JP2001105523A - Metallically glossy laminate and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate showing metal glossiness rich in brilliancy and a method for producing the same. SOLUTION: A metallically glossy laminate is produced by providing a resin layer 3 on a support 2 and providing a metallically glossy layer 4 comprising metal floss pigment particles wherein flat glass pieces are coated with titanium oxide on the resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metallic glossy laminate and a method for producing the same. More specifically, the present invention relates to a metallic glossy laminate having a metallic luster color having excellent glitter and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, there has been disclosed a surface decoration method for a molded article such as a container in which a pattern is appropriately printed on the surface of the molded article, and a paint containing a pearl material is further applied thereon. -116599). The proposal proposes to enhance the decorativeness by imparting glitter to a molded product.

[0003]

However, the metallic luster layer formed by applying a coating material containing a pearl material contains additives such as resin contained in the coating material because the pearl material is dispersed in the layer. However, the gloss of the pearl material is hindered, and it is difficult to sufficiently exhibit glitter. The present inventor has conducted intensive studies to enhance the glitter of this type of metallic glossy laminate,
The present inventors have found that a metal laminate having a flat glass piece coated with titanium oxide is located on the surface, thereby obtaining a laminated body excellent in glitter and glitter, thereby completing the present invention.

[0004]

According to the present invention, there is provided a laminate comprising a resin layer provided on a support and a metallic gloss layer provided on the resin layer, wherein the metallic gloss layer oxidizes a flat glass piece. A requirement is a metallic glossy laminate in which metallic gloss pigment particles coated with titanium are fixed on the surface of the resin layer. Furthermore, the support or the resin layer is colored, and the requirement that a colored layer is interposed between the support and the resin layer, further, on the support, a resin solution or uncured A resin layer is formed by coating or applying a liquid resin, and the flat glass piece coated with titanium oxide is sprayed with metallic luster pigment particles in a state where the resin layer is in an undried or uncured state, and is fixed to the resin layer to form a metal layer. A method for producing a metallic glossy laminate for forming a gloss layer is required.

[0005] The material and form of the support are not particularly limited. Examples of the material include paper, synthetic paper, cloth, flocking or raised cloth, non-woven fabric, synthetic leather, leather, plastic, glass, ceramic, wood, and stone. And the like.

Conventionally, various general-purpose resin films are also effective as the support, such as high-pressure polyethylene film, medium-low pressure polyethylene film, cross-linked polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-acrylate copolymer film. , Ionomer resin film, ethylene-propylene copolymer film,
Propylene film, vinyl chloride-propylene film, polystyrene film, polyvinyl chloride film,
Examples include a polyvinylidene chloride film, a polyvinyl alcohol film, a fluororesin film, a polycarbonate film, an acetate film, a polyester film, a polyamide film, a hydrochloric acid rubber film, a polyimide film, and a polyurethane film.

The resin layer provided on the support is formed by painting or applying a resin solution or an uncured liquid resin. The resin is a conventional alkylphenol resin, rosin-modified phenolic resin, rosin-modified alkyd resin, styrene-modified alkyd resin, acryl-modified alkyd resin, aminoalkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, acrylic resin. Acid ester resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene
Butadiene emulsion resin, acrylate emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, water-soluble polybutadiene resin, cellulose derivative, ionomer resin, isobutylene- Maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile chlorinated polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene -Vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer Resins, chlorinated polyethylene resins, chlorinated polypropylene resins, polyamide resins, high-density polyethylene resins, medium-density polyethylene resins, linear low-density polyethylene resin, polyethylene terephthalate resin,
Polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, high-impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethylmethacrylate resin, epoxy acrylate resin, epoxy resin-modified alkyd resin, styrene-modified alkyd resin, Resins such as acrylic-modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, unsaturated polyester resin, cellulose acetate, cellulose nitrate, and ethyl cellulose are exemplified.

