JPS5966462A - Curable resin composition for coating - Google Patents

Abstract

PURPOSE:To provide the titled resin composition having excellent curing characteristics and giving a coating film having excellent film properties, by compounding specific amounts of an aliphatic polyepoxy compound poly(meth)acrylate, an alkanepolyol poly(meth)acrylate, and a polymerization initiator. CONSTITUTION:The objective composition is composed of (A) 100pts.wt. of an aliphatic polyepoxy compound poly(meth)acrylate having at least two epoxy groups in the molecule [containing the unit of formula (R<1> is H or CH3)], (B) more than 0pt.wt. and up to 1,000pts.wt. of a 2-12C alkanepolyol ply(meth) acrylate (e.g. 2,2-dimethyl-1,3-diacryloyloxypropane) and (C) 0.01-20pts.wt., based on 100pts.wt. of (A)+(B), of a polymerization initiator (e.g. benzoin, benzophenone, etc.).

Description

Detailed Description of the Invention The present invention provides excellent curing properties in air by coating the substrate surface of a molded article such as a resin, and improves the surface hardness, scratch resistance, abrasion resistance, flexibility, and surface properties of the coating. gloss, heat resistance,
The present invention relates to a curable resin composition for coating that has excellent coating properties such as water resistance, solvent resistance, weather resistance, and adhesion to the surface of a molded body.

Generally, molded products such as thermoplastic resins and thermosetting resins are
Compared to metal products, glass products, etc., it is not only lightweight and has excellent impact resistance, but also has various advantages such as being inexpensive and easy to mold.
It is widely used in place of other materials such as chives in household appliances, daily necessities, and many other fields. However, molded substrates made of these resins have a lower surface hardness than metals, glass, etc., and are susceptible to scratching and friction, so they have the drawback of being easily scratched on the surface. For example, the use of these molded bodies is severely restricted due to defects in surface properties such as susceptibility to surface damage due to contact, collision, scratching, etc. during installation or transportation of parts of molded bodies or during use of the product. has been done.

Many proposals have been made as methods for improving the above-mentioned defects on the surface of molded body substrates such as resins. Most of these methods involve coating the surface of these molded bodies with an outer coating layer made of a crosslinked curable resin. Among these film-forming elements, specifically as resins or resin-forming components,
Silicone monomers or compositions of these components and various polymers, resin compositions of methylolmelamine and other curing components, polyfunctional acrylic thread carboxylic acid ester derivatives, or compositions of this and other polymeric components. Things are being suggested. Even if a coating layer consisting 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 resin molded product base layer is generally not good. There is a drawback that the coating layer is easily peeled off. Furthermore, methods are known in which various treatments are applied to the surface of the base layer of a resin molded body in order to completely eliminate 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 so as to be practical.

Furthermore, among the film-forming elements described above, silicone thread 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 are used as film-forming elements, such as methacrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, and poly(meth)acrylates of aromatic (phenolic) polyhydroxyl compounds. Even if these polyfunctional acrylic yarn carboxylic acid ester derivatives are used alone as a film-forming element to form a film on the substrate surface of a resin molded product, for example, these films will not be cured. Poor curing properties such as curing speed in the air, surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. In many cases, film properties such as physical properties or many of these properties are inferior, and it has not been possible to fully satisfy the requirements for industrial scale use.In addition, two of these film forming elements Attempts have been made to improve these drawbacks by using a combination of the above compounds, but although these drawbacks can be improved to some extent, they do not affect the surface of the base of resin molded products such as polyolefin. There were other new difficulties in coating.

The present inventors have worked diligently to develop a coating composition that has excellent curing properties during curing and has excellent coating properties when coated on the surface of a molded article substrate made of thermoplastic resin, thermosetting resin, etc. As a result of investigation, we found that poly(meth)acrylate of aliphatic polyepoxy compound (a), poly(methacrylate of a specified amount of alkane polyol) (
It has been found that the above object can be achieved by using a composition containing b) and a specific amount of a polymerization initiator (C), and the present invention has been achieved. According to the present invention, when the curable resin composition for coating of the present invention is coated on the surface of a molded body substrate such as a resin to form an outer coating layer, the curing characteristics such as the curing speed in air during curing can be improved. 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 overall.

