JP5005924B2 - Tin film undercoat layer molding composition, tin film undercoat layer and tin film coated resin molded product - Google Patents

Description

  The present invention relates to a composition for forming an undercoat layer of a tin film, and more specifically, for forming an undercoat layer that can be cured by irradiation with active energy rays to form a tin film on the surface of a resin molded product. Relates to the composition. The present invention also provides a tin film-coated resin having a metallic appearance, wherein an undercoat layer of a tin film obtained by curing an undercoat layer molding composition, and an undercoat layer and a tin metal are sequentially laminated on a resin molded product. Regarding molded products.

In the field of decorative products and home appliances, particularly reflectors, resin molded products subjected to metal processing instead of metal processed products are used for advantages such as productivity, moldability, and weight reduction. Metal processing is a technique in which an undercoat layer (primer layer) is formed on the surface of a resin molded product, and metallization such as ionized vapor deposition or sputtering is performed. Especially in home appliances, resin molded products such as ABS and PC, which are excellent in moldability and weight reduction, are frequently used. As a method for forming the undercoat layer used for such metallization treatment, a film is formed from a resin composition such as acrylic, melamine, or urethane, and the film is cured using heat or ultraviolet rays. There is. Among these, the ultraviolet curing method for curing the film using ultraviolet rays has been put into practical use because it has advantages such as superior productivity compared to other methods. Aluminum, chromium, and the like are frequently used as the metal film for the metallization treatment, but in recent years tin has been used from the viewpoint of imparting a high-class feeling and creating a discontinuous film. Adhesion of sufficient tin film when using an undercoat layer of the same material as the conventional undercoat layer applied to metal processing such as aluminum and chromium in a resin molded product that has been subjected to metal treatment using tin Sex cannot be obtained.
JP-A-7-70474

  In recent years, in mobile phone cases, there are increasing cases of using tin vapor deposition instead of aluminum vapor deposition, which is capable of discontinuous vapor deposition, which has high design and does not affect the structure with a built-in antenna. However, the tin film is not sufficiently adherent to the undercoat layer used for the deposited film of aluminum or chromium, and an undercoat layer excellent in adherence to the tin film has not been obtained.

  An object of the present invention is to provide a composition for forming an undercoat layer of a tin film, which can easily form an undercoat layer having excellent adhesion to a tin film and other excellent physical properties and smoothness of a coating film. There is to do.

  Another object of the present invention is to provide an undercoat of a tin film that is excellent in adhesion to a tin film, has good physical properties and smoothness of a coating film, and can be easily molded by curing with active energy rays. It is to provide a coat layer.

  The subject of the present invention can be applied to a cosmetic container, a mobile phone, a portable music player, etc. that adheres well to the undercoat layer, has a high-class feeling, and has a high design and excellent design. It is another object of the present invention to provide a tin film-coated resin molded product that can be easily formed into a discontinuous tin film and can be applied to a cellular phone having an antenna built-in structure.

  As a result of intensive studies to solve the above problems, the present inventors have found that the adhesion of the undercoat layer to the tin vapor deposition film is excellent by blending a specific amount of a specific polyfunctional monomer. It came to be completed.

  That is, the present invention relates to a polyester diol obtained by reacting (A) (a1) adipic acid and (a2) one or more diols selected from alkanediols having 2 to 6 carbon atoms, 20 to 40% by mass of urethane (meth) acrylate obtained by reacting diisocyanate or isophorone diisocyanate and (a4) hydroxyl group-containing (meth) acrylic ester, (B) one or more (meth) acryloyloxy in the molecule (Meth) acrylate having a group (however, a compound other than the above (A)) 45 to 79.9% by mass, (C) a composition for forming an undercoat layer of a tin film containing 0.1 to 15% by mass of a photopolymerization initiator Related to things.

  The present invention also relates to a tin film undercoat layer obtained by curing a film formed by using the above-described tin film undercoat layer molding composition on the surface of a resin molded product by irradiation with active energy rays.

  The present invention also relates to a tin film-coated resin molded product in which the above-described tin film undercoat layer and a tin film are sequentially laminated on the surface of the resin molded product.

  The composition for molding an undercoat layer of a tin film of the present invention can easily form an undercoat layer having excellent adhesion to a tin film and other excellent physical properties and coating film smoothness.

