JP5336925B2 - Active energy ray-curable coating composition and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable coating material composition that has scratch resistance comparable to a cured product of a thermosetting silicone composition, good productivity, and excellent crack resistance even under severe environment and a laminate in which the cured film of the active energy ray-curable coating material composition is laminated on a substrate. <P>SOLUTION: The active energy ray-curable coating material composition and a laminate thereof are provided. The active energy ray-curable coating material composition contains 10-30 pts.mass of an alkyl (meth)acrylate polymer (B) with a mass-average molecular weight in polystyrene conversion of 3,000-20,000 and 1-5 pts.mass of a photoacid generator (C) based on 100 pts.mass of a silicone-based compound (A) containing at least one of an organoalkoxysilane and a hydrolysis condensate thereof. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an active energy ray-curable coating composition and a laminate.

  Thermoplastics have useful physical and chemical properties and are applied in various fields. For example, polycarbonate resin is widely used for automobile headlamps, spectacle lenses, safety shields and the like because it has high transparency, heat resistance and impact resistance, and good injection moldability.

  However, since most of the thermoplastics are easily scratched, the surface is often hard-coated in many cases where the thermoplastic is actually used. For example, when a polycarbonate resin is used as the thermoplastic, a laminate in which a cured product of an acrylic active energy ray curable composition is laminated on the surface of the polycarbonate resin, a primer resin layer having an ultraviolet absorber on the surface of the polycarbonate resin, and Laminated body in which cured products of thermosetting silicone composition are sequentially laminated, primer resin layer having ultraviolet absorber on polycarbonate resin surface, cured product of thermosetting silicone composition, and oxidized organic silicone obtained by plasma coating The laminated body in which the hardened | cured material of the composition was laminated | stacked one by one is mentioned.

  However, in fields where abrasion resistance similar to that of inorganic glass is required, the polycarbonate resin coated with a cured product of an acrylic active energy ray curable composition may have insufficient abrasion resistance. Further, a primer resin layer having an ultraviolet absorber on the surface of the polycarbonate resin, a laminate in which a cured product of the thermosetting silicone composition is sequentially laminated, a primer resin layer having an ultraviolet absorber on the surface of the polycarbonate resin, and thermosetting A laminate obtained by sequentially laminating a cured product of a silicone composition and a cured product of an oxidized organic silicone composition obtained by plasma coating has a high production cost and is not sufficient in terms of productivity.

  Under such circumstances, attempts have recently been made to use ultraviolet curable silicone compositions instead of thermosetting silicone compositions. For example, Patent Document 1 discloses specific alkyl silicates and organosilanes in order to form an inorganic coating having excellent appearance, transparency, adhesion to a substrate, scratch resistance and abrasion resistance in a short time. A coating composition containing a condensate of at least one of the above and a specific colloidal silica and an active energy ray-sensitive acid generator has been proposed. However, cracks may occur depending on various environmental conditions such as heat and water.

Patent Document 2 discloses specific alkyl silicates and specific organosilanes as active energy ray-curable compositions that are excellent in scratch resistance, crack resistance, appearance and adhesion, and have short-time film-forming properties. There has been proposed a composition comprising, as a main component, a silicon oligomer (siloxane compound) obtained by hydrolysis / condensation of an aldehyde, an active energy ray-sensitive cationic polymerization initiator, and an organic compound having two or more hydroxyl groups. . However, the crack suppression effect may not be sufficient in an environment such as outdoors where the temperature and humidity change greatly.
Japanese Patent Laid-Open No. 2007-16,191 JP 2007-217,501 A

  An object of the present invention is an active energy ray-curable coating composition having scratch resistance comparable to that of a cured product of a thermosetting silicone composition, good productivity, and excellent crack resistance even in harsh environments. It is providing the laminated body by which the thing and its cured film were laminated | stacked on the base material.

  The gist of the present invention is that in terms of polystyrene, 100 parts by mass of a silicone compound (A) (hereinafter referred to as “component (A)”) containing at least one of an organoalkoxysilane and a hydrolysis condensate thereof. (Meth) acrylic acid alkyl polymer (B) (hereinafter referred to as “component (B)”) having a mass average molecular weight of 3,000 to 20,000 and 10 to 30 parts by weight of photoacid generator (C) The active energy ray-curable coating material composition (hereinafter referred to as “the present coating material composition”) containing 1 to 5 parts by mass) (referred to as “component (C)”) is the first invention.

  Moreover, let the laminated body by which the cured film of this coating material composition was laminated | stacked on the base material is made into 2nd invention.

  Furthermore, a laminated film in which a cured film of an active energy ray-curable acrylic coating material composition (hereinafter referred to as “the present acrylic coating material composition”) and a cured film of the present coating material composition are sequentially laminated on a substrate. The body is the third invention.

  The cured coating of this coating composition has the same level of scratch resistance as the cured product of the thermosetting silicone composition, has good productivity, and is excellent in crack resistance even in harsh environments. Laminates in which a cured film of this coating composition is coated on the surface of a transparent thermoplastic resin such as resin are used for automobile headlamp lenses, vehicle sensors, outdoor signage, greenhouses and window glass of outdoor buildings, terraces and garages. It can be used for various purposes such as roofs, balconies, instrument covers, etc.

Organoalkoxysilane The organoalkoxysilane used in the present invention can be used as a component of the component (A).