To summarize the present invention, the present invention provides (a) a poly(meth)acrylate of an aliphatic polyepoxy compound having at least two or more epoxy groups in one molecule; (b) a poly(meth)acrylate of the polyepoxy compound; (Meth)acrylate (a) More than 0 and 1 per 100 parts by weight
000 parts by weight, containing 2 to 12 carbon atoms
A total of 100 parts by weight of a poly(meth)acrylate of the alkane polyol, and (C) a poly(meth)acrylate of the polyepoxy compound (a,) and (b) II (meth)acrylate of the alkane polyol. The gist of the present invention is 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 based on the amount of a polymerization initiator.

The (meth)acrylate compound (a) of the polyepoxy compound blended in the curable resin composition for coating of the present invention is 1
It is a poly(meth)acrylate of a polyepoxy compound formed from an aliphatic polyepoxy compound having at least two or more epoxy groups in the molecule and acrylic acid or methacrylic acid. Here, specific examples of aliphatic polyepoxy compounds having at least two epoxy groups in one molecule include methylene glycol, ethylene gelicol, propylene glycol, butylene glycol, benchlene gelicol, hexylene glycol, and octylene glycol. Glycol, decylene gelylcol, dodecylene glycol, glycerin, trimethylolpropane, pentaerythritol, polyoxyethylene glycol,
Polyoxypropylene glycol, polyoxyethylene polyoxybrobylene glycol, diglycerin, ditrimethylolpropane, tritrimethylolpropane,
Polyglycidyl ethers of aliphatic polyols such as dipentaerythritol and tripentaerythritol can be mentioned, and more specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene gellicol diglycidyl ether, and glycerin. Triglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol diglycidyl ether, polyoxyethylene glycol diglycidyl ether, poly Oxypropylene glycol diglycidyl ether, diglycidyl ether, diglycidyl ether, diglycerin diglycidyl ether, ditrimethylolpropane tetraglycidyl ether, ditrimethylolpropane triglycidyl ether, ditrimethylolpropane diglycidyl ether, dipentaerythritol Examples include xaglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol tetraglycidyl ether, dipentaerythritol triglycidyl ether, dipentaerythritol diglycidyl ether, and even mixtures of two or more of these. good.

The poly(meth)acrylate compound (a) of a polyepoxy compound blended into the curable resin composition for coating of the present invention is:
It is a poly(meth)acrylated product of the polyepoxy compound formed from the polyepoxy compound and acrylic acid or methacrylic acid, and more specifically, the epoxy group of the polyepoxy compound is ring-opened to form a hydroxyl group ( General formula (1) in which a meth)acryloyloxyl group is bonded to an adjacent carbon atom [wherein R represents a hydrogen atom or a methyl group]. ], and this unit is included in at least 2 units in the molecule.
Therefore, it is a compound having two or more (meth)acryloyloxyl groups and two or more hydroxyl groups in the molecule. 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, their salts, quaternary ammonium compounds, organic acid salt compounds, Lewis acids or their complexes, alkaline earth metal halides or hydroxides, halogenated Examples include hydrogen. 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, hydroxide) , hydrogen chloride, hydrogen bromide, etc., and mixtures of two or more of these 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 per mole of epoxy groups of the polyepoxy compound.
．． 6 to 1.5 mol, preferably 0.9 to 1.1
It is in the molar range. The reaction is usually carried out at -10 to 160'C.
carried out at a temperature of

The poly(meth)acrylate (b) of an alkane polyol blended into the curable resin composition for coating of the present invention is a poly(meth)acrylate of an alkane polyol having 2 to 12 carbon atoms.

Here, the alkane polyol is a dihydric alcohol, a trihydric alcohol, a tetrahydric alcohol, a higher polyhydric alcohol, or a mixture thereof. Further, the number of carbon atoms constituting the alkane polyol component must be in the range of 2 to 12, and more preferably in the range of 2 to 8.

