JPH0410490B2 - - 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 extremely limited due to shortcomings in surface properties such as susceptibility to surface damage due to contact, collision, scratching, etc. during installation or transportation of molded parts, or during use of the product. Limited. 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 coating layer made of these film-forming elements is formed on the surface of a resin molded body substrate such as polyolefin, the adhesion between the coating layer and the resin molded body base layer is generally not good. There is a drawback 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. Attempts have also 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 investigation, it was found that the product contains a poly(meth)acrylate of a polyester polyol (a), a specific amount of a poly(meth)acrylate of a polyoxyalkane polyol (b), and a specific amount of a polymerization initiator (c). It has been found that the use of a composition satisfies the above objects, and the present invention has been achieved. 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. To summarize the present invention, the present invention comprises (a) a poly(meth)acrylated product of a polyester polyol having at least two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule and having no urethane bond; (b) Exceeding 0 based on 100 parts by weight of the poly(meth)acrylate of the polyester polyol (a)
1000 parts by weight of a poly(meth)acrylate of a polyoxyalkane polyol having at least one ether bond and three or more hydroxyl groups in one molecule, and (c) the polyester system. polyol poly(meth)
A coating characterized by containing a polymerization initiator in a range of 0.01 to 20 parts by weight based on a total of 100 parts by weight of the acrylate (a) and the poly(meth)acrylate of the polyoxyalkane polyol (b). The gist is a curable resin composition for The poly(meth)acrylate of polyester polyol (a) blended into the curable resin composition for coating of the present invention has at least two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule, and It is a poly(meth)acrylate of a polyester polyol that does not have any bonds. Here, at least two or more hydroxyl groups are formed at the molecular terminal or branch terminal formed by polycondensing the polyester polyol, polycarboxylic acid, and polyol constituting the poly(meth)acrylate of the polyester polyol. It is a polyester polyol having the following. Examples of the polycarboxylic acid component units constituting the polyester polyol include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, decanedicarboxylic acid, Brazilian acid,
Aliphatic polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, butanetricarboxylic acid, butanetetracarboxylic acid, hymic acid, 1,3-
Alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. Examples include aromatic polycarboxylic acids. Examples of the polyol component units constituting the polyester polyol include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, Aliphatic polyols such as dibutylene glycol, tributylene glycol, dihexylene glycol, diglycerin, ditrimethylolpropane, dipentaerythritol, polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol , cyclohexylene glycol, 2,2-bis(4-hydroxycyclohexyl)propane,
2,2-bis(4-hydroxycyclohexyl)
Ethane, bis(4-hydroxycyclohexyl)
Alicyclic polyols such as methane, xylene glycol, 2,2-bis(4-hydroxyphenyl)
Examples include aromatic polyols such as propane, 2,2-bis(4-hydroxyphenyl)ethane, and bis(4-hydroxyphenyl)methane. Among the polyester polyol components formed from these polycarboxylic acid component units and polyol component units, a polyester polyol component composed of aliphatic, alicyclic, or a mixture thereof is preferable.
Particularly preferred is an aliphatic polyester polyol component. By reacting the polyester polyol with acrylic acid or methacrylic acid in the presence of a catalyst, if necessary, a poly(meth)acrylate of the polyester polyol can be obtained. The number average molecular weight of the poly(meth)acrylate of the polyester polyol is usually 300 to 7000, preferably 300 to 7000.
5000 range. The poly(meth)acrylate of polyoxyalkane polyol (b) 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 product of polyoxyalkane polyol having 3 or more acryloyloxyl groups or methacryloyloxy groups in one molecule, and may also have hydroxyl groups in some cases. can not use. 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 and at least one molecule of an alkane polyol having two or more hydroxyl groups are condensed,
It has at least one ether bond. Specifically, the polyoxyalkane polyols include diglycerin, triglycerin,
Examples include tetraglycerin, ditrimethylolethane, tritrimethylolethane, tetratrimethylolethane, ditrimethylolpropane, tritrimethylolpropane, tetratrimethylolpropane, dipentaerythritol, and tripentaerythritol. The poly(meth)acrylate of polyoxyalkane polyol usually has 1 to 3, preferably 1 to 2 ether bonds in one molecule, and 3 to 10, preferably acryloyloxyl or methacryloyloxyl groups. has 3 to 8 molecules, and 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, Ditrimethylol ethane tetraacrylate, ditrimethylol ethane tetramethacrylate, ditrimethylol propane triacrylate, ditrimethylol propane trimethacrylate, ditrimethylol propane tetraacrylate, ditrimethylol propane tetra acrylate, tritrimethylol propane triacrylate, tritrimethylol propane pentaacrylate, di Examples include pentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. The poly(meth)acrylates of the polyoxyalkane polyols can also be used in combination of two or more.
