JPS5941366A - Curable coating resin composition - Google Patents

Abstract

PURPOSE:To provide titled composition of excellent curability in the air, capable of giving coating films of high surface hardness and scratch resistance, comprising each specific polymerizable (iso)cyanurate and urethane-based poly (meth)acrylate, and polymerization initiator. CONSTITUTION:The objective composition comprising (A) 100pts.wt. of a poly [(meth)acryloyloxyalkyl] (iso)cyanurate of formula I or II [X<1>, X<2> and X<3> are each (meth)acryloyl, H, or alkyl, at least two of them being (meth)acryloyl; R<1> and R<2> are each (poly)oxyalkylene], (B) up to 1,000pts.wt. (excepting zero) of an urethane-based poly(meth)acrylate having in one molecule, two or more (meth)acryloyloxy group and (C) an initiator such as benzoin methyl ether in such amount as to be 0.01-20pts.wt. per 100pts.wt. of the components (A) plus (B).

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 film 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 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 hindered 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. severely 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 yarn threads or compositions of these components and various polymers, resin compositions of methylolmelamine and other curing components, polyfunctional acrylic carboxylic acid ester derivatives or combinations thereof with other polymeric components. compositions have been proposed. Even if a film layer consisting of these film-forming elements is formed on the surface of a base material of a resin molded product such as polyolefin, the adhesion between the film layer and the base layer of the resin molded product is generally not good. The disadvantage is that the coating layer is easily peeled off. Furthermore, in order to improve these drawbacks, a method is also known in which the surface of the resin molded body base layer is subjected to Type 4 treatment. For example, surface treatments using corona discharge, surface treatments using brimer, etc. have been proposed. However, even if surface treatment is performed, it is often difficult to sufficiently improve the adhesion between the base layer of a resin molded product such as polyolefin and the coating layer made of the crosslinked curable resin 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.

Furthermore, among the film-forming elements described in f41J, various types of compounds have been proposed as polyfunctional acrylic carbonaceous 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) polyhydrogycyl compounds. It is proposed that. 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 has excellent curing properties during curing and has excellent coating properties when coated on the substrate surface of a molded article such as a thermoplastic resin or thermosetting resin. As a result of our investigation, we found that poly[(meth)acryloyloxyalkyl](iso)cyanurate (a), urethane-based poly(meth)acrylate compound (
It has been discovered that the above object can be achieved by using a composition containing 1)) and a specific amount of a polymerization initiator (c), 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 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 relates to (a) general formula [1] 1 [1a] [1b] [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 R, R and R represent an oxyalkylene group or a polyoxyalkylene group. ] represented by poly[(
meth)acryloyloxyalkyl](iso)cyanurate, (b) in the range of more than 0 to 100 parts by weight based on 100 parts by weight of the poly[(meth)acryloyloxyalkyl/L/)(iso)cyanurate (a) A urethane-based poly(meth)acrylate compound having two or more acryloyloxyl groups or methacryloyloxyl groups in one molecule, and (,) the poly[(meth)acryloyloxyalkynoly(iso)cyanurate (a) and the urethane-based poly(meth)acrylate compound (1,,) in total 100
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 poly[(
meth)acryloyloxyalkynoly(yne)cyanuride) (ω is the general formula (1)% formula% () [wherein χ1, 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 RXR and R represent an oxyalkylene group or a polyoxyalkylene group. bianurate or poly[(meth)acryloyloxyalkyl]cyanurate, tris[(meth)acryloyloxyalkyl](iso)cyanurate, bis[(meth)acryloyloxyalkyl](iso)cyanurate, or a mixture thereof There is Tris [(
Those containing meth)acryloyloxyalkyl]incyanurate as a main component are preferred. xl, x2 and x3
The alkyl group is usually an alkyl group having 1 to 4 carbon atoms. Further, RSR and R3 are oxyalkylene groups having 1 to 12 carbon atoms, preferably 2 to 4 carbon atoms, or multimers of the oxyalkylene groups, usually dimers to dodecamers, Preferably it is a dimer or a tetramer. Specifically, the poly[(meth)acryloyloxyalkyl]isocyanurate includes tris(acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, tris(2-acryloyloxypropyl)isocyanurate, and tris(2-acryloyloxypropyl)isocyanurate. -Methacryloyloxypropyl) isocyanurate -Bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)methoxyethyl isocyanurate, bis(2-acryloyloxypropyl)
-2-ethoxypropyl incyanurate, bis(2-
Examples include methacryloyloxypropyl)-2-hydroxypropyl isocyanurate, tris[acryloyl group (oxyethylene)]isocyanurate, tris[methacryloyloxy(oxyethylene)]isocyanurate, and mixtures of two or more of these. You can also use Further, the poly[(meth)acryloyloxyalkyl]cyanurate is specifically tris(acrylic).

