JPH0430979B2 - - Google Patents

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 polyolefin molded articles and the like. [Prior art] By coating the surface of polyolefin molded products, etc., it has excellent curing characteristics such as curing speed in air, and the surface hardness, scratch resistance, abrasion resistance, etc. of the coating are improved.
Regarding the curable resin composition for coating, which has excellent coating properties such as flexibility, surface gloss, heat resistance, water resistance, solvent resistance, and adhesion to base material polyolefin, etc.
The applicant's proposal has been previously disclosed (Japanese Patent Application Laid-Open Nos. 59-20313, 59-30810, 59-25840,
59-33311, 59-36113, 59-41366, 59
-56462, 59-66462, 59-78242, 59-
78242, 59-89331, 59-89367, 59-66410
etc.) However, further improvement of the above characteristics is desired. BACKGROUND ART Conventionally, a technique of adding an ultraviolet absorber as a weathering stabilizer to a coating material or a curable resin for coating used for molded articles such as a polymer is already known. For example, JP-A-56-127635 discloses a technique in which a specific ultraviolet absorber is added to a specific monomer mixture that is cured by ultraviolet rays. However, this curable resin composition has a slow curing speed with ultraviolet rays, and is inferior in paintability and adhesion to coating substrates that do not have functional groups, such as polyolefin molded products. lacking in performance. Further, JP-A No. 58-215428 discloses a paint consisting of 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. In addition, JP-A No. 55-102652, No. 56-81242,
58-213075, 56-92059, 56-92060, 57
-57772, 57-167327, 59-4626, 59-
No. 24728, etc., discloses a technique in which a specific ultraviolet absorber is added to a specific paint composition when coating a specific resin molded product in one or two layers. The composition is essentially different from the composition, the coating thickness is large, special UV absorbers are expensive, the objects to be coated are limited to specific items, and the Depending on the content, there are various drawbacks such as poor strength of the coating film. [Problems to be Solved by the Invention] The object of the present invention is to be applicable to polyolefin molded products, to have excellent film properties even when applied relatively thinly, to avoid the problems described above, and to have excellent weather resistance. The object of the present invention is to provide a stable curable resin composition for coating. [Summary of the present invention] The present invention provides one or more types of curable (meta)
Acrylate monomer (A): 100 parts by weight, polymerization initiator (B): 0.01 to 20 parts by weight, maximum absorption wavelength is 260 to 370 nm, and
Molar extinction coefficient at 300nm is 5000/mol・cm
Ultraviolet absorber (C): in the range of 0.1 to 20 parts by weight, and fine powder inorganic filler with an average particle size of 1.5 mμ to 1μ
(D): a curable resin composition for coating a polyolefin resin molded article, comprising in a range of 0.5 to 100 parts by weight;
The main points are as follows. [Curable (meth)acrylate monomer (A)] As the curable (meth)acrylate monomer (A) used in the composition of the present invention, for example, JP-A-59
-20313 or poly[(meth)acryloyloxyalkyl](iso)cyanurate (a ₁ ) described in JP-A-59-30810, bis[(meth)acryloyloxyalkyl](iso) described in JP-A-59-98115. )
Cyanurate (a ₂ ), JP-A-59-66462 or JP-A-Sho
Poly(meth)acrylates (a ₃ ) of polyepoxy compounds described in JP-A No. 59-78242; meth)acrylate compounds ( _a4 ), poly(meth)acrylates of polyester polyols having no urethane bond ( _a5 ) described in JP-A-59-89367, and those described in JP-A-59-66410. and poly(meth)acrylates of alkane polyols having at least three or more hydroxyl groups in one molecule or polyoxyalkane polyols having one or more ether bonds and three or more hydroxyl groups in one molecule. It is a poly(meth)acrylate compound (a ₆ ) having at least three or more acryloyloxyl groups or methacryloyloxy groups, and these poly(meth)acrylate compounds may have a hydroxyl group. can not use. Furthermore, as another (A),
