JPS5930810A - Curable resin composition for coating - Google Patents

Abstract

PURPOSE:The titled composition, containing a specific compound, a polyoxyalkylene di(meth)acrylate and a polymerization initiator, capable of giving coating films having improved surface hardness, adhesive properties, etc., suitable for coating molded articles of a polyolefin, and having improved curability. CONSTITUTION:A composition obtained by incorporating (A) 100pts.wt. poly [(meth)acryloyloxyalkyl](iso)cyanurate of the formula [X<1>-X<3> are (meth)acryloyl group, H, etc., and two or more thereof are (meth)acryloyl group; R<1>-R<3> are (poly)oxyalkylene group], e.g. tris(acryloyloxyethyl)isocyanurate, with (B)>0- 1000pts.wt. polyoxyalkylene di(meth)acrylate, e.g. polyoxypropylene dimethacrylate, and (C) 0.01-20pts.wt., based on 100pts.wt. total amount of the components (A) and (B), polymerization initiator, e.g. a photosensitizer or radical initiator.

Description

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

In general, molded bodies of polyolefins such as polyethylene and polypropylene are not only lighter and have better impact resistance than metal products and glass products, but also have various advantages such as being inexpensive and easy to mold. It is widely used in place of these materials in automobiles, motorcycles, household appliances, daily necessities, and many other fields. However, these polyolefin molded bodies have a disadvantage in that their surface hardness is lower than that of metals, glass, etc., and they are susceptible to scratching and friction, so they are 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 to improve the above-mentioned drawbacks of molded bodies made of these polyolefins. Most of these methods involve coating the surface of these molded bodies with an outer coating layer made of a crosslinked curable resin. Among these film-forming elements, specific examples of resins or resin-forming components include silicone monomers or compositions of these components with various polymers, and resin compositions consisting of methylolmelamine and other curing components. , polyfunctional acrylic carboxylic acid ester derivatives, and compositions of these and other polymeric components have been proposed. Even if a film layer made of these film-forming elements is formed on the surface of a polyolefin molded product such as polyethylene or polypropylene, the adhesion between the film layer and the polyolefin base layer is generally not good, so these laminate molded products There is a drawback that the coating layer is easily peeled off.

Furthermore, methods are known in which various treatments are applied to the surface of polyolefin molded articles in order to improve these defects. For example, surface treatments using corona discharge, surface treatments using brimer, etc. have been proposed.

However, even if surface treatment is performed, it is often difficult to sufficiently improve the adhesion between the base layer made of polyolefin and the coating layer made of the crosslinked curable resin for practical use. 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. Various types of compounds are used as film-forming elements, for example, poly(meth)acrylates of alkane polyols, poly(meth)acrylates of polyoxyalkylene glycols, poly(meth)acrylates of aromatic (phenolic) polyhydroxyl compounds, etc. It is proposed to do so. Even if these polyfunctional parallel acrylic carboxylic acid ester derivatives are used alone as a film-forming element to form a film on the substrate surface of a polyolefin molded article, these films will not be affected by the curing speed in air during curing. Poor curing properties or poor coating properties such as surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, weather resistance, and adhesion to the substrate. However, many of these physical properties are often inferior, and the requirements for industrial scale use cannot 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 these methods can improve these drawbacks to some extent. Even if it were possible, there were other new difficulties when coating the surface of a polyolefin substrate.

The present inventors have conducted intensive studies on a coating composition that has excellent curing properties during curing and has excellent coating properties by coating the surface of a base resin made of polyolefin. (meth)acryloyloxyalkynoly(iso)cyanuride) (a), a specified amount of polyoxydialkylene di(meth)acrylate (b), and a specified amount of a polymerization initiator (, ). The inventors have found that the object is satisfied 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 polyolefin molded article to form an outer coating layer, the curing properties such as the curing speed in air are excellent during curing, and it is possible to obtain surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance,
It is characterized by excellent overall coating properties such as weather resistance and adhesion to substrates.