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 trihydric or higher polyhydric alcohol, the poly(meth)acrylate of the alkane polyol
In the acrylate, as long as two or more hydroxyl groups are (meth)acrylated, there is no problem even if free hydroxyl groups remain. Specifically, the (meth)acrylate of the alkane polyol includes 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, rhodimethacryloyloxypropane, 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-1,5-diacrylate, glycerin-1,3-dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolethane diacrylate, Trimethylolethane dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane diacrylate,
Examples include trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, etc. can do. 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, 1,6-diacryloyloxyhexane, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate Preference is given to using erythritol tetraacrylate. Poly(meth)acrylate of the alkane polyol
) The blending ratio of (b) needs to be in the range of 1000 parts by weight exceeding O to the poly(meth)acrylate of the polyepoxy compound <8.3100 parts by weight, and furthermore, it is necessary to In the range of 600 parts by weight, especially 2
It is preferably in the range of 0 to 300 parts by weight. Poly(meth)acrylate (b) of the alkane polyol
When the blending ratio of the polyepoxy compound to 100 parts by weight of poly(meth)acrylate (a) exceeds 1000 parts by weight, the polymerizability of the composition decreases, and the surface hardness of the coating obtained from the composition decreases. Performance such as scratch resistance and abrasion resistance deteriorates.

The film-forming element component (polymerizable monomer component) blended into the curable resin composition for coating of the present invention may consist only of the above-mentioned essential components, but may further include other polymerizable monomer components. Copolymerization is also possible. Other polymerizable monomer components include by-products or intermediates during the production of poly(meth)acrylates of the polyepoxy compounds or poly(meth)acrylates of alkane polyols, such as (meth)acrylates of monoepoxy compounds. In addition to acrylates, mono(meth)acrylates of polyepoxy compounds, mono(methacrylates) of alkane polyols, (meth)acrylic acid, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. Nisder (meth)acrylate and the like 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 film, it is necessary to blend a polymerization initiator (C) into this composition. It is. As a 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,
Benzophenone compounds such as p-chlorobenzophenone and p-methoxybenzophenone; benzyl compounds such as benzyl dimethyl ketal and benzyl diethyl ketal; 1-(4-isopropylphenyl)-
2-Hydroxy-2-hydroxy-2-methyl-1-propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-tart-butylphenyl)-2-hydroxy-2-methyl Examples include hydroxyalkylphenylketone compounds such as -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, and di-tθr.
Examples include peroxides such as t-butyl peroxide, dicumyl peroxide, and cumene hydroperoxide. Furthermore, it is also possible to adopt a method in which both a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and UV curing and heat curing proceed simultaneously. It is also possible to adopt a method in which heat curing is progressed after the heat curing is progressed. Furthermore, it is also possible to adopt a method of proceeding with ultraviolet curing after proceeding with heat curing. The blending ratio of the polymerization initiator (c) is 0.00 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 of the alkane polyol (b). It is necessary that the polymerization initiator be in the range of 0.1 to 20 parts by weight, and more preferably in the range of 0.1 to 10 parts by weight. Acrylate (a)
If the amount is less than 0.01 part by weight based on the total of 100 parts by weight of the poly(meth)acrylate (b) of the alkane polyol, the polymerizability of the composition decreases, making it impossible to obtain a hard film; If there are more than
The coating obtained from the composition becomes yellow colored.

The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned three essential components, but may further include a polymerization inhibitor, a transparent filler, a pigment, a dye, a solvent, and an ultraviolet absorber as required. stabilizers such as antioxidants, fluorescent brighteners,
Various additives such as (reactive) oligomers such as methyl (methane acrylate, polyurethane acrylate, and polyester acrylate) and polymers such as polymethyl methacrylate can be blended. The blending ratio of these additives is appropriate.

In the curable resin composition for coating of the present invention, a finely powdered inorganic filler may be blended as necessary within a range that maintains the transparency of the cured film obtained therefrom.

