JPS61136529A - Curable resin composition for coating - Google Patents

Abstract

PURPOSE:The titled composition which, when applied to the surface of a polyolefin molding or the like, can exhibit markedly excellent weather resistance, comprising one or more curable acrylate monomers, a polymerization initiator, a specified ultraviolet absorber and a finely powdered inorganic filler. CONSTITUTION:A curable resin composition for coating is obtained by mixing 100pts.wt one or more curable (meth)acrylate monomers with 0.01-20pts.wt. polymerization initiator, 0.1-20pts.wt. ultraviolet absorber having a maximum absorption wavelength in the range of 260-370nm and a molar extinction coefficient at 300nm>=5,000l/mol.cm and 0-200pts.wt. finely powdered inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a curable resin composition for coating, which exhibits extremely excellent weather resistance when coated on the surface of a polyolefin molded article or the like.

[Conventional technology]

By coating the surface of polyolefin molded products, etc.
Excellent curing properties such as curing speed in air, surface hardness, scratch resistance, abrasion resistance, flexibility, surface gloss, heat resistance, water resistance, solvent resistance, and adhesion to substrate polyolefin, etc. Regarding curable resin compositions for coating with excellent coating properties, those proposed by the present applicant have been previously disclosed (% 59-20313, 59-30810,
59-25840, 59-33311, 59-3
6113, 59-41366, 59-56462,
59-66462, 59-78242, 59-7
8242゜59-89331, 59-89367,
59-66410, etc.) However, further improvement of the above characteristics is desired.

Conventionally, the technology of adding ultraviolet absorbers as weather stabilizers to coatings and curable coating resins used for molded products such as polymers has been
Already known. For example, JP-A-56-127655
discloses a technique in which a specific ultraviolet absorber is added to a specific monomer mixture that is cured by ultraviolet light. but,
This curable resin composition has a slow curing speed due to ultraviolet rays,
Moreover, it lacks basic performance as a curable resin for coating, such as poor paintability and adhesion to coated substrates that do not have functional groups, such as polyolefin molded articles.

Further, JP-A-58-215428 discloses a paint comprising a curing component and an ultraviolet absorber that is applied to the surface of a polycarbonate molded product, but it is still inferior in paintability and adhesion to polyolefin molded products.

Others: JP-A No. 55-102652, No. 56-8124
2, 58-213075, 56-92059, 5
6-92060゜57-57772, 57-167
327, 59-4626, 59-24728, etc., when applying a specific coating composition to a specific resin molded article in one or two layers, a specific ultraviolet absorber is added to the coating composition. However, the composition is essentially different from the composition of the present application, the coating thickness is large, the use of special ultraviolet absorbers is expensive, and the coating may be coated on specific objects. There are various drawbacks such as limited UV absorber content and poor strength of the coating film depending on the content of the UV absorber0 [Problems to be solved by the invention] The object of the present invention can also be applied to polyolefin molded products. The object of the present invention is to provide a curable resin composition for coating that has excellent coating properties even when applied relatively thinly, is free from the problems described above, and has excellent weather resistance stability.

[Summary of the invention]

The present invention includes 100 parts by weight of one or more curable (meth)acrylate monomers (CA), a polymerization initiator (Bl
: Range of 0.01 to 20 parts by weight, maximum absorption wavelength is 2
60 to 370 nm and a molar extinction coefficient at 300 nm of 7>(500011/mol-cm or more) UV absorber CI: Q, in the range of 1 to 20 !i parts, 2 and finely powdered inorganic filler 0: The gist of the present invention is a curable resin composition for coating in a range of 0 to 200 parts by weight.

[Curable (meth)acrylate monomer (g)] Examples of the curable (meth)acrylate monomer (6) used in the composition of the present invention include! TF Kaisho 59-2031
6 or poly[(meta) described in JP-A-59-30810
Acryloyloxyalkyl](iso)cyanurate (
a,), bis[(meth)acryloyloxyalkyl](iso)cyanurate (fa,) described in JP-A-59-98115, JP-A-59-66462 or JP-A-59-
Poly(meth)acrylate of polyepoxy compound described in No. 78242 (a, > S JP-A-59-89331
The urethane poly(meth)acrylate compound (a4) having two or more meta (acryloyloxy groups) in one molecule described in JP-A-59-89367; (Meth)acrylate compound (a5>% JP-A-59-6
6410, which has at least 3 or more hydroxyl groups in one molecule and still has one or more ether bonds in 1 molecule and 6410.
A poly(meth)acrylate product (a6) of a polyoxyalkane polyionyl having at least three hydroxyl groups, a poly(methane acrylate product (a6)) having at least three or more acryloyloxyl groups or methacryloyloxyl groups; The poly(meth)acrylate may have a hydroxyl group.