Poly(meth)acrylate of aliphatic polyol ( _a7 ) described in No. 59-124961, JP-A No. 59-124-
Di(meth) of alkane polyols described in 20313
Examples include acrylate or polyoxyalkylene di(meth)acrylate (a ₈ ), arylene bis[polyoxyalkylene (meth)acrylate] (a ₉ ) described in JP-A-59-33311, and the like. The monomers exemplified here can be used singly as long as they are trifunctional or higher functional monomers, but usually not only bifunctional monomers but also trifunctional or higher monomers can be used. It is preferable to use a mixture of two or more species. Examples of such mixed systems include (a ₁ ) and (a ₈ ) (Japanese Unexamined Patent Publications No. 59-20313, No. 59-30810), (a ₁ ) and (a ₆ ) (No. 59-25840), (a ₁ ) and (a ₉ ) (same 59−
33311), (a ₁ ) and (a ₃ ) (59-36113), (a ₁ ) and (a ₄ ) (59-41366), (a 1 ) and (a 5 ) (59-36113), (a ₁ ) and (a ₅ ) (59-41366)
56462), ( _a4 ) and ( _a8 ) (59-89331), ( _a5 ) and ( _a9 ) (59-89367), ( _a7 ) and other units belonging to (A) (a ₂ ) and other monomers belonging to (A) (same 59-124961)
98115). [Specific examples of component (A)] Specifically, (a ₁ ) in (A) above includes tris(acryloyloxyethyl)(iso)cyanurate, tris(methacryloyloxyethyl)(iso)cyanurate, and tris(methacryloyloxyethyl)(iso)cyanurate. (2-acryloyloxypropyl)(iso)cyanurate, tris(2-methacryloyloxypropyl)(iso)cyanurate, bis(acryloyloxyethyl)
Hydroxyethyl(iso)cyanurate, bis(methacryloyloxyethyl)methoxyethyl(iso)cyanurate, bis(2-acryloyloxypropyl)-2-ethoxypropyl(iso)
Examples include cyanurate, bis(2-methacryloyloxypropyl)-2-hydroxypropyl(iso)cyanurate, tris[acryloyldi(oxyethylene)](iso)cyanurate, tris[methacryloyldi(oxyethylene)](iso)cyanurate, etc. can be done, and (a ₂ ) is
Specifically, bis[acryloyloxyethyl]
(iso)cyanurate, bis(methacryloyloxyethyl)(iso)cyanurate, bis(2-
acryloyloxypropyl) (iso) cyanurate, bis(2-methacryloyloxypropyl) (iso) cyanurate, bis[acryloyloxydi(oxyethylene)](iso)cyanurate, bis[methacryloyloxydi(oxyethylene)](iso) Examples of (a ₃ ) include aliphatic, alicyclic, or aromatic polyepoxy compounds having at least two epoxy groups in one molecule, and acrylic acid or methacrylate. It is a poly(meth)acrylate of a polyepoxy compound formed from an acid, and more specifically, it is disclosed in JP-A-59-66462 or JP-A-59
-78242, and (a ₄ ) is specifically a urethane-based poly(meth) obtained by the reaction of a (meth)acrylic acid ester having a hydroxyl group with a diisocyanate compound. ) acrylate compounds, urethane-based poly(meth)acrylate compounds consisting of poly(meth)acrylates of polyurethane polyols, urethane-based poly(meth)acrylate compounds consisting of poly(meth)acrylates of polyester-based polyurethane polyols, etc. More specifically, it is disclosed in JP-A-59-89331, and ( _a5 ) is a polyol formed from an aliphatic, alicyclic or aromatic polyol and a polycarboxylic acid. It is obtained by reacting a polyester polyol with acrylic acid or methacrylic acid in the presence of a catalyst if necessary, and is more specifically described in JP-A-59-89367. In addition, (a ₆ ) specifically includes glycerin triacrylate, glycerin trimethacrylate, trimethylolethane triacrylate,
Trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate diglycerin triacrylate, diglycerin trimethacrylate, diglycerin tetraacrylate, diglycerin tetra Methacrylate, triglycerin triacrylate, triglycerin trimethacrylate, triglycerin tetraacrylate, triglycerin tetramethacrylate, triglycerin pentaacrylate, triglycerin pentamethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, Tritrimethylolpropane triacrylate, tritrimethylolpropane pentaacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipenta Examples include erythritol hexaacrylate and dipentaerythritol hexamethacrylate. For (a ₇ ),
