JPH0238095B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has excellent curing properties in air by coating the surface of a polyolefin molded product,
Curing for polyolefin 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 base polyolefin. The present invention relates to a mold resin composition. In general, polyolefin molded products such as polyethylene and polypropylene have various advantages such as being lighter and having better impact resistance than metal products and glass products, as well as being inexpensive and easy to mold. cars, motorcycles,
It is widely used in place of these materials in household electrical appliances, daily necessities, and many other fields. However, these polyolefin molded bodies have a disadvantage in that their surface hardness is lower than that of metals, glass, etc., and they are susceptible to scratching and friction, so that they are 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 drawbacks of molded bodies made of these polyolefins. 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 polyolefin molded product such as polyethylene or polypropylene, the adhesion between the coating layer and the polyolefin base layer is generally not good, so these laminate molded products are 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 polyolefin molded articles in order to improve these drawbacks. 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 made of polyolefin and the coating layer made of the crosslinked curable resin so as to be practical. Furthermore, among the film-forming elements, silicone-based film-forming elements have the disadvantage of being expensive and poor 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 polyolefin molded article, these films will not be affected by the curing speed in air during curing. 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 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. However, other new difficulties have arisen when coating polyolefin substrate surfaces. The present inventors have conducted intensive studies on a coating composition that has excellent curing properties during curing and has excellent film properties by coating the surface of a base resin made of polyolefin. poly(meth)acrylate compound (a),
Poly(meth)acrylate or polyoxyalkylene di(meth) of a specified amount of alkane polyol
It has been discovered that the above object can be achieved by using a composition containing an acrylate (b), a specific amount of a hydroxyalkyl phenyl ketone photopolymerization initiator (c), and a silica filler having specific properties, and the present invention reached. According to the present invention, when the curable resin composition for coating of the present invention is coated on the surface of a polyolefin molded article to form an outer coating layer, it has excellent curing properties such as curing speed in air during curing,
The resulting coating is generally excellent in many coating properties such as surface hardness, scratch resistance, abrasion resistance, and adhesion to the substrate. To summarize the present invention, the present invention comprises: (a) a poly(meth)acrylate of an aromatic or alicyclic polyepoxy compound having at least two or more epoxy groups in one molecule; More than 0 per 100 parts by weight of poly(meth)acrylate of polyepoxy compound (a)
2 to 1000 parts by weight of carbon atoms
(c) a poly(meth)acrylate of the polyepoxy compound (a) and a poly(meth)acrylate of the alkane polyol within the range of 12; A hydroxyalkyl phenyl ketone photopolymerization initiator in the range of 0.01 to 20 parts by weight based on a total of 100 parts by weight of acrylate or polyoxyalkylene di(meth)acrylate (b), and (d) polyester of the polyepoxy compound. A particle size of 1 μm in a range of 0.5 to 200 parts by weight based on a total of 100 parts by weight of the (meth)acrylate compound (a) and the poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. 1μ to 1μ and a refractive index of 1.4 to 1.6. A curable resin composition for polyolefin coating, characterized in that it contains a silica filler having a refractive index of 1.4 to 1.6. The most characteristic feature is the combination of using a photopolymerization initiator and, among various fillers, using a silica filler with a particle size of 1 μm to 1 μm and a refractive index of 1.4 to 1.6. Conventionally, coating compositions containing epoxy (meth)acrylate (component (a)) and specific polyhydric acrylate (component (b)) mixed with a common polymerization initiator have been coated onto a substrate such as polyolefin, for example, in a range of only a few microns to tens of microns. A few μ
