JPS5980472A - Curable coating resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a polyepoxy compound poly(meth)acrylate, a specific polyester polyol poly(meth)acrylate, and a polymerization initiator, having excellent curing characteristics and surface hardness of the cured film, etc., and useful for the coating of automobile, etc. CONSTITUTION:The objective composition is prepared by compounding (A) 100pts.wt. of a polyepoxy compound poly(meth)acrylate containing two or more epoxy groups in a molecule with (B) 0-1,000pts.wt. (excluding 0) of a polyester polyol poly(meth)acrylate containing two or more (meth)acryloloxy groups in a molecule and devoid of urethane bond and (C) 0.01-20pts.wt. (based on 100pts. wt. of the sum of the components A and B) of a polymerization initiator. EFFECT:The composition has excellent scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weatherability, and adhesivity to the surface of the molded resin article. USE:Coating of motorbike, domestic appliance, ordinary utensils, etc.

Description

Detailed Description of the Invention The present invention provides excellent whipping properties in the air by coating the base surface of a molded article such as a resin, and improves the surface hardness, scratch resistance, abrasion resistance, flexibility, surface 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., scales are not only lightweight and have excellent impact resistance, but also have various advantages such as being inexpensive and easy to mold.
It is widely used in place of these materials in household electrical 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 extremely difficult due to shortcomings in surface properties such as susceptibility to surface damage due to contact, collision, scratching, etc. during installation or transportation of molded parts, or during use of the product. Limited.

Many proposals have been made as methods for improving the above-mentioned defects on the surface of molded body substrates such as resins. Most of these methods involve coating the surface of these molded bodies with an outer coating layer made of a crosslinked curable resin. Among these film-forming elements, specific examples of resin-forming components include silicone monomers, compositions of these components with various polymers, and methylolmelamine and other curing components. A resin composition consisting of a polyfunctional acrylic carboxylic acid ester derivative, or a composition of this and other polymeric components has 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 and surface treatment using brimer have been proposed. However, even if surface treatment is performed, it is often difficult to completely 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 to a point where it can be put to practical use. First, among the film-forming elements mentioned above, silicone-based film-forming elements have the disadvantage that they are expensive and have poor 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 such as poly(meth)acrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, and poly(meth)acrylates of aromatic (phenolic) polyhydroxyl compounds are used as film-forming elements. It is proposed to use. Even if these polyfunctional acrylic carboxylic acid ester derivatives are used alone as a film-forming element to form a film on the substrate surface of a resin molded article, the curing speed of these films in air during curing is low. poor curing properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance and adhesion to substrates; However, many of these physical properties were often inferior, and the requirements for industrial scale use could not be fully satisfied.

In addition, attempts have been made to improve these drawbacks by using a combination of two or more of these film-forming elements, but none of 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 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 our investigation, we found that a poly(meth)acrylate of a polyepoxy compound (no, a specific amount of a poly(meth)acrylate of a polyester polyol (c))
The inventors have also discovered that the above object can be achieved by using a composition containing a specific amount of 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 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. Overall, the resulting coating has many properties such as surface hardness, scratch resistance, abrasion resistance, readability, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. It has excellent characteristics.

To summarize the present invention, the present invention comprises (a poly(meth)acrylate of a poly-^-epoxy compound having at least two or more epoxy groups in the molecule, (b)
) having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule in a range of more than 0 to 1000 parts by weight per 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound) and (C) a poly(meth)acrylate of the polyepoxy compound (- and a poly(meth)acrylate of the polyester polyol) which does not have a urethane bond. A curable resin composition for coating, characterized in that it contains a polymerization initiator in a range of 0.01 to 20 parts by weight per 100 parts by weight in total,
The main points are as follows.

A poly(meth)acrylate of a polyepoxy compound to be blended into the curable resin composition for coating of the present invention (1)
A poly(meth)acrylate product of a polyepoxy compound formed from an aliphatic, alicyclic or aromatic polyepoxy compound having at least two or more epoxy groups in the molecule and acrylic acid or methacrylic acid. be.