Dipentaerythritol penta(meth)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 penta[ (meth)acryloyloxycaprolactoate], dipentaerythritol hexa[(meth)acryloyloxycaprolactoate], dipentaerythritol pentaacrylate mono[(meth)acryloyloxydi(caprolactoate)], dipentaerythritol tetra(meth)acrylate bis[(meth)acryloyloxydi(caprolactoate)], dipentaerythritol tri(meth)acrylate tris[(meth)acryloyloxydi(caprolactoate)], dipentaerythritol di(meth)acrylate tetra[(meth)acryloyloxydi(caprolactoate)], dipentaerythritol mono(meth)acrylate penta[(meth)acryloyloxydi(caprolactoate)], Dipentaerythritol hexa[(meth)acryloyloxydi(caprolactoate)], dipentaerythritol hexa[(meth)acryloyloxytri(caprolactoate)], dipentaerythritol hexa[(meth)acryloyl oxytetra(caprolactoate)], dipentaerythritol hexa[(meth)acryloyloxypenta(caprolactoate)], dipentaerythritol hexa[(meth)acryloyloxyhexa(caprolactoate)], Examples of (a ₈ ) include 1,2-diacryloyloxyethane, 1,2-dimethacryloyloxyethane, 1,2-diacryloyloxypropane, and 1,2-diacryloyloxyethane. -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-dimethacryloyloxyoctane, 1,10-diacryloyloxydecane, 1,10-dimethacryloyloxydecane, glycerin-1,3-diacrylate, glycerin-1,3- Dimethacrylate, glycerin triacrylate, pentaerythritol diacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate,
Examples include pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate, and (a ₉ ) is a compound in which the phenolic hydroxyl group of a divalent phenol and two polyoxyalkylene glycols are bonded together by forming an ether bond. It is an acrylic ester or methacrylic ester of a glycol compound. More specifically, those described in JP-A-59-33311 can be mentioned. [Polymerization initiator (B)] 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 a polymerization initiator to this composition. agent
It is necessary to blend (B). 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. Specifically, the photosensitizer is benzoin or its like, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. ether,
Benzophenone, p-chlorobenzophenone, p
-benzophenone compounds such as methoxybenzophenone, benzyl, benzyl methyl ketal,
Benzyl compounds such as benzyl diethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone, 1-( Examples include hydroxyalkyl phenyl ketone compounds such as 4-tert-butylphenyl)-2-hydroxy-2-methyl-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 azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide,
Examples include peroxides such as dicumyl peroxide and cumene hydroperoxide. Furthermore, it is also possible to adopt a method in which both a photosensitizer and a radical initiator are blended into the curable resin composition for coating of the present invention, and UV curing and heat curing proceed simultaneously. It is also possible to adopt a method in which heat curing is progressed after heat curing, or conversely, a method in which ultraviolet curing is progressed after heat curing is progressed. The blending ratio of the polymerization initiator (B) is 0.01 to 20 parts by weight based on 100 parts by weight of the curable (meth)acrylate monomer (A), which is one type or a mixture of two or more types.
It must be within the range of parts by weight, and
Preferably, it is in the range of 0.1 to 10 parts by weight.
If the blending ratio of the polymerization initiator is less than 0.01 part by weight based on 100 parts by weight of the above (A), the polymerizability of the composition will decrease and a hard coating will not be obtained. Moreover, if the amount exceeds 20 parts by weight, the coating obtained from the composition will be colored yellow. [Ultraviolet absorber (C)] The ultraviolet absorber in the present invention includes not only an ultraviolet absorber used in a narrow sense but also a quencher. The ultraviolet absorber (C) used in the composition of the present invention has a maximum absorption wavelength of 260 to 370 nm, preferably 270 to 360 nm, more preferably 275 to 360 nm.
