JPS5989332A - Curable resin composition for coating - Google Patents

Abstract

PURPOSE:To provide the titled composition having collectively excellent curing characteristics and coating film characteristics, and containing a urethane poly (meth)acrylate, a specific amount of polyhydroxyalkanepolyol poly(meth)acrylate and a specific amount of a polymerization initiator. CONSTITUTION:The objective curable resin composition for coating use can be prepared by compounding (A) a urethane poly(meth)acrylate compound having >=2 (meth)acryloyloxy groups in the molecule with (B) 0-10,000pts.wt., based on 100pts.wt. of the component (A), of a polyhydroxyalkanepolyol poly(meth)acrylate having one or more ether bonds and >=3 hydroxyl groups in the molecule (e.g. diglycerol triacrylate) and (C) 0.01-20pts.wt., based on 100pts.wt. of A+B, of a polymerization initiator (e.g. benzoin), and if necessary, adding various additives to the composition.

Description

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

In general, resin molded products 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. It has the following advantages and is widely used in place of these materials in automobiles, motorcycles, household appliances, daily necessities, and many other fields.

However, these resin molded substrates have a lower surface hardness than metals, glass, etc., and are weak against scratches and friction, so they have the disadvantage of being easily scratched on the surface.For example,
The use of these molded bodies is severely limited due to defects in their surface properties, such as susceptibility to surface damage due to contact, collision, scratching, etc. during installation or transportation of the parts of the molded body, or during use of the product. ing.

Many proposals have been made as methods for improving the above-mentioned defects of the surface of the resin molded body substrate.

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 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 resin molded body base layer in order to improve these defects. For example, surface treatments using corona discharge, surface treatments using brimer, etc. 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. Also,
Among the film-forming elements mentioned above, silicone-based film-forming elements have the drawback 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. Various types of compounds are used as film-forming elements, for example, poly(meth)acrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, poly(meth)acrylates of aromatic (phenolic) polyhydroxyl compounds, etc. 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 product, these films will not be affected during curing. Poor curing properties such as curing speed in air, surface hardness, scratch resistance,
It is often inferior in any or many of the physical properties of the coating, such as abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate, and is not suitable for industrial use. It was not possible to fully satisfy the requirements for scale utilization. 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, there were other new difficulties when coating the substrate surface of a resin molded article such as polyolefin.

The present inventors have developed a coating composition that exhibits excellent curing properties during curing and excellent coating properties when coated on the surface of a resin molded body such as a thermoplastic resin or thermosetting resin. As a result of extensive research, we found that the product contains urethane poly(meth)acrylate (a), a specific amount of poly(meth)acrylate of polyoxyalkane polyol (b), and a specific amount of polymerization initiator (C). It has been discovered that the above object can be achieved by using a composition, 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 resin molded body substrate to form an outer coating layer, it has excellent curing properties such as curing speed in air during curing, Many coating properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate are comprehensively evaluated. It has excellent characteristics.

To summarize the present invention, the present invention provides (a) a urethane-based poly(meth)acrylate having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule; (b) the urethane-based poly(methane acrylate ( a
) A polyoxyalkane polyol tane acrylate having at least one ether bond and three or more hydroxyl groups in one molecule, in a range of more than 0 to 1000 parts by weight per 100 parts by weight; and (Q) a polymerization initiator in the range of 0.01 to 20 parts by weight based on a total of 100 parts by weight of the urethane-based poly(methane acrylate compound (a) and the poly(meth)acrylate (b) of the polyoxyfurcane polyol). A curable resin composition for resin coating, comprising:
The main points are as follows.

The urethane-based poly(meth)acrylate compound (a) which can be incorporated into the curable resin composition for coating of the present invention has one or more urethane bonds in one molecule and two or more acroyloxyl groups, or It is a (meth)acrylate-based polyfunctional compound having a methacryloyloxyl group.

