JP2012016851A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel laminate which has excellent design properties and can exhibit bacteria-proof properties or mildewproof properties efficiently.SOLUTION: The laminate is obtained by layering a pattern layer on a bacteria-proof/mildewproof layer. The bacteria-proof/mildewproof layer contains a bacteria-proof/mildewproof agent and the pattern layer contains: a synthetic resin (A) for forming a coating film having a reflection zone exhibiting ≥10% reflectance to the light having a 300-500 nm wavelength; a colored aggregate (B) having a 0.01-5 mm average particle size; humidity-controllable powder (C); and a photocatalytic metal oxide (D) exhibiting photocatalysis to the reflection zone as essential components.

Description

  The present invention relates to a novel laminate.

  As building materials for interiors of buildings, natural stones, which are relatively thick in the image of natural stones, are becoming increasingly popular because they have various concavo-convex patterns and excellent design characteristics. Examples of such building materials include building materials formed by laminating a composition in which a binder, such as an acrylic resin emulsion, and a natural aggregate, an artificial aggregate, or the like are blended on a base material. For example, Japanese Patent Laid-Open No. 4-347251 (Patent Document 1) describes a decorative material in which a base material made of a synthetic resin fabric is laminated on one surface of a plate of a spray material obtained by mixing aggregate with synthetic resin. Has been.

In recent years, interest in safe and comfortable living spaces has increased, and interior building materials have various functions such as anti-contamination performance, prevention of dew condensation and mold generation, and antibacterial properties in addition to design. In addition, it is required to have excellent workability due to flexibility and weight reduction. Along with this, many products have been developed. As such a material, for example, JP-A-7-113272 (Patent Document 2) describes a building material in which a coating containing a hygroscopic agent and a photocatalyst is formed on the surface of a base material.

JP-A-4-347251 JP-A-7-113272

  If a hygroscopic agent or a photocatalyst is added to the plate-like material of the spray material as in Patent Document 1, it can be expected that a building material having design properties, hygroscopicity, and photocatalytic properties can be obtained. However, in the case of a building material obtained by molding such a spray material, since the building material contains a large amount of aggregate, there is a possibility that the photocatalytic action cannot be exhibited efficiently. As a result, inside the building material containing moisture due to the moisture absorption action, there is a possibility that bacteria may propagate or mold may occur.

  This invention is made | formed in view of such a point, and it aims at obtaining the novel laminated body which can exhibit germicidal property and antifungal property efficiently while being excellent in design property. It is.

As a result of intensive studies to achieve the above object, the present inventor has conceived a laminated body in which a specific pattern layer is laminated on the antibacterial and antifungal layer, thereby completing the present invention.
That is, the laminate of the present invention has the following characteristics.

1. A laminate in which a pattern layer is laminated on an antibacterial / antifungal layer, wherein the antibacterial / antifungal layer includes an antibacterial / antifungal agent, and the pattern layer is a synthetic resin (A) In addition, a colored aggregate (B) having an average particle diameter of 0.01 to 5 mm, a humidity-controlling powder (C), and a photocatalytic metal oxide (D) are essential components, and the synthetic resin (A) has a wavelength of 300 to 500 nm. 1. A laminate having a reflection region having a reflectance of 10% or more in the above-described layer, and the photocatalytic metal oxide (D) exhibits a photocatalytic action in the reflection region. The antibacterial / antifungal layer is formed from a film of a composition containing an antibacterial / antifungal agent and / or a sheet impregnated with the antibacterial / antifungal agent. 2. Laminate described in 3. The synthetic resin (A) contains an acrylic resin derived from a (meth) acrylic acid alkyl ester and a silicone resin in a solid content weight ratio of 95: 5 to 30:70. ~ 2. The laminate according to any one of

The laminate of the present invention is superior in design and performance in antibacterial and antifungal properties by laminating a specific pattern layer having humidity control properties on the antibacterial and antifungal layer containing the antibacterial and antifungal agent. It is what has.