To summarize the present invention, the present invention comprises (a) general formula (1)%
Formula % [In the formula, Xl, x2 and x5 are an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these are (meth)acryloyl groups, and R1, R2 and R3 are an oxyalkylene group or Indicates a polyoxyalkylene group. ] represented by poly[(
meth)acryloyloxyalkyl](iso)cyanurate h (b) Exceeding 0 and in the range of 1000 parts by weight per 100 parts by weight of the poly[(meth)acryloyloxyalkynoly(iso)cyanurate (a) , polyoxydialkylene di(meth)acrylate, and (C)
The poly[(meth)acryloyloxyalkyl](
It is characterized by containing a polymerization initiator in the range of 0.01 to 20 parts by weight per 100 parts by weight of the iso)cyanurate (a) and the polyoxydialkylene di(meth)acrylate (b). The gist is a polyolefin-coated curable resin composition.

The poly[(
meth)acryloyloxyalkyl](iso)cyanurate (a) has the general formula (+)[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 are (meth)acryloyl groups, and R1, R2 and R3 represent oxyalkylene groups or polyoxyalkylene groups. ] is poly[(meth)acryloyloxyalkyl]isocyanurate or poly[(meth)acryloyloxyargyl]cyanurate, tris[(meth)acryloyloxyalkynoly(iso)cyanurate, bis[(meth)acryloyl] tris[oxyalkyl](iso)cyanurate or mixtures thereof;
Those containing (meth)acryloyloxyalkyl coin cyanurate as a main component are preferred. The alkyl group among x 1 , x 2 and x5 is usually an alkyl group having 1 to 4 carbon atoms. Further, R1, R2 and R3 are oxyalkylene groups having a hydrogen atom number of 1 to 12, preferably 2 to 4, or a multimer of the oxyalkylene group, usually 21 to 12 units. body, preferably dimer or tetramer. The poly [(
Specifically, the meth)acryloyloxyalkyl coin cyanurate includes tris(acryloyloxyethyl)in cyanurate 1 tris(methacryloyloxyethyl)in cyanurate, tris(2-acryloyloxypropyl)isocyanurate, tris(2-methacryloyl oxypropyl) isocyanurate, bis(
acryloyloxyethyl) hydroxyethyl isocyanurate\bis(methacryloyloxyethyl)methoxyethyl inocyanurate, bis(2-acryloyloxypropyl)-2-ethoxypropyl isocyanurate, bis(2-methacryloyloxypropyl)-2-
Examples include hydroxypropyl isocyanurate, tris [acryloyl group (oxyethylene)] in cyanurate, tris [methacryloyl group (oxyethylene)] isocyanurate, and mixtures of two or more of these can also be used. . Furthermore, the poly [
(Meth)acryloyloxyalkyl]cyanurate, specifically, tris(acryloyloxyethyl)
Cyanurate, Tris(methacryloyloxyethyl)
Cyanurate, tris(2-acryloyloxypropyl) cyanurate, tris(2-methacryloyloxypropyl) cyanurate, bis(acryloyloxyethyl)hydroxyethyl cyanurate, bis(methacryloyloxyethyl)methoxyethyl cyanurate-bis(2-acryloyloxy propyl)-2-ethoxypropyl cyanurate, bis(2-methacryloyloxypropyl)-2-hydroxypropyl cyanurate,
Tris [acryloyl di(oxyethylene)] diacrylate tris [methacrylic acid di(oxyethylene)]
] Cyanure Nato can be given as an example, and these two
Mixtures of more than one species can also be used.

The polyoxyalkylene di(meth)acrylate (b) blended into the curable resin composition for coating of the present invention is an acrylic ester or methacrylic ester of polyoxyalkylene glycol. The oxyalkylene group constituting the polyoxydialkylene di(meth)acrylate is usually represented by the general formula (It) [wherein R4, R5, R6 and R7 are each a hydrogen atom or a carbon atom number of 1 to 1]
2 shows an alkyl group. ] is a compound represented by
The degree of polymerization of the oxyalkylene group is usually in the range of 1 to 40, preferably 1 to 20. Number average molecule of the polyoxydialkylene di(meth)acrylate! (+, t
n) usually ranges from 200 to 600, preferably from 200 to 1000. Specifically, the polyoxydialkylene di(meth)acrylate-F includes polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, polyoxybropylene diacrylate, polyoxypropylene diacrylate, polyoxypropylene dimethacrylate, Examples include polyoxyethylene polyoxypropylene diacrylate, polyoxyethylene polyoxypropylene dimethacrylate, etc. Among the polyoxyalkylene di(meth)acrylates, polyoxyethylene di(meth)azirylate or polyoxy Propylene dimethacrylate is preferred.The blending ratio of the polyoxydialkylene di(meth)acrylate (b) is 10
It is necessary that the amount is in the range of more than 0 to 1000 parts by weight, and more preferably in the range of 5 to 200 parts by weight. Poly[(meth)acryloyloxyargyl](iso)cyanuride) (a) of the polyoxydialkylene di(meth)azilylate (b) 10
If the blending ratio exceeds 1000 parts by weight to 0 parts by weight, the curability of the outer coating layer in air decreases and ~
Abrasion resistance and pencil hardness will decrease.

