JP2000135772A - Metal gloss-like laminate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a uniform bright surface excellent in brightness by forming a metal gloss-like laminate having a metal gloss layer wherein metal gloss pigment particles are fixed on the surface of a resin layer. SOLUTION: A metal gloss-like laminate 1 is obtained by applying a resin soln. of an alkylphenol resin or the like or an uncured liquid resin to a support 2 comprising appropriate material quality and having an appropriate shape by screen printing or spray coating to form a resin layer 3 and spraying particles of a metal gloss pigment such as titanium dioxide coated mica, guanine or silk mica on the resin layer 3 by spray coating before the resin layer 3 is dried or cured and subsequently drying or curing the resin layer 3. When the support 2 shows a shape of each article, an article having brightness is obtained from the metal gloss-like laminate 1 but, when the support 2 comprises a material of every kind, it is also possible to cut the obtained metal gloss-like laminate 1 if necessary to bond or sew the cut laminate to other article. By this constitution, a uniform and dense coating surface excellent in metal glossiness of gold or silver is obtained and decoration properties and outstanding properties are imparted.

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 such as gold, silver or the like, 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 a method for producing the above-mentioned laminate, in which the metallic glitter pigment particles are located on the surface, whereby a laminate excellent in glitter can be obtained and a uniform glitter surface can be obtained.

[0004]

According to the present invention, there is provided a laminate having a resin layer provided on a support and a metallic gloss layer provided on the resin layer, wherein the metallic gloss layer comprises a metallic luster pigment particle. A requirement is a metallic glossy laminate which is a layer fixed to the layer surface. Further, the support or the resin layer may be colored, a colored layer may be interposed between the support and the resin layer, and further, a resin solution or an uncured liquid resin may be formed on the support. A resin layer is formed by painting or applying the resin layer, and in a state where the resin layer is in an undried state or an uncured state, a metallic glossy laminate is formed by spraying metallic gloss pigment particles and fixing the resin layer to the metallic gloss layer. Require manufacturing method.

[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 include polyurethane acrylate resin, polyether acrylate resin, polyester acrylate resin, epoxy acrylate resin, polyether acrylate resin, melamine acrylate resin, and the like. Examples of the photopolymerizable monomer include 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, 1,6-hexanediol acrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylolpropane triacrylate. And pentaerythritol triacrylate. 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 are fixed to the surface of a resin layer, and is formed by spraying a metallic luster pigment in the form of particles while the resin layer formed on the support is in an undried state. can do. 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.

The metallic luster pigment particles include hitherto known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, bismuth oxychloride and the like. Metallic luster pigment particles can be applied. The metallic luster pigment particles are obtained by coating the surface of natural mica with 14 to 68% by weight of titanium oxide. The coating layer has an optical thickness of 110 to 415 nm and a particle size of 5 to 300 μm, preferably 30 to 300 μm. Gloss pigment particles are preferably used.

The optical thickness of the coating layer in the metallic luster pigment particles is a refractive index × geometric thickness,
This thickness is related to reflecting light of a certain wavelength, in other words, a particular optical thickness reflects light of a particular wavelength.

As the metallic luster pigment particles, for example, natural metallic mica particles are coated with 26 to 57% by weight of titanium oxide, and have a coating layer having an optical thickness of 180 to 240 nm and a particle size of 5 to 125 μm. The particles selectively transmit light of a violet wavelength, and have a complementary color relationship of 550-6.
It gives a characteristic of reflecting light of a yellow wavelength of 00 nm and becomes gold. Therefore, for example, when the support or the resin layer has a black color, the violet transmitted light is absorbed and the gold color is reflected by the yellow light reflected by the gold metallic luster pigment particles. here,
The support or the resin layer is not limited to black. Since the color of the support or the resin layer can be visually recognized from the gaps between the metallic glossy layers, the color can be sufficiently golden even in a color tone such as orange or brown, and preferably gold can be visually recognized by being ocher.

The surface of natural mica particles is coated with 26% by weight of titanium oxide, and the coating layer has an optical thickness of 180 to 240 nm and a particle size of 10%.
１２５125 μm, 43% by weight of the surface of natural mica particles
The optical thickness of the coating layer is from 180 to
Those having a thickness of 240 nm, a particle size of 10 to 60 μm, and a coating layer having an optical thickness of 180 to 240 nm and a particle size of 5 to 25 μm obtained by coating the surface of natural mica particles with 57% by weight of titanium oxide are preferably used.

Next, when silver metallic luster pigment particles are used as the metallic luster pigment particles, the silver metallic luster pigment particles are formed by coating the surface of natural mica particles with 14 to 43% by weight of titanium oxide. 110-170 nm, particle size 1
Those having a thickness of up to 180 μm are preferably used.

Metallic luster pigment particles in which the surface of natural mica particles are coated with titanium oxide and metallic luster pigment particles in which the titanium oxide layer is coated with iron oxide are also used as the metallic luster pigment particles. Is done. Further, dichroic metallic luster pigment particles having a titanium oxide coating coated with a colored dye or pigment are also used.