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

The laminate of the present invention is obtained by laminating a specific pattern layer (hereinafter also referred to as “pattern layer”) having humidity control properties on an antibacterial and antifungal layer. By using such a laminate, the photocatalyst contained in the pattern layer and the antibacterial / antifungal agent contained in the antibacterial / antifungal layer function complementarily, thereby providing excellent antibacterial and antifungal properties. It can be demonstrated. Specifically, by using a specific synthetic resin (A) for the pattern layer, the light irradiated to the pattern layer diffuses and reflects within the pattern layer, making it easy to reach the inside of the pattern layer and disperse to the pattern layer. The activity of the prepared photocatalyst can be increased. However, only the action of the photocatalyst may result in insufficient antibacterial and antifungal properties depending on conditions such as light irradiation conditions, temperature, and humidity. Therefore, in the present invention, an antibacterial / antifungal layer is provided in the lower layer of the pattern layer, whereby excellent antibacterial / antifungal properties can be exhibited. In particular, excellent antibacterial and antifungal properties can be exhibited even when the light is weak or in a dark place.
The mechanism of action is not clear, but it is presumed that the following points contributed.
-Since the photocatalyst and the antibacterial / antifungal agent are mixed in separate layers, the antibacterial / antifungal agent in the lower layer is hardly deteriorated by the photocatalyst of the pattern layer, and the antibacterial / antifungal effect can be maintained.
-The antibacterial / antifungal agent is appropriately transferred from the lower antibacterial / antifungal layer to the pattern layer, and exhibits an antibacterial / antifungal effect.
-Preventing the invasion of bacteria and sputum from the back of the laminate by providing a fungicidal and fungicidal layer in the lower layer.

(Antibacterial and antifungal layer)
The antibacterial / antifungal layer of the present invention is impregnated with a film of a composition containing an antibacterial / antifungal agent (hereinafter also referred to as “a composition for an antibacterial / antifungal layer”) and / or an antibacterial / antifungal agent. It is formed from the made sheet | seat.
The “antibacterial / antifungal layer” of the present invention refers to a layer having antibacterial and / or antifungal properties against at least one type of bacteria or fungus. In addition, the “antibacterial / antifungal agent” refers to a substance having antibacterial and / or antifungal properties against at least one type of fungus or sputum.

As the antibacterial / antifungal agent of the present invention, both organic and inorganic antibacterial / antifungal agents can be used.
Examples of organic antifungal agents include, for example, isothiazoline compounds, nitroalcohol compounds, nitrile compounds, dithiol compounds, phenolic compounds, phenylurea compounds, carbamate compounds, sulfamide compounds, phthalimide compounds, Examples thereof include at least one selected from the group consisting of pyridine compounds, pyrithione compounds, triazine compounds, guanidine compounds, triazole compounds, thiazole compounds, and benzimidazole compounds.

Examples of the isothiazoline compound include 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT), 4,5-dichloro-2-n. -Octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one (OIT), 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI), N -N-butyl-1,2-benzisothiazolin-3-one (Bu-BIT) and the like.
Nitroalcohol compounds include 2,2-dibromo-2-nitroethanol (DBNE), 2-bromo-2-nitropropane-1,3-diol (BNPD), 2-hydroxymethyl-2-nitro-1, Examples include 3-propanediol.

Examples of the nitrile compound include tetrachloroisophthalonitrile, 2,4,5,6-tetrachloroisophthalonitrile (TPN), and the like.
Examples of the dithiol-based compound include 4,5-dichloro-1,2-dithiol-3-one, 4,5-dibromo-1,2-dithiol-3-one, and the like.
Examples of phenolic compounds include o-phenyl-phenol and p-chlorometaxylenol.