Specifically, a urethane-based poly(meth)acrylate compound having a hydroxyl group (obtained by the reaction of a methacrylic acid ester and a diisocyanate compound,
Examples include urethane-based poly(meth)acrylate compounds made of poly(meth)acrylate of polyurethane polyol, urethane-based poly(meth)acrylate compounds made of poly(meth)acrylate of polyester-based polyurethane polyol, and the like. The polyol component units constituting these urethane-based poly(meth)acrylate compounds include aliphatic polyols, alicyclic polyols, aromatic polyols, polyoxyalkylene glycols, polyoxyalkane polyols, arylene bis[polyoxyalkane] Examples include polyol, polyester polyol, polyurethane polyol, polyurea polyol, polyester polyurethane polyol, and more specifically, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, glycerin, and Methylolpropane, pentaerythritol,
Diethylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol, diethylene glycol, diglycerin, ditrimethylolpropane, dipentaerythritono/, polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol recall, cyclohexylene glycol,
2.2-bis(4-hydroxycyclohexyl)propane, bis(4-hydroxycyclohexyl)methane, 2
, 2-bis(4-hydroxyphenyl)propane, 2,
2-bis(4-hydroxyphenyl)ethane, bis(4
- methane acrylate of polyglycidyl ether of bis(qryloyloxyethyl)methane, bis(qryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl) polyhydric alcohol; the various polyhydric alcohol component units and succinic acid; Glutaric acid, adipic acid, speric acid, sebacic acid, maleic acid,
fumaric acid, itaconic acid, tetrahydrophthalic anhydride,
hexahydrophthalic anhydride, phthalic acid, phthalic anhydride,
Polyvalent carbone M such as trimellitic acid and pyromellitic acid
Polyester polyols formed from component units; and pyriurethane polyols formed from the various polyol component units described above and various diisocyanate component units described later. In addition, the diisocyanate component units constituting these urethane-based poly(meth)acrylate compounds may be any of aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Of course, dinitrile biscarbonate compounds corresponding to these diisocyanate component units or biscarbacyanate component units corresponding to these diisocyanate component units include trimethylene diisocyanate, tetra methylene diisocyanate, hexamethylene diisocyanate,
Octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, methylcyclohexane-2,4-diisocyanate, 3-incyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4.4 Examples include -dicyclohexylmethane diisocyanate, isopropylidene bis(4-cyclohexyl isocyanate), phenylene diisocyanate, 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 or By reacting with methacrylic acid, poly(meth)acrylate of polyester-based polyurethane polyol is obtained.

Among the urethane-based poly(meth)acrylate compounds, urethane-based poly(meth)acrylate compounds obtained by the reaction of a (meth)acrylic acid ester having a hydroxyl group with a diisocyanate compound have hydroxyl groups ( Polyhydroxyl group-containing compound and (meth)acrylic acid ester component unit
Examples include reactants with acrylic acid, reactants with epoxy compounds and (meth)acrylic acid, and specific examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and methacrylate. 2-hydroxypropyl acid, acrylate of glycidyl acrylate, methacrylate of glycidyl acrylate, acrylate of glycidyl methacrylate, methacrylate of glycidyl methacrylate, glycerin monoacrylate, glycerin monomethacrylate, glycerin-1
゜6-diacrylate, glycerin-1,3-dimethacrylate, trimethylolpropanol, noacrylate-4
,) IJ Methylolpropane monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol monoacrylate , dipentaerythritol monomethacrylate,
Dipentaerythritol diacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)-droxyethyl isocyanurate, diacrylate of propylene glycol diglycidyl ether, dimethacrylate of glycerin-1,6-sibricidyl ether, glycerin triglycidyl Triacrylate of ether, trimethacrylate of glycerin triglycidyl ether, diacrylate of pentaerythritol diglycidyl ether, dimethacrylate of pentaerythritol diglycidyl ether, triacrylate of pentaerythritol triglycidyl ether, pentaerythritol triglycidyl ether Trimethacrylate of 2.2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, 2.2-bis(4-hydroxycyclohexyl)propane diglycidyl ether of dimethacrylate, 2.2 - Diacrylate of his(4-hydroxyphenyl)propane diglycidyl ether, 2.2
Examples include dimethacrylates of -bis(4-hydroxyphenyl)propane diglycidyl ether, and examples of the diisocyanate component units include the compounds listed above. Among the urethane-based poly(methacrylate compounds (a)), urethane-based poly(methacrylates) containing an aliphatic alkylene diisocyanate component unit and an alicyclic diisocyanate component unit as the diisocyanate component unit are used. It is preferable to use a compound because it improves the hue, weather resistance, flexibility, etc. of the cured film.