Because the coating is applied to a relatively large thickness and the exposed area per unit weight of coating material is significantly large, the polymerization inhibiting effect of atmospheric oxygen is considerable, and curing takes a considerable length of time and is difficult to achieve in an economically reasonable short period of time. The extent of curing of the film obtained by polymerization within a certain period of time is insufficient, and as a result, the surface hardness of the coating film
However, they still suffer from insufficient scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to substrates. On the other hand, the hydroxyalkyl phenyl ketone type photoinitiator used in the present invention has a higher photopolymerization rate than other photopolymerization initiators such as a phenone type polymerization initiator, which is a typical photopolymerization initiator. The silica filler with a particle size of 1 μm to 1 μm and a refractive index of 1.4 to 1.6 used in combination with this filler has a significantly high speed, and is more effective at imparting thixotropy to uncured resin than other inorganic fillers. It has a very strong effect, and after the solvent evaporates, it keeps the coating material on the base material in a pseudo-cured state and blocks oxygen. In the coating composition of the present invention, these two effects are organically related and integrated, so that even when the coating is extremely thin, the polymerization inhibiting (inhibiting or delaying) effect caused by atmospheric oxygen is suppressed, and relatively Within a short period of time, the composition is highly and effectively polymerized and cured, and the aforementioned improvements in the various physical properties of the coating film are achieved. The poly(meth)acrylate compound (a) of the polyepoxy compound blended into the curable resin composition for coating of the present invention is an alicyclic or aromatic compound having at least two or more epoxy groups in one molecule. It is a poly(meth)acrylate of a polyepoxy compound formed from a polyepoxy compound and acrylic acid or methacrylic acid. Here, specific examples of polyepoxy compounds having at least two epoxy groups in one molecule include 1,2-cyclohexylene glycol, 1,4-cyclohexylene glycol, 2,2-bis(4-hydroxycyclohexyl ) Polyglycidyl ethers of alicyclic polyols such as propane, 1,1-bis(4-hydroxycyclohexyl)ethane, and bis(4-hydroxycyclohexyl)methane; polyglycidyl ethers of polyhydric phenols such as hydroquinone, resorcinol, catechol, and phloroglucin. Glycidyl ether, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, novolac type phenolic resin, resol type phenolic resin Examples include polyglycidyl ethers of aromatic polyols such as polyglycidyl ethers of aromatic polynuclear polyhydric phenols. More specifically, the polyepoxy compound includes 1,2-cyclohexylene glycol diglycidyl ether, 1,4-cyclohexylene glycol diglycidyl ether, 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, and bis(4-hydroxycyclohexyl)propane diglycidyl ether. Alicyclic polyepoxy compounds such as (4-hydroxycyclohexyl)methane diglycidyl ether, hydroquinone diglycidyl ether, resorcin diglycidyl ether, catechol diglycidyl ether, phloroglucin triglycidyl ether, phloroglucin diglycidyl ether, 2, 2-bis(4-hydroxyphenyl)propane diglycidyl ether, 1,1-bis(4-hydroxyphenyl)propane diglycidyl ether, bis(4-hydroxyphenyl)methane diglycidyl ether, novolak type phenolic resin Aromatic polyepoxy compounds such as polyglycidyl ether and polyglycidyl ether of resol type phenol resin can be exemplified, and a mixture of two or more of these may be used. The poly(meth)acrylate of a polyepoxy compound (a) 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. It is a meth)acrylate compound, and more specifically, it is 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. ]
It is a compound that forms a unit represented by and has at least two of these units in one molecule, and therefore has two or more (meth)acryloyloxyl groups and two or more hydroxyl groups in one molecule. It is a compound. The poly(meth)acrylate product (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 in the range of 0.005 to 5 parts by weight per 100 parts by weight of the epoxy compound. The proportion of acrylic acid or methacrylic acid used is usually 0.6 to 1.5 per mole of epoxy group of the polyepoxy compound.