  In addition, the undercoat layer of the tin film of the present invention has excellent adhesion to the tin film, and other physical properties and smoothness of the coating film, and can be easily molded by curing using active energy rays. it can.

  Furthermore, the tin film-coated resin molded product of the present invention is applied to cosmetic containers, mobile phones, portable music players, etc. that adhere well to the undercoat layer, have a high-class feel, and have a high design. Furthermore, the discontinuous tin film can be easily formed, and can be applied to a cellular phone having a built-in antenna structure.

  The tin film undercoat layer molding composition of the present invention is a kind selected from (A) (a1) adipic acid (hereinafter referred to as “(a1)”) and (a2) an alkanediol having 2 to 6 carbon atoms. Or a polyester diol obtained by reacting two or more diols (hereinafter referred to as “(a2)”) with (a3) tolylene diisocyanate or isophorone diisocyanate (hereinafter referred to as “(a3)”) and (a4) 20 to 40% by mass of urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester (hereinafter referred to as “(a4)”), (B) one or more (meth) in the molecule (Meth) acrylate having an acryloyloxy group (however, a compound other than the above (A)) 45-79.9% by mass, (C) 0.1-15 photopolymerization initiator % Is intended to include.

  The component (A) urethane (meth) acrylate used in the tin film undercoat layer molding composition of the present invention exhibits good polymerization activity upon irradiation with active energy rays, and particularly exhibits adhesion to the tin film. It is an ingredient.

  Specific examples of (a2) constituting the component (A) urethane (meth) acrylate include ethylene glycol, propylene glycol, 1,4 butanediol, and 1,6 hexanediol. Among these, the combination containing ethylene glycol is preferable from the viewpoint of adhesion of the obtained composition to the tin film.

  In addition, as component (A) urethane (meth) acrylate (a4), hydroxy group-containing (meth) acrylic having at least one (meth) acryloyloxy group and at least one hydroxy group in the molecule If it is an acid ester, it will not specifically limit. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate and caprolactone adduct, 4-hydroxybutyl (meth) acrylate and Examples include adducts of caprolactone, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Among these, from the viewpoint of reducing the viscosity of the resulting composition, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) Acrylate and 4-hydroxybutyl (meth) acrylate are preferred.

  Here, “(meth) acryl” is a general term for “acryl” and “methacryl”, and other “(meth) acryl ...” is a group derived from “acryl” and “methacryl”. Is a general term.

  As a method for synthesizing component (A), there may be mentioned a method in which (a1) and (a2) are first reacted to obtain a polyester diol, and (a3) and (a4) are reacted therewith for synthesis.

  The conditions for the reaction with the above (a1) and (a2) include a condition in which a polyester diol is obtained by reacting at a temperature of about 200 ° C. and dehydrating and condensing. Alternatively, these polyester diols already synthesized may be obtained and used.

  The obtained polyester diol preferably has a weight average molecular weight by GPC in the range of 10,000 to 18,000 from the viewpoint of leveling properties of the coating film appearance.

  Furthermore, in a mixture of a polyester diol and a catalyst such as di-n-butyltin dilaurate, (a3) is dropped and reacted at 50 to 90 ° C. to obtain a urethane prepolymer, and (a4) The component (A) can be produced by reacting. Further, after reacting (a3) and (a4), the polyester diol obtained from (a1) and (a2) may be reacted. The end point of this reaction can be determined by, for example, quantifying the component (a3). The reaction rate during the synthesis of component (A) is preferably 97 mol% or more, more preferably 99 mol% or more.

  Specific examples of the component (B) used in the tin film undercoat layer molding composition of the present invention include trimethylolpropane tri (meth) acrylate, trisethoxylated trimethylolpropane tri (meth) acrylic. Acid ester, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated Pentaerythritol tetra (meth) acrylic acid ester, tris (2-acryloyloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylic acid ester, dipentaerythritol hexa (meth) Acrylic acid ester, caprolactone-modified dipentaerythritol penta (meth) acrylic acid ester, caprolactone-modified dipentaerythritol hexa (meth) acrylic acid ester, C2-C5 aliphatic hydrocarbon-modified trimethylolpropane triacrylate, carbon number 2 Mentioning polyfunctional (meth) acrylic acid esters such as -5 aliphatic hydrocarbon-modified dipentaerythritol penta (meth) acrylate and C2-C5 aliphatic hydrocarbon-modified dipentaerythritol tetra (meth) acrylate Can do.

