JP5826123B2 - Metal-like film and metal-like article - Google Patents

Description

  The present invention relates to a metallic film excellent in design.

2. Description of the Related Art Conventionally, various metallic resin films that are applied to the surface of a plastic molded product to give a metal-like texture to the surface are used for automobile parts, home appliances, and the like.

  Such a metallic resin film is, for example, as in Patent Document 1 and Patent Document 2, a coating layer made of paint or ink using a vapor-deposited metal film piece obtained by pulverizing a vapor-deposited metal film as a glittering material. It is formed on the surface, and it is pasted on the surface of the article as it is, or it is attached to the article after being given a shape by vacuum pressure forming etc., or the film and the article are simultaneously molded like insert molding The design property is imparted to the article. In particular, when elongation occurs in the film by post-molding, the coating layer containing the vapor-deposited metal film piece is extremely thin, so that there is a problem that the metal feeling is impaired and the design property is lowered. On the other hand, for example, as in Patent Document 3, two or more resin layers having a film thickness of 0.2 to 3.0 μm formed of metal flakes obtained by pulverizing a resin and a deposited metal film are formed on a film substrate made of a thermoplastic resin In addition, a decorative film is proposed in which the metal flakes are arranged substantially parallel to the surface of the resin layer, and the content of the metal flakes in the resin layer is in the range of 30 to 80% by weight. Yes.

  However, in the decorative film, at least two components of the resin constituting the resin layer and the metal flakes obtained by pulverizing the vapor-deposited metal film were dissolved in a solvent having an absolute value of the difference in solubility parameter SP value from the resin in the range of 1 to 3. The mixed solution is applied to a film substrate made of a thermoplastic resin. Depending on the type of thermoplastic resin of the substrate, the surface of the substrate is dissolved by a solvent, and the orientation of the metal flakes in the resin layer is disturbed. There was a problem that a metal feeling could not be obtained.

JP 2008-110513 A JP 2008-110515 A JP 2002-301789 A

  An object of the present invention is to provide a metal-tone film that is uniform in the presence of metal flakes in a coating layer and has excellent design properties even when a film having low solvent resistance is used.

As a result of intensive studies to solve the above problems, the inventors of the present invention contain a hydroxyl group-containing acrylic resin and flake metal powder on a specific transparent resin film, and 35 isopropyl alcohol as an organic solvent. It has been found that the above problems can be solved by forming a coating layer of a metallic paint containing at least mass% on a transparent resin film, and the present invention has been completed.

  That is, the present invention contains (A) a hydroxyl group-containing acrylic resin, (B) flake metal powder, and (C) an organic solvent on the transparent resin film (I) having a solubility by ethyl acetate of 30% by mass or more. A metallic film characterized in that the organic solvent (C) has a coating layer (II) made of a metallic paint containing isopropyl alcohol in an amount of 35% by mass or more, and this is applied to the substrate surface It is related with the metal-like article formed.

  According to the present invention, by forming a coating layer with a metallic paint containing a hydroxyl group-containing acrylic resin and flaky metal powder and further containing 35% by mass or more of isopropyl alcohol as an organic solvent on the transparent resin film, Without dissolving the surface of the film having low solvent resistance, it is possible to obtain a metallic film having a uniform appearance of the metal flakes in the coating layer and having an excellent design.

  The metallic film of the present invention has a hydroxyl group-containing acrylic resin (A), flake metal powder (B), and an organic solvent (C) on a transparent resin film (I) having a solubility by ethyl acetate of 30% by mass or more. ) Containing a metallic paint layer (II).

Transparent resin film (I)
The transparent resin film (I) used in the present invention is a resin film having a solubility by ethyl acetate of 30% by mass or more, particularly 70% by mass or more, and further 95% by mass or more.

  Here, the dissolution rate with ethyl acetate is the mass reduction rate after the resin film piece is immersed in ethyl acetate. Specifically, the resin film piece is immersed in ethyl acetate, and the frequency is 28 kHz and the output is 100 W. After applying ultrasonic vibration for 10 minutes, the resin film piece taken out from the immersion bath is dried at 50 ° C. for 24 hours, and the mass reduction rate of the resin film before and after immersion is calculated, and this is taken as the dissolution rate.

