WO2013002335A1

WO2013002335A1 - Laminate body

Info

Publication number: WO2013002335A1
Application number: PCT/JP2012/066565
Authority: WO
Inventors: 筧田　晃嗣; 尾上　誠一; 洋史黒田; めぐみ山口
Original assignee: 株式会社エフコンサルタント
Priority date: 2011-06-29
Filing date: 2012-06-28
Publication date: 2013-01-03
Also published as: KR20130114182A; HK1184762A1; KR101492760B1; CN103313853A; MY158501A; CN103313853B; SG191769A1

Abstract

The present invention obtains a laminate body that has superior aesthetics and can effectively suppress a temperature rise during solar light irradiation. The laminate body laminates a decorative layer and a base layer, and is characterized by the decorative layer containing colored particles and silica having an average primary particle size of 1-200 nm, and the colored particles being the result of adhering a metal oxide to the surface of inorganic particles.

Description

Laminated body

The present invention relates to a novel laminate. The laminate of the present invention can be used as, for example, a building material applied to an outer wall surface of a building.

Building materials used for building exteriors are required to have aesthetics from a landscape perspective. In recent years, as a building material, for example, an image of natural stone has been attracting attention, and a material having a relatively thick thickness and being given a heavy feeling by various uneven patterns has been adopted.

On the other hand, in recent years, in urban areas, a climate unique to urban areas has been created by artificial radiant heat discharged from concrete buildings and cooling. In particular, the outdoor temperature rise in urban areas in summer is significant, causing a problem called the heat island phenomenon. For such problems, various materials have been proposed in order to suppress the temperature rise of the building exterior surface.

Under such a background, for example, Patent Document 1 proposes a material in which a coating material containing a heat shielding aggregate is applied on a base material. In this material, a heat shielding aggregate in which a heat reflecting pigment is adhered to the surface of the aggregate is adopted, and the temperature reducing effect is exerted by the heat reflecting pigment exhibiting a near-infrared reflecting action.

JP 2007-217586 A

However, the surface of the material described in Patent Document 1 has a fine uneven shape derived from the aggregate, and contaminants are likely to adhere to the recess. Especially in urban areas, pollution is likely to proceed because oily pollutants are floating in the atmosphere due to exhaust gases from automobiles and the like. Such pollutants not only cause a decrease in aesthetics, but also have a very high ability to absorb infrared rays in sunlight, so that they act as a heat storage field and may promote a temperature rise. Furthermore, an excessive temperature rise caused by such contaminants may cause material deterioration and the like.

This invention is made | formed in view of such a problem, and while obtaining the outstanding aesthetics, the temperature rise at the time of sunlight irradiation is suppressed effectively, and the laminated body which can maintain it is obtained. It is for the purpose.

As a result of intensive studies to achieve the above object, the inventor is a laminate in which a decoration layer and a base layer are laminated, and the decoration layer has a specific colored particle and a specific average particle diameter. The present inventors have conceived of a laminate containing silica and have completed the present invention.

That is, the laminate of the present invention is a laminate in which a decoration layer and a base layer are laminated, wherein the decoration layer contains colored particles and silica having an average primary particle size of 1 nm to 200 nm, and the colored particles Is characterized in that a metal oxide is adhered to the surface of the inorganic particles.

In the laminate of the present invention, the decorative layer is a single layer of a colored layer, or a layer in which a transparent layer is laminated on the colored layer, and the colored layer contains a synthetic resin and the colored particles. And it is preferable that the said transparent layer contains a synthetic resin.

In the laminate of the present invention, it is preferable that the colored layer contains 3 to 50 parts by weight of the synthetic resin in a solid weight ratio with respect to 100 parts by weight of the colored particles.

In the laminate of the present invention, it is preferable that the single layer of the colored layer contains 0.003 to 50 parts by weight of the silica with respect to 100 parts by weight of the colored particles.

In the laminate of the present invention, the surface of the colored layer preferably has a microscopic uneven shape derived from the colored particles.

In the laminate of the present invention, it is preferable that the surface of the colored layer further has a macroscopic uneven pattern.

In the laminate of the present invention, the transparent layer preferably contains 5 to 500 parts by weight of the synthetic resin in a solid weight ratio with respect to 100 parts by weight of the silica.

In the construction method of the present invention, it is preferable that the laminate is attached to a base material via an adhesive.

More specifically, the laminate of the present invention has the following characteristics.

The laminate of the present invention is a laminate in which a colored layer is laminated on a base layer, and the colored layer comprises 3 to 50 parts by weight of a synthetic resin emulsion in a solid content weight ratio with respect to 100 parts by weight of colored particles. In addition, 0.003 to 50 parts by weight of water-dispersible silica having an average primary particle size of 1 to 200 nm in solid weight ratio, and the surface of the layer has a microscopic uneven shape derived from the colored particles. The colored particles are characterized in that metal oxides adhere to the surfaces of the inorganic particles.

The laminate of the present invention is a laminate in which a colored layer is laminated on a base layer, and the colored layer comprises 3 to 50 parts by weight of a synthetic resin emulsion in a solid content weight ratio with respect to 100 parts by weight of colored particles. And 0.003 to 50 parts by weight of water-dispersible silica having an average primary particle size of 1 to 200 nm in terms of solid content, and the surface of the layer has a microscopic uneven shape derived from the colored particles, and It has a macroscopic concavo-convex pattern, and the colored particles are formed by adhering a metal oxide to the surface of inorganic particles.

Further, the laminate of the present invention is a laminate in which a transparent layer is laminated on a colored layer, and the colored layer has a synthetic resin in a solid content weight ratio of 3 to 50 with respect to 100 parts by weight of the colored particles. Including parts by weight, the surface of the layer has a microscopic uneven shape derived from the colored particles, the colored particles are formed by attaching a metal oxide to the surface of the inorganic particles, The transparent layer is characterized by containing 5 to 500 parts by weight of a synthetic resin in a solid weight ratio with respect to 100 parts by weight of silica having an average primary particle diameter of 1 to 200 nm.

The laminate of the present invention is a laminate in which a transparent layer is laminated on a colored layer, and the colored layer contains 3 to 50 parts by weight of a synthetic resin in a solid weight ratio with respect to 100 parts by weight of the colored particles. The surface of the layer has a microscopic uneven shape derived from the colored particles, and has a macroscopic uneven pattern, and the colored particles have a metal oxide on the surface of the inorganic particles. The transparent layer is characterized by containing 5 to 500 parts by weight of a synthetic resin in a solid weight ratio with respect to 100 parts by weight of silica having an average primary particle diameter of 1 to 200 nm.