Furthermore, as another (3), JP-A-59-124961
Poly(meth)acrylates (a?) of aliphatic polyols described in JP-A-59-20313, di(meth)acrylates or polyoxydialkylene di(meth)acrylates-Bag) of alkane polyols described in JP-A-59-20313, esp. Examples include arylene bis[polyoxyalkylene (meth)acrylate] (as) described in 1983-33311. The monomers exemplified here can be used singly as long as they are monomers with trifunctionality or more, but usually not only difunctional monomers but also monomers with hexafunctionality or more can be used. It is preferable to mix and use more than one species. Such a mixed system is 1, for example, (al) and (as) (%
1986-20313, 1973-30810), (al
) and (a6) (59-25840), (”+) and (
as) (59-33311), (a,) and (as) (
59-36113), (al) and (a4) (59-36113), (al) and (a4)
41366), (al) and (as) (59-5646)
2), (a4) and (as) (59-89331), (
a, ) and (8,9) (59-89367>, (a,
) and other monomers (59-
124961), a mixture of (-) and other monomers belonging to (3) (59-98115), and the like.

[(G) Specific examples of ingredients]

Specifically, (a,) in the above hole is tris(acryloyloxyethyl)(iso)cyanurate, tris(methacryloyloxyethyl)(iso)cyanurate, tris(2-acryloyloxypropyl)(iso)
Cyanurate, tris(2-#'acryloyloxypropyl)(iso)cyanurate, his(acryloyloxyethyl)hydroxyethyl(iso)cyanurate, bis(methacryloyloxyethyl)methoxyethyl(iso)cyanurate.

Bis(2-acryloyloxypropyl)-2-ethoxypropyl(yne) cyanurate, bis(2-methacryloyloxypropyl)-2-hydroxypropyl(yne) cyanurate, tris[acryloyldi(oxyethylene)](iso)cyanurate, Examples include tris[, di(oxyethylene) methacrylate](iso)cyanurate, and (a?) is
- specifically, his[acryloyloxyethyl](iso)
Cyanurate, bis(methacryloyloxyethylbis(2-acryloyloxy/propyl)(yne)cyanurate, bis(2-methacryloyloxypropyl)
(iso) cyanurate, hiss[acryloyl oxy, 7 di(oxy 7 ethylene))(yne) cyanurate, bis[methacryloyl oxy 7 di(oxy 7 ethylene)](iso) cyanurate, etc. can be exemplified, and (aS ) is a polyepoxy compound formed from an aliphatic, alicyclic or aromatic polyepoxy compound having at least two epoxy groups in one molecule and acrylic acid or methacrylic acid. meth) acrylate, more specifically disclosed in JP-A-59-66462 or JP-A-59-66462.
9-78242, and (a4) is specifically a urethane-based poly(meth) obtained by the reaction of a (meth)acrylic acid ester having a hydroxyl group and a diisocyanate compound. Acrylate compounds, urethane-based poly(meth)acrylate compounds consisting of poly(meth)acrylates of polyurethane polyols, poly(meth)acrylate compounds of polyester-based polyurethane polyols,
Examples include urethane-based poly(meth)azilylate compounds consisting of meth)acrylate, and more specifically, those disclosed in JP-A-59-89331, where ali and (a,) are aliphatic It is obtained by reacting a polyester polyol formed from an alicyclic, alicyclic or aromatic polyol and a polycarboxylic acid with acrylic acid or methacrylic acid in the presence of a catalyst if necessary, and further Specifically, Japanese Patent Publication No. 59-893
67. fd as mat; au),
iSpecifically, glycerin triac no/-1・, g・
Note・no/i Rimethacrylate, Trimethylolethane Triacrylate, Trimethylolethane Trimethacrylate, Trimethylolpropane Triacrylate, Trimethylolpropane Trimethacrylate, Pentaerythritol Tetraacrylate, Pentaerythritol Tetramethacrylate, Pentaerythritol Trimethacrylate Triglycerin Acrylate, diglycerine trimethacrylate, diglycerine tetraacrylate, diglycerine tetramethacrylate, triglycerine triacrylate, triglycerine trimethacrylate, triglycerine tetraacrylate, triglycerine tetramethacrylate, triglycerine pentaacrylate, triglycerine pentamethacrylate, ditrimethylolpropane Triacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, tritrimethylolpropane triacrylate.

tritrimethylolpropane pentaacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate,
Examples include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate.