  As said transparent resin film (I), what uses acrylic resins, such as polymethylmethacrylate, and a polycarbonate resin as a base material, for example is preferable from a surface of a weather resistance. Further, the transparent resin film (I) may not be completely colorless and transparent, and may be colored with a pigment, a dye or the like depending on the desired design and metallic feeling. The thickness of these film bases is 25 to 250 μm, preferably 50 to 200 μm. These film base materials may be appropriately subjected to surface treatment, and examples thereof include chemical resistance treatment and hard coat treatment.

Coating layer (II)
The coating layer (II) is formed on the transparent resin film (I) by a metallic paint containing a hydroxyl group-containing acrylic resin (A), a flaky metal powder (B) and an organic solvent (C). It is.

  The hydroxyl group-containing acrylic resin (A) is usually obtained by copolymerizing the hydroxyl group-containing polymerizable unsaturated monomer (a) and other polymerizable unsaturated monomers (b) by a known polymerization method such as solution polymerization. Is.

  Examples of the hydroxyl group-containing polymerizable unsaturated monomer (a) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , Monoesterified products of polyhydric alcohols such as polyethylene glycol mono (meth) acrylate and polypropylene glycol (meth) acrylate and (meth) acrylic acid, and monoesterified products of polyhydric alcohol and (meth) acrylic acid -A compound obtained by ring-opening polymerization of caprolactone (caprolactone-modified hydroxyalkyl (meth) acrylate) and the like. These can be used alone or in combination of two or more. In particular, the hydroxyl group-containing polymerizable unsaturated monomer (a) preferably contains caprolactone-modified hydroxyalkyl (meth) acrylate from the viewpoints of the design properties and adhesion of the resulting metal film.

  Examples of other polymerizable unsaturated monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, etc. (Meth) acrylic acid alkyl ester; (meth) acrylic acid, maleic acid, maleic anhydride and other carboxyl group-containing polymerizable unsaturated monomers; N, N-dimethylaminoethyl (meth) acrylate, N, N-di Aminoalkyl (meth) acrylates such as tilaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; acrylamide, methacrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylamino (Meth) acrylamide or a derivative thereof such as ethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylolacrylamide, N-methylolacrylamide methyl ether, N-methylolacrylamide butyl ether; 2- (methacryloyloxy) ) Quaternary ammonium base-containing monomers such as ethyltrimethylammonium chloride and 2- (methacryloyloxy) ethyltrimethylammonium bromide; (Meth) acrylamide-alkanesulfonic acid such as amido-2-methylpropanesulfonic acid, sulfoalkyl (meth) acrylate such as 2-sulfoethyl (meth) acrylate; acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyltoluene, α -Methylstyrene; Polyvinyl compounds such as allyl methacrylate; -Hydrolysis of-(meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane Polymerizable silyl group-containing polymerizable unsaturated monomer; 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 4- (meth) acryloyloxy-1,2,2,6,6- Pentame UV absorbing or UV stability polymerizable unsaturated monomer and the like, such as Rupiperijin, which can be used either alone or in combination of two or more.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. “(Meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylamide” means acrylamide or methacrylamide.

  The proportion of the hydroxyl group-containing polymerizable unsaturated monomer (a) and other polymerizable unsaturated monomer (b) used is such that the component (a) is 2 to 50% by mass, preferably based on the total solid content mass. 7 to 40% by mass, more preferably 10 to 30% by mass, component (b) in the range of 50 to 98% by mass, preferably 60 to 93% by mass, more preferably 70 to 90% by mass, It is suitable from the point of the designability, adhesiveness, etc. of the metal tone film obtained. When the hydroxyl group-containing polymerizable unsaturated monomer (a) contains caprolactone-modified hydroxyalkyl (meth) acrylate, the proportion of use is 2 to 50% by mass based on the total solid mass of components (a) and (b). In view of the design properties and adhesion of the resulting metallic film, it is preferably 7 to 40% by mass, more preferably 10 to 30% by mass.

