JPS5958035A - Curable coating resin composition - Google Patents

Abstract

PURPOSE:To provide titled composition of outstanding curing characteritics, capable of giving coating films with various excellent properties, comprising each specific amount of a poly(meth)acrylate compound from a specific aliphatic polyepoxy compound, polyoxyalkylene di(meth)acrylate, and polymerization initiator. CONSTITUTION:The objective composition comprising (A) a poly(meth)acrylate derived from (1) an aliphatic polyepoxy compound having in one molecule, at least two epoxy groups and (2) (meth)acrylic acid, (B) up to 1,000pts.wt. (excepting zero) per 100pts.wt. of the component (A), of a polyoxy alkylene di(meth)acrylate [e.g., polyoxyethylene di(meth)acrylate], and (C) 0.01-20pts.wt. per 100pts.wt. of the components (A) plus (B), of a polymerization initiator (e.g., benzoin, azobisisobutylonitrile).

Description

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

Generally, molded products such as thermoplastic resins and thermosetting resins are
Compared to metal products, glass products, etc., it is not only lightweight and has excellent impact resistance, but also has various advantages such as being inexpensive and easy to mold.
It is widely used in place of these materials in home 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 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 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, specifically as resins or resin-forming components,
Silicone monomers or compositions of these components and various polymers, resin compositions of methylolmelamine and other curing components, polyfunctional acrylic carboxylic acid ester derivatives or compositions of these and other polymeric components. Things are being suggested. 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 17.7 in order to improve these defects. For example, surface treatments using corona discharge and primers have been proposed. However, even if surface treatment is performed, it may be 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. many. Moreover, among the film-forming elements, silicone-based film-forming elements are expensive and have a disadvantage of being inferior in economic efficiency.

Among the film-forming elements, various types of compounds have been proposed as polyfunctional acrylic carboxylic acid ester derivatives. For example, four 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. 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 worked diligently to develop a coating composition that can be coated onto the surface of a molded body made of thermoplastic resin, thermosetting resin, etc., and has excellent curing properties in the curing gap and the resulting coating properties. As a result of investigation, a composition containing a poly(meth)acrylate of an aliphatic polyepoxy compound (a), a specified amount of polyoxyalkylene dimethacrylate (b), and a specified polymerization initiator (0) was found. It has been discovered that the above object can be achieved by using the following, and the present invention has been achieved. According to the present invention, when the curable resin composition for coating of the present invention is coated on the surface of a molded body substrate such as a resin to form an outer coating layer, the curing characteristics such as the curing speed in air during curing can be improved. Surface of the resulting coating ■■Hardness, scratch resistance,
It is characterized by a comprehensive range of film properties such as abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. .

To summarize the present invention, the present invention comprises (a) a poly(meth)acrylate of an aliphatic polyepoxy compound having at least two or more -L epoxy groups in one molecule;
Poly(meth)acrylate of the polyepoxy compound (a) 100 fi! 10DD over O for the part
and (c) a total of 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (a) and the polyoxyalkylene di(meth)acrylate (a). 0 for part
．． The gist of the present invention is a curable resin composition for coating, characterized in that it contains a polymerization initiator in a range of 0.01 to 20 parts by weight.

