JP5595200B2 - Laminated body - Google Patents

Description

  The present invention relates to a novel laminate.

Conventionally, white pigments such as titanium oxide and alumina have been used as pigments having heat shielding properties. Such a white pigment exhibits a certain reflection performance in the infrared light region.
However, such a white pigment generally has a high hiding power. For this reason, a coating film formed using a white pigment often becomes a monotonous coating film containing almost only white regardless of the color of the base.

Japanese Patent Laid-Open No. 2005-90042

On the other hand, for example, Patent Document 1 describes that not only a monotone color tone of white but also various colors can be given by using a paint composed of a color pigment having a high reflectance. ing.
However, it is difficult for the coating film obtained by the technique of Patent Document 1 to obtain a material having an excellent heat shielding effect as compared with a white pigment-based heat shielding material.

The present invention has been made in view of the problems as described above, has excellent reflection performance in the infrared light region, exhibits a temperature rise suppressing effect, has transparency, and has a base pattern, color tone, and the like. It is an object to obtain a laminate capable of imparting various colors by utilizing the above.
In addition, it is intended to provide a heat-insulating property and / or infrared reflectiveness to the decorative layer, and further to obtain a laminate having excellent heat shielding properties and design properties by laminating a heat insulating layer and an infrared reflective layer. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has obtained a transparent layer having both heat shielding properties and transparency obtained by combining two or more kinds of metal oxide-coated particles exhibiting a chromatic interference color, and a decorative layer It has been found that a laminate including a heat-shielding property and a design design utilizing the pattern and color tone of the decorative layer is possible, and the present invention has been completed.

That is, this invention relates to the following laminated bodies.
1. A laminate including a decorative layer and a transparent layer,
It is a laminate in which a transparent layer and a decorative layer are laminated in order from the surface,
The transparent layer includes a binder and two or more kinds of metal oxide-coated particles exhibiting a chromatic interference color, and exhibits an interference color with high brightness by additive color mixing by a combination of the metal oxide-coated particles,
The combination of chromatic colors of the metal oxide-coated particles is
From two combinations of complementary colors selected from magenta (purple) and green, blue and yellow, cyan (light blue) and red, or from three combinations of red, green and blue, or cyan, magenta and yellow. A laminate characterized by being selected .
2. 1. The binder of the transparent layer contains an acrylic component and a silicon component. The laminated body as described in.
3. The decorative layer has heat insulating properties and / or infrared reflectiveness. Or 2. The laminated body as described in.
4). Further, one or more layers selected from a heat insulating layer, an infrared reflecting layer, and a reinforcing layer are laminated. To 3. The laminated body in any one of.

The present invention is a laminate having excellent design properties that exhibits excellent heat shielding properties and enables design design that can make use of the pattern and color tone of the decorative layer.
Furthermore, the laminated body which is excellent in heat-shielding property and designability can be obtained by providing heat insulation and / or infrared reflectiveness to a decoration layer, or laminating | stacking a heat insulating layer and an infrared reflective layer.

  Hereinafter, modes for carrying out the present invention will be described.

  The laminate of the present invention includes a decorative layer and a transparent layer.

<Transparent layer>
The transparent layer of the present invention is formed of a transparent coating material containing a binder and two or more kinds of metal oxide-coated particles exhibiting a chromatic interference color.

  The metal oxide-coated particles used in the present invention are those in which the surface layer of the substrate particles is coated with a metal oxide, and can exhibit a chromatic color due to the interference of light reflected from the surface of the metal oxide coating layer and the surface of the substrate particles. It is also excellent in the infrared reflection effect. Such metal oxide-coated particles can be produced according to a known method.

The substrate particles are not particularly limited as long as they have transparency, and examples thereof include mica, glass, sericite, talc, kaolin, smectite, synthetic mica, synthetic sericite, silica, aluminum oxide, boron nitride and the like. 1 or more types can be used among these. In the present invention, mica, glass, and synthetic mica are particularly preferably used.
Examples of the shape of the base particles include acicular, spherical, and scaly shapes, and a scaly shape is preferably used. The size (minor axis and major axis) of the base particles may be appropriately set within the range of 0.1 μm to 1 mm (preferably 1 μm to 500 μm).

The metal oxide coated on the surface layer of the substrate particles is not particularly limited as long as it has a high refractive index. For example, titanium dioxide, silicon dioxide, iron oxide, aluminum oxide, zirconium oxide, cobalt oxide, oxidation Zinc, tin oxide, chromium oxide, nickel oxide and the like can be mentioned. Among these, titanium dioxide is preferable.
What is necessary is just to set suitably the thickness of a metal oxide coating layer with the chromatic color to express, and it is about 50 to 200 nm in general.

Examples of the shape of the metal oxide-coated particles include acicular, spherical, and scaly shapes. Among these, a scaly shape is preferable.
When the metal oxide-coated particles are scale-like, the size (minor axis and major axis) is usually 0.1 μm or more and 1 mm or less (preferably 1 μm or more and 500 μm or less, more preferably 2 μm or more and 200 μm or less, more preferably 5 μm or more. The thickness is preferably about 0.01 μm or more and 5 μm or less (preferably 0.05 μm or more and 1 μm or less).
The size and thickness of the metal oxide-coated particles can be measured by observation with a scanning electron microscope.