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 also include other polymerizable monomer components. It is also possible to copolymerize by adding. Other polymerization components include, for example, by-products or production intermediates during the production of poly[(meth)acryloyloxyalkyl](iso)cyanurate (a), such as mono[(
meth)acryloyloxyalkyl bis(hydroxyalkyl)(iso)cyanurate, by-product or intermediate during the production of polyoxydialkylene di(meth)acrylate (b), such as mono(meth)acrylate of polyoxyalkylene glycol , (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate.

The curable resin composition for coating of the present invention is applied to the surface of a molded article made of polyolefin, and in order to form a film by crosslinking and curing the composition, a polymerization initiator (Q) is added to the composition.
) is required.

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, and specific examples of the photosensitizer include benzoin, benzoin methyl ether,
Benzoin such as benzoin ethyl ethyl, benzoin isopropyl ether, benzoin isobutyl ether or so(r):X--f, benzophenone, p-
Benzophenone compounds such as chlorbenzophenone and p-methoxybenzophenone; benzyl compounds such as benzyl dimethyl ketal and benzyl diethyl ketal; 1-(4-isopropylphenyl)-2-
Hydroxy-2-methyl-1-propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone,
Examples include hydroxyalkylphenylketone compounds such as 1-(4-tert-butylphenyl)-2-hydroxy-2-methy/L'-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 azobisin butyronitrile, benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, dicumyl peroxide, Examples include peroxides such as cumene hydroperoxide. Furthermore, it is also possible to adopt a method in which both a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and UV curing and thermosetting proceed simultaneously.
It is also possible to adopt a method of proceeding with heat curing after proceeding with ultraviolet curing, or conversely, a method of proceeding with ultraviolet curing after proceeding with heat curing. The blending ratio of the polymerization initiator (0) is 0 with respect to a total of 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the polyalkylene di(meth)acrylate (b). It is necessary that the amount is in the range of .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 the same as the poly[(meth)acryloyloxyalkyl](iso)cyanuride)
) and the polyalkylene di(meth)methacrylate (a), if the amount is less than 0.01 part by weight, the polymerizability of the composition decreases and a hard coating cannot be obtained. Moreover, 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,
Stabilizers such as antioxidants, fluorescent brighteners, methyl (meth)
Various additives such as (reactive) oligomers such as acrylate/polyurethane acrylate and polyester acrylate, and polymers such as polymethyl methacrylate can be blended. The blending ratio of these additives is appropriate.

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

The average particle size of the fine powder inorganic filler is arbitrary as long as it is in the form of a powder, but it is usually 1 mμ to 10μ.
, preferably in the range of 1.5 mμ to 1μ. Further, in order to maintain the transparency of the outer coating layer, the refractive index of the fine powder 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, geriatric earth,
Examples include anhydrous silica, hydrated silica, silica stone, silica sand, quartz, kaolinite, montmorillonite, sericite, talc, chlorite, chinastone, and feldspar. Also,
The surface of these finely powdered inorganic fillers is coated with alkyl carboxylates, silane couplers, titanium couplers, Cl
2S1(CH3)2, those whose surface has been treated with alcohol etc. can also be used for 'WJ'. Further, colloidal silica, methanol silica sol, ethanol silica sol, isopropatol silica sol, etc. in which the inorganic filler is suspended in water or alcohol can also be used.