  The copolymerization of the polymerizable unsaturated monomer is preferably a copolymerization by a solution polymerization method. For example, a mixture of the polymerizable unsaturated monomer and the radical polymerization initiator is dissolved or dispersed in an organic solvent. Examples of the polymerization method include heating at 80 ° C. to about 200 ° C. with stirring for about 1 to 10 hours. As the organic solvent that can be used in the copolymerization, those exemplified in the organic solvent (C) described later are preferably used.

  Examples of the radical polymerization initiator include ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3 Peroxyketals such as 1,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate; cumene hydroperoxide Hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5 -Di (tert-butylperoxy) hexane, diisopropylbenzene Dialkyl peroxides such as zenperoxide and tert-butylcumyl peroxide; diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide and 2,4-dichlorobenzoyl peroxide; bis (tert-butylcyclohexyl) ) Peroxycarbonates such as peroxydicarbonate; organic peroxide polymerization such as peroxyesters such as tert-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane Initiator: 2,2′-azobisisobutyronitrile, 1,1-azobis (cyclohexane-1-carbonitrile), azocumene 2,2′-azobismethylvaleronitrile, 4,4′-azobis (4- Azo polymerization initiators such as cyanovaleric acid) Can be mentioned. Although the usage-amount of these radical polymerization initiators is not specifically limited, Usually, 0.1-10 mass parts per total 100 mass parts of a polymerizable unsaturated monomer, especially 0.3-10 mass parts It is desirable to be within the range.

  The hydroxyl group-containing acrylic resin (A) obtained as described above has an acid value of 30 to 70 mgKOH / g, preferably 40 to 60 mgKOH / g, particularly preferably, from the viewpoint of the design properties and adhesion of the resulting metal-tone film. It is desirable that the hydroxyl value is within the range of 45 to 55 mgKOH / g, and the hydroxyl value is within the range of 20 to 120 mgKOH / g, preferably 40 to 100 mgKOH / g, and particularly preferably 60 to 80 mgKOH / g. From the viewpoints of designability, adhesion, etc., the weight average molecular weight is preferably in the range of 5,000 to 100,000, preferably 10,000 to 80,000, particularly preferably 20,000 to 50,000. .

  In addition, in this specification, a weight average molecular weight is the value computed on the basis of the molecular weight of standard polystyrene from the chromatogram measured by the gel permeation chromatograph (GPC). As the gel permeation chromatograph, “HLC8120GPC” (manufactured by Tosoh Corporation) was used. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.

The flaky metal powder (B) is generally obtained by crushing and grinding a metal such as aluminum using a grinding aid in the presence of a grinding medium liquid in a ball mill or attritor mill, or a plastic or other metal. It is obtained by a method such as vapor deposition on a substrate and peeling or pulverizing a film or sheet, and usually a volume-based average particle diameter (D ₅₀ ). Having an average thickness of 5 nm to 10 μm, particularly 5 nm to 5 μm. The average particle diameter (D ₅₀ ) represents a value of 50% of the particle size distribution measured by a laser diffraction particle size distribution analyzer, and the average thickness (nm) is measured by observing a cross section using a scanning electron microscope. It is a value calculated by this.

  As the flake shaped metal powder (B), an aluminum flake having a thickness of 5 to 50 nm is particularly suitable because it is excellent in metallic design.

  The content of the flake metal powder (B) in the metallic paint is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, particularly preferably 100 parts by weight of the resin solid content of the hydroxyl group-containing acrylic resin (A). 20 to 60 parts by mass is preferable from the viewpoint of improving the metallic design and improving the adhesion between the film (I) and the coating layer (II).