The laminate of the present invention is obtained by laminating a colored layer containing specific colored particles and specific silica on a base layer, and aesthetics are imparted by the color of the colored layer. Furthermore, the temperature rise at the time of sunlight irradiation is effectively suppressed by synergistic actions such as infrared reflectivity and contamination prevention of the colored layer. Furthermore, the anti-contamination action of the colored layer keeps the surface of the colored layer aesthetics based on the color of the colored layer for a long period of time, and can prevent a temperature increase due to the adhesion of contaminants for a long period of time.

The laminate of the present invention has a transparent layer containing specific silica on a colored layer containing specific colored particles. In the present invention, aesthetics are imparted by the color of the colored layer. Furthermore, the temperature rise at the time of sunlight irradiation is effectively suppressed by synergistic actions such as the infrared reflectivity of the colored layer and the anti-contamination property of the transparent layer. In addition to such an action, in the present invention, an increase in the temperature of the transparent layer can be suppressed by the infrared reflecting action of the colored layer. If the temperature of the transparent layer rises excessively, the inherent anti-contamination action may not be exhibited due to the softening of the synthetic resin contained in the transparent layer, or the anti-contamination action may be impaired early due to a decrease in durability. On the other hand, in this invention, the temperature rise of a transparent layer is suppressed by the effect | action of a colored layer, and sufficient pollution prevention effect is exhibited over a long period of time. Thereby, the aesthetics based on the color etc. of a colored layer are maintained over a long period of time, and the temperature rise resulting from adhesion of a contaminant can also be avoided for a long period of time.

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

The laminate of the present invention is a laminate in which a decoration layer and a base layer are laminated, wherein the decoration layer contains colored particles and silica having an average primary particle diameter of 1 nm to 200 nm, and the colored particles are It is characterized in that a metal oxide is adhered to the surface of the inorganic particles.

In the laminate of the present invention, the decorative layer is a single layer of a colored layer or a layer in which a transparent layer is laminated on the colored layer, and the colored layer is a synthetic resin and the colored particles. It is preferable that the transparent layer contains a synthetic resin. In particular, when the decorative layer is a single layer of a colored layer, the colored layer preferably contains a synthetic resin, colored particles, and silica having an average primary particle diameter of 1 nm to 200 nm, and the decorative layer is on the colored layer. When the transparent layer is a laminated layer, the colored layer may contain a synthetic resin and colored particles, and the transparent layer may contain a synthetic resin and silica having an average primary particle size of 1 nm to 200 nm. preferable.

The decorative layer in the present invention can impart design properties and infrared antireflection properties to the laminate by containing specific colored particles, and further, by containing specific silica, it has antifouling properties. It can be imparted and is a preferred embodiment.

In the present invention, (A) colored particles (hereinafter also referred to as “component (A)”) are formed on the surface of (a1) inorganic particles (hereinafter also referred to as “component (a1)”), and (a2) metal oxide (hereinafter referred to as “component”). (Also referred to as “component (a2)”). The component (A) is different from the case of using a general coloring pigment having a small average particle diameter, and the small dot of the component (A) is visually recognized as a colorful pattern and imparts excellent color tone and texture. . Moreover, (A) component forms microscopic unevenness | corrugation in the colored layer surface, and contributes also to provision of a three-dimensional design.

The component (a1) constituting the component (A) is not particularly limited as long as the material is inorganic, and both natural products and artificial products can be used. Specifically, for example, mica, kaolin, clay, china clay, china clay, talc, aluminum hydroxide, magnesium hydroxide, calcium carbonate, shells, barite powder, marble, granite, serpentine, granite, fluorite, cold water stone , Pulverized materials such as feldspar, silica stone, and silica sand, ceramic pulverized materials, ceramic pulverized materials, glass beads, glass pulverized materials, and metals.

The component (a2) attached to the surface of the component (a1) is for coloring the surface of the component (a1). Examples of the component (a2) include transition metal elements such as scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, and copper; rare earth elements such as holmium, praseodymium, neodymium, and erbium; gold, platinum, silver, A metal oxide containing at least one metal element selected from noble metal elements such as palladium and rhodium, or a composite oxide of these metal oxides can be used. The composite oxide includes at least one selected from the above metal oxides and metal oxides such as silicon, aluminum, zirconium, zinc, lead, antimony and tin; alkaline earths such as magnesium, calcium, strontium and barium Examples thereof include composite oxides with at least one oxide selected from metal oxides; inorganic oxides such as boron and phosphorus.

By having the component (a2), the component (A) can maintain a color tone with excellent aesthetics over a long period of time, and can also exhibit an excellent infrared reflection effect.

The component (A) of the present invention is not limited as long as the component (a2) is attached to the surface of the component (a1). At this time, the component (a1) and the component (a2) may be directly attached or may be attached via a binder component. As the binder component, known ones such as organic, inorganic and organic-inorganic composites can be used. In the present invention, an inorganic binder containing at least one selected from silicate, aluminum salt, phosphate and the like is particularly preferable.

The component (A) preferably contains colored particles having an average particle size of 22 to 600 μm. Particularly in the present invention, the component (A) preferably contains 10% by weight or more of colored particles (A1) having an average particle size of 22 μm or more and less than 150 μm. The ratio of the colored particles (A1) in the component (A) is more preferably 10 to 80% by weight, still more preferably 20 to 70% by weight, and most preferably 30 to 60% by weight.
The component (A) preferably contains 10 to 45% by weight of colored particles (A2) having an average particle diameter of 150 μm or more and less than 212 μm. The ratio of the colored particles (A2) in the component (A) is more preferably 15 to 40% by weight, still more preferably 20 to 35% by weight.
Further, the component (A) preferably contains 10 to 45% by weight of colored particles (A3) having an average particle diameter of 212 μm or more and less than 600 μm. The ratio of the colored particles (A3) in the component (A) is more preferably 15 to 40% by weight, still more preferably 20 to 35% by weight.

The component (A) having such a particle size distribution can be obtained by combining at least two kinds, preferably three or more kinds of colored particles having different average particle diameters. A preferred embodiment includes a combination of colored particles having an average particle size of 53 μm or more and less than 125 μm and colored particles having an average particle size of 125 μm or more and less than 500 μm. As a more preferred embodiment, a combination of colored particles having an average particle diameter of 53 μm or more and less than 125 μm, colored particles having an average particle diameter of 125 μm or more and less than 212 μm, and colored particles having an average particle diameter of 212 μm or more and less than 500 μm can be mentioned. The average particle diameter of the component (A) is a value obtained by sieving using a metal mesh sieve specified in JIS Z8801-1: 2000 and calculating the average value of the weight distribution.