(a?) is dipentaerythritol penta(
Methane acrylate mono[(meth)acryloyloxycaprolactoate], dipentaerythritol-tetra(meth)acrylate bis[(meth)acryloyloxycaprolactoate], dipentaerythritol tri(meth)acrylate Tris [(meth)acryloyloxycaprolactoate], dipentaerythritol di(meth)acrylate tetra[(meth)acryloyloxycaprolactoate], dipentaerythritol di(meth)acrylate base/tetra[(meth)acrylate] ) acryloyloxycaprolactoate], dipentaerythritol hexa[(meth)acryloyloxycaprolactoate], dipentaerythritol pentaacrylate mono[(methane acryloyl leokinodine)
caprolactoate)], dipentaerythritol tetra(meth)acrylate bis[(meth)acryloyloxib (caprolactone i), dipentaerythritol tri(meth)acrylate tris[(meth)acryloyloxib (caprolactone)] ate)], dipentaerythritol di(meth)acrylate tetra[(meth)acryloyloxib (caprolactoate)],
Dipentaerythritol mono(meth)acrylate pen/di[(meth)acryloyloxydi(caprolactoate)], dipentaerythritol hexa[(meth)
acryloyloxib (caprolactoate)), dipentaeri, thritol hexa[(meth)acryloyloxytri(caprolactoate)], dipentaerythritol hexa[(meth)acryloyloxytetra(caprolactoate)] ], dipentaerythritol hexa[(meth)acryloyloxypenta(caprolactoate)], dipentaerythritol hexa[(
(meth)acryloyl ox-7 hexa(caprolactoate)], etc., and (a8) is,
Specifically, 1,2-diacryloyloxyethane, 1
, 2-dimethacryloyloxyethane, 1.2-diacryloyloxypropane, 1.2-dimethacryloyloxypropane, 1.3-diacryloyloxypropane, 1.3-dimethacryloyloxypropane, 2,2-
Dimethyl-1゜3-diacryloyloxypropane, 2
．． 2-dimethyl-1,3 dimethacryloyloxypropane, 1,4-diacryloyloxybutane, 1,4-dimethacryloyloxybutane, 1,3-diacryloyloxypentane, 1,3-dimethacryloyloxypentane, 1.6-diacryloyloxyhexane, 1,
6-dimethacryloyloxyhexane, 1,8-diacryloyloxyoctane, 1,8-dimethacryloyloxyethane, 1,10-diacryloyloxydecane, 1,10-dimethacryloyloxydecane, glycerin-1,6- Diacrylate, glycerin-1,3-dimethacrylate, glycerin triacrylate, pentaerythritol diacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol dimethacrylate, be/taerythritol trimethacrylate Examples include acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, etc. As for (a), a phenolic hydroxyl group of a dihydric phenol and two polyoxyalkylene glycols are combined into an ether. Acrylic or methacrylic esters of glycol compounds combined by the formation of polymers. In the summer, specifically, Japanese Patent Application Publication No. 1987-
33311 can be mentioned.

[Polymerization initiator 0] 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, it is necessary to add 0 polymerization initiator to this composition. It is necessary to incorporate Curing methods include ultraviolet curing method,
A curing method using hot wire is usually employed. In the case of ultraviolet curing, a photosensitizer is blended as a polymerization initiator, and specific photosensitizers include penzoin maters such as benzoin, benzoin methyl ether, benzine ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. The ether, benzophenone, p
- Benzophenone compounds such as chlorobenzophenone and p-methoxybenzophenone; benzyl compounds such as benzyl, pencil methyl ketal, and benzyl diethyl ketal (1z compound, 1-(4-isopropylphenyl))
-2-hydroxy-2-meth-1-propanone, 1-
Phenyl-2-hydroxy-2-methyl-1-propano:y, 1-(4-tert-butylphenyl)-
Examples include hydroxyalkylphenyl keto/type compounds such as 2-hydroxy-2-methyl-1-7'Opanone. 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, and citrate.
Examples include peroxides such as -butyl peroxide, dicumyl peroxide, and cumene hydroperoxide. Furthermore, in the curable resin composition for coating of the present invention,
It is possible to adopt a method in which both a photosensitizer and a radical initiator are blended and to proceed with ultraviolet curing and heat curing simultaneously, or a method in which heat curing proceeds after ultraviolet curing can be adopted. Alternatively, it is also possible to use a method in which UV curing is performed after heat curing. The blending ratio of the polymerization initiator 0 is:
0.0 parts by weight per 100 parts by weight of the curable (meth)acrylate monomer (A) which is one type or a mixture of two or more types.
It is necessary that the amount is in the range of 1 to 20 parts by weight, and preferably in the range of 0.1 to 10 parts by weight for awns. If the blending ratio of the polymerization initiator is less than 0.01 part by weight per 100 parts by weight of the adhesive, the polymerizability of the composition will decrease and a hard coating will not be obtained. Moreover, if the amount exceeds 20 parts, the coating obtained from the composition will be colored yellow.

[Ultraviolet absorber 0] The ultraviolet absorber as used in the present invention includes not only an ultraviolet absorber used in a narrow sense but also a quencher.