  The organic solvent (C) contains isopropyl alcohol in an amount of 35% by mass or more, preferably 55 to 95% by mass, and more preferably 65 to 85% by mass. If the amount of isopropyl alcohol is less than 35% by mass, the design property of the resulting metallic film is lowered, which is not preferable. Here, the organic solvent (C) corresponds to all organic solvents contained in the metallic paint forming the coating layer (II).

  The organic solvent (C) is less than 65% by weight of ester solvent, preferably 5 to 45% by weight, more preferably 10 to 35% from the viewpoint of improving the adhesion between the film (I) and the coating layer (II). It is desirable that the content is 1% by mass.

  Examples of the ester solvent include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, and pentyl acetate. These may be used alone or in combination. Of these, ethyl acetate and i-propyl acetate are preferred, and ethyl acetate is particularly preferred from the viewpoint of improving the adhesion between the film (I) and the coating layer (II).

  Furthermore, the organic solvent (C) may contain other solvents other than those described above for viscosity adjustment and storage stability improvement. Examples of other solvents include alcohol solvents such as ethanol, n-propanol, i-propanol, n-butanol and i-butanol; n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Ether solvents such as butyl ether and ethylene glycol monoethyl ether acetate; hydrocarbon solvents such as pentane, hexane and heptane; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone, petroleum naphtha, mineral spirits and water It is done. These may be used alone or in combination. These contents are preferably 10% by mass or less.

  The metallic paint essentially comprises the component (A), the component (B) and the component (C), and if necessary, a resin other than the component (A) (for example, acrylic resin, polyester resin, polyurethane) Resin, cellulose derivative), colored pigment, extender pigment, non-aqueous dispersion resin, fine polymer particles, curing catalyst, UV absorber, light stabilizer, coating surface modifier, antioxidant, fluidity modifier, wax, etc. can do.

  In the present invention, the coating layer (II) is formed by applying and drying the metallic paint obtained as described above on the transparent resin film (I). The method for applying the metallic paint is not particularly limited, and a known method can be adopted, and examples thereof include a bar coater, spray, Mayer bar, air knife, gravure, reverse gravure, offset printing, flexographic printing, and screen printing. It is done. Drying conditions are not specifically limited, For example, it can carry out at 30-100 degreeC, Preferably it is 50-90 degreeC for 1 to 15 minutes.

  The thickness of the coating layer (II) is not particularly limited, and is preferably 1 to 40 μm in dry film thickness, more preferably 2 to 25 μm, and further preferably in the range of 2 to 10 μm. is there.

  The metallic film of the present invention obtained as described above may be further provided with an adhesive layer, or an adhesive layer and a release layer on the coating layer (II). It becomes possible to decorate the molded product with a metal film through the adhesive layer. The material of the molded product is not particularly limited. For example, iron, aluminum, brass, copper, stainless steel, tinplate, galvanized steel, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) Metal materials such as plated steel; polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, and various FRP Examples thereof include plastic materials.

  The adhesive layer is provided in order to improve the adhesion between the metallic film and the molded product, and a heat-sensitive or pressure-sensitive resin suitable for the material of the molded product is preferably used as appropriate. As such a resin, for example, an acrylic resin-based, rubber-based, or olefin-based one can be used.

  The release layer is provided to facilitate handling when stacking and storing metal-like films, or winding and storing in a cylindrical shape, and decorating a molded product with a metal-like film. Is peeled off from the adhesive layer. As the release layer, for example, a plastic sheet such as a polyethylene terephthalate sheet, or a paper, cloth, or plastic sheet that has been treated with a release agent (silicon, wax, fluorine, etc.) can be generally used.

  The use of the molded product with the metallic film attached as described above is not particularly limited. For example, automobile bodies such as passenger cars, trucks, motorcycles, buses, bumpers, moldings, grills, spoilers, dashboards, consoles, audio grills. Automobile parts such as personal computers, mobile phones, and home appliances such as audio equipment.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples. Note that “part” and “%” indicate “part by mass” and “% by mass”, respectively, unless otherwise specified.