The (meth)acrylate compound (a) of the polyepoxy compound blended in the curable resin composition for coating of the present invention is 1
It is a poly(meth)acrylate compound of a polyepoxy compound formed from an aliphatic polyepoxy compound having at least two -F epoxy groups in the molecule and acrylic acid or methacrylic acid. Here, specific examples of aliphatic polyepoxy compounds having at least two epoxy groups in one molecule include methylene glycol, ethylene glycol, propylene glycol, butylene glycol, pentylene gelylcol, hegylene glycol, and octylene glycol. , decylene gelicol, dodecylene glycol, glycerin, trimethylolpropane, pentaerythritol, polyoxyethylene glycol, polypropylene glycol, polyA xyethylene polypropylene glycol, diglycerin,
Examples include polyglycidyl ethers of aliphatic polyols such as ditrimethylolpropane, tritrimethylolpropane, dipentaerythritol, tripentaerythritol, and more specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and butylene. Glycol diglycidyl ether, glycerin triglycidyl ether, glycerin diglycidyl ether, trimethylolpropane tridalisidyl ether, trimethylolpropane diglycidyl 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, ditrimethylolpropane diglycidyl ether, dipentaerythritol hexaglycidyl ether, dipentaerythritol pentaglycidyl ether,
Examples include dipentaerythritol tetraglycidyl ether, dipentaerythritol triglycidyl ether, dipentaerythritol diglycidyl ether, and mixtures of two or more of these may 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:
It is a poly(meth)acrylate product of the polyepoxy compound formed from the polyepoxy compound and acrylic acid or methacrylic acid, and more specifically, the epoxy group of the polyepoxy compound is ring-opened to form a hydroxyl group. and (meth)acryloyloxyl group bonded to adjacent carbon atoms to form a single f)γ represented by 1 (1 represents a hydrogen atom or a methyl group) in the general formula (1) C formula, and this It is a compound that has at least two or more units in its molecule, and therefore it is a compound that has two or more (meth)acryloyloxyl groups and two or more hydroxyl groups in its molecule. The poly(meth)acrylate ratio (,) of the polyepoxy compound is
It 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, secondary amines, tertiary amines, their salts KL quaternary ammonium C aggregate organic acid salt compounds, Lewis acids or their εPIf-does, alkaline earth metal halides or hydroxides. Examples include hydrogen halides, hydrogen halides, etc. More specifically, butylamine, hexylamine 1 dipropylamine, dibutylamine, trimethylamine, triethylamine, dimethylamine JM
rV Jli, diethylamine acetate, tetramethylammonium chloride, tetraethylammonium bromide, sodium acetate, sodium trichloroacetate, phthalate, potassium phthalate, tin chloride, zinc chloride, boron trifluoride ethylamine complex, trifluoride 011j IJ
Examples include hydrogen chloride, hydrogen bromide, etc.
A mixture of two or more of these can also be used. Its usage ratio is usually (1 part by weight) per 100 parts by weight of the epoxy compound.
,0 (in the range of 115 to 5 parts by weight.The proportion of the acrylic acid or methacrylic acid used is in the range of 0.9 to 1.1 moles of epoxy of the polyepoxy compound.The reaction is usually -10 Or 'Ii at a humidity of 160℃
It's going to be a city.

Curing for coating of the present invention! 1! Polyoxyalkylene di(meth)azilylate (January 1, acrylic saturated ester or methacrylic acid ester of polyoxyalkylene glycol) blended into I Resin X11 composition. The alkylene group usually has the general formula (n) R2rdog4 [wherein R2, R5, R4 and R5 each represent a hydrogen atom or an argyl group having 1 to 12 carbon atoms.

], and the degree of polymerization of the oxyalkylene group is usually in the range of 1 to 40, preferably 1 to 20. The number average molecular weight (M n ) of the polyoxydialkylene di(meth)acrylate is usually 214
It ranges from 214 to 1D00, preferably from 214 to 1D00. Specifically, the polyoxyalkylene di(meth)acrylates include polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, polyoxyethylene polyoxypropylene diacrylate, Examples include oxyethylene polyoxybrobylene dimethacrylate. Among the polyoxydialkylene di(meth)acrylates, polyoxydiethylene di(meth)acrylate or polyoxypropylene dimethacrylate is preferred. The polyoxydialkylene di(meth)acrylate)
The blending ratio of (b) needs to be in the range of more than 0 to 1000 parts by weight, and more preferably 5 to 200 parts by weight, based on 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (a). Parts by weight range, especially 5
Preferably, the amount is in the range of 100 to 100 parts by weight. If the blending ratio of the polyoxydialkylene di(meth)acrylate (b) to 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (a) exceeds 1,000 parts by weight, the composition will not react in air. As the curing properties deteriorate, the surface hardness, abrasion resistance, etc. of the outer coating also decrease.

The film-forming element components (polymerizable 4S, polymer component) blended into the curable resin composition for coating of the present invention may consist of only the above-mentioned two essential components, but may also include other polymerizable monomer components. It is also possible to add and copolymerize. Other polymerizable monomer components include by-products or production intermediates during the production of the poly(meth)acrylate of the polyepoxy compound or the polyoxydialkylene di(meth)acrylate, such as the (meth)acrylate of the monoepoxy compound. ) acrylates, mono(meth)acrylates of polyepoxy compounds, mono(meth)acrylates of polyoxyalkylene glycol, etc., as well as (meth)acrylic acid, methyl (meth)acrylate, (meth)acrylic acid-2- Examples include methyl (meth)acrylate such as hydroxyethyl.