Here, specific examples of polyepoxy compounds having at least two epoxy groups in one molecule include methylene glycol, ethylene glycol, propylene glycol, butylene glycol, pentylene gelylcol, hexylene glycol, octylene glycol, and tethylene glycol. Glycol, totecylene glycol, chrycerin, trimethylolpropane, pentaeryth IJ)-ol, polyoxyethylene glycol, polyoxypropylene glycol, diglycidyl, ditrimethylolpropane, tritrimethylolpropane, dipentaeryth IJ)-ol,
) Polyglycidyl ethers of aliphatic polyols such as dipentaerythritol; 1,2-cyclohexylene glycol, 1,4-cyclohexylene glycol, 2.2
-bis(4-hydroxycyclohexyl)furopane, 1
．． 1-bis(4-hydroxycyclohexyl)ethane,
Polyglycidyl ethers of alicyclic polyols such as bis(4-hydroxycyclohexyl)methane; polyglycidyl ethers of polyhydric phenols such as hydroquinone, resorcinol, catechol, phloroglucin, 2゜2-bis(4-hydroxyphenyl)propane , 1.1-bis(
Polyglycidyl ethers of aromatic polyols such as polyglycidyl ethers of aromatic polynuclear polyhydric phenols such as 4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, novolac type phenolic resins, and resol type phenolic resins, phthal acid, isophthalic acid,
Examples include polyglycidyl esters of aromatic polycarboxylic acids such as terephthalic acid.

More specifically, the polyepoxy compound includes ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, phethylene gelicol 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 dicrycidyl ether, ditrimethylolpropane tetraglycidyl ether, ditrimethylolpropane triglycidyl ether, dimethylolpropane diglycidyl ether, dipentaerythritol hexacrycidyl ether, dipentaerythritol pentaglycidyl ether,
Aliphatic polyepoxy compounds such as dipentaerythritol tetraglycidyl ether, dipentaerythritol triglycidyl ether, diventaerythritol dicrycidyl ether, 1,2-cyclohexylene glycol diglycidyl ether, 1,4-cyclohexylene glycol diglycidyl Alicyclic polyepoxy compounds such as ether, 212-bis(4-hydroxycyclohexyl)propane dicrycidyl ether, and bis(4-hydroxycyclohexyl)methane diglycidyl ether;
Hydroquinone diglycidyl ether, resorcin diglycidyl ether, catechol diglycidyl ether, 7
0 Loglucin triglycidyl ether, fluorocurcin diglycidyl ether, 2.2-bis(4-hydroxyphenyl)propane diglycidyl ether, 1.1-
Bis(4-hydroxyphenyl)propane diglycidyl ether, bis(4-hydroxyphenyl)methane diglycidyl ether, polyglycidyl ether of novolak type phenolic resin, polyglycidyl ether of resol type phenolic resin, phthalic acid diglycidyl ester,
Examples include aromatic polyepoxy compounds such as isophthalic acid diglycidyl ester and terephthalic acid diglycidyl ester, 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:
poly(meth) of the polyepoxy compound formed from the polyepoxy compound and acrylic acid or methacrylic acid;
It is an acrylate compound, and more specifically, the epoxy group of a polyepoxy compound is ring-opened to form a hydroxyl group (
General formula [1] 1 in which a meth)acryloyloxyl group is bonded to an adjacent carbon atom [wherein, R1 represents a hydrogen atom or a methyl group]. ], and has at least two of these units in the molecule, and thus has two or more (meth)acryloyloxyl groups and two or more hydroxyl groups in the molecule. It is. 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. Examples of catalysts include primary amines, tertiary amines, tertiary amines, salts thereof, quaternary ammonium compounds, organic acid salt compounds, Lewis acids or their complexes, alkaline earth metal rogides or hydroxides,・Hydrogen chlorides, etc. are included. More specifically, butylamine, hexylamine, dibutylamine, dibutylamine, trimethylamine, triethylamine, dimethylamine hydrochloride, diethylamine acetate, tetramethylammonium chloride, tetraethylammonium bromide, sodium acetate, tri2
0-mouth thorium acetate, sodium phthalate, potassium phthalate, tin chloride, zinc chloride, boron trifluoride ethylamine complex, boron trifluoride alcohol complex, lithium chloride, sodium bromide, calcium chloride, calcium bromide, hydroxide Examples include lithium, hydroxide, hydrogen chloride, and hydrogen bromide, and mixtures of two or more of these can also be used. The usage ratio is 100% of the epoxy compound
It is usually in the range of 0.005 to 5 parts by weight. The ratio of the acrylic acid or methacrylic 13-acid used is based on the epoxy group 1 of the polyepoxy compound.
It is usually in the range of 0.6 to 1.5 mol, preferably 0.9 to 1.1 mol. The reaction is usually -1
It is carried out at temperatures between 0 and 160°C.