Such metal oxide-coated particles are basically transparent, but due to the interference action based on the optical path difference between the reflected light on the surface of the metal oxide coating layer and the reflected light on the surface of the base particle, A chromatic color can be expressed.
The chromatic hue can be controlled by, for example, the thickness of the metal oxide coating layer. For example, if the thickness of the metal oxide coating layer is about 90 nm to 110 nm, red, about 110 nm to 120 nm, magenta (purple), about 120 nm to 135 nm, blue, about 135 nm to 155 nm. For example, green-colored reflected light can be obtained.

In the transparent layer of the present invention, two or more kinds of metal oxide-coated particles exhibiting a chromatic interference color are mixed and used. By mixing two or more kinds, the reflected lights from the respective metal oxide-coated particles are overlapped, and an interference color with high brightness can be obtained by additive color mixing.
“High brightness” means a state in which the brightness after mixing is higher than the brightness before mixing when other metal oxide-coated particles are mixed with the metal oxide-coated particles having relatively low brightness. Means.

In the present invention, by increasing the brightness, a transparent layer having both heat shielding properties and transparency can be obtained. In particular, the effect of the present invention can be further enhanced by combining the chromatic metal oxide-coated particles so as to obtain an achromatic hue.
Examples of combinations of chromatic colors include two or more selected from magenta (purple), blue, cyan (light blue), green, yellow, orange, red, and the like. In the present invention, in particular, two combinations of complementary colors such as magenta (purple) and green, blue and yellow, cyan (light blue) and red, or red, green and blue, or cyan, magenta and yellow are used. Three combinations or the like are preferable because a more achromatic hue is obtained.

In addition, the metal oxide-coated particles are excellent in transparency, do not have a higher hiding power than white pigments such as titanium oxide, and do not easily cause coating film deterioration. Furthermore, the metal oxide-coated particles of the present invention have a property of absorbing almost no light in the visible light region and transmitting almost no reflected light.
Therefore, when two or more kinds of metal oxide-coated particles are present, even if the metal oxide-coated particles are overlapped, the reflection intensity can be increased by the action of each metal oxide-coated particle.

When there is only one kind of metal oxide-coated particle that exhibits a chromatic interference color, a chromatic hue due to the interference color appears, and the pattern and color tone of the decorative layer are likely to be hindered. Moreover, it may be inferior to heat insulation performance.
White (silver) metal oxide-coated particles have high hiding power and cannot make good use of the pattern and color tone of the decorative layer. In addition, it is difficult to obtain sufficient heat shielding performance.

On the other hand, when two or more kinds of ordinary coloring pigments are used, the subtractive color mixture results in a dark and dark hue, and the decorative layer pattern and color tone are concealed.
A normal color pigment has a wavelength that is absorbed and a wavelength that is not absorbed in the visible light region, and a wavelength that is not absorbed is reflected, and a hue corresponding to the reflected wavelength can be seen. For example, in the case of a blue pigment, in the visible light region, the wavelengths other than the wavelength indicating blue are absorbed by the pigment, and the wavelengths indicating blue that have not been absorbed are reflected and appear blue.
When two or more kinds of such color pigments are used, a subtractive color mixture results in a blackish and dark hue. This is because, if there is an absorption wavelength region in any one of the absorption wavelength region and reflection wavelength region present in each color pigment, the wavelength is absorbed in that region. This is because the strength is reduced. For example, when a red pigment and a green pigment are mixed, the red pigment is absorbed except for the wavelength indicating red, and the green pigment is absorbed except for the wavelength indicating green because the colors are in a complementary color relationship. The light is absorbed over almost the entire area, resulting in a dark and dark hue.

The binder in the transparent layer of the present invention can be used without particular limitation as long as it acts as a binder and can form a transparent film. Examples of such binders include water-soluble resins, water-dispersible resins, solvent-soluble resins, non-water-dispersed resins, solvent-free resins, and powder resins. Among these, in the present invention, a water-dispersible resin and / or a water-soluble resin is preferable, and an embodiment including a water-dispersible resin (synthetic resin emulsion) is particularly preferable. As the synthetic resin emulsion, those having an average particle size of 30 to 500 nm (more preferably 50 to 300 nm) are suitable.
Examples of usable resins include silicon resin, ethylene resin, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, acrylic urethane resin, and fluorine resin. , Cellulose, polyvinyl alcohol, biogum, galactomannan derivatives, alginic acid derivatives, cellulose derivatives, etc., or a composite system thereof.

  As the binder in the transparent layer of the present invention, a binder containing an acrylic component and a silicon component is particularly suitable. The weight ratio of the acrylic component to the silicon component is preferably 100: 10 to 100: 90, more preferably 100: 20 to 100: 70, in terms of solid content. If such a binder is used, the effect of the present invention can be enhanced due to the difference in refractive index between two or more resins.

The acrylic component can be obtained by polymerizing various acrylic monomers or copolymerizing various acrylic monomers and other monomers.
Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, and isoamyl (meth) ) Acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid N-methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, diacetone (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meta ) Acrylic nitrile and the like.

Examples of the silicon component include silica, silicone and the like, and silica is particularly preferable.
Such silica can be produced using, for example, sodium silicate, lithium silicate, potassium silicate, or a silicate compound as a raw material. Among these, as silicate compounds, for example, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetra-t-butoxy Examples thereof include silane, tetraphenoxysilane, and their condensates. A catalyst etc. can also be used at the time of manufacture. Further, after the production process or after production, the metal contained in the catalyst or the like can be removed by ion exchange treatment or the like. The particle diameter of silica is usually 1 to 200 nm, preferably about 5 to 100 nm.

