JPH0324507B2 - - 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 significantly reduced 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 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 of a resin molded product such as polyolefin and the coating layer made of the crosslinked curable resin for practical use. 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 is low. Poor curing properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to substrates, etc. In many cases, one or many of these physical properties are inferior, and the requirements for industrial scale use cannot be fully satisfied. In addition, attempts have been made to improve these drawbacks by using a combination of two or more of these film-forming elements, but none of these methods can improve these drawbacks to some extent. However, there were other new difficulties when coating the surface of a resin molded body 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 substrate surface of a molded article such as a thermoplastic resin or thermosetting resin. As a result of investigation, poly[(meth)acryloyloxyalkyl]
It has been discovered that the above object can be achieved by using a composition containing (iso)cyanurate (a), a specific amount of a urethane-based poly(meth)acrylate compound (b), and a specific amount of a polymerization initiator (c), We 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 characteristic of being excellent. To summarize the present invention, the present invention comprises (a) General formula []

[expression] or

[Formula] [In the formula, X ¹ , X ² and X ³ are acryloyl groups,
methacryloyl group, hydrogen atom or alkyl group, at least two of which are (meth)acryloyl groups, R ¹ , R ² and
R ³ represents an oxyalkylene group or a polyoxyalkylene group. ] poly[(meth)acryloyloxyalkyl](iso)cyanurate, (b) more than 0 to 1000 parts by weight based on 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) a urethane poly(meth)acrylate compound having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule, and (c) the poly[(meth)acryloyloxyaalkyl](iso) Total of cyanurate (a) and the urethane-based poly(meth)acrylate compound (b)
A curable resin composition for coating, characterized in that it contains a polymerization initiator in a range of 0.01 to 20 parts by weight per 100 parts by weight. Poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) used in the curable resin composition for coating of the present invention has the general formula []

[expression] or

[Formula] [In the formula, X ¹ , X ² and X ³ represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of them are (meth)
It is an acryloyl group, and R ¹ , R ² and R ³ represent an oxyalkylene group or a polyoxyalkylene group. ] is poly[(meth)acryloyloxyalkyl]isocyanurate or poly[(meth)acryloyloxyalkyl]cyanurate represented by tris[(meth)acryloyloxyalkyl](iso)cyanurate, bis[(meth)acryloyloxy Although it may be alkyl](iso)cyanurate or a mixture thereof, those containing tris[(meth)acryloyloxyalkyl]isocyanurate as a main component are preferred. The alkyl group among X ¹ , X ² and X ³ is usually an alkyl group having 1 to 4 carbon atoms. In addition, R ¹ , R ² and R ³ have 1 to 12 carbon atoms,
It is preferably an oxyalkylene group in the range of 2 to 4 or a multimer of the oxyalkylene group, usually a dimer to a dodecamer, preferably a dimer to a tetramer. The poly [(meta)
Specific examples of the acryloyloxyalkyl isocyanurate include tris(acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, tris(2-acryloyloxypropyl)isocyanurate, and tris(2-methacryloyloxypropyl)isocyanurate. nurate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)methoxyethyl isocyanurate, bis(2-acryloyloxypropyl)-2-ethoxypropylisocyanurate, bis(2-methacryloyloxypropyl)-2 -Hydroxypropyl isocyanurate, tris[acryloyl di(oxyethylene)]isocyanurate, tris[methacryloyl di(oxyethylene)]isocyanurate, etc. can be exemplified, and mixtures of two or more of these can also be used. . Furthermore, specific examples of the poly[(meth)acryloyloxyalkyl]cyanurate include tris(acryloyloxyethyl)cyanurate, tris(methacryloyloxyethyl)cyanurate, tris(2-acryloyloxypropyl)cyanurate, tris(2- methacryloyloxypropyl) cyanurate, bis(acryloyloxyethyl)hydroxyethyl cyanurate, bis(methacryloyloxyethyl)methoxyethyl cyanurate, bis(2-acryloyloxypropyl)-2-ethoxypropyl cyanurate, bis(2-methacryloyloxy) Propyl)-2-hydroxypropyl cyanurate, tris[acryloyldi(oxyethylene)]cyanurate, tris[methacryloyldi(oxyethylene)]cyanurate, etc.
