JPH0224847B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has excellent curing properties in air by coating the base surface of a molded article such as a resin,
For coatings with excellent coating properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the surface of the molded body. The present invention relates to a curable resin composition. In general, molded objects such as thermoplastic resins and thermosetting resins are not only lighter and have better impact resistance than metal products and glass products, but also are inexpensive and easy to mold. Due to its advantages, it is widely used to replace these materials in automobiles, motorcycles, household appliances, household goods, and many other fields. However, molded substrates made of these resins have a lower surface hardness than metals, glass, etc., and are vulnerable to scratching and friction, so they have the drawback of being easily scratched on the surface. For example, the use of these molded bodies is severely restricted due to defects in surface properties such as susceptibility to surface damage due to contact, collision, scratching, etc. during installation or transportation of parts of molded bodies or during use of the product. has been done. Many proposals have been made as methods for improving the above-mentioned defects on the surface of molded body substrates such as resins. Most of these methods involve coating the surface of these molded bodies with an outer coating layer made of a crosslinked curable resin. Among these film-forming elements, specific examples of resins or resin-forming components include silicone monomers or compositions of these components with various polymers, and resin compositions consisting of methylolmelamine and other curing components. , polyfunctional acrylic carboxylic acid ester derivatives, and compositions of these and other polymeric components have been proposed. Even if a film layer made of these film-forming elements is formed on the surface of a base material of a resin molded product such as polyolefin, the adhesion between the film layer and the base layer of the resin molded product is generally not good. The disadvantage is that the coating layer is easily peeled off. Furthermore, methods are known in which various treatments are applied to the surface of the resin molded body base layer in order to improve these defects. For example, surface treatments using corona discharge and primers have been proposed. However, even if surface treatment is performed, it is often difficult to sufficiently improve the adhesion between the base layer of a resin molded product such as polyolefin and the coating layer made of the crosslinked curable resin so as to be practical. Moreover, among the film-forming elements, silicone-based film-forming elements are expensive and have a disadvantage of being inferior in economic efficiency. Among the film-forming elements, various types of compounds have been proposed as polyfunctional acrylic carboxylic acid ester derivatives. for example,
Various types of compounds can be used as film-forming elements, such as poly(meth)acrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, and poly(meth)acrylates of aromatic (phenolic) polyhydroxyl compounds. is proposed. Even if these polyfunctional acrylic carboxylic acid ester derivatives are used alone as a film-forming element to form a film on the substrate surface of a resin molded article, the curing speed of these films in air during curing will be low. poor curing properties or poor coating properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. However, many of these physical properties are often inferior, and it has not been possible to fully satisfy the requirements for industrial scale use. In addition, attempts have been made to improve these drawbacks by using a combination of two or more of these film-forming elements, but none of them have been able to improve these drawbacks to some extent. Even if you can,
Another new difficulty arose when coating the substrate surface of a resin molded article such as polyolefin. The present inventors have worked diligently to develop a coating composition that has excellent curing properties during curing and has excellent coating properties when coated on the surface of a molded article substrate made of thermoplastic resin, thermosetting resin, etc. As a result of our investigation, we found that poly(meth), an aliphatic polyepoxy compound,
Acrylate product a, poly(meth)acrylate product b of a specific amount of polyoxyalkane polyol