Poly(meth)acrylate of polyester polyol blended into the curable resin composition for coating of the present invention)
is a poly(
It is a meth)acrylate product. Here, the polyester polyol constituting the poly(meth)acrylate of the polyester polyol has at least two or more hydroxyl groups at the molecular terminal or branch terminal formed by polycondensing a polycarboxylic acid and a polyol. It is a polyester polyol having the following. Examples of the polycarboxylic acid component units constituting the polyester polyol include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, tecanedicarboxylic acid, maleic acid, Aliphatic polycarboxylic acids such as fumaric acid, itaconic acid, butanetricarboxylic acid, butanetetracarboxylic acid, hymic acid, 1,3-cyclohexanedicarboxylic acid, 1.
Alicyclic polycarboxylic acids such as 4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride; aromatic polycarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. Examples include acids.

Examples of the polyol component units constituting the polyester polyol include ethylene glycol, fluoropylene glycol, fluorine glycol, hexylene glycol, octylene glycol,
IJ, trimethylolpropane, pentaerythritol, diethyl glycol, triethylene glycol, dipropylene glycol, diptylene glycol, triethylene glycol, cyhexylene glycol, diglycerin, ditrimethylolpropane, dipentaerythritol, polyoxyethylene glycol , aliphatic polyols such as polyoxyethylene polyoxypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, cyclohexylene glycol, 2.2-bis(4-hydroxycyclohexyl)furopane, 2.2-bis(4-hydroxy) cyclohexyl)
Alicyclic polyols such as ethane, bis(4-hydroxycyclohexyl)methane, xylylene glycol, 2.
2-bis(4-hydroxyphenyl)propane, 2. bis(4-hydroxyphenyl)ethane, bis(4-
Among polyester polyol components formed from aromatic polyol component units such as (hydroxyphenyl)methane, polyester polyol components composed of aliphatic, alicyclic, or a mixture thereof are preferred; Particularly preferred is a family polyester polyol component. By reacting the polyester polyol with acrylic acid or methacrylic acid in the presence of a catalyst, if necessary, a poly(meth)acrylate of the polyester polyol can be obtained. The number average molecular weight of the poly(meth)acrylate of the polyester polyol is usually 300 to 7000,
Preferably it is in the range of 300 to 5000. The blending ratio of the poly(meth)acrylate (b) of the polyester polyol is the same as the poly(meth)acrylate of the polyepoxy compound (b).
For 100 parts by weight of the meth)acrylate, it is necessary to be in the range of over 1,000 parts by weight, and more preferably in the range of 5 to 700 parts by weight, and particularly preferably in the range of 20 to 500 parts by weight. . Poly(meth)acrylate of the polyester polyol (b
) to 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (iii)) 5100 parts by weight
If the amount exceeds 0 parts by weight, the composition will wet the substrate;
The flexibility of the film decreases.

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 for the curing method, in the case of ultraviolet curing, a photosensitizer is blended as a polymerization initiator, and specific examples of the photosensitizer include benzoin, benzoin methyl ether,
Benzoin or its ethers such as pentwin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone; benzyl compounds such as benzyl, pendimethyl ketal, and benzyl diethyl ketal; ,
1-(4-isopropylphenyl)-2-hydroxy-
2-Methyl-1=propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-te
Examples include hydroxyalkylphenylketone compounds such as rt-butylphenyl)-2-hydroxy-2-methyl-1-propanone.

In the case of curing by heat, a radical initiator is mixed. Specifically, as a radical initiator, an azo compound such as azobisisobutyronitrile, penzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, dicumyl is used. Examples include peroxides such as 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 (3) is a total of 1 of the poly(meth)acrylate of the polyepoxy compound (-) and the poly(meth)acrylate of the polyester polyol (c).
It is necessary that the amount is in the range of 0.01 to 20 parts by weight, and more preferably in the range of 0.1 to 10 parts by weight. The blending ratio of the polymerization initiator is 0.01 part by weight based on a total of 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (b) and the poly(meth)acrylate of the polyester polyol (b). If the amount is less than 20%, the polymerizability of the composition decreases and a hard film cannot be obtained.
If the amount exceeds the heavy weight portion, 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 pigment, a dye, a solvent, and an ultraviolet absorber as required. stabilizers such as antioxidants, fluorescent brighteners,
Various additives such as (reactive) ribomers such as methyl (meth)acrylate and urethane-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 coating obtained therefrom.