Examples of carbamate compounds include 3-iodo-2-propynylbutyl carbamate (IPBC).
Examples of the sulfamide-based compound include N-dimethylaminosulfonyl-N-tolyl-dichlorofluoromethanesulfamide, N-dimethylaminosulfonyl-N-phenyl-dichlorofluoromethanesulfamide and the like.
Examples of the phthalimide compound include N-1,1,2,2-tetrachloroethylthio-tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-dichlorofluoromethylthiophthalimide, and N-trichloromethylthiophthalimide.

Examples of the pyrithione compounds include halopyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, and pyrithione compounds such as zinc pyrithione (ZPT) and sodium pyrithione.
Examples of triazine compounds include hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine.
Examples of guanidine compounds include dodecyl guanidine hydrochloride, dodecyl guanidine hydrobromide, decyl guanidine hydrochloride, 1,1′-hexamethylenebis [5- (4-chlorophenyl) biguanide] dihydrochloride, and the like.

Examples of triazole compounds include α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (tebuconazole), 1- [ [2- (2,4-Dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (propiconazole), 1-[[2 -(2,4-Dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (azaconazole), α- (4-chlorophenyl) -α- (1-cyclopropyl Ethyl) -1H-1,2,4-triazole-1-ethanol (cyproconazole) and the like.
Examples of thiazole compounds include 2- (4-thiocyanomethylthio) benzothiazole (TCMTB).
Examples of the benzimidazole compound include methyl-2-benzimidazole carbamate (MBC) and 2- (4-thiazolyl) benzimidazole (TBZ).

Examples of the inorganic antibacterial / antifungal agent include inorganic compounds substituted or supported with metals or metal ions mainly composed of silver, copper and zinc. Examples of the inorganic compound include activated carbon, activated alumina, silica gel, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrous bismuth, hydrous zirconium, hydrotalcite, and the like. Examples of such inorganic antifungal agents include silver, zinc-substituted zeolite, silver-supported apatite, and silver-supported silica gel.
In addition, the said antifungal agent may be used independently, or 2 or more types may be mixed and used for it.

  The antibacterial and antifungal agent of the present invention preferably has water solubility. The water solubility of the antibacterial and antifungal agent is preferably about 1 to 1000 ppm (under 25 ° C.). By being in such a range, when moisture is retained in the pattern layer by the humidity control action of the pattern layer, which will be described later, the antibacterial and antifungal agent is appropriately transferred to the pattern layer, and has excellent antibacterial and antibacterial properties. It can demonstrate inertia.

It is preferable that the composition for antibacterial / antifungal layers of the present invention contains a binder in addition to the antibacterial / antifungal agent.
As the binder, various binders such as water-soluble resins, water-dispersible resins, solvent-soluble resins, solvent-free resins, non-water-dispersed resins, and powder resins, or binders obtained by combining these are used. be able to. These may have crosslinking reactivity. Further, the form of the binding material is not particularly limited, and may be either one liquid type or two liquid type. In the present invention, a water-soluble resin and / or a water-dispersible resin is particularly preferably used. Usable types of resin include, for example, cellulose, polyvinyl alcohol, ethylene resin, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, silicone resin, acrylic resin, urethane resin, acrylic silicon resin, fluorine Examples thereof include resins and the like, and composites thereof.

   The mixing ratio of the binder and the antibacterial / antifungal agent is preferably 0.01 to 5 parts by weight, more preferably 0.05 in terms of solid content (active ingredient) with respect to 100 parts by weight of the solid content of the binder. ~ 3 parts by weight. By being in such a range, the effect of the present invention can be sufficiently obtained.

  In addition to the components described above, the composition for the antibacterial and antifungal layer of the present invention includes a coloring pigment, an extender pigment, an aggregate, a fiber, a film-forming aid, a plasticizer, an antifreezing agent, an antiseptic, an antifoaming agent, and an increase. Adhesives, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, UV absorbers, light stabilizers, antioxidants, adsorbents, photocatalysts, etc., to the extent that they do not impair the effects of the present invention. It can also be contained. The composition for an antibacterial / antifungal layer of the present invention can be produced by uniformly mixing these components by a conventional method.