The average particle size of the fine powder inorganic filler is arbitrary as long as it forms a fine powder, but it is usually 1 mμ to 10 μm.
, preferably in the range of 1.5 mμ to 17z. 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 is in the range of 1842 to 1.58. Specifically, such fine powder inorganic fillers include glass powder, mica, glass peas, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, silica stone, silica sand, quartz,
Examples include kaolinite, montmorillonite, sericite, talc, chlorite, pottery stone, and feldspar. In addition, the surface of Konera's finely powdered inorganic filler can be coated with alkyl carboxylate, silane coupler, titanium coupler, etc.
Those surface-treated with cI 5i (CH3,)2, alcohol, etc. can also be used in the same way. Further, it is also possible to use fluid silica, methanol silica sol, conitanol silica sol, isopropanol silica sol, etc. in which the inorganic filler is suspended in water or alcohol.

Among these finely powdered inorganic fillers, blending finely powdered 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 inorganic fillers is 10 in total of the poly(meth)acrylate of the polyepoxy compound (a) and the poly(meth)acrylate of the alkane polyol (b).
The amount is usually 0.5 to 200 parts by weight, preferably 0.5 to 100 parts by weight.

A solvent is added to the curable resin composition for coating of the present invention as necessary to improve its coating workability, and the composition is maintained in a solution state or a suspended state.

The solvent is also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. Specifically, as a solvent,
Hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin, cyclohegizane, methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, bromoform, trichlene, ethylene dichloride, perchloren, Halogenated hydrocarbons such as ethane chloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobenzene, methanol, ethanol, isopropanol,
Alcohols such as butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol, acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glyfur 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, and other esters. The blending ratio of these organic solvents is usually 5 to 6000 parts by weight, preferably 5 to 6000 parts by weight, based on the total of 100 parts by weight of the poly(methacrylate (a) of the polyepoxy compound and the poly(methane acrylate (b)) of the alkane polyol. ranges from 10 to 2000 parts by weight.

In the composition of the present invention, a solution composition or suspension composition is obtained from a composition containing the above-mentioned essential components and various additive components such as inorganic or organic fillers, solvents, and stabilizers added as necessary. As a method for preparing cj1, the above-mentioned raw material mixture is prepared, and the mixture is prepared using a regular roll, Banbury mixer,
Examples of kneading and mixing methods include ball mills, attritors, whitpers, oak mixers, dissolvers, homogenizers, colloid mills, sand mills, vibration mills, mixers, and mixing/stirring beds. A composition is obtained. Methods for applying the solution composition and suspension composition to the substrate surface of the molded article include brush coating, spraying, dipping, barcoding, roll coater, spin coater, gel coater, etc. Conventionally known methods can be employed. Examples of methods for drying the coating film include natural drying, forced drying using a carrier gas, heating drying using an infrared oven, far-infrared oven, and hot air oven. Examples of methods for curing the above-mentioned coating film to form a film include a method of polymerizing and crosslinking hardening with light, particularly ultraviolet rays, a method of polymerizing and crosslinking hardening with heat, and the like. Among these polymerization and crosslinking curing methods, 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 from isea to 1 hr, preferably from 1sθC to 130°C. 1i]min. In addition, in the thermosetting method, the temperature during curing is usually -10 to 150'C,
The temperature is preferably 5 to 130°C, and the time required for curing is usually 0.05 to 10 hours, preferably 0.1 to 8) hours.

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 polyolefins such as an α-olefin homopolymer or a copolymer containing α-olefin as a main component;
Polyacrylic acid ester resin, polycarbonate resin,
Examples include polyester resin and polyamide resin. Among these thermoplastic resins, the base layer fEJI constituting the laminate molded product is preferably made of polyolefins, polyacrylic acid ester resin, or polycarbonate resin. Specifically, the polyolefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-
A monopolymer of α-olefin such as decene, a copolymer consisting of a mixture of two or more of the above α-olefins, or a lower aliphatic carbonaceous compound containing the above α-olefin as a main component and vinyl acetate, vinyl propionate, etc. A small amount (for example, 60 mol% or less) of other components such as vinyl acid, methyl acrylate, metal salts of acrylic acid, methyl methacrylate, acrylic carboxylic acid esters such as metal salts of methacrylic acid, and salts of acrylic carboxylic acids. ) can be exemplified. Among these polyolefins, polyolefins having crystallinity are usually used. Specific examples of the polyacrylic carboxylic acid ester resin include homopolymers or copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. can. Among these polyacrylic carboxylic acid ester resins, polymethyl methacrylate is preferably used in the thermoplastic resin base resin layer of the present invention. Specific examples of the polycarbonate resin include bisphenol A polycarbonate. Specific examples of the polyester resin include polyethylene terephthalate, polytetramethylene terephthalate, bisphenol A/isophthalic acid/terephthalic acid copolycondensate, and oxybenzoic acid polycondensate. Specific examples of the polyamide resin include nylon 6, nylon 6-6, nylon 10, and nylon 12.

