JP5439547B2 - Laminated body - Google Patents

Description

  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.

From the viewpoint of landscape, aesthetics are required for building materials used for building exteriors and the like. 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 concavo-convex shape derived from the aggregate, and contaminants are likely to adhere to the concave portion. 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 present inventor includes specific colored particles, synthetic resin emulsion, specific water-dispersible silica in a specific weight ratio on the base layer, and the surface of the layer is The inventors have conceived of a laminate having a colored layer having a microscopic uneven shape derived from the colored particles, and have completed the present invention.

That is, the laminate of the present invention has the following characteristics.
1. A laminate in which a colored layer is laminated on a base layer,
The colored layer has a solid resin weight ratio of 3 to 50 parts by weight and a water-dispersible silica having an average primary particle diameter of 1 to 200 nm in a solid content weight ratio of 0.003 to 100 parts by weight of the colored particles. 50 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 inorganic particles.
2. A laminate in which a colored layer is laminated on a base layer,
The colored layer has a solid resin weight ratio of 3 to 50 parts by weight and a water-dispersible silica having an average primary particle diameter of 1 to 200 nm in a solid content weight ratio of 0.003 to 100 parts by weight of the colored particles. 50 parts by weight, the surface of the layer has a microscopic uneven shape derived from the colored particles, and has a macroscopic uneven pattern,
The colored particles are formed by attaching a metal oxide to the surface of inorganic particles.

  The laminate of the present invention is a laminate in which a colored layer is laminated 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.

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

(Colored layer)
The colored layer of the present invention contains colored particles (A), a synthetic resin emulsion (B), and water-dispersible silica (C) having an average primary particle diameter of 1 to 200 nm as essential components, and has a design property in the laminate. It is a layer that imparts antifouling properties.

  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 particle diameter, and the small dot of the component (A) is visually recognized as a multicolored pattern, and gives 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 any of natural products and artificial products can be used. Specifically, for example, mica, kaolin, clay, porcelain 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.

  In the component (A) of the present invention, the component (a2) may be 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.
Moreover, it is preferable that 10-45 weight% of colored particles (A2) with an average particle diameter of 150 micrometers or more and less than 212 micrometers are contained in (A) component. 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. In addition, the average particle diameter of (A) component is a value obtained by sieving using the metal net sieve prescribed | regulated to JISZ8801-1: 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.

The (B) synthetic resin emulsion (hereinafter also referred to as “component (B)”) in the colored layer plays a role of immobilizing the component (A). Such a component (B) can be obtained, for example, by copolymerizing various polymerizable monomers. As the polymerizable monomer component constituting the component (B), for example, 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 and 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 the polymerizable monomer, physical properties of the coating film can be improved by interaction with the component (C).

  Although the minimum film-forming temperature of (B) component can be set suitably, it is 80 degrees C or less normally, Preferably it is 50 degrees C or less, More preferably, it is 30 degrees C or less. 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.

  Although the manufacturing method of (B) component is not specifically limited, For example, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, feed emulsion polymerization, feed dispersion polymerization, seed emulsion polymerization, seed dispersion polymerization, etc. are employable. (B) The average particle diameter of a component is about 0.05-0.3 micrometer normally. 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, a crosslinking reaction type synthetic resin emulsion, a core-shell type synthetic resin emulsion, and the like can also be used as the component (B). 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.

Moreover, it is preferable that (B) component can react with the (C) component mentioned later. Component (B) is, for example, an emulsion having a functional group such as a hydroxyl group or hydrolyzable silyl group (preferably hydrolyzable silyl group) that can react with the silanol group present in component (C). Is preferred.
By chemically bonding the component (B) and the component (C), it becomes possible to exhibit the stain resistance while ensuring the coating film properties such as crack resistance.

  The component (C) in the present invention is water-dispersible silica having an average primary particle size of 1 to 200 nm. (C) The particle | grains which comprise a component are the compounds which have high hardness in order to have a silica as a main component, and have the silanol group on the particle | grain surface. Such a component (C) greatly contributes to the effect of improving the contamination resistance.

  The average primary particle diameter of (C) component is 1-200 nm normally as a primary particle diameter, Preferably it is 5-100 nm, More preferably, it is 10-50 nm, More preferably, it is 20-40 nm. 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. (C) The average primary particle diameter of a component is 5-100 nm, More preferably, it is 10-50 nm, More preferably, it is 20-40 nm. In the present invention, two or more kinds of water-dispersible silica having different average primary particle sizes can be used. In addition, the average primary particle diameter of (C) component is a value measured by the light-scattering method.

  The pH of the component (C) 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 (C) adjusted to such a pH can exhibit hydrophilicity due to the abundant silanol groups on the particle surface, and greatly contributes to the improvement of stain resistance.