mol, preferably in the range of 0.9 to 1.1 mol. The reaction is usually carried out at a temperature of -10 to 160°C. The poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of an alkane polyol blended in the curable resin composition for coating of the present invention is a poly(meth)acrylate of an alkane polyol having a carbon number of 2 to 12. (meth)acrylate or di(meth) of polyoxyalkylene glycol
It is acrylate. Alkane polyols constituting the poly(meth)acrylate of alkane polyols include dihydric alcohols, trihydric alcohols, tetrahydric alcohols having a carbon atom number in the range of 2 to 12,
It is preferably a polyhydric alcohol containing more than 10% or a mixed component of two or more thereof, and more preferably an alkane polyol having 2 to 8 carbon atoms. When the number of carbon atoms in the alkane polyol constituting the poly(meth)acrylate of the alkane polyol exceeds 12, the surface hardness, scratch resistance, abrasion resistance, etc. of the coating obtained from the composition will decrease. When the alkane polyol component constituting the poly(meth)acrylate of the alkane polyol is a trivalent or higher polyhydric alcohol, the poly(meth)acrylate of the alkane polyol has two or more hydroxyl groups in the (meth)acrylate. If the hydroxyl group is Specific examples of the (meth)acrylate of the alkane polyol include 1,2-diacryloyloxyethane, 1,2-dimethacryloyloxyethane, 1,2-diacryloyloxypropane,
1,2-dimethacryloyloxypropane, 1,
3-diacryloyloxypropane, 1,3-dimethacryloyloxypropane, 2,2-dimethyl-1,3-diacryloyloxypropane,
2,2-dimethyl-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, trimethylolethane triacrylate, trimethylol ethane trimethacrylate,
Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerin-1,3-diacrylate, glycerin-
Examples include 1,3-dimethacrylate, glycerin triacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate. Among these poly(meth)acrylates of alkane polyols, it is preferable to use poly(meth)acrylates of alkane polyols having 2 to 8 carbon atoms, especially 2,
2-dimethyl-1,3-diacryloyloxypropane, 1,4-diacryloyloxybutane,
Preference is given to using 1,6-diacryloyloxyhexane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate. Moreover, polyoxyalkylene di(meth)acrylate is an acrylic ester or methacrylic ester of polyoxyalkylene glycol. The oxyalkylene group constituting the polyoxyalkylene di(meth)acrylate usually has the general formula [] [In the formula, R ² , R ³ , R ⁴ and R ⁵ 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, and the number average molecular weight (n) of the oxyalkylene di(meth)acrylate is usually 200 to 3000,
Preferably it is in the range of 200 to 2000. Specifically, the polyoxyalkylene di(meth)acrylates include polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, polyoxyethylene polyoxypropylene diacrylate, polyoxy Examples include ethylene polyoxypropylene dimethacrylate. Among the polyoxyalkylene di(meth)acrylates, polyoxyethylene di(meth)acrylate or polyoxypropylene di(meth)acrylate is preferred. The blending ratio of poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) in the alkane polyol is based on the poly(meth)acrylate of the polyepoxy compound.
(a) It must be in the range of more than 0 to 1000 parts by weight per 100 parts by weight, and furthermore, it must be between 5 and 1000 parts by weight.
in the range of 300 parts by weight, particularly preferably 10 to 300 parts by weight
Preferably, it is in the range of parts by weight. When the blending ratio of the poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol to 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (a) is more than 1000 parts by weight, The curability of the outer coating in air decreases, and the surface hardness, abrasion resistance, etc. also 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 can also be carried out. Other polymerization components include, for example, by-products or production intermediates during the production of the poly(meth)acrylate (a) of the polyepoxy compound, such as (meth)acrylate of the monoepoxy compound.