yloxyethyl) cyanurate, tris(methacryloyloxyethyl) cyanurate, tris(2-acryloyloxypropyl) cyanurate, tris(2-methacryloyloxypropyl) cyanurate, bis(acryloyloxyethyl)hydroxyethyl cyanurate, bis(methacryloyloxyethyl) ) Methoxyethyl cyanurate, bis(2-acryloyloxypropyl)-2-ethoxypropyl cyanurate, bis(2-
methacryloyloxypropyl)-2-hydroxypropyl cyanurate, Tris[acryloyldi(oxyethylene)]cyanurate, Tris[methacryloyldi(oxyethylene)]
(oxyethylene)] cyanurate, and mixtures of two or more of these may also be used.

The urethane-based poly(meth)acrylate compound (b) blended into the curable resin composition for coating of the present invention has one or more urethane bonds in one molecule and two or more acryloyloxyl groups or methacryloyl groups. It is a (meth)acryle-F based polyfunctional compound having an oxyl group. Specifically, urethane-based poly(meth)acrylate compounds obtained by the reaction of acrylic acid hydroxyalkyl ester and diisocyanate compounds, urethane-based poly(meth)acrylates made of polyurethane polyol poly(meth)acrylates, etc. Examples include acrylate compounds, urethane-based poly(meth)acrylate compounds made of poly(meth)acrylate of polyester-based polyurethane polyols, and the like. The polyol component units constituting these urethane-based poly(meth)acrylate containers include aliphatic polyols, alicyclic polyols, aromatic polyols, polyoxyalkylene glycols, polyoxyalkane polyols, and arylene bis[
Polyoxyalkane copolyol, polyester base I
Examples include ethylene glycol, propylene glycol, butylene glycol,
Hexylene glycol, octylene glycol, glycerin, triltyrrolpropane, pentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol, diethylene glycol, diglycene, ditrimethylolpropane, dipentaerythritol, polyoxyethylene glycol, polyoxyethylene Polyoxypropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, cyclohexylene glycol,
2.2-bis(4-hydroxycyclohexyl)propane, bis(4-hydroxycyclohexyl)methane, 2
, 2-bis(4-hydroxyphenyl)propane, 2.
2-bis(4-hydroxyphenyl)ethane, bis(4
- Hydroxyphenyl)methane, trishydroxyethyl isocyanurate, trishydroxypropylisocyanurate, (meth)acrylates of polyglycidyl ethers of the various polyhydric alcohols; excess of the various polyhydric alcohol component units, succinic acid, and glutaric acid; acid,
Polycarboxylic acid component units such as adipic acid, nouberic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, etc. and polyurethane polyols formed from excess polyol component units of Type 4 described above and diincyanate component units of Type 4 described below.

Furthermore, the diincyanate component units constituting these urethane-based poly(meth)acrylate compounds may be any of aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Of course, it may also be a stryl biscarbonate compound corresponding to these diisocyanate component units or a biscarbamate compound corresponding to these diisocyanate component units. Specifically, the diisocyanate component units of the constituent components include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate,
Decamethylene diisocyanate, dodecamethylene diisocyanate, methylcyclohexane-2,4-diisocyanate, 6-indianatomethyl-3.5.5-
), 4.4'-
Examples include dicyclohexylmethane diisocyanate, isopropylidene bis(4-cyclohexylisocyanate), phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and bistolylene diisocyanate.

A poly(meth)acrylate of a polyurethane polyol is obtained by reacting the polyurethane polyol with acrylic acid or methacrylic acid according to a conventional method in the presence of a catalyst if necessary, and similarly the polyester-based polyurethane polyol and acrylic acid or Poly(meth)acrylate of polyester-based polyurethane polyol is obtained by reacting with methacrylic acid.