    Further, as component (B), ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, di (meth) acrylic acid 1 , 6-hexanediol, nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, methylpentanediol di (meth) acrylate, diethylpentanediol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylic acid ester, di (meth) acrylic acid tetraethylene glycol, di (meth) acrylic acid tripropylene glycol, di (meth) acrylic acid polybutylene glycol, di (meth) acrylic acid tricyclodecane dimethanol , Bis (2-acryloyloxyethyl) 2-hydroxyethyl isocyanurate, di (meth) acrylic acid cyclohexanedimethanol, di (meth) acrylic acid polyethoxylated cyclohexanedimethanol, di (meth) acrylic acid polypropoxylated cyclohexanedimethanol, di (meth) acrylic Acid polyethoxylated bisphenol A, di (meth) acrylic acid polypropoxylated bisphenol A, di (meth) acrylic acid hydrogenated bisphenol A, di (meth) acrylic acid polyethoxylated hydrogenated bisphenol A, di (meth) ) Acrylic acid polypropoxylated hydrogenated bisphenol A, bisphenoxyfluorene ethanol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, hydroxypi Ε-Caprolactone 2-5 mol addition di (meth) acrylic acid ester of neopentyl glycol phosphate, γ-butyrolactone 2-5 mol addition di (meth) acrylate ester of hydroxypivalate neopentyl glycol, caprolactone of neopentyl glycol 2-5 mol addition di (meth) acrylic acid ester, butylene glycol caprolactone 2-5 mol addition di (meth) acrylic acid ester, cyclohexanedimethanol caprolactone 2-5 mol addition di (meth) acrylic acid ester, dicyclo 2-5 mol addition di (meth) acrylate of caprolactone of pentanediol, 2-5 mol addition di (meth) acrylate of caprolactone of bisphenol A, 2-5 mol addition di (meth) a of caprolactone of hydrogenated bisphenol A Acrylic acid esters, and di (meth) acrylic acid esters such as caprolactone 2-5 mols di (meth) acrylate of bisphenol F.

  Further, as component (B), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) Phenoxyethyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 2- (meth) acryloyloxymethyl-2-methylbicycloheptane, adamantyl (meth) acrylate, (meth ) Benzyl acrylate, phenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-methoxyethyl ( ) Acrylate, 3-methoxybutyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 4-acryloyloxymethyl-2-methyl-2- Ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, trimethylolpropane formal (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, caprolactone modified phosphorus Examples include (meth) acrylic acid esters such as acid (meth) acrylate.

Further, as component (B), vinyl ester monomers such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, divinyl adipate; ethyl vinyl ether, Vinyl ethers such as phenyl vinyl ether;
Acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylenebis Acrylamides such as acrylamide;
Polybasic acids such as phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, adipic acid, polyhydric alcohols such as ethylene glycol, hexanediol, polyethylene glycol, polytetramethylene glycol and (meta ) Polyester poly (meth) acrylates obtained by reaction with acrylic acid or its derivatives;
Epoxy (meth) acrylates obtained by reacting bisphenol type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and epichlorohydrin with (meth) acrylic acid or its derivatives Can be mentioned.

  In addition, as the component (B), an organic diisocyanate compound is added to the hydroxyl group of an alcohol composed of one or a mixture of two or more of alkanediol, polyetherdiol, polyesterdiol, spiroglycol compound, etc. Urethane poly (meth) acrylates other than the component (A) obtained by reacting one or more (meth) acryloyloxy groups in the molecule with a hydroxy group-containing (meth) acrylic acid ester having one hydroxy group Can be mentioned.

  These specific examples can be used alone or in combination of two or more.

  The photopolymerization initiator component (C) used in the tin film undercoat layer molding composition of the present invention includes benzoin, benzoin monomethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1- Carbonyl compounds such as phenylpropan-1-one and 2-ethylanthraquinone; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethyl And acyl phosphine oxides such as benzoyl diphenyl phosphine oxide, and the like. These can be used alone or in combination of two or more. Among these, benzophenone and 1-hydroxycyclohexyl phenyl ketone are more preferable.