  Such a component (C) 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. 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 (C), 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 (C), it is possible to reduce the coating material to a low-volatile organic solvent (low VOC). Moreover, the aggregate generation | occurrence | production at the time of mixing with (B) component can also be suppressed.

  (C) Solid content of a component is 5 to 60 weight% normally, Preferably it is 10 to 55 weight%, More preferably, it is 15 to 50 weight%. If the solid content of the component (C) is within such a range, the stability of the component (C) itself, and the stability when the component (B) and the component (C) are mixed can be ensured. . If the solid content is too large, the component (C) 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 (C) 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, in terms of solid content, 100 parts by weight of the component (A), and the component (B) is usually 3 to 50 parts by weight, preferably 4 to 30 parts by weight. Parts by weight or less, more preferably 5 parts by weight or more and less than 20 parts by weight, still more preferably 6 parts by weight or more and 19 parts by weight or less. The mixing ratio of the component (A) and the component (C) is, in terms of solid content, 100 parts by weight of the component (A), and the component (C) 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, 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.

In the colored layer of the present invention, various colored or colorless particles other than the above components may be included for the purpose of improving the design properties. Examples of such particles include coloring pigments, bright pigments, fluorescent pigments, extender pigments, and aggregates. In the present invention, colored particles (organic colored particles, colored aggregates, etc.) other than the colored particles having a metal oxide adhered to the surface of the inorganic particles can be included to such an extent that the effects of the present invention are not impaired. .
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.

In the present invention, it is particularly preferable that the colored layer contains a bright pigment. By including the glitter pigment in the colored layer, the glitter of the glitter pigment appears while having the design of the colored layer, and a high-quality and excellent design can be obtained.
Examples of glitter pigments include aluminum flake pigments, vapor-deposited aluminum flake pigments, metal oxide-coated aluminum flake pigments, colored aluminum flake pigments, metal oxide-coated mica pigments, metal oxide-coated synthetic mica pigments, and metal oxide-coated alumina. Flake pigment, metal oxide coated silica flake pigment, metal coated glass flake pigment, metal oxide coated glass flake pigment, metal oxide coated plate iron oxide, graphite, stainless steel flake, metal titanium flake pigment, plate molybdenum sulfide, plate Bismuth chloride, holographic pigment, cholesteric liquid crystal polymer, crushed product of metal-deposited polymer film, and the like. What is necessary is just to use what the average particle diameter of such a luster pigment is 0.1 micrometer or more and less than 0.3 mm normally.
The ratio of the luster pigment is not particularly limited, but is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of component (A).

  The colored layer of the present invention has a microscopic uneven shape derived from the component (A) on the surface. This microscopic unevenness is caused by the particle size, aggregation state, etc. of the component (A), preferably 1.5 mm or less (more preferably 0.005 mm or more and 1.2 mm or less, more preferably 0.01 mm). 1 mm or less, most preferably 0.02 mm or more and 0.8 mm or less).

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, for example, 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.

(Base layer)
The base layer of the present invention can be used by being 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, more preferably 0.2 to 1.0 mm), and a basis weight of 5 to 300 g / m. ² (more preferably 10 to 250 g / m ² , still more preferably 20 to 200 g / m ² ) containing inorganic fibers, and the like. 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, as long as the colored layer is laminated on the base layer, the production method is not particularly limited. For example, the following methods (1) and (2) are exemplified, and particularly, the following (2). A production method in which a colored layer is formed on the base layer is preferred.
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 (C), and the thin film is unevenly distributed in the concave portion 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 the components (A), (B) and (C) 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.
(2) A method of forming a colored layer by applying a colored layer composition containing the components (A), (B) and (C) on the base layer.

The releasable substrate in (1) may be any substrate that can be removed after curing. For example, a mold made of silicon resin, urethane resin, metal, or release paper may be used.
Moreover, in said (1) and (2), it is desirable to install a releasable foundation | substrate or base layer horizontally, and to laminate | stack the composition for colored layers on it.

  In the above (1) and (2), the composition for the colored layer can contain a known additive as required unless the effects of the present invention are 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) and (2), when applying the composition for the colored layer, for example, a known application device 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) and (2), the colored layer composition can be dried at room temperature, but it is preferably heated in the present 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 a thin film containing the component (B) and the component (C) is easily formed on the outermost surface of the colored layer, and the effect of the present invention can be obtained. It is easy to be done.

(Laminate 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). Such bases 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. Can be mentioned. These foundations may be treated with a filler, putty, sealer or the like.

  When the laminate of the present invention is attached to the base, for example, an adhesive, a pressure-sensitive adhesive, a pressure-sensitive adhesive tape, a nail, a heel 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 the base | substrate through an adhesive agent. Since this invention laminated body has moderate water vapor permeability, when it sticks to the foundation | substrate via an adhesive agent, the effect which accelerates | stimulates the drying property of an adhesive agent is exhibited.