The ultraviolet absorber 0 used in the composition of the present invention has a maximum absorption wavelength of 260 to 370 nm, preferably 270 nm.
360 nm to 360 nm, more preferably 275 to 350 nm
and has a molar extinction coefficient of 50 at 300 nm.
00#/ipo1-cm or more, preferably 80006/
rr+ol-m or more, more preferably 100004/m
ol·m or more. Maximum absorption wavelength is 2 above
Is it outside the range of 60 to 370 nm or has a molar extinction coefficient of 5000j? Even if less than /mol・m is used, the objective of the present invention is to obtain aS with better weather resistance.
T fat cannot be obtained.

The ratio of ◎ to the curable monomer surface is 0.1 to 2.
0M parts, preferably in the range of 0.5 to 18 parts by weight, more preferably in the range of 1 to 15 parts by weight, and if it is less than this essential range, sufficient weather resistance will not be obtained as described above; Exceeding this is generally not only uneconomical, but also tends to cause the cured film to become discolored, and furthermore, the surface hardness, sweep resistance, abrasion resistance, adhesion, etc. of the film become poor.

Specific examples of the ultraviolet absorber ◎ include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2゜2'-
Hydroxy-4'-benzophenone, 4-hydroxy-
2-hydroxybenzophenone, 2-hydroxy-2I
-Carboxy-4-methoxybenzophenol etc./
Siphenone series, ethyl-2-/ano-6,3-diphenylacrylate, methyl-2-/ano-3-methyl-3
-(4'-Methoxyphenyl)acrylate, substituted acrylonitriles such as 2-ethylheyacyl-2-cyano-6゜3-diphenylacrylate, 2-(2'-hydroxy-5'-methyl-phenyl)penztriazole, 2 -(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5
1-t-octylphenyl)penztriazole, 2-
(2'-hydroxy-3,'5'-di-t-butylphenyl)-5-chlorobenzazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-
Benzotriazole series such as 5-10 Lopenzotriazole, N-(2-ethylphenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic acid diamide, N-(
p-ethoxycarbonylphenyl)-N'-ethyl-N
'-Phenylformamibuin, etc. are used. Among these, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
Ethyl-2-cyano-3,3-diphenylacrylate, Methyl-2-cyano-6-methyl-3-(4'-methoxyphenyl)acrylate, 2-(2'-hydroxy-5/-methyl-phenyl)benzo Triazole, 2-
(2'-hydroxy 5r + t-butylphenylnohensotriazole, N-(2-ethylphenyl)-N'
-(2-Ethoxy-5-t-butylphenyl)oxalic acid diamide and the like are excellent in terms of compatibility with the curing composition and weather resistance imparting effect.

[Fine powder inorganic filler 0] In the curable resin composition for coating of the present invention, fine powder inorganic filler 0 may be blended as necessary within the range that maintains the transparency of the cured film obtained therefrom. There is no problem. The average particle size of the finely powdered inorganic filler is arbitrary as long as it is in the form of a powder, but it is usually between 1 mμ and 10 mμ.
μ, preferably in the range of 1.5 mμ to 1 μ. In addition, in order to maintain the transparency of the outer coating layer, the refractive index of the finely powdered inorganic filler is usually 1.40 to 1.60,
It is preferably in the range of 1.42 to 1.58. Specific examples of such fine powder inorganic fillers include crow powder, mica, glass peas, crow flakes, anhydrous silica, hydrated silica, silica, silica sand, quartz, kaolinite, montmorillonite, and seri. Examples include silica, talc, chlorite, chinastone, and feldspar.

Further, these finely powdered inorganic fillers whose surfaces have been surface-treated with an alkyl carboxylate salt, a sila/coupler, a titanium coupler, Cjt2Sl (GH3)2, alcohol, etc. can also be used. Further, colloidal silica, methanol silica sol, ethanol silica sol, ingropanol silica sol, etc. in which the inorganic filler is suspended in water or alcohol can also be used. Among these fine powder inorganic fillers,
Incorporation of finely powdered silica is particularly preferred because the surface hardness, scratch resistance, and abrasion resistance of the outer core coating layer are significantly improved, and transparency and surface gloss are not impaired. The blending ratio of these finely powdered inorganic fillers is Ofc 200 parts by weight, preferably 0.
The amount ranges from 5 to 100 parts by weight.

[Bear ingredients]

The curable resin composition for coating of the present invention may be a composition consisting only of the above-mentioned four components, but may also contain stabilizers such as polymerization inhibitors, transparent fillers, solvents, and antioxidants, if necessary. , fluorescent brighteners, leveling agents, wetting improvers, (reactive) oligomers such as methyl (meth)acrylate, polyurethane acrylate, polyester acrylate, and polymers such as polymethyl methacrylate. can. The blending ratio of these additives can be determined as appropriate.