350 and the molar extinction coefficient at 300nm is
5000/mol・cm or more, preferably 8000/cm
mol・cm or more, more preferably 10000/mol・
cm or more. Maximum absorption wavelength is above
Even if a resin having a wavelength outside the range of 260 to 370 nm or a molar extinction coefficient of less than 5000/mol·cm is used, a coating resin with superior weather resistance, which is the object of the present invention, cannot be obtained. The ratio of (C) to the curable monomer (A) is 0.1 to 20 parts by weight, preferably 0.5 to 18 parts by weight,
More preferably, the amount is in the range of 1 to 15 parts by weight; if it is less than the end of this essential range, sufficient weather resistance cannot be obtained as described above, and if it exceeds this range, it is generally not only uneconomical but also hard to cure. It tends to form a film and become discolored, and furthermore, the surface hardness, scratch resistance, abrasion resistance, adhesion, etc. of the film become poor. Specific examples of the ultraviolet absorber (C) include 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-octoxybenzophenone, 2,2'-hydroxy-4'-benzophenone,
Benzophenone series such as 4-hydroxy-2-hydroxybenzophenone, 2-hydroxy-2'-carboxy-4-methoxybenzophenone, ethyl-2-cyano-3,3-diphenyl acrylate, methyl-2-cyano -3-methyl-3-
Substituted acrylonitriles such as (4'-methoxyphenyl)acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2
-(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2-(2'-hydroxy-5'-
t-butylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-t-octylphenyl)
Benzotriazole, 2-(2'-hydroxy-3',
Benzotriazole-based compounds such as 5'-di-t-butylphenyl)-5-chlorobenzazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, N-
(2-ethylphenyl)-N'-(2-ethoxy-5
-t-butylphenyl)oxalic acid diamide, N-(p
-ethoxycarbonylphenyl)-N'-ethyl-
Examples include N'-phenylformamiidein. Among these, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone ethyl-2-cyano-3,3
-diphenyl acrylate, methyl-2-cyano-3-methyl-3-(4'-methoxyphenyl)acrylate, 2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2-(2'-Hydroxy-5'-t-butylphenyl)bunzotriazole,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 (D)] The curable resin composition for coating polyolefin resin molded articles of the present invention contains a filler that improves the surface hardness, scratch resistance, and abrasion resistance of the cured film obtained therefrom, and In order to improve the thixotropic performance of the coating film during application, a finely powdered inorganic filler (D) with a specific particle size is blended. The average particle size of the finely powdered inorganic filler used in the present invention is in the range of 1.5 mμ to 1μ. If the average particle size is larger than 1 μm, the uniform dispersibility in the resin composition will be poor, the effect of improving thixotropic performance during application will be small, and the transparency of the coating film will be impaired. On the other hand, particles with an average particle size smaller than 1 mμ are not economical and are inconvenient in handling and compounding work. In order to maintain the transparency of the coating layer, the finely powdered inorganic filler usually has a refractive index of 1.40 to 1.40.
1.60, preferably in the range 1.42 to 1.58. Specifically, such fine powder inorganic fillers include glass powder, mica, glass beads, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, silica, silica sand, quartz, kaolinite, montmorillonite, and sericite. , talc, chlorite, chinastone, feldspar, etc. Further, these finely powdered inorganic fillers whose surfaces have been surface-treated with alkyl carboxylic acid salts, silane couplers, titanium couplers, Cl ₂ Si (CH ₃ ) ₂ , alcohol, etc. can also be used. Furthermore, colloidal silica, methanol silica sol, ethanol silica sol, isopropanol 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 does not impair transparency and surface gloss. This is especially preferable because there is no such thing. The proportion of these finely powdered inorganic fillers is in the range of 0.5 to 100 parts by weight per 100 parts by weight of (A). If the blending ratio is more than the above range, the flexibility and transparency of the coating film will be impaired, while if it is less than the above range, the effects of filler blending mentioned above cannot be fully achieved. [Other components] The curable resin composition for coating of the present invention may be a composition consisting only of the above four components, but may also contain a polymerization inhibitor, a transparent filler, a solvent, and an antioxidant, if necessary. Various additives such as stabilizers such as fluorescent whitening agents, leveling agents, wetting improvers, (reactive) oligomers such as methyl (meth)acrylate, polyurethane acrylate, polyester acrylate, and polymers such as polymethyl methacrylate. can be blended. The blending ratio of these additives is appropriate. The curable resin composition for coating of the present invention is maintained in a suspended state by adding a solvent as necessary to improve its coating workability. The solvent is also used for the purpose of suspending the composition, adjusting the viscosity of the composition, or improving wetting of the composition. Specific examples of solvents include hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, hexane, heptane, octane, petroleum ether, ligroin, cyclohexane, and methylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, bromoform, trichlene, Halogenated hydrocarbons such as ethylene dichloride, perchloride, ethane trichloride, ethane tetrachloride, propylene dichloride, chlorobenzene, bromobenzene, methanol, ethanol, isopropanol, butanol, pentanol, hexanol,