Among the urethane-based poly(meth)acrylate compounds, (meth)acrylated hydroxyalkyl which constitutes the urethane-based poly(meth)acrylate compound obtained by the reaction of a (meth)acrylic acid hydroxyalkyl ester and a diisocyanate compound. Examples of the ester component unit include a reaction product of a polyhydroxyl group-containing compound and (meth)acrylic acid, a reaction product of an epoxy compound and (meth)acrylic acid, etc. Specifically, acrylic #!
2-hydroxyethyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylate of glycidyl acrylate, methacrylate of glycidyl acrylate, acrylate of glycidyl methacrylate, Methacrylate of metafluric acid glycidyl ether, glycerin monoacrylate-glycerin monomethacrylate, glycerin-1
, 3-diacrylate, glycerin-1,3-dimethacrylate, trimethylolpropane monoacrylate,
Trimethylolpropane monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate,
dipentaerythritol monoacrylate, dipentaerythritol monomethacrylate, dipentaerythritol diacrylate, dipentaerythritol dimethacrylate, dipentaerythritol triacrylate,
Dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)hydroxyethyl isocyanurate Nurate, diacrylate of propylene glycol diglycidyl ether, dimethacrylate of propylene glycol diglycidyl ether, diacrylate of glycerin-1,3-diglycidyl ether, glycerin-1
, dimethacrylate of 3-diglycidyl ether,
Triacrylate of glycerin triglycidyl ether, trimethacrylate of glycerin triglycidyl ether, diacrylate of pentaerythritol diglycidyl ether, dimethacrylate of pentaerythritol diglycidyl ether, triacrylate of pentaerythritol triglycidyl ether, pentaerythritol Trimethacrylate of triglycidyl ether, diacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, dimethacrylate of 2,2-bis(4-hydroxycyclohexyl)propane diglycidyl ether, 2. Examples include diacrylates of 2-bis(4-hytoexyphenyl)propane diglycidyl ether, dimethacrylates of 2,2-bis(4-hydroxyphenyl)propane diglycidyl ether, and diisocyanates. As the component unit, the compounds exemplified above can be similarly exemplified. Among the urethane-based poly(meth)acrylate compounds (b), urethane-based poly(meth)acrylate compounds containing aliphatic alkylene diisocyanate component units and alicyclic diisocyanate component units as diisocyanate component units are used. ) It is preferable to use an acrylate compound because it improves the hue, weather resistance, and flexibility of the cured film. The blending ratio of the urethane-based poly(meth)acrylate compound (b) is in the range of more than 0 to 1000 parts by weight based on 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a). The amount is preferably in the range of 5 to 500 parts by weight. When the blending ratio of the urethane-based poly(meth)acrylate compound (b) to 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanuride) (a) exceeds 1000 parts by weight, the wear resistance of the coating decreases. surface hardness, etc.

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, a by-product or production intermediate during the production of the urethane-based poly(meth)acrylate compound (b), for example, a urethane-based mono(meth)azirylate compound , and (meth)acrylic acid,
Methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc.
Examples include meth)acrylic acid esters.

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 (0) 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,
As a photosensitizer, benzoin or its ethers such as benzoin, benzoisomethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone such as benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, etc. Benzyl, benzyl dimethyl ketal, benzyl diethyl ketal and other benzyl compounds, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone,
1-phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-tert.

-butylphenyl)-2-hydroxy-2-methyl-1
Examples include hydroxyalkylphenylketone compounds such as -propanone. In the case of curing by heat, a radical initiator is blended, and specific examples of the radical initiator include azo compounds such as azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, di-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 heat curing proceed simultaneously. It is also possible to adopt a method of proceeding with heat curing after proceeding with the heat curing, or conversely, a method of proceeding with ultraviolet curing after proceeding with heat curing. The blending ratio of the polymerization initiator (0) is as follows: the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the urethane poly(meth)acrylate compound (b).
), it is necessary to range from 0.01 to 20 parts by weight, and more preferably from 0.1 to 10 parts by weight, based on a total of 100 parts by weight. The blending ratio of the polymerization initiator is 0 with respect to a total of 100 parts by volume of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (θ) and the urethane-based poly(meth)acrylate compound (b). When the amount is less than 0.011 parts by weight, the polymerizability of the composition decreases, making it impossible to obtain a hard coating, and when it exceeds 20 parts by weight, the coating obtained from the composition becomes yellow colored.