  Examples of the organoalkoxysilane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltrisilane. Methoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (meth) acryloyloxy Propyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, p-vinylphenylenetrimethoxysilane, p- Vinylphenylenetriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 Phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, Diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylmethyl Rudimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, methyl silicate, ethyl silicate, IM -1000, IS-1000 and the like imidazole silanes (all manufactured by Nikko Metal Co., Ltd., product name), 3- (2,2,6,6-tetramethylpiperidi-4-yloxypropyl) trimethoxysilane, 3- (2,2,6,6-tetramethylpiperidi-4-yloxypropyl) triethoxysilane, 3-ethyl-3- [3- (trimethoxysilyl) propoxymethyl] oxetane, 3-ethyl-3 -[3- (triethoxysilyl) propoxymethyl] oxetane, 3-trimethoxy Silylpropyl succinic acid, 3-triethoxysilylpropyl succinic acid, tris- (3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilylpropyl) isocyanurate, 3- (4-methylpiperazino) propyltrimethoxy Examples thereof include silane coupling agents represented by silane and 3- (4-methylpiperazino) propyltriethoxysilane. These can be used alone or in combination of two or more.

  In the present invention, the hydrolyzed condensate of the above organoalkoxysilane can be used as a component of the component (A) together with the organoalkoxysilane.

  As a method for hydrolyzing the organoalkoxysilane, for example, an acid such as hydrochloric acid or acetic acid is added to an aqueous solution in which about 1 to 1,000 mol of water and alcohol are mixed with respect to 1 mol of the organoalkoxysilane, and the pH is 2 to 5. The method of hydrolyzing by making it about acidic aqueous solution is mentioned.

  Moreover, as a hydrolysis method of organoalkoxysilane, a method of hydrolyzing by mixing about 1 to 1,000 mol of water with respect to 1 mol of organoalkoxysilane and heating to about 30 to 100 ° C. is mentioned. It is done.

  The alcohol generated during the hydrolysis can be distilled out of the system.

  Condensation following hydrolysis of the organoalkoxysilane can proceed by leaving the hydrolyzate of the organoalkoxysilane to stand. In that case, the progress of the condensation is accelerated by heating the hydrolyzate of organoalkoxysilane at about 30 to 100 ° C. or controlling the pH of the hydrolyzate of organoalkoxysilane to around pH 6 to 7 neutral. Can do. The water generated during the condensation of the organoalkoxysilane hydrolyzate can be distilled out of the system.

(A) component (A) component used by this invention contains at least one of organoalkoxysilane and its hydrolysis-condensation product.

  In the present invention, the component (A) preferably contains a hydrolytic condensate of organoalkoxysilane from the viewpoint of transparency, hardness and scratch resistance of the cured film of the present coating material composition.

  In the present invention, as the component (A), a hydrolyzed condensate of methyltrimethoxysilane and phenyltrimethoxysilane (hereinafter referred to as the component (A)) in terms of transparency, hardness and toughness of the cured film of the present coating material composition , "(A-1) component") is more preferable.

  The mass average molecular weight of the component (A-1) is preferably 500 to 5,000 in terms of polystyrene by gel permeation column chromatography. (A-1) When the mass average molecular weight of the component is 500 or more, the film forming property of the cured film of the present coating material composition tends to be good, and when it is 5,000 or less, the scratch resistance of the cured film of the present coating material composition Tend to improve.

  (A-1) As the compounding ratio of methyltrimethoxysilane and phenyltrimethoxysilane (number of moles of methyltrimethoxysilane charged / number of moles of phenyltrimethoxysilane) in obtaining the component, (50/50) to ( 95/5) is preferable, and (70/30) to (93/7) are more preferable. When the charged molar ratio of methyltrimethoxysilane is 50 or more, the scratch resistance of the cured film of the present coating material composition tends to be improved. Moreover, when the charged molar ratio of methyltrimethoxysilane is 95 or less, the adhesion between the cured film of the present coating material composition and the cured film of the acrylic coating material composition described later tends to be improved.

  Furthermore, in the present invention, as the component (A), the (A-1) component and the 3- More preferably, glycidoxypropyltrimethoxysilane is used in combination. The blending amount of 3-glycidoxypropyltrimethoxysilane in component (A) is preferably 0.05 to 5,000 parts by mass, and 0.5 to 500 parts by mass with respect to 100 parts by mass of component (A-1). Part is more preferred. When the blending amount of 3-glycidoxypropyltrimethoxysilane is 0.05 parts by mass or more, the adhesion between the cured film of the present coating material composition and the cured film of the present acrylic coating material composition tends to be improved, When the amount is 5,000 parts by mass or less, the scratch resistance and transparency of the cured film of the present coating material composition tend to be good.

(B) component The (B) component used by this invention is mix | blended in order to provide the favorable crack resistance in a severe environment to the cured film of this coating | covering material composition.

  In the present invention, “(meth) acryl” means at least one of “acryl” and “methacryl”.

  The weight average molecular weight of the component (B) is 3,000 to 20,000 in terms of polystyrene of gel permeation column chromatography, and preferably 3,000 to 15,000. When the mass average molecular weight of the component (B) is 3,000 or more, the crack resistance and heat resistance of the cured film of the present coating material composition are improved. Further, when the mass average molecular weight of the component (B) is 20,000 or less, the compatibility with the component (A) and the scratch resistance of the cured film of the present coating material composition are improved.

  (B) As (meth) acrylic-acid alkyl (b) which is a raw material for comprising a component, the (meth) acrylic acid ester which has a C1-C6 linear or branched alkyl group is mentioned, for example.