Alcohols such as cyclohexanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, butyl ethyl ether, dibutyl ether, ethylene glycol Ethers such as dimethyl ether and diethylene glycol dimethyl ether, nitriles such as acetonitrile, propionitrile, and capronitrile, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, methyl benzoate, and ethyl benzoate. etc. can be exemplified. The blending ratio of these organic solvents is usually 5 to 3000 parts by weight per 100 parts by weight of the monomer (A),
The preferred range is 10 to 2000 parts by weight. [Preparation method, etc.] In the composition of the present invention, a suspension composition is prepared from a composition containing the above-mentioned essential components and various additive components such as organic fillers, solvents, and stabilizers added as necessary. The method is to prepare the above-mentioned raw material mixture, and perform kneading and mixing operations using a regular roll, Banbury mixer, ball mill, attritor, whizpah, Oaks mixer, desolver, homogenizer, colloid mill, sand mill, vibration mill, mixer, mixing stirring tank, etc. A uniformly dispersed composition is obtained. Methods for applying the suspension composition onto the substrate surface of the molded article include brush coating, spraying, dipping,
Conventionally known methods such as a bar coat 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 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 -10 to 150°C, preferably 5 to 130°C, and the time is usually 1 sec to 1 hr.
Preferably it is 1 sec to 10 min. In addition, in the thermosetting method, the temperature during curing is usually -10 to 150℃,
The temperature is preferably 5 to 130°C, and the time required for curing is usually 0.05 to 10 hr, preferably 0.1 to 8 hr. [Substrate] The curable resin composition for coating of the present invention can be coated on the basic surface of any molded product made of thermoplastic resin, thermosetting resin, metal, wood, ceramics, etc. It can be suitably used for coating the surface of a substrate of a molded article made of a plastic resin, particularly for coating the surface of a polyolefin resin substrate. The shape of the molded product may be a film, a sheet, a plate, or any other shape. Specific examples of the polyolefin resin constituting the base layer include α-olefin homopolymers and copolymers containing α-olefin as a main component, such as ethylene, propylene, 1-olefin, etc. Butene, 1-hexene, 4-methyl-
A homopolymer of α-olefin such as 1-pentene, 1-octene, 1-decene, a copolymer consisting of a mixture of two or more of the above α-olefins, or a copolymer consisting of a mixture of two or more of the above α-olefins, or a copolymer containing the above α-olefin as a main component and vinyl acetate. , lower aliphatic vinyl carboxylates such as vinyl propionate, acrylic carboxylic acid esters such as methyl acrylate, metal salts of acrylic acid, methyl methacrylate, metal salts of methacrylic acid, and other components such as salts of acrylic carboxylic acids. Examples include copolymers containing a small amount (for example, 30% mole or less) of Among these polyolefins, polyolefins having crystallinity are usually used. As mentioned above, the curable resin composition for coating of the present invention is preferably used for base resin molded articles of polyolefins, and the effects of the present invention are particularly exhibited particularly when these are colored with pigments. That is, the present inventors found that when the base resin is colored with a pigment, the weather resistance of the coating is poor even if a curable coating composition for a normal coating is used. It has been found that the use of the composition significantly improves weather resistance. Coloring pigments in the above case include calcium carbonate, zinc white, titanium oxide, carbon black yellow, cadmium yellow, iron oxide, cadmium red, para red, cadmium orange, cobalt purple, manganese purple, Fast Bio There are retto B, ultramarine, navy blue, cobalt blue, phthalocyanine blue, chrome green, chromium oxide, zinc sulfide, aluminum powder, copper powder, etc., but there are white colored bases made of titanium oxide, cobalt purple, and manganese. Violet colored substrate with purple, ultramarine, cobalt blue, dark blue (milory blue)