Poly(meth) of the polyoxyalkane polyol
The blending ratio of the acrylate (b) needs to be in the range of more than 0 to 100 parts by weight based on 100 parts by weight of the poly(meth)acrylate (a) of the polyester polyol, and more preferably 5
It is preferably in the range from 20 to 700 parts by weight, particularly preferably from 20 to 500 parts by weight. When the proportion of the poly(meth)acrylate of the polyoxyalkane polyol (b) to 100 parts by weight of the poly(meth)acrylate of the polyester polyol (a) is more than 1000 parts by weight, the coating obtained from the composition The flexibility of the film decreases, causing 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 also include other polymerizable monomer components. It is also possible to copolymerize by adding. Other polymerization components include, for example, by-products or production intermediates during the production of the poly(meth)acrylate of the polyester polyol (a), such as the mono(meth)acrylate of the polyester polyol, the polyoxyalkane. By-products or production intermediates during the production of poly(meth)acrylates of polyols (b), such as mono(meth)acrylates of polyoxyalkane polyols, di(meth)acrylates of polyoxyalkane polyols, etc. Examples include (meth)acrylic acid esters such as (meth)acrylic acid, methyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. 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 film, 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, and specific examples of the photosensitizer include benzoin or its ethers such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, and benzoin isobutyl ether. , benzophenone compounds such as benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, benzyl, benzyl dimethyl ketal, benzyl ethyl ketal, etc., 1
-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 1-phenyl-
2-hydroxy-2-methyl-1-propanone,
Examples include hydroxyalkyl phenyl ketone compounds such as 1-(1-tert-butylphenyl)-2-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. moreover,
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 of proceeding with heat curing after the treatment. 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 based on a total of 100 parts by weight of the poly(meth)acrylate of the polyester polyol and the poly(meth)acrylate of the polyoxyalkane polyol (b). It is necessary that the amount is in the range of 0.1 to 10 parts by weight, and more preferably in the range of 0.1 to 10 parts by weight. The blending ratio of the polymerization initiator is 0.01 parts by weight based on a total of 100 parts by weight of the poly(meth)acrylate of the polyester polyol (a) and the poly(meth)acrylate of the polyoxyalkane polyol (b). When the amount is less than 20 parts by weight, the polymerizability of the composition decreases, making it impossible to obtain a hard film, and when the amount exceeds 20 parts by weight, the film obtained from the composition becomes yellowish in color. 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, optical brighteners, (reactive) oligomers such as methyl (meth)acrylate, polyurethane acrylate, and polymers such as polymethyl methacrylate. Additives can be added. The blending ratio of these additives is appropriate. In the curable resin composition for coating of the present invention, a fine powdery 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 1.5 mμ.
It ranges from 1μ 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 1.42.
It ranges from 1.58 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, gaolinite, 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. So I like it a lot. The blending ratio of these fine powder inorganic fillers is based on a total of 100 parts by weight of the poly(meth)acrylate of the polyester polyol (a) and the poly(meth)acrylate of the polyoxyalkane polyol (b). Usually 0.5 or
200 parts by weight, preferably in the range of 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 100% in total of the poly(meth)acrylate of the polyester polyol (a) and the poly(meth)acrylate of the polyoxyalkylene polyol (b).