Manufacture example 1 of acrylic resin (A)
A typical acrylic resin production reactor equipped with a stirrer, a thermometer, a reflux condenser and the like was charged with 30 parts of isopropyl alcohol and 23 parts of propylene glycol monomethyl ether, heated to 85 ° C. The monomer mixture was added dropwise over 4 hours.

Methyl methacrylate 30 parts n-butyl acrylate 47 parts 2-hydroxyethyl methacrylate 16.5 parts Acrylic acid 6.5 parts 2,2'-azobis (2,4-dimethylvaleronitrile) 2 parts

  After completion of dropping the monomer mixture, the mixture was further maintained at 85 ° C. for 30 minutes, and then a mixture of 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts of propylene glycol monomethyl ether was added for 30 minutes. In short, it was dripped. The mixture was then stirred for 2 hours while maintaining at 85 ° C. After cooling, 19 parts of isopropyl alcohol was added and diluted to obtain an acrylic resin solution (A-1) having a solid content concentration of 55%. The obtained acrylic resin had an acid value of 50 mgKOH / g, a hydroxyl value of 71 mgKOH / g, and a weight average molecular weight of 30,000.

Production Example 2
A typical acrylic resin production reactor equipped with a stirrer, a thermometer, a reflux condenser and the like was charged with 30 parts of isopropyl alcohol and 23 parts of propylene glycol monomethyl ether, heated to 85 ° C. The monomer mixture was added dropwise over 4 hours.

Methyl methacrylate 25 parts n-butyl acrylate 45 parts caprolactone methacryl FM3 (Note 1) 10 parts 2-hydroxyethyl methacrylate 13.5 parts acrylic acid 6.5 parts 2,2'-azobis (2,4-dimethylvaleronitrile) 2 parts

  After completion of dropping the monomer mixture, the mixture was further maintained at 85 ° C. for 30 minutes, and then a mixture of 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts of propylene glycol monomethyl ether was added for 30 minutes. In short, it was dripped. The mixture was then stirred for 2 hours while maintaining at 85 ° C. After cooling, 19 parts of isopropyl alcohol was added and diluted to obtain an acrylic resin solution (A-2) having a solid content concentration of 55%. The obtained acrylic resin had an acid value of 50 mgKOH / g, a hydroxyl value of 70 mgKOH / g, and a weight average molecular weight of 30,000.

  (Note 1) Product name, ε-caprolactone-modified hydroxyalkyl methacrylate, manufactured by Daicel Chemical Industries.

Production Example 3
A typical acrylic resin production reactor equipped with a stirrer, a thermometer, a reflux condenser and the like was charged with 12 parts of isopropyl alcohol and 40 parts of propylene glycol monomethyl ether, and heated to 90 ° C. The monomer mixture was added dropwise over 4 hours.

Methyl methacrylate 25 parts n-butyl acrylate 45 parts caprolactone methacryl FM3 (Note 1) 10 parts 2-hydroxyethyl methacrylate 13.5 parts acrylic acid 6.5 parts 2,2'-azobis (2,4-dimethylvaleronitrile) 3 parts

  After completion of dropping the monomer mixture, the mixture was further maintained at 85 ° C. for 30 minutes, and then a mixture of 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts of propylene glycol monomethyl ether was added for 30 minutes. In short, it was dripped. Thereafter, the mixture was stirred for 2 hours while maintaining at 90 ° C., and after cooling, 20 parts of isopropyl alcohol was added and diluted to obtain an acrylic resin solution (A-3) having a solid content concentration of 55%. The obtained acrylic resin had an acid value of 50 mgKOH / g, a hydroxyl value of 70 mgKOH / g, and a weight average molecular weight of 12,000.

Production Example 4
A typical acrylic resin production reactor equipped with a stirrer, a thermometer, a reflux condenser and the like was charged with 12 parts of isopropyl alcohol and 40 parts of propylene glycol monomethyl ether, heated to 95 ° C. The monomer mixture was added dropwise over 4 hours.