Mixtures of more than one species can also be used. Urethane poly(meth)acrylate compound (b) blended into the curable resin composition for coating of the present invention
is a (meth)acrylate-based polyfunctional compound having one or more urethane bonds and two or more acryloyloxy groups or methacryloyloxyl groups in one molecule. Specifically, (meta)
Urethane-based poly(meth)acrylate compounds obtained by the reaction of acrylic acid hydroxyalkyl ester and diisocyanate compounds, urethane-based poly(meth)acrylate compounds consisting of poly(meth)acrylate of polyurethane polyol, polyester-based polyurethane Examples include urethane-based poly(meth)acrylate compounds made of poly(meth)acrylate of polyol. These urethane poly(meth)
The polyol component units constituting the acrylate compound include aliphatic polyols, alicyclic polyols, aromatic polyols, polyoxyalkylene glycols, polyoxyalkane polyols, arylene bis[polyoxyalkane] polyols, polyester polyols, and polyurethane. Examples include polyols, polyurea polyols, polyester polyurethane polyols, and more specifically ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, Triethylene glycol, dipropylene glycol, dibutylene glycol, dihexylene glycol, diglycene, ditrimethylolpropane, dipentaerythritol, polyoxyethylene glycol, polyoxyethylene/polyoxypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, Cyclohexylene glycol, 2,2-bis(4-hydroxycyclohexyl)propane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, (meth)acrylates of polyglycidyl ethers of the various polyhydric alcohols;
An excess of the various polyhydric alcohol component units and succinic acid, glutaric acid, adipic acid, nouberic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride. Examples include polyester polyols formed from polyhydric carboxylic acid component units such as acid, trimellitic acid, and pyromellitic acid; polyurethane polyols formed from excess of the various polyol component units described above and various diisocyanate component units described below. be able to. Furthermore, the diisocyanate component units constituting these urethane-based poly(meth)acrylate compounds may be any of aliphatic diisocyanates, aliphatic diisocyanates, and aromatic diisocyanates. Of course, it may also be a dinitrile biscarbonate compound corresponding to these diisocyanate component units or a biscarbamate compound corresponding to these diisocyanate component units. Specifically, the diisocyanate component units of the constituent components include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, Methylcyclohexane-2,4-diisocyanate, 3-isocyanatomethyl-3,5,5
-trimethylcyclohexyl isocyanate,
4,4'-dicyclohexylmethane diisocyanate, isopropylidene bis(4-cyclohexyl isocyanate), phenylene diisocyanate,
Examples include tolylene diisocyanate, diphenylmethane diisocyanate, and bistolylene diisocyanate. A poly(meth)acrylate of a polyurethane polyol is obtained by reacting the polyurethane polyol with acrylic acid or methacrylic acid according to a conventional method in the presence of a catalyst if necessary, and similarly the polyester-based polyurethane polyol and acrylic acid are reacted. Poly(meth)acrylate of polyester-based polyurethane polyol can be obtained by reacting with acid or methacrylic acid. Among the urethane-based poly(meth)acrylate compounds, (meth)acrylic acid constituting the urethane-based poly(meth)acrylate compound obtained by the reaction of a (meth)acrylic acid hydroxyalkyl ester and a diisocyanate compound. Examples of the hydroxyalkyl ester component unit include a reaction product of a polyhydroxyl group-containing compound and (meth)acrylic acid, a reaction product of an epoxy compound and (meth)acrylic acid, etc. Specifically, 2-hydroxy acrylic acid Ethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylate of glycidyl acrylate, methacrylate of glycidyl acrylate, acrylate of glycidyl methacrylate, glycidyl methacrylate Ether methacrylate, glycerin monoacrylate, glycerin monomethacrylate, glycerin-1,3-diacrylate, glycerin-
1,3-dimethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate,
Pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol monoacrylate, dipentaerythritol monomethacrylate, dipentaerythritol diacrylate, dipentaerythritol dimethacrylate, dipentaerythritol triacrylate,
Dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)hydroxyethyl isocyanurate Nurate, diacrylate compound of propylene glycol diglycidyl ether, dimethacrylate compound of propylene glycol diglycidyl ether, diacrylate compound of glycerin-1,3-diglycidyl ether, dimethacrylate compound of glycerin-1,3-diglycidyl ether, Triacrylate of glycerin triglycidyl ether, trimethacrylate of glycerin triglycidyl ether, diacrylate of pentaerythritol diglycidyl ether, dimethacrylate of pentaerythritol diglycidyl ether, triacrylate of pentaerythritol triglycidyl ether, pentaerythritol Trimethacrylate of triglycidyl ether, diacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, dimethacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, 2, 2-bis (4
-Hydroxyphenyl) diacrylate of punpan diglycidyl ether, 2,2-bis(4
-Hydroxyphenyl) propane diglycidyl ether dimethacrylate, etc., and as the diisocyanate component unit, the above-mentioned compounds can be similarly exemplified.