The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned three essential components, but may further include a polymerization inhibitor, a transparent filler, a solvent, an ultraviolet absorber, Various additives such as stabilizers such as antioxidants, fluorescent brighteners, (reactive) oligomers such as methyl (meth)acrylate 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 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 seri. site, talc,
Examples include chlorite, pottery stone, and feldspar. In addition, the surface of these finely powdered inorganic fillers can be coated with alkyl carboxylates, silane couplers, titanium couplers, c
/2s1(cH3)2, those surface-treated with alcohol, etc. can also be used in the same way. 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 finely powdered inorganic fillers, blending finely powdered silica significantly improves the surface hardness, 1 m scratch resistance and abrasion resistance of the outer coating layer, and also impairs transparency and surface gloss. This is especially preferable because it does not cause any problems. The blending ratio of these fine powder inorganic fillers is the same as that of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the urethane-based poly(meth)acrylate compound (
b) Usually 0.5 to 20 for a total of 100 jushabu
0 parts by weight, preferably in the range of 0.5 to 100 parts by weight.

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

The solvent is also used for the purpose of liquefying or suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. 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, 1 bromoform, trichlene, ethylene dichloride, perchloren, Halogenated hydrocarbons such as ethane chloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobenzene, methanol, ethanol, isopropanol,
Alcohols such as butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol, acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, 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, + Examples include esters such as ethyl acetate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate.The proportions of these organic solvents are as described above. Usually 5 to 3000 parts by weight per 100 parts by weight of the mixture of poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and niJ Uziurethane-based polyta)acrylate compound (1)),
Range 9E is preferably 10 to 2000 parts by weight.

In the composition of the present invention, a composition containing the above-mentioned essential components and various additive components such as an inorganic or organic filler, a solvent, a stabilizer, etc. added as necessary, or a solution composition or a suspension composition. The method for preparing is to prepare the above-mentioned raw material mixture and use a regular roll, Banbury mixer,
A uniformly dissolved or dispersed composition can be obtained by kneading and mixing operations using a ball mill, attritor, whipper, oak mixer, dissolver, homogenizer, colloid mill, sand mill, vibration mill, mixer mixing tank, etc. Methods for applying the solution composition and suspension composition onto the substrate surface of the molded article include a brush coating method,
Conventionally known methods such as a spray method, a dipping method, a bar code method, a roll coater method, a spin coater method, and a gel coater method can be employed. Examples of methods for drying the film include natural drying, forced drying using a carrier gas, and heating drying using an infrared oven, far-infrared oven, and hot air oven.

Examples of methods for curing the above-mentioned film to form a film include a method of polymerizing and crosslinking hardening with light, particularly ultraviolet rays, a method of polymerizing and crosslinking hardening with heat, and the like. Among these polymerization crosslinking and curing methods, in the photocuring method, light irradiation is usually carried out at a temperature of -1°C to 150°C, preferably 5 to 130°C, and the time is usually from 1 to 1 hour.

Preferably it is 18θC to 10 min. Also,
In the thermosetting method, the temperature during curing is usually -10 to 150℃.
C1 is preferably 5 to 130'C, and the time required for curing is usually 0.05 to IQhr, preferably 0.1 to 811r.

The curable resin composition for coating of the present invention can be corrugated on the surface of any molded body made of thermoplastic resin, thermosetting resin, metal, etc. It is preferable to coat the substrate surface of the body. The shape of the molded product may be a film, a sheet, a plate, or any other shape.

Specifically, the thermoplastic resin constituting the base layer includes polyolefins such as an α-olefin homopolymer or a copolymer containing α-olefin as a main component;
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 a polyolefin, a polyacrylic ester resin, or a polycarbonate resin, and particularly preferably a polyolefin. Specifically, the polyolefins include ethylene, propylene, 1-butene, 1-hexene, 4-
A homopolymer of α-olefins such as methyl-1-pentene, 1-octene, 1-decene, a copolymer consisting of a mixture of two or more of the α-olefins, or a copolymer containing the α-olefin as a main component, 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, salts of acrylic carboxylic acids, etc. Examples include copolymers containing a small amount (for example, 30 mol% or less) of the component. 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 nacrylate, 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. A specific example of the polycarbonate resin is bisphenol A polycarbonate. Specific examples of the polyester resin include polyethylene terephthalate, polytetramethylene terephthalate, bisphenol A/isophthalic acid/terephthalic acid copolycondensate, and oxybenzoic acid polycondensate. Specific examples of the polyamide resin include nylon 6, nylon 6.6, nylon 1G, and nylon 12. In addition to the above resins, polyacetal, polystyrene, acrylonitrile,
Examples include styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polysulfone resin, polyphenylene oxide, modified polyphenylene oxide, polyphenylene sulfide resin, and polyethersulfone resin.