  Specific examples of the component (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Examples include isobutyl acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, and n-hexyl (meth) acrylate. These can be used alone or in combination of two or more. Further, as the alkyl (meth) acrylate (b), methyl (meth) acrylate is preferable from the viewpoint of compatibility with the component (A).

  Examples of the polymerization method for obtaining the component (B) include a solution polymerization method, a suspension polymerization method, and an emulsion polymerization, and the polymerization initiator, the chain transfer agent, the solid content, or the reaction conditions can be adjusted by adjusting a desired condition. A polymer can be obtained.

  In the present invention, as the shape of the component (B), since the state of solid particles is preferable in that the component (B) can be dissolved in various organic solvents, the polymerization method for obtaining the component (B) Is preferably a suspension polymerization method.

  As a polymerization method for obtaining the component (B), for example, a polymerization initiator is added to an aqueous suspension containing water, a dispersant and a monomer, and then the polymerization initiator-containing aqueous suspension is heated. Examples include a method in which polymerization is carried out and then the aqueous suspension after polymerization is filtered, washed, dehydrated and dried.

  Examples of the dispersant include poly (meth) acrylic acid alkali metal salts, alkali metal salts of copolymers of (meth) acrylic acid and methyl (meth) acrylate, and polyvinyl alcohol having a saponification degree of 70 to 100%. -Methyl and methylcellulose. These can be used alone or in combination of two or more.

  The amount of the dispersant added in the aqueous suspension polymerization is a monomer 100 to be polymerized in view of dispersion stability in suspension polymerization and washing, dehydrating, drying and fluidity of the resulting granular polymer. It is about 0.005-5 mass parts per mass part, and 0.01-1 mass part is preferable.

  In the present invention, for the purpose of improving the dispersion stability of aqueous suspension polymerization, an electrolyte such as sodium carbonate, sodium sulfate or manganese sulfate can be used in the aqueous suspension polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvalero). Azo compounds such as nitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl And organic peroxides such as peroxy 2-ethylhexanoate and t-hexyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, sodium persulfate and ammonium persulfate. These can be used alone or in combination of two or more.

  In the present invention, a chain transfer agent can be used for the purpose of adjusting the molecular weight of the component (B).

  Examples of chain transfer agents include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, cobalt metal complexes such as bis (borondifluorodiphenylglyoxymate) cobalt (II), and α-methylstyrene. Dimers and terpinolene are mentioned. These can be used alone or in combination of two or more. Among these, a cobalt metal complex is preferable in terms of the influence on the odor and weather resistance of the component (B).

  As an addition amount of a chain transfer agent, 0.001-10 mass parts is preferable with respect to 100 mass parts of monomers which are the raw materials for comprising (B) component, and 0.05-5 mass parts is more preferable. . When the addition amount of the chain transfer agent is 0.001 part by mass or more, the molecular weight of the copolymer can be lowered by chain transfer of radicals. Moreover, the addition amount of a chain transfer agent is 10 mass parts or less, the residual amount of an unreacted monomer and a chain transfer agent can be suppressed, and the odor of (B) component can be suppressed.

  The aqueous suspension polymerization temperature is preferably from 50 to 130 ° C, more preferably from 60 to 100 ° C, from the viewpoint of polymerization in a short time and polymerization stability.

(C) component (C) component used by this invention is an additive for advancing a polymerization reaction by an active energy ray.

  Examples of the component (C) include organic halogen compounds such as a trihalomethyltriazine compound, nitrobenzyl ester, diazosulfone, oxime sulfonate, N-sulfonyloxyimide, and onium salt. Of these, onium salts are preferred.

  As the counter anion in the case of using an onium salt, hexafluoroantimonate or tetra (pentafluorophenyl) borate is preferable from the viewpoint of scratch resistance of the cured film of the present coating material composition.

  A commercial item can be used for said onium salt. Examples of commercial names of onium salts include WPI-116 (manufactured by Wako Pure Chemical Industries, Ltd.), MPI-103 (manufactured by Midori Chemical Co., Ltd.) and BBI-, whose counter anion is hexafluoroantimonate. 103 (manufactured by Midori Chemical Co., Ltd.) and Rhodorsil 2074 (manufactured by Rhodia Japan Co., Ltd.) whose counter anion is tetra (pentafluorophenyl) borate.

  In addition to the above, specific examples of the component (C) include CPI-200 (manufactured by Sun Apro Co., Ltd.) and Adeka optomer SP-300 (manufactured by Adeka Co., Ltd.).

  (C) A component can be used individually by 1 type or in combination of 2 or more types.

This coating | covering material composition This coating | covering material composition contains (A) component, (B) component, and (C) component.

  (B) The compounding quantity of a component is 10-30 mass parts with respect to 100 mass parts of (A) component, and 15-25 mass parts is preferable. (B) The compounding quantity of a component is 10 mass parts or more, and the crack resistance after the environmental test of the cured film of this coating | covering material composition becomes favorable. Moreover, the compounding quantity of (B) component is 30 mass parts or less, and the abrasion resistance of the cured film of this coating | covering material composition becomes favorable.

  (C) As a compounding quantity of a component, 1-5 mass parts is preferable with respect to 100 mass parts of (A) component. When the blending amount of the component (C) is 1 part by mass or more, the scratch resistance of the cured film of the present coating material composition tends to be good. Moreover, the compounding amount of the component (C) is 5 parts by mass or less, more preferably 4 parts by mass or less, and the initial yellowing of the cured film of the present coating material composition tends to be suppressed.

