mixture of 10 parts by weight of ethyl cellosolve and 3 parts by weight of aminomethyltrimethoxysilane was added to this rice lees liquid, and the mixture was applied onto a transparent material and cured by heating. The cured films obtained were colorless, transparent, uniform films in all cases, and no change in appearance was observed even after treatment with hot water at 60°C. The results obtained are shown in Table 3. Table-3

Claims (1)

[Scope of Claims] 1. At least one aminosilane compound selected from the following group 1, 2. At least one epoxy group-containing vinyl compound or a polymer thereof selected from the following formula II, and 3. from the following group III. A thermosetting resin composition consisting of at least one selected polymerizable monomer or its polymer, and two solvents; Group I; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Group II; ▲Mathematical formulas, chemical formulas , tables, etc. ▼ Group III; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, in the above general formula, R_1 is a straight chain or branched alkylene group with 6 or less carbon atoms; R_2 is a straight chain with 4 or less carbon atoms or a branched alkyl group; R_3 is OR_2 or a straight chain or branched alkyl group having up to 4 carbon atoms; R_4 is a straight chain or branched alkylene group having up to 6 carbon atoms; R_5 is hydrogen, a straight chain having up to 10 carbon atoms or branched alkyl group, cyclohexyl group, benzyl group, tolyl group, aminoalkyl group, or hydroxyalkyl group; R_6 is a straight chain or branched lower alkyl group; R_7 is ethylene or propylene group; R_8 is hydrogen or lower alkyl group; R_9 is carbon an alkylene group having 6 or less atoms; X is hydrogen or a methyl group; Y is a lower alkylene group; m is an integer of 2 to 20;