JPH0414148B2 - - 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 difficult 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 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 hardening, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to substrates. 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 it were possible, other new difficulties arose when coating the surface of a substrate of a molded resin 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)acrylates of specific polyols (a), specific amounts of di(meth)acrylates or polyoxyalkylene di(meth)acrylates of alkane polyols (b), and specific amounts of 1-( The use of a composition containing a photopolymerization initiator (c) and a finely powdered inorganic filler (d) satisfies the above objectives. We have discovered that this is the case, 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. The resulting coating has many 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. It has the characteristics of being excellent. To summarize the present invention, the present invention provides (a) an alkane polyol having at least three or more hydroxyl groups in one molecule, or an alkane polyol having one or more ether bonds and three or more hydroxyl groups in one molecule; (b) a poly(meth)acrylate of a polyoxyalkane polyol having at least three or more acryloyloxyl groups or methacryloyloxyl groups; (b) a poly(meth)acrylate of the polyol; (a) di(meth)acrylate or polyoxyalkylene di(meth)acrylate of an alkane polyol in a range of more than 0 to 1000 parts by weight per 100 parts by weight; (c) poly(meth)acrylate of the polyol; 1-(4-isopropylphenyl)-2-hydroxy-2-methyl in the range of 0.01 to 20 parts by weight per 100 parts by weight of the compound (a) and the polyoxyalkylene di(meth)acrylate (b). -1-propanone photopolymerization initiator, and (d) the total of the poly(meth)acrylate of the polyol (a) and the polyoxyalkylene di(meth)acrylate (b)
A curable resin composition for coating, characterized in that it contains a finely powdered inorganic filler in the range of 0.5 to 200 parts by weight per 100 parts by weight, the composition comprising, among various photopolymerization initiators, It is characterized by using a specific amount of 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone photopolymerization initiator in combination with a specific amount of finely powdered inorganic filler. It is something that you have. A coating composition containing a poly(methacrylate) of a polyol (component (a)) and a polyoxyalkylene di(meth)acrylate (component (b)) mixed with other ordinary polymerization initiators can be coated onto a substrate, for example, by a few μm. Because it is applied to a thickness of about 10 to 10-odd microns, and the exposed area per unit weight of the coating material is extremely large, the polymerization inhibiting effect of atmospheric oxygen, etc. is quite large, and it takes quite a long time to cure. , the degree of curing of the resulting coating is insufficient within an economically reasonable short period of time, and as a result, the surface hardness, scratch resistance, abrasion resistance,
Flexibility, surface gloss, heat resistance, water resistance, solvent resistance,
However, they still had disadvantages such as insufficient weather resistance and adhesion to the substrate surface. On the other hand, the 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-propanone photopolymerization initiator used in the present invention is a phenone polymerization initiator, which is a typical photopolymerization initiator. It has a higher photopolymerization rate than other photopolymerization initiators such as Together with the effect of imparting thixotropy to the polymer, it exhibits properties of the cured coating that cannot be obtained in combination with other polymerization initiators. Poly(meth)acrylate of polyol (a) blended into the curable resin composition for coating of the present invention
is a poly(meth)acrylate of an alkane polyol having at least three or more hydroxyl groups in one molecule or a polyoxyalkane polyol having one or more ether bonds and three or more hydroxyl groups in one molecule. It is a poly(meth)acrylate compound having at least three or more acryloyloxyl groups or methacryloyloxyl groups, and these poly(meth)acrylate compounds may have a hydroxyl group. The alkane polyol constituting the poly(meth)acrylate of the alkane polyol usually has 2 to 2 carbon atoms.
12, preferably a trihydric alcohol, a tetrahydric alcohol, a polyhydric alcohol having an alcohol content of 2 to 8, or a mixture of two or more thereof.
Specifically, the poly(meth)acrylates of the alkane polyols include glycerin triacrylate, glycerin trimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol. Examples include tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Furthermore, the poly(meth)acrylate of polyoxyalkane polyol is a poly(meth)acrylate of polyoxyalkane polyol having one or more ether bonds and at least three or more hydroxyl groups in one molecule. Yes, at least 3
It is a compound having 1 or more acryloyloxyl groups or methacryloyloxyl groups. 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. It has a condensed structure of at least one molecule of an alkane polyol and 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, ditrimethylolpropane, tritrimethylolpropane, tetratrimethylolpropane, dipentaerythritol, tripentaerythritol, and tetrapentaerythritol. I can do it. The poly(meth)acrylate of the polyoxyalkane polyol usually contains 1 in 1 molecule.
It has 3 to 3, preferably 1 to 2 ether bonds, 3 to 10, preferably 3 to 8 acryloyloxyl groups or methacryloyloxyl groups, and its molecular weight is usually 260.