In the present invention, the aesthetics can be further enhanced by the particle size constitution of the component (A) as described above, and further advantageous in terms of suppressing temperature rise of the laminate, preventing deterioration (preventing swelling, etc.) and the like. . Although the mechanism of this action is not clear, it is presumed that the (A) component is densely aggregated in the colored layer and the gap between the (A) components is reduced, resulting in the following actions.
-The light diffuse reflection effect near the surface of the colored layer is enhanced.
-The degree of unevenness on the surface of the colored layer is alleviated, and contaminants serving as a heat storage source are more difficult to adhere.
-The thermal diffusion effect of the colored layer is increased by the thermal conductivity of the component (A), and the local temperature rise is suppressed.

(B) Synthetic resin (hereinafter also referred to as “component (B)”) in the colored layer plays a role of immobilizing the component (A).

Examples of such component (B) include acrylic resin, silicone resin, acrylic silicone resin, fluorine resin, vinyl acetate resin, acrylic / vinyl acetate resin, vinyl chloride resin, urethane resin, acrylic urethane resin, epoxy resin, and alkyd. Examples include resins, polyvinyl alcohol resins, polyester resins, ethylene resins, polyvinyl alcohol, cellulose, and derivatives thereof. Examples of the form of component (B) include water-dispersed types (synthetic resin emulsions), water-soluble types, non-water-dispersed types, solvent-soluble types, and non-solvent types. Any of these may be used.

The glass transition temperature of the component (B) is preferably −60 ° C. to 60 ° C., more preferably −40 ° C. to 30 ° C., and further preferably −30 ° C. to 20 ° C. When the glass transition temperature of the component (B) is in such a range, it is possible to impart moderate flexibility. In the present invention, even if a component having a relatively low glass transition temperature is used as the component (B), a sufficient anti-contamination effect can be obtained by the action of the transparent layer. The glass transition temperature is a value determined by the Fox formula.

The ratio of the component (B) is usually 3 parts by weight or more and 50 parts by weight or less, preferably 4 parts by weight or more and 30 parts by weight or less, more preferably 5 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content. More than 20 parts by weight, more preferably 6 parts by weight or more and 19 parts by weight or less. If it is such a ratio, the design property which utilized the texture of (A) component will be provided, and also a temperature rise can be suppressed effectively. Further, since the colored layer has sufficient water vapor permeability, swelling of the colored layer can be prevented.

Further, the (B) synthetic resin (hereinafter also referred to as “component (B)”) in the colored layer plays a role of immobilizing the component (A). In the present invention, it is particularly preferable to use a synthetic resin emulsion as the component (B). Such a component (B) can be obtained, for example, by copolymerizing various polymerizable monomers. Examples of the polymerizable monomer component constituting the component (B) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n- Amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) (Meth) acrylic esters such as acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate;
Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or its monoalkyl ester, itaconic acid or its monoalkyl ester, fumaric acid or its monoalkyl ester;
Contains amino groups such as N-methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl vinyl ether, N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide monomer;
Pyridine monomers such as vinylpyridine;
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
Vinyl ester monomers such as vinyl acetate and vinyl propionate;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Aromatic monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene;
Amide group-containing monomers such as acrylamide, methacrylamide, maleic acid amide, N-methylol (meth) acrylamide, diacetone acrylamide;
Epoxy group-containing monomers such as glycidyl (meth) acrylate, diglycidyl (meth) acrylate, and allyl glycidyl ether;
Carbonyl group-containing monomers such as acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone;
Alkoxysilyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane Containing monomers;
Vinylidene halide monomers such as vinylidene chloride and vinylidene fluoride;
Other examples include ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride, vinyl ether, vinyl ketone, vinyl amide, and chloroprene. These can be used alone or in combination of two or more. Among these, when an alkoxysilyl group-containing monomer is included as a polymerizable monomer, physical properties of the coating film can be improved by interaction with the component (D) described later (silica having an average primary particle diameter of 1 to 200 nm).

The minimum film-forming temperature of the component (B) can be appropriately set, but is usually 80 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower. If the minimum film-forming temperature of (B) component is in such a range, it will become possible to exhibit stain resistance while ensuring the coating film properties such as crack resistance.

(B) Although the manufacturing method of a component is not specifically limited, For example, as a manufacturing method of a synthetic resin emulsion, emulsion polymerization, soap free emulsion polymerization, dispersion polymerization, feed emulsion polymerization, feed dispersion polymerization, seed emulsion polymerization, seed dispersion | distribution Polymerization or the like can be employed.

The average particle size of the component (B) is usually about 0.05 to 0.3 μm. The solid content ratio in the total amount of component (B) is not particularly limited, but is usually about 10 to 60% by weight.

In the present invention, when the component (B) is a synthetic resin emulsion, a crosslinking reaction type synthetic resin emulsion, a core-shell type synthetic resin emulsion, or the like can also be used. Two or more synthetic resin emulsions can be used in combination. Among these, as the crosslinking reaction in the crosslinking reaction type synthetic resin emulsion, for example, carboxyl group and metal ion, carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group , A combination of carbonyl group and hydrazide group, epoxy group and hydrazide group, epoxy group and amino group, hydrolyzable silyl groups, and the like. Among these, preferred crosslinking reactions include a carboxyl group and an epoxy group, a carboxyl group and an oxazoline group, a carbonyl group and a hydrazide group, an epoxy group and a hydrazide group, and hydrolyzable silyl groups.

The component (B) is preferably capable of reacting with the component (D) described later (silica having an average primary particle diameter of 1 to 200 nm). The component (B) is, for example, a synthetic resin having a functional group such as a hydroxyl group or a hydrolyzable silyl group (preferably a hydrolyzable silyl group) that can react with the silanol group present in the component (D). It is preferable. In particular, when the component (B) is a synthetic resin emulsion, the component (D) is preferably water-dispersible silica having an average primary particle size of 1 to 200 nm. By chemically bonding the component (B) and the component (D), it becomes possible to exhibit the stain resistance while ensuring the coating film properties such as crack resistance.