In the present invention, the heat shielding property can be enhanced by using a binder containing an acrylic component and a silicon component. The reason is not clear, but first, the difference in refractive index between the acrylic component and the silicon component exerts an effect of reflecting light at the interface, and second, the silicon component is present in the coating. By arranging regularly, the reflection wavelength region is widened, and thirdly, a coating is formed in the presence of a silicon component, thereby forming fine voids and lowering thermal conductivity. It is conceivable. Furthermore, it is thought that the effect | action etc. which disperse | distribute metal oxide covering particle | grains efficiently contribute.
In the present invention, by using a binder containing an acrylic component and a silicon component, the transparent layer can be prevented from being contaminated over time, excellent in weather resistance, and heat ray absorption caused by the contaminant can be suppressed.

  As the binder in the present invention, those containing an acrylic resin emulsion and silica are particularly suitable. Among these, as the acrylic resin emulsion, those capable of reacting with silica are preferable. Specifically, the emulsion is preferably an emulsion having a functional group such as a hydroxyl group or a hydrolyzable silyl group (preferably a hydrolyzable silyl group) capable of reacting with a silanol group present in silica. By using such a binder, the effect of the present invention can be further enhanced.

  The mixing ratio of the binder and the metal oxide-coated particles is not particularly limited, but the total amount of the metal oxide-coated particles is 0.1 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the solid content of the binder. More preferred is 0.5 to 200 parts by weight, still more preferred is 1.0 to 100 parts by weight, and most preferred is 2.0 to 30 parts by weight. With such a mixing ratio, it is easy to obtain a transparent layer having both heat shielding properties and transparency.

  In the transparent coating material of this invention, you may mix and use various additives other than the said component as needed. Examples of additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, preservatives, antifungal agents, antialgae agents, antibacterial agents, dispersants, Examples include antifoaming agents, adsorbents, fibers, water repellents, crosslinking agents, ultraviolet absorbers, matting agents, antioxidants, catalysts, humidity control agents, low pollution agents, flame retardants, and flame retardants. In addition, metal oxide-coated particles may be contained within a range in which the effects of the present invention are not significantly impaired.

As described above, the transparent layer of the present invention exhibits a high-lightness interference color by additive color mixing using a combination of metal oxide-coated particles. Brightness of the transparent layer can be measured by a colorimeter, it is possible to evaluate than ^{L *} value in CIE1976L ^* a ^* b ^* color space. That is, the lightness is high when the L ^* value is high, and the lightness is low when the L ^* value is low, and the evaluation is made by comparing the L ^* value when two or more kinds are mixed with the L ^* value when only one kind is mixed. it can.
In the present invention, the L ^* value is preferably 35 or more and 90 or less, and more preferably 45 or more and 80 or less. If it is such a range, it is excellent in heat-shielding property and can utilize the pattern, color tone, etc. of a decoration layer.

The hue of the transparent layer can be measured with a color difference meter, and can be evaluated from the a ^* value and b ^* value in the CIE1976L ^* a ^* b ^* color space. That is, the closer the a ^* value and b ^* value are to 0, the more achromatic hue can be evaluated. Specifically, the evaluation can be made by comparing the a ^* value and b ^* value when two or more kinds are mixed with the a ^* value and b ^* value when only one kind is mixed.
In the present invention, the a ^* value and the b ^* value are preferably such that {(a ^* ) ² + (b ^* ) ² } ^1/2 is 30 or less, more preferably 20 or less, and even 15 or less.

  The transparency of the transparent layer may be such that the pattern and color tone of the decorative layer can be seen. Specifically, the transparency of the transparent layer can be evaluated by measuring the concealment rate with a color difference meter. The measurement may be performed according to JIS K 5600-4-1 “Paint General Test Method (Concealing Power)” Method B (Concealment Rate Test Paper). In the present invention, the concealment rate is particularly preferably 60% or less, and more preferably 50% or less.

  In addition, the brightness, hue, and transparency of the transparent layer may be measured as a test piece by coating the coating material on the concealment rate test paper so that the dry film thickness is 40 μm and drying it. . Among these, the brightness and hue are measured for the black base portion.

  The thickness of the transparent layer of the present invention may be appropriately selected depending on the application, but is usually 0.01 mm or more and 0.5 mm or less, and more preferably about 0.02 mm or more and 0.3 mm or less.

<Decoration layer>
As a decoration layer of this invention, if it has a multicolor pattern and / or an uneven | corrugated pattern, it will not specifically limit and it can apply. In addition, the multicolor pattern referred to in the present invention is a pattern in which at least two or more colors are mixed in a visually recognizable state. The uneven pattern is a surface pattern having a height difference of about 0.2 to 5 mm.
Examples of such a decorative layer include a decorative layer formed from a decorative coating material such as a stone finish finish coating material, a JIS K5667 multi-color paint, and a JIS A6909 thin finish coating material or thick finish coating material. It is done.

[Stone finish coating material]
The stone finish finishing coating material is a coating material capable of forming a multicolor pattern by coloring the aggregate, and is a coating material having a binder and an aggregate as essential components as constituent components.

  Examples of the binder include water-soluble resins, water-dispersible resins, solvent-soluble resins, non-water-dispersible resins, solvent-free resins, and powder resins, and particularly water-dispersible resins (synthetic resin emulsions). The aspect containing is suitable. In addition, the type of resin is not particularly limited. For example, silicon resin, ethylene resin, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, acrylic urethane Resins, fluororesins, cellulose, polyvinyl alcohol, biogum, galactomannan derivatives, alginic acid derivatives, cellulose derivatives, and the like can be used. These may be crosslinkable with a curing agent or a curing catalyst.