Among these fine powder inorganic fillers, blending fine powder silica significantly improves the surface hardness, scratch resistance and abrasion resistance of the outer coating layer, and impairs transparency and surface gloss. It is particularly preferable because there is no The blending ratio of these fine powder inorganic fillers is based on a total of 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the polyoxyalkylene di(meth)acrylate (b). Usually 0.5 to 2
00 parts by weight, preferably in the range of 0.5 to 100 parts by weight.

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

The solvent is also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. 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, Halogenated hydrocarbons such as ethane chloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobenzene, methanol, ethanol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol Alcohols such as monomethyl ether and diethylene glycol, acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, butyl ethyl ether dibutyl ether,
Ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, nitriles such as acetonitrile, propionitrile, and 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. The blending ratio of these organic solvents is 100% of the mixture of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the polyoxydialkylene di(meth)acrylate (b).
The amount is usually 5 to 3000 parts by weight, preferably 10 to 2000 parts by weight.

In the composition of the present invention, a solution composition or suspension composition is obtained from a composition containing the above-mentioned essential components and various additive components such as inorganic and organic fillers, solvents, and stabilizers added as necessary. The preparation method is to mix the above-mentioned raw material mixture and knead it using a regular roll, Banbury mixer, ball mill, attritor, Witspur, Oakes mixer, Dinluver, homogenizer, colloid mill, sand mill, vibration mill, mixer mixing tank, etc. A uniformly dissolved or dispersed composition can be obtained by the mixing operation. The method for applying the solution composition and suspension composition onto the surface of a molded body made of polyolefin includes:
Conventionally known methods such as a brush coating method, 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. Also 1
Examples of the method for drying the coating include a natural drying method, a forced drying method using a carrier gas, a heating drying method using an infrared oven, a far-infrared oven, and a hot air oven. Further, methods for curing the above-mentioned film to form a film include a method of polymerizing crosslinking and curing with light, especially ultraviolet rays;
Examples include a method of polymerization crosslinking and curing by heat. 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 160°C, and the time is usually 1 sec to 1 hr, preferably 1 hr. sec to 10 m1r). In addition, in the thermosetting method, the temperature for curing is usually -10 to 150°C, preferably 5 to 130°C, and the time required for curing is usually 0.05°C.
to I Q h r % preferably 0.1 to 8 h
It is r.

A polyolefin laminate molded product can be obtained by curing the outer coating layer of a polyolefin molded product coated with the curable resin composition for coating of the present invention. The base resin layer constituting the laminate molded product is a molded product made of polyolefins, and its shape is film-like, sheet-like,
It may be a plate-like or any other shaped molded object.

Specifically, the polyolefins constituting the base resin layer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1
- Homopolymers of α-olefins such as decene, the α-
A copolymer consisting of a mixture of two or more olefins, or a copolymer containing the above α-olefin as a main component, and vinyl acetate,
Vinyl lower aliphatic carboxylates such as vinyl propionate,
Contains a small amount (for example, 30 mol% or less) of other components such as acrylic carboxylic acid esters such as methyl acrylate, metal salts of acrylic acid, methyl methacrylate, and metal salts of methacrylic acid, and salts of acrylic carboxylic acids. Examples include copolymers.

Among these polyolefins, polyolefins having crystallinity are usually used.

When the surface of the base of the polyolefin molded body is coated with a film of the curable resin composition for coating of the present invention, the surface of the base resin layer of the molded body is washed with various solvents, washed with an alkaline aqueous solution, and subjected to surfactant treatment. Various cleaning methods such as chemical cleaning, ultrasonic cleaning, electrolytic cleaning, blasting treatment, sandblasting treatment, acid or alkali etching treatment, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, chemical conversion treatment, etc. surface treatment can be applied. Further, when laminating an outer coating layer made of the curable resin composition for coating of the present invention on the base surface of the molded article made of the polyolefin, an intermediate adhesive layer made of a primer is provided between the base layer and the coating layer. It is also possible to improve the adhesion between both layers by forming a three-layer laminate. As a primer, α, β-unsaturated carboxylic acids, their acid anhydrides, their esters, etc.
- Modified polyolefins grafted with unsaturated carboxylic acids or derivative components thereof are usually used.

In this manner, the composition of the present invention is coated on the surface of the base layer of the polyolefin molded article, which has been subjected to surface treatment or primer treatment as necessary, by the method described above, and is subjected to a curing treatment.