The poly(meth)acrylate of polyoxyalkane polyol (b) blended into the curable resin composition for coating of the present invention has one or more ether bonds and 5 or more hydroxyl bonds in one molecule. It is a poly(meth)acrylate of a polyoxyalkane polyol having three or more acryloyloxyl or methacryloyloxyl groups in one molecule, and may also contain a hydroxyl group in some cases. can not use. The polyoxyalkane polyol constituting the poly(meth)acrylate of the polyoxyalkane polyol has one or more ether bonds and has three or more hydroxyl groups, and has three or more hydroxyl groups. At least one molecule of an alkane polyol and at least one molecule of an alkane polyol having two or more hydroxyl groups
The molecules are condensed and have at least one ether bond.

Specific examples of the polyoxyalkane polyol include diglycerin, triglycerin, tetraglycerin, ditrimethylolethane, tritrimethylolethane, tetratrimethylolethane, ditrimethylolpropane, tritrimethylolpropane, tetratrimethylolpropane 1 dipentaerythritol. , tripentaerythritol, and the like. The poly(methacrylate) of the polyoxyalkane polyol usually has 1 to 6, preferably 1 to 2 ether bonds in one molecule, and has 6 to 10, preferably acryloyloxyl or methacryloyloxyl groups. The molecular weight is usually in the range of 260 to 3,000, preferably 260 to 1,000.Specifically, the photo(meth)acrylate of the polyoxyalkane polyol includes diglycerol triacrylate, Diglycerol trimethacrylate, diglycerol tetraacrylate, diglycerol tetramethacrylate, ditrimethylolethane triacrylate, ditrimethylolethane trimethacrylate, ditrimethylolethane tetraacrylate, ditrimethylolethane tetramethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane trimethacrylate , ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, tritrimethylolpropane triacrylate, tritrimethylolpropane pentaacrylate, dipentaerythritol triacrylate, dipentaerythri, tol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, di Examples include pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the poly(meth)acrylate of the polyoxyalkane polyol is a mixture of two or more types. The blending ratio of the poly(meth)acrylate compound (b) of the polyoxyalkane polyol is the same as that of the urethane-based poly(meth)acrylate compound (a).
It is necessary that the amount is in the range of more than 0 and 1000 parts by weight, more preferably in the range of 5 to 700 parts by weight, and particularly preferably in the range of 2a to 50 parts by weight.
Preferably, the amount is in the range of 0 parts by weight. The poly(meth)acrylate of the polyoxyalkane polyol (b
) of the urethane-based poly(meth)acrylate compound 'f
h (a) i The blending ratio is 100 parts by weight
When the amount exceeds 0 parts by weight, the flexibility of the coating obtained from the composition decreases, causing problems such as cranking of the coating.

The film forming element component (polymerizable monomer component) blended into the curable resin composition for coating of the present invention may consist of only the above-mentioned two essential components, but may further include other polymerizable monomer components. In addition, copolymerization is also possible. Other polymerizable monomer components include by-products or intermediates during the production of the urethane-based poly(meth)acrylate compound or the poly(methanoacrylate) of the polyoxyalkane polyol, such as urethane-based mono(meth)
In addition to acrylates, mono(methanoacrylates) of polyoxyalkane polyols, di(meth)acrylates of polyoxyalkane polyols, (meth)acrylic acid, methyl (meth)acrylate, (ethyl methacrylate, (methane) Examples include (meth)acrylic acid esters such as 2-hydroxyethyl acrylate.

In order to apply the curable resin composition for coating of the present invention to the surface of a substrate of a molded body and crosslink and cure the composition to form a film, it is necessary to blend a polymerization initiator (C) into this composition. is necessary. 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 includes benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isofuroyl ether, and benzoin isobutyl ether. or its ether, benzophenone,
Benzophenone compounds such as p-chlorobenzophenone and p-methoxybenzophenone, benzyl compounds such as hensyl, benzyl dimethyl ketal, and benzyl diethyl ketal, 1-(4-isopropylphenyl)-
2-Hydroxy-2-methyl-1-propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-tart-butylphenyl)-2-hydroxy-2-methyl-1-propanone Examples include hydroxyalkylphenes such as; and ketone compounds. 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 thermosetting proceed simultaneously.
It is also possible to adopt a method of proceeding with heat curing after proceeding with ultraviolet curing. 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 o, based on a total of 100 parts by weight of the urethane-based poly(meth)acrylate (a) and the poly(meth)acrylate of polyoxyalkane polyol (b). It is necessary that the amount of the polymerization initiator is in the range of 0 to 20 parts by weight, and more preferably in the range of 0.1 to 10 parts by weight. Compound (a) and poly(meth)acrylate of the polyoxyalkane polyol (b)
) If the amount is less than 1.01 parts by weight based on 100 parts by weight in total, the polymerizability of the composition will decrease and a hard coating will not be obtained, and if it is more than 20 parts by weight, the coating obtained from the composition will decrease. 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 if necessary, it may further include a polymerization inhibitor, a transparent filler, a pigment, a dye, a solvent,
Various additives such as UV absorbers, stabilizers such as antioxidants, fluorescent brighteners, (reactive) oligomers such as methyl (meth)acrylate, polyester acrylate, and polymers such as polymethyl methacrylate may be blended. I can do it. The blending ratio of these additives is appropriate.