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 the elasticity of the molded product. Examples of solvents include hydrocarbons such as bene, toluene, xylene, kume, ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, and methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, and bromoform. , tricrene, ethylene dichloride, perchlorene, ethane trichloride, ethane tetrachloride, propylene dichloride, chlorobenzene,
Halogenated hydrocarbons such as bromobenzene, alcohols such as methanol, ethanol, impropatol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, chrycerin, ethylene glycol monomethyl ether, diethylene glycol, acetone, methyl ethyl ketone , methyl isobutyl ketone, ketones such as cyclohexanone, dibutyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethers of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, nitriles such as acetonitrile, propionitrile, capronitrile, methyl formate , ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, methyl benzoate, ethyl benzoate, and other esters.

The blending ratio of these organic solvents is 10% of the above monomer (8).
The amount is usually 5 to 3,000 parts by weight, preferably 10 to 2,000 parts by weight.

[Preparation method, etc.]

In the composition of the present invention, the above-mentioned essential components and various additive components such as inorganic or organic fillers, solvents, stabilizers, etc. added as necessary can be mixed into a solution composition or a suspension liquid composition. The method for preparing is to prepare the above-mentioned raw material mixture and use a regular roll or Banbury mixer.
A uniformly dissolved or dispersed composition can be obtained by cross-mixing operations using a ball mill, an attritor, a whisker, an oak mixer, a dissolver, a homogenizer, a colloid mill, a sand mill, a vibration mill, a mixer, a mixing tank, or the like. Methods for applying the solution composition and suspension composition onto the substrate surface of the molded article include a brush coating method, a spray method, a dipping method, a bar code method, a roll coater method, a spin coater method, Conventionally known methods such as the gel coater method can be employed. Examples of methods for drying the film include natural drying, forced drying using a carrier gas, heating drying using an infrared oven, far-infrared oven, and hot air oven. Examples of methods for curing the material to form a film include a method of polymerizing and crosslinking hardening with light, particularly ultraviolet rays, and a method of polymerizing and crosslinking hardening with 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 130°C, and the time is usually I519C to 1 hr, preferably 1SeC to 130°C. It is 1Qmin. In the heat curing method, the temperature during curing is usually -10 to 150°C, preferably 5 to 1
The temperature is 30° C., and the time required for curing is usually 0.605 to 10 hr, preferably 0.1 to 8 hr.

[Basic body]

The multi-use curable resin composition of the present invention can be coated on the substrate surface of any molded body made of thermoplastic resin, thermosetting resin, metal, wood, ceramics, etc.
It is preferable to coat the substrate surface of a molded article made of thermoplastic resin. The shape of the molded product is film-like, sheet-like,
It may be a plate-like or any other shaped molded object.

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, and 4-metallic acid.
- A homopolymer of α-olefins such as pentene, 1-octene, and 1-decennato, 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 vinyl acetate, propion A small amount of other ingredients such as lower aliphatic vinyl carboxylates such as vinyl acrylates, acrylic carboxylic acid esters such as methyl acrylate, metal salts of acrylic acid, methyl methacrylate, metal salts of methacrylic acid, and salts of acrylic carboxylic acids. (For example, 3
0 mol% or less) can be exemplified. Among these polyolefins, polyolefins having crystallinity are usually used. Specifically, the polyacrylic carboxylic acid ester resin is
Examples include homopolymers or copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Among these polyacrylic carboxylic acid ester resins, it is preferable to use polymethyl methacrylate in the thermoplastic resin base resin layer of the present invention. Specific examples of the polycarbonate resin include bisphenol A polycarbonate.

Specifically, the polyester resin includes polyethylene terephthalate, polytetramethylene terephthalate,
Examples include bisphenol A/inphthalic acid/terephthalic acid copolycondensate and oxybenzoic acid polycondensate. Specifically, the polyamide resin may be nylon 6, nylon 6.6, nylon 0, nylon 12, or the like. In addition to the above resins, polyacetal, polystyrene, acrylonitrile/styrene copolymer, acrylonitrile/butaje/styrene copolymer, polysulfone resin, polyphenylene oxide,
Examples include modified polyphenylene oxide, polyphenylene sulfide resin, and polyether sulfone resin.

Specifically, the thermosetting resin constituting the base layer (''i
Examples include unsaturated polyester resins, epoxy resins, polybismaleimide resins, diallyl phthalate $ttJIW, and Horiyori glycol carbonate resins.

Furthermore, specific examples of the metal constituting the base layer include aluminum, iron, stainless steel, and the like.

As mentioned above, the curable resin composition for coating of the present invention is preferably used for base resin molded articles of polyolefins, polyacrylic acid ester resins, or polycarbonate resins, but especially when these are colored with pigments, the present invention It has a remarkable effect. That is, the present inventors found that when the base resin is colored with a pigment, the weather resistance of the film is poor even if a normal long-curable composition is used. It has been found that using the compositions of the invention, the weather resistance is significantly the same.