The component (D) in the present invention is silica having an average primary particle size of 1 to 200 nm, preferably water-dispersible silica. The particles constituting the component (D) are compounds having a high hardness because of silica as a main component, and having silanol groups on the particle surfaces. Such a component (D) greatly contributes to the effect of improving contamination resistance.

The average primary particle diameter of the component (D) is usually 1 to 200 nm, preferably 3 to 100 nm, more preferably 5 to 60 nm, and further preferably 20 to 40 nm as the primary particle diameter. If the average primary particle size is too large, the appearance of the formed coating film may be adversely affected. When the average primary particle diameter is too small, there is a possibility that a sufficient effect cannot be obtained in the stain resistance. In the present invention, two or more kinds of silicas having different average primary particle diameters can be used. The particle diameter of the component (D) is a value measured by a light scattering method.

The pH of the component (D) is usually 5 or more and 12 or less, preferably 6 or more and 10 or less, more preferably 6 or more and 9 or less. The component (D) prepared at such pH can exhibit hydrophilicity due to abundant silanol groups on the particle surface, and greatly contributes to the improvement of stain resistance.

Such a component (D) can be produced using, for example, sodium silicate, lithium silicate, potassium silicate, or a silicate compound as a raw material. Among these, as the silicate compound, 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. In addition, alkoxysilane compounds other than the above silicate compounds, alcohols, glycols, glycol ethers, fluorine alcohols, silane coupling agents, polyoxyalkylene group-containing compounds, and the like can also be used. 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.

As the medium of component (D), water and / or a water-soluble solvent can be used. Examples of the water-soluble solvent include alcohols, glycols, glycol ethers and the like. In the present invention, it is particularly desirable that the medium is composed only of water. By using such a component (D), the coating material can be made to have a low volatile organic solvent (low VOC). Moreover, generation | occurence | production of the aggregate at the time of mixing with (B) component (preferably synthetic resin emulsion) can also be suppressed.

The solid content of the component (D) is usually 5 to 60% by weight, preferably 10 to 55% by weight, and more preferably 15 to 50% by weight. When the solid content of the component (D) is within such a range, the stability of the component (D) itself, and further when the component (B) (preferably a synthetic resin emulsion) and the component (D) are mixed. Stability can be ensured. If the solid content is too large, the component (D) itself may become unstable, or the coating material may become unstable when mixed with the component (B). If the solid content is too small, a large amount of component (D) must be mixed in order to obtain a sufficient anti-staining effect, which is not practical.

The mixing ratio of the component (A) and the component (B) is preferably 3 parts by weight or more and 50 parts by weight or less, more preferably 4 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content. Part by weight to 30 parts by weight, more preferably 5 parts by weight to less than 20 parts by weight, particularly preferably 6 parts by weight to 19 parts by weight. The mixing ratio of the component (A) and the component (D) is, in terms of solid content, 100 parts by weight of the component (A), and the component (D) is usually 0.003 parts by weight or more and 50 parts by weight or less, preferably 0. 0.01 parts by weight or more and 30 parts by weight or less. If it is such a mixing ratio, the design property which utilized the texture of (A) component is provided, and also a temperature rise can be suppressed effectively. Further, since the colored layer has sufficient water vapor permeability, swelling of the colored layer can be prevented.

In the colored layer, in addition to the above components, (C) a light stabilizer (hereinafter also referred to as “(C) component”) may be used. By including such a component (C), it is possible to maintain excellent adhesion with a transparent layer described later over a long period of time, and the effects of the present invention can be sufficiently exhibited.

Such a component (C) includes a hindered amine light stabilizer. Specifically, for example, bis (2,2,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy- 2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2 , 6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2 , 6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like.

The ratio of the component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the component (A). is there.

In the colored layer, in addition to the above components, glass powder of less than 1 μm can be used to the extent that the effects of the present invention are not impaired. By including such glass powder of less than 1 μm, it is possible to more effectively suppress the temperature rise during sunlight irradiation.

The colored layer of the present invention may contain various colored or colorless particles other than the above components for the purpose of improving the design properties. Examples of such particles include coloring pigments, bright pigments, fluorescent pigments, extender pigments, and aggregates. Moreover, unless the effect of this invention is impaired remarkably, a colored layer can contain another component as needed. Examples of such components include plasticizers, algae inhibitors, antibacterial agents, deodorants, adsorbents, flame retardants, fibers, ultraviolet absorbers, light stabilizers, antioxidants, catalysts, and the like.

The colored layer of the present invention preferably has a microscopic uneven shape derived from the component (A) on the surface thereof. This microscopic unevenness is caused by the average particle diameter, the degree of aggregation and the like of the component (A), and is preferably 1.5 mm or less (more preferably 0.005 mm or more and 1.2 mm or less, and still more preferably 0.8. The height difference is from 01 mm to 1 mm, most preferably from 0.02 mm to 0.8 mm.

As the colored layer of the present invention, a layer having a macroscopic concavo-convex pattern in addition to the above microscopic concavo-convex can be used. In the present invention, particularly advantageous effects can be obtained when the colored layer has such an embodiment.
The macroscopic concavo-convex pattern imparts a stereoscopic effect to the colored layer. This macroscopic concavo-convex pattern is larger than the above-mentioned microscopic concavo-convex pattern, and preferably has a height difference of 1 mm to 10 mm (more preferably 1.5 mm to 8 mm). Examples of the uneven pattern having such a height difference include a yuzu skin pattern, a ripple pattern, a stucco pattern, a sand wall pattern, a stone pattern, a rock texture pattern, a sandstone pattern, a blown pattern, a moon pattern, a comb pattern, and an insect pattern. , Etc.

The thickness of the colored layer may be appropriately set according to the purpose, but is preferably 0.5 mm to 10 mm, more preferably 1 mm to 8 mm. In such a range, it is advantageous for the formation of a deeply carved uneven pattern (macroscopic uneven pattern), and an excellent design with a three-dimensional effect is easily obtained.

The laminate of the present invention can also be provided with a transparent layer on the outermost surface. As the transparent layer, (E) silica having an average primary particle diameter of 1 to 200 nm (hereinafter also referred to as “(E) component”) was immobilized with (F) synthetic resin (hereinafter also referred to as “(F) component”). Is.

The component (E) in the transparent layer exhibits an excellent antifouling effect due to the high hardness of the particles themselves and the fact that they have many silanol groups on the surface of the particles.