Acrylates, mono(meth)acrylates of polyepoxy compounds, poly(meth)acrylates of the alkane polyols, or by-products or intermediates in the production of polyoxyalkylene di(meth)acrylates (b), such as alkane polyols. In addition to mono(meth)acrylate or mono(meth)acrylate of polyoxyalkylene glycol, (meth)acrylic acid, (meth)
Examples include (meth)acrylic acid esters such as methyl 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 made of polyolefin and crosslink and cure the composition to form a film,
A hydroxyalkyl phenyl ketone photopolymerization initiator is added to this composition, and a film is formed by a photopolymerization curing method using ultraviolet rays or the like. Specifically, the photopolymerization initiator (photosensitizer) to be blended is 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-(4-tert-butylphenyl)-2-hydroxy-2-methyl-1-propanone. 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 polyepoxy compound (a) and the poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. The amount is preferably within a range of 0.1 to 10 parts by weight. The blending ratio of the polymerization initiator is a total of 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (a) and the poly(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 is more than 20 parts by weight, the film obtained from the composition is colored yellow. Become. In the curable resin composition for coating of the present invention, a fourth essential component is added in order to improve the surface hardness, scratch resistance and abrasion resistance of the cured film obtained therefrom, and also to improve the thixotropic performance during application. , a specific silica-based filler is added. The properties of the silica filler used in the present invention are 1 mμ to 1μ, preferably 1.5 mμ to 1μ.
It has an average particle size in the range of 1μ and a refractive index of 1.40 to
A fine powder in the range of 1.60, preferably 1.42 to 1.58 is used. When the average particle size is larger than 1 μm, uniform dispersibility in the resin composition is poor, and thixotropic performance and film transparency during coating curing are inhibited. On the other hand, particles with an average particle size smaller than 1 mμ are not economical. If the refractive index is outside the above range, the transparency of the coating will be impaired due to its relationship with the refractive index of the coating resin composition itself. Specifically, such fine powder silica fillers include glass powder, mica, glass beads, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, silica, silica sand, quartz, kaolinite, montmorillonite, and seri. Examples include silica, talc, chlorite, chinastone, and feldspar. In addition, these finely powdered silica fillers whose surfaces have been surface-treated with alkyl carboxylates, silane couplers, titanium couplers, Cl ₂ Si (CH ₃ ) ₂ , alcohol, etc. can also be used. . Also,
It is also possible to use colloidal silica, methanol silica sol, ethanol silica sol, isopropanol silica sol, etc. in which the silica-based filler is suspended in water or alcohol. Among these fine powder silica-based fillers, blending fine powder silica significantly improves the surface hardness, scratch resistance, and abrasion resistance of the outer coating layer, and does not impair transparency and surface gloss. This is especially preferable because there is no such thing. The blending ratio of these fine powder silica fillers is the poly(meth)acrylate of the polyepoxy compound (a) and the poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. Usually 0.5 to 200 parts by weight, preferably 0.5 to 200 parts by weight per 100 parts by weight of
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
In addition, polymerization inhibitors, pigments, dyes, solvents, UV absorbers, stabilizers such as antioxidants, optical brighteners, oligomers such as methyl (meth)acrylate, polyurethane acrylate, polyester acrylate, and polymethyl (meth)acrylate, etc. ) 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 the poly(meth) of the polyepoxy compound.
The amount is usually 5 to 3000 parts by weight, preferably 10 to 2000 parts by weight, based on 100 parts by weight of the acrylate (a) and the poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. It is. 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.
By these methods, a uniformly dissolved or dispersed composition can be obtained. Methods for applying the suspension composition to the surface of the substrate of the molded body made of polyolefin include brush coating, spraying, dipping,
Conventionally known methods such as a bar coat 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 a natural drying method, a forced drying method using a carrier gas, a heating drying method using an infrared oven, a far-infrared oven, and a 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, and the time is usually 1 sec to 1 hr, preferably 1 sec to 1 hr.