Further, an ultraviolet curable resin can be used as the resin, and the photopolymerizable prepolymer resin as the photopolymerizable resin composition is a polyester acrylate resin,
Examples thereof include a polyurethane acrylate resin, a polyether acrylate resin, an epoxy acrylate resin, and a melamine acrylate resin. Examples of the photopolymerizable monomer include 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, 1,6-hexanediol acrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and pentane. Erythritol triacrylate and the like. Examples of the photoinitiator include thioxanthones. In addition, the said resin can also be used in mixture of 2 or more types.

As the coating or coating method for forming the resin layer, conventionally known methods, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spraying It can be formed by means such as coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating.

The metallic luster layer is a layer in which metallic luster pigment particles obtained by coating a flat glass piece with titanium oxide are fixed on the surface of a resin layer. It can be formed by spraying the pigment in a particle state. Examples of the method for spraying the metallic luster pigment particles include dry air spray coating, airless spray coating, and sand blast.

By spraying the metallic luster pigment in the form of particles on the surface of the resin layer, the pigment can be uniformly and densely adhered, and the metallic luster pigment particles are easily oriented parallel to the support surface. It is considered that since the reflected light of the gloss pigment particles is regularly reflected, the glitter is increased. Compared with the conventional system in which metallic luster pigment particles are dispersed in a binder, the metallic luster pigment particles are less likely to be oriented in parallel to the support surface, and light is irregularly reflected by the binder, as compared with a system in which the particles are sprayed as they are. It is presumed that the brilliancy is weakened.

Specifically, the metallic luster pigment is a pigment in which flaky glass pieces are coated with titanium oxide. The product name is “Metashine” manufactured by Nippon Glass Fiber Co., Ltd.
X-5450TS (6041) [average thickness 5 ± 2 μm,
Average particle size 450 ± 145 μm, gold], RCFSX-5
200TS (6042) [Average thickness 5 ± 2 μm, average particle size 200 ± 70 μm, silver color], RCFSX-5140T
S (6043) [average thickness 5 ± 2 μm, average particle size 140
± 45 μm, silver color], RCFSX-5080TS (60
44) [Average thickness 5 ± 2 μm, average particle size 80 ± 30 μm
m, silver color], RCFSX-2080TS (6046)
[Average thickness 2 ± 1 μm, average particle size 80 ± 30 μm, silver color], RCFSX-K120TS (6049) [Average thickness 20 ± 5 μm, average particle size 120 ± 20 μm, silver color],
RCFSX-5090RC (8052) [Average thickness 5 ±
2 μm, average particle size 90 ± 30 μm, gold], RCFSX
-5090RC (8053) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic green], RCF
SX-5090RC (8069) [Average thickness 5 ± 2μ
m, average particle size 90 ± 30 μm, metallic blue], R
CFSX-5090RC (8070) [Average thickness 5 ± 2
μm, average particle size 90 ± 30 μm, metallic purple], RCFSX-5090RC (8071) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic red] and the like. The metallic luster pigment is formed by using a flat glass piece as a core substance, and is excellent in transparency as compared with a pearl luster pigment in which the surface of mica is coated with titanium oxide. The flat glass piece may be a scale-like glass piece.

The metallic luster layer is not limited to a continuous layer, but may be a discontinuous layer or may be formed by being scattered. Particularly, a metal such as a combination of characters, symbols, patterns, and lines may be used. By providing a glossy image, decorativeness can be further provided.

In the present invention, the color tone of the support or the resin layer is not particularly limited, but the support or the resin layer may be colored in order to make the metallic luster layer effectively exhibit the glitter. preferable. Accordingly, a colored resin layer may be used by coating or applying a material in which a colorant is contained in a resin solution for forming a resin layer or an uncured liquid resin, or a colored resin layer. Is provided. In addition, by providing a colored layer between the support and the resin layer, the metallic luster layer can effectively exhibit the glitter. The colored support, a resin layer, or a colorant used to obtain a colored layer, a general colored dye or pigment, a fluorescent dye or pigment is used, and if desired, a luminous pigment, a white pigment such as titanium oxide, Reversible thermochromic materials can also be used. In particular, when a reversible thermochromic material is used as a coloring agent, the color changes from color to colorless due to a change in temperature, so that a laminate having excellent decorativeness in which the glitter of the metallic gloss layer changes can be obtained.

