JPS5936113A - Curable resin composition for coating - Google Patents

Abstract

PURPOSE:To provide titled composition of excellent curability, capable of giving coating film of high hardness, wear and heat resistance, and adhesivity, comprising a poly(acryloyloxyalkyl) isocyanurate, polyacrylate-modified polyepoxy compound, and polymerization initiator. CONSTITUTION:The objective composition comprising (A) a [(meth)acryloyloxyalkyl](iso)cyanurate of formula I [X<1>, X<2>, and X<3> are each (meth)acryloyl, H, or alkyl, among them, at least two being (meth)acryloyl; R<1>, R<2> and R<3> are each oxyalkylene, or polyoxyalkylene] or II, (B) 0-1,000pts.wt. per 100pts.wt. of the component (A) of a poly(meth)acrylate-modified polyepoxy compound having at least two epoxy groups in one molecule, and (C) 0.01-20pts.wt. per 100pts.wt. of the components (A) plus (B), of polymerization initiator.

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 lighter than metal products, glass products, etc., have excellent impact resistance, are cheap, and are easy to mold. It has various advantages and is widely used in place of these materials in automobiles, motorcycles, household appliances, daily necessities, and many other fields.

However, the surface hardness of these resin molded substrates is lower than that of metals, glass, etc., and they 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 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 molded body parts, 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 thread monomers, compositions of these components and 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 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 base layer of the resin molded product is generally not good. The disadvantage is that the coating layer is easily peeled off.

Furthermore, methods are known in which various treatments are applied to the surface of the resin molded body base layer in order to improve these defects. For example, surface treatment using corona discharge, surface treatment 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 for practical use. 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. Different types of compounds are used as film-forming elements, for example, poly(meth)acrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, poly(metallaacrylates of aromatic (phenolic) polyhydroxyl compounds). Even if these polyfunctional acrylic carboxylic acid ester derivatives are used alone as film-forming elements to form a film on the base surface of a resin molded product, these films will not be cured during curing. curing properties such as curing speed in air, surface hardness, scratch resistance,
Coating properties such as abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to substrates are often inferior to many of these physical properties, making them difficult to use industrially. It was not possible to fully satisfy the requirements for scale utilization. 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 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 onto the surface of a resin molded body such as a thermoplastic resin or thermosetting resin. As a result of extensive research, we found that poly[(meth)acryloyloxyalkyl](iso)cyanurate (a)
The inventors have discovered that the above object can be achieved by using a composition containing a specific amount of a poly(meth)acrylate of a polyepoxy compound (b) and a specific amount of a polymerization initiator (C), and have arrived at the present invention. According to the present invention, when the curable resin composition for coating of the present invention is coated on the surface of a resin molded body substrate to form an outer coating layer, it has excellent curing properties such as curing speed in air during curing, The surface hardness of the resulting film,
It is characterized by excellent overall coating properties such as scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. are doing.

To summarize the present invention, the present invention comprises (a) general formula (1) (
) () [In the formula, X, Indicates an alkylene group or a polyoxyalkylene group. ] Poly[(meth)acryloyloxyalkyl](isocyanurate, (b) poly[(meth)acryloyloxyalkyl](iso)cyanurate) (a) more than 0 and 1000 parts by weight based on 100 parts by weight a poly(meth)acrylate of a polyepoxy compound having at least two or more epoxy groups in one molecule in the range of parts by weight, and (C) the poly[(meth)acryloyloxyalkynoly(iso)cyanurate ( a) and 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 poly(meth)acrylate (l) of the polyepoxy compound. The gist is a curable resin composition for