  In the present invention, in the present coating material composition, colloidal silica, colloidal metal, photosensitizer, filler, dye, pigment, pigment dispersant, flow modifier, leveling agent, extinguishing agent, if necessary. Various additives such as a foaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, gel fine particles, and fine particle powder can be blended.

  In the present invention, an organic solvent is blended in the coating material composition for the purpose of adjusting the solid content concentration of the coating material composition, improving dispersion stability, improving coating properties, and improving adhesion to a substrate. can do.

  Examples of the organic solvent include alcohol solvents such as isobutanol and ester solvents such as n-butyl acetate and diethylene glycol acetate. These can be used alone or in combination of two or more.

  As a compounding quantity of an organic solvent, 10-1,000 mass parts is preferable with respect to 100 mass parts of solid content of this coating | covering material composition.

  The present coating material composition is applied on a base material described later or a cured film of the present acrylic coating material composition on the base material, and then cured to form a laminate.

  Examples of the method for applying the coating material composition include a spray coating method, a spin coating method, a shower flow coating method, a curtain flow coating method, and a dip method.

  The film thickness of the cured coating of the present coating material composition is preferably 1 to 20 μm, and more preferably 2 to 10 μm. When the film thickness of the cured film of the present coating material composition is 1 μm or more, the scratch resistance of the cured film of the present coating material composition tends to be good. Moreover, when the film thickness of the cured film of the present coating material composition is 20 μm or less, cracks tend not to occur in the cured film of the present coating material composition.

  Examples of active energy rays for curing the coating composition include vacuum ultraviolet rays, ultraviolet rays, visible rays, near infrared rays, infrared rays, far infrared rays, microwaves, electron beams, β rays, and γ rays. Among these, it is preferable to use ultraviolet light or visible light in combination with a photoacid generator from the viewpoint of a high polymerization rate and relatively little deterioration of the substrate.

  Specific examples of active energy ray light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, fusion lamps, incandescent bulbs, xenon lamps, halogen lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, Examples include gallium lamps, excimer lasers, and the sun.

The irradiation energy of the active energy ray is preferably 0.1 to 10 J / cm ² with an integrated energy of a wavelength of 340 to 380 nm.

  The irradiation atmosphere of active energy rays may be air or an inert gas such as nitrogen or argon.

  In the present invention, the coating material composition preferably does not contain a polymer having a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, or an alkoxysilyl group. For example, a copolymer of methyl methacrylate and methacrylic acid, a copolymer of methyl methacrylate and glycidyl methacrylate, or a copolymer of methyl methacrylate and 3-methacryloyloxypropyltrimethoxysilane is blended in the coating composition. Then, the stability in the present coating material composition may be lowered. Moreover, when the copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate is mix | blended, the water resistance of the cured film of this coating | covering material composition may fall.

Base material As a base material used by this invention, various thermoplastic resins are mentioned, for example.

  Specific examples of the substrate include acrylic resin such as polymethyl methacrylate, polycarbonate resin, polyester resin, poly (polyester) carbonate resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate resin. , Polymethacrylimide resin, polyallyl diglycol carbonate resin, polyolefin resin and amorphous polyolefin resin. These can be used alone or in combination of two or more. Among these, acrylic resins, polycarbonate resins, polystyrene resins, polymethacrylimide resins, and amorphous polyolefin resins are preferable in terms of transparency and wear resistance.

Laminated body In this invention, a laminated body is formed by laminating | stacking the cured film of this coating material composition on the said base material.

  In the present invention, for the purpose of improving the weather resistance of the laminate or the adhesion between the substrate and the cured coating of the present coating material composition, the acrylic system is provided between the substrate and the cured coating of the present coating material composition. A cured film of the coating material composition can be formed.

  The laminate of the present invention is suitably used for products for outdoor use such as automotive headlamp lenses, vehicle sensors, outdoor signage, greenhouses and window glass of outdoor buildings, terraces and garage roofs, balconies, instrument covers, etc. Can do.

This acrylic coating material composition As this acrylic coating material composition, what contains the monomer or oligomer (henceforth "(D) component") which has a (meth) acryloyl group is mentioned, for example.

  Examples of the component (D) include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, organic-inorganic hybrid (meth) acrylate obtained by condensing colloidal silica and (meth) acryloylalkoxysilane, and the like. And monofunctional (meth) acrylates or polyfunctional (meth) acrylates having a polymerizable unsaturated bond. These can be used alone or in combination of two or more.

  Specific examples of the monofunctional (meth) acrylate having a polymerizable unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. I-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, morpholyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, tricyclodecane (meth) acrylate, polyethylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, isobornyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, (2-methyl-2-ethyl -1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate and phthalic anhydride and 2-hydroxyethyl (meth) acrylate Adducts of bets can be mentioned.