The inventors have also discovered that the above object can be achieved by using a composition containing a specific amount of polymerization initiator c, and have arrived at the present invention. According to the present invention, when the curable resin composition for coating of the present invention is coated on the surface of a molded body substrate such as a resin to form an outer coating layer, the curing characteristics such as the curing speed in air during curing can be improved. excellent,
Many coating properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate are comprehensively evaluated. It has excellent characteristics. According to the present invention, (a) an aliphatic polyepoxy compound having at least two or more epoxy groups in one molecule and acrylic acid or methacrylic acid; In the formula, R ₁ is a poly(meth)acrylate having at least two units represented by a hydrogen atom or a methyl group, (b) 5 to 1000 parts by weight per 1 molecule of the above component (a) 100 parts by weight A polyoxyalkane polyol (poly( meth) acrylate; and (c) a polymerization initiator in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the above-mentioned components (a) and (b). things are provided. The poly(meth)acrylate compound a of a polyepoxy compound blended in the curable resin composition for coating of the present invention is an aliphatic polyepoxy compound having at least two or more epoxy groups in one molecule and an acrylic acid or It is a poly(meth)acrylate of a polyepoxy compound formed from methacrylic acid. Here, specific examples of aliphatic polyepoxy compounds having at least two epoxy groups in one molecule include methylene glycol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, and octylene glycol. , decylene glycol, dodecylene glycol, glycerin,
Aliphatic polyols such as trimethylolpropane, pentaerythritol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, diglycerin, ditrimethylolpropane, tritrimethylolpropane, dipentaerythritol, tripentaerythritol Examples include polyglycidyl ether, more specifically ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, Trimethylolpropane diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol diglycidyl ether, polyoxyethylene glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, diglycerin tetraglycidyl ether, diglycerin triglycidyl ether Glycidyl ether, diglycerin diglycidyl ether, ditrimethylolpropane tetraglycidyl ether, ditrimethylolpropane triglycidyl ether, ditrimethylolpropane diglycidyl ether, dipentaerythritol hexaglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol tetraglycidyl ether , dipentaerythritol triglycidyl ether,
Examples include dipentaerythritol diglycidyl ether, and a mixture of two or more of these may be used. The poly(meth)acrylate compound a of a polyepoxy compound blended into the curable resin composition for coating of the present invention is a poly(meth)acrylate of the polyepoxy compound formed from the polyepoxy compound and acrylic acid or methacrylic acid. ) is an acrylate compound, more specifically a general formula [] in which the epoxy group of the polyepoxy compound is ring-opened and a hydroxyl group and a (meth)acryloyloxyl group are bonded to adjacent carbon atoms. [In the formula, R ¹ represents a hydrogen atom or a methyl group. ] A compound that forms a unit represented by the following and has at least two of these units in its molecule, and thus has two or more (meth)acryloyloxyl groups and two or more hydroxyl groups in its molecule. It is. The poly(meth)acrylate a of the polyepoxy compound can be produced by reacting the polyepoxy compound with acrylic acid, methacrylic acid, or a mixture thereof. The reaction is carried out, if necessary, in the presence of a catalyst. As catalysts, primary amines, secondary amines, tertiary amines, salts thereof, quaternary ammonium compounds, organic acid salt compounds, Lewis acids or their complexes, alkali (earth) metal halides or hydroxides, Examples include hydrogen halides.
More specifically, butylamine, hexylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, dimethylamine hydrochloride, diethylamine acetate, tetramethylammonium chloride, tetraethylammonium bromide, sodium acetate, sodium trichloroacetate, phthalic acid. Sodium, potassium phthalate, tin chloride, zinc chloride, boron trifluoride ethylamine complex,
Boron trifluoride alcohol complex, lithium chloride, sodium bromide, calcium chloride, calcium bromide,
Lithium hydroxide, sodium hydroxide, hydrogen chloride,
Examples include hydrogen bromide, and these two
Mixtures of more than one species can also be used. The proportion used is usually based on 100 parts by weight of the polyepoxy compound.
It ranges from 0.005 to 5 parts by weight. The ratio of acrylic acid or methacrylic acid used is usually 0.6 per mole of epoxy group of the polyepoxy compound.