The average particle size of the finely powdered inorganic filler can be determined arbitrarily as long as it is in the form of a powder, but it is usually between 1 mμ and 10 μm.
, preferably in the range of 1.511μ to 1μ. In addition, in order to maintain the transparency of the outer coating layer, the refractive index of the finely powdered inorganic filler is usually 1.40 to 1.60,
Preferably it is 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 stone, silica sand, quartz,
Examples include kaolinite, montmorillonite, sericite, talc, chlorite, pottery stone, and feldspar. In addition, surface care alkyl carboxylates or silane couplers and titanium couplers of these fine powder inorganic fillers,
Those surface-treated with cz, 5i (CH,), alcohol, etc. can also be used in the same way. Further, colloidal silica, methanol silica sol, ethanol silica sol, in which the inorganic filler is suspended in water or alcohol,
Improper tool silica sol and the like can also be used. Among these fine powder inorganic fillers, blending fine powder silica significantly improves the surface hardening, 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 the poly(meth)acrylate of the polyepoxy compound (~ and the poly(meth)acrylate of the polyester polyol υ
) is usually 0.5 to 200 parts by weight.
Parts by weight, preferably in the range of 0.5 to 100 N parts.

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.

G field is also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving the adhesion of molded products. 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, perclene , ethane trichloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobenzene, etc...logenated hydrocarbons, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, furopylene glycol Recall, alcohols such as chrycerin, ethylene glycol monomethyl ether, diethylene glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dithyl ether, etc. Examples include nitrites such as acetonitrile, propionitrile, and capronitrile, esters such as methyl formate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate. can do. The blending ratio of these organic solvents is determined based on the poly(methacrylate) of the polyepoxy compound and the poly(methacrylate) of the polyester polyol.
The amount is usually 5 to 3,000 parts by weight, preferably 10 to 2,000 parts by weight, based on the total IUO parts by weight of the meth)acrylate (b).

In the composition of the present invention, a solution composition or a suspension can be obtained from a composition containing the above-mentioned essential components and various night-heat machining components such as inorganic or mechanical fillers, solvents, and stabilizers added as necessary. The entire liquid composition can be prepared by blending the above-mentioned raw material mixture and using a regular roll, Banha IJ mixer, ball mill, attritor, whipper, oak mixer, dissolver, homogenizer, colloid mill, sand mill, vibration mill, or mixer. For example, a cross-current mixing method using a stirring mixing tank or the like can be exemplified, and a uniformly dissolved or dispersed composition can be obtained by these methods.

Methods for applying the solution composition and @turbid liquid composition onto the substrate surface of the molded article include brush coating, spraying,
Conventionally known methods such as a dipping method, a barcode method, a roll coater method, a spin coater method, and a Kelcoter method can be employed. In addition, methods for completely 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. In addition, as a method of curing the coating film and forming a film, there is also a method of polymerization and crosslinking curing with light, especially ultraviolet rays, and a method of polymerization and crosslinking curing with heat.
For example, how to 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'ft to 130°C, and the time is usually 1 sec to 11 sec.
1r, preferably 1 sec to 1 Qmin.

Further, in the thermosetting method, the temperature during curing is usually -10 to 150°C, preferably 5 to 160°C, and the time required for curing is usually 0.05 to 10 hr, preferably 0.1 to 8 hr.

The curable resin composition for coating of the present invention can be coated on the 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 ester resin, polycarbonate resin,
Polyester resin, polyamide resin, etc.? (J can be shown. Among these thermoplastic resins, the base resin layer constituting the laminate molded product is made of polyolefins,
Preferably, it is a polyacrylic ester resin or a polycarbonate resin. Specifically, the polyolefins include ethylene, propylene, 1-hexene, 4
- Homopolymers of α-olefins such as methyl-1-pentene, 1-octene, and 1-decene, copolymers of mixtures of two or more of the α-olefins, or α-olefins as described above;
The main component is olefin gold, and lower aliphatic vinyl carboxylates such as vinyl acetate and vinyl propionate, acrylic carboxylic acid esters such as methyl acrylate, metal salts of acrylic acid, methyl methacrylate, and metal salts of methacrylic acid, and acrylic-based Small amounts of other ingredients such as salts of carboxylic acids (
For example, a copolymer containing 60 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 ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. be able to. Among these polyacrylic carboxylic acid ester resins, it is preferable to use polymethyl methacrylate 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, and bisphenol A.