  Moreover, when sticking a laminated body with an adhesive agent, adjacent laminated bodies can be stuck and stuck, or a laminated body can be stuck at a predetermined | prescribed space | interval and a joint can be provided. 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 1 to 11)
According to the composition shown in Table 1, colored layers Compositions 1 to 11 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
-Bright pigment: vapor-deposited aluminum flake pigment (average particle size 150 μm)
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 3 ° 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)

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

(Test Example 1)
On the base layer A (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m ² ), the colored layer composition 1 is applied with a coater so as to have a dry thickness of 2 mm, and dried at 60 ° C. for 60 minutes. As a result, a laminate 1 was obtained. The height difference of the microscopic unevenness in the colored layer was 0.2 mm.
The obtained laminate 1 was subjected to the following test. The results are shown in Table 2.

(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 2 to 5)
Laminates 2 to 5 were produced in the same manner as in Test Example 1 except that the colored layer composition 1 was replaced with the colored layer compositions 2 to 5 (the difference in level of microscopic unevenness in the colored layer) 0.2 mm).
About the obtained laminated body, the test similar to Test Example 1 was done. The results are shown in Table 2.

(Test Example 6)
On the base layer A, the colored layer composition 5 is applied with a coater so that the dry thickness is 4 mm, dried at 60 ° C. for 10 minutes, and then embossed to form a sandstone-like uneven pattern on the surface. A laminate 6 was produced. (3 mm height difference of uneven pattern, 0.1 mm height difference of microscopic unevenness in the colored layer)
About the obtained laminated body 6, the test similar to Test Example 1 was done. The results are shown in Table 2.

(Test Example 7)
A laminate 7 was prepared in the same manner as in Test Example 6 except that the colored layer composition 5 was replaced with the colored layer composition 6 (the height difference of the uneven pattern was 3 mm, the height difference of the microscopic unevenness was 0.00. 1 mm).
About the obtained laminated body 7, the test similar to Test Example 1 was done. The results are shown in Table 2.

(Test Example 8)
A laminated body 8 was produced in the same manner as in Test Example 6 except that the colored layer composition 5 was replaced with the colored layer composition 9 (the height difference of the uneven pattern was 3 mm, the height difference of the microscopic unevenness was 0.00. 1 mm).
About the obtained laminated body 8, the test similar to Test Example 1 was done. The results are shown in Table 2.

(Test Example 9)
On the base layer A, the colored layer composition 5 is sprayed in a ball shape using wind pressure to form a concavo-convex pattern having a dry thickness of 1 to 3 mm (2 mm height difference), dried at 60 ° C. for 60 minutes, and laminated A body 9 was produced (microscopic unevenness difference 0.1 mm).
About the obtained laminated body 9, the test similar to Test Example 1 was done. The results are shown in Table 2.

(Test Example 10)
On the base layer A, the colored layer compositions 5, 7, and 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), and at 60 ° C. for 60 minutes. It dried and produced the laminated body 10 (0.1-mm height difference of microscopic unevenness | corrugation).
About the obtained laminated body 10, the test similar to Test Example 1 was done. The results are shown in Table 2.

(Test Example 11)
A laminate 11 was produced in the same manner as in Test Example 1 except that the colored layer composition 1 was replaced with the colored layer composition 10. (The difference in level of microscopic unevenness in the colored layer is 0.2 mm). About the obtained laminated body 11, the test similar to Test Example 1 was done. The results are shown in Table 2.

(Test Example 12)
A laminate 12 was produced in the same manner as in Test Example 1 except that the colored layer composition 1 was replaced with the colored layer composition 11. (The difference in level of microscopic unevenness in the colored layer is 0.2 mm). The obtained laminate 12 had an excellent design with a high-class feeling. About the obtained laminated body 12, the test similar to Test Example 1 was done. The results are shown in Table 2.

Claims (3)

A laminate in which a colored layer is laminated on a base layer,
The colored layer comprises 3 to 30 parts by weight of a synthetic resin emulsion in a solid weight ratio and 0.003 to 3 in weight ratio of water-dispersible silica having an average primary particle diameter of 1 to 200 nm with respect to 100 parts by weight of colored particles. 50 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 inorganic particles. A laminate in which a colored layer is laminated on a base layer,
The colored layer comprises 3 to 30 parts by weight of a synthetic resin emulsion in a solid weight ratio and 0.003 to 3 in weight ratio of water-dispersible silica having an average primary particle diameter of 1 to 200 nm with respect to 100 parts by weight of colored particles. 50 parts by weight, the surface of the layer has a microscopic uneven shape derived from the colored particles, and has a macroscopic uneven pattern,
The colored particles are formed by attaching a metal oxide to the surface of inorganic particles. The laminate according to claim 1 or 2, wherein the colored particles contain at least two kinds having different average particle diameters.