The poly[(
meth)acryloylalkyl](iso)cyanurate (
a) is represented by the general formula (1) [where xl, x2 and x3 represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these are (methacryloyl groups), and RSR and R represents an oxyalkylene group or a polyoxyalkyrezo group.
meth)acryloyloxyalkyl coin cyanurate or poly[(meth)acryloyloxyalkyl]cyanurate, tris[(meda)acryloyloxyalkyl](iso)cyanurate, bis[(meth)acryloyloxyalkyl](iso)cyanurate or Although it may be a mixture of these, it is preferable that the main component is tris[(metatholiloyloxyalkyl)isocyanurate.The alkyl group of Xl, x2 and χ3 usually has 1 to 4 carbon atoms. R1, R2 and R3 each have 1 carbon atom.
to 12, preferably 2 to 4, or a multimer of the oxyalkylene group, usually a dimer to a dodecamer, preferably a dimer to a tetramer. Specifically, the poly[(meth)acryloyloxyalkyl]isocyanurate includes tris(acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, and tris(2-acryloyloxypropyl).
Incyanurate, tris(2-methacryloyloxypropyl)incyanurate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(
(methacryloyloxyethyl)methoxyethyl isocyanurate, bis(2-acryloyloxypropyl)-
Examples include 2-ethoxypropyl isocyanurate, bis(2-methacryloyloxypropyl)-2-hydroxypropyl isocyanurate, tris[acryloyldi(oxyethylene)]isocyanurate, tris[methacryloyldi(oxyethylene)]in cyanurate, etc. It is also possible to use a mixture of two or more of these. Further, the poly[(methaneacryloyloxyalkyl) specifically includes 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-methacryloyloxypropyl)-2-hydroxypropyl cyanurate, Tris[acryloyldi(oxyethylene)]cyanurate, Tris[methacryloyldi(oxyethylene)] Examples include ethylene)] cyanurate, and mixtures of two or more of these may also be used.

The poly(meth)acrylate compound (a) of a polyepoxy compound blended into the curable resin composition for coating of the present invention is:
A poly(meth)acrylate of a polyepoxy compound formed from an aliphatic, alicyclic or aromatic polyepoxy compound having at least two or more epoxy groups in one molecule and acrylic or methacrylic acid. It is. Here, specific examples of polyepoxy compounds having at least two epoxy groups in one molecule include methylene glycol, ethylene glycol, and propylene glycol IJ-3.
-ol, phtylene gelicol, pentylene glycol, hexylene glycol, octyl glycol, decylene gelicol, dodecylene glycol, chrycerin, trimethylolpropane, pentaerythritol, polyoxyethylene glycol, polyoxypropylene glycol, diglycidyl, ditri Polyglycidyl ethers of aliphatic polyols such as methylolpropane, tritrimethylolpropane, dipentaerythritol, tripentaerythritol; 1,2-cyclohexylene glycol, 1,4-cyclohexylene glycol, 2,2-bis(4-hydroxycyclohexyl) ) propane, 1.1
- polyglycidyl ethers of alicyclic polyols such as bis(4-hydroxycyclohexyl)ethane and bis(4-hydroxycyclohexyl)methane; hydroquinone,
Polyglycidyl ethers of polyhydric phenols such as resorcinol, catechol, and phloroglucin, 2,2-bis(
4-hydroxyphenyl]propane, 1,1-bis(4
- Polyglycidyl ethers of aromatic polyols such as polyglycidyl ethers of aromatic polynuclear polyhydric phenols such as -hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, novolac type phenolic resins, and resol type phenolic resins, phthalic acid, Examples include polyglycidyl ethers of aromatic polycarboxylic acids such as isophthalic acid and terephthalic acid. More specifically, the polyepoxy compound includes ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether,
Glycerin triglycidyl ether, glycerin diglycidyl ether, trimethylolpropane tricridyl ether, trimethylolpropane dicrycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol diglycidyl ether, polyoxyethylene glycol diglycidyl ether , polyoxypropylene glycol diglycidyl ether, diglycerin tetraglycidyl ether, diglycerin triglycidyl ether, diglycerin diglycidyl ether, ditrimethylolpropane tetraglycidyl ether, ditrimethylolpropane triglycidyl ether, dimethylolpropane diglycidyl ether, dipenta Erythritol hexaglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol tetraglycidyl ether, dipentaerythritol triglycidyl ether, dipentaerys IJ)
-Aliphatic polyepoxy compounds such as diglycidyl ether, 1,2-cyclohexylene glycol diglycidyl ether, 1,4-cyclohexylene glycol diglycidyl ether, 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether ,Screw(
Alicyclic polyepoxy compounds such as (4-hydroxycyclohexyl)methane diglycidyl ether, hydroquinone diglycidyl ether, resorcin diglycidyl ether, catechol diglycidyl ether, phloroglucin triglycidyl ether, 70-glucin diglycidyl ether, etc.
Zyl ether, 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether, 1,1-bis(4
-Hydroxyphenyl)propane diglycidyl ether, bis(4-hydroxyphenyl)methane diglycidyl ether, phthalic acid glycidyl ether, isophthalic acid glycidyl ether, terephthalic acid glycidyl ether, polyglycidyl ether of novolac type phenolic resin, resol type phenolic resin Examples include aromatic polyepoxy compounds such as polyglucidyl ether, and mixtures of two or more thereof may be used.