As the aggregate, an aggregate having a particle diameter of 0.05 to 5 mm is usually used. As such an aggregate, at least one selected from natural aggregates such as natural stone and natural stone pulverized products, and artificial aggregates such as colored aggregates can be suitably used. Specifically, for example, marble, granite, serpentine, granite, fluorite, cryolite, feldspar, limestone, quartzite, quartz sand, crushed stone, mica, siliceous shale, and pulverized products thereof, ceramic pulverized products, ceramic pulverized products Products, crushed glass, glass beads, crushed resin, resin beads, rubber particles, metal particles, and the like. In addition, pulverized products such as shells, shells, wood, charcoal, activated carbon and the like can be used. Furthermore, those whose surfaces are colored and coated by performing surface treatment with pigments, dyes, glazes, and the like can also be used. By using two or more kinds of such aggregates in appropriate combination, various multicolor patterns can be expressed.
The aggregate is usually mixed at a ratio of 100 to 4000 parts by weight, preferably 150 to 3000 parts by weight, and more preferably 200 to 2000 parts by weight with respect to 100 parts by weight of the solid content of the binder. If the mixing ratio of the aggregate is within such a range, it is preferable in terms of the design properties of the formed coating film, crack prevention properties, and the like.

  Components other than those described above can be mixed in the stone finish finishing coating material. Examples of such components include coloring pigments, extender pigments, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusters, antiseptics, antifungal agents, and algae. Agent, antibacterial agent, dispersant, antifoaming agent, adsorbent, fiber, water repellent, crosslinking agent, UV absorber, matting agent, antioxidant, catalyst, humidity control agent, low pollution agent, flame retardant, Incombustible agents and the like are listed. In addition, a color pigment, an extender pigment, an aggregate, and the like may be mixed within a range that does not impair the effects of the present invention.

  In the case of forming a decorative layer with a stone finish coating material, for example, means such as spray, roller, trowel, brush, reciprocating, coater, and pouring can be used, and one or more coating materials can be used. A decorative layer may be formed by overlapping. In such a stone finish finishing coating material, various uneven patterns can be provided.

[Multicolored paint]
The multicolor paint is a liquid or gel-like color particle having two or more colors suspended in a dispersion medium. These are (1) oil-in-water type (O / W type), (2) water-in-oil type (W / O type), (3) oil-in-oil type (O / O type), (4) water-in-water type (W / W type). Among these, the oil-in-water type (O / W type) and the water-in-water type (W / W type) multicolored paints are both preferable in terms of environment and the like because the dispersion medium is aqueous.

  The color particles in the multicolored paint are obtained by dispersing a colored paint containing a binder, a coloring pigment, and various additives as necessary in a dispersion medium.

  As the binding material, for example, the same materials as those exemplified in [Stone Finishing Coating Material] can be used.

  When the resin is a solvent-soluble resin and / or a non-water-dispersible resin, a solvent-type colored paint is obtained. When this resin is dispersed in an aqueous dispersion medium, an oil-in-water type (O / W type) is obtained. It becomes a multicolored paint. Further, when the resin is a water-soluble resin and / or a water-dispersible resin, an aqueous colored paint is obtained. When this resin is dispersed in an aqueous dispersion medium, a water-in-water type (W / W type) multicolor pattern paint and Become.

  As the color pigment in the color paint, those which can be generally blended into the paint can be used. Specifically, for example, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, brown, molybdate orange, permanent red, permanent Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, ocher, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, Dioxazine violet, an aluminum pigment, a pearl pigment, etc. are mentioned, These 1 type (s) or 2 or more types can be used.

  In the colored paint, known paint additives can be appropriately used. Examples of such additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, algaeproofing agents, antibacterial agents, Dispersants, antifoaming agents, adsorbents, fibers, water repellents, crosslinking agents, UV absorbers, matting agents, antioxidants, catalysts, humidity control agents, low pollution agents, flame retardants, flame retardants, etc. It is done. In addition, metal oxide-coated particles may be contained within a range in which the effects of the present invention are not significantly impaired.

The method for dispersing the colored paint in a granular form is not particularly limited, and a known method can be adopted. Specifically, a method of dispersing a colored paint in an aqueous dispersion medium containing a dispersion stabilizer or the like can be employed.
The dispersion stabilizer is a component that stabilizes the colored paint in a granular form, and can be selected according to the type of the colored paint. Specific examples of the dispersion stabilizer include, for example, a component that acts as a crosslinking agent for a colored paint. Examples of such components include epoxies, isocyanates, amines, alkoxysilanes, organic titanates, aluminum chelates, magnesium salts, calcium salts, barium salts, aluminum salts, sodium salts, potassium salts, boron Examples include acid salts and phosphates. Other dispersion stabilizers include polyvinyl alcohol, polyacrylic acid, polyethylene oxide, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, casein, cellulose acetate phthalate, bentonite, gelatin, sodium alginate, gum arabic, pectin, xanthan gum, starch Etc. can also be used.

The particle diameter and shape of the color particles can be set as appropriate. Specifically, the shape of the stirring blade at the time of manufacture, the size and position of the stirring blade with respect to the stirring tank, the rotation speed of the stirring blade, the viscosity of the colored paint, the method and concentration of the dispersion stabilizer, the viscosity of the aqueous dispersion medium, etc. What is necessary is just to select and adjust suitably.
Although the particle diameter of a color grain is not specifically limited, Usually, it is about 0.01-10 mm (preferably 0.1-5 mm).