  Examples of the antibacterial / antifungal layer of the present invention include, for example, those obtained by molding the composition for the antibacterial / antifungal layer (I), sheets (II) impregnated with the antibacterial / antifungal agent, and (I) What combined (II) etc. are mentioned.

  In (I) above, the thickness of the antibacterial / antifungal layer may be set as appropriate, but is preferably 0.01 to 3 mm, more preferably 0.05 to 1 mm.

The (II) is not particularly limited as long as it is a sheet impregnated with the antibacterial and antifungal agent. Examples of such sheets include fibrous sheets such as woven fabrics and nonwoven fabrics, glass meshes, glass cloths, ceramic papers, synthetic papers, and non-combustible papers. Moreover, what laminated | stacked these combining can also be used. The thickness of such a sheet is preferably 0.01 to 5 mm, more preferably 0.05 to 3 mm. The impregnation with the antibacterial and antifungal agent may be performed by a known method.

(Pattern layer)
The patterned layer of the present invention contains, as essential components, a synthetic resin (A), a colored aggregate (B) having an average particle diameter of 0.01 to 5 mm, a humidity control powder (C), and a photocatalytic metal oxide (D). It is formed by the pattern layer composition.
The moisture absorption / release amount of the pattern layer is not particularly limited, but is preferably 30 g / m ² or more, more preferably 40 g / m ² or more. By using such a pattern layer, a sufficient humidity control effect can be obtained in the indoor space. In addition, the moisture absorption / release amount said here is a value measured by the procedure of JIS A6909: 2003 "finishing coating material for construction" 7.32.2.

The synthetic resin (A) of the present invention (hereinafter also referred to as “component (A)”) has a reflective region having a reflectance of 10% or more, preferably 15% or more and 50% or less at a wavelength of 300 to 500 nm. A film is formed. By using such a component (A), the light irradiated to the pattern layer of the present invention diffuses and reflects in the pattern layer, reaches the inside of the pattern layer, and is dispersed in the pattern layer. Absorbed by the oxide, the photocatalytic activity is increased, thereby improving the antibacterial and antifungal properties.
The reflectance is obtained by forming a component (A) into a film having a dry film thickness of 0.1 mm, a black plate is placed behind the sample, and a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) is used. ). In addition, let the black board piled up behind the sample be a blank, and let it be the converted value. Specifically, it is obtained by subtracting the reflectance of the black plate from the reflectance of the sample at each wavelength.

Examples of such component (A) include acrylic resin, silicone resin, acrylic silicon resin, fluorine resin, vinyl acetate resin, acrylic / vinyl acetate resin, vinyl chloride resin, urethane resin, acrylic urethane resin, epoxy resin, and alkyd. Resin, polyvinyl alcohol resin, polyester resin, ethylene resin, polyvinyl alcohol, water dispersion type such as cellulose and derivatives thereof, water soluble type, NAD type, solvent soluble type, solventless type, etc. A two-component type or the like is not particularly limited and can be used.

In the present invention, as the component (A), an acrylic resin (a1) derived from (meth) acrylic acid alkyl ester (hereinafter also referred to as “(a1) component”), and a silicone resin (a2) (hereinafter referred to as “( It is preferable to use what contains a2) component ". The solid content weight ratio of the acrylic resin and the silicone resin in the component (A) is usually 95: 5 to 30:70, preferably 93: 7 to 40:60, and more preferably 90:10 to 60:40. By including both components in such a ratio, the photocatalytic action of the photocatalytic metal oxide can be enhanced. In the component (A) of such an embodiment, a film having moderate reflectivity can be formed at a wavelength of 300 to 500 nm, and the light diffusion effect is enhanced in the film due to the difference in refractive index between the acrylic resin and the silicone resin. It is considered that the photocatalytic activity of the photocatalytic metal oxide can be further improved.