The amount ranges from 0.9 to 1.5 mol, preferably from 0.9 to 1.1 mol. The reaction is usually carried out at a temperature of -10 to 160°C. The poly(meth)acrylate b of polyoxyalkane polyol blended into the curable resin composition for coating of the present invention has one or more ether bonds and three or more hydroxyl groups in one molecule. It is a poly(meth)acrylate of polyoxyalkane polyol, and has three or more acryloyloxyl or methacryloyloxyl groups in one molecule, and may contain hydroxyl groups in some cases. do not have. The polyoxyalkane polyol constituting the poly(meth)acrylate of the polyoxyalkane polyol has one or more ether bonds and has three or more hydroxyl groups, and has three or more hydroxyl groups. At least one molecule of an alkane polyol is condensed with at least one molecule of an alkane polyol having two or more hydroxyl groups, and has at least one ether bond. Specific examples of the polyoxyalkane polyol include diglycerin, triglycerin, tetraglycerin, ditrimethylolethane, tritrimethylolethane, tetratrimethylolethane, ditrimethylolpropane, tritrimethylolpropane, tetratrimethylolpropane, and dipentaerythritol. , tripentaerythritol, and the like. There are usually 1 to 3 poly(meth)acrylates of the polyoxyalkane polyol in one molecule,
Preferably has 1 to 2 ether bonds,
3 to 10 acryloyloxyl or methacryloyloxyl groups, preferably 3 to 8
Its molecular weight is usually in the range of 260 to 3,000, preferably 260 to 1,000. Specifically, the poly(meth)acrylates of the polyoxyalkane polyols include diglycerol triacrylate, diglycerol trimethacrylate, diglycerol tetraacrylate, diglycerol tetramethacrylate, ditrimethylolethane triacrylate, ditrimethylolethane trimethacrylate, Ditrimethylolethane tetraacrylate, ditrimethylolethane tetramethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, tritrimethylolpropane triacrylate, tritrimethylolpropane pentaacrylate, dipenta Examples include erythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. The above poly(meth)acrylates of polyoxyalkane polyols can also be used in combination of two or more.
Poly(meth) of the polyoxyalkane polyol
The blending ratio of acrylate b is the poly(meth)acrylate of the polyepoxy compound.
It is necessary that the amount is in the range of more than 0 and 1000 parts by weight per 100 parts by weight, and more preferably 5 parts by weight.
It is preferably in the range from 20 to 700 parts by weight, particularly preferably from 20 to 500 parts by weight. When the blending ratio of the poly(meth)acrylate b of the polyoxyalkane polyol to 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound is more than 1000 parts by weight, the flexibility of the film obtained from the composition decreases. This causes problems such as cracks in the film. The film forming element component (polymerizable monomer component) blended into the curable resin composition for coating of the present invention may consist of only the above-mentioned two essential components, but may further include other polymerizable monomer components. In addition, copolymerization is also possible. Other polymerizable monomer components include by-products or intermediates during the production of the poly(meth)acrylate of the polyepoxy compound or the poly(meth)acrylate of the polyoxyalkane polyol, such as a monoepoxy compound. In addition to (meth)acrylates of polyepoxy compounds, mono(meth)acrylates of polyepoxy compounds, mono(meth)acrylates of polyoxyalkane polyols, (meth)acrylic acid, methyl (meth)acrylate, (meth)acrylic Examples include (meth)acrylic acid esters such as 2-hydroxyethyl acid. In order to apply the curable resin composition for coating of the present invention to the surface of a substrate of a molded article and crosslink and cure the composition to form a coating, a polymerization initiator c is added to the composition.