In the above-described structure of the metallic glossy laminate, a light stabilizer layer may be appropriately provided. Specifically, the light stabilizer layer is selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state.
In addition, an anti-aging agent, an antistatic agent, a polarity-imparting agent, a thixotropic agent, an antifoaming agent, and the like are added to the liquid resin forming the resin layer or the uncured liquid resin as needed to improve the function. You can also. In addition, a protective layer can be provided on the metallic gloss layer in a range that does not impair the glitter.

The form of the metallic glossy laminate obtained as described above may be not only planar but also uneven. Specific examples include clothing, footwear, lighting equipment, toys, artificial flowers, stationery, daily necessities, cosmetics, accessories, sports equipment, printed matter, vehicles, indoor decorations, and the like.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The metallic glossy laminate of the present invention is obtained by coating or applying a resin solution or an uncured liquid resin on a support having an appropriate material and shape to form a resin layer. Is obtained by spraying metallic luster pigment particles by spray coating before drying or curing, and then drying or curing the resin layer. In the case of the metallic glossy laminate, an article having glitter can be obtained when the support has the shape of each article,
In addition, when the support is made of various materials, the obtained metallic glossy laminate can be cut as necessary and attached to other articles or sewn. Further, it can be cut into small widths to form flat yarns and used for hair for dolls, handicraft yarns, and the like, or can be cut into fine pieces to form fine pieces and used in the cosmetics field and decorative field.

[0018]

EXAMPLES All parts in the examples are parts by weight. Example 1 (see FIG. 1) 20.0 parts by weight of a vinyl chloride-vinyl acetate copolymer resin, 40.0 parts by weight of cyclohexanone, 40.0 parts by weight of an aromatic hydrocarbon solvent, and 1.0 part by weight of an antifoaming agent The mixture was uniformly stirred and mixed to obtain an oily screen printing resin solution. A resin layer 3 having a pattern of Kinkakuji was provided on a telephone card as the support 2 by screen printing using the oily screen resin solution. Before the resin layer 3 dries, a metallic luster pigment obtained by coating a scale-like glass piece with titanium oxide [trade name:
Metashine, part number RCFSX-5450TS (604
1) An average thickness of 5 ± 2 μm and an average particle size of 450 ± 145 μm, manufactured by Nippon Glass Fiber Co., Ltd.] are spray-coated on the resin layer 3 in the form of particles using a spray gun to fix the metallic gloss layer. 4 were provided. After the metallic gloss layer 4 was provided, the resin layer 3 was dried by heating at 70 ° C. for 1 hour to obtain a metallic glossy laminate 1 on which a golden pattern of Kinkaku-ji Temple with rich glitter was formed.