  As content of said each component (A), (B), (C), content of a component (A) is 20-40 mass% in a composition, and it is preferable that it is 25-34 mass%. . If content of a component (A) is 20 mass% or more, the adhesive fall of the tin film laminated | stacked can be suppressed. Moreover, if it is 40 mass% or less, the fall of the smoothness in an undercoat layer can be suppressed.

  In the composition, the content of the component (B) is 45 to 79.9% by mass, and preferably 65 to 74% by mass. If content of a component (B) is 45 mass% or more, the fall of the smoothness in an undercoat layer can be suppressed. Moreover, if it is 79.9 mass% or less, the fall of the adhesiveness of a tin film can be suppressed.

  In the composition, the content of the component (C) is 0.1 to 15% by mass, and preferably 1 to 10% by mass. If content of a component (C) is 0.1 mass% or more, hardening of an undercoat layer will become enough, and if it is 15 mass% or less, the fall of the adhesiveness of a tin film can be suppressed.

  Furthermore, the composition of the present invention can be added to methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylamino, as necessary, as long as the performance is not impaired. A photosensitizer such as acetophenone can also be added.

  In the composition of the present invention, an organic solvent can be used to adjust the viscosity as necessary. Specific examples of organic solvents include ketone compounds such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; diethyl ether, ethylene glycol Ether compounds such as dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and dioxane; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane, hexane and petroleum naphtha; isopropyl alcohol, isobutanol and n-butanol An alcohol type compound can be mentioned.

  Further, the composition of the present invention includes additives such as a leveling agent, an antifoaming agent, an anti-settling agent, a lubricant, an abrasive, a rust inhibitor, an antistatic agent, a light stabilizer, an ultraviolet absorber, and a polymerization inhibitor. May be added.

  Furthermore, a polymer such as an acrylic polymer or an alkyd resin may be added in order to improve adhesion as long as the effect of the present invention is not impaired.

  As a method for preparing the composition for forming an undercoat layer of a tin film of the present invention, a method of stirring, mixing, heating, etc., if necessary, each of the above-described components and the above-mentioned additive added as necessary Can be mentioned.

  The undercoat layer of the tin film of the present invention is obtained by curing a film formed by using the above-described composition for forming an undercoat layer of a tin film on the surface of a resin molded product by irradiation with active energy rays.

  The material of the resin molded product in which the undercoat layer of the present invention is used may be any material, but specifically, ABS resin, AES resin, PC resin, acrylic resin; polyolefin resin such as polypropylene and polyethylene And polyester resins such as PET resin and PBT resin. Among these, it is particularly useful for ABS resin, polycarbonate resin, acrylic resin, etc. used for cosmetic containers and housings of home appliances.

  To form a film using the above-mentioned tin film undercoat layer molding composition on the surface of these resin molded products, methods such as brush coating, spray coating, dip coating, spin coating, and flow coating can be used. The spray coating method and the flow coating method are preferred from the viewpoints of coating workability, coating smoothness, and uniformity.

  The film thus formed is cured. When the film is cured, when the composition contains an organic solvent, it is preferable to remove the solvent before curing. As the removal of the solvent, it is preferable that the organic solvent is volatilized under conditions of, for example, 60 to 130 ° C. and 5 to 20 minutes by heating with an IR heater and / or warm air.

Curing of the coating can be performed by irradiation with active energy rays. Examples of active energy rays to be used include ultraviolet rays and electron beams. For example, when a high-pressure mercury lamp is used, the amount of ultraviolet energy irradiated is preferably about 500 to 4000 mJ / cm ² .

  The thickness of the undercoat layer of the present invention is preferably in the range of 3 to 40 μm after curing. If it is this range, adhesion of the upper tin film can be strengthened.

  The tin film-coated resin molded product of the present invention is obtained by sequentially laminating the tin film undercoat layer and the tin film on the surface of the resin molded product.

  The tin film provided on the tin film-coated resin molded product of the present invention is molded by metallization of the undercoat layer formed by applying and curing the resin molded product with the above-described tin film undercoat layer molding composition. be able to. As metallization treatment, PVD (Physical Vapor Deposition) by vacuum deposition, ion platein, sputtering, etc., and metal sprayed material such as powder, wire, rod-like, etc. are melted or semi-molten and struck against resin molded products at high speed. It is preferable to use a dry process such as thermal spraying to form a film or CVD (Chemical Vapor Deposition).