It is particularly preferable to use the composition of the present invention for blue colored substrates produced by chromium oxide, green colored substrates produced by chromium oxide, and the like. [Coating] When coating the substrate surface of a molded object such as a resin with the curable resin composition for coating of the present invention, the substrate surface of the molded object is washed with various solvents, washed with an alkaline aqueous solution, and subjected to interfacial treatment. Cleaning with activator, ultrasonic cleaning, electrolytic cleaning, blasting treatment, sandblasting treatment, etching treatment with acid or alkali, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, plasma discharge treatment, chemical conversion treatment, etc. Various surface treatments can be applied. Furthermore, when laminating an outer coating layer made of the curable resin composition for coating of the present invention on the substrate surface of the molded article, an intermediate adhesive layer made of a primer may be placed between the substrate layer and the outer coating layer. It is also possible to improve the adhesion between both layers by forming a three-layer laminate. When the base resin layer is polyolefin, the primer may be a modified polyolefin grafted with an α,β-unsaturated carboxylic acid or its derivative component such as α,β-unsaturated carboxylic acid, its acid anhydride, its ester, etc. 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 required, by the method described above, 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, for example, lighting boards, sky domes,
Solar water heater panels, glove box panels, watch glasses, various lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, coffee maker shower domes and coffee containers, water tanks, and illuminator covers. , covers for stereo equipment such as players, dials and covers for various meters, covers for headlights and taillights in automobiles, level sensors, various films such as shatterproof films for glass, release films, insulating films, agricultural films, etc., and lights. Recycled video discs, observation windows for various equipment such as clothes dryers, electric washing machines, dryers, oil tanks, windshields for motorcycles, jeeps, motorboats, etc., automobile glass (windshields, etc.)
rear windows, opera windows, triangular windows, sunroofs), window glass for greenhouses, houses, aquariums, etc.
Tableware, mirrors, various containers such as oil bottles and cosmetic bottles,
Relay cases, fuse boxes, motorcycle side covers and mudguards, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulating films, floor tiles, floor sheets,
Doors, table boards, wall tiles, countertop decorative boards, shelf boards, wall sheets, wallpaper, furniture, lightweight wall boards, tableware, chairs, bathtubs, toilets, refrigerators, wall panels, water supply and drainage pipes, raceways, ducts, curtain rods , rain gutters, insulation materials, waterproof coatings, curtains, window frames, automobile foils, various containers, automobile interior materials, vanity tables, flower boxes, particle boards,
Examples include tiles, shutters, shutters, waterproof pans, pipes, wiring materials, gear cams, knobs, solenoid valve frames, fans, instrument panels, bumpers, and brakes.
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. [Example] 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 Add 2wt% of a sufficiently dried inorganic substance to a liquid with a known refractive index, thoroughly disperse it, and then visually check its transparency. The refractive index should be the same as that of the most transparent liquid. (2) Surface gloss (gloss) Performed according to 60 degree specular gloss in JISK5400-1979. (3) Light transmittance Conducted according to JISK6714. (4) Adhesion The test was conducted according to the cross-cut test in JISK5400-1979. Judgment is based on how many of the 100 pieces are glued together. (5) Sand-falling abrasion 800g of silicon carbide abrasive material is dropped on the broken membrane according to the method of JIST8147-1975. For opaque substrates, abrasion resistance is expressed by the difference in surface gloss before and after the test. For transparent materials, abrasion resistance is expressed by the difference in haze before and after the test. Incidentally, haze was measured according to ASTM D-1003. As for these wear values, the smaller the number, the better the wear resistance. (6) Taber wear Abraded wheels according to ASTM D-1044 method.
CS-10 is rotated 1000 times on the coating with a load of 500g. For opaque materials, wear resistance is expressed by the amount of wear of the coating after the test. The smaller the amount of wear, the better the wear resistance. For transparent materials, wear resistance is expressed by the amount of increase in haze after the test. (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 cm is
It is expressed as the angle at which the coating cracks or peels off from the substrate by folding it along the outer circumference of a cm cylinder. 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 aging tester at 80°C for 400 hours, the appearance and adhesion of the outer coating layer were evaluated. (11) Gasoline resistance The appearance and adhesion of the outer coating layer were evaluated after the test piece was immersed in regular gasoline for 24 hours at room temperature. (12) Heat cycle resistance After holding the test piece in an air oven at 80°C for 2 hours, it was left at room temperature for 1 hour, and then heated at −30°C for 1 hour.