In the curable horse chestnut resin composition for 11M of the present invention, finely powdered inorganic fillers may be blended as necessary within a range that maintains the transparency of the cured film obtained therefrom. The average particle size of the finely powdered inorganic filler is arbitrary as long as it is in the form of a powder, but it is usually in the range of 1 mμ to 10μ, preferably 1.5 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 1.6.
0, preferably in the range of 1.42 to 1.58.

Specifically, such fine powder inorganic fillers include glass powder, mica, glass peas, 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, those in which the surface of these finely powdered inorganic fillers is treated with an alkyl carboxylate, a silane coupler, a titanium coupler, c (12S 1 (c H3) 2, alcohol, etc.) can also be used.
It is also possible to use colloidal silica, methanol silica sol, ethanol silica sol, isopropatol silica sol, etc. in which the inorganic filler is suspended in water or alcohol. Among these finely powdered inorganic fillers, when finely powdered silica is added, the surface hardness of the outer coating layer increases.
It is particularly preferred because the scratch resistance and abrasion resistance are significantly improved and the transparency and surface gloss are not impaired. The blending ratio of these fine powder inorganic fillers is the same as that of the urethane-based poly(meth)acrylate compound (a) and the poly(meth)acrylate of the polyalkane polyol (
Usually 0.5 to 20 parts per 100 parts by weight of b)
0 parts by weight, preferably in the range of 0.5 to 100 parts by weight.

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

The solvent is also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition.

Specific examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, hexane, heptane, octane, petroleum ether, monochloroin, cyclohexane, and methylcyclohexane, methylene chloride, chloroform, tetracyclic carbon, bromoform, Trichloride, bicyclic ethylene, perchlorene, titanium trichloride,
Titanium tetrachloride, propylene dichloride, chlorobenzene, bromobenzenato halogenated hydrocarbons, methanol,
Ethanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, phosphoric acid, ethylene glycol monomethyl ether, diethylene glycol monoalcohol, methyl ethyl ketone,
Methyl isobutyl ketone ether, cyfuropyl ether,
Ethers such as phthyl ethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetonide 1 nor,'
Examples include nitriles such as globionitrile and capronitrile, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate. . The blending ratio of these organic solvents is determined based on the urethane-based poly(meth)acrylate compound (a
) and the poly(meth)acrylate of the polyoxyalkane polyol (b) in a total of 100 parts by weight, the amount is usually 5 to 3,000 parts by weight, preferably 10 to 2,000 parts by weight.

In the composition of the present invention, a composition containing the above-mentioned essential components and various additive components such as an inorganic or organic filler, a solvent, a stabilizer, etc. added as necessary, or a solution composition or a suspension composition. The method for preparing is to prepare the above-mentioned raw material mixture and use 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 tanks. A composition is obtained. Methods for applying the solution composition and suspension composition to the substrate surface of the resin molding include brush coating, spraying,
Conventionally known methods such as a dipping method, a barcode method, a roll-to-tar method, a spin coater method, and a gel coater method can be employed. In addition, methods for drying the coating film include natural drying method, forced drying method using carrier gas,
Examples include heating drying methods using an infrared oven, a far-infrared oven, and a 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, the photocuring method usually has a temperature of -10 to 1
The light irradiation is carried out at a temperature of 50°C, preferably 5 to 130°C, and the duration is usually 1 sec to 1 hr%.
Preferably it is 1 sec to ICIn1n. In addition, in the thermosetting method, the temperature during curing is usually -10 to 15
0°C, preferably 5 to 130'C, and the time required for curing is usually 0.05 to 10 hr%, preferably 0.
．． 1 to 8 hours.