The urethane-based poly(meth)acrylate compound
Among (b), when a urethane poly(meth)acrylate compound containing an aliphatic alkylene diisocyanate component unit or an alicyclic diisocyanate component unit as a diisocyanate component unit is used, the cured coating This is preferable because the hue, weather resistance, and flexibility of the material are improved. The blending ratio of the urethane-based poly(meth)acrylate compound (b) is in the range of more than 0 to 1000 parts by weight based on 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a). The amount is preferably in the range of 5 to 500 parts by weight. The poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) of the urethane-based poly(meth)acrylate compound (b) 100
If the blending ratio is more than 1000 parts by weight, the abrasion resistance, surface hardness, etc. of the coating will 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 also include other polymerizable monomer components. It is also possible to copolymerize by adding. Other polymerization components include, for example, by-products or intermediates during the production of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a), such as mono[(meth)acryloyloxyalkyl](iso)cyanurate (a).
[acryloyloxyalkyl]bis(hydroxyalkyl)(iso)cyanurate, by-products or production intermediates during the production of the urethane-based poly(meth)acrylate compound (b), such as urethane-based poly(meth)acrylate compounds, etc. (meth)acrylic acid, methyl (meth)acrylate,
(meth)ethyl acrylate, (meth)acrylic acid-
Examples include (meth)acrylic esters such as 2-hydroxyethyl. 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, it is necessary to add a polymerization initiator to the composition.
It is necessary to incorporate (c). As the curing method, a curing method using ultraviolet rays, a curing method using heat rays, etc. are usually employed. In the case of ultraviolet curing, a photosensitizer is blended as a polymerization initiator. Specifically, the photosensitizer is benzoin or its like, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. ether,
Benzophenone, p-chlorobenzophenone, p
-Benzyl compounds such as methoxybenzophenone, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, 1-(4-isopropylphenyl)-2-
Hydroxy-2-methyl-1-propanone, 1-
Phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-tert-butylphenyl)-2
Examples include hydroxyalkyl phenyl ketone compounds such as -hydroxy-2-methyl-1-propanone. In the case of curing by heat, a radical initiator is blended, and specific examples of the radical initiator include azo compounds such as azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, dicumyl peroxide, Examples include peroxides such as cumene hydroperoxide. Furthermore, it is also possible to adopt a method in which both a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and UV curing and heat curing proceed simultaneously. It is also possible to adopt a method of proceeding with heat curing after proceeding with the heat curing, or conversely, a method of proceeding with ultraviolet curing after proceeding with heat curing. The blending ratio of the polymerization initiator (c) is based on a total of 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the urethane-based poly(meth)acrylate compound (b). It is necessary to range from 0.01 to 20 parts by weight, and more preferably from 0.1 to 10 parts by weight. The blending ratio of the polymerization initiator is the sum of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the urethane-based poly(meth)acrylate compound (b).