℃ in a cold room for 2 hours and then 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. (13) Weather resistance (adhesion retention time) The test piece was held in a sunshine weatherometer, 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 1 part of ethanol. This solution was placed in a 1 cm thick cell, and a spectrophotometer (manufactured by Shimadzu Corporation, MPS-
5000) was used to measure the spectrum in the wavelength range of 235 to 400 mm. The wavelength showing the maximum absorption in this spectrum was read and defined as the maximum absorption wavelength.
Moreover, the molar extinction coefficient (ε) was calculated by the following formula. ε=1/Cllog(To/T) where C: Concentration (mole/) l: Cell thickness (cm) To, T: Intensity of incident light and transmitted light Ultraviolet absorption used in Examples and Comparative Examples The abbreviations, maximum absorption wavelengths, and molar extinction coefficients of the agents are summarized below.

[Table] Furthermore, the following abbreviations were used for the curable (meth)acrylate monomer (A) and polymerization initiator (B) in the Examples and Comparative Examples of this patent.

【table】

[Table] Non

In addition, the following reference examples show a method for synthesizing an acrylate of a polyester polyol and a method for producing an n-butanol silica sol. Reference example 1 Pentaerythritol 136g, succinic acid 59g,
3 g of paratoluenesulfonic acid and 100 g of toluene were charged, and an esterification reaction was carried out at 150°C for 2 hours in a nitrogen atmosphere. After cooling, 220 g of acrylic acid, 3 g of hydroquinone, and 200 g of toluene were added, and an esterification reaction was carried out at 120°C for 4 hours. After washing the reaction solution with weak alkaline water and water, 0.05 g of hydroquinone was added and low-boiling substances were distilled off to obtain a polyacrylate of polyester polyol having an average molecular weight of 700. The average number of polymerizations in one molecule of the polyacrylate of this polyester polyol is 4.2.
Confirmed by NMR. This curable acrylate monomer is hereinafter abbreviated as PEPA. Reference example 2 300g of methanol silica sol (manufactured by Nissan Chemical)
After adding 210 g of n-butanol to a 1.5 mm pear-shaped flask, the water bath was attached to a rotary evaporator and the water bath was set at 80° C., and methanol was distilled off at a reduced pressure of 30 mmHg.
The silica sol produced in this manner will be hereinafter referred to as n-butanol silica sol. Examples 1 to 4, Comparative Example 1 70 g of TAEIC, 30 g of DPHA, 1.5 g of IHP, 80 g of butanol silica sol, 180 g of n-butanol, and 700 g of 1,1,1-trichloroethane were placed in a 4-necked flask with a 1.5-inch stirrer, and heated at 40°C. A transparent coating composition [A] was prepared by heating and stirring for 4 hours. Add UV absorbers to this [A] in Table 1.
A coating composition was prepared by adding the types and amounts shown in . On the other hand, polypropylene [Mitsui Petrochemical Industries KK]
manufactured by Mitsui Petrochemical Polypropylene J440W (colored blue with 1.2% ultramarine)] was exposed to 1,1,1-trichloroethane vapor for 30 seconds, and then After drying at room temperature for 1 minute, various coating compositions were applied by air spray (discharge pressure 3 kg/cm ² ), and after setting for 3 minutes, drying was performed at 80° C. for 5 minutes. This test piece was then irradiated with ultraviolet light for about 30 seconds at a distance of 15 cm under a 3kW high-pressure mercury lamp to harden the outer coating layer. Table 1 shows the performance of these various coatings. still,
In the following Examples and Comparative Examples, curing was performed under the same conditions as in Example 1. Comparative Examples 2 to 3 A test piece was prepared in the same manner as in Example 3 except that the fine powder inorganic filler was not used (Comparative Example 2). The results are shown in Table 1. Further, a test piece was prepared in the same manner as in Example 3 except that the fine powder inorganic filler was not used and the amount of the ultraviolet absorber was increased to 16 parts by weight (Comparative Example 3).