In order to apply the curable resin composition for coating of the present invention to the substrate surface of a 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 added as a polymerization initiator,
Specific examples of photosensitizers include benzoin or its ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isoflobil ether, and benzoin isobutyl ether, benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone. Benzophenone compounds, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal and other benzyl compounds, 1-(4-isopropylphenyl)
-2-H)”oxy-2-methyl-1-propanone, 1
Examples include hydroxyalkylphenylketone compounds such as -phenyl-2=hydroxy-2-methyl-1-propanone and 1-(4-tert-butylphenyl)-2-hydroxy-2-methyl-1-propanone. Can be done. 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 a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and UV curing and thermal curing proceed simultaneously. It is also possible to adopt a method of proceeding with heat curing after proceeding. 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 the poly(ivy) acrylate of the polyepoxy compound (,)
and the polyoxydialkylene di(meth)acrylate
) 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, based on the total of 100 parts by weight of (1)).

The blending ratio of the polymerization initiator is 1 in total of the poly(meth)acrylate of the polyepoxy compound (a) and the polyoxydialkylene di(meth)acrylate (b).
If the amount is less than 0.01 part by weight, the polymerizability of the composition will decrease and a hard film will not be obtained, and if it is more than 20 parts by weight, the film obtained from the composition will be It will turn 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 1 line absorbers, stabilizers such as antioxidants, fluorescent brighteners,
Various additives such as (reactive) oligomers such as methyl (meth)acrylate, polyurethane acrylate, and poly-11 ester acrylate, and polymers such as polymethyl methacrylate can be blended. The blending ratio of these additives is appropriate.

The curable coating resin & 11 composition of the present invention contains, within the range of maintaining the transparency of the cured film obtained from it,
If necessary, a finely powdered inorganic filler may be added. 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 1111μ to 10μ, preferably 1.5μ to 111μ. Further, in order to maintain the transparency of the outer coating layer, the refractive index of the finely powdered inorganic filler is usually in the range of 1.40 to 1.60, preferably 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 I.J.
Examples include ferrite, melk, chlorite, chinastone, and feldspar. Further, these finely powdered inorganic optical 4X agents whose surfaces have been surface-treated with alkyl carboxylic acid salts, silane couplers, titanium couplers, ce2S1(cll,5)2, alcohol, etc. can also be used. In addition, colloidal silica, methanol silica sol, in which the inorganic filler is suspended in water or alcohol,
It is also possible to use ethanol silica/°ol, isopropanol silica sol, and the like. Among these finely powdered inorganic fillers, when finely powdered silica is blended, the six-sided hardness, scratch resistance and abrasion resistance of the jacket III 11 are improved. It is particularly preferred because it does not have any stains that impair transparency and surface gloss. The blending ratio of these finely powdered inorganic fillers is a total of 1ooifftg of the poly(meth)acrylate (8) of the polyethoxy compound and the axially kylene di(meth)acrylate (b) in 7. (Usually 0 for ~
．． 5 to 200 parts by weight, preferably (], 5 to 1
00 parts by weight of the curable resin composition for coating according to the present invention, in order to improve its coating workability, a melting force (1) is applied to the curable resin composition of the present invention in a solution state or The state of suspension is maintained.

The solvent may be used to liquefy or suspend the composition, or to adjust the viscosity of the composition. Specifically, 1j includes hydrogen ash such as benzene, toluene, xylene, cumene, ethylbenzene, hexane, hebutalohexane, and methylcyclohexane, methylene chloride, chlorine coform, ash tetrachloride, bromoform, trichlene, and ethylene dichloride. , nocuculene, ethane trichloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobenzene and other halogenated carbons arsenic, methanol, ethanol, isopropanol, butanol, pentanol, hegizanol, cyclohekylinol, ethylene glycol , propylene glycol, lycerine, ethylene glycol monomethyl ether, ethylene glycol sodium alcohol, acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone, ethers such as diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, nitrites such as acetonitrile, propionitrile, capronitrile, methyl formate, ethyl formate, Examples include esters such as methyl acetate, ethyl acetate, propyl acetate, inbutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate. The blending ratio of these organic solvents is
Poly(meth)acrylate of epoxy compound (11
) and the polyoxydialkylene di(meth)acrylate) (b).