The curable resin composition for coating of the present invention can be coated on the substrate surface of any molded article made of a thermoplastic resin or a thermosetting resin. 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 ester resin, polycarbonate resin,
All examples include polyester resin and polyamide resin. Among these thermoplastic resins, the base material that constitutes the laminate molded product! The fat layer is preferably made of polyolefins, polyacrylate resin or polycarbonate resin. Specifically, the polyolefins include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1--\xene, 4-methyl-1-pentene, 1-octene, and 1-decene; - a copolymer consisting of a mixture of two or more 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 metal salts of acrylic acid; Examples include copolymers containing a small amount (for example, 60 mol % or less) of other components such as methyl methacrylate and acrylic carboxylic acid salts such as metal salts of methacrylic acid. can. 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 W FM 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 1o1 nylon 12, and the like.

In addition to the above resins, polyacetal, polystyrene,
Acrylonitrile/styrene copolymer, acronitrile/butadiene/styrene copolymer, polysulfone resin,
Examples include polyphenylene oxide, modified polyphenylene oxide, polyphenylene sulfide resin, and polyether sulfone 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.

When coating the base surface of a resin molded body with the curable resin composition for coating of the present invention, the base surface of the molded body may be washed with various solvents, alkaline aqueous solution, surfactant, or ultraviolet. Perform various surface treatments such as sonic cleaning, electrolytic cleaning, blasting, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, and chemical conversion treatment. be able to.

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. Usually used. In this way, the composition of the present invention is coated on the surface of the base layer of the horse chestnut 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 resin 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, clock glasses,
Various lenses such as glasses, cameras, and camera lenses,
Optical prisms, blood bags, coffee maker shower domes and coffee containers, water tanks, illuminator covers,
Covers for stereo equipment such as players, dials and covers for various meters, covers for headlamps and tail lamps in automobiles, level sensors, various films such as glass shatter prevention films and release films, insulating films, agricultural films, and lights. Playable video discs, viewing windows for various equipment such as clothes dryers, electric washing machines, dryers, oil tanks, windshields for motorcycles, jeeps, motorboats, etc., automobile glass (windshields, rear windows, opera windows, triangular windows) , sunroofs, window glass for greenhouses, houses, aquariums, etc., appliances, mirrors, various containers for pre-showers and cosmetics, relay cases, fuse boxes, side covers and mudguards for motorcycles, fenders, etc.
, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulating films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative boards, shelves, wall sheets, wallpaper, furniture, light needles Wallboards, tableware, chairs, bathtubs, toilet bowls, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, taritos, curtain rods, rain gutters, insulation materials,
Waterproof coating materials, curtains, frames, automobile foil, various containers, automobile interior materials, vanity tables, flower boxes, particle boards, roof tiles, shutters, shutters, waterproof pans, pipes,
Wiring materials, gear cams, knobs, solenoid valve frames, fans, instrument panels, bumpers L, brakes, etc. 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.

(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 60 degree specular gloss in JIS K 5400-1979.

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

(4) Adhesion The test was conducted according to the cross-cut test in JIS x 5400-1979. The judgment is based on how many of the 100 gobans were glued together.

(5) Sandfall abrasion 80 according to the method of JIS T 814'7-1975
0 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 According to the method of ASTM D-1044, wear ring C8-
10. Rotate the coating 1000 times with a load of 500 g.

Wear resistance can be measured 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 and a diameter of 2 mm.
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 the tr 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 set aging tester at 80° C. for 400 hours and 4 hours, the appearance and adhesion of the outer coating layer were evaluated.

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

(12) Gasoline resistance test pieces were immersed in regular gasoline at N2 temperature for 24 hours, and then the appearance and adhesion of the outer coating layer was evaluated.

(13) The 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 at a low temperature of -30°C for 2 hours, and then heated to 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/Weather Resistance Test pieces were held in a sunshine weatherometer for 400 hours to evaluate the appearance and adhesion of the outer coating layer.

In addition, the following reference example shows a synthesis example of urethane-based polyacrylate.

Reference Example 1 Diacrylate of propylene glycol diglycidyl ether (manufactured by Kyoeisha Yushi Kagaku KK, trade name epoxy ester 70PA>100g (0.3 mol2 to 500 rJ
20 g (0.121 vol) of xamethylene diisocyanate was added to a 4-tube flask under a nitrogen atmosphere, and stirred at room temperature for 15 hours to form a diacrylate of propylene glycol diglycidyl ether, which consists of hexamethylene diisocyanate component unit. Urethane-based polyacrylate) (PGAHI, 1) was prepared.