The average primary particle diameter of the component (E) is usually 1 to 200 nm, preferably 3 to 100 nm, more preferably 5 to 60 nm. Within this range, a plurality of silicas having different average primary particle sizes can be used in combination. When the average primary particle size of the component (E) is larger than 200 nm, the specific surface area becomes small, and silanol groups are reduced, so that the anti-contamination property becomes insufficient. When the average primary particle diameter is smaller than 1 nm, the silica itself becomes unstable, so it is not practical. In addition, the average primary particle diameter said here is a value measured by the light-scattering method.

As such component (E), those derived from silica sol are preferable, and those derived from water-dispersible silica sol having a pH of 5 or more and 12 or less (preferably 6 or more and 10 or less, more preferably 6 or more and 9 or less). preferable.

Such a water-dispersible silica sol can be produced using, for example, sodium silicate, lithium silicate, potassium silicate, a silicate compound or the like 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. In addition, alkoxysilane compounds other than the silicate compounds, alcohols, glycols, glycol ethers, fluoroalcohols, silane coupling agents, polyoxyalkylene group-containing compounds, and the like can also be used.

Various resins can be used as the component (F) for immobilizing the component (E). Specifically, the same thing as said (B) component is mentioned, These 1 type (s) or 2 or more types can be used. Such a resin is preferably a water-soluble resin and / or a water-dispersible resin.

The ratio of the component (F) is usually 5 to 500 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the solid content of the component (E). By being such a ratio, while being excellent in the adhesiveness to a colored layer, the sufficient contamination prevention effect is acquired and it is advantageous also at the point of temperature rise suppression. And such an effect is exhibited over a long period of time. Further, the water vapor permeability of the colored layer is not hindered, which is advantageous in terms of preventing swelling. It is considered that the local temperature rise is also suppressed by the thermal diffusion action based on the thermal conductivity of the component (E).

Further, in the transparent layer, in addition to the above components, glass powder of less than 1 μm can be used to the extent that the effects of the present invention are not impaired. By including such glass powder of less than 1 μm, it is possible to more effectively suppress the temperature rise during sunlight irradiation.

The transparent layer of the present invention can contain other components as necessary, in addition to the above-mentioned components (E) and (F), to the extent that the effects of the present invention are not impaired. Such components include, for example, plasticizers, algae inhibitors, antibacterial agents, deodorants, adsorbents, flame retardants, fibers, UV absorbers, light stabilizers, antioxidants, catalysts, glitter pigments, fluorescent And pigments.

The transparent layer may be in a form that covers the entire surface of the colored layer. The weight per unit area of the transparent layer is preferably 0.1 to 50 g / m ² , more preferably 0.5 to 20 g / m ² in terms of solid content. Such a transparent layer can cover the entire colored layer including the surface of the individual colored particles above the colored layer, the vicinity of the colored particles, the gap between the colored particles, and the like.

In the present invention, the transparent layer may be unevenly distributed in a concave portion having a microscopic uneven shape. In such an embodiment, effects such as contamination prevention and temperature rise suppression can be further enhanced without impairing the aesthetics of the colored layer. And the effect can be exhibited over a long period of time. The mechanism of action is not clear, but it is presumed that the following points are involved.
-Unevenness on the surface of the colored layer is alleviated and adhesion of contaminants and the like is suppressed.
-The interface between the colored particles and the synthetic resin on the colored layer surface is reinforced.
-Since the thickness of the recess is increased, it is less susceptible to erosion and the like.

(Base layer)
In the present invention, as long as the effects of the present invention are not impaired, for example, a base layer can be laminated on the inside or the back surface of the colored layer. As the material used for the base layer, a material having flexibility, water vapor permeability and the like is preferable. Examples of such a material include fibrous materials such as woven fabric, non-woven fabric, mesh, and cloth. Specifically, the fibrous material has a thickness of 0.05 to 1.5 mm (more preferably 0.1 to 1.2 mm, and still more preferably 0.2 to 1 mm), a basis weight of 5 to 300 g / m ² , Examples include those containing inorganic fibers (more preferably 10 to 250 g / m ² , still more preferably 20 to 200 g / m ² ). Further, the fibrous material is preferably coated with a treatment liquid containing a silicon compound, and the flexibility can be further improved. By using such a fibrous material, it is possible to improve the crack prevention property of the laminate. Moreover, when constructing a laminated body to an outer wall surface etc., a laminated body can be supported stably.

(Laminate manufacturing method)
In the present invention, the production method is not particularly limited as long as the transparent layer is laminated on the colored layer, but the colored layer is formed after the colored layer is formed as in the following (1) or (2). The manufacturing method which forms a transparent layer on this is preferable. According to this method, it is easy to obtain a mode in which the transparent layer covers the entire surface of the colored layer and is unevenly distributed in the concave portion having a microscopic uneven shape, which is also preferable from the viewpoint of the effect of the present invention. In the following (2), a laminate in which a colored layer and a transparent layer are sequentially laminated on the base layer is obtained.

In the present invention, as long as the colored layer is laminated on the base layer, the production method is not particularly limited. Examples thereof include the following methods (3) and (4), and particularly the following (4). Thus, the manufacturing method which forms a colored layer on a base layer is preferable. According to this method, the entire outermost surface of the colored layer is covered with the thin film containing the component (B) and the component (D), and the thin film is unevenly distributed in the concave portions having the microscopic uneven shape. It is easy and is suitable also from the point of expression of the effect of the present invention.

(1) A colored layer composition containing (A) colored particles and (B) synthetic resin is applied on a releasable substrate to form a colored layer, and then (E) silica and (F) synthesis A method of forming a transparent layer by applying a composition for a transparent layer containing a resin, removing the releasable substrate after curing, and then laminating the base layer with an adhesive or the like.
(2) After applying a colored layer composition containing (A) colored particles and (B) synthetic resin on the base layer to form a colored layer, (E) transparent containing silica and (F) synthetic resin A method of forming a transparent layer by applying a layer composition.
(3) A colored layer composition containing the components (A), (B) and (D) is applied on the releasable substrate to form a colored layer, and then the base layer is laminated and cured. A method for removing the releasable substrate later.
(4) A method of forming a colored layer by applying a colored layer composition containing the component (A), the component (B) and the component (D) on the base layer.

The releasable substrate in the above (1) and (3) may be any substrate that can be removed after curing. For example, a mold made of silicon resin, urethane resin, metal, or release paper can be used. .
In the above (1) to (4), it is desirable that a releasable base or base layer is installed horizontally, and a colored layer composition and a transparent layer composition are laminated thereon.