Methyl methacrylate 25 parts n-butyl acrylate 45 parts caprolactone methacryl FM3 (Note 1) 10 parts 2-hydroxyethyl methacrylate 13.5 parts acrylic acid 6.5 parts 2,2'-azobis (2,4-dimethylvaleronitrile) 5 copies

  After completion of dropping the monomer mixture, the mixture was further maintained at 85 ° C. for 30 minutes, and then a mixture of 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts of propylene glycol monomethyl ether was added for 30 minutes. In short, it was dripped. Thereafter, the mixture was stirred for 2 hours while maintaining at 85 ° C. After cooling, 20 parts of isopropyl alcohol was added and diluted to obtain an acrylic resin solution (A-4) having a solid content concentration of 55%. The obtained acrylic resin had an acid value of 50 mgKOH / g, a hydroxyl value of 70 mgKOH / g, and a weight average molecular weight of 6,000.

Production Example 5
A typical acrylic resin production reactor equipped with a stirrer, a thermometer, a reflux condenser and the like was charged with 30 parts of isopropyl alcohol and 23 parts of propylene glycol monomethyl ether, heated to 85 ° C. The monomer mixture was added dropwise over 4 hours.

Methyl methacrylate 45 parts n-butyl acrylate 47.5 parts Acrylic acid 7.5 parts 2,2'-Azobis (2,4-dimethylvaleronitrile) 2 parts

  After completion of dropping the monomer mixture, the mixture was further maintained at 85 ° C. for 30 minutes, and then a mixture of 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts of propylene glycol monomethyl ether was added for 30 minutes. In short, it was dripped. Thereafter, the mixture was stirred for 2 hours while maintaining at 85 ° C. After cooling, 19 parts of isopropyl alcohol was added and diluted to obtain an acrylic resin solution (A-5) having a solid content concentration of 55%. The obtained acrylic resin had an acid value of 58 mgKOH / g and a weight average molecular weight of 30,000.

Production and production example 6 of metallic paint
182 parts of the 55% acrylic resin solution (A-1) obtained in Production Example 1 and 300 parts of 10% aluminum paste (Note 2) and 820 parts of isopropyl alcohol were blended according to a conventional method, and the solid content was 10%. A metallic paint (1) was obtained.

Production Examples 7-20
In Production Example 6, operations were carried out in the same manner as in Production Example 6 except that the composition was as shown in Table 1, to obtain metallic paints (2) to (15).

In Table 1, (Note 2) to (Note 4) are as follows.
(Note 2) Aluminum paste: “Metacene KM100”, trade name, 20 nm thickness, 10% of aluminum powder with an average particle size of 12 μm (ethyl acetate / isopropyl acetate = 5/5 mixed solvent) diluted paste, manufactured by Toyo Aluminum Co., Ltd.
(Note 3) Aluminum paste: “Metalure L55350”, trade name, thickness 35 to 40 nm, 10% ethyl acetate diluted paste of aluminum powder with an average particle diameter of 11 μm, manufactured by ECKART
(Note 4) Aluminum paste: “Metalure L55700”, trade name, 35-40 nm thickness, 10% propylene glycol monomethyl ether acetate diluted paste of aluminum powder with an average particle diameter of 11 μm, manufactured by ECKART

Transparent resin film film (I-1): “Acryprene HBS010P”, manufactured by Mitsubishi Rayon Co., Ltd., trade name, acrylic resin film, thickness 125 μm, dissolution rate with ethyl acetate is 100% by mass.
Film (I-2): “Panlite PC-2151”, manufactured by Teijin Chemicals Ltd., trade name, polycarbonate film, thickness 125 μm, dissolution rate with ethyl acetate is 100% by mass.

Production Example 1 of Metallic Film and Decorated Molded Body
A film (I-1) having a thickness of 125 μm is used as a base material, and the metallic paint (1) having a solid content of 10% obtained in Production Example 6 is applied to one surface thereof so as to have a dry film thickness of 5 μm, followed by drying. After drying at a temperature of 80 ° C. for 3 minutes, the adhesive surface of a release film made of polypropylene having a thickness of 50 μm having an acrylic adhesive layer is bonded to the surface of the coating layer made of a metallic paint, and the metallic tone film of Example 1 is bonded. Produced.