A polyolefin 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, panels for solar water heaters, panels for glove boxes, various lenses such as watch glasses, glasses, and contact lenses, optical prisms, blood bags, and coffee makers. Shower domes, coffee dispensers, water tanks, covers for lighting equipment, covers for stereo equipment such as brake cameras, dials and covers for various meters, covers for car headlamps and tail lamps, level controllers, shatterproof films and separation plates for glass. Various types of films such as molded films, insulating films, and agricultural films; optically regenerated video discs; viewing windows for various devices such as clothes dryers, electric washing machines, dryers, and oil tanks; windshields for motorcycles, jeeps, and motorboats; Automobile glass (windshield, rear window, opera window, triangular window,
Sunroofs), window glass for greenhouses, houses, aquariums, tableware, mirrors, oil bottles, makeup skin, etc. Relay cases, fuse boxes, motorcycle side covers and mudguards, fenders, curtains, screens , tablecloths, waterproof and moisture-proof films, tarpaulins, insulation films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative boards, shelf boards, wall sheets, wallpaper, 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 interior materials, vanity tables, flower boxes, particle boards, roof tiles, rain shutters, shutters, waterproof pans, pipes, wiring materials, gear cams, knobs, solenoid valve frames, fans, 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.

(1) Refractive index 2wt of a sufficiently dried inorganic substance is placed in a liquid with a known refractive index.
% and visually check the transparency after sufficient dispersion.The refractive index should be the same as that of the most transparent liquid.

(2) Surface gloss (gloss) Measured according to 60 degree specular gloss in JISK5400-1979. (3) Light transmittance Measured according to JISK6714.

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

(5) Dropping sand abrasion 800 g of silicon carbide abrasive material is dropped onto the coating according to the method of JIST 8147-1975. 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-
101 Rotate the coating 1000 times with a load of 500 g.

Wear resistance can be measured by the amount of wear on the coating after the test.

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

(7) Pencil hardness Measured according to JISK5651.

(8) Flexibility A strip-shaped test piece with a width of 5 mm and a length of 10 Cr is folded along the outer periphery of a cylinder with a diameter of 2a, and the angle is expressed as the angle at which the coating cracks or peels off from the substrate. The larger the value, the better the flexibility.

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

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

θ1) Volatile oil resistance The 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.

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

('13) After holding the heat cycle resistance test piece at 80°C for 2 hours in an air-open environment, it was left at room temperature for 1 hour, and then kept at -3°C in a cold room for 2 hours, and then at 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.

(14) Weather resistance test The sample was kept in a sunshine weather rotator for 400 hours to evaluate the appearance and adhesion of the outer coating layer.

Example 1 Tris(acryloyloxyethyl)incyanuride)
80gs diethylene glycol diacrylate 20g%
Benzoin isopropyl ether 5g
110g of /I/ene was placed in a 500mff4 tube flask and stirred for 1 hour at room temperature to obtain a transparent coating composition (A).
was created.゛Meanwhile, an injection square plate (thickness 3 mm) made from polypropylene (manufactured by Mitsui Petrochemical Industries KK, trade name Mitsui Petrochemical Voliv OSJ-313) was exposed to 1.1.1~trichloroethane vapor for 1 minute and then heated to room temperature. After drying for 1 minute, the injection square plate was immersed for 20 seconds in a toluene solution CB of 15 g/β of maleic anhydride-modified PIER (propylene content 67 mol%, maleic anhydride content 6 wt%) and slowly pulled up. After drying at room temperature for 5 minutes, at 80 °C for 3
Heat drying was performed for 0 minutes. Next, the coating composition (A
) The polypropylene square plate subjected to the brimer treatment was immersed for 30 seconds, slowly pulled up, and then dried at 60° C. for 5 minutes.

This test piece was heated using a 1-5KW high pressure mercury lamp (12Cw/an).
Below, ultraviolet rays were irradiated for 30 seconds at a distance of 15 CIn to cure the outer coating layer. The film performance is shown in Table 1.