It is necessary to incorporate As the curing method, a curing method using ultraviolet rays, a curing method using heat rays, etc. are usually employed. In the case of ultraviolet curing, a photosensitizer is blended as a polymerization initiator. Specifically, the photosensitizer is benzoin or its like, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. ether,
Benzophenone, p-chlorobenzophenone, p
-Benzyl compounds such as methoxybenzophenone, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, 1-(4-isopropylphenyl)-2-
Hydroxy-2-methyl-1-propanone, 1-
Phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-tert-butylphenyl)-2
Examples include hydroxyalkyl phenyl ketone compounds such as -hydroxy-2-methyl-1-propanone. In the case of curing by heat, a radical initiator is blended, and specific examples of the radical initiator include azo compounds such as azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, dicumyl peroxide, Examples include peroxides such as cumene hydroperoxide. Furthermore, it is also possible to adopt a method in which both a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and UV curing and heat curing proceed simultaneously. It is also possible to adopt a method in which heat curing is progressed after the heat curing is progressed. Furthermore, it is also possible to adopt a method of proceeding with ultraviolet curing after proceeding with heat curing. The blending ratio of the polymerization initiator c is 0.01 to 20 parts by weight per 100 parts by weight of the poly(meth)acrylate a of the polyepoxy compound and the poly(meth)acrylate b of the polyoxyalkane polyol. The amount is preferably within a range of 0.1 to 10 parts by weight. When the blending ratio of the polymerization initiator is less than 0.01 parts by weight based on the total of 100 parts by weight of the poly(meth)acrylate a of the polyepoxy compound and the poly(meth)acrylate b of the polyoxyalkane polyol, The polymerizability of the composition decreases, making it impossible to obtain a hard coating, and if the amount exceeds 20 parts by weight, the coating obtained from the composition will be colored yellow. The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned three essential components, but may further include a polymerization inhibitor, a transparent filler,
Pigments, dyes, solvents, UV absorbers, stabilizers such as antioxidants, fluorescent brighteners, (reactive) oligomers such as methyl (meth)acrylate, polyurethane acrylate, polyester acrylate, and polymers such as polymethyl methacrylate, etc. Various additives and the like can be blended. The blending ratio of these additives is appropriate. In the curable resin composition for coating of the present invention, a finely powdered inorganic filler may be blended as necessary within a range that maintains the transparency of the cured film obtained therefrom. The average particle size of the fine powder inorganic filler is arbitrary as long as it is in the form of a powder, but it is usually 1 mμ to 10μ, preferably 1.5μ.
It ranges from mμ to 1μ. In addition, in order to maintain the transparency of the outer coating layer, the refractive index of the finely powdered inorganic filler is usually 1.40 to 1.60, preferably
It ranges from 1.42 to 1.58. Specifically, such fine powder inorganic fillers include glass powder, mica, glass beads, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, silica stone, silica sand,
Examples include quartz, kaolinite, montmorillonite, sericite, talc, chlorite, chinastone, and feldspar. In addition, the surface of these finely powdered inorganic fillers can be coated with alkyl carboxylates, silane couplers, titanium couplers, Cl ₂ Si (CH ₃ ) ₂ ,
Those surface-treated with alcohol or the like can also be used in the same way. Furthermore, colloidal silica, methanol silica sol, ethanol silica sol, isopropanol silica sol, etc. in which the inorganic filler is suspended in water or alcohol can also be used. Among these fine powder inorganic fillers, blending fine powder silica significantly improves the surface hardness, scratch resistance, and abrasion resistance of the outer coating layer without impairing transparency and surface gloss. Therefore, it is particularly preferable. The blending ratio of these fine powder inorganic fillers is usually 0.5 to 200 parts by weight per 100 parts by weight of the poly(meth)acrylate A of the polyepoxy compound and the poly(meth)acrylate B of the polyoxyalkane polyol.
The preferred range is 0.5 to 100 parts by weight. A solvent is added to the curable resin composition for coating of the present invention as necessary to improve its coating workability, and the composition is maintained in a solution state or a suspended state. The solvent is also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition.
Specifically, the solvents include benzene, toluene, xylene, cumene, ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin,
Hydrocarbons such as cyclohexane and methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, bromoform, trichrene, ethylene dichloride, perchloroethane, trichloroethane, tetrachloroethane,
Halogenated hydrocarbons such as propylene dichloride, chlorobenzene, bromobenzene, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol,
Alcohols such as ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol Ethers such as dimethyl ether, acetonitrile,
Examples include nitrites such as propionitrile and capronitrile, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate. . The blending ratio of these organic solvents is based on the poly(meth)acrylate of the polyepoxy compound a.