In addition to the above resins, polyacetal, polystyrene,
Examples include acrylonitrile-styrene copolymer, acrylonitrile [phase] butadiene-pupil styrene copolymer, polysulfone resin, polyphenylene oxide, modified polyphenylene oxide, polyphenylene sulfide resin, and polyethersulfone resin.

Specifically, the thermosetting resin constituting the base layer includes unsaturated polyester resin, epoxy resin, melamine 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. Ultrasonic cleaning, electrolytic cleaning,
Various surface treatments such as blasting, sandblasting, acid or alkali etching, 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, an intermediate adhesive layer made of a primer may be placed between the substrate layer and the outer coating layer. It is also possible to improve the adhesion between both layers by forming a three-layer laminate. When the base layer is polyolefin, the primer may be α,β-unsaturated carboxylic acid, its acid anhydride, Modified polyolefins grafted with σ, β-unsaturated carboxylic acids or derivatives thereof, such as esters thereof, are commonly 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 necessary, 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, examples include daylight panels, sky domes, solar water heater panels, glove box panels, watch glasses, glasses, cameras, various lenses such as camera lenses, optical prisms, blood bags, and coffee makers. Shower domes and fuhi containers, water tanks, covers for lighting equipment, covers for stereo equipment such as brake cameras, dials and covers for various meters, cover level sensors for car headlamps and tail lamps, glass shatter prevention films and separation panels. Various types of films such as molded films, insulating films, agricultural films, optical playback type video discs, viewing windows for various equipment such as clothes dryers, electric washing machines, dryers, and oil tanks, windshield glasses for motorcycles, jeeps, motor boats, etc. Automobile glass (windshield, rear window, opera window, triangular window, Zanru 7), window glass for greenhouses, houses, aquariums, etc., tableware, mirrors, various containers such as oil bottles and makeup skin, relay cases,
Fuse boxes, motorcycle side covers and i-bays, fenders, curtains, screens, tablecloths, heather and moisture-proof films, waterproof sheets, insulation films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorations Boards, shelves, wall sheets, wallpaper, furniture, lightweight wallboards, tableware, chairs, bathtubs, toilets, refrigerators, wall panels,
Water supply and drainage pipes, plumbing, ducts, curtain rods, rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile boilers, various containers, automobile interior materials, vanity tables, flower boxes,
Examples include particle boards, roof tiles, 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 with reference to Examples.

In addition, in the main text of the specification or the examples, evaluation was performed by the following method.

/' 7. -'//'7-' 2/ / (1) Refractive index A sufficiently dried inorganic substance is placed in a liquid with a known refractive index by 2w.
After adding t% and thoroughly dispersing, visually check the transparency. The refractive index is the same as that of the most transparent liquid.

(2) Surface gloss (gloss) Measured according to (7) 60 degree specular gloss in JIS K 5400-1979.

(5) Light transmittance It was conducted according to JIS K 6714.

(4) Adhesion It was carried out according to the cross-cut test in JIS K 5400-1979. Judgment is indicated by how many of the 100 cross-holes were adhered.

(5) Sandfall abrasion 800 according to the method of JIS T 8147-1975
g of silicon carbide abrasive material is dropped onto the coating.

Abrasion resistance can be determined by the difference in surface gloss before and after the test. The smaller the number, the better the wear resistance.

(6) Taper wear As'r+x According to the method of D-1044, wear ring C
8-10, rotate the coating 1000 times with a load of 500 g.