  When the decorative layer is formed with a multicolored paint, means such as a spray, a roller, and a brush can be used.

[Thin finish coating material / Thick finish coating material]
The thin finish coating material / thick finish coating material specified in JIS A6909 is a binder and a coloring pigment, extender pigment, aggregate, and other admixtures (thickener, film-forming aid, leveling). Agent, wetting agent, plasticizer, antifreezing agent, pH adjusting agent, antiseptic agent, antifungal agent, anti-algae agent, antibacterial agent, dispersant, antifoaming agent, adsorbent, fiber, water repellent agent, crosslinking agent, ultraviolet ray Absorbent, matting agent, antioxidant, catalyst, humidity control agent, low pollution agent, flame retardant, flame retardant, etc.) can be obtained by uniformly mixing.

  As the binding material, for example, the same materials as those exemplified in [Stone Finishing Coating Material] can be used.

  As the color pigment, for example, the same pigments as exemplified in [Multicolored paint] can be used. The mixing ratio of the color pigment is usually about 1 to 300 parts by weight (preferably 2 to 200 parts by weight) with respect to 100 parts by weight of the solid content of the binder.

  The extender pigment mainly acts as a filler, and is an effective component for forming a thick film. Specific examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, porcelain clay, china clay, diatomaceous earth, hydrous finely divided silicic acid, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, carbonate Examples include magnesium, silica powder, and aluminum hydroxide. The particle size of the extender pigment is usually less than 50 μm (preferably 0.5 μm or more and less than 50 μm). The mixing ratio of the extender pigment is usually about 10 to 1000 parts by weight (preferably 20 to 500 parts by weight) with respect to 100 parts by weight of the solid content of the binder.

  As the aggregate, for example, those similar to those exemplified in [Stone Finishing Coating Material] can be used. The mixing ratio of the aggregate is usually about 10 to 2000 parts by weight (preferably 30 to 1500 parts by weight) with respect to 100 parts by weight of the solid content of the binder.

  In such a coating material, various uneven patterns, for example, sand wall shape, yuzu skin shape, fiber wall shape, ripple shape, stucco shape, uneven shape, lunar surface shape, comb drawing shape, insect worm shape and the like are formed. be able to.

  The decorative layer may further be provided with heat insulation and / or infrared reflectivity.

By imparting heat insulation to the decorative layer, heat conduction can be suppressed, temperature rise on the back surface of the laminate can be suppressed, and heat shielding properties can be improved.
Examples of the method of imparting heat insulation include a method of creating a void portion in the decorative layer. For example, by mixing hollow particles and / or porous particles or the like as a constituent of the decorative coating material, a void portion can be formed in the decorative layer, and a heat-insulating decorative layer with heat insulation is obtained. be able to.

Examples of the hollow particles include hollow ceramic particles and hollow resin particles. Examples of the ceramic component constituting the hollow ceramic particles include sodium silicate glass, aluminum silicate glass, borosilicate sodium glass, fly ash, alumina, shirasu, obsidian and the like. Examples of the resin component constituting the hollow resin particles include acrylic resin, styrene resin, acrylic-styrene copolymer resin, acrylic-acrylonitrile copolymer resin, acrylic-styrene-acrylonitrile copolymer resin, acrylonitrile-methacrylonitrile copolymer resin, Examples thereof include acrylic-acrylonitrile-methacrylonitrile copolymer resins and vinylidene chloride-acrylonitrile copolymer resins. The hollow particles can be obtained by foaming these components by a known method. The average particle diameter of the hollow particles is usually about 0.1 to 200 μm (preferably 1 to 150 μm). The density of the hollow particles is usually about 0.01 to 1 g / cm ³ (preferably 0.01 to 0.8 g / cm ³ ).

Examples of porous particles include silica gel, zeolite, sodium sulfate, alumina, allophane, diatomaceous earth, siliceous shale, sepiolite, attabargite, montmorillonite, zonolite, imogolite, Oya stone powder, activated clay, charcoal, activated carbon, wood powder, porous Examples thereof include resin particles. Among these, as the porous resin particles, pulverized products such as urethane foam and styrene foam can be used. The average particle diameter of the porous particles is usually about 0.1 to 5.0 mm. The specific surface area of the porous particles is preferably 100 m ² / g or more. The specific surface area is a value measured by the BET method.

By imparting infrared reflectivity to the decorative layer, in combination with the infrared reflective effect of the transparent layer, more excellent infrared reflectivity can be imparted, and the heat shielding property can be improved.
Examples of the method for imparting infrared reflectivity include a method of mixing infrared reflective powder as a constituent component of the decorative coating material. By mixing infrared reflective powder or the like, an infrared reflective decorative layer imparted with infrared reflectivity can be obtained.
Examples of the infrared reflecting powder include aluminum flake, titanium oxide, barium sulfate, zinc oxide, calcium carbonate, silicon oxide, magnesium oxide, zirconium oxide, yttrium oxide, indium oxide, alumina, iron-chromium composite oxide, manganese- Bismuth complex oxide, manganese-yttrium complex oxide, manganese-iron-cobalt complex oxide, perylene pigment, azo pigment, quinacridone pigment, dial, vermilion, titanium red, cadmium red, isoindolinone, isoindoline, benzimidazo Ron, phthalocyanine green, phthalocyanine blue, cobalt blue, indanthrene blue, ultramarine blue, and bitumen can be used, and one or more of these can be used. Moreover, the above-mentioned metal oxide coated particles can also be used.