It ranges from 260 to 1000, preferably from 260 to 1000. Specifically, the poly(meth)acrylate of the polyoxyalkane polyol includes:
Diglycerin triacrylate, diglycerin trimethacrylate, diglycerin tetraacrylate, diglycerin tetramethacrylate, triglycerin triacrylate, triglycerin trimethacrylate, triglycerin tetraacrylate, triglycerin tetramethacrylate,
Triglycerin pentaacrylate, triglycerin pentamethacrylate, ditrimethylolpropane acrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, tritrimethylolpropane triacrylate, tritrimethylolpropane pentaacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate , dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. The di(meth)acrylate of an alkane polyol or the polyoxyalkylene di(meth)acrylate (b) blended into the curable resin composition for coating of the present invention is a di(meth)acrylate of an alkane polyol having a carbon number of 2 to 12. (meth)acrylate or di(meth)acrylate of polyoxyalkylene glycol. The alkane polyol constituting the di(meth)acrylate of the alkane polyol is a dihydric alcohol, trihydric alcohol, tetrahydric alcohol having a carbon atom number in the range of 2 to 12, a polyhydric alcohol with higher carbon atoms, or a mixture of two or more of these. component, and furthermore, the number of carbon atoms is 2 to 8
Preferably, it is an alkane polyol within the range of . When the alkane polyol component constituting the di(meth)acrylate of the alkane polyol is a trivalent or higher polyhydric alcohol, the di(meth)acrylate of the alkane polyol is
As long as more than one hydroxyl group is (meth)acrylated, there is no problem even if some free hydroxyl groups remain. Specifically, the di(meth)acrylate of the alkane polyol includes 1,2-diacryloyloxyethane, 1,2-dimethacryloyloxyethane, 1,2-diacryloyloxypropane, 1,2-dimethacryloyloxy Propane, 2,2-dimethyl-1,3-diacryloyloxypropane, 2,2-dimethyl-1,3-
Dimethacryloyloxypropane, 1,3-diacryloyloxypropane, 1,3-dimethacryloyloxypropane, 1,4-diacryloyloxybutane, 1,4-dimethacryloyloxybutane, 1,6-diacryloyloxyhexane, 1,6-dimethacryloyloxyhexane,
1,8-diacryloyloxyoctane, 1,8
-dimethacryloyloxyoctane, 1,10-diacryloyloxydecane, 1,12-diacryloyloxydodecane, glycerin-1,3-diacrylate, glycerin-1,3-dimethacrylate, pentaerythritol diacrylate, trimethylolethane Examples include diacrylate, trimethylolethane dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane dimethacrylate.
Among these di(meth)acrylates of alkane polyols, 2,2-dimethyl-
1,3-diacryloyloxypropane, 1,4
-didiacryloyloxybutane or 1,6-
Preference is given to using diacryloyloxyhexane. Also polyoxyalkylene di(meth)
Acrylates are acrylic or methacrylic esters of polyoxyalkylene glycols. The oxyalkylene group constituting the polyoxyalkylene di(meth)acrylate is
Normal general formula [] [In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. ], the degree of polymerization of the oxyalkylene group is usually in the range of 1 to 40, preferably 1 to 20, and the number average molecular weight (n) of the oxyalkylene di(meth)acrylate is
is usually 200 to 3000, preferably 200 to 2000
is within the range of Specifically, the polyoxyalkylene di(meth)acrylates include polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, polyoxyethylene polyoxypropylene diacrylate, and polyoxyethylene di(meth)acrylate. Examples include oxyethylene polyoxypropylene dimethacrylate. Among the polyoxyalkylene di(meth)acrylates, polyoxyethylene di(meth)acrylate or polyoxypropylene di(meth)acrylate is preferred. The blending ratio of di(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol is more than 0 and 1000 parts by weight per 100 parts by weight of the poly(meth)acrylate of the polyol (a).
It is preferably in the range of 5 to 300 parts by weight, particularly 20 to 150 parts by weight. Di(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol, poly(meth)acrylate of the above polyol (a)
If the blending ratio exceeds 1000 parts by weight relative to 100 parts by weight, the curability of the composition in air decreases, and the surface hardness, abrasion resistance, and other performances of the outer coating decrease. 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 polymerization components include, for example, poly(meth)acrylates of the above polyols.