Examples include isophthalic acid/te-rephthalic acid copolycondensate and oxybenzoic acid polycondensate.

Specifically, the polyamide resin may be nylon 6, nylon 6/6, nylon 10, nylon 12, etc. In addition to the above-mentioned street oil, polyacetal, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer,
Examples include polysulfone resin, polyphenylene oxide, modified polyphenylene oxide, polyphenylene sulfide resin, and polyethersulfone resin.

Specific examples of the thermosetting resin constituting the base layer include polyester resin, epoxy resin, melamine resin, 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 substrate surface of a molded article such as a resin with the curable resin composition for coating of the present invention, the substrate surface of the molded article is washed with various solvents, an alkaline aqueous solution, and a surfactant. Various surface treatments such as ultrasonic cleaning, electrolytic cleaning, blasting, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, chemical conversion treatment, etc. can be applied. 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 core 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, examples of the primer include α, β-unsaturated carboxylic acids, acid anhydrides thereof, esters thereof, and the like.

Modified polyolefins grafted with β-unsaturated carboxylic acid or derivative components thereof are commonly used. In this way, the composition of the present invention is coated on the surface of the base layer of the molded article, which has been surface-treated or primed as necessary, by the method described above, and then 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, various lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, and coffee makers. Shower domes, coffee dispensers, water fountains, covers for lighting equipment, covers for stereo equipment such as players, dials and covers for various meters, covers for car headlamps or tail lamps, level sensors, shatterproof films for glass, etc. Various films such as release films, insulating films, agricultural films, optical playback video discs, viewing windows for various equipment such as clothes dryers, electric washing machines, dryers, and oil tanks, motorcycles, jeeps, and motor boats. windshield glass, automobile glass (windshield, rear window, opera window, triangular window, sunroof), glass for greenhouses, houses, aquariums, etc.
Tableware, mirrors, containers such as oil bottles and cosmetic bottles, relay cases, fuse boxes, motorcycle side covers and mudguards, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, waterproof sheets, and insulation films. ,
Floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative boards, shelf boards, wall sheets, wallpaper, furniture, lightweight wall boards, tableware, chairs, bathtubs, toilet bowls, refrigerators, wall panels, water supply and drainage pipes, raceway, duct, curtain rod,
Rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foils, various containers, automobile interior materials, vanity tables, flower boxes, particle boards, tiles, shutters, shutters, waterproof pans, pipes, wiring materials , gear cams, knobs, solenoid valve frames, doors, instrument panels, bumpers, 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 using examples.

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

+11 refractive index sufficiently dry inorganic substance r1 in a liquid with known refractive index 2
After adding wt% and sufficiently dispersing, visually check the transparency. The refractive index is the same as that of the most transparent liquid.

+21 Surface gloss (cross) It was performed according to the 60 degree specular gloss in JIS K 5400-1979.

13) Light transmittance It was carried out according to JIS K 6714.

(4) Adhesion The test was carried out according to the double-sided test in JIS K 5400-1979. The judgment is shown by how many of the 1[]0 gobans are glued together.

(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 (cross) 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 aS-
10. Rotate the coating 1000 times with a load of 500I.

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 hard copy Measured according to JIS K 5651.

(8) Flexibility Fold a rectangular test piece with a width of 5 mm and a length of up to 10 mm along the outer periphery of a cylinder with a diameter of 2 mm, and check whether the coating is cracked or not.
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 pure water at 40°C for 240 hours, the appearance and adhesion of the outer coating layer were evaluated.

θ1 Heat Resistance The test piece was kept in a gear set aging tester at 80° C. for a total of 400 hours, and the appearance and adhesion of the outer coating layer were evaluated.

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

(121 Gasoline Resistance Test Piece) The appearance and adhesion of the outer coating layer after being immersed in regular gasoline for 24 hours at room temperature was evaluated.

After holding 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, and then placed in a cold room at -30°C for 2 hours.
Hold for an hour and then leave at room temperature for 1 hour. This cycle was repeated 10 times, and changes in the appearance of the outer coating layer were visually observed and adhesion was evaluated.