Reference example 2 Dipentaerythritol pentaacrylate 50g (0
, 095 mol), 30 g (0,064 mol) of dipentaerythritol tetraacrylate) and 20 g of dipentaerythritol hexaacrylate, and 120 g of methyl isobutyl ketone were charged into a 50 [] m (14 mm) flask and heated under a nitrogen atmosphere. -Icyanatomethyl-3.5.5-Trimethylcyclohexyl isocyanate (17.6 g (0.0e, mol)) was added and stirred at room temperature for 15 hours to form dipentaerythritol polyacrylate component units and 6-indianatomethyl Lou 3.5.
5-) Urethane polyacrylate (DPAIP) consisting of remethylcyclohexyl isocyanate component units
A methyl isobutyl ketone solution was synthesized.

Reference Example 6 74 g (0.2 M) of bis(acryloyloxyethyl) hydroxyethyl isocyanurate and 100 g of methyl isobutyl ketone were placed in a 500 m 14 tube flask, and 3-isocyanatomethyl-3 was added under a nitrogen atmosphere.
,5,5-)limethylcyclohegysyl isocyaner)2
2g (0.1M) was added and stirred at room temperature for 15 hours to form bis(acryloyloxyethyl)hydroxyethyl isocyanurate component unit and 6-isocyanatomethyl-3.
．． 5. Urethane polyacrylate (BAII) consisting of 5-trimethylcyclohexyl isocyanate component units
A methyl isobutyl ketone solution of P) was synthesized.

Example 1 Urethane polyacrylate (pGA
HI) 70E, 30 g of dipentaerythritol hexaacrylate, 5 g of benzoin isopropyl ether, and 120 g of methyl isobutyl ketone were placed in a 500 ml 1!4 tube flask and stirred at room temperature for 1 hour to prepare a transparent coating composition [A].

On the other hand, an injection square plate (thickness 3 mm) made from polypropylene (manufactured by Mitsui Petrochemical Industries KW, trade name Mitsui Petrochemical Polypro 5J-313) was exposed to vapor of 1.1.1-) IJ chloroethane for 1 minute, and then After drying for 1 minute at room temperature, maleic anhydride modified PER (propylene content 67
The injection square plate was immersed for 20 seconds in a 15 g/n toluene solution [B] of mol%, maleic anhydride content 6 wt%) and slowly pulled up. After drying at room temperature for 5 minutes, 80'C
Heat drying was performed for 30 minutes. Next, the primer-treated polypropylene square plate was immersed in the coating composition (A) for 60 seconds, slowly pulled up, and then soaked at room temperature for 1 hour.
Drying was then carried out at 60°C for 5 minutes. This test piece was heated under a 1.5KW high-pressure mercury lamp (120W/an) for 15 minutes.
The outer coating layer was cured by irradiating it with ultraviolet light for 30 seconds at the same distance.

Table 1 shows the performance of this coating.

Example 2 In Example 1, the coating composition described in Example 1 (
Instead of using A), 141.4 gs of the urethane polyacrylate (DPAIA) solution described in Reference Example 2 was used.
Diglycerin tetraacrylate 30g.

After using a coating composition consisting of 5 g of benzoin isopropyl ether and 48.6 g of methyl isobutyl ketone, 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 6 In Example 2G, the urethane-based polyacrylate (BAIIP) solution described in Reference Example B was used instead of the urethane-based polyacrylate solution described in Reference Example 2. A test piece whose surface was coated with polypropylene was prepared using the method described above. The results are shown in Table 1.

Examples 4-6 In Example 1, the coating composition described in Example 1 (
Instead of using A), a coating composition prepared using urethane poly(meth)acrylate, polyoxyalkane polyol polyacrylate, polymerization initiator, and solvent in the amounts listed in Table 1 was used. A test piece having a surface coated with polypropylene was prepared in the same manner as in Example 1, except that the test piece was coated with polypropylene. The results are shown in Table 1.