  Specific examples of the polyfunctional (meth) acrylate having a polymerizable unsaturated bond include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (number of repeating units = 2 to 15) di (meth) acrylate, polypropylene glycol (number of repeating units = 2 to 15) Di (meth) acrylate, polybutylene glycol (number of repeating units = 2 to 15) di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (Meth) acryloxydiethoxyphenylacryloxydiethoxy Nyl) propane, trimethylolpropane diacrylate, bis (2- (meth) acryloxyethyl) -hydroxyethyl-isocyanurate, trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanate Nurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A diepoxy compound Of epoxy poly (meth) acrylates such as epoxy di (meth) acrylate obtained by reacting (meth) acrylic acid with 1,6-hexamethylene diisocyanate Urethane tri (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with a monomer, urethane di (meth) acrylate obtained by reacting isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate, isophorone diisocyanate And pentaerythritol tri (meth) acrylate are reacted with urethane hexa (meth) acrylate, dicyclomethane diisocyanate and 2-hydroxyethyl (meth) acrylate are reacted with urethane di (meth) acrylate, dicyclo Urethane di (medium) obtained by reacting 2-hydroxyethyl (meth) acrylate with a urethanization reaction product of methane diisocyanate and poly (repeating unit number = 6 to 15) tetramethylene glycol. ) Urethane poly (meth) acrylates such as acrylate, polyester poly (meth) acrylate obtained by reacting trimethylolethane with succinic acid and (meth) acrylic acid, trimethylolpropane, succinic acid, ethylene glycol and An organic-inorganic hybrid (meth) acrylate obtained by condensing polyester poly (meth) acrylate such as polyester poly (meth) acrylate obtained by reacting (meth) acrylic acid, colloidal silica and (meth) acryloylalkoxysilane, etc. Can be mentioned.

  Specific examples of the organic-inorganic hybrid (meth) acrylate include colloidal silica, vinyltrimethoxysilane, vinyltriethoxysilane, p-vinylphenylenetrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3 -(Meth) acryloxypropyltrimethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- Examples of the organic / inorganic hybrid vinyl compound and organic / inorganic hybrid (meth) acrylate compound include a combination with a silane coupling agent such as (meth) acryloxypropyltriethoxysilane.

  (D) A component can be used individually by 1 type or in combination of 2 or more types.

  In this invention, the composition containing the said monofunctional acrylate, polyfunctional acrylate, and urethane poly (meth) acrylate as (D) component for motor vehicle lamp lenses is preferable.

  Specific examples of the component (D) for automobile lamp lenses include 10 to 40% by mass of poly (meth) acrylate of mono- or polypentaerythritol, 5 to 40% by mass of urethane poly (meth) acrylate, and poly [(meth) acryloyl. Oxyalkyl] (iso) cyanurate is preferable in that a composition containing 20 to 70% by mass can obtain a cured film having excellent heat resistance, chemical resistance, weather resistance, and adhesion to thermoplastics. Can be mentioned.

  In this invention, a photoinitiator (E) (henceforth "(E) component") can be contained in this acrylic type coating material composition. (E) As a component, what melt | dissolves uniformly in this acrylic type coating material composition is mentioned. Specific examples of the component (E) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxy Carbonyl compounds such as cyclohexyl phenyl ketone, methylphenyl glyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide; 6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzo Phosphoric acid compounds such as (l) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide; 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butanone-1 and camphorquinone. These can be used alone or in combination of two or more.

  (E) As a compounding quantity of a component, 0.1-10 mass parts is preferable with respect to 100 mass parts of (D) component, and 2-4 mass parts is more preferable. When the blending amount of the component (E) is 0.1 parts by mass or more, the curability of the acrylic coating material composition becomes sufficient, and sufficient wear resistance, adhesion, and weather resistance tend to be obtained. Further, when the blending amount of the component (E) is 10 parts by mass or less, coloring of the cured film of the acrylic coating material composition is prevented, and the weather resistance tends to be improved.

  In the present invention, the acrylic coating material composition includes an ultraviolet absorber (F) (hereinafter referred to as “component (F)”) and a hindered amine light stabilizer (G) for the purpose of improving the weather resistance as required. (Hereinafter referred to as “component (G)”).

  Examples of the component (F) include compounds derived from benzophenone-based, benzotriazole-based, phenyltriazine-based, phenyl salicylate-based, and phenyl benzoate-based compounds. Otsuka Chemical Co., Ltd.'s PUVA-M series (trade name), Shannan Synthetic Chemical Co., Ltd. RSA series (trade name) ) (Meth) acrylic resin-based polymer ultraviolet absorbers such as USL series (trade name) manufactured by the company) are preferable. These can be used alone or in combination of two or more.

  (F) As a compounding quantity of a component, 2-100 mass parts is preferable with respect to 100 mass parts of (D) component, and 5-60 mass parts is more preferable. When the blending amount of the component (F) is 2 parts by mass or more, the weather resistance of the cured coating of the acrylic coating composition tends to be improved, and when it is 100 parts by mass or less, the curability of the acrylic coating composition is improved. However, the toughness, heat resistance and wear resistance of the cured coating of the present acrylic coating material composition tend to be improved.

  Examples of the component (G) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1- Pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-heptyloxy-2, , 6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-nonyloxy-2,2,6,6) -Tetramethyl-4-piperidyl) sebacate, bis (1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1-dodecyloxy-2,2,6,6-tetramethyl- 4-piperidyl) sebacate. Among these, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferable in terms of weather resistance.

  (G) As a compounding quantity of a component, 0.1-5 mass parts is preferable with respect to 100 mass parts of (D) component, and 0.5-2 mass parts is more preferable. When the blending amount of the component (G) is 0.1 parts by mass or more, the weather resistance and durability of the cured coating of the present acrylic coating material composition tend to be improved, and the present acrylic coating material composition is less than 5 parts by mass. The curability of the acrylic coating material composition tends to improve, and the toughness and wear resistance of the cured coating of the acrylic coating material composition tend to improve.

  In the present invention, in the acrylic coating material composition, if necessary, a silane coupling agent, an antioxidant, a yellowing inhibitor, a blooming agent, a pigment, a leveling agent, an antifoaming agent, a thickening agent. Further, various additives such as an anti-settling agent, an antistatic agent and an antifogging agent can be contained.