In the composition of the present invention, the above-mentioned essential components and various additives such as inorganic or organic fillers, solvents, and stabilizers added as necessary can be mixed to form a solution composition or a W1 suspension composition. The method for preparing the precursor is usually to prepare a mixture of raw materials for the precursor. -Banbury mixer
Examples include kneading and mixing methods using a ball mill, an attritor, a one-piece bar, an oak mixer, a dissolver, a homogenizer, a colloid mill, a sand mill, a vibration mill, and a mixer mixing tank. A composition is obtained. Methods for applying the solution composition and suspension composition to the substrate surface of the molded article include brush coating method, spray method, dipping method, bar code method, roll coater 4, spin coater rk, KEL:I Conventionally known methods such as the tater method can be employed. Examples of methods for drying the coating include natural drying, forced drying using a carrier gas, stirrup drying using an infrared oven, far-infrared oven, and hot air oven. Examples of methods for curing the above-mentioned coating film to form a film include a method of polymerizing and crosslinking hardening with light, particularly ultraviolet rays, a method of polymerizing and crosslinking hardening with heat, and the like. Among these polymerization crosslinking and curing methods, the photocuring method usually uses -1o
Light irradiation is carried out at a temperature of from 5 to 150'Cs, preferably from 5 to 130'C, and the time is usually 1seat.
(ishi hr, preferably 1BθC to 11]r
It is nin. In addition, in the thermosetting method, the temperature during curing is usually -10 to 150°C, preferably 5 to 130°C.
°C, and the time required for curing is usually 0.05 to 1
Qhr, preferably o. i to 811r.

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.

Specific examples of the thermoplastic resin constituting the base layer include polyolefins such as α-olefin homopolymers or copolymers containing α-olefin as a main component;
Polyacrylic ester resin, polycarbonate resin,
Examples include polyester resin and polyamide resin. Among these thermoplastic resins, the base resin layer constituting the laminate molded product is preferably polyolefins, polyacrylic ester resins, or polycarbonate resins. Specifically, the polyolefins include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hegycene, 4-methyl-1-pentene, 1-octene, and 1-decene, and the α-olefins mentioned above. The main component is two or more types of innes, and lower aliphatic vinyl carboxylates such as vinyl acetate and vinyl propionate, methyl acrylate, gold KJS salt of acrylic acid, methyl methacrylate, and metal salts of methacrylic acid. Examples include copolymers containing a small amount (for example, 60 mol % or less) of a component such as an acrylic carboxylic acid ester or a salt of an acrylic carboxylic acid. Among these polyolefins, polyolefins having crystallinity are usually used.

Specific examples of the polyacrylic carboxylic acid ester resin include homopolymers or copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. can. Among these polyacrylic carboxylic acid ester resins, polymethyl methacrylate is preferably used in the thermoplastic resin base resin layer of the present invention. Specific examples of the polycarbonate resin include bisphenol A and polycarbonate. Specific examples of the polyester resin include polyethylene terephthalate, polytetramethylene terephthalate, bisphenol A/isophthalic acid/terephthalic acid copolycondensate, and benzoic acid condensate. Specific examples of the polyamide resin include nylon 6, nylon 6.6, nylon 10, and nylon 12. In addition to the above resins, examples include polyacetal, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyphenylene oxide, modified polyphenylene oxide, polyphenylene sulfide resin, polyether sulfone resin, etc. be able to.

Specifically, the thermosetting resin constituting the base layer includes unsaturated polyester resin, epoxy resin, melamine resin,
Examples include diallyl phthalate resin 1 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, washed with an alkaline aqueous solution, and has a surface active Cleaning with a single agent, ultrasonic cleaning, electrolytic cleaning, blast treatment, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, chemical conversion treatment, etc. It is possible to apply surface treatment to the insert. In addition, when laminating an external wave film layer made of the curable resin composition for coating of the present invention on the base surface of the molded body, an intermediate adhesive layer made of a primer is provided between the base j1d and the external wave film layer. It is also possible to improve the adhesion between the two layers by forming a three-layer laminate. When the base layer is polyolefin, the brimers are α, β.
- A modified polyolefin grafted with an α,β-unsaturated carboxylic acid or its derivative component such as an unsaturated carboxylic acid, acid #1 (hydrate, ester thereof, etc.) is usually used. The composition of the present invention is coated on the surface of the base layer of the molded body that has been subjected to surface treatment or primer treatment by the method described above, and is then subjected to a curing treatment.