Specific examples of the thermosetting resin constituting the base layer include unsaturated polyester resin, epoxy 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 base surface of a molded body such as a resin with the curable resin composition for coating of the present invention, the base surface of the molded body may be washed with various solvents, aqueous alkaline solution, surfactant, etc. Ultrasonic cleaning, electrolytic cleaning,
Various surface treatments such as blasting, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, and chemical conversion treatment can be performed.

Furthermore, when laminating an outer coating layer made of the curable resin composition for coating of the present invention on the substrate surface of the molded article, an intermediate adhesive layer made of a primer may be placed between the substrate layer and the outer coating layer. By forming a three-layer laminate, it is also possible to improve the adhesion between both layers. When the base layer is made of polyolefin, the primer may be α,β-unsaturated carboxylic acid anhydride, ester thereof, etc.
-, β-carboxylic acid or a modified polyolefin grafted with a derivative component thereof is usually used. In this manner, the composition of the present invention is coated on the surface of the base layer of the molded article, which has been subjected to surface treatment or primer treatment as necessary, by the above-described method, and is subjected to a curing treatment.

A molded article on which a coating made of the curable resin composition for containers of the present invention is laminated can be used for various purposes.

Specifically, for example, lighting panels, sky domes, panels for Taishi thermal water heaters, panel panels for glove boxes, watch glasses, glasses, cameras, various lenses such as contact lenses, optical prisms, blood bags, Shower domes and coffee containers for coffee makers, water tanks, covers for lighting equipment, covers for stereo devices such as players, dials and covers for various meters, covers for automobile headlamps and taillamps, level sensors, shatterproof films for glass. various films such as mold release films, insulating films, agricultural films, optically playable video discs, viewing windows for various devices such as clothes dryers, electric washing machines, dryers, and oil tanks, windshields for motorcycles, jeeps, motor boats, etc. Glass, automobile glass (windshield, rear window, opera window, triangular window, sunroof), window glass for greenhouses, houses, aquariums, etc., tableware,
Mirrors, various containers such as mirrors and cosmetic bottles, relay cases, fuse boxes, motorcycle side covers and mudguards,
fender) curtains, screens, tablecloths,
Waterproof and moisture-proof film, tarpaulin sheet, insulation film, floor tile, floor sheet, door, chiffle board, wall tile, countertop decorative board, shelf board, wall sheet, wallpaper, furniture, lightweight wallboard, tableware, chairs, bathtub, Toilet bowls, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, ducts, curtain ronds, rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile holes,
Various containers, automobile interior materials, vanity tables, flower boxes, particle boards, roof tiles, shutters, waterproof pans, pipes, wiring materials, hooks, knobs, 1 "If"
m Valve rods, fans, instrument panels, bumpers, brakes, etc. In addition to the above, home appliances, automobile parts,
It can also be used for motorcycle parts, vending machine parts, civil engineering and construction materials, general industrial materials, office information equipment, '#W child parts, packaging materials, sports equipment, medical equipment, and nuclear power related parts.

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 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 JIS K 5400-1979 60 degree specular gloss.

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

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

(5) Sandfall wear according to JIS T 8147-1975 (7) method 8
oog silicon carbide abrasive material is dropped onto the coating. Abrasion resistance can be determined by the difference in surface gloss before and after the test.

The smaller the number, the better the wear resistance.

(6) Taper wear According to the method of ASTM D-1044, wear @cs-
10. Rotate the ruptured membrane 1000 times with a load of 500 g.

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

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

(No Pencil hardness Measured according to JIS K5651.

(8) Flexibility Width: 5 mm) A strip-shaped test piece with a length of 10α is folded along the outer periphery of a cylinder with a diameter of 2α, 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.

(1G) After holding the test piece in a gear set deterioration tester with heat resistance of 8D'C for 400 hours, the appearance and adhesion of the outer coating layer were evaluated.