The amount of wear on the coating after the test did not indicate wear resistance.

The smaller the amount of wear, the better the wear resistance.

(7) Pencil hardness Measured according to JISK 5651.

(8) Flexibility: A strip-shaped test piece with a width of 5 mm and a length of 10 m is 2 cm in diameter.
Folded along the outer periphery of the cylinder of I, it is expressed as the angle at which the coating cracks or peels off from the substrate. 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.

θ0 Heat Resistance After holding the test piece in a gear set aging tester at 80°C for 400 hours, the appearance and adhesion of the outer coating layer were evaluated.

0]) Volatile oil resistance test piece was immersed in petroleum benzine at room temperature for 24 hours, and then the appearance and adhesion of the outer coating layer were evaluated.

0 [F] Gasoline resistance test pieces were immersed in regular gasoline for 2-1 hours at room temperature, and then the appearance and adhesion of the outer coating layer were evaluated.

α TO heat cycle resistance test piece was kept in an air oven at 80°C for 2 hours, then left at room temperature for 1 hour, then kept in a cold room at -50°C for 2 hours, then kept at room temperature for 1 hour. Leave it for a while. This cycle was repeated 10 times, and changes in the appearance of the outer coating layer were visually observed and adhesion was evaluated.

θ→ The weather resistance test piece was held in a Sunshine Weatherometer for 400 hours, and the appearance and adhesion of the outer coating layer were evaluated.

Example 1 75 g of diacrylate of propylene glycol diglycidyl ether, 25 g of neopentyl glycol diacrylate, 5 g of benzoin isopropyl ether, and 11 g of toluene were placed in a 500 m14 Tulo flask and stirred at room temperature for ihr to obtain a transparent coating composition (A).
) was created.

On the other hand, an injection square plate (thickness 3 mm) made from polypropylene (manufactured by Mitsui Petrochemical Industries KK, trade name Mitsui Petrochemical Polypro 5J-313) was exposed to the vapor of 1.1.1-)lychloroethane for 1 minute, and then at room temperature. After drying for 1 minute at . After drying at room temperature for 5 minutes, heat drying was performed at 80° C. for 50 minutes.The polypropylene square plate treated with the brimer was then immersed in the coating composition CA) for 30 seconds and slowly pulled up. Afterwards at room temperature 1
Drying was then carried out at 60° C. for 5 minutes. This test piece was irradiated with ultraviolet rays for 30 seconds at a distance of 15 degrees under a 1.5 KW high-pressure mercury lamp (120 W/l) to harden the outer coating layer.

Table 1 shows the performance of this coating.

Examples 2-5 In Example 1, coating composition C described in Example 1
Instead of using A), a coating composition (A) was prepared using a polyacrylate of a polyepoxy compound, a polyacrylate of an alkane polyol, a polymerization initiator, and a solvent listed in Table 1 in the amounts listed in Table 1. ) A test piece having a surface coated with polypropylene was prepared in the same manner as in Example 1, except that the polypropylene surface was coated with the same method as in Example 1. The results are shown in Table 1.

Examples 6 to 9, Comparative Examples 1 to 2 Polyacrylates of polyepoxy compounds listed in Table 1, polyacrylates of alkane polyols, polymerization initiators, and 1,1.1-trichloroethane were measured using the measurements listed in Table 1. and stirred to this mixture, the average particle size was 20.
Finely powdered silica (manufactured by Nippon Aerosil KK, trade name 1 (-972)) having a refractive index of 1645 was gradually added (the amount used is shown in Table 1), and the mixture was thoroughly stirred until uniform dispersion was obtained. Thereafter, the mixture was transferred to an attritor (manufactured by Mitsui Miike Seisakusho) filled with Sudeatite balls, and mixed for 3 hours by rotating the agitator at 15 Orpm while cooling the tank with water. - after adding butanol and mixing for a further 10 minutes,
Remove the mixture from the attritor and add the coating composition (A
, ). In Example 1, instead of using the coating composition [A] described in Example 1, the coating composition (A) described above was used.
) A test piece having a polypropylene surface coated thereon was prepared by the method described in Example 1, except that the method described in Example 1 was used. The results are shown in Table 1.