04 Weather resistance test pieces were kept in a purple sunlight weatherometer for 400 hours, and the appearance and adhesion of the outer coating layer were evaluated.

64- Note that the following reference example shows a synthesis example of a polyacrylate compound of a polyester polyol.

Reference example 1 Pentaerythritol 136fIs succinic acid 59g,
6 g of para-toluenesulfonic acid and 100 g of toluene were charged, and a 150'cX2hr esterification reaction was carried out in a nitrogen atmosphere. After cooling, acrylic acid 22 (19, hydroquinone 3 g,) Leu f-7200 g'! The reaction solution was washed with weak alkaline water and water, then hydroquinone'i 0.05.!9 was added, and low-boiling substances were distilled off to obtain a polyester with an average molecular weight of 700. A polyacrylate of polyester polyol was obtained. It was confirmed by NMF that the average number of double bonds in one molecule of this polyacrylate of polyester polyol was 4.2.

Reference example Trimethylolpropane 138 & Adipic acid 7311
3 g of para-toluenesulfonic acid, 220 g of acrylic acid,
Using 3 g of hydroquinone and 400 g of toluene in the same manner as in Reference Example 1, a polyacrylated polyester yarn volume IJ, l--ole having an average molecular weight of 620.1 and an average number of double bonds in each molecule of 6.6 was obtained.

Reference example 6 Pentaerythritol 136! j, itaconic acid 65.5
g, acrylic acid 140. ! 9. Methacrylic 5ioo,y
, 800 g of toluene, 98% 6-P sulfuric acid and 0.2 g of phenothiazine were added, and the mixture was heated to 100-110 g in a nitrogen atmosphere.
The stellation reaction was carried out at ℃ for 8 hours. After washing the reaction solution with weak alkaline water and water, 0.05% of hydroquinone was added. ! 9 added and 1 low boiling point 't'/jk distilled off, average molecular weight 750.
A poly(meth)acrylate of a polyester polyol having 5.3 AkuIJOyloxyl groups in one molecule was obtained.

Reference Example 4 An average molecular weight of 1200 was obtained by the method described in Reference Example 6 except that 136 g of pentaerythritol, 1 []66 g of diethylene glycol, 177 g of succinic acid, and 240 I of acrylic acid were used.
．． A polyacrylate of polyester polyol having an average number of double bonds in one molecule of 5.5 was obtained.

Example 1 70 g of diacrylate of propylene glycol diglycidyl ether 60 g of polyacrylate of the polyester thread polyol described in Reference Example 1, benzoin isopropyl ether 5. ! 9 and toluene 150. !
iT k 500 m 4 Turow flask and at room temperature 2
A transparent coating composition [A] was prepared by stirring for hours.

On the other hand, an injection square plate (thickness: 3 tnm) 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-)lichloroethane for 1 minute and then heated to room temperature. After drying for 1 minute with maleic anhydride modified PER (propylene content 6
7 mol%, anhydrous maleic W@itbwt%) is,y
The injection square plate (t-20 seconds was immersed in toluene solution CB) of /z and slowly pulled up. After drying at room temperature 67-5 minutes for 5 minutes, it was heated and dried at 80 degrees Celsius for 30 minutes.Then, the above-mentioned coating material The polypropylene square plate subjected to primer treatment was immersed in composition [A] for 30 seconds,
After being slowly pulled up, it was dried at room temperature for 1 minute and then at 60°C for 5 minutes. This test piece was heated using a 1.5KW high pressure mercury lamp (1
The outer coating layer was cured by irradiating ultraviolet light for 60 seconds at a distance of 20 W/□, )TXl 5 an.

Table 1 shows the performance of this coating.

Examples 2-5 In Example 1, the coating composition described in Example 1 [
Instead of using A), a coating composition prepared using a polyacrylate of a polyepoxy compound described in 1, a polyacrylate of a polyester polyol, a polymerization initiator, and a bath agent 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 used. The results are shown in Table 1.