The amount is usually 5 to 3,000 parts by weight, preferably 10 to 2,000 parts by weight, based on a total of 100 parts by weight of the poly(meth)acrylate b of the polyoxyalkane polyol. In the composition of the present invention, a composition containing the above-mentioned essential components and various additive components such as an inorganic or organic filler, a solvent, a stabilizer, etc. added as necessary, or a solution composition or a suspension composition. The method for preparing is to prepare the above-mentioned raw material mixture,
Regular roll, Banbury mixer, ball mill,
Examples include kneading and mixing methods using an attritor, a whipper, an oak mixer, a desolver, a homogenizer, a colloid mill, a sand mill, a vibration mill, a mixer, a mixing tank, etc., and compositions uniformly dissolved or dispersed by these methods. is obtained. The method for applying the solution composition and suspension composition to the substrate surface of the molded article includes:
Conventionally known methods such as a brush coating method, a spray method, a dipping method, a bar coating method, a roll coater method, a spin coater method, and a gel coater method can be employed. Examples of methods for drying the coating film include natural drying, forced drying using carrier gas, heating drying using an infrared oven, far-infrared oven, and hot air oven. Examples of methods for curing the above-mentioned coating film to form a film include a method of polymerizing and crosslinking hardening with light, particularly ultraviolet rays, a method of polymerizing and crosslinking hardening with heat, and the like. Among these polymerization and crosslinking curing methods, the photocuring method is usually -10 to 150℃,
Light irradiation is preferably carried out at a temperature of 5 to 130°C, and the time is usually 1 sec to 1 hr, preferably 1 sec to 10 min. Further, in the thermosetting method, the temperature during curing is usually -10 to 150°C, preferably 5 to 130°C, and the time required for curing is usually 0.05 to 10 hr, preferably 0.1 to 8 hr. The curable resin composition for coating of the present invention can be coated on the surface of any molded body made of thermoplastic resin, thermosetting resin, metal, or the like. The shape of the molded product may be a film, a sheet, a plate, a molded product having a curved surface or an uneven surface, or any other shape. Specifically, the thermoplastic resin constituting the base layer includes, for example, polyolefins such as a homopolymer of α-olefin or a copolymer mainly composed of α-olefin, polyacrylic acid ester resin, polycarbonate resin, polyester resin,
Examples include polyamide resin. Among these thermoplastic resins, the base resin layer constituting the laminate molded product is preferably polyolefins, polyacrylic ester resins, or polycarbonate resins. Specifically, the polyolefins include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene; or a copolymer consisting of a mixture of two or more of the above-mentioned α-olefins, and a lower aliphatic vinyl carboxylate such as vinyl acetate or vinyl propionate;
Contains small amounts (for example, 30 mol% or less) of other components such as acrylic carboxylic acid esters such as methyl acrylate, metal salts of acrylic acid, methyl methacrylate, and metal salts of methacrylic acid, and salts of acrylic carboxylic acids. Examples include copolymers. Among these polyolefins,
Polyolefins having crystallinity are commonly used. Specific examples of the polyacrylic carboxylic acid ester resin include homopolymers or copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. can. Among these polyacrylic carboxylic acid ester resins, polymethyl methacrylate is preferably used in the thermoplastic resin base resin layer of the present invention. Specific examples of the polycarbonate resin include bisphenol A polycarbonate. Specific examples of the polyester resin include polyethylene terephthalate, polytetramethylene terephthalate, bisphenol A/isophthalic acid/terephthalic acid copolycondensate, and oxybenzoic acid polycondensate. Specifically, the polyamide resin includes nylon 6, nylon 6/6, nylon
10, nylon 12, etc. In addition to the above resins, polyacetal, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer,
polysulfone resin, polyphenylene oxide,
Examples include modified polyphenylene oxide, polyphenylene sulfide resin, and polyether sulfone resin. Specifically, the thermosetting resin constituting the base layer includes unsaturated polyester resin, epoxy resin,
Examples include melamine resin, diallyl phthalate resin, and polyallyl glycol carbonate resin. Furthermore, specific examples of the metal constituting the base layer include aluminum, iron, stainless steel, and the like. When coating the substrate surface of a molded article such as a resin with the curable resin composition for coating of the present invention, the substrate surface of the molded article is washed with various solvents, an alkaline aqueous solution, and a surfactant. Various surface treatments such as ultrasonic cleaning, electrolytic cleaning, blasting, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, chemical conversion treatment, etc. can be applied. Furthermore, when laminating an outer coating layer made of the curable resin composition for coating of the present invention on the substrate surface of the molded article, an intermediate adhesive layer made of a primer may be placed between the substrate layer and the outer coating layer. It is also possible to improve the adhesion between both layers by forming a three-layer laminate. When the base layer is polyolefin, the primer may be α, β-unsaturated carboxylic acid, its acid anhydride, its ester, etc.