  When the acrylic coating material composition is applied on a substrate, an organic solvent can be added to the acrylic coating material composition. For example, when a polycarbonate resin is used as the base material, at least one of an alcohol solvent such as isobutanol and an ester solvent such as n-butyl acetate and diethylene glycol acetate is added to the acrylic coating material composition. can do.

  As a compounding quantity of an organic solvent, 30-500 mass parts is preferable at the point of workability | operativity at the time of apply | coating on a base material with respect to 100 mass parts of (D) component.

  Examples of the method for applying the present acrylic coating material composition onto a substrate include the same methods as those for applying the present coating material composition onto a substrate.

  The film thickness of the cured coating of the acrylic coating material composition is preferably 3 to 30 μm. When the film thickness of the cured coating of the present acrylic coating material composition is 3 μm or more, good adhesion to the substrate tends to be obtained, and when it is 30 μm or less, the production cost tends to be favorable.

  In the present invention, as a method of curing the acrylic coating material composition, a method of completely curing before coating of the coating material composition or making the acrylic coating material composition uncured or semi-cured, Any method of applying the present coating material composition to the surface and then irradiating the active energy ray to simultaneously cure the present acrylic coating composition and the present coating material composition may be used.

  Examples of the active energy ray for curing the present acrylic coating material composition include the same active energy rays as those for curing the present coating material composition.

The irradiation energy of the active energy ray for curing the acrylic coating material composition is preferably 0.1 to 10 J / cm ² with an integrated energy of a wavelength of 340 to 380 nm.

  Examples of the irradiation atmosphere of the active energy ray for curing the acrylic coating material composition include the same atmosphere as the irradiation atmosphere for curing the coating material composition.

  Hereinafter, the present invention will be described by way of examples. In the following, “part” and “%” indicate “part by mass” and “% by mass”, respectively.

  In the present invention, the glass transition temperature (hereinafter referred to as “Tg”), the mass average molecular weight (hereinafter referred to as “Mw”) of the polymer, and the liquid appearance 30 minutes after blending the active energy ray-curable coating material composition. The appearance, initial adhesion, initial haze, scratch resistance, hot water test and environmental test of the cured coating of the active energy ray-curable coating material composition of the laminate were evaluated by the following methods.

(1) Tg
Using DSC (Seiko Electronics Co., Ltd., DSC22 system), the sample was shown as a shoulder value measured while the temperature was raised at 10 ° C./min.

(2) Mw
It measured using gel permeation chromatography (GPC) "HLC-8120" (the Tosoh Co., Ltd. make, brand name). As the column, TSKgel G5000HXL * GMHXL-L (trade name, manufactured by Tosoh Corporation) was used. Moreover, the calibration curve was created using F288 / F80 / F40 / F10 / F4 / F1 / A5000 / A1000 / A500 (trade name, manufactured by Tosoh Corporation) and styrene as standard polystyrene.
Measurement was performed at 40 ° C. using 100 μl of a solution in which the polymer was dissolved in tetrahydrofuran to a concentration of 0.4%. Mw was calculated in terms of standard polystyrene.

(3) Liquid appearance 30 minutes after blending The appearance after 30 minutes of the active energy ray-curable coating composition obtained by blending was visually observed, and the liquid appearance 30 minutes after blending according to the following criteria. evaluated.
○: No abnormality is observed ×: Abnormality is observed

(4) Hardened film appearance The test piece was observed visually, and the cured film appearance was evaluated according to the following criteria.
○: No abnormality is observed ×: Abnormality is observed (in parentheses indicate abnormal state)

(5) on the cured coating of the initial adhesion test piece was cross-cut reaching the substrate at 1mm intervals of 1mm ² and go cross grain creates 100. Next, after attaching the cellophane tape on the grid, the cellophane tape was abruptly peeled off, the peeled grid was counted, and the initial adhesion was evaluated according to the following criteria.
○: No peeling at all ×: Peeling off

(6) Initial haze The initial diffuse transmittance (haze value) was measured using a haze meter (HM-65W, manufactured by Murakami Color Research Laboratory Co., Ltd.).

(7) Scratch resistance (a) Steel wool abrasion test Using a surface friction tester (manufactured by Coating Tester Industry Co., Ltd.), steel wool # 000, load 143 g / cm ² , 100 mm / second and 11 reciprocations After abrasion under the conditions, the diffuse transmittance (haze value) was measured in the same manner as (6) initial haze.
(B) Taber abrasion test Using a Taber abrasion tester, after 500 cycles of wear treatment with wear wheel CS-10F and 500 g load, (6) Measure the diffuse transmittance (haze value) in the same manner as the initial haze, The scratch resistance by the Taber abrasion test was evaluated.

(8) Warm water test The appearance and adhesiveness of the cured film of the active energy ray-curable coating material composition after the test piece was immersed in an 80 ° C. water bath for 2 hours were evaluated according to the following criteria.
(A) Appearance The appearance of the test piece was visually evaluated.
○: No abnormality is observed ×: Abnormality is observed (in parentheses indicate abnormal state)
(B) Adhesion A crosscut reaching the substrate at 1 mm intervals was put on the cured coating of the test piece, and 100 1 mm ² grids were prepared. Next, after attaching the cellophane tape on the grid, the cellophane tape was abruptly peeled off, the peeled grid was counted, and the adhesion was evaluated according to the following criteria.
○: No peeling at all ×: Peeling off