  Further, for the purpose of preventing corrosion of the tin film, a thermosetting top coat or an ultraviolet curable top coat may be formed on the surface of the formed tin film, or a treatment such as a plasma polymerization film may be performed.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. In the following, “part” means “part by mass” and “%” means “% by mass”. Various measurements and evaluations in the examples and comparative examples were performed by the following methods.

1. Smoothness of cured coating The composition was applied to an ABS test piece by spraying so that the film thickness after curing was about 15 μm, and after metalizing by tin deposition after curing, the appearance was visually evaluated. The visual evaluation was determined according to the following criteria.

◎ The surface of the undercoat layer is smooth and has a mirror surface. ○ The surface of the undercoat layer is smooth. △ The surface of the undercoat layer is slightly uneven. × The surface of the undercoat layer is not smooth.

2. Adhesion The composition is applied to the ABS test piece by spraying so that the film thickness after curing is about 15 μm. After curing, metallization treatment by tin vapor deposition is performed, and then the substrate is spaced at 1 mm intervals with a cutter knife. The cuts to reach were made, 100 grids of 1 mm ² were made, cellotape was pasted on them and peeled off rapidly, and the peeled grids were counted.

〇 No peeling △ Number of peels 1 to 50 × Number of peels 51 to 100.

[Synthesis Example 1] Production of urethane acrylate (UA1: component A) (1) Adipic acid 1606 g, ethylene glycol 589 g and propylene glycol 152 g were charged into a 3 L four-necked flask equipped with a distillation column and heated at 200 ° C. The water formed was distilled off. The end point was the time when the outflow of water disappeared and the acid value became 1.0 or less.
(2) A 3 L four-necked flask was charged with 174 g of tolylene diisocyanate and 0.3 g of dibutyltin dilaurate and heated in a water bath so that the internal temperature became 50 ° C.
(3) 1950 g of the polyester diol synthesized in the above (1) was charged into a heat retaining dropping funnel (60 ° C. heat retaining) with a side tube. While stirring the contents in the flask prepared in (2) above, the liquid in the dropping funnel was dropped at a constant rate over 4 hours while maintaining the flask internal temperature at 50 ° C., followed by stirring at the same temperature for 2 hours. And reacted.
(4) Next, the temperature of the flask contents was raised to 60 ° C. and stirred at the same temperature for 1 hour. A liquid in which 116 g of 2-hydroxyethyl acrylate, 0.3 g of 2,6-di-tert-butyl-4-methylphenol and 0.3 g of hydroquinone monomethyl ether were uniformly mixed and dissolved was charged into another dropping funnel. While keeping the temperature inside the flask at 75 ° C., the liquid in the dropping funnel was dropped at a constant rate over 2 hours, and then reacted at the same temperature for 4 hours. The weight average molecular weight in terms of polystyrene by GPC measurement was 11,000. The resulting urethane acrylate UA1 was produced.

[Synthesis Example 2] Production of urethane acrylate (UA2: Component A) Synthesis was performed except that 651 g of ethylene glycol and 90 g of tetramethylene glycol were charged instead of 589 g of ethylene glycol and 152 g of propylene glycol in (1) of [Synthesis Example 1]. In the same manner as in Example 1, urethane acrylate UA2 having a polystyrene equivalent weight average molecular weight of 13,000 as measured by GPC was produced.

[Synthesis Example 3] Production of Urethane Acrylate (UA3: Component A) Instead of 589 g of ethylene glycol and 152 g of propylene glycol in (1) of [Synthesis Example 1], 372 g of ethylene glycol and 495 g of hexamethylene glycol were charged. [1] The same procedure as in [Synthesis Example 1] except that 174 g of tolylene diisocyanate in (2) was replaced with 222 g of isophorone diisocyanate and the amount of polyester diol 1950 g in [Synthesis Example 1] (3) was changed to 2075 g. Thus, urethane acrylate UA3 having a polystyrene-reduced weight average molecular weight of 18,000 as measured by GPC was produced.