A molded article on which 4" coatings are laminated from the curable resin composition for coating of the present invention is used for A4 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, white liquid bags, and coffee makers. Shower domes and coffee dispensers, water tanks, covers for lighting devices, covers for stereo devices such as players, dials and covers for various meters, covers for car headlamps or tail lamps, level sensors, and for preventing glass from scattering. films, release films, insulation films,
Famous films such as agricultural film, optically playable video discs, viewing windows for various devices such as clothes dryers, electric washers, hair dryers, and oil tanks, windshield glasses for motorcycles, jeeps, and motorboats, and automobile glass ( Windshields, rear windows, obera windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, etc.
Tableware, mirrors, various containers such as oil layers and cosmetics, relay cases, fuse boxes, fifth wheel side covers, mud, fenders, horns, screens, etc.
Table cloths, waterproof moisture-proof films, tarpaulins, insulating films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative plates, shelving boards, wall sheets,
Wallpaper, furniture, 11m wallboards, tableware, chairs, bathtubs, toilets, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, ducts, curtain rods 1 rain gutters 1 insulation, waterproof coating, curtains, window frames, Automotive foil, various containers, automobile interior materials, vanity tables, flower boxes, particle boards, roof tiles, shutters,
Shutters, waterproof pans, pipes, wiring materials, gear cams,
Examples include knobs, solenoid valve frames, fans, instrument panels, bumpers, players, 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 for 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 corner test in JIS K5400-1979. The judgment is based on how many of the 100 gobans were glued together.

(5) Due to the method of falling sand abrasion JIS ']' 8147-1975
oog silicon carbide abrasive material is dropped onto the coating. The difference in surface gloss before and after the test will affect the abrasion resistance, and the smaller the 0 number, the better the abrasion resistance.

(6) Taper wear AsTu According to the method of D-1[]44, wear ring Cs
-10, rotate the coating 1000 times with a load of 5F''10g.

Abrasion resistance can be determined by simply abrading the coating after the test.

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

(7) Pencil hardness JIS K 5651: 1 to 11! I'r stranded.

(8) Flexibility A strip-shaped test piece with a width of 5 m + n% and a length of 10 C horns is folded along the outer circumference of a cylinder with a diameter of 2 COIL, and the angle is expressed as the angle at which the coating cracks or peels off from the substrate. .

Flexibility is better in the direction where the value is larger.

(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 was rated 11.

(10) 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.

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

(12) Gasoline resistance test piece was immersed in regular gasoline for 24 hours at room temperature with N4
The appearance and adhesion of the outer coating layer after the coating was evaluated.

(16) Heat cycling resistance The test piece was kept in an air oven at 80°C for 2 hours, then left at room temperature for 1 hour, then kept in a cold room at -3°C for 2 hours, and then heated to room temperature. Leave it 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.

The test piece was held in a sunshine weather roller for 400 hours, and the appearance and adhesion of the outer coating layer were evaluated.

Example 1 Diacrylate of ethylene glycol diglycidyl ether (85 g 1 diethylene glycol diacrylate)
15g of benzoin isopropyl ether and 110g of toluene were charged into a 500me4 Tulo flask.
Press the transparent coating composition for 1 hour at room temperature.
A] was produced.

On the other hand, an injection square plate (thickness 3 mm) made from polypropylene (manufactured by Mitsui Petrochemical Industries KK, trade name Mitsui Petrochemical Boripuni 5J-313) was exposed to the vapor of 1.1.1-) lychloroethane for 1 minute, and then at room temperature. After drying for 1 minute with maleic anhydride modified PER (propylene content 67
The injection square plate was immersed for 20 seconds in a 15 g/6 toluene solution CB) containing 6 wt % of maleic anhydride, and slowly pulled up. After drying at room temperature for 5 minutes, 80°C
Heat drying was performed for 30 minutes. Next, the polypropylene square plate subjected to the brimer treatment was immersed in the coating composition (A) for 50 seconds, slowly pulled up, and then soaked at room temperature for 1 hour.
drying was carried out for 5 minutes and then at 60°C for 5 minutes. This test piece was heated using a 1.5KW high pressure mercury lamp (120w/CIn).
The outer coating layer was cured by irradiating ultraviolet light for 30 seconds at a distance of 15C-II.

The film performance is shown in Table 1.

Examples 2 to 6 In Example 1, instead of using the composition for broken 8U [A] described in Example 1, poly(meth)acrylates of polyepoxy compounds and polyoxyalkylene diamides described in Table 1 were used. A test piece was prepared by coating the surface of polypropylene in the same manner as in Example 1, except that a coating composition prepared using the amounts of methacrylate, polymerization initiator, and solvent shown in Table 1 was used. The results are shown in Table 1.