It is usually in the range of 5 to 3000 parts by weight, preferably 10 to 2000 parts by weight. 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, and a mixing tank. You can get things. 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 mm. Further, in the thermosetting method, the temperature during curing is usually -10 to 50°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 ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, 1
- A homopolymer of α-olefins such as octene and 1-decene, a copolymer consisting of a mixture of two or more of the above α-olefins, or a copolymer containing the above α-olefins as a main component, such as vinyl acetate, vinyl propionate, etc. A small amount of other components such as lower aliphatic vinyl carboxylates, methyl acrylate, metal salts of acrylic acid, methyl methacrylate, acrylic carboxylic acid esters such as metal salts of methacrylic acid, and salts of acrylic carboxylic acids (for example, 30 mol% or less) can be exemplified. Among these polyolefins, polyolefins having crystallinity are usually 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,
I can give you things like Ninelon 12. In addition to the above resins, polyacetal, polystyrene,
Examples include acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyphenylene oxide, modified polyphenylene oxide, polyphenylene sulfide resin, and polyethersulfone 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 base surface of a molded body such as a resin with the curable resin composition for coating of the present invention, the base surface of the molded body may be washed with various solvents, aqueous alkaline solution, surfactant, etc. 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 administered. 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 a polyolefin, a modified polyolefin in which a derivative component thereof such as an α,β-unsaturated carboxylic acid, its acid anhydride, or its ester is grafted is usually used as the primer. In this way, the composition of the present invention is coated on the surface of the base layer of the molded body, which has been subjected to surface treatment or primer treatment as necessary, by the above-mentioned method, and is 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, shatterproof films for glass, release films, insulation films, agricultural films, and other films. Light-reproducing video discs, observation windows for various devices such as clothes dryers, electric washing machines, dryers, and oil tanks, windshields for motorcycles, jeeps, and motorboats, and automobile glass (windshields,
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 gums, 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, thoroughly disperse it, and then visually check its 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) Sand-falling abrasion 800g of silicon carbide abrasive material is dropped onto the coating according to the method of JIST8147-1975. 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) Taber wear According to ASTM D-1044 method, wear theory 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 After holding the test piece in a gear aging tester at 80°C for 400 hours, the appearance and adhesion of the outer coating layer were evaluated. (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 membrane layer were visually observed and adhesion was evaluated. (14) The test piece was held in a sunshine weatherometer for 400 hours, and the appearance and adhesion of the outer coating layer were evaluated. In addition, the following reference example shows a synthesis example of a polyacrylate compound of a polyester polyol. Reference example 1 Pentaerythritol 136g, succinic acid 59g,
3 g of paratoluenesulfonic acid and 100 g of toluene were charged, and an esterification reaction was carried out at 150°C for 2 hours in a nitrogen atmosphere. After cooling, 220 g of acrylic acid, 3 g of hydroquinone, and 200 g of toluene were added, and an esterification reaction was carried out at 120°C for 4 hours. After washing the reaction solution with weak alkaline water and water, 0.05 g of hydroquinone was added and low-boiling substances were distilled off to obtain a polyacrylate of polyester polyol having an average molecular weight of 700. The average number of double bonds in one molecule of this polyacrylate polyester polyol is 4.2.
Confirmed by NMR. Reference example 2 Trimerolpropane 138g, adipic acid 73g,
Paratoluenesulfonic acid 3g, acrylic acid 220g,
Reference example 1 from 3g of hydroquinone and 400g of toluene
A polyacrylate of a polyester polyol having an average molecular weight of 620 and an average number of double bonds per molecule of 3.6 was obtained in the same manner as above. Reference example 3 Pentaerythritol 136g, itaconic acid 65.5g
g, acrylic acid 140g, methacrylic acid 100g, toluene 800g, 98% sulfuric acid 6ml and phenothiazine
Prepare 0.2g and heat at 100 to 110℃ for 8 hours in nitrogen atmosphere.
An esterification reaction was performed. After washing the reaction solution with weak alkaline water and water, 0.05 g of hydroquinone was added, and low-boiling substances were distilled off to obtain a poly(meth)acrylate of polyester polyol with an average molecular weight of 750 and the number of acryloyloxyl groups per molecule of 5.3. Obtained. Reference example 4 Pentaerythritol 136g, diethylene glycol 106g, succinic acid 177g, acrylic acid 240g
The average molecular weight was determined by the method described in Reference Example 3 except that
1200, a polyacrylate of polyester polyol having an average number of double bonds in one molecule of 5.5 was obtained. Example 1 500 ml of 70 g of the polyacrylate of the polyester polyol described in Reference Example 1, 30 g of dipentaerythritol hexaacrylate, 5 g of benzoin isopropyl ether, and 150 g of toluene
The mixture was charged into a two-necked flask and stirred at room temperature for 2 hours to prepare a transparent coating composition [A]. On the other hand, polypropylene (Mitsui Petrochemical Industries KK)
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/l 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, heat 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 dried at room temperature for 1 minute and then at 60° C. for 5 minutes. This test piece was placed under a 1.5KW high-pressure mercury lamp (120w/cm) for 15 minutes.