[Examples 1 to 3, Comparative Examples 1 to 4]
[Preparation of undercoat layer]
Next, the components of Examples 1 to 3 and Comparative Examples 1 to 4 shown in Table 1 were weighed into a stainless steel container, and stirred for about 30 minutes until the whole became uniform to prepare a hardening liquid. Next, spray coating was performed on a rectangular test piece of 9 cm in length, 5 cm in width, and 3 mm in thickness molded with ABS resin so that the film thickness upon curing was about 15 μm.

Next, the organic solvent was volatilized by heating at 60 ° C. for 3 minutes using a hot air dryer, and then cured by irradiating energy of 1000 mJ / cm ² with an integrated light amount of 340 to 380 nm in air. A coating film was formed.

[Vapor deposition of tin]
Tin was vapor-deposited on the thus-treated substrate by a vacuum vapor deposition method under a vacuum degree of 1.33 × 10 ^{−2 to} 2.66 × 10 ⁻² Pa to obtain a metallized resin molded product. Table 1 shows the evaluation results of the obtained metallized resin molded product.

〔実施例４〜９〕
実施例１と同様に、表２、表３に示す配合比で錫膜のアンダーコート層成形用組成物を調製し、アンダーコート層を作製し、錫の蒸着を行い、評価を行った。結果を表２、表３に示す。

[Examples 4 to 9]
In the same manner as in Example 1, compositions for forming an undercoat layer of a tin film were prepared at the compounding ratios shown in Tables 2 and 3, an undercoat layer was prepared, and tin was deposited and evaluated. The results are shown in Tables 2 and 3.

表１〜３中、略号は、以下の化合物を表わす。
ＰＡＲ−３００：ポリエステルアクリレート（日本化薬株式会社製）
ＰＥＴＡ ：ペンタエリスリトールテトラトリアクリレート（新中村化学工業株式会社製）
２−ＨＰＡ ：２−ヒドロキシプロピルアクリレート（大阪有機株式会社製）
Ｉｒ−１８４ ：１−ヒドロキシシクロヘキシルフェニルケトン（チバガイギー社製）・ＢＮＰ ：ベンゾフェノン

In Tables 1 to 3, abbreviations represent the following compounds.
PAR-300: Polyester acrylate (manufactured by Nippon Kayaku Co., Ltd.)
PETA: Pentaerythritol tetratriacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
2-HPA: 2-hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.)
Ir-184: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy Corp.), BNP: benzophenone

Claims (3)

(A) 20 to 40% by mass of urethane (meth) acrylate obtained by reacting (a3) and (a4) with polyester diol obtained by reacting (a1) and (a2), (B) in the molecule (Meth) acrylate having one or more (meth) acryloyloxy groups (however, it is a compound other than the above (A), including at least one selected from (b1) and at least one selected from (b2)) A composition for forming an undercoat layer of a tin film containing 45) to 79.9% by mass and (C) 0.1 to 15% by mass of a photopolymerization initiator.
(A1) Adipic acid (a2) One or more diols selected from alkanediols having 2 to 6 carbon atoms (a3) Tolylene diisocyanate or isophorone diisocyanate (a4) Hydroxyl group-containing (meth) acrylic acid ester (b1) Trimethylolpropane tri (meth) acrylate, trisethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylic acid ester, ethoxylated pentaerythritol tri (meth) acrylic acid ester, ethoxylated pentaerythritol tetra (meth) acrylic acid ester, tris (2 (Acryloyloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylic ester, dipentaerythritol hexa (meth) acrylic ester, caprolactone modified dipentaerythritol penta (meth) acrylic ester, caprolactone modified dipentaerythritol hexa (meta) ) acrylic acid ester, charcoal aliphatic prime 2-5 hydrocarbon-modified dipentaerythritol penta (meth) acrylate, aliphatic C2-5 hydrocarbon-modified dipentaerythritol tetra (meth) acrylate (b2) (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxy (meth) acrylate Ethyl, cyclohexanedimethanol mono (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methoxydipropylene glycol ( (Meth) acrylate, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, trimethylolpropane formal (meta ) Acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, caprolactone modified phosphoric acid (meth) acrylate   A tin film undercoat layer obtained by curing a film formed on the surface of a resin molded product using the tin film undercoat layer molding composition according to claim 1 by irradiation with active energy rays.   A tin film-coated resin molded product in which the tin film undercoat layer according to claim 2 and a tin film are sequentially laminated on the surface of the resin molded product.