The poly(methacrylate compound (b)) of the polyepoxy compound blended into the curable resin composition for coating of the present invention is
It is a poly(methacrylate) 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 and (
(meth)acryloyloxyl groups bonded to adjacent carbon atoms to form a unit represented by the general formula (1) % formula % ([in the formula, R is a hydrogen atom or a methyl group], and this unit is at least 2 inside
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 (b) 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, tertiary amines, tertiary amines, salts thereof, quaternary ammonium compounds, organic acid salt compounds, Lewis acids or their complexes, alkaline earth metal halides or hydroxides, halogen Examples include hydrogen chloride. 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,
Examples include lithium hydroxide, sodium hydroxide, hydrogen chloride, and hydrogen bromide, and mixtures of 21 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 generally 0.6 to 1.5 mol, preferably 0.9 to 1.1 mol, per 1 mol of epoxy groups in the polyepoxy compound. The reaction is usually -10 to 8
It is carried out at a temperature of 0°C. The blending ratio of the poly(meth)acrylate (bJ) of the polyepoxy compound is the poly(methacryloyloxyalkyl)(iso)
It is necessary that O is present in a range of more than 1000 parts by weight per 100 parts by weight of cyanurate (a,), and more preferably in a range of 5 to 500 parts by weight. poly(meth)acrylate) of the polyepoxy compound
When the compounding ratio of compound (b) to 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) is more than 1000 parts by weight, the abrasion resistance, surface hardness, weather resistance, etc. of the coating decrease. I come to do it.

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, co-existence is also possible. Other polymerization components include, for example, by-products or production intermediates during the production of poly[(meth)acryloyloxyalkyl](iso)cyanuride) (a), such as mono[(
meth)acryloyloxyalkyl]bis(hydroxyalkyl)(iso)cyanurate, a by-product or production intermediate during the production of poly(methacrylate compound (b)) of the above-mentioned polyepoxy compound, for example, (meth)acrylate of a monoepoxy compound compounds, mono(meth)acrylates of polyepoxy compounds, and other (meth)acrylates
Examples include (meth)acrylic acid esters such as methyl acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate.

In order to apply the curable resin composition for coating of the present invention to the surface of a base of a resin molded article and crosslink and cure the composition to form a film, a polymerization initiator (c) is blended 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 is benzoin or its like, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Ether, benzophenone compounds such as benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, benzyl compounds such as 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-tθrt-butylphenyl)-2-
Examples include hydroxyalkylphenylketone 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-tθrt-butyl peroxide, and dicumyl peroxide. Examples include peroxides such as hydroxide, cumene hydroperoxide, and the like.