By-products or production intermediates in producing (a), such as mono(meth)acrylates and di(meth)acrylates of the above polyol, di(meth)acrylates of the alkane polyol (b) By-products or production intermediates, such as mono(meth)acrylates of alkylene glycols, by-products or production intermediates during the production of the polyoxyalkylene di(meth)acrylate (b), such as mono(meth)acrylates of polyoxyalkylene glycols, In addition to meth)acrylates, (meth)acrylic acid esters such as methyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate can be exemplified. 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, this composition must be mixed with 1-(4-isopropylphenyl)-2 -Hydroxy-2-methyl-propanone A photopolymerization initiator is blended, and a film is formed by a photopolymerization curing method using ultraviolet rays or the like. The blending ratio of the polymerization initiator (c) is 100% by weight of the poly(meth)acrylate of the polyol (a) and the di(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. It needs to be in the range of 0.01 to 20 parts by weight, and even more preferably 0.1 parts by weight.
The amount is preferably in the range of 10 to 10 parts by weight. The blending ratio of the polymerization initiator is based on a total of 100 parts by weight of the poly(meth)acrylate of the polyol (a) and the di(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. When the amount is less than 0.01 part by weight, the polymerizability of the composition decreases and a hard film cannot be obtained, and when it exceeds 20 parts by weight, the film obtained from the composition becomes yellow colored. Among the components of the curable resin composition for coating of the present invention,
In order to improve the surface hardness, abrasion resistance, etc. of the cured film obtained therefrom, and to further improve the thixotropic performance during application, a finely powdered inorganic filler is blended as a fourth essential component. The average particle size of the finely powdered inorganic filler is arbitrary as long as it is in the form of a powder, but it is usually 1 mμ to 10μ, preferably
It ranges from 1.5mμ 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 finely powdered inorganic fillers is the total weight of the poly(meth)acrylate of the polyol (a) and the di(meth)acrylate or polyoxyalkylene di(meth)acrylate of the alkane polyol (b). Usually 0.5 to 200 parts by weight, preferably
It ranges from 0.5 to 100 parts by weight. If the blending ratio exceeds the above range, the transparency of the film and the workability during coating will be impaired, and if the blending ratio is less than the above range, the effect of filler blending will not be achieved. The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned four essential components, but may also contain a polymerization inhibitor, a pigment, a dye, a solvent, an ultraviolet absorber, and an antioxidant, if necessary. Stabilizers such as fluorescent brighteners, (reactive) oligomers such as methyl (meth)acrylate, polyurethane acrylate, polyester acrylate and polymethyl (meth)acrylate.
Various additives such as polymers such as acrylates can be blended. The blending ratio of these additives is appropriate. The curable resin composition for coating of the present invention is maintained in a suspended state by adding a solvent as necessary to improve its coating workability. The solvent is also used for the purpose of suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. Specific examples of solvents include hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, and methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, bromoform, trichlene, Halogenated hydrocarbons such as ethylene dichloride, perchloride, ethane trichloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobenzene, methanol, ethanol, isopropanol, butanol, pentanol, hexanol,
Alcohols such as cyclohexanol, 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 Ethers such as dimethyl ether, diethylene glycol dimethyl ether, nitriles such as acetonitrile, propionitrile, capronitrile, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, ethyl benzoate Examples include esters such as. The blending ratio of these organic solvents is based on a total of 100 parts by weight of the poly(meth)acrylate of the polyol (a) and the di(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. The amount usually ranges from 5 to 300 parts by weight, preferably from 10 to 2000 parts by weight. In the composition of the present invention, a method for preparing a suspension composition from a composition containing the above-mentioned essential components and various additive components such as a solvent and a stabilizer added as necessary is to prepare the suspension composition by adding the above-mentioned raw material mixture. Examples of kneading and mixing methods include a normal roll, a Banbury mixer, a ball mill, 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.
Uniformly dispersed compositions are obtained by these methods. Methods for applying the suspension composition to the substrate surface of the molded article include brush coating method, spray method, dipping method, bar coating method, roll coater method,
Conventionally known methods such as 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, and heating drying using an infrared oven, far-field oven, and hot air oven. Further, as a method for curing the above-mentioned coating film to form a film, a method of polymerization crosslinking and curing using light, particularly ultraviolet rays, can be used. In the photocuring method, light irradiation is usually carried out at a temperature of -10 to 150°C, preferably 5 to 130°C,
The time is usually 1sec to 1hr, preferably 1sec
or 10min. 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 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 polyolefin, α,β-unsaturated carboxylic acids, their acid anhydrides, their esters, etc. can be used as primers.
Modified polyolefins grafted with 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, operating windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, tableware, mirrors, various containers such as oil bottles and cosmetic bottles, relay cases, fuse boxes, motorcycle side covers, and dirt. Fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulating films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative boards, shelves, wall sheets, wallpaper, furniture , lightweight wallboards, tableware, chairs, bathtubs, toilet bowls, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, ducts, curtain rods, rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foil, 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) Taber wear According to the method of AASTM D-1044, wear wheel 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 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 Diglycerol tetraacrylate 70g, neopentyl glycol diacrylate 30g, methanol silica sol) manufactured by Nissan Chemical KK, average particle size approx.