If it is less than 0.01 part by weight per 100 parts by weight,
The polymerizability of the composition decreases, making it impossible to obtain a hard coating, and if the amount exceeds 20 parts by weight, the coating obtained from the composition will be colored yellow. The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned three essential components, but
Furthermore, if necessary, polymerization inhibitors, transparent fillers, solvents, ultraviolet absorbers, stabilizers such as antioxidants, fluorescent brighteners, methyl (meth)acrylate,
Various additives can be included, such as (reactive) oligomers such as polyester acrylate and polymers such as polymethyl methacrylate. The blending ratio of these additives is appropriate. In the curable resin composition for coating of the present invention, a finely powdered inorganic filler may be blended as necessary within a range that maintains the transparency of the cured film obtained therefrom. The average particle size of the fine powder inorganic filler is arbitrary as long as it is in the form of a powder, but it is usually 1 mμ to 10μ, preferably 1.5μ.
It ranges from mμ to 1μ. In addition, in order to maintain the transparency of the outer coating layer, the refractive index of the finely powdered inorganic filler is usually 1.40 to 1.60, preferably
It ranges from 1.42 to 1.58. Specifically, such fine powder inorganic fillers include glass powder, mica, glass beads, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, silica stone, silica sand,
Examples include quartz, kaolinite, montmorillonite, sericite, talc, chlorite, chinastone, and feldspar. In addition, the surface of these finely powdered inorganic fillers can be coated with alkyl carboxylates, silane couplers, titanium couplers, Cl ₂ Si (CH ₃ ) ₂ ,
Those surface-treated with alcohol or the like can also be used in the same way. Furthermore, colloidal silica, methanol silica sol, ethanol silica sol, isopropanol silica sol, etc. in which the inorganic filler is suspended in water or alcohol can also be used. Among these fine powder inorganic fillers, blending fine powder silica significantly improves the surface hardness, scratch resistance, and abrasion resistance of the outer coating layer without impairing transparency and surface gloss. Therefore, it is particularly preferable. The blending ratio of these fine powder inorganic fillers is the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the urethane-based poly(meth)acrylate compound (b).
The amount is usually 0.5 to 200 parts by weight, preferably 0.5 to 100 parts by weight, based on a total of 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 nitriles such as propionitrile and capronitrile, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, benzyl acetate, methyl benzoate, and ethyl benzoate. . The blending ratio of these organic solvents is based on the poly[(meth)acryloyloxyalkyl](iso)
The amount is generally 5 to 3,000 parts by weight, preferably 10 to 2,000 parts by weight, per 100 parts by weight of the mixture of cyanurate (a) and the urethane poly(meth)acrylate compound (b). 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,
A uniformly dissolved or dispersed composition can be obtained by kneading and mixing operations using an attritor, a whipper, an oak mixer, a desolver, a homogenizer, a colloid mill, a sand mill, a vibration mill, a mixer mixing tank, etc. Methods for applying the solution composition and suspension composition onto the substrate surface of the molded article 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 natural drying, forced drying using carrier gas, and 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 crosslinking and curing methods, 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 it is 1 sec to 10 min. In addition, in the thermosetting method, the temperature during curing is usually -10 to 150℃,
The temperature is 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 substrate surface of any molded article made of thermoplastic resin, thermosetting resin, metal, etc.
It is preferable to coat the substrate surface of a molded body made of a thermoplastic resin. The shape of the molded product may be a film, a sheet, a plate, 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 a polyolefin, a polyacrylic ester resin, or a polycarbonate resin, and particularly preferably a polyolefin. 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 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, the primer may be a modified polyolefin grafted with an α,β-unsaturated carboxylic acid or a derivative component thereof such as an α,β-unsaturated carboxylic acid, its acid anhydride, or its ester. is usually used. In this manner, 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 required, by the method described above, 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, various films such as shatterproof films for glass, release films, insulating films, agricultural films, etc., and lights. Recycled video discs, observation windows for various equipment such as clothes dryers, electric washing machines, dryers, oil tanks, windshields for motorcycles, jeeps, motorboats, etc., automobile glass (windshields, etc.)
rear windows, opera windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, etc.
Tableware, mirrors, various containers such as oil bottles and cosmetic bottles,
Relay cases, fuse boxes, motorcycle side covers and mudguards, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulating films, floor tiles, floor sheets,
Doors, table boards, wall tiles, countertop decorative boards, shelf boards, wall sheets, wallpaper, furniture, lightweight wall boards, tableware, chairs, bathtubs, toilets, refrigerators, wall panels, water supply and drainage pipes, raceways, ducts, curtain rods , rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foils, various containers, automobile interior materials, vanity tables, flower boxes, particle boards,
Examples include tiles, shutters, shutters, waterproof pans, pipes, wiring materials, gear cams, knobs, solenoid valve frames, fans, instrument panels, bumpers, and brakes.