In the above (1) to (4), the composition for the colored layer and the composition for the transparent layer can contain known additives as necessary, as long as the effects of the present invention are not significantly impaired. 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, Examples include deodorants, dispersants, antifoaming agents, adsorbents, flame retardants, color pigments, extender pigments, fibers, water repellents, crosslinking agents, ultraviolet absorbers, antioxidants, and catalysts.

In the above (1) to (4), when applying the composition for the colored layer, for example, a known applicator such as spray, roller, scissors, reciprocator, coater, and pouring can be used. When applying the composition for transparent layer, well-known applicators, such as a spray and a roller, can be used, for example.

In the above (1) to (4), the colored layer composition and the transparent layer composition may be dried separately, or the transparent layer composition may be dried in an undried state. It may be applied at the same time. Although drying can also be performed at normal temperature, it is preferable to heat in this invention. The heating temperature is preferably about 40 ° C. or more and less than 170 ° C.

As a method for forming a macroscopic uneven pattern on the colored layer, for example, the following method can be employed.
(A) When applying the colored layer composition, a pattern is applied.
(B) After uniformly applying the colored layer composition, a part thereof is removed or pressed in an uncured state.
(C) The surface of the colored layer composition is partially cut after curing.

In said (I), various uneven | corrugated patterns are obtained by selecting suitably the kind of application tool, its usage, or adjusting the viscosity of the composition for colored layers.
In the above (b), before the colored layer composition is dried, the coated surface is removed or pressed by using a tool such as a design roller, scissors, brush, comb, spatula, stamp, emboss, etc. An uneven pattern is obtained.
In (c) above, a polishing tool, a cutting tool, or the like can be used.

Among these, in the present invention, the above methods (a) and / or (b) are preferable.
In the case of (i) above, a method of applying the ball-shaped product of the colored layer composition by accelerating it is preferable. Examples of such a method include a method of spraying the colored layer composition in a ball shape using centrifugal force, wind pressure, or the like.
In (b) above, a method of pressing the coating surface of the colored layer composition is preferred. Examples of such a method include a method of embossing the coated surface after applying the colored layer composition.
According to such a method, the component (A) tends to agglomerate densely, and the effects of the present invention can be easily obtained. Moreover, the thin film containing (B) component and (D) component is easy to be formed in the outermost surface of a colored layer, and the effect of this invention is easy to be acquired.

<Lamination body construction method>
The laminate of the present invention can be applied mainly as an exterior building material for buildings. That is, in the construction of the laminate of the present invention, the laminate may be attached to the building exterior surface (base) that is a base material. Such base materials (underlying) include concrete, mortar, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, gypsum board, tile, ALC board, siding board, extrusion board, steel sheet, plastic board, Wood board etc. are mentioned. These foundations may be treated with a filler, putty, sealer or the like.

When adhering the laminate of the present invention to a substrate (underlying), for example, an adhesive, a pressure-sensitive adhesive, a pressure-sensitive adhesive tape, a nail, a ridge or the like may be used. In addition, it can also be fixed using pins, fasteners, rails or the like. Especially, it is preferable to stick to a base material (base | substrate) through an adhesive agent. Since this invention laminated body has moderate water vapor permeability, when it sticks to a base material (base | substrate) via an adhesive agent, the effect which promotes the drying property of an adhesive agent is exhibited.

Moreover, when adhering the laminate with an adhesive, the adjoining laminates can be abutted and adhered, or the laminate can be adhered at a predetermined interval to provide joints. In this invention, a joint part can be easily formed by sticking a laminated body so that an adhesive agent may be exposed between laminated bodies. In this case, the interval (joint width) for adhering the laminate is preferably about 1 to 30 mm. Within such a range, a decorative finish utilizing the joint pattern can be obtained. The adhesive at the joint may be smoothed with a spatula or the like as necessary. In addition, although the atmospheric temperature at the time of hardening an adhesive agent can be set suitably, it may be normal temperature normally.

Examples are given below to clarify the features of the present invention.

(Colored layer compositions I-1 to I-9)
According to the formulation shown in Table 1, colored materials Compositions I-1 to I-9 were produced by mixing and stirring the respective raw materials by a conventional method. In addition, the following were used as a raw material.

Colored particles 1: Black particles (average particle size 90 μm) with complex oxide (manganese oxide, cobalt oxide, iron oxide) attached to the surface of silica
Colored particles 2: Black particles (average particle size 160 μm) with complex oxide (manganese oxide, cobalt oxide, iron oxide) attached to the surface of silica stone
Colored particles 3: Black particles (average particle size 300 μm) with complex oxide (manganese oxide, cobalt oxide, iron oxide) attached to the surface of silica stone
Colored particles 4: Brown particles (average particle size 80 μm) with metal oxides containing iron oxide attached to the surface of silica
-Colored particles 5: Brown particles (average particle size 170 μm) with a metal oxide containing iron oxide attached to the surface of silica stone
Colored particle 6: Brown particle (average particle size 280 μm) with a metal oxide containing iron oxide attached to the surface of silica
Colored particles 7: White particles (average particle size 95 μm) in which a metal oxide containing titanium oxide is adhered to the surface of silica
-Colored particles 8: White particles (average particle size 140 μm) in which a metal oxide containing titanium oxide adheres to the surface of silica
Colored particle 9: White particle (average particle diameter 350 μm) in which a metal oxide containing titanium oxide adheres to the surface of silica
Synthetic resin 1 (acrylic resin emulsion, solid content 50% by weight, glass transition temperature 0 ° C.)
・ Light stabilizer (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate)

In the colored particles of the colored layer composition I-5, the colored particles (A1) having an average particle size of 22 μm or more and less than 150 μm are 40% by weight, and the colored particles (A2) having an average particle size of 150 μm or more and less than 212 μm are 30% by weight. The colored particles (A3) having an average particle diameter of 212 μm or more and less than 600 μm were 30% by weight.
In the colored particles of the colored layer composition I-6, (A1) was 45% by weight, (A2) was 31% by weight, and (A3) was 24% by weight.
In the colored particles in the colored layer composition I-7, (A1) was 52% by weight, (A2) was 22% by weight, and (A3) was 26% by weight.
The colored layer compositions I-8 and I-9 were the same as the colored layer composition I-5.

(Transparent layer composition)
As the composition for transparent layer, the following were prepared.

-Composition 1 for transparent layer
Silica (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 60 (solid weight ratio) aqueous dispersion.

・ Transparent layer composition 2
Silica (water-dispersible silica sol, pH 7.3, average primary particle size 43 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 38 (solid weight ratio) aqueous dispersion.