  The thickness of the decorative layer of the present invention may be appropriately selected depending on the use, but is usually 0.05 mm or more and 10.0 mm or less, and further about 0.1 mm or more and 5.0 mm or less.

  Furthermore, the laminated body of this invention may laminate | stack one or more layers chosen from a heat insulation layer, an infrared reflective layer, and a reinforcement layer with a decoration layer and a transparent layer.

<Insulation layer>
In the present invention, by laminating the heat insulating layer, heat conduction can be suppressed, temperature rise on the back surface of the stacked body can be suppressed, and the heat shielding property can be improved.
Examples of the heat insulating layer include those formed from a heat insulating material including hollow particles and / or porous particles, a binder, and the like.
The hollow particles, porous particles, and binders described above can be used. Besides these, various additives (thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezes). Agent, pH adjuster, antiseptic agent, antifungal agent, anti-algae agent, antibacterial agent, dispersant, antifoaming agent, adsorbent, fiber, water repellent agent, crosslinking agent, UV absorber, matting agent, antioxidant , Catalyst, humidity control agent, low pollution agent, flame retardant, flame retardant) can be mixed to obtain a heat insulating material.
In addition, a color pigment, an extender pigment, an aggregate, etc. can be mixed to give a decorative property, or an infrared reflecting powder can be mixed to give an infrared reflecting property.
Moreover, foam materials, such as a urethane foam and a styrene foam, can also be used as a heat insulation layer.

  The thickness of the heat insulating layer of the present invention may be appropriately selected depending on the use, but is usually 0.05 mm or more and 10.0 mm or less, and further about 0.1 mm or more and 5.0 mm or less.

<Infrared reflective layer>
In the present invention, by laminating the infrared reflecting layer, combined with the infrared reflecting effect of the transparent layer, a more excellent infrared reflecting property can be imparted and the heat shielding property can be improved.
Examples of the infrared reflective layer include those formed from an infrared reflective material including an infrared reflective powder and a binder.
Infrared reflective powders and binders may be those described above, in addition to various additives (thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, antiseptics, antifungal agents, algaeproofing agents, antibacterial agents, dispersants, antifoaming agents, adsorbents, fibers, water repellents, crosslinking agents, UV absorbers, matting agents, antioxidants, catalysts , A humidity control agent, a low pollution agent, a flame retardant, and a flame retardant) can be mixed to obtain an infrared reflective material.
In addition, a color pigment, an extender pigment, an aggregate, and the like can be mixed to give decorativeness, and hollow particles and / or porous particles can be mixed to give heat insulation.

  Although the thickness of the infrared reflective layer of the present invention may be appropriately selected depending on the application, it is usually from 0.01 mm to 3.0 mm, and more preferably from 0.05 mm to 2.0 mm.

<Reinforcing layer>
In the present invention, by laminating the reinforcing layer, the strength, heat insulation, etc. of the laminate are improved, and when used by laminating on the base substrate as will be described later, such as prevention of misalignment of the laminate, adhesion, etc. An effect can also be exhibited.
As the reinforcing layer, for example, a fibrous sheet such as a woven fabric, a nonwoven fabric, or a mesh is used.
Examples of fibers include pulp fibers, polyester fibers, polypropylene fibers, aramid fibers, vinylon fibers, polyethylene fibers, polyarylate fibers, PBO fibers, nylon fibers, acrylic fibers, vinyl chloride fibers, cellulose fibers, rock wool, glass fibers, Examples thereof include fibers such as silica fiber, silica-alumina fiber, carbon fiber and silicon carbide fiber, and fine metal wires such as iron and copper.

<Laminated body>
The laminate of the present invention includes a decorative layer and a transparent layer, but may be a laminate of three or more layers including one or more layers selected from a heat insulating layer, an infrared reflective layer, a reinforcing layer, and the like.
The laminated structure of such a laminated body is not particularly limited as long as the effects of the present invention can be obtained, but a preferred laminated structure is shown below as an embodiment.

(Embodiment 1)
Embodiment 1 is a laminate in which a transparent layer and a decoration layer are laminated in order from the surface.

(Embodiment 2)
Embodiment 2 is a laminate in which a transparent layer, a decorative layer, and a heat insulation layer are laminated in order from the surface.

(Embodiment 3)
Embodiment 3 is a laminate in which a transparent layer, a decorative layer, and an infrared reflective layer are laminated in order from the surface.

(Embodiment 4)
Embodiment 4 is a laminate in which a transparent layer, a decorative layer, and a reinforcing layer are laminated in order from the surface.

(Embodiment 5)
Embodiment 5 is a laminate in which a transparent layer, a decorative layer, a heat insulating layer, and a reinforcing layer are laminated in order from the surface.

(Embodiment 6)
Embodiment 6 is a laminate in which a transparent layer, a decorative layer, an infrared reflecting layer, and a reinforcing layer are laminated in order from the surface.

(Embodiment 7)
Embodiment 7 is a laminate in which a transparent layer, a decorative layer, a heat insulating layer, and an infrared reflective layer are laminated in order from the surface.

(Embodiment 8)
Embodiment 8 is a laminate in which a transparent layer, a decorative layer, an infrared reflective layer, and a heat insulating layer are laminated in order from the surface.

(Embodiment 9)
Embodiment 9 is a laminate in which a transparent layer, a decorative layer, a reinforcing layer, and an infrared reflective layer are laminated in order from the surface.