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 to simultaneously proceed with ultraviolet curing and thermal curing. 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 the poly[(meth)acryloyloxyalkyl](iso)
It needs to be in the range of 0.01 to 20 parts by weight, and more preferably 0.1 to 20 parts by weight, based on a total of 100 parts by weight of cyanurate (a) and the poly(meth)acrylate of the polyepoxy compound (b). Preferably, the amount is in the range of 10 parts by weight. The blending ratio of the polymerization initiator is the same as that of the poly[(methanoacryloyloxyalkyl](iso)
When the amount is less than 1 part by weight based on the total of 100 parts of cyanurate (a) and the poly(meth)acrylate of the polyepoxy compound (b), the polymerizability of the composition decreases and a hard film cannot be obtained. 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 may further include a polymerization inhibitor, a transparent filler, a solvent, an ultraviolet absorber,
Various additives such as stabilizers such as antioxidants, fluorescent brighteners, (reactive) oligomers such as methyl-(meth)acrylate, polyurethane acrylate, and 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 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 finely powdered inorganic filler' is arbitrary as long as it is in the form of a powder, but it is usually between 1 mμ and 1 mμ.
0/7. Preferably it is in the range of 1.5m7z to 111m. 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 in the range of 1.42 to 1.58. Specifically, such fine powder inorganic fillers include:
glass powder, mica, glass peas, glass flakes,
Examples include diatomaceous earth, anhydrous silica, hydrated silica, silica stone, silica sand, quartz, kaolinite, montmorillonite, sericite, talc, chlorite, chinastone, and feldspar. In addition, the surface of these finely powdered inorganic fillers may be coated with an alkyl carboxylate, a silane coupler, a titanium coupler, cj? Those surface-treated with 2si (cHρ2, alcohol, etc.) can also be used.Also, colloidal silica, methanol silica sol, ethanol silica sol, isopropanol silica sol, etc. in which the inorganic filler is suspended in water or alcohol can be used. 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. It is particularly preferable because the inorganic filler in the form of fine powder is blended in the proportion of the above-mentioned poly[(
methacryloyloxyalkyl](iso)cyanuride
) (a) and the poly(meth)acrylate (b) of the polyepoxy compound in a total amount of 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, cyclohexane, methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, bromoform, trichlene, ethylene dichloride, perchlorene, Halogens ([
Alcohols such as J hydrogen hydride, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, nitriles such as acetonitrile, propionyl, capronitrile, methyl formate, ethyl formate, methyl acetate, ethyl acetate,
Examples include esters such as propyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate. (Usually 5 to 3000 parts by weight, preferably 1 to 100 parts by weight in total of cyanurate and poly(meth)acrylate of the polyepoxy compound (b))
The range is from 0 to 2,000, with the focus area being 0.

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,
A uniformly dissolved or dispersed composition can be obtained by kneading and mixing operations using a ball mill, an attritor, a whipper, an oak mixer, a dissolver, a homogenizer, a colloid mill, a sand mill, a vibration mill, a mixer mixing tank, or the like. Methods for applying the solution composition and suspension composition onto the substrate surface of the molded article include a brush coating method,
Conventionally known methods such as a spray method, a dipping method, a bar code method, a roll coater method, a spin coater method, and a gel coater method can be employed. Examples of methods for drying the film include natural drying, forced drying using a carrier gas, and heating drying using an infrared oven, far-infrared oven, and hot air oven.

Examples of methods for curing the above-mentioned 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 18θC to 1hr, preferably 1SθC to 1SθC. It is 1Qmin. In addition, in the thermosetting method, the temperature during curing is usually -10 to 150°C, preferably 5 to 1°C.
30°C, and the time required for curing is usually 0.05 to 1 Qhr, 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 a thermoplastic resin or a thermosetting resin, but the thermoplastic resin composition is made of a thermoplastic resin. It is preferable to coat the surface of the base of the molded article. 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 polyolefins such as an α-olefin homopolymer or a copolymer containing α-olefin as a main component;
Examples include polyacrylic acid nysten resin, polycarbonate resin, polyester resin, and 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 are:
Ethylene, propylene, 1-butene, 1-hexene, 4
- Homopolymers of α-olefins such as methyl-1-pentene, 1-octene, and 1-decene, copolymers consisting of a mixture of two or more of the above-mentioned σ-olefins, or the above-mentioned α-olefins.
Acrylic carboxylic acid esters and acrylic carboxylic acid esters that contain olefin as a main component and include lower aliphatic vinyl carboxylates such as vinyl acetate and vinyl propionate, methyl acrylate, metal salts of acrylic acid, methyl methacrylate, and metal salts of methacrylic acid. Small amounts of other ingredients such as salts of carboxylic acids (
For example, a copolymer containing 30 mol% or less) 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 ff1f 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-mentioned resins, polyacetal, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyphenylene oxide 1. Examples include modified polyphenylene oxide, polyphenylene sulfide resin, and polyether sulfone resin.

Specifically, the thermosetting resin constituting the base layer includes:
Examples include unsaturated polyester resin, epoxy resin, diallyl phthalate resin, and polyallyl glycol carbonate resin.

When coating the base surface of a resin molded body with the curable surface for coating and the resin composition of the present invention, the base surface of the molded body is washed with various solvents, aqueous alkaline solutions, and surfactants. , ultrasonic cleaning, electrolytic cleaning, blasting, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment,
Arc discharge treatment, glow discharge treatment, plasma discharge treatment,
Various surface treatments such as chemical conversion treatment can be performed.