-Sq- Examples 6 to 7 Polyacrylates of polyepoxy compounds listed in Table 1, polyacrylates of polyester polyols, polymerization initiators, and i,i,i-trichloroethane were weighed as described in Table 1. Finely powdered silica (manufactured by Nippon Aerosil KK, trade name R-972) with an unstirred average particle size of 20 mμ and a refractive index of 1.45 was gradually added to this mixture (the amount used is listed in Table 1). Thoroughly stirred until uniform dispersion was obtained. Thereafter, the mixture was transferred to an attritor (manufactured by Mitsui Miike Seisakusho) filled with steatite balls, and the agitator was heated to 15 or more while cooling the tank with water.
Mixed for 6 hours by rotating at m. Is that the amount of toluene listed in 1? After adding and mixing for an additional 10 minutes, remove the mixture from the attritor and add the coating composition (Al
And so. In Example 1, a test piece was prepared in which the optical surface of polypropylene was coated 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 and 2 Polyacrylic V-) of the polyepoxy compound listed in Table 1
Compound, polyacrylate of polyester polyol, polymerization initiator, and solvent were prepared by weighing out the amounts described in Coating 1 and stirring and mixing at room temperature for 2 hours.
A test piece in which the narrow side of polypropylene was covered was prepared by the method described in Example 1 except that A) was used. The results are shown in Tatsu 1.

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

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

PGGA... diacrylate of propylene glycol diglycidyl ether GGA... triacrylate of glycerin triglycidyl ether BCHGA... diacrylate of 2-bis(4-hydroxycyclohexyl)propane diglycidyl ether BPC , A...Diacrylate compound of 2,2 bis(4-hydroxyphenyl)propane diglycidyl ether BIE...Penzoin isoglobyl ether BP
H...benzophenone 11 (P...1l-(4-isopropylphenyl)-
2-Hydroxy-2-methyl-1-propanone-41--603- Example 8 Poly-4-methyl-1-pentene (Mitsui Petrochemical Industries K
K'R1 trade name; TPX MXOO4) cD3m
m-thick injection coating 7) e, maleic anhydride modified EPR (
1”J/l of maleic anhydride containing arsenic; 7.7wt%)
Primer treatment was performed by immersing the sample in a chloroethane solution having a concentration of 1.1.1-1 for 10 seconds. After being left at room temperature for 5 minutes, it was immersed in the coating composition described in Example 7 for 10 seconds. After drying at room temperature for 1 minute and then at 60° C. for 5 minutes, photocombining was carried out using the method described in Example 7 to prepare a purple test piece coated with the surface of IJ-4-methyl-1-pentene. The results are shown in Table 2.

7M Examples 9-10 In Example 8, instead of using poly-4-methyl-1-pentene as the base polymer, a polymer sheet having a baseness of 61 mm and a thickness of 61 mm as shown in Table 2 was used. A test piece was prepared using the method described in Example 8, except that the pretreatment was carried out, and the narrow surface of the polymer was measured. The results will be shown to the public.

44- Clothing 2 Comparative Examples 4 to 6 Poly-4-methyl-1-pentene (Mitsui Petrochemical Industries KKW, TPX=
MXOO4)% Poly h-bonate (large quantity Kasei KK
Table 2 shows the performance of polymethyl methacrylate (Acrylite L, manufactured by Mitsubishi Rayon KK).

=45- Example 11, Comparative Example 7 In Example 1, the coating composition described in Example 1 (
Instead of using Al, the coating composition [A] described in Example 7 was used, and instead of using all polypropylene as the base of the molded body, a 2 mm thick unsaturated polyester resin (Revolac, manufactured by Showa Kobunshi KK) was used. A test piece having a surface coated with an incompatible polyester resin was prepared by the method described in Example 1 except that MC8-302) was used. The film thickness of this test piece is 8μ, the surface gloss (cross) is 81, and the layer density is 100/
100, and the pencil hardness was 4H (Example 11). On the other hand, the unsaturated polyester resin not coated with the coating composition of the present invention had a surface gloss (cross) of 63 and a pencil hardness of 6H (Comparative Example 7).

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi 47- 606-

Claims (2)

[Claims] (1) ((1) A poly(meth)acrylate of a polyepoxy compound having at least two or more epoxy groups in one molecule; (w) A poly(meth)acrylate of the polyepoxy compound ((1) 100% by weight over 0 to 1000
a poly(meth)acrylate of a polyester polyol having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule and having no urethane bond, within the range of parts by weight; (C) of the polyepoxy compound; Contains 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 (a) and the poly(meth)acrylate of the polyester polyol). Characteristic curable resin composition for coating. (2) 0.5 to 200 parts by weight based on a total of 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound ((1) and the poly(meth)acrylate of the polyester-based polyester polyol); The curable resin composition for coating according to claim 11, which contains a finely powdered inorganic filler in the range of parts by weight.