(Embodiment 10)
Embodiment 10 is a laminate in which a transparent layer, a decorative layer, a heat insulating layer, a reinforcing layer, and an infrared reflecting layer are laminated in order from the surface.

(Embodiment 11)
Embodiment 11 is a laminate in which a transparent layer, a decorative layer, an infrared reflecting layer, a reinforcing layer, and a heat insulating layer are laminated in order from the surface.

(Embodiment 12)
Embodiment 12 is a laminate in which a transparent layer, a decorative layer, a heat insulating layer, an infrared reflective layer, and a reinforcing layer are laminated in order from the surface.

(Embodiment 13)
Embodiment 13 is a laminate in which a transparent layer, a decorative layer, an infrared reflective layer, a heat insulating layer, and a reinforcing layer are laminated in order from the surface.

(Embodiment 14)
Embodiment 14 is a laminate in which a transparent layer, a decoration layer, a reinforcement layer, a decoration layer, and a reinforcement layer are laminated in order from the surface.

  In Embodiments 1 to 14, the transparent layer and the decorative layer are laminated in order from the surface. However, when the decorative layer has transparency, the decorative layer (transparency) ), A transparent layer may be laminated. Further, an infrared reflecting layer having transparency may be included between the transparent layer and the decorative layer.

It does not specifically limit as a manufacturing method of a laminated body, It can manufacture suitably with the wet method, the dry method, or the method that combined them. For example, it can be suitably produced by using means such as spray, roller, trowel, brush, reciprocator, coater, pouring, etc., and curing may be promoted by adjusting temperature or the like.
Moreover, what is necessary is just to laminate | stack suitably by the same method also in an infrared reflective layer, a heat insulation layer, and a reinforcement layer.

The laminate of the present invention can be suitably used in buildings, civil engineering structures, home appliances, vehicles, and the like. For example, the laminate can be used by being laminated on a base material.
The base material is not particularly limited as long as it is a material used for buildings, civil engineering structures, home appliances, vehicles, etc. For example, gypsum board, plywood, concrete, mortar, porcelain tile, fiber-mixed cement board, cement silicate Examples include calcium plates, slag cement pearlite plates, ALC plates, siding plates, extruded plates, steel plates, plastic plates, wood plates, glass plates, vinyl sheets, films, and the like.

  The method of laminating the laminate on the base substrate is not particularly limited, and is a method of sticking on the base substrate via an adhesive or the like, for example, on the base substrate, as described above. Examples include a method of forming a decorative layer by applying and laminating a decorative coating material, and further forming a transparent layer by applying and laminating the above-described transparent coating material thereon.

  Experimental examples are shown below to clarify the features of the present invention.

(Manufacture of transparent coating materials)
According to the formulation shown in Tables 1 and 2, each raw material was uniformly mixed by a conventional method to produce a transparent coating material.

The concealment rate and hue of each transparent coating material are as follows.
Transparent coating material A: L ^* value: 49.9, a ^* value: 1.1, b ^* value: −11.3, {(a ^* ) ² + (b ^* ) ² } ^1/2 : 11.4 , Concealment rate: less than 50% Transparent coating material B: L ^* value: 50.3, a ^* value: 1.5, b ^* value: −12.3, {(a ^* ) ² + (b ^* ) ² } ^1/2 : 12.3, Concealment rate: less than 50% Transparent coating material C: L ^* value: 63.3, a ^* value: 1.0, b ^* value: −10.7, {(a ^* ) ² + (B ^* ) ² } ^1/2 : 10.7, Concealment rate: less than 50% Transparent coating material D: L ^* value: 51.9, a ^* value: 1.7, b ^* value: −3.5 ^{, {(a *) 2 +} (b *) 2} 1/2: 3.9, contrast ratio: less than 50% transparent dressing E: ^{L *} value: 50.2, ^{a *} value: -0.3, b ^{* values: -8.4, {(a *)} 2 + (b *) 2} 1/2: 8 4, contrast ratio: less than 50% transparent dressing F: ^{L *} value: 49.7, ^{a *} value: 1.4, ^{b * values: 0.8, {(a *)} 2 + (b *) 2} ^1/2 : 1.6, concealment rate: less than 50% Transparent coating material G: L ^* value: 67.7, a ^* value: 0.5, b ^* value: −10.0, {(a ^* ) ² + (B ^* ) ² } ^1/2 : 10.0, Concealment rate: less than 50% Transparent coating material H: L ^* value: 67.9, a ^* value: 0.2, b ^* value: -10. 3 , {(A ^* ) ² + (b ^* ) ² } ^1/2 : 10.3, Concealment rate: less than 50% Transparent coating material I: L ^* value: 68.0, a ^* value: 0.1, b ^{* value: -10.4, {(a *)} 2 + (b *) 2} 1/2: 10.4, contrast ratio: less than 50% transparent dressing J: ^{L *} value: 68.1, ^{a *} value: -0.2, ^{b * values: -9.5, {(a *)} 2 + (b ^* ) ² } ^1/2 : 9.5, Concealment rate: less than 50% Transparent coating material K: L ^* Value: 44.8, a ^* value: 1.4, b ^* value: −5.0, {( ^{a *) 2 + (b *} ) 2} 1/2: 5.2, contrast ratio: less than 50% transparent dressing L: ^{L *} value: 38.7, ^{a *} value: -0.4, ^{b *} value ^{: -1.4, {(a *)} 2 + (b *) 2} 1/2: 1.5, contrast ratio: less than 50% transparent dressing M: ^{L *} value: 81.7, ^{a *} value: -1.7, ^{b * values: -3.5, {(a *)} 2 + (b *) 2} 1/2: 3.9, contrast ratio: 50% or more transparent dressing N: ^{L *} values: 50.1, a ^* value: −2.2, b ^* value: −5.6, {(a ^* ) ² + (b ^* ) ² } ^1/2 : 6.0, concealment rate: less than 50% Transparent dressing O: ^{L *} value: 31.3, ^{a *} value: 21.3, ^{b *} values: -17.4, ^{(A *) 2 + (b} *) 2} 1/2: 27.5, contrast ratio: less than 50% transparent dressing P: ^{L *} value: 31.3, ^{a *} value: 4.4, ^{b *} value ^{: -27.5, {(a *)} 2 + (b *) 2} 1/2: 27.8, contrast ratio: less than 50% transparent dressing Q: ^{L *} value: 45.4, ^{a *} value: -13.6, ^{b * values: 0.3, {(a *)} 2 + (b *) 2} 1/2: 13.6, contrast ratio: less than 50% transparent dressing R: ^{L *} value: 48 .7, a ^* value: −2.5, b ^* value: 21.5, {(a ^* ) ² + (b ^* ) ² } ^1/2 : 21.6, concealment rate: less than 50% Transparent coating material S: L ^* value: 36.5, a ^* value: 15.6, b ^* value: 1.8, {(a ^* ) ² + (b ^* ) ² } ^1/2 : 15.7, concealment rate: Less than 50% Transparent coating material T: L ^* value: 21.5, a ^* value: 0 .2, b ^* value: 0.8, {(a ^* ) ² + (b ^* ) ² } ^1/2 : 0.8, concealment rate: less than 50%