Further, when laminating an outer coating layer made of the curable resin composition for coating of the present invention on the substrate surface of the resin molded article, an intermediate adhesive layer made of a primer may be provided between the substrate layer and the outer coating layer. It is also possible to improve the adhesion between both layers by forming a three-layer laminate. When the base resin layer is polyolefin, the primer may be α, β-unsaturated carboxylic acid, its acid anhydride, its ester, etc.
, a modified polyolefin grafted with a β-unsaturated carboxylic acid or a derivative component thereof is usually used. In this manner, the composition of the present invention is coated on the surface of the base layer of the resin molded body, 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 resin laminate 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, various lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, and coffee makers. Covers for shower domes, coffee dispensers, water tanks, lighting devices, covers for stereo equipment such as players, dials and covers for various meters, covers for automobile headlamps and taillights, level sensors, shatterproof films and separation panels for glass. Various films such as molded films, insulation films, agricultural films, optically playable video discs,
Peep windows of various devices such as clothes dryers, electric washing machines, dryers, oil tanks, windshields of motorcycles, jeeps, motorboats, etc., automobile glass (windshields, etc.)
(rear windows, opera windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, tableware, mirrors, various containers such as oil bottles and makeup skin, relay cases, fuse boxes, motorcycle side covers, and mudguards. fences, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulation films, floor tiles, floor sheets, door 1 table boards, wall tiles, countertop decorative boards, shelf boards, wall sheets, wallpapers, furniture, lightweight wallboards,
Tableware, chairs, bathtubs, toilet bowls, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, ducts, curtain rods, rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foil, various containers, automobile interiors Materials, vanity table 1 flower box, particle board, roof tiles, shutters, waterproof pans, pipes, wiring materials, cabam, knobs, solenoid valve frame, fan,
Examples include instrument panels, bumpers, and brakes. In addition to the above, we also offer 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,
It can also be used for nuclear power related parts.

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 for 2w.
After adding t% and thoroughly drying, the transparency is visually checked. 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 K5400-1979.

(3) Light transmittance This was done in accordance with JIS K6714.

(4) Adhesion, conducted according to the cross-cut test in RRS x5400-1979. The judgment is based on how many of the 100 gobans were glued together.

(5) Sandfall abrasion 800g according to the method of JIS K8147-1975
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 is determined by the amount of wear of the coating after the test.The smaller the amount of wear, the better the wear resistance.

(7) Pencil hardness Measured according to JIS x5651.

(8) A strip-shaped test piece with a flexible width of 5 mm and a length of 10 openings was prepared with a diameter of 2c7n.
Fold it along the outer circumference of the cylinder to see if the coating cracks or
It is expressed as the angle at which it peels off from the substrate. The larger the value, the better the flexibility.

(9) Water resistance After immersing the test piece in 40°C pure water for 240 hours,
The appearance and adhesion of the outer coating layer were evaluated.

00 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.

θυ 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.

The appearance and adhesion of the outer coating layer were evaluated after the gasoline resistance test piece of a was immersed in regular gasoline at room temperature for 24 hours.

After keeping the heat cycle resistance test piece in an air oven at 80'C for 2 hours, it was left at room temperature for 1 hour, then kept in a cold room at -30℃ for 2 hours, and then at room temperature for 1 hour. put. This cycle was repeated 10 times, and changes in the appearance of the outer coating layer were visually observed and adhesion was evaluated.

α→ 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 Tris(acryloyloxyethyl)isocyanurate 85g1 diacrylate of propylene glycol diglycidyl ether 15g1 benzoyl isopropyl ether 5g and toluene 110g t-500md4
The mixture was placed in a Tulo flask and pressed for 1 hrffl at room temperature to produce a transparent coating composition (A).

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 IJ chloroethane vapor for 1 minute, and then After drying for 1 minute at room temperature, 15 [/
The injection square plate was immersed in the toluene solution (B) of No. 6 for 20 seconds and slowly pulled up. After drying at room temperature for 5 minutes,
Heat drying was performed at 0°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 6
Drying was performed at 0°C for 5 minutes. This test piece was
The outer coating layer was cured by irradiating ultraviolet rays at 15 distances for 30 seconds under a high-pressure mercury lamp (12 (law/cm)).Table 1 shows the performance of this coating.