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

(12) Gasoline resistance test 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) Heat cycle 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 -30°C for 2 hours, and then kept at room temperature for 1 hour. Leave it for a while. 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 held in a sunshine weather rotator for 400 hours to evaluate the appearance and adhesion of the outer coating layer.

In addition, the synthesis example of polyurethane acrylate-F is shown in the following reference example.

Reference Example 1 100 g (0.3 mol) of propylene glycol diglycidyl ether modified with acrylic acid (manufactured by Kyoeisha Yushi Kagaku KK, trade name: Epoxy Ester 70PA) was placed in a 500J4 Turow flask, and 20 g (0.3 mol) of xamethylene diisocyanate was added under a nitrogen atmosphere. , 12 M) and 15 m at room temperature.
After stirring for hours, a urethane-based polyacrylate (PG) consisting of an acrylic acid modified product of propylene glycol diglycidyl ether and a hexamethylene diisocyanate component unit
AHI) was synthesized.

Reference example 2 Dipentaerythritol pentaacrylate 50g (0
,095 mol), 30 g (0-064 mol) of dipentaerythritol tetraacrylate and 20 g of dipentaerythritol tetraacrylate and 120 g of methyl imbutyl ketone were added to 500 m14
The mixture was charged into a Tulo flask, and 17.6 g (0.08 mol) of 6-cyanatomethyl-3.5.5-)limethylcyclohexyl isocyanate was added under a nitrogen atmosphere.
After stirring at room temperature for 15 hours, the dipentaerythritol polyacrylate component unit and 3-incyanatomethyl-3,
Urethane polyacrylate (DPAIP) consisting of 5,5-)limethylcyclohexyl isocyanate component units
) was synthesized in methyl isobutyl ketone.

Reference Example 3 74 g (0.2 M) of bis(acryloyloxyethyl)hydroxyethyl isocyanurate and 100 g of methyl isobutyl ketone were placed in a 500 ml solo flask, and 3.5.
5-) Limethylcyclohexyl isocyaner) 22g
(0.1M) was added, stirred at room temperature for 15 hours, and bis(
acryloyloxyethyl) hydroxyethyl isocyanurate component unit and 3-isocyanatomethyl-3,5
, 5-) Urethane polyacrylate consisting of liminal cyclohexyl isocyanate component units) (BAIIP)
A methyl isobutyl ketone solution was synthesized.

Example 1 Tris(acryloyloxyethyl)isocyanurate)
85g5 Urethane polyacrylate described in Reference Example 1
) (P()AHI) 15 g, benzoin isopropyl ether 5 g and methyl isobutyl ketone 110
Pour g into a 500me4 tube flask and incubate at room temperature for Ihr.
A transparent coating composition (A) was prepared by stirring.

On the other hand, an injection square plate (thickness 3 m + n) made from polypropylene (manufactured by Mitsui Petrochemical Industries KK, trade name Mitsui Petrochemical Polypro S, Y-313) was immersed in 1.1.1-) dichloroethane vapor for 1 minute. After exposing and drying for 1 minute at room temperature, maleic anhydride-modified PER (propylene content km 67 mol%, maleic anhydride content 6 wt%)
20 injection square plates in i5g/# toluene solution [B]
Dip it for a second and slowly pull it out. After drying at room temperature for 5 minutes, heat drying was performed at 80°C for 30 minutes. Next, the polypropylene square plate subjected to the brimer treatment was immersed in the coating composition (A) for 30 seconds, slowly pulled up, and then dried at 60° C. for 5 minutes. This test piece
．． 5 KW high pressure mercury lamp (120W/(711) bottom, 15
The outer coating layer was cured by irradiating it with ultraviolet light for 30 seconds at a distance of cm. The film performance is shown in Table 1.

Example 2 In Example 1, instead of using the coating composition [A] described in Example 1-, tris(acryloyloxyethyl)incyanure ~) 85g5 fE urethane polyacrylate (DpArA) described in Example 2 was used. ) After using a coating composition consisting of 31 g of solution m5, 5 g of benzoin isopropyl ether, and 100 g of methyl isobutyl ketone, a test piece was prepared in which the surface of polypropylene was coated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 In Example 2, the method described in Example 2 was used, except that instead of using the urethane-based polyacrylate solution described in Reference Example 2, the urethane-based polyacrylate (BAIIP) solution described in Reference Example B was used. A test piece was prepared by coating the surface of polypropylene. The results are shown in Table 1.