Examples 2-5 In Example 1, the coating composition described in Example 1 (
A) for coatings made using poly[(meth)acryloyloxyalkyl]isocyanurates, polyoxyalkylene diacrylates, photosensitizers and solvents listed in Table 1 in the amounts listed in Table 1 instead of using A). A test piece whose surface was coated with polypropylene was prepared in the same manner as in Example 1 except that the composition was used. The results are shown in Table 1.

Examples 6 to 7 Poly[acryloyloxyalkyl]isocyanurate, polyoxyalkylene diacrylate, photosensitizer, solvent, and methanol silica sol (manufactured by Nissan Chemical, average particle size of about 15 mμ, refractive index of about 1.0 mm) listed in Table 1. A 30% methanol suspension of anhydrous silica (No. 50) was weighed out in the amount shown in Table 1, and mixed with stirring at room temperature for 2 hours to prepare a coating composition (A).

On the other hand, the polypropylene injection rectangular plate used in Example 1 was washed with 1.1.1-) lychloroethane vapor for 30 seconds, dried at room temperature for 1 minute, and then added to the coating composition [η] in the test described above. The piece was immersed for 30 seconds and slowly pulled out. After drying at 60° C. for 5 minutes, the specimen was photopolymerized as described in Example 1 to harden the outer coating layer. The results are shown in Table 1.

Comparative Examples 1 to 3 Prepared by weighing out the amounts of poly[acryloyloxyalkyl]in cyanurate, polyoxyalkylene diacrylate, photosensitizer, and solvent listed in Table 1 and stirring and mixing at room temperature for 1 hour. A test piece was prepared by coating the surface of polypropylene by the method described in Example 1, except that the coating composition [A] was used (Comparative Example 1.2). The results are shown in Table 1. In addition, Table 1 shows the physical properties of polypropylene alone.
The following abbreviations used in Table 1 and Table 2 below represent the following compounds, respectively.

TAEIC...Tris (acryloyloxyethyl)
Isocyanurate BAEIC...Bis(acryloyloxyethyl)hydroxyethyl isocyanurate TMEIC...Tris(methacryloyloxyethyl)in cyanurate DEGDA...Diethylene glycol diacrylate TP()DA...Tripropylene glycol diacrylate NEGDA・・・Nonaethylene glycol diacrylate BIE ・・Benzoin isopropyl ether IHP ・・1-(4-Isofuropylphenyl)-2-Examples 8 to 9, Comparative Example 4 BoIJ = 4-Methyl-1-pentene (Manufactured by Mitsui Petrochemical Industries KK, trade name TPX) 3 mm thick injection molded sheet was molded with maleic anhydride modified EPR (maleic anhydride content 7.7 wt%) (D 15 g/(l concentration (7
)1,1yl-)') Primer treatment was performed by immersing the sample in a li-olethane solution for 10 seconds. After being left at room temperature for 5 minutes, it was immersed in the coating composition described in Example 6 or 7 for 10 seconds. After drying at 60°C for 5 minutes, the sample was photopolymerized by the method described in Example 6 to produce a test piece coated with poly-4-methyl-1-pentene (Example 8.9). The results are shown in Table 2.

In addition, the coating composition of the present invention is not coated with the coating composition of the present invention.
-The physical properties of methyl-1-pentene are shown in Table 2.
2 Applicant Mitsui Petrochemical Industries Co., Ltd. Agent Kazu Yamaguchi

Claims (2)

[Claims] (1) (a) General formula CI) [1a] [Ib] [In the formula, xl, x2 and x3 represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these represent (meth) It is an acryloyl group, and RSR and R3 represent an oxyalkylene group or a polyoxyalkylene group. ] poly[(meth)acryloyloxyalkyl](iso)cyanurate, (b) the poly[(meth)acryloyloxyalkynoly(iso)cyanurate (→0 based on 100 parts by weight)
and (C) the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the polyoxydialkylene di(meth)acrylate in a range of more than 1000 parts by weight. ('b) total 100
A curable resin composition for coating polyolefin, which contains a polymerization initiator in a range of 0.01 to 20 parts by weight. (2) The poly[(meth)acryloyloxyalkyl]
A patent claim containing 0, 5 to 200 parts by weight of a finely powdered inorganic filler based on a total of 100 parts by weight of (iso)cyanurate (a) and the polyoxydialkylene di(meth)acrylate (b). The curable resin composition for polyolefin coating according to scope item (1).