The outer coating layer was cured by irradiating it with ultraviolet light for 30 seconds at a distance of cm. Table 1 shows the performance of this coating. Examples 2 to 5 In Example 1, instead of using the coating composition [A] described in Example 1, polyacrylates of polyester polyols and polyacrylates of polyoxyalkane polyols listed in Table 1 were used. 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 a polymerization initiator and a solvent in the amounts shown in Table 1 was used. The results are shown in Table 1. Examples 6 to 7 Weigh out the amounts of polyacrylates of polyester polyols, polyacrylates of polyoxyalkane polyols, polymerization initiators, and 1,1,1-trichloroethane listed in Table 1, and The mixture has an average particle size of
Finely powdered silica (manufactured by Nippon Aerosil KK, trade name R-972) having a diameter of 20 mμ and a refractive index of 1.45 was gradually added (the amount used is shown in Table 1), and the mixture was thoroughly stirred until uniform dispersion was obtained. Thereafter, the mixture was transferred to an attritor (manufactured by Mitsuiike Seisakusho) filled with steatite balls, and mixed for 3 hours by rotating an agitator at 50 rpm while cooling the tank with water. Thereafter, toluene in the amount shown in Table 1 was added, and after further mixing for 10 minutes, the mixture was taken out from the attritor to form a 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 A polyacrylate of a polyester polyol, a polyacrylate of a polyoxyalkane polyol, a polymerization initiator, and a solvent listed in Table 1 were weighed out and mixed at room temperature for 2 hours with stirring. A test piece was prepared by coating the surface of polypropylene by the method described in Example 1 except that the coating composition [A] was used. The results are shown in Table 1. Comparative Example 3 Single polypropylene (manufactured by Mitsui Petrochemical Industries KK, SJ-
Table 1 shows the performance of 313). The abbreviations used in Table 1 below represent the following compounds, respectively. 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] Example 8 A 3 mm thick injection molded sheet of poly-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries KK, trade name: TPX MX004) was coated with maleic anhydride-modified EPR.
(maleic anhydride content: 7.7 wt%) 1,1,1-trichloroethane solution with a concentration of 15 g/l for 10 seconds to perform primer treatment. After being left at room temperature for 5 minutes, it was immersed in the coating composition described in Example 7 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 7 to obtain poly-4
- A test piece coated with methyl-1-pentene was prepared. The results are shown in Table 2. Examples 9-10 In Example 8, poly-
Instead of using 4-methyl-pentene, a 3 mm thick polymer sheet listed in Table 2 was used and the surface of the polymer was coated in the manner described in Example 8, but with the pretreatment listed in Table 2. A test piece was prepared. 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)
Table 2 shows the performance of polycarbonate (Panlite L-1250, manufactured by Teijin Kasei KK), and polymethyl methacrylate (Acrylite L, manufactured by Mitsubishi Rayon KK).

[Table] Example 11, Comparative Example 7 In Example 1, the coating composition [A] described in Example 7 was used instead of the coating composition [A] described in Example 1, and the molding The surface of the unsaturated polyester resin was coated by the method described in Example 1, except that instead of using polypropylene as the substrate, a 2 mm thick unsaturated polyester resin (Rigorakku MCS-302, manufactured by Showa Kobunshi KK) was used. A test piece was prepared. The film thickness of this test piece is
8μ, surface gloss 83, adhesion 100/10
0, and the pencil hardness was 4H (Example 11). on the other hand,
The surface gloss of the unsaturated polyester resin not coated with the coating composition of the present invention is 63,
The pencil hardness was 3H (Comparative Example 7).

Claims (1)

[Scope of Claims] 1 (a) A poly(meth)acrylate of a polyester polyol having at least two acryloyloxyl or methacryloyloxyl groups in one molecule and having no urethane bond, (b) Polyester polyol poly(meth)
A polyoxyalkane polyol having one or more ether bonds and three or more hydroxyl groups in one molecule, in a range of more than 0 to 1000 parts by weight based on 100 parts by weight of the acrylate (a). a poly(meth)acrylate, and (c) a poly(meth) of the polyester polyol;
Acrylate compound (a) and poly(meth)acrylate compound of the polyoxyalkane polyol
A curable resin composition for coating, comprising: a polymerization initiator in a range of 0.01 to 20 parts by weight based on a total of 100 parts by weight of (b). 2 Poly(meth) of the polyester polyol
Claims include a fine powder inorganic filler in a range of 0.5 to 200 parts by weight based on a total of 100 parts by weight of the acrylate (a) and the poly(meth)acrylate of the polyoxyalkane polyol (b). The curable resin composition for coating according to item 1.