In the present invention, it is particularly preferable to use a synthetic resin emulsion (water-dispersed resin) as the component (A). As such a component (A), for example, a mixture of an acrylic resin emulsion derived from a (meth) acrylic acid alkyl ester and a silicone resin emulsion can be used. By using such a synthetic resin emulsion, the reflectance can be increased and the photocatalytic action of the photocatalytic metal oxide can be enhanced. Furthermore, it is possible to obtain a patterned layer having excellent fire resistance and flexibility while utilizing the original texture of the aggregate.

In the present invention, as the component (A), an acrylic-silicone synthetic resin emulsion (A-1) (hereinafter referred to as “(A-1) component”) in which the component (a1) and the component (a2) are mixed in the emulsion particles. It is also preferred to use (also referred to as). The form of the (a1) component and the (a2) component in the component (A-1) is not particularly limited, and may be a uniformly mixed form, but a form separated from each other by a sea-island structure or the like is preferable. The weight ratio of the component (a1) to the component (a2) in the component (A-1) is usually 95: 5 to 30:70, preferably 93: 7 to 40:60. By mixing both components at such a ratio, the photocatalytic action of the photocatalytic metal oxide can be enhanced. Furthermore, it is possible to further improve fire resistance and flexibility by utilizing the original texture of the aggregate. In addition, advantageous effects can be obtained in each physical property such as water resistance, weather resistance, and contamination resistance.

The acrylic resin (a1) is a polymer mainly composed of (meth) acrylic acid ester, and is obtained by copolymerizing other monomers as necessary. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (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) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like. The amount of the (meth) acrylic acid alkyl ester used is usually 30% by weight or more, preferably 40 to 99.9% by weight, more preferably 50 to 99.9%, based on all monomers constituting the component (A). 5% by weight.

In the present invention, the (meth) acrylic acid ester preferably contains a (meth) acrylic acid ester having 6 or more carbon atoms in the alkyl group as an essential component. Among these, 2-ethylhexyl acrylate is particularly preferable. In the present invention, the (meth) acrylic acid ester having 6 or more carbon atoms in the alkyl group is preferably 10% by weight or more, more preferably 15% by weight or more, based on all monomers constituting the component (A). Contains 50% by weight or less. In this case, the fire resistance of the obtained pattern layer can be improved.

  Examples of other monomers include carboxyl group-containing monomers, amino group-containing monomers, pyridine monomers, hydroxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, carbonyl group-containing monomers, and alkoxysilyl group-containing monomers. And aromatic monomers. The usage-amount of these monomers is 0.1 to 60 weight% normally with respect to all the monomers which comprise (A) component, Preferably it is 0.5 to 50 weight%.

  Among these, when a carboxyl group-containing monomer is copolymerized to obtain a carboxyl group-containing acrylic resin, the stability of the component (A) can be increased, and a compound capable of reacting with a carboxyl group is added separately. Thus, various physical properties of the pattern layer can be improved. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid or a monoalkyl ester thereof, itaconic acid or a monoalkyl ester thereof, fumaric acid or a monoalkyl ester thereof. Among these, at least one selected from acrylic acid and methacrylic acid is particularly preferable. The usage-amount of a carboxyl group-containing monomer is 0.1 to 40 weight% normally with respect to all the monomers which comprise (A) component, Preferably it is 0.5 to 20 weight%.

Moreover, as a compound which can react with a carboxyl group, the compound which has 1 or more types of functional groups chosen from a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group etc. is mentioned, for example. Among these, in the present invention, a reactive compound having an epoxy group is particularly suitable.