15 mμ, methanol suspension of anhydrous silica with a refractive index of about 1.50) 33 g (including 10 g of anhydrous silica), 5 g of 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-propanone and n-butanol
Pour 110g into a 500ml 4-necked flask and store at room temperature.
A transparent coating composition was prepared by stirring for 2 hours. 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/toluene solution 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 for 30 seconds, slowly pulled up, and then immersed at room temperature for 1 minute at 60°C.
It was dried for 5 minutes. This test piece was exposed to ultraviolet light at a distance of 15cm under a 1.5kW high-pressure mercury lamp (120W/cm).
The outer coating layer was cured by irradiation for 30 seconds. Table 1 shows the performance of this coating. Examples 2 to 3 In Example 1, instead of using the coating composition described in Example 1, a coating composition prepared using the compounds listed in Table 1 in the amounts listed in Table 1 was used. A test piece whose surface was covered with polypropylene was prepared in the same manner as in Example 1 except for the above. The results are shown in Table 1. Comparative Example 1 Same as Example 3 except that 5 g of benzoin isopropyl ether was used in place of the polymerization initiator 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone 5. Example 3 using the coating composition prepared in Example 3
A test piece with a polypropylene surface coated was prepared in the same manner as above, and the coating performance was evaluated. Table 1 shows the results.
Shown below. From the evaluation results of Comparative Example 1, it can be seen that the abrasion resistance such as falling sand abrasion and taper abrasion, and the surface hardness indicated by pencil hardness are inferior to those of the examples. Comparative Example 2 In Example 3, a test piece was coated on the surface of polypropylene in the same manner as in Example 3 using a coating composition prepared in the same manner as in Example 3 except that methanol silica sol was not added. The coating performance was evaluated. The results are shown in Table 1. Comparative Example 2 also had poor wear resistance and surface hardness. The abbreviations used in the table below represent the following compounds, respectively. NPA...neopentyl glycol diacrylate HDA...1,6 hexanediol diacrylate PETA...pentaerythritol tetraacrylate DPHA...dipentaerythritol hexaacrylate DGTA...diglycerin tetraacrylate BIE...benzoin isopropyl ether IHP...1-(4-isopropylphate) enyl)-2-hydroxy-2-methyl-1-propanone

[Table] Example 4 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.
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 3 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 3 to obtain poly-4
- A test piece coated with methyl-pentene was prepared. The results are shown in Table 2. Examples 5-6 In Example 4, poly-
Instead of using 4-methyl-pentene, a 3 mm thick polymer sheet as listed in Table 2 was used and the surface of the polymer was coated in the manner described in Example 4, but with the pretreatment as listed in Table 2. A test piece was prepared.
The results are shown in Table 2. Comparative Examples 3 to 5 Poly 4-methyl-1-pentene (Mitsui Petrochemical Industries, Ltd.) not coated with the coating composition of the present invention
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 7, Comparative Example 6 The coating composition described in Example 3 was used, and instead of using polypropylene as the molded body base, a 2 mm thick unsaturated polyester resin (Rigorak MCS- A test piece whose surface was coated with unsaturated polyester resin was prepared by the method described in Example 3 except that 302) was used. The film thickness of this test piece was 8μ, the surface gloss was 82, the adhesion was 100/100, and the pencil hardness was 4H (Example 7). On the other hand, the unsaturated polyester resin that was not coated with the coating composition of the present invention had a surface gloss of 63 and a pencil hardness of 3H (Comparative Example 6).

Claims (1)

[Scope of Claims] 1 (a) an alkane polyol having at least three or more hydroxyl groups in one molecule;
has one or more ether bonds in the molecule and 3
(b) a poly(meth)acrylate product of a polyoxyalkane polyol having at least three hydroxyl groups, the poly(meth)acrylate product having at least three or more acryloyloxyl groups or methacryloyloxyl groups; (meth)acrylate (a) Di(meth)acrylate or polyoxyalkylene di(meth)acrylate of an alkane polyol in a range of more than 0 to 1000 parts by weight per 100 parts by weight; (c) of the polyol; Poly(meth)acrylate (a) and di(meth) of the alkane polyol
1-(4-isopropylphenyl)2-hydroxy-2-methyl-1-propanone in a range of 0.01 to 20 parts by weight per 100 parts by weight of the acrylate or the polyoxyalkylene di(meth)acrylate (b). a photopolymerization initiator, and (d)
Poly(meth)acrylate of the polyol
Based on a total of 100 parts by weight of (a) and the di(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol.
A curable resin composition for coating, characterized in that it contains a finely powdered inorganic filler in a range of 0.5 to 200 parts by weight.