Modified polyolefins grafted with β-unsaturated carboxylic acid or derivative components thereof are commonly used. In this way, the composition of the present invention is coated on the surface of the base layer of the molded article, which has been subjected to surface treatment or primer treatment as necessary, by the method described above, and then subjected to a curing treatment. A molded article on which a coating made of the curable resin composition for coating of the present invention is laminated can be used for various purposes.
Specifically, for example, lighting boards, sky domes,
Solar water heater panels, glove box panels, watch glasses, various lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, coffee maker shower domes and coffee containers, water tanks, and illuminator covers. , covers for stereo equipment such as players, dials and covers for various meters, covers for headlights and taillights in automobiles, level sensors, various films such as shatterproof films for glass, release films, insulating films, agricultural films, etc., and lights. Recycled video discs, observation windows for various equipment such as clothes dryers, electric washing machines, dryers, oil tanks, windshields for motorcycles, jeeps, motorboats, etc., automobile glass (windshields, etc.)
rear windows, opera windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, etc.
Tableware, mirrors, various containers such as oil bottles and cosmetic bottles,
Relay cases, fuse boxes, motorcycle side covers and mudguards, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulating films, floor tiles, floor sheets,
Doors, table boards, wall tiles, countertop decorative boards, shelf boards, wall sheets, wallpaper, furniture, lightweight wall boards, tableware, chairs, bathtubs, toilets, refrigerators, wall panels, water supply and drainage pipes, raceways, ducts, curtain rods , rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foils, various containers, automobile interior materials, vanity tables, flower boxes, particle boards,
Examples include tiles, shutters, shutters, waterproof pans, pipes, wiring materials, gear cams, knobs, solenoid valve frames, fans, instrument panels, bumpers, and brakes.
In addition to the above, it is also used in home appliances, automobile parts, motorcycle parts, vending machine parts, civil engineering and construction materials, general industrial materials, office information equipment, electronic parts, packaging materials, sports equipment, medical equipment, and nuclear power-related parts. can do. Next, the present invention will be specifically explained using examples. In addition, in the main text of the specification or the examples, evaluation was performed by the following method. (1) Refractive index Add 2wt% of a sufficiently dried inorganic substance to a liquid with a known refractive index, and after sufficiently dispersing it, visually check the transparency. The refractive index should be the same as that of the most transparent liquid. (2) Surface gloss (gloss) Measured according to 60 degree specular gloss in JIS K 5400-1979. (3) Light transmittance Measured according to JIS K 6714. (4) Adhesion The test was conducted according to the cross-cut test in JIS K 5400-1979. Judgment is based on how many of the 100 pieces are glued together. (5) Dropping sand abrasion 800 g of silicon carbide abrasive material is dropped onto the coating according to the method of JIS T 8147-1975. Abrasion resistance is expressed by the difference in surface gloss before and after the test. The smaller the number, the better the wear resistance. (6) Taper wear According to ASTM D-1044 method, wear ring CS
−10, rotate the film 1000 times with a load of 500 g. Wear resistance is expressed by the amount of wear on the coating after the test. The smaller the amount of wear, the better the wear resistance. (7) Pencil hardness Measured according to JIS K 5651. (8) Flexibility A strip test piece with a width of 5 mm and a length of 10 cm is 2 cm in diameter.