It is 10min. A polyolefin laminate molded product can be obtained by curing the outer coating layer of a polyolefin molded product coated with the curable resin composition for coating of the present invention. The base resin layer constituting the laminate molded product is a molded product made of polyolefins, and the shape thereof may be a film-like, sheet-like, plate-like, curved or uneven molded product, or any other shaped molded product. There is no problem. Specifically, the polyolefins constituting the base resin layer include α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-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-olefin as a main component, and lower aliphatic vinyl carboxylates such as vinyl acetate and vinyl propionate, methyl acrylate, and acrylic acid. metal salts, methyl methacrylate,
Examples include copolymers containing a small amount (for example, 30 mol % or less) of other components such as acrylic carboxylic acid esters such as metal salts of methacrylic acid, and salts of acrylic carboxylic acids. Among these polyolefins, polyolefins having crystallinity are usually used. When coating the base surface of the molded body made of the polyolefins with a film of the curable resin composition for coating of the present invention, on the surface of the molded body base resin layer,
Cleaning with various solvents, alkaline aqueous solution, surfactant cleaning, ultrasonic cleaning,
Electrolytic cleaning, blasting, sandblasting, acid or alkali etching,
Various surface treatments such as flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, and chemical conversion treatment can be performed. 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 made of the polyolefins, an intermediate layer made of a primer may be provided between the substrate layer and the outer coating layer. It is also possible to improve the adhesion between both layers by providing a three-phase laminate with an adhesive layer. As a primer, α,β-unsaturated carboxylic acid, its acid anhydride,
Modified polyolefins grafted with α,β-unsaturated carboxylic acids or derivatives thereof, such as esters thereof, are commonly used. As described above, the composition of the present invention is coated on the surface of the base layer of the polyolefin molded article, 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 polyolefin laminate molded product on which a film made of the curable resin composition for coating of the present invention is laminated can be used for various purposes. Specifically, examples include daylight panels, sky domes, solar water heater panels, glove box panels, watch glasses, various lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, and coffee maker panels. Shower dome, coffee maker, water tank,
Covers for lighting devices, covers for stereo devices such as players, dials and covers for various meters, covers for headlights or taillights in automobiles, level sensors, glass shatterproof films and release films, insulating films, agricultural films, etc. various films, optically reproducing video discs, observation windows for various devices such as clothes dryers, electric washing machines, dryers, oil tanks, windshields for motorcycles, jeeps, motorboats, etc., automobile glass (windshields, rear windows, etc.) opera 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 mudguards, and fenders. , curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulin sheets, insulating films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative boards, shelves, wall sheets, wallpaper, furniture, lightweight walls Boards, tableware, chairs, bathtubs, toilet bowls, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, ducts, curtain rods, rain gutters, insulation materials,
Waterproof coating materials, curtains, window frames, automobile foil, various containers, automobile interior materials, vanity tables, flower boxes, particle boards, tiles, shutters, shutters, waterproof pans, pipes, wiring materials, gear cams, knobs, Solenoid valve frame, fan, instrument panel, bumper,
Examples include 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 Abraded wheels according to ASTM D 1044 method.
CS-10 is rotated 1000 times on the coating with a load of 500g. 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-shaped test piece with a width of 5 mm and a length of 10 cm is
It is expressed as the angle at which the coating cracks or peels off from the substrate by folding it along the outer circumference of a cm cylinder. The larger the value, the better the flexibility. (9) Water resistance After immersing the test piece in pure water at 40°C 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 After holding the test piece in an air oven at 80℃ for 2 hours, it was left at room temperature for 1 hour, and then heated at −30℃ for 1 hour.
℃ in a cold room for 2 hours and then at room temperature for 1 hour. 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 85 g of diacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, 15 g of neopentyl glycol diacrylate, 1-(4-isopropylphenyl)-
2-hydroxy-2-methyl-1-propanone 5
g, and 100 g of 1,1,1-trichloroethane
Weigh out each of the particles and add to this mixture while stirring an average particle size of 20.
Finely powdered silica (manufactured by Nippon Aerosil KK, trade name R-972) having a mμ and a refractive index of 1.45 was gradually added (amount used: 5 g) and stirred thoroughly 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, then n
- After adding 120 g of butanol and mixing for an additional 10 minutes, the mixture was taken out from the attritor and used as a 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/toluene solution [B] of PER (propylene content: 67 mol%, maleic anhydride content: 6 wt%) for 20 seconds, and then 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 heated at 60°C for 5 seconds.