-Composition 3 for transparent layer
Silica (water-dispersible silica sol, pH 7.8, average primary particle size 12 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 72 (solid weight ratio) aqueous dispersion.

-Composition 4 for transparent layer
Silica (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 320 (solid weight ratio) aqueous dispersion.

-Composition 5 for transparent layer
An aqueous dispersion of an acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature 18 ° C.).

(Test Example I-1)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the colored layer composition I-1 was applied with a coater so that the dry thickness was 2 mm, and the temperature was 60 ° C. for 60 minutes. Dried. Next, the transparent layer composition 1 was spray-coated so that the solid content weight after drying was 5 g / m ^2, and then dried at 80 ° C. for 60 minutes to obtain a laminate I-1. The height difference of the microscopic unevenness in the colored layer was 0.2 mm.
The following tests were performed on the obtained laminate I-1. The results are shown in Table 2.

(Test method)
The laminate obtained by the above-described method was immersed in a contaminant suspension (concentration: 1% by weight) for 2 hours, pulled up and allowed to stand for 24 hours in a standard state, and then washed and dried. The laminated body subjected to the above treatment was irradiated with an infrared lamp from a distance of 50 cm, and the back surface temperature of the test body when the temperature rise reached equilibrium was measured to evaluate the temperature rise inhibitory property. The evaluation was “A” when the temperature was lower than 55.0 ° C., and “A ′” when the temperature was higher than 55.0 ° C. and lower than 57.5 ° C. “B” for what was 60.0 ° C. or more and less than 62.5 ° C., “C” for what was 62.5 ° C. or more and less than 65.0 ° C., 65.0 What was more than degree C was set to "C '".

(Test Examples I-2 to I-5)
Laminates I-2 to I-5 were prepared in the same manner as in Test Example I-1, except that the colored layer composition I-1 was replaced with the colored layer compositions I-2 to I-5. (The height difference of microscopic unevenness in the colored layer was 0.2 mm).
The obtained laminate was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Examples I-6 to I-7)
Laminates I-6 to I-7 were prepared in the same manner as in Test Example I-1 except that the transparent layer composition 1 was replaced with the transparent layer compositions 2 to 3 (fine layers in the colored layer). Visual unevenness height difference 0.2 mm).
The obtained laminate was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-8)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the colored layer composition I-5 was applied with a coater so that the dry thickness would be 4 mm, and at 60 ° C. for 10 minutes. After drying, it was embossed to form a sandstone-like uneven pattern (3 mm height difference) (microscopic uneven height difference 0.1 mm). Next, the transparent layer composition 1 was spray-coated so that the solid content weight after drying was 5 g / m ^2, and then dried at 80 ° C. for 60 minutes to obtain a laminate I-8.
The obtained laminate I-8 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example 9)
A laminate I-9 was produced in the same manner as in Test Example I-8 except that the colored layer composition I-5 was replaced with the colored layer composition I-8 (the height difference of the uneven pattern was 3 mm, fine Visual unevenness height difference 0.1 mm).
The obtained laminate I-9 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-10)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the colored layer composition 5 is sprayed into a ball shape using wind pressure, and has a dry thickness of 1 to 3 mm (height difference 2 mm). A pattern was formed and dried at 60 ° C. for 60 minutes (microscopic unevenness difference 0.1 mm). Next, the transparent layer composition 1 was spray-coated so that the solid content weight after drying was 5 g / m ^2, and then dried at 80 ° C. for 60 minutes to obtain a laminate I-10.
The obtained laminate I-10 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-11)
A laminate I-11 was produced in the same manner as in Test Example I-10 except that the colored layer composition I-5 was replaced with the colored layer composition I-9 (the height difference of the uneven pattern was 2 mm, fine Visual unevenness height difference 0.1 mm).
The obtained laminate I-11 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-12)
A laminate I-12 was produced in the same manner as in Test Example I-10 except that the composition 1 for the transparent layer was replaced with the composition 4 for the transparent layer (the height difference of the uneven pattern was 2 mm, the microscopic unevenness was Height difference 0.1 mm).
The obtained laminate I-12 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-13)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the colored layer compositions I-5, I-6, and I-7 were each sprayed into a ball shape using wind pressure, and then dried thickness A concavo-convex pattern of 1 to 3 mm (height difference 2 mm) was formed and dried at 60 ° C. for 60 minutes (microscopic concavo-convex height difference 0.1 mm). Next, the transparent layer composition 1 was spray-coated so that the solid content weight after drying was 5 g / m ^2, and then dried at 80 ° C. for 60 minutes to obtain a laminate I-13.
The obtained laminate I-13 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-14)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the colored layer composition I-1 was applied with a coater so that the dry thickness was 2 mm, and the temperature was 60 ° C. for 60 minutes. After drying, it was further dried at 80 ° C. for 60 minutes to obtain a laminate I-14 (microscopic difference in unevenness in the colored layer: 0.2 mm).
The obtained laminate I-14 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-15)
A laminate I-15 was produced in the same manner as in Test Example I-1 except that the transparent layer composition 1 was replaced with the transparent layer composition 5 (microscopic height difference of the unevenness in the colored layer was 0. 0). 2 mm). The obtained laminate I-15 was tested in the same manner as in Test Example I-1. The results are shown in Table 2.

(Test Example I-16)
The above laminate I-10 and laminate I-11 were exposed for 1200 hours in an accelerated weather resistance tester, and then the same test as in Test Example I-1 was performed. As a result, the laminate I-10 after exposure was evaluated as “B”, and the laminate I-11 after exposure was evaluated as “A”.

(Colored layer compositions II-1 to II-10)
According to the composition shown in Table 3, the colored layer compositions II-1 to II-10 were produced by mixing and stirring the respective raw materials by a conventional method. The following were used as raw materials. The colored particles 1 to 9 were used as the colored particles.