Example 2 60.0 parts by weight of a hard liquid epoxy resin, 1.0 part by weight of a pink pigment, 2.0 parts by weight of a thixotropic agent, and 1.
A cold-curable aliphatic polyamine (30.0 parts by weight) was added to a liquid resin composition containing 0 parts by weight, and uniformly stirred and mixed to obtain a pink epoxy ink for screen printing (uncured liquid resin). . As a support, printing was performed on the side surface of a plastic container using the epoxy ink with a curved surface printing machine, and a resin layer having a heart pattern having a thickness of about 50 μm was provided.
Before the resin layer is cured, a metallic luster pigment obtained by coating a flaky glass piece with titanium oxide [trade name: Metashine, product number RCFSX-5090RC (8070), manufactured by Nippon Glass Fiber Co., Ltd.] Average thickness 5 ± 2 μm, average Particle size 90 ± 30 μm,
Metallic purple color] was spray-coated in a particle state using a spray gun to fix the metallic gloss layer, and the resin layer was cured by heating at 70 ° C. for 1 hour. And a liquid resin composition containing 60.0 parts by weight of a hard liquid epoxy resin, 0.5 parts by weight of a blue pigment, 2.0 parts by weight of a thixotropic agent, and 1.0 part by weight of an antifoaming agent next to the heart pattern. Room temperature-curable aliphatic polyamine 30.0%
A blue star pattern resin layer having a thickness of about 50 μm is provided by using a blue epoxy ink (uncured liquid resin) which is uniformly mixed with stirring by adding weight parts, and the phosphorous layer is cured before the resin layer is cured. Metallic luster pigment obtained by coating a glass flake with titanium oxide [trade name: Metashine, product number RCFSX-5090]
RC (8069) Nippon Glass Fiber Co., Ltd. Average thickness 5 ± 2μ
m, average particle size 90 ± 30 μm metallic blue-color],
A metallic glossy layer was formed by applying a spray coating in a particulate state using a spray gun and fixing the same.
C. for 1 hour to cure the resin layer. As described above, a metallic glossy laminate (container) having a metallic purple heart pattern and a metallic blue star pattern, which was full of glitter, was obtained.

Example 3 30.0 parts by weight of acrylic resin / xylene, 30.0 parts by weight of methyl isobutyl ketone, 30.0 parts by weight of cyclohexanone
Thus, an oil-based spray resin solution consisting of 10.0 parts by weight of a polyisocyanate-based curing agent was obtained. The resin solution was spray-coated on the entire surface of a black plastic trophy as a support to form a resin layer. Before the resin layer sprayed on the trophy dries, a metallic luster pigment (trade name: Metashine, product number RCFSX-5080RC (6044) manufactured by Nippon Glass Fiber Co., Ltd.) having a scaly glass piece covered with titanium oxide before drying. 5 ± 2μm, average particle size 80 ± 30
[μm, silver color] using a spray gun to apply and fix the particles in the form of particles to form a metallic luster layer, and then heat the resin layer at 70 ° C. for 1 hour to cure the resin layer, which is rich in glitter. A silver metallic glossy laminate (trophy) was obtained.

Example 4 2.0 parts by weight of 2- (2-chloroanilino) -6-di-n-butylaminofluoran, 6.0 parts by weight of 1,1-bis- (4-hydroxyphenyl) ethane, stearyl A reversible thermochromic composition comprising a homogenous solution obtained by mixing 5.0 parts by weight of alcohol, 20.0 parts by weight of cetyl alcohol, and 25.0 parts by weight of stearyl laurate was mixed with an epoxy resin /
A reversible thermochromic microcapsule pigment was obtained by encapsulation in an epoxy resin film by an interfacial polymerization method using an amine curing agent. The reversible thermochromic microcapsule pigment has a temperature of 35 ° C.
Below, it exhibits black color and becomes colorless above 38 ° C.

The reversible thermochromic microcapsule pigment 4
0.0 parts by weight, 60.0 parts by weight of hard liquid epoxy resin,
Room temperature curable aliphatic polyamine 3 in a liquid resin composition comprising 2.0 parts by weight of a thixotropic agent and 1.0 part by weight of an antifoaming agent
0.0 parts by weight was added and uniformly stirred and mixed to obtain a reversible thermochromic epoxy ink for screen printing (uncured liquid resin). As a support, a side surface of a white porcelain (Inoguchi) was printed with a curved surface printer using the epoxy ink, and a reversible thermochromic resin layer of a folded crane pattern having a thickness of about 50 μm was provided. Before the reversible thermochromic resin layer printed on the pottery surface is cured, a metallic luster pigment obtained by coating a scale-like glass piece with titanium oxide [trade name: Metashine, product number RCF]
SX-5450TS (6041), manufactured by Nippon Glass Fiber Co., Ltd.
An average thickness of 5 ± 2 μm, an average particle size of 450 ± 145 μm, and a gold color] are spray-coated on the reversible thermochromic resin layer in the form of particles using a spray gun and fixed to form a metallic gloss layer. At 70 ° C. for 1 hour to cure the reversible thermochromic resin layer to obtain a metallic glossy laminate (reversible thermochromic Inoguchi).