(9) Environmental test Using Satake constant temperature and humidity layer KHWW-40HP (manufactured by Satake Chemical Machinery Co., Ltd.), the test piece is left in an environment of 85 ° C. and 95% RH for 16 hours, and then at −20 ° C. A state of standing for 3 hours and further at 85 ° C. and 0% RH for 6 hours was defined as one cycle, and this operation was performed for 5 cycles. The appearance and adhesion of the cured film of the active energy ray-curable coating material composition after this treatment were evaluated according to the following criteria.
(A) Appearance The appearance of the test piece was visually evaluated.
○: No abnormality is observed ×: Abnormality is observed (in parentheses indicate abnormal state)
(B) Adhesion A crosscut reaching the substrate at 1 mm intervals was put on the cured coating of the test piece, and 100 1 mm ² grids were prepared. Next, after attaching the cellophane tape on the grid, the cellophane tape was abruptly peeled off, the peeled grid was counted, and the adhesion was evaluated according to the following criteria.
○: No peeling at all ×: Peeling off

[Production Example 1] Production of component (A-1) 90.0 g of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-13) in a flask equipped with a stirrer, a condenser and a thermometer 0.66 mol), 10.0 g (0.05 mol) of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-103) and 77.0 g of isopropyl alcohol were mixed and stirred to obtain a uniform solution. . At this time, the charged molar ratio of methyltrimethoxysilane and phenyltrimethoxysilane (the charged molar amount of methyltrimethoxysilane / the charged molar amount of phenyltrimethoxysilane) is 93/7.

  77.0 g of deionized water was added to the homogeneous solution and heated at 80 ° C. for 3 hours with stirring, followed by hydrolysis and condensation to obtain component (A-1). The weight average molecular weight of the component (A-1) was about 1,800 in terms of polystyrene.

[Production Example 2] Production of Dispersant (I) 900 parts of deionized water, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate and methacrylic acid in a flask equipped with a stirrer, a condenser and a thermometer 12 parts of methyl was added and stirred, and the temperature was raised to 50 ° C. while purging the inside of the flask with nitrogen. Next, 0.08 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride was added to the flask as a polymerization initiator, and the temperature was further raised to 60 ° C. After the temperature rise, 18 parts of methyl methacrylate was continuously dropped at a rate of 0.24 part / minute using a dropping pump. The obtained reaction solution was held at 60 ° C. for 6 hours and then cooled to room temperature to obtain a dispersant (I) having a solid content of 10% as a transparent aqueous solution.

[Production Example 3] Production of chain transfer agent (α) In a flask equipped with a stirrer, 1.00 g of cobalt acetate (II) tetrahydrate, 1.93 g of diphenylglyoxime and nitrogen bubbling in advance under a nitrogen atmosphere 80 ml of diethyl ether deoxygenated by the above was added and stirred at room temperature for 30 minutes. Next, 10 ml of boron trifluoride diethyl ether complex was added, and the mixture was further stirred for 6 hours. The obtained reaction product was filtered, the solid content was washed with diethyl ether, and vacuum dried for 15 hours to obtain 2.12 g of a chain transfer agent (α) as a reddish brown solid.

[Production Example 4] Production of polymer (a) In a flask equipped with a stirrer, a condenser tube and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate and 0.25 part of dispersant (ii) were added. The mixture was stirred to obtain a uniform aqueous solution. Next, a monomer mixture of 100 parts of methyl methacrylate, 0.01 part of chain transfer agent (α) and 0.8 part of 2,2′-azobis (2-methylbutyronitrile) was added to the flask. A suspension was obtained. Thereafter, the inside of the flask was purged with nitrogen, heated to 80 ° C. and reacted for about 1 hour, and further heated to 93 ° C. and held for 1 hour in order to further increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous polymer suspension. This aqueous polymer suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain a polymer. The polymer Tg was 50 ° C. and Mw was 3,200. This polymer was dissolved in 1-methoxy-2-propanol to obtain a polymer (A) having a solid content of 20%.

[Production Example 5] Production of polymer (ii) Production example except that chain transfer agent (α) is changed to 0.005 part and 2,2′-azobis (2-methylbutyronitrile) is changed to 0.4 part. In the same manner as in Example 4, a polymer (i) having a solid content of 20% was obtained. The obtained polymer had Tg of 82 ° C. and Mw of 7,800.

[Production Example 6] Production of polymer (U) Production example except that chain transfer agent (α) is changed to 0.002 part and 2,2′-azobis (2-methylbutyronitrile) is changed to 0.3 part. In the same manner as in Example 4, a polymer having a solid content of 20% was obtained. The obtained polymer had Tg of 98 ° C. and Mw of 13,500.

[Production Example 7] Production of polymer (E) Production example except that chain transfer agent (α) is changed to 0.005 part and 2,2′-azobis (2-methylbutyronitrile) is changed to 0.5 part. In the same manner as in Example 4, a polymer (E) having a solid content of 20% was obtained. The obtained polymer had Tg of 78 ° C. and Mw of 5,300.

[Production Example 8] Production of polymer (O) As a monomer mixture, 90 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, 0.005 part of chain transfer agent (α) and 2,2′-azobis (2 -Methylbutyronitrile) A polymer (20) having a solid content of 20% was obtained in the same manner as in Production Example 4 (α) except that the mixture was changed to 0.5 part. The obtained polymer had Tg of 51 ° C. and Mw of 5,700.

[Production Example 9] Preparation of active energy ray-curable acrylic coating material composition (X) The active energy ray-curable acrylic coating material composition (X) is mixed and stirred at the composition ratio of the raw materials shown in Table 1. Obtained.