Examples 7 to 8 The polyacrylates of polyepoxy compounds listed in Table 1, polyoxyalkylene diacrylate, polymerization initiators, and 1,1.1-)lychloroethane were weighed out and added to the mixture. Average particle size during stirring is 20m
71. Finely powdered silica having a refractive index of 1.45 (manufactured by Nippon Aerosil KK, trade name R-972) was gradually added (the amount used is shown in Table 1), and stirred thoroughly until uniform dispersion was obtained. After that, the attritor filled with steatite balls (
The mixture was transferred to a tank (manufactured by Mitsui Miike Seisakusho) and mixed for 3 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 after further mixing for 10 minutes, the mixture was taken out of the attritor to form a coating composition (A). In Example 1, a test piece having a polypropylene surface coated was prepared by the method described in Example 1, except that the coating composition described in Example 1 was used instead of the coating composition described in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 2 The polyacrylates of polyepoxy compounds, polyoxyalkylene diacrylates, polymerization initiators, and solvents listed in Table 1 were weighed out in the amounts listed in Table 1, and the mixture was heated at room temperature for 11 days.
A test piece was prepared in which the surface of polypropylene was coated by the method described in Example 1, except that the coating composition [A] prepared by stirring and mixing for 1 hour was used. The results are shown in Table 1.

Comparative Example 3 Table 1 shows the performance of single polypropylene (manufactured by Mitsui Petrochemical Industries KK, 5J-313) not coated with the coating composition of the present invention.

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

gGGA ... Diacrylate of ethylene glycol diglycidyl ether EG G rA ・°゛ Ethylene glycol cidalisidyl ether dimethacrylate PGGA ... Diacrylate of propylene glycol diglycidyl ether GGA ... Glycerin triglycidyl ether Triacrylate DgODA...Diethylene glycol diacrylate TPGDA...Tripropylene glycol diacrylate NEGDA...Nonaethylene glycol diacrylate BIE benzoin isopropyl ether I kl
P...1-(4-isopropylphenyl)-2
-Hydroxy-2-methyl-1-propa Example 9 3mu of phosphory-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries KK, trade name: TPX 1, 1Xoo4)
A + thick injection molded sheet was molded with maleic anhydride modified GPN (
i4t containing maleic anhydride: 7.7wt%) (7)
15g/l? ILF 1.1,1-) IJ was immersed in chloroethane solution for 10 seconds to perform brimer treatment. 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 then at 60"C for 5 minutes, photopolymerization as described in Example 8,
A test piece whose surface was coated with poly-4-methyl-1-pentene was prepared. 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 3 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 Petrochemical Industries KK, +vx0) not coated with the coating composition of the present invention
04), Polycarbonate (Manufactured by Yudai Kasei KK, Panlite L-1250), Polymethylnotacrylate (Manufactured by Mitsubishi Rayon KK, Acrylite I) / / /' / / / / / / /' / / / /' , / /'/''' / / / / / Example 12, Comparative Example 7 In Example 1, the Hitagawa composition described in Example 1 (
Instead of using A), the Hitagawa composition [Δ] described in Example 8 was used, and instead of using polypropylene as the molded body base, an unsaturated polyester resin with a thickness of 2m+n (manufactured by Showa Kobunshi KK, Reblank+) was used. ,,+cs-502
) was used to prepare a test piece whose surface was coated with unsaturated polyester resin using the method described in Example 1. The film thickness of this test piece was 10/'s, the surface gloss was 82, the adhesion was IOO, '1OO1, and the pencil hardness was 4I (Example 12).On the other hand, the coating composition of the present invention The surface luminosity (gloss) of the unsaturated polyester resin, which had no Vl, was 63 and the pencil hardness was 3H (Comparative Example 7).

Applicant: Mitsui Petrochemical Industries, Ltd.

Claims (2)

[Claims] (1) (a) Poly(meth)acrylate of an aliphatic polyepoxy compound having at least two or more epoxy groups in one molecule, (Shun) Poly(meth)acrylate of the polyepoxy compound (a) 100 More than 0 to 1000 parts by weight
Polyoxydialkylene di(
meth)acrylate, and (.) o, o i to 20 parts by weight based on a total of 100 parts by weight of the poly(meth)acrylate of the polyepoxy compound (a) and the polyoxydialkylene di(meth)acrylate (b) A curable resin composition for coating, comprising: a polymerization initiator in a range of 1. (2) Poly(meth)acrylate of the polyepoxy compound
h compound (a) and the polyoxydialkylene di(meth)
0.5 per 100 parts by weight of acrylate (b)
The curable resin composition for coating according to claim 1, which contains a finely powdered inorganic filler in a range of from 20 parts by weight to 20 parts by weight.