At 35 ° C. or less, the reversible thermochromic resin layer of the metallic glossy laminate obtained as described above has a black color, so that a glittering and bright golden crane pattern is visually recognized. Since the reversible thermochromic resin layer becomes colorless, the folded crane pattern becomes invisible. The golden folded crane pattern having a temperature of 35 ° C. or less was visually recognized again, and this aspect change could be repeatedly performed by changing the temperature.

Comparative Example 1 Using the reversible thermochromic epoxy medium of Example 4, a reversible thermochromic resin layer of a folded crane pattern having a thickness of about 50 μm was formed on a side surface of a similar white ceramic (Inoguchi) by a curved surface printing machine. Was provided.
The porcelain was heated at 70 ° C. for 1 hour to cure the reversible thermochromic resin layer.

On the reversible thermochromic resin layer, a metallic luster pigment (trade name: Metashine, product number RCFSX-5450TS (604)
1) Nippon Glass Fiber Co., Ltd., average thickness 5 ± 2 μm, average particle size 450 ± 145 μm, gold] 10.0 parts by weight of hard liquid epoxy resin 60.0 parts by weight, thixotropic agent 2.0 parts by weight, defoaming After adding, mixing and stirring into a liquid resin composition comprising 1.0 part by weight of an agent, 30.0 parts by weight of a room temperature-curable aliphatic polyamine was further added, and the mixture was uniformly stirred and mixed. Using an ink, printing was performed with a curved surface printing machine to provide a metallic glossy layer of a folded crane pattern, and heated at 70 ° C. for 1 hour to cure the metallic glossy layer, thereby obtaining a metallic glossy laminate.

In the metallic glossy thermochromic laminate obtained as described above, a golden folded crane pattern was observed at 35 ° C. or lower, but a golden folded crane visually observed by the metallic glossy laminate of Example 4. It was poor in brilliancy as compared with.

[0027]

The laminate obtained by the method for producing a metallic glossy thermochromic laminate of the present invention exhibits a metallic luster rich in glitter, a uniform and dense coating surface, and a decoration. The present invention can provide a metallic glossy thermochromic laminate having properties, novelty and remarkability.

[Brief description of the drawings]

FIG. 1 is an enlarged vertical cross-sectional explanatory view of one embodiment of the metallic glossy laminate of the present invention.

[Explanation of symbols]

 Reference Signs List 1 metal glossy laminate 2 support 3 resin layer 4 metal gloss layer

Continued on the front page F-term (reference) 4D075 AE06 CB04 CB13 DB13 DB14 DB18 DB20 DB31 EC03 EC23 4F100 AA21C AA21H AG00C AG00H AK01B AK15 AK15J AK22 AK22J AL01 AT00A BA03 BA04 BA07 BA10A BA10C CA13C DE01B00E GBH DEB GB HB00D HB31 JL00D JL10A JL10B JN24 JN24C JN24H 4J037 AA08 CA09 DD05 EE03 FF03

Claims (4)

[Claims] 1. A laminate comprising a support having a resin layer provided thereon, and a metal gloss layer provided on the resin layer, wherein the metal gloss layer is formed by coating a flat glass piece with titanium oxide. Is a layer adhered to the surface of the resin layer. 2. The metallic glossy laminate according to claim 1, wherein the support or the resin layer is colored. 3. The metallic glossy laminate according to claim 1, wherein a colored layer is interposed between the support and the resin layer. 4. A resin layer is formed by coating or applying a resin solution or an uncured liquid resin on a support, and the flat glass piece is coated with titanium oxide in a state where the resin layer is in an undried or uncured state. A method for producing a metallic glossy laminate in which the metallic luster pigment particles are sprayed and fixed to the resin layer to form a metallic luster layer.