Coloring pigments in the above case include calcium carbonate, zinc zinc, titanium oxide, carbon black yellow lead (chrome yellow),
cadmium yellow, iron oxide, cadmium red,
Rose red, cadmium orange, cobalt purple, manganese purple, fast violet 81 ultramarine (Ultramarine), dark blue (Milo IJ-7'#-) cobalt flu, phthalocyanine blue, chrome green, chromium oxide, zinc sulfide, aluminum powder, copper There are powders etc.
The composition of the present invention is used for white colored substrates with titanium oxide, purple colored substrates with cobalt violet and manganese violet, blue colored substrates with ultramarine, cobalt blue, and navy blue (milory blue), green colored substrates with chromium oxide, etc. It is particularly preferable to do so. Furthermore, among the basic resins, it is particularly preferable to use them for polyolefin bases.

[Covering]

When coating the substrate surface of a molded object such as a resin with the curable resin composition for coating plates of the present invention, the substrate surface of the molded object is washed with various solvents, washed with an alkaline aqueous solution, and washed with a surfactant. Cleaning, ultrasonic cleaning, electrolytic cleaning, blasting, sandblasting, acid or alkali etching.

Various surface treatments such as 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 Ln body, it is also possible to improve the adhesion between both layers. When the base resin layer is a polyolefin, the primer may be a modified resin grafted with an α,β-unsaturated carboxylic acid or its derivative component such as an α,β-unsaturated carboxylic acid, its acid anhydride, or its ester. Polyolefins are commonly 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 coating of the present invention is laminated can be used for various purposes.

Specifically, examples include daylight panels, sky domes, solar water heater panels, glove box panels, watch glasses, individual lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, and coffee makers. 7 Lower domes, coffee containers, water tanks, covers for lighting equipment, covers for stereo equipment such as players, dials and covers for various meters, covers for car headlamps or tail lamps, level sensors, shatterproof films for glass, etc. Various films such as release films, insulating films, agricultural films, optically playable video discs, sight windows for various equipment such as clothes dryers, electric washers, dryers, oil tanks, etc., and for motorcycles, jeeps, motor boats, etc. Windshield glass, automobile glass (windshield, rear window, opera window, triangular window,
sunroofs), window glass for heat sinks, houses, aquariums, etc., tableware, mirrors, various containers for makeup and cosmetics, relay cases, fuse boxes, motorcycle side covers and mudguards, fenders, curtains, screens. , - Table cloth, waterproof moisture-proof film, tarpaulin sheet, loquat film, floor tile, floor sheet, door, table board, wall tile, countertop decorative board, sill board, wall/sheet, wallpaper, furniture, lightweight wall board , tableware, utensils, bathtubs, toilets, refrigerators, wall panels, water supply and drainage pipes, wiring pipes, ducts, curtain ronds,
Rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foil, and various containers.

Examples include automobile interior materials, vanity tables, flower boxes, particle boards, roof tiles, shutters, waterproof pans, pipes, wiring materials, gear cams, knobs, solenoid valve frames, fans, instrument panels, pan bars, and brakes. In addition to the above, we also produce home appliances, automobile parts, motorcycle parts, vending machine parts, civil engineering and construction materials, general industrial materials, office information equipment, electronic parts, and packaging materials.

It can also be used in sports equipment, medical equipment, and nuclear power related parts.

〔Example〕

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 (cloth) It was performed according to the 60 degree specular gloss in JISK5400-1979.

(8) Light transmittance It was carried out according to JISk6714.

(4) Adhesion A cross-over test in JIS K5400-1979 was conducted. The judgment is based on how many out of 100 gopans are glued together.

(5) Sandfall abrasion 800 according to JIST8147-1975 (7) method
FO silicon carbide abrasive material is dropped onto the ruptured membrane. For opaque substrates, abrasion resistance can be determined by the difference in surface gloss (cross) before and after the test.

For transparent materials, wear resistance is determined by the difference in haze before and after the test. Yes, Haze is ASTM D
Measured according to -1003K.

As for these wear values, the smaller the number, the better the wear resistance.

(6) Taper wear ASTM D-1044c7) Based on method, worn wheel O
3-10, rotate the coating 1000 times with a load of 500 g.

For opaque materials, the abrasion resistance can be measured by the amount of abrasion of the coating after the test. The smaller the amount of wear, the better the wear resistance.

In addition, regarding the transparent material, the wear resistance was not improved due to the increase in haze after the test.

(7) Pencil hardness Measured according to JISk5651.

(8) A strip-shaped test piece with a flexible width of 511L and a length of 10 crn 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 acceptability.

(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.

After holding the test piece in a gear aging tester at 80° C. for 400 hours, the appearance and adhesion of the outer coating layer were evaluated.

(11) 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.