16 UV absorbers without blending fine powder inorganic fillers
The coating film of Comparative Example 3, which was mixed with the same amount, did not cure. Comparative Examples 4 to 5 The same procedure as in Example 1 was carried out except that HMB was not used as the ultraviolet absorber in Example 1, and instead, the ultraviolet absorbers listed in Table 1 were blended in the amounts listed in Table 1. A test piece was prepared for each. The results are shown in Table 1.

【table】

[Table] *Due to poor initial adhesion, other physical properties of the coating were not evaluated.
Examples 5 to 6, Comparative Example 6 Various coating compositions were prepared in the same manner as in 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. I prepared something. On the other hand, polypropylene (Mitsui Petrochemical Industries KK)
Manufactured by Mitsui Petrochemical Polypropylene J640W [colored white with 1% TiO ₂ added] An injection square plate (thickness 2 mm) was thoroughly wiped with gauze soaked in toluene to degrease it. A 5 wt % toluene solution of maleic anhydride-modified PER (propylene content 67 mol %, maleic anhydride content 6 wt %) was applied by air spray (discharge pressure 4 Kg/cm ² ) and left at room temperature for about 10 minutes. Then, a coating composition was applied by air spray (discharge pressure 2.5 kg/cm ² ),
After setting at room temperature for about 5 minutes, the coating was dried in an air oven at 80° C. for 5 minutes and irradiated with ultraviolet rays to harden the coating, and various test pieces were prepared. Table 2 shows the physical properties of these test pieces.

【table】

[Table] Examples 7 to 8, Comparative Example 7 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 3. On the other hand, an injection square plate (thickness: 2 mm) of poly-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries KK, trade name: TPX MX004) was washed with toluene and then treated with maleic anhydride-modified EPR (propylene content: 67 mol%, Primer treatment was performed by immersing the sample in a 15 g solution of maleic anhydride (7.7 wt%) in toluene/cyclohexane (1/1 wt ratio) for 1 minute, pulling it up slowly, and drying it at room temperature for about 5 minutes. Further, the above TPX was immersed in the coating composition shown in Table 3 for 1 minute, slowly pulled up, and then dried at 80°C for 5 minutes.
A test piece was prepared by immediately irradiating it with ultraviolet light. Table 3 shows the performance of these coated TPXs. Examples 9 to 11, Comparative Example 8 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 3. On the other hand, 2 mm thick polycarbonate [Takiron]
Co., Ltd., trade name Sunroid Polyca Ace] was thoroughly wiped with gauze impregnated with isopropyl alcohol, and then immersed in the coating composition for 1 minute and slowly pulled up and applied. After setting for about 3 minutes, dry at 80℃ for 10 minutes.
Further, a test piece was prepared by irradiating it with ultraviolet rays. Table 3 shows the performance of these various coatings.

【table】

[Table] Examples 12, 13, Comparative Example 9 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, polyethylene (Mitsui Petrochemical Industries KK)
A 2 mm thick sheet produced by injection molding from a product manufactured by HIZEX 2100J (trade name: HIZEX 2100J) was subjected to electrical discharge treatment using a plasma deposition system Model BP-1 manufactured by Samoco Co., Ltd. The discharge treatment was performed using O ₂ gas, gas flow rate 20 ml/min, pressure 0.7 Torr, 13.56 MHz high frequency power supply, output power 100 W, processing time 10
I went under the conditions of seconds. At this time, 23℃, relative humidity 65%
The contact angle θ between the polyethylene surface and water measured at
The θ of untreated polyethylene was 99 degrees, whereas it was 64 degrees, a decrease of 35 degrees. Various coating compositions were applied to this polyethylene sheet in the same manner as in Example 1 and cured. Table 4 shows the physical properties of various coatings.
Shown below.

【table】

【table】

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 is between 260 and 370nm and
Molar extinction coefficient at 300nm is 5000/mol・cm
A polyolefin resin consisting of the above ultraviolet absorber (C) in a range of 0.1 to 20 parts by weight, and a fine powder inorganic filler (D) with an average particle size of 1.5 to 1 micron in a range of 0.5 to 100 parts by weight. Curable resin composition for coating molded products.