The metallic metallic luster pigment particles will be described in more detail. The metallic metallic luster pigment particles are formed by coating the surface of natural mica with 29 to 68% by weight of titanium oxide. Effectively, those having a thickness of 245 to 415 nm and a particle size of 5 to 125 μm are effective. In particular, the optical thickness of the coating layer is 245 to 415 nm, and the particle size is 5 to 125 μm.
μm, natural mica surface coated with 46-57% by weight of titanium oxide, optical thickness of coating layer 245-415
nm, particle size 10-60 μm, natural mica surface 5
A coating layer having an optical thickness of 245 to 415 nm and a particle size of 5 to 25 μm coated with 8 to 68% by weight of titanium oxide is preferably used. Further, the optical layer has a coating thickness of 245 to 415 in which the surface of natural mica is coated with 29 to 68% by weight of titanium oxide, and the surface thereof is coated with 4 to 10% by weight of iron oxide.
nm or a particle size of 5 to 125 μm, or the surface of natural mica particles was coated with 29 to 68% by weight of titanium oxide, and the upper layer was coated with 0.5 to 10% by weight of a non-thermochromic colored pigment. Dichroic metallic metallic pigment particles having an optical thickness of 245 to 415 nm and a particle size of 5 to 125 μm of the coating layer can be used.

The mica coated with titanium oxide disperses visible light of red to purple into light of each color wavelength and reflects only light of a specific wavelength depending on the coating weight of the titanium oxide and the optical thickness of the coating. Has the function of transmitting other light. On the other hand, mica does not diffusely reflect light but reflects light in parallel lines, so the light has a metallic luster. Light transmitted through the metallic luster layer is absorbed if the resin layer or the support is dark. In this way, the light of the metallic luster of a specific wavelength is reflected, so that the metallic color becomes a specific color. Further, the metallic gloss layer is not limited to a continuous layer, and may be a discontinuous layer or may be formed in a dotted manner. can do.

In the present invention, the color tones of the support and the resin layer are not particularly limited. However, in order to effectively exhibit the glittering effect of the metallic luster layer, the support or the resin layer must be colored. 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 colored to colorless due to a temperature change, so that a laminate excellent in decorativeness in which the glitter of the metallic gloss layer changes can be obtained. Further, the metallic glossy layer is a character,
It may be a design such as a combination of symbols, patterns, and lines.

In the structure of the metallic glossy laminate described above, 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 irregular. 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.

[0023]

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.

[0024]

EXAMPLES All parts in the examples are parts by weight. Example 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 (trade name: Solvesso 100), 1.0 part by weight of an antifoaming agent The parts were 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 a support 2 by screen printing using the above resin solution.

Before the resin layer 3 is dried, the surface of natural mica is coated with titanium oxide and further coated with iron oxide. The coverage of titanium oxide is 38%, the coverage of iron oxide is 7%, and the particle size is 1%.
The metallic luster layer 4 is formed by spray-coating the metallic luster pigment particles (trade name: Iriodin 300, manufactured by Merck Japan Co., Ltd.) on the resin layer 3 in a particle state using a spray gun and fixing the particles. 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 pattern of Kinkakuji having excellent metallic luster was formed.

Example 2 60.0 parts by weight of a hard liquid epoxy resin, 1.0 part by weight of a black general pigment, 2.0 parts by weight of a thixotropic agent, and 1.
A cold curing type aliphatic polyamine (30.0 parts by weight) was added to a 0 part by weight liquid resin composition, and the mixture was stirred and mixed uniformly to obtain a black epoxy ink for screen printing (uncured liquid resin).

Printing is performed on a side surface of a white ceramic (Inoguchi) as a support by a curved surface printing machine using the above-mentioned medium.
A resin layer of a black woven crane pattern having a thickness of about 50 μm was provided.

Before the resin layer printed on the surface of the earthenware was cured, the surface of natural mica was coated with titanium oxide. Metallic luster pigment particles having a coverage of 57% and a particle size of 10 to 60 μm (trade name: Iliodin 201, Merck Co., Ltd.) (Made in Japan) was spray-coated on the resin layer in the form of particles using a spray gun and fixed to form a metallic gloss layer. After the metallic luster layer was provided, the resin layer was cured by heating at 70 ° C. for 1 hour to obtain a metallic luster-like laminate on which a woven crane pattern excellent in golden metallic luster was formed.

Example 3 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). .

On the side of the plastic container as a support,
Printing was performed using the medium with a curved surface printing machine, and a resin layer having a pink heart pattern with a thickness of about 50 μm was provided.

Before the resin layer printed on the plastic container was cured, the surface of natural mica was coated with titanium oxide. Metallic luster pigment particles having a coverage of 48% by weight and a particle size of 10 to 60 μm (trade name: Iliodin 219; (Merck Japan Co., Ltd.) using a spray gun to apply and spray-fix the particles in the form of particles to form a metallic luster layer. After providing the metallic gloss layer, the resin layer was cured by heating at 70 ° C. for 1 hour to obtain a metallic gloss-like laminate in which a heart-shaped metallic pink color excellent in metallic gloss was formed.