  Examples of the reactive compound having an epoxy group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol poly Examples thereof include glycidyl ether, dihydroxyalkane polyglycidyl ether, polyhydroxyalkane polyglycidyl ether, and sorbitol polyglycidyl ether. In addition, a water-soluble resin or emulsion made of a polymer (homopolymer or copolymer) of an epoxy group-containing monomer can also be used. The mixing amount of such a compound is usually 0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the resin solid content of the component (A).

The silicone resin (a2) is obtained by polymerizing a siloxane compound. Examples of the siloxane compound include cyclic siloxane compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. When polymerizing such a cyclic siloxane compound, a linear siloxane compound, a branched siloxane compound, an alkoxysilane compound, or the like can also be used. Of these, as the alkoxysilane compound, a silane compound having one or more alkoxyl groups in the molecule can be used. For example, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, γ- Silane coupling agents such as (meth) acryloyloxytrimethoxysilane and 3-mercaptopropyltrimethoxysilane can be used. The average molecular weight of the silicone resin is usually 10,000 or more, preferably 50,000 or more.

Furthermore, the component (A-1) in the present invention is a synthetic resin emulsion in which the acrylic resin (a1) and the silicone resin (a2) component as described above are mixed in emulsion particles, and (a1) and (a2) A multilayer structure type synthetic resin emulsion (A-2) having an outer layer in which is mixed and an inner layer containing the component (a1) is suitable. Moreover, what is necessary is just to set the glass transition temperature of a multilayer structure type synthetic resin emulsion (A-2) normally to about -60-30 degreeC. In particular, those in which the glass transition temperature of the acrylic resin in the inner layer is set lower than the glass transition temperature of the acrylic resin in the outer layer are suitable. By using such a synthetic resin emulsion, compared to a normal synthetic resin emulsion, a pattern layer having various physical properties such as flexibility, fire resistance, and adhesion to a substrate with a smaller amount of resin can be obtained. Can design. It is also advantageous in terms of improving the texture of the aggregate. The weight ratio of the outer layer to the inner layer in the component (A-2) is usually 80:20 to 20:80, preferably 70:30 to 30:70.

  Such component (A-2) can be obtained, for example, by a method of synthesizing an acrylic resin constituting the inner layer by emulsion polymerization and then synthesizing an acrylic resin and a silicone resin constituting the outer layer by emulsion polymerization. In the component (A-2), the silicone resin (a2) as described above may be contained as a resin constituting the inner layer. By including a silicone resin in the inner layer, the fire resistance, flexibility, stain resistance, etc. of the pattern layer can be enhanced.

  In the present invention, when the carboxyl group-containing acrylic resin is contained in the component (A-2), the effects of swelling prevention, peeling prevention and the like can be enhanced by separately adding a compound capable of reacting with the carboxyl group. it can. Furthermore, the tackiness of the pattern layer surface is reduced, and the stain resistance is increased. Examples of such a compound include those similar to the component (A-1).

In the present invention, in addition to the component (A) described above, a colored aggregate (B) having an average particle diameter of 0.01 to 5 mm (hereinafter referred to as “component (B)”) is an essential component. This (B) component can give a fine unevenness | corrugation to the pattern layer surface, and can express the three-dimensional design which has a shadow feeling. Also, unlike the case of using colored pigments with a small particle diameter, etc., the colored particles can be mixed to change the color tone, texture, etc. It is visually recognized and has excellent decorative properties. The component (B) suitable for the present invention is not particularly limited, and any of natural products and artificial products can be used. Specifically, for example, heavy calcium carbonate, cryolite, kaolin, clay, porcelain clay, china clay, talc, aluminum hydroxide, magnesium hydroxide, barite powder, marble, granite, serpentine, granite, fluorite, cold water Examples thereof include pulverized materials such as stone, feldspar, silica stone, and silica sand, ceramic pulverized materials, ceramic pulverized materials, glass beads, glass pulverized materials, resin beads, resin pulverized materials, and metal particles. Colored ones can also be used.
The particle size of the component (B) is desirably 0.01 to 5 mm. If the particle size is less than 0.01 mm, the natural stone-like variety of aggregates will decrease, and if it exceeds 5 mm, the workability tends to decrease.