For the measurement of the concealment rate and hue, each transparent coating material was applied onto the concealment rate test paper with a film applicator so that the dry film thickness was 40 μm, and the temperature was 23 ° C. and the humidity was 50%. Cured for 48 hours under RH (hereinafter also referred to as “standard state”),
Using a color difference meter “CR-300” (manufactured by Minolta Co., Ltd.), the concealment rate is measured by measuring the luminous reflectance of the black ground coating film and the white ground coating film on the specimen, and the visibility of the black ground coating film. The L ^* value, a ^* value, and b ^* value were calculated by measuring the reflectance.

Example 1
On the glass nonwoven fabric (thickness 0.4 mm, basis weight 50 g / m ² ), the decorative coating material A is applied at 5.0 kg / m ² , and the transparent coating material A is further applied at 0.1 kg / m ² . And dried at 80 ° C. for 60 minutes to obtain a laminate (decorative layer thickness: 3.5 mm, transparent layer thickness: 40 μm).
The obtained laminate was cut to 400 mm × 200 mm, and a glass nonwoven fabric surface of the laminate was stuck on a slate plate (400 mm × 200 mm × 6 mm) using an acrylic adhesive to obtain a test body. The obtained specimen had a clear design of the decorative layer (decorative coating material A) and had excellent design properties.
Decorative coating material A: 200 parts by weight of acrylic resin emulsion (solid content 50% by weight), 150 parts by weight of water, colored aggregate (yellow colored silica sand: red colored silica sand = 50: 50 (weight ratio), average particle diameter 50 to 500 μm) 600 parts by weight, hollow glass particles (average particle diameter 40 μm, density 0.45 g / cm ³ ) 4 parts by weight, thickener 5 parts by weight, dispersing agent 2 parts by weight, defoaming agent 5 parts by weight The following test was done about the obtained test body.

(1) Thermal insulation test The obtained test specimen was irradiated with an infrared lamp (250 W) from a distance of 40 cm, and the test specimen back surface temperature after 1 hour of irradiation was measured using a contact thermometer. Evaluation is based on the blank (Comparative Example 10), the lowest temperature is A, and in the following order, A ′, B, B ′, C, C ′, and those that do not replace the blank, or temperatures that are higher than the blank. D was the one with a higher value. The results are shown in Table 3.

(Examples 2 to 10, Comparative Examples 1 to 10)
A test body was prepared in the same manner as in Example 1 except for the transparent coating material shown in Table 3, and the same test as in Example 1 was performed. The results are shown in Table 3.
In Examples 2-10, the design by the decorative coating material A was clear, and the outstanding design was shown.
In Comparative Examples 1 and 3, whiteness was applied, and the design of the decorative coating material A was blurred.
In Comparative Examples 5 to 9, the colors of the metal oxide-coated particles were recognized, and the original color of the decorative coating material was blurred.

Claims (4)

A laminate including a decorative layer and a transparent layer,
It is a laminate in which a transparent layer and a decorative layer are laminated in order from the surface,
The transparent layer includes a binder and two or more kinds of metal oxide-coated particles exhibiting a chromatic interference color, and exhibits an interference color with high brightness by additive color mixing by a combination of the metal oxide-coated particles,
The combination of chromatic colors of the metal oxide-coated particles is
From two combinations of complementary colors selected from magenta (purple) and green, blue and yellow, cyan (light blue) and red, or from three combinations of red, green and blue, or cyan, magenta and yellow. A laminate characterized by being selected .   The laminate according to claim 1, wherein the binder of the transparent layer contains an acrylic component and a silicon component.   The laminate according to claim 1 or 2, wherein the decorative layer has a heat insulating property and / or an infrared reflective property. Furthermore, 1 or more layers chosen from a heat insulation layer, an infrared reflective layer, and a reinforcement layer are laminated | stacked, The laminated body in any one of the Claims 1-3 characterized by the above-mentioned.