Examples 2 to 7 In Example 1, the coating composition described in Example 1 (
Instead of using A), poly[(meth)acryloyloxyalkyl]isocyanurate, polyacrylate of polyepoxy compound, photosensitizer, and solvent listed in Table 1 were used in the amounts listed in Table 1. A test piece having a polypropylene surface coated was prepared in the same manner as in Example 1 except that the coating composition was used. The results are shown in Table 1.

Examples 8-9 Poly[oxyalkyl in acryloino] described in Table 1
The amounts of isocyanurate, polyacrylate of polyepoxy compound, photosensitizer and i,i,1-trichloroethane listed in Table 1 are weighed out, and the mixture is stirred to give an average particle diameter of 20 mμ and a refractive index of 1. .45 of finely powdered silica (Nippon Aerosil KKfi, trade name R-972) was gradually added (the amount used is shown in Table 1) and thoroughly stirred 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 5 hours by rotating an agitator at 150 rpm while cooling the tank with water. Thereafter, the amount of n-butanol listed in Table 1 was added, and an additional 10
After mixing for a minute, remove the mixture from the attritor and
This was designated as coating composition [A]. Example 1 in Example 1
A test piece having a surface coated with polypropylene was prepared by the method described in Example 1, except that the coating composition described in Example 1 was used instead of the coating composition described in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 2 The amounts of poly[acryloyloxyalkyl]incyanerate, polyacrylate of polyepoxy compound, photosensitizer, and solvent listed in Table 1 were weighed out and mixed under stirring at room temperature for 1 hour. A film composition prepared using
A test piece whose surface was coated with polypropylene was prepared by the method described in Example 1 except that A) was used. The results are shown in Table 1.

Comparative JIJ 3 Table 1 shows the performance of single polypropylene (manufactured by Mitsui Petrochemical Industries KK, SJ-316) not coated with the coating composition of the present invention.

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

TAEIC...Tris (acryloyloxyethyl)
Isocyanurate BAEIC... Bis(acryloyloxyethyl) hydroxyethyl isocyanurate TMEIC... Tris(methacryloyloxyethyl) isocyanurate PGGA... Diacrylate of propylene glycol diglycidyl ether GGA... Triacrylate of glycerin triglycidyl ether B CH() A... Diacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether BPGA...P2,2-bis(4-hydroxyphenyl) ) diacrylate of propane diglycidyl ether BIE...benzoin isopropyl ether IHP.
...1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone/Example 10 Poly-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries, product name: TPX MxO04 ) of 3 mm thick injection molded sheet was mixed with 15 g/j? of maleic anhydride-modified EPR (maleic anhydride content near, 7 wt%). Concentration 1.
1. Primer treatment was performed by immersing in a 1-1-lichloroethane solution for 10 seconds. After being left at room temperature for 5 minutes, it was immersed 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 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 carried out. 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
Mχ004), polycarbonate (manufactured by Kijin KK, Pante 4) L-1250), polymethyl methacrylate (
Table 2 shows the performance of Mitsubishi rayon (manufactured by acrylic)
Shown below.

/

Claims (2)

[Claims] (1) (a) General formula (I) 1 (Ia) (Ib) [wherein xl, X2 and X3 represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these It is a (meth)acryloyl group, and R, R and R3 represent an oxyalkylene group or a polyoxyalkylene group. ] represented by poly[
(meth)acryloyloxyalkyl](iso)cyanurate, (b) the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) 100 Jiffl
in a range of 1000 parts by weight exceeding O for t parts;
A poly(meth)acrylate of a polyepoxy compound having at least two or more epoxy groups in one molecule, and (C) the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the polyepoxy compound A total of 1 of the poly(meth)acrylates (b) of
1. A curable resin composition for resin coating, comprising: a polymerization initiator in a range of 0.01 to 20 parts by weight per 0.00 parts by weight. (2) A total of 1 of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the poly(meth)acrylate of the polyepoxy compound (b)
Claim (1) contains a finely powdered inorganic filler in the range of 0.5 to 200 parts by weight per 00 parts by weight.
The curable resin composition for resin coating as described in 2.