((2) Heat cycle resistance The test piece was kept in an air-open environment at 80°C for 2 hours, then left at room temperature for 1 hour, and then placed in a cold room at -30°C for 2 hours.
Hold for an hour and then leave at room temperature for 1 hour. This cycle was repeated 10 times, and changes in the appearance of the outer coating layer were visually observed and adhesion was evaluated.

(15) Weather resistance (adhesion retention time) A test piece was held in a sunshine weather rotator, and the time required for the adhesion of the outer coating to pass was evaluated.

(14) Maximum absorption wavelength and molar extinction coefficient 10 g of the ultraviolet absorber was accurately weighed and dissolved in 1β ethanol. This solution was placed in a cell with a thickness of 1 (11,771 mm) and measured using a spectrophotometer (manufactured by Shimadzu Corporation, MPS-5000).
Spectra were measured in the 400u wavelength range. The wavelength showing the maximum absorption in this spectrum was read and defined as the maximum absorption wavelength. Moreover, the molar extinction coefficient (1) was calculated by the following formula.

TO ε=Log (=7) where C: i degrees (mole//l) β: cell thickness cIn) To, T: Intensity of incident light and transmitted light Ultraviolet rays used in Examples and Comparative Examples Abbreviation symbol for absorber Ultraviolet absorber Abbreviation Maximum absorption wavelength Molar extinction coefficient (BO)
(mole/#) Benzophenone BP 257
504-t-butylph BPS 2
45 4,500 enyl salicylate 2-hydroxy-HMB 287
12,0004-methoxybenzophenoneethyl-2-thia ECDA 305
10,300 No 3,5-diphenylacrylate methyl-2-thia MCIAA 318
11.500 No 3-methyl-3-(4'-methoxyphenyl) (mole Otsu no 2-(2'-human) HMPB 340
14,000 Roxy 51 methyl-phenyl)benzotriazole 2-(2'-human HBPB 340
24,800 Roxy5'-t-butylphenyl)benzotriazole N-(2-xf EPEA 305
21,100 phenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic acid amide Also, in the Examples and Comparative Examples of this patent, curable (meth)acrylate monomer and polymerization initiator◎ The following abbreviations were used for each.

(al) TAEIC) Lis(acryloyloxyethyl)in cyanurate (a,) BAEIC Bis(acryloyloxyethyl)in cyanurate (a,) PGGA Diacrylate of propylene glycol diglycidyl ether BPGA 2,2-bis(4 -Hydroxyphenyl) diacrylate of propane diglycidyl ether (a4) HOAU PIHA (a6) PETA Pentaerythritol tetraacrylate DPHA Dipentaerythritol hexaacrylate (at) DPCA Dipentaerythritol hexa[acryloyloxyly(caprolactoate) )] (a,), HDA 1.6-Hexanediol diacrylate NPA Neo-pentyl glycol diacrylate (aJ 88D) VP 2.2-bis(4-
Acryloyloxyjetoxyphenyl)propane (El) B Engineering E Penzoin isopropylethe IHP 1-(4-isopropylphenyl)-2-hydroxy-2-methyl- 1-propanone HMPP 2-hydroxy-2-methyl-1- Phenyl-1-propanone In addition, the following reference examples include a method for synthesizing acrylates of polyester polyols and n-butanol silica J.
The manufacturing method for this was shown.

Reference example 1 Pentaerythritol 136L Cono-1 hydric acid 59g Para-toluenesulfonic acid 3.5', Toluene 10'Og
The esterification reaction was carried out at 150°C for 2 hours in a nitrogen atmosphere, and after cooling, 220 g of acrylic acid was added. No Idoroki/: y5g, Toluei y200. ! Add i', 120
The esterification reaction was carried out at ℃f for 4 hours. After washing the reaction solution with weak alkaline water and water, hydroquinone was removed by o. osy was added and low-boiling substances were distilled off to obtain a polyacrylate of polyester polyol having an average molecular weight of 700. It was confirmed by N~(H) that the average number of double bonds in one molecule of the polyacrylate of this polyester polyol is 4.2.This curable acrylate monomer is hereinafter referred to as PE.
It is abbreviated as PA.

Reference example 2 300g of methanol silica sol (manufactured by Nichichi Kagaku) is 1.5
After adding 210 g of n-butanol to the pear-shaped flask in Step 4, set the water bath at 80℃ and filter the filter Qmx.
Methanol was distilled off at a reduced pressure of Hg.

The silica sol produced in this manner will be hereinafter referred to as n-butanol silica sol.