In addition, the symbol in Table 1 shows the following compounds.
DPHA: dipentaerythritol hexaacrylate TAIC: tris (2-acryloyloxyethyl) isocyanurate UA-1: Mw2 obtained by synthesis from 2 mol of dicyclohexylmethanediol, 1 mol of nonabutylene glycol and 2 mol of 2-hydroxyethyl acrylate , 500 urethane acrylate BP: Benzophenone IRG651: Benzyldimethyl ketal MPG: Methylphenylglyoxylate RSA-0199: Sannan Synthetic Chemical Co., Ltd. UV absorber, trade name, pure content 40%
BOTS: A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (Sankyo Lifetech Co., Ltd.) Product name: Sanol LS-292)
PGM: 1-methoxy-2-propanol ECA: ethyl diglycol acetate

[Examples 1 to 9 and Comparative Examples 1 to 6]
On the surface of a polycarbonate resin plate having a thickness of 3 mm (manufactured by Teijin Chemicals Ltd., trade name: Panlite L-1225Z-100K), the thickness of the cured coating is applied to the active energy ray-curable acrylic coating material composition (X). Air spray coating was applied to a thickness of 8 μm. The polycarbonate resin plate coated with air spray is heated in a far-infrared heating furnace so that the substrate temperature reached after 90 seconds is 60 ° C., and the organic solvent is volatilized. A cured film of the active energy ray-curable acrylic coating material composition (X) is laminated on the substrate by irradiating it with ultraviolet rays in the air with an energy of 3,000 mJ / cm ^{2 and} an accumulated light amount of ˜380 nm. A laminate was obtained. In addition, the ultraviolet irradiation amount was measured with the ultraviolet light quantity meter (Corporation | KK Oak Seisakusho make, UV-351SN type | mold (brand name)).

The active energy ray-curable coating composition having the composition shown in Table 2 or Table 3 is applied to the bar coating method on the cured film of the active energy ray-curable acrylic coating composition (X) of the laminate obtained above. The cured coating was applied to a thickness of 5 μm and heated in a hot air dryer set at 120 ° C. for 10 minutes. Next, an active energy ray-curable acrylic coating material composition is cured on the substrate by irradiating with ultraviolet light with an energy of 1,000 mJ / cm ² with an integrated light quantity of wavelength 340 to 380 nm using a high-pressure mercury lamp. A laminate in which the cured coating of (X) and the cured coating of the active energy ray-curable coating composition were sequentially laminated was obtained as a test piece. Table 2 or Table 3 shows the liquid appearance 30 minutes after preparation of the active energy ray-curable coating material composition and various evaluation results of the test pieces.

In addition, the symbol in Table 2 and Table 3 shows the following compounds.
MS-1: Methyl silicate 53A (manufactured by Colcoat Co., Ltd., trade name, average molecular weight 1,000)
MS-2: Methyl silicate 51 (manufactured by Colcoat Co., Ltd., trade name, average molecular weight 600)
GPTMS: 3-Glycidoxypropyltrimethoxysilane QP8-5314: Siloxane oligomer (trade name, manufactured by Toray Dow Corning Co., Ltd.)
PhTMS: Phenyltrimethoxysilane SI-100L: Photoacid generator (trade name, manufactured by Sanshin Chemical Co., Ltd.)
CPI-200: Photoacid generator (manufactured by San Apro Co., Ltd., trade name)
SI-80L: Photoacid generator (trade name, manufactured by Sanshin Chemical Co., Ltd.)
Polymer (ka): Mitsubishi Rayon Co., Ltd. polymethylmethacrylate, Dianal BR-83 (trade name, polymer of Mw 40,000) with 1-methoxy-2-propanol to a solid content of 20% Dissolved.
Leveling agent A: Silwet L-7001 (trade name, manufactured by Toray Dow Corning Co., Ltd.) dissolved in 1-methoxy-2-propanol so as to have a solid content of 1%.
Leveling agent B: BYK-333 (manufactured by Big Chemie Co., Ltd., trade name) dissolved in 1-methoxy-2-propanol so as to have a solid content of 10%.
γ-BL: γ-butyrolactone PGM: 1-methoxy-2-propanol IPA: isopropyl alcohol

  In Examples 1 to 9, good results were obtained in all evaluations of the test pieces.

  In Comparative Examples 1 to 4, since the active energy ray-curable coating material composition does not contain the component (B) or the amount of the component (B) is small, occurrence of cracks was recognized in the environmental test of the test piece. It was.

In Comparative Example 5, the amount of component (B) in the active energy ray-curable coating material composition was large, so that the scratch resistance of the test piece was low.
In Comparative Example 6, since the (meth) acrylic acid alkyl polymer having a large molecular weight was contained, the liquid for 30 minutes after blending the active energy ray-curable coating composition became cloudy.

Claims (4)

  An alkyl (meth) acrylate having a weight average molecular weight in terms of polystyrene of 3,000 to 20,000 with respect to 100 parts by mass of the silicone compound (A) containing at least one of organoalkoxysilane and its hydrolysis condensate. An active energy ray-curable coating composition containing 10 to 30 parts by mass of the combined body (B) and 1 to 5 parts by mass of the photoacid generator (C).   The laminated body by which the cured film of the active energy ray-curable coating material composition of Claim 1 was laminated | stacked on the base material.   The laminated body by which the cured film of the active energy ray-curable acrylic coating material composition and the cured film of the active energy ray-curable coating material composition of Claim 1 were laminated | stacked sequentially on the base material.   The laminate according to claim 3, wherein the substrate is a polycarbonate resin.