In addition to the above, it is also used in home appliances, automobile parts, motorcycle parts, vending machine parts, civil engineering and construction materials, general industrial materials, office information equipment, electronic parts, packaging materials, sports equipment, medical equipment, and nuclear power-related parts. can do. Next, the present invention will be specifically explained using examples. In addition, in the main text of the specification or the examples, evaluation was performed by the following method. (1) Refractive index Add 2wt% of a sufficiently dried inorganic substance to a liquid with a known refractive index, and after sufficiently dispersing it, visually check the transparency. The refractive index should be the same as that of the most transparent liquid. (2) Surface gloss (gloss) Performed according to JIS K5400-1979 60 degree specular gloss. (3) Light transmittance Conducted according to JIS K6714. (4) Adhesion The test was conducted according to the cross-cut test in JIS K5400-1979. Judgment is based on how many of the 100 pieces are glued together. (5) Sand abrasion 800g of silicon carbide abrasive material is dropped onto the coating according to the method of JIS T8147-1975. Abrasion resistance is expressed by the difference in surface gloss before and after the test. The smaller the number, the better the wear resistance. (6) Taper wear Abrasion wheel 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 less abrasive, the better the abrasion resistance. (7) Pencil hardness Measured according to JIS K5651. (8) Flexibility A strip-shaped test piece with a width of 5 mm and a length of 10 cm was
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-type deterioration 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. In addition, the synthesis example of polyurethane acrylate is shown in the following reference example. Reference Example 1 100 g (0.3 mol) of propylene glycol diglycidyl ether modified with acrylic acid (manufactured by Kyoeisha Yushi Kagaku KK, trade name: Epoxy Ester 70PA)
20g (0.12M) of hexamethylene diisocyanate was added to a 500ml four-necked flask under a nitrogen atmosphere, and stirred at room temperature for 15 hours to form a mixture consisting of an acrylic acid modified product of propylene glycol diglycidyl ether and a hexamethylene diisocyanate component unit. We synthesized urethane-based polyacrylate (PGAHI). Reference example 2 Dipentaerythritol pentaacrylate 50
(0.095 mol), a mixture of 30 g (0.064 mol) dipentaerythritol tetraacrylate, 20 g dipentaerythritol hexacrylate, and 120 g of methyl isobutyl ketone were placed in a 500 ml four-necked flask, and 3-isocyanatomethyl-3,5 was added under a nitrogen atmosphere. , 17.6 g (0.08 mol) of 5-trimethylcyclohexyl isocyanate was added and stirred at room temperature for 15 hours to separate dipentaerythritol polyacrylate component units and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate component units. A methyl isobutyl ketone solution of urethane polyacrylate (DPAIP) was synthesized. Reference Example 3 74 g (0.2 M) of bis(acryloyloxyethyl) hydroxyethyl isocyanurate and 100 g of methyl isobutyl ketone were placed in a 500 ml four-necked flask, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate was prepared under a nitrogen atmosphere. Add 22g (0.1M) of Nato and leave at room temperature for 15 hours.
Stir to synthesize a methyl isobutyl ketone solution of urethane polyacrylate (BAIIP) consisting of bis(acryloyloxyethyl)hydroxyethyl isocyanate component units and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate component units. did. Example 1 85 g of tris(acryloyloxyethyl) isocyanurate, 15 g of the urethane polyacrylate (PGAHI) described in Reference Example 1, 5 g of benzoin isopropyl ether, and 110 g of methyl isobutyl ketone were placed in a 500 ml four-necked flask and stirred at room temperature for 1 hour. A transparent coating composition [A] was prepared. 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 dried at 60° C. 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. Example 2 In Example 1, instead of using the coating composition [A] described in Example 1, 85 g of tris(acryloyloxyethyl)isocyanurate and the urethane polyacrylate (DPAIA) solution described in Reference Example 2 were used. 31g, benzoin isopropyl ether 5g and methyl isobutyl ketone 100g
After using the coating composition consisting of the following, a test piece was prepared in which the surface of polypropylene was coated in the same manner as in Example 1. The results are shown in Table 1. Example 3 In Example 2, the method described in Example 2 was used, except that the urethane-based polyacrylate (BAIIP) solution described in Reference Example 3 was used instead of the urethane-based polyacrylate solution described in Reference Example 2. A test piece was prepared by coating the surface of polypropylene. The results are shown in Table 1. Examples 4 to 8 In Example 1, instead of using the coating composition [A] described in Example 1, the poly[(meth)acryloyloxyalkyl]isocyanurate and urethane-based poly(meth) described in Table 1 were used. Example 1 except that a coating composition prepared with the amounts of acrylate, photosensitizer, and solvent listed in Table 1 was used.