  About the obtained metallic tone film, the result used for the performance test according to the following test method is combined with Table 2, and is shown. In addition, the decorative molded body to be used for the test was obtained by peeling the release film of the above metallic tone film and then bonding the adhesive layer to the surface of the ABS plate.

Examples 2-18 and Comparative Examples 1-7
In Example 1, the transparent resin film and the metallic paint were selected as shown in Table 2, and each metallic film and the additive film were added in the same manner as in Example 1 except that the coating layer having the dry film thickness shown in Table 2 was formed. A decorative molded body was produced.

Performance test (* 1) Metal feeling: The metal feeling of the metallic film was visually observed, and the glitter of the sheet was determined according to the following criteria. A sample having an excellent metal feeling was evaluated as ◎, a sample having excellent metal feeling was evaluated as ◯, a sample having unevenness and a slightly inferior metal feeling was evaluated as Δ, and a sample having unevenness and no metal feeling was evaluated as ×.

  (* 2) Adhesiveness: Each decorative molded body is cut with a cutter knife to the substrate (ABS molded base plate) according to JIS K 5600-5-6 (1990), and 2 mm × 2 mm goban Made 100 eyes. Adhesive tape was affixed to the surface, and the number of Gobang eye coats remaining on the coated surface after abrupt peeling was evaluated.

◎: Residual number / total number = 100/100, no chipping on the surface of the decorative molded body ○: Residual number / total number = 100/100, the surface of the decorative molded body has a chipped edge Δ: Remaining number of surfaces of decorative molded body / total number of pieces = 99 to 90/100 ×: Remaining number of surfaces of decorative molded body / total number of pieces = 89 or less / 100

  (* 3) Water resistance adhesion: Each decorative molded body is immersed in warm water at 40 ° C. for 10 days, pulled up and dried, and then the adhesion test is performed in the same manner as the adhesion test of (* 2) above. The number of remaining coating films was examined and evaluated in the same manner as described above.

Claims (11)

A metallic paint containing (A) a hydroxyl group-containing acrylic resin, (B) flaky metal powder, and (C) an organic solvent on the transparent resin film (I) having a dissolution rate by ethyl acetate of 30% by mass or more. An organic solvent (C) has a coating film layer (II) made of a metallic paint containing isopropyl alcohol in an amount of 35% by mass or more. The metallic film according to claim 1, wherein the transparent resin film (I) comprises at least one selected from an acrylic resin and a polycarbonate resin. The metal tone according to claim 1 or 2, wherein the hydroxyl group-containing acrylic resin (A) is obtained by copolymerizing a hydroxyl group-containing polymerizable unsaturated monomer (a) and another polymerizable unsaturated monomer (b). the film. The metal-tone film according to claim 3, wherein the hydroxyl group-containing polymerizable unsaturated monomer (a) contains caprolactone-modified hydroxyalkyl (meth) acrylate. The metal-tone film according to any one of claims 1 to 4, wherein the hydroxyl group-containing acrylic resin (A) has a weight average molecular weight of 5,000 to 100,000. Furthermore, the metal-tone film in any one of Claims 1-5 in which an organic solvent (C) contains 5-60 mass% of ester solvents. The metal-like film according to any one of claims 1 to 6, wherein the flaky metal powder (B) is an aluminum flake. The metal-tone film according to claim 7, wherein the flaky metal powder (B) is an aluminum flake having a thickness of 5 to 50 nm. The content of the flaky metal powder (B) in the metallic paint is 5 to 100 parts by mass with respect to 100 parts by mass of the resin solid content of the acrylic resin (A). Metal-tone film. The metal-tone film according to any one of claims 1 to 9, wherein an adhesive layer, or an adhesive layer and a release layer are further provided on the coating layer (II). The metal-like article formed by sticking the metal-like film of Claim 10 on the molded article surface.