Dry for a minute. This test piece was heated using a 1.5kW high-pressure mercury lamp (120W/cm).
Below, the outer coating layer was cured by irradiating it with ultraviolet light for 15 seconds at a distance of 15 cm. The results of this film performance test are shown in Table 1. Example 2 A test piece was prepared in the same manner as in Example 1 except that the ultraviolet irradiation time was 30 seconds, and the film performance was evaluated. The results are shown in Table 1. Example 3 2,2-M-bis(4-hydroxyphenyl)
Example 1 except that 50 g of diacrylate of propane diglycidyl ether and 50 g of pentaerythritol tetraacrylate were blended in place of the polyacrylate of polyepoxy compound and polyacrylate of alkane polyol in Example 1.
A test piece was prepared using the formulation and treatment method described in . The results are shown in Table 1. Comparative Example 1 85 g of diacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, 15 g of neopentyl glycol diacrylate, 1-(4-isopropylphenyl)-
2-hydroxy-2-methyl-1-propanone 5
g, and 110 g of toluene were stirred at room temperature for 1 hour to prepare a coating composition [A]. In Example 1, a test piece having a surface coated with polypropylene 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 Example 2 Photopolymerization initiator of Example 1, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-
A test piece was prepared in the same manner as in Example 1, except that 5 g of benzoin isopropyl ether was added instead of 1-propanone. The results are shown in Table 1. Comparative Example 3 5 g of diacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether and 95 g of neopentyl glycol diacrylate were substituted for the polyacrylate of polyepoxy compound and polyacrylate of alkane polyol in Example 1. A test piece was prepared using the formulation and treatment method described in Example 1, except that the following ingredients were used: The results are shown in Table 1. The abbreviations used in Table 1 below represent the following compounds, respectively. BCHGA...Diacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether BPGA...Diacrylate of 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether NPA...Neopentyl glycol diacrylate PETA...Pentaerythritol tetraacrylate BIP...Benzoin isopropyl ether IHP...1-(4-isopropylphenyl)-
2-hydroxy-2-methyl-1-propanone

【table】

[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 (maleic anhydride content 7.7 wt%). ) of 15g/concentration of 1,
Immerse in 1,1-trichloroethane solution for 10 seconds,
Primer treatment was performed. 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 60° C. for 5 minutes, photopolymerization was performed using the method described in Example 3 to prepare a test piece whose surface was coated with poly-4-methyl-1-pentene. The results are shown in 2. Comparative Example 4 Polymer not coated with the coating composition of the present invention
4-Methyl-1-bentene (Mitsui Petrochemical Industries)
Table 2 shows the performance of the product manufactured by KK (trade name: TPX MX004).

【table】

Claims (1)

[Scope of Claims] 1 (a) a poly(meth)acrylate of an aromatic or alicyclic polyepoxy compound having at least two or more epoxy groups in one molecule; (b) the polyepoxy compound More than 0 per 100 parts by weight of poly(meth)acrylate (a)
1000 parts by weight of a poly(meth)acrylate or polyoxyalkylene di(meth)acrylate of an alkane polyol having from 2 to 12 carbon atoms, and (c) a poly(meth)acrylate of the polyepoxy compound. Hydroxyalkyl phenyl ketone light in the range of 0.01 to 20 parts by weight per 100 parts by weight of the acrylate compound (a) and the poly(meth)acrylate or polyoxyalkylene di(meth)acrylate (b) of the alkane polyol. A polymerization initiator, and (d) a poly(meth)acrylate of the polyepoxy compound (a) and a poly(meth)acrylate or polyoxyalkylene di(meth)acrylate of the alkane polyol (b) based on a total of 100 parts by weight. Particle size ranging from 0.5 to 200 parts by weight1
A curable resin composition for coating polyolefin, characterized in that it contains a silica filler with mμ to 1μ and refraction of 1.4 to 1.6.