It is expressed as the angle at which the coating cracks or peels off from the substrate when the coating is folded along the outer circumference of the cylinder. The larger the value, the better the flexibility. (9) Water resistance After immersing the test piece in pure water at 40℃ for 240 hours,
The appearance and adhesion of the outer coating layer were evaluated. (10) Heat resistance The appearance and adhesion of the outer coating layer were evaluated after holding the test piece in a gear aging tester at 80°C for 400 hours. (11) Volatile oil resistance The appearance and adhesion of the outer coating layer after immersing the test piece in petroleum benzine for 24 hours at room temperature was evaluated. (12) Gasoline resistance The appearance and adhesion of the outer coating layer were evaluated after the test piece was immersed in regular gasoline for 24 hours at room temperature. (13) Heat cycle resistance The test piece was kept in an air oven at 80℃ for 2 hours, then left at room temperature for 1 hour, then kept in a cold room at -30℃ for 2 hours, and then at room temperature for 1 hour. put. This cycle was repeated 10 times, and changes in the appearance of the outer coating layer were visually observed and adhesion was evaluated. (14) Weather resistance Place the test piece in a sunshine weatherometer.
After holding for 400 hours, the appearance and adhesion of the outer coating layer were evaluated. Example 1 500 ml of 75 g of diacrylate of ethylene glycol diglycidyl ether, 20 g of dipentaerythritol tetraacrylate, 5 g of dipentaerythritol pentaacrylate, 5 g of benzoin isopropyl ether and 120 g of toluene
The mixture was charged into a two-necked flask and stirred at room temperature for 1 hour to prepare a transparent coating composition A. On the other hand, polypropylene (Mitsui Petrochemical Industries)
An injection square plate (thickness: 3 mm) made from 1,1,1-trichloroethane vapor (manufactured by Mitsui Petrochemical Polypropylene SJ-313) was exposed to 1,1,1-trichloroethane vapor for 1 minute, then dried at room temperature for 1 minute, and then exposed to anhydrous maleic acid. Acid denaturation
The injection square plate was immersed in a 15 g/toluene solution B of PER (propylene content 67 mol%, maleic anhydride content 6 wt%) for 20 seconds and slowly pulled up. After drying at room temperature for 5 minutes, heating drying was performed at 80° C. for 30 minutes. Next, the primer-treated polypropylene square plate was immersed in the coating composition A for 30 seconds, slowly pulled up, and then heated at room temperature for 1 minute.
Drying was performed at 60°C for 5 minutes. This test piece
The outer coating layer was cured by irradiating ultraviolet light for 30 seconds at a distance of 15 cm under a 1.5KW high-pressure mercury lamp (120W/cm). Table 1 shows the performance of this coating. Examples 2 to 7 In Example 1, instead of using coating composition A described in Example 1, polyacrylates of polyepoxy compounds described in Table 1, polyacrylates of polyoxyalkane polyols,
A test piece was prepared by coating the surface of polypropylene in the same manner as in Example 1, except that a coating composition prepared using the polymerization initiator and solvent in the amounts shown in Table 1 was used. The results are shown in Table 1. Examples 8 to 9 Polyacrylates of polyepoxy compounds listed in Table 1, polyacrylates of polyoxyalkane polyols, polymerization initiators, and 1,1,1
- Weigh out the amount of trichloroethane listed in Table 1, and add to this mixture, while stirring, fine powdered silica with an average particle size of 20 mμ and a refractive index of 1.45 (manufactured by Nippon Aerosil).
(trade name: R-972) was gradually added (the amount used is shown in Table 1), and the mixture was thoroughly stirred until uniform dispersion was obtained. Then, transfer the mixture to an attritor (manufactured by Mitsui Miike Seisakusho) filled with steatite balls, and turn on the agitator while cooling the tank with water.