Examples 1-4. Comparative Examples 1 to 6 TAEIo 70g, DPHA 30p, IHP 1.
5g. Butanol silica sol 80g, n-butanol 1
80g and i. 1. 1. -Trichloroethane 70
0.9 was charged into four 1.56-meter flasks equipped with a stirrer, heated to 40°C and stirred for 4 hours to prepare a transparent coating composition C A ). A coating composition was prepared by adding ultraviolet absorbers in the types and amounts shown in Table 1 to this [I. Mitsui Petrochemical Polypropylene J440W (1.2% Gunjo)
The injection square plate (which was colored blue) was made from
Thickness 2) to 1.1.1-17 chloroethane vapor to 30
After being exposed for 2 seconds and then dried at room temperature for 1 minute, various coating compositions were applied by air spray (discharge pressure 3 kg/ca), set for 6 minutes, and then dried at 80° C. for 5 minutes. This test piece was then irradiated with ultraviolet rays for about 60 seconds at a distance of 15 cIIL under a 3KW high-pressure mercury lamp to crush the outer coating layer. Table 1 shows the performance of these various coatings. In the following Examples and Comparative Examples, curing was performed under the same conditions as in Example 1.

Examples 5 to 10, Comparative Example 7 Example 1 except that in the preparation of the coating composition of Example 1, those listed in Table 2 were used instead of each component.
While various coating compositions were prepared in the same manner as above, a coating composition was prepared from polypropylene (manufactured by Mitsui Petrochemical Industries KK, product name Mitsui Petrochemical Polyglo J640W (colored white by adding one amount of TiO2). Injection square plate (thickness: 2 mm) i) After thoroughly wiping with gauze impregnated with toluene to degrease it, it was coated with maleic anhydride-modified PER (propylene content: 67 mol).

A Swt% toluene solution of maleic anhydride-containing iI6wt4) was applied by air spray (discharge pressure 4 kg/cd) and left at room temperature for about 10 minutes. Next, the coating composition was applied by air spray (discharge pressure 2.5 kg/cn), and after setting at room temperature for about 5 minutes, it was dried in an air oven at 80°C for 5 minutes, and then irradiated with ultraviolet rays. Then, the coating was cured and various test pieces were prepared.

The physical properties of these test pieces are shown in Table 2. On the other hand, a poly-4-methyl-1-pentene (manufactured by Mitsui Petroleum Chemical Industry Co., Ltd., trade name TPX MXOO4) injection square plate (thickness 22I11) was washed with toluene and then treated with anhydrous maleic acid. It was immersed in a 15 g/β toluene/cyclohexane (1/1 wt ratio) solution of acid-modified EPR (propylene content 67 molt, maleic anhydride content 7.7 wt%) for 1 minute, then slowly pulled out and left at room temperature for about 5 minutes. After drying and primer treatment, the above TPX was immersed in the coating composition shown in Table 6 for 1 minute, slowly pulled up, and then 80%
The sample was dried at ℃ for 5 minutes and immediately irradiated with ultraviolet light to prepare a test piece. The performance of these film-treated TPX is shown in Table 6. Examples 14 to 17. Comparative Example 9.10 Various compositions were prepared in the same manner as in Example 1, except that each component of the coating composition was used as shown in Table 6.

On the other hand, after thoroughly wiping a 2-inch thick polycarbonate sheet [manufactured by Takiron Kiki, trade name: Tenroit Polyca Ace] with gauze soaked in isopropyl alcohol, immerse it in the coating composition for 1 minute, then slowly pull it up and apply it. I did it. Then, add 80% to the sand that has been set for about 3 minutes.
It was dried at ℃ for 10 minutes and further irradiated with ultraviolet rays to prepare a test piece. Table 6 shows the performance of these various coatings.

Examples 18 and 19, Comparative Example 11 Various coating compositions were prepared in the same manner as in Example 1, except that each component of the coating composition was blended as shown in Table 4.

On the other hand, a two-thickness sheeter fabricated by injection molding from polyethylene (manufactured by Mitsui Petrochemical Industries, Ltd., trade name HIZEX 2100J), Samokoki Plasma Deposition System Mode, I BP-1f was used. Discharge treated. The discharge treatment was performed using 02 gas and a gas flow rate of 20 mJ/
The treatment was carried out under the following conditions: min, pressure 0.7 Torr, 13.56 MH2 high frequency power source, output power 100 W, and processing time 10 seconds. At this time, the contact angle 0 between the polyethylene surface and water measured at 23°C and 65% relative humidity is 64 degrees and 35 degrees, while the θ of untreated polyethylene is 99 degrees.
degree was decreasing. Various coating compositions are applied to this polyethylene 7-t in the same manner as in Example 1 and cured.
Table 4 shows the physical properties of various coatings.

Claims (1)

[Claims] (1) One or more curable (meth)acrylate monomers (A): 100 parts by weight, polymerization initiator (B): in the range of 0.01 to 20 parts by weight, maximum absorption wavelength of 260 and 370 nm and 3
An ultraviolet absorber having a molar absorption coefficient at 00 nm of 5000 l/mol·cm or more. : in the range of 0.1 to 20 parts by weight; and fine powder inorganic filler (D) in the range of 0 to 200 parts by weight.