Example 4 Acrylic resin / xylene 30.0 parts by weight, methyl isobutyl ketone 30.0 parts by weight, cyclohexanone 30.0 parts by weight
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 provide a resin layer.

Before the resin layer sprayed on the trophy is dried, the surface of natural mica is coated with titanium oxide and further coated with iron oxide. The coverage of titanium oxide is 38%, and the coverage of iron oxide is 4%. A metallic luster layer was provided by spray-coating and fixing metallic luster pigment particles (trade name: Iriodin 320, manufactured by Merck Japan) having a particle size of 10 to 60 μm in a particle state using a spray gun. After providing the metallic gloss layer, the resin layer was cured by heating at 70 ° C. for 1 hour to obtain a metallic glossy laminate excellent in golden metallic gloss.

Example 5 2- (2-chloroanilino) -6-di-n-butylaminofluorane 2.0 parts by weight, 1,1-bis- (4-hydroxyphenyl) -2-methylpropane 5.0 Parts by weight,
A reversible thermochromic composition comprising a homogeneous solution in which 5.0 parts by weight of stearyl alcohol, 20.0 parts by weight of cetyl alcohol, and 25.0 parts by weight of stearyl laurate is mixed is used to obtain an interfacial weight using an epoxy resin / amine curing agent. A reversible thermochromic microcapsule pigment was obtained by being encapsulated in an epoxy resin film by a legal method. The reversible thermochromic microcapsule pigment exhibits a black color at 35 ° C or lower, and becomes colorless at 38 ° C or higher.

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).

A side surface of a white porcelain (Inoguchi) as a support is printed with a curved surface printing machine using the above-mentioned medium.
A reversible thermochromic resin layer having a black woven crane pattern with a thickness of about 50 μm was provided.

Before the reversible thermochromic resin layer printed on the ceramic surface was cured, the surface of natural mica was coated with titanium oxide, and a metallic luster pigment particle having a coverage of 57% and a particle size of 10 to 60 μm (trade name: A metallic luster layer was formed by applying spray coating of Iriodin 201 (manufactured by Merck Japan Co., Ltd.) on the resin layer in a particle state using a spray gun to fix the resin layer. After providing the metallic luster layer,
For 1 hour to cure the reversible thermochromic resin layer to obtain a metallic glossy laminate.

In the metallic glossy laminate obtained as described above, at 35 ° C. or lower, the reversible thermochromic resin layer exhibits a black color, so that a woven crane pattern exhibiting a golden metallic glossy color with excellent glitter is visually recognized. , 38 ° C or higher, the reversible thermochromic resin layer becomes colorless, so that the golden woven crane pattern cannot be seen. A golden woven 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 for screen printing of Example 5 on the side of a white porcelain similar to that of Example 5, a reversible heat of a woven crane pattern having a thickness of about 50 μm by a curved printing machine. A discolorable resin layer was provided. The porcelain was heated at 70 ° C. for 1 hour to cure the reversible thermochromic resin layer.

The surface of natural mica was coated with titanium oxide on the reversible thermochromic resin layer.
60 μm metallic luster pigment particles (trade name: Iriodin 20)
1, manufactured by Merck Japan) was added to a liquid resin composition comprising 60.0 parts by weight of a hard liquid epoxy resin, 2.0 parts by weight of a thixotropic agent, and 1.0 part by weight of an antifoaming agent. After mixing and stirring, 30.0 parts by weight of a room temperature-curable aliphatic polyamine was added, and printing was performed with a curved printing machine using a metallic glossy epoxy ink uniformly stirred and mixed. A metallic luster layer of a pattern was provided, and heated at 70 ° C. for 1 hour to cure the luster layer to obtain a metallic luster layered product.

The metallic glossy thermochromic laminate obtained as described above shows a golden woven crane pattern at 35 ° C. or lower, but the golden glossy laminate shown in Example 5 shows a golden woven crane pattern. The metal luster was poor compared to the woven crane.

[0044]

The laminate obtained by the method for producing a metallic glossy thermochromic laminate of the present invention has excellent metallic luster such as gold and silver, as well as a uniform and dense coated surface, and has a decorative property. , A novel metallic glossy thermochromic laminate having novelty and conspicuousness can be provided. .

[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 metallic glossy laminate 2 support 3 resin layer 4 metallic gloss layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D075 AE04 AE06 CB13 DB11 DB13 DB14 DB16 DB18 DB20 DB31 EA02 EB01 EB15 4F100 AA21 AA23 AB01C AC05 AK01A AK01B AK15 AK22 AL01 AT00A BA03 BA07 BA10A BA10C CA13C E01E12E01H GB71 HB00 HB00A HB31 JB15B JK14 JL10A JN24 JN24C

Claims (4)

[Claims] 1. A laminate having a resin layer provided on a support and a metallic gloss layer provided on the resin layer, wherein the metallic gloss layer is a layer in which metallic gloss pigment particles are fixed to the surface of the resin layer. Metallic glossy laminate. 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 spraying metallic luster pigment particles while the resin layer is in an undried or uncured state. A method for producing a metallic glossy laminate in which a metallic gloss layer is formed by being fixed to a resin layer.