A test piece with a polypropylene surface coated was prepared in the same manner as above. The results are shown in Table 1. Examples 9 to 10 Poly[acryloyloxyalkyl]isocyanurate, urethane poly(meth)acrylate, photosensitizer and 1,1,1-
Weigh out the amount of trichloroethane listed in Table 1,
Finely powdered silica (manufactured by Nippon Aerosil KK, manufactured by Nippon Aerosil KK,
(trade name: R-972) was gradually added (the amount used is shown in Table 1) and stirred thoroughly until uniform dispersion was obtained. Thereafter, the mixture was transferred to an attritor (manufactured by Mitsui Miike Seisakusho KK) filled with steatite balls, and mixed for 3 hours by rotating an agitator at 150 rpm while cooling the tank with water. Thereafter, n-butanol 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 to 2 Films prepared by weighing out the amounts of poly[acryloyloxyalkyl]isocyanurate, urethane polyacrylate, photosensitizer, and solvent listed in Table 1 and stirring and mixing at room temperature for 1 hour. A test piece having a polypropylene surface coated was prepared by the method described in Example 1 except that 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.

【table】

【table】

[Table] Example 11 A 3 mm thick injection molded sheet of poly-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries KK, trade name TPX MX004) was molded 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 leaving it at room temperature for 5 minutes,
It was dipped in the coating composition described in Example 9 for 10 seconds. After drying at 60° C. for 5 minutes, photopolymerization was performed using the method described in Example 9 to prepare a test piece whose surface was coated with poly-4-methyl-1-pentene. The results are shown in Table 2. Examples 12-13 In Example 11, polyester was used as the base polymer.
Instead of using 4-methyl-1-bentene, Table 2
Using a polymer sheet with a thickness of 3 mm described in Table 2, a test piece was prepared by coating the surface of the polymer by the method described in Example 11, except that the pretreatment described in Table 2 was performed. The results are shown in Table 2. Comparative Examples 4 to 6 Polymers not coated with the coating composition of the present invention
4-Methyl-1-pentene (Mitsui Petrochemical Industries)
Table 2 shows the performance of polycarbonate (Panlite L-1250, manufactured by Teijin KK), and polymethyl methacrylate (Acrylite L, manufactured by Mitsubishi Rayon KK).

【table】

Claims (1)

[Claims] 1 (a) General formula [Formula] or [Formula] [In the formula, X ¹ , X ² and X ³ are acryloyl groups,
methacryloyl group, hydrogen atom or alkyl group, at least two of which are (meth)acryloyl groups, R ¹ , R ² and
R ³ represents an oxyalkylene group or a polyoxyalkylene group. ] poly[(meth)acryloyloxyalkyl](iso)cyanurate, (b) more than 0 to 1000 parts by weight based on 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) a urethane-based poly(meth)acrylate compound having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule, and (c) the poly[(meth)acryloyloxyalkyl](iso)cyanurate; Total of (a) and the urethane poly(meth)acrylate compound (b)
A curable resin composition for coating, characterized in that it contains a polymerization initiator in a range of 0.01 to 20 parts by weight per 100 parts by weight. 2 Fine powder in a range of 0.5 to 200 parts by weight based on a total of 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the urethane-based poly(meth)acrylate compound (b). The curable resin composition for coating according to claim 1, which contains an inorganic filler.