Synthetic resin emulsion 1: Acrylic resin emulsion (methyl methacrylate-cyclohexyl methacrylate- (2-ethylhexyl acrylate) -methacrylic acid copolymer, pH 8.7, solid content 50% by weight, glass transition temperature 15 ° C., minimum film-forming temperature 19 ℃)
Synthetic resin emulsion 2: Acrylic resin emulsion (methyl methacrylate- (n-butyl acrylate)-(2-ethylhexyl acrylate)-(γ-methacryloyloxypropyltrimethoxysilane) -methacrylic acid copolymer, pH 8.9, solid content 50% by weight, glass transition temperature 23 ° C, minimum film-forming temperature 25 ° C)
Water-dispersible silica 1: silica sol (pH 7.6, solid content 20% by weight, average primary particle size 27 nm)
Water-dispersible silica 2: silica sol (pH 9.3, solid content 20% by weight, average primary particle size 20 nm)
Water-dispersible silica 3: silica sol (pH 9.5, solid content 40% by weight, average primary particle size 20 nm)

Of the colored particles of the colored layer composition II-5, colored particles (A1) having an average particle size of 22 μm or more and less than 150 μm are 40% by weight, and colored particles (A2) having an average particle size of 150 μm or more and less than 212 μm are 30% by weight. The colored particles (A3) having an average particle diameter of 212 μm or more and less than 600 μm were 30% by weight.
In the colored particles of the colored layer composition II-7, (A1) was 45% by weight, (A2) was 31% by weight, and (A3) was 24% by weight.
In the colored particles in the colored layer composition II-8, (A1) was 52% by weight, (A2) was 22% by weight, and (A3) was 26% by weight.
The colored layer compositions II-6, II-9 and II-10 were the same as the colored layer composition II-5.

(Test Example II-1)
On the base layer A (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the colored layer composition II-1 was applied with a coater so as to have a dry thickness of 2 mm. Drying for 2 minutes yielded laminate II-1. The height difference of the microscopic unevenness in the colored layer was 0.2 mm.
The following tests were performed on the obtained laminate II-1. The results are shown in Table 4.

(Infrared reflectivity test)
The laminate obtained by the above-described method was immersed in a contaminant suspension (concentration: 1% by weight) for 2 hours, pulled up and allowed to stand for 24 hours in a standard state, and then washed and dried. The laminated body subjected to the above treatment was irradiated with an infrared lamp from a distance of 50 cm, and the back surface temperature of the test body when the temperature rise reached equilibrium was measured to evaluate the temperature rise inhibitory property. The evaluation was “A” when the temperature was lower than 55.0 ° C., and “A ′” when the temperature was higher than 55.0 ° C. and lower than 57.5 ° C. “B” for what was 60.0 ° C. or more and less than 62.5 ° C., “C” for what was 62.5 ° C. or more and less than 65.0 ° C., 65.0 What was more than degree C was set to "C '".

(Test Examples II-2 to II-5)
Laminates II-2 to II-5 were prepared in the same manner as in Test Example 1 except that the colored layer composition II-1 was replaced with the colored layer compositions 2 to 5 (fine layers in the colored layer). Visual unevenness height difference 0.2 mm).
The obtained laminate was tested in the same manner as in Test Example II-1. The results are shown in Table 4.

(Test Example II-6)
The colored layer composition II-5 was applied onto the base layer A with a coater so that the dry thickness was 4 mm, dried at 60 ° C. for 10 minutes, and then embossed to give a sandstone-like uneven pattern on the surface. Thus, a laminate II-6 was produced. (3 mm height difference of uneven pattern, 0.1 mm height difference of microscopic unevenness in the colored layer)
The obtained laminate II-6 was tested in the same manner as in Test Example II-1. The results are shown in Table 4.

(Test Example II-7)
A laminate II-7 was produced in the same manner as in Test Example II-6 except that the colored layer composition II-5 was replaced with the colored layer composition II-6 (the height difference of the uneven pattern was 3 mm, fine Visual unevenness height difference 0.1 mm).
The obtained laminate II-7 was tested in the same manner as in Test Example II-1. The results are shown in Table 4.

(Test Example II-8)
A laminate II-8 was produced in the same manner as in Test Example II-6 except that the colored layer composition II-5 was replaced with the colored layer composition II-9 (the height difference of the concavo-convex pattern was 3 mm, Visual unevenness height difference 0.1 mm).
The same test as in Test Example 1 was performed on the obtained laminate II-8. The results are shown in Table 4.

(Test Example II-9)
The colored layer composition II-5 is sprayed onto the base layer A in a ball shape using wind pressure to form a concavo-convex pattern having a dry thickness of 1 to 3 mm (height difference of 2 mm) and dried at 60 ° C. for 60 minutes. Then, a laminate II-9 was produced (microscopic unevenness difference 0.1 mm).
The obtained laminate II-9 was tested in the same manner as in Test Example II-1. The results are shown in Table 4.

(Test Example II-10)
On the base layer A, the colored layer compositions II-5, II-7, and II-8 are each sprayed in a ball shape using wind pressure to form a concavo-convex pattern having a dry thickness of 1 to 3 mm (height difference of 2 mm). The laminate was dried at 60 ° C. for 60 minutes to prepare a laminate II-10 (microscopic unevenness difference 0.1 mm).
The obtained laminate II-10 was tested in the same manner as in Test Example II-1. The results are shown in Table 4.

(Test Example II-11)
A laminate II-11 was produced in the same manner as in Test Example II-1, except that the colored layer composition II-1 was replaced with the colored layer composition II-10. (The difference in level of microscopic unevenness in the colored layer is 0.2 mm). The obtained laminate II-11 was tested in the same manner as in Test Example II-1. The results are shown in Table 4.

Claims

A laminate in which a decorative layer and a base layer are laminated,
The decorative layer contains colored particles and silica having an average primary particle diameter of 1 nm to 200 nm;
A laminate having the colored particles obtained by attaching a metal oxide to the surface of inorganic particles.
The decorative layer is a single layer of a colored layer, or a layer in which a transparent layer is laminated on the colored layer,
The colored layer contains a synthetic resin and the colored particles,
The laminate according to claim 1, wherein the transparent layer contains a synthetic resin.
3. The laminate according to claim 2, wherein the colored layer contains 3 to 50 parts by weight of the synthetic resin in a solid weight ratio with respect to 100 parts by weight of the colored particles.
The laminate according to claim 2 or 3, wherein the single layer of the colored layer contains 0.003 to 50 parts by weight of the silica with respect to 100 parts by weight of the colored particles.
The laminate according to any one of claims 2 to 4, wherein the surface of the colored layer has a microscopic uneven shape derived from the colored particles.
6. The laminate according to claim 2, wherein the surface of the colored layer further has a macroscopic uneven pattern.
7. The transparent layer contains 5 to 500 parts by weight of the synthetic resin in a solid weight ratio with respect to 100 parts by weight of the silica. Laminated body.
A construction method comprising sticking the laminate according to any one of claims 1 to 7 to a substrate via an adhesive.