Examples 7-8 Urethane poly(methanoacrylate,
The polyacrylate of the polyoxyalkane polyol, the polymerization initiator, and 1.1.1-trichloroethane were weighed out in the amounts listed in Table 1, and the mixture was added with stirring to a fine powder with an average particle size of 20 mμ and a refractive index of 1.45. Powdered silica (manufactured by Nippon Aerosil KK, trade name R-972) was gradually added (amounts used are listed in Table 1) and stirred thoroughly until uniform dispersion was obtained. The mixture was transferred to a tank (manufactured by Miike Seisakusho), and the agitator was rotated at 150 rpm while the tank was cooled with water, and mixed for 6 hours. Thereafter, the amount of n-butanol listed in Table 1 was added, and the mixture was further mixed for 10 minutes. rear,
Take out the mixture from the attritor and add the 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 Uretayu/based polyacrylates listed in Table 1, polyacrylates of polyoxyalkane polyols, polymerization initiators, and solvents listed in Table 1 were weighed out in the amounts listed in Table 1, and heated under ih at room temperature.
A test piece was prepared by coating the surface of polypropylene by the method described in Example 1, except that the film composition [A] prepared by stirring and mixing was used. The results are shown in Table 1.

Comparative Example 6 Table 1 shows the performance of single polypropylene (manufactured by Mitsui Petrochemical Industries KK, 5J-316) not coated with the coating composition of the present invention.

The abbreviations used in Table 1 below represent the following compounds, respectively.

(1) DPTA/Rydipentaerythritol tetraacrylate (2) D P P A... Dipentaerythritol pentaacrylate (3) D P HA... Dipentaerythritol hexaacrylate (4) DGTA... Diglycerin tetra Acrylate (5) BIB...Benzoin isopropyl ether (6) HPH...Benzophenone (7) IHP...1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-pronog Non-O -0 Example 9 Poly-4-methyl-1-pentene (Mitsui Petrochemical Industries K
A 3 mm thick injection-molded sheet of TPX MXOO4 manufactured by K. K., was treated with i, i,
Brimer treatment was performed by immersing it in an i-trichloroethane solution for 10 seconds. After being left at room temperature for 5 minutes, it was immersed in the coating composition described in Example 8 for 10 seconds.

After drying at room temperature for 1 minute and at 60"C for 5 minutes, photopolymerization was performed as described in Example 8 to obtain poly-4-methyl-1-
A test piece was prepared by coating the surface of pentene.

The results are shown in Table 2.

Examples 10-11 In Example 9, instead of using poly-4-methyl-1-pentene as the base polymer, the thickness 5 listed in Table 2 was used.
A test piece was prepared by using a polymer sheet having a thickness of mm and coating the surface of the polymer by the method described in Example 9, except that the pretreatment described in Table 2 was performed.

The results are shown in Table 2.

Comparative Examples 4 to 6 Poly-4-methyl-1-pentene (manufactured by Mitsui Seki M Chemical Industry KK, TPX) not coated with the coating composition of the present invention
Mχ004, polycarbonate (manufactured by Ondai Kasei KK, Panlite L-1250), polymethyl methacrylate (
Table 2 shows the performance of KiL Acrylite L) on Mitsubishi Rayon.
Shown below.

Example 12, Comparative Example 7 In Example 1, coating composition C described in Example 1
A) instead of using the coating composition described in Example 8 (Al) and instead of using polypropylene as the molded body substrate, a 2 mm thick unsaturated polyester resin (
A test piece having a surface coated with unsaturated polyester resin was prepared by the method described in Example 1, except that a slide rack IJLcs-12) manufactured by Showa Kobunshi KK was used. The film thickness of this test piece is 8μ, the surface gloss is 85, and the adhesion is 100.
/100, and the pencil hardness was 4H (Example 12). 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 3H (Comparative Example 7).

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (2)

[Claims] (1) (a) A urethane-based poly(meth)acrylate compound having two or more acryloylreo-thousyl groups or methacryloyloxyl groups in one molecule, (b) The urethane-based poly(methacrylate compound (a) 100 weight polyoxyalkane polyol having at least one ether bond and three or more hydroxyl groups in the range of more than 0 to 1000 parts by weight, and (C) 0.01 to 20 parts by weight based on a total of 100 parts by weight of the urethane-based poly(meth)acrylate compound (a) and the poly(meth)acrylate) compound of the polyoxyalkane polyol (b). A curable composition for resin coating, comprising a polymerization initiator within the range of the following. (2) Urethane poly(meth)acrylate compound (a) and poly(meth)acrylate compound of the polyoxyalkane polyol
The curing type for coating according to claim (1), which contains a finely powdered inorganic filler in a range of 0.5 to 200 parts by weight based on a total of 100 parts by weight of the meth)acrylate (b). Resin composition.