Rotate at 150 rpm and mix for 3 hours. Thereafter, the amount of n-butanol listed in Table 1 was added, and after an additional 10 minutes of mixing, the mixture was removed from the attritor and designated as Coating Composition A. In Example 1, a test piece having a polypropylene surface coated was prepared by the method described in Example 1, except that the coating composition described in Example 1 was used instead of the coating composition described in Example 1. The results are shown in Table 1. Comparative Examples 1 and 2 The polyacrylates of polyepoxy compounds, polyacrylates of polyoxyalkane polyols, polymerization initiators and solvents listed in Table 1 were
A test piece having a polypropylene surface coated thereon was prepared by the method described in Example 1, except that coating composition A prepared by measuring the amount described in Example 1 and stirring and mixing at room temperature for 1 hour was used. The results are shown in Table 1. Comparative Example 3 Single polypropylene (manufactured by Mitsui Petrochemical Industries, Ltd., SJ-
Table 1 shows the performance of 313). The abbreviations used in Table 1 below represent the following compounds, respectively. EGGA...Diacrylate of ethylene glycol diglycidyl ether EGGM...Dimethacrylate of ethylene glycol diglycidyl ether PGGA...Diacrylate of propylene glycol diglycidyl ether GGA...Triacrylate of glycerin triglycidyl ether DPTA...Dipentaerythritol tetraacrylate DPPA... Dipentaerythritol pentaacrylate DPHA... Dipentaerythritol hexaacrylate DGTA... Diglycerin tetraacrylate BIE... Benzoin isopropyl ether BPH... Benzophenone IHP... 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1- propanone

【table】

【table】

[Table] Example 10 A 3 mm thick injection molded sheet of poly-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries, Ltd., product name: TPX MX004) was molded with maleic anhydride-modified EPR.
Primer treatment was performed by immersing the sample in a 1,1,1-trichloroethane solution containing 15 g/concentration of (maleic anhydride content: 7.7 wt%) for 10 seconds. After being left at room temperature for 5 minutes, it was immersed in the coating composition described in Example 9 for 10 seconds. After drying at room temperature for 1 minute and then at 60°C for 5 minutes, photopolymerization was performed as described in Example 9 to obtain poly-4
- A test piece coated with methyl-1-pentene was prepared. The results are shown in Table 2. Examples 11 and 12 In Example 10, polyester was used as the base polymer.
Instead of using 4-methyl-1-pentene, Table 2
A test piece was prepared using a polymer sheet having a thickness of 3 mm as described in Example 10, and the surface of the polymer was coated by the method described in Example 10, except that the pretreatment described in Table 2 was performed. The results are shown in Table 2. Comparative Examples 4 to 6 Polymers not coated with the coating composition of the present invention
4-Methyl-1-pentene (Mitsui Petrochemical Industries)
manufactured by Teijin Kasei, MX004), polycarbonate (Teijin Kasei)
Table 2 shows the performance of Panlite L-1250 (manufactured by Mitsubishi Rayon) and polymethyl methacrylate (Acrylite L, manufactured by Mitsubishi Rayon).

[Table] Example 13, Comparative Example 7 In Example 1, the coating composition A described in Example 9 was used instead of the coating composition A described in Example 1, and polypropylene was used as the molded body base. Instead of using 2 mm thick unsaturated polyester resin (manufactured by Showa Kobunshi, Rigoratsu
A test piece whose surface was coated with unsaturated polyester resin was prepared by the method described in Example 1 except that MCS-302) was used. The film thickness of this test piece was 9μ, the surface gloss was 81, the adhesion was 100/100, and the pencil hardness was 4H (Example 13). On the other hand, the unsaturated polyester resin not coated with the coating composition of the present invention has a surface gloss of 63 and a pencil hardness of
3H (Comparative Example 7).

Claims (1)

[Scope of Claims] 1 (a) A compound obtained by the reaction of an aliphatic epoxy compound having at least two or more epoxy groups in one molecule with acrylic acid or methacrylic acid and having the formula (b) 5 to 1000 parts by weight per 100 parts by weight of ^component (a), 1 A polyoxyalkane polyol derived from a polyoxyalkane polyol having one or more ether bonds and three or more hydroxyl groups in the molecule, and having three or more acryloyloxy or methacryloyloxyl groups in the molecule. A curable resin for coating, characterized in that it contains a (meth)acrylate, and (c) a polymerization initiator in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the above-mentioned components (a) and (b). Composition. 2 0.5 per 100 parts by weight of the total amount of component (a) and component (b)
The curable resin composition for coating according to claim 1, which contains 200 parts by weight of a finely powdered inorganic filler.