Examples 4-8 In Example 1, the coating composition described in Example 1 (
A) Instead of using poly[(meta)
Polypropylene was coated in the same manner as in Example 1, except that a coating composition prepared using acryloyloxyalkyl isocyanurate, urethane poly(meth)acrylate, photosensitizer, and solvent as listed in Table 1 was used. A test piece whose surface was coated was prepared. The results are shown in Table 1.

Examples 9-10 Table 1 shows III! Weigh out the amounts of poly[acryloyloxyalkyl]inocyanurate, urethane poly(meth)acrylate, photosensitizer, and 1,1.1-)lychloroethane listed in Table 1, and add to this mixture, stirring, the average particle size. Fine powder silica with a diameter of 20 +all and a refractive index of 1.45 (manufactured by Nippon Aerosil KK, trade name R-972)
was added gradually (amounts used are listed in Table 1) and thoroughly stirred until uniform dispersion was obtained. Thereafter, the mixture was transferred to an attritor (manufactured by Mitsui Miike Seisakusho KK) filled with steatite balls, and mixed for 3 hours by rotating an agitator at 150 rpm while cooling the tank with water. Thereafter, n-butanol in the amount shown in Table 1 was added, and after further mixing for 10 minutes, the mixture was taken out from the attritor to form a coating composition [A]. In Example 1, a test piece having a surface coated with polypropylene was prepared by the method described in Example 1, except that the coating composition described in Example 1 was used instead of the coating composition described in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 2 The amounts of poly[acryloyloxyalkyl]isocyanurate, urethane polyacrylate, photosensitizer, and solvent listed in Table 1 were weighed out and incubated 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) prepared by stirring and mixing with rf'4 was used. The results are shown in Table 1.

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

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

(1) R=H... T'AEIc R: CH6...'IIMEIc (2) ... BAEIC (3) Example 11 Bo IJ -4-methyl-1-pentene (Mikata Petrochemical Industries KK li, product name TPX MXOO4) 5mm
A thick injection molded sheet with maleic anhydride modified to 441 mil>
It was immersed for 10 seconds in a pR (power 1 (water maleic content f1.7wt, %) i5g/e concentration of 1.1.1-) dichloroethane solution to perform brimer treatment. After being left at room temperature for 5 minutes 1a, it was immersed in the coating composition described in Example 9 for 10 seconds.

After drying at 60'C for 5 minutes, photopolymerization was performed using the method described in Example 9 to prepare a test piece whose surface was coated with poly-4-methyl-1-pentene. The results are shown in Table 2.

Examples 12 to 13 In Example 11, instead of using poly-4-methyl-1-pentene as the base polymer, a polymer sheet with a thickness of 3+nro listed in Table 2 was used, and the pretreatments listed in Table 2 were carried out. A test piece whose surface was coated with a polymer was prepared by the method described in Example 11, except that the same procedure was followed. The results are shown in Table 2.

Poly-4-methyl-1-pentene (manufactured by Mikata Petrochemical Industries KK, TPX) not coated with the coating composition of the present invention
Mχ004), polycarbonate (f1 person x Kii!j
, Panlite L-1250) and polymethyl methacrylate (Acrylite R, manufactured by Mitsubishi Rayon KK) are shown in Table 2. 7/ // 7/ / / / / / /

Claims (2)

[Claims] (1) (a) General formula % Formula % () [wherein XXX and X represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these are (meth)acryloyl groups; , RSR and R3 represent an oxyalkylene group or a polyoxyalkylene group. ] Poly[(meth)acryloyloxyalkyl](iso)cyanurate 1 (b) The poly[(meth)acryloyloxyalkyl]
(iso)cyanure) (a) Urethane poly(meth) 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. acrylate compound, and (c) 0.01 to 20 parts by weight based on a total of 100 parts by weight of the poly[(meth)acryloyloxyalkyl](iso)cyanurate (a) and the urethane-based poly(meth)acrylate compound (b). A curable resin composition for coating, comprising: a polymerization initiator in a range of parts by weight. (2) The poly[(meth)acryloyloxyalkyl]
(iso)cyanurate (a) and the urethane poly(
The curing mold for coating according to claim (1), which contains a finely powdered inorganic filler in a range of 0.5 to 200 parts by weight based on a total of 100 parts by weight of the meth)acrylate compound (b). Resin composition.