Comparative Example 5 Table 1 shows the performance of single polypropylene (manufactured by Mitsui Petrochemical Industries KK, 5J-513) that was not coated with the coating composition of the present invention.

The abbreviations used in Table 1 below indicate the respective compounds.

EC) A... Diacrylate of ethylene glycol diglycidyl ether PC) GA... Diacrylate of propylene glycol diglycidyl ether GOA... Triacrylate of glycerin triglycidyl ether TGA... Tri Triacrylate of methylolpropane triglycidyl ether N1) A: Neopentyl glycol diacrylate BDA: 1,4-butanediol diacrylate HD A: 1,6-hexanediol diacrylate TTA ... Trimethylolpropane triacrylate PETA ... Pentaerythritol tetraacrylate B I E ... Benzoin isopropyl ether BPH ... Benzophenone II ■ 1) ... 1-(4-1 Sobropylf) enil)
-2-hydroxy-2-methyl-1-propanone / / Example 10 Poly-4-methyl-1-pentene (Mitsui Petrochemical Industries K
A 3 mm thick injection molded sheet of TPX MXOO4) manufactured by K.K. was mixed with 15 g of maleic anhydride-modified EPR (containing maleic anhydride, ffi + 7.7 wt%) in a 1.1.1-) dichlorethane solution with a concentration of 15. was immersed in water for 10 seconds to perform primer treatment. After being left at room temperature for 5 minutes, the coating composition described in Example 8 was immersed in Al for 10 seconds. After drying at room temperature for 1 minute and at 60°C for 5 minutes, photopolymerization was performed using the method described in Example 8. A test piece was prepared by coating the surface of poly-4-methyl-1-pentene.The results are shown in Table 2.

Example 11.12 In Example 10, instead of using poly-4-methyl-1-pentene as the base polymer, a 3 mm thick polymer sheet listed in Table 2 was used, and the pretreatment listed in Table 2 was applied. A test piece having a polymer surface coated thereon was prepared by the method described in Example 10, except for the above steps. The results are shown in Table 2.

Comparative Examples 4 to 6 Poly-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries KK, TPX+) not coated with the coating composition of the present invention
, 1XOO4), polycarbonate (manufactured by Daikasei KK,
Panlight L 1250. ) and polymethyl methacrylate (Acrylite L, manufactured by Mitsubishi Rayon KK) are shown in Table 2.

Example 13, Comparative Example 7 In Example 1, the coating composition described in Example 1 (
A) was replaced with the coating composition (A) described in Example 8, and instead of using polypropylene as the molded body base, a 2 mm thick saturated polyester resin (manufactured by Showa Kobunshi KK, Rivolac MC5- A test piece whose surface was coated with an unsaturated polyester resin was prepared by the method described in Example 1 except that 302) was used. The film thickness of this test piece was 9 Its, the surface gloss was 80, the adhesion was I Do/I DO, and the pencil hardness was 4H (Example 13).

On the other hand, the unsaturated polyester resin not coated with the coating composition of the present invention had a surface gloss of 66 and a pencil hardness of 6H (Comparative Example 7).

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi -45--469- 44-

Claims (2)

[Claims] (1) (a) A poly(meth)acrylate of an aliphatic polyepoxy compound having at least two or more epoxy groups in one molecule, (b) A poly(meth)acrylate of the polyepoxy compound ( a) More than 0 to 1 per 100 parts by weight
000 parts by weight of a poly(meth)acrylate of an alkane polyol having 2 to 12 carbon atoms, and (C) a poly(meth)acrylate of the polyepoxy compound (a) and a poly(meth)acrylate of the alkane polyol.
A curable resin composition for coating, comprising: a polymerization initiator in a range of 0.01 to 20 parts by weight based on a total of 100 parts by weight of meth)acrylate (b). (2) 0.00% based on a total of 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (a) and the poly(meth)acrylate of the alkane polyol (b).
The curable resin composition for coating according to claim 1, which contains a finely powdered inorganic filler in a range of 5 to 200 parts by weight.