 (B) The compounding quantity of a component becomes like this. Preferably it is 300-2000 weight part with respect to 100 weight part of solid content of (A) component, More preferably, it is 500-1500 weight part, More preferably, it is 800-1300. By including much (B) component with respect to (A) component like the said range, the outstanding designability which utilized the texture of the aggregate can be obtained, and fire prevention property can be improved further.

  Furthermore, in the present invention, the humidity-controlling powder (C) or lower (referred to as “component (C)”) is an essential component. This component (C) can impart humidity control to the pattern layer. Examples of the component (C) include boehmite, silica gel, zeolite, sodium sulfate, alumina, allophane, diatomaceous earth, siliceous shale, sepiolite, attabargite, montmorillonite, zonorite, imogolite, Otani stone powder, activated clay, charcoal, bamboo charcoal, activated carbon, wood Examples thereof include powder, shell powder, and porous synthetic resin particles. The average particle diameter of the humidity control powder is preferably about 0.001 to 1 mm, more preferably about 0.01 to 0.5 mm.

  The amount of component (C) is preferably 5 to 500 parts by weight, more preferably 10 to 400 parts by weight, and still more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the solid content of component (A). In such a range, excellent humidity control can be exhibited.

  Furthermore, in the present invention, the photocatalytic metal oxide (D) (hereinafter referred to as “component (D)”) is an essential component. Component (D) exhibits a photocatalytic action in a reflective region (hereinafter also simply referred to as “reflective region”) in which the reflectance of the coating formed by component (A) of wavelengths 300 to 500 nm is 10% or more. It is. By containing such a component (D), the photocatalytic activity can be efficiently exhibited. The photocatalytic action of the present invention means that when the catalyst is exposed to light (ultraviolet rays and / or visible light), the catalyst absorbs and excites light, and the resulting excited electrons and holes are oxidized and reduced. Acid radicals and active oxygen are generated, and the hydroxyl radicals and active oxygen have an action of decomposing organic substances.

Examples of such a component (D) include metal oxides such as titanium oxide, tin oxide, zinc oxide, ferric oxide, dibismuth trioxide, and tungsten trioxide, or composite oxides thereof. These 1 type (s) or 2 or more types can be used. (D) The average particle diameter of a component is 0.3 micrometer or less, Preferably it is 0.1 micrometer or more and 0.25 micrometer or less. When the photocatalytic metal oxide in the above range is used, it has an excellent photocatalytic action and can further utilize the texture of the aggregate of the patterned layer.
The average particle size referred to here is obtained from measurement by centrifugal sedimentation or the like.

In particular, it is preferable to use titanium oxide as the component (D) of the present invention. Titanium oxide may be either anatase-type titanium oxide or rutile-type titanium oxide. In the present invention, it is particularly preferable to use anatase-type titanium oxide. When titanium oxide is used as the component (D), the photocatalytic action is excellent, and furthermore, the total calorific value at the time of fire can be suppressed, and fire resistance can be improved. The action mechanism is presumed to be because titanium oxide can block radiant heat and suppress the temperature rise of the laminate. Furthermore, fireproofness improves more by using anatase type titanium oxide. The mechanism of action is not clear, but it is considered that the catalytic action of anatase-type titanium oxide by heating is involved. Further, the amount of exhaust gas can be reduced by the decomposition action of anatase type titanium oxide. Furthermore, the anatase-type titanium oxide has a lower effect of concealing the coating film than the rutile-type titanium oxide, so that the texture of the aggregate can be further utilized.

 The amount of component (D) is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and even more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the solid content of component (A). is there. When it is in such a range, it has excellent photocatalytic action and fire resistance, and can further utilize the texture of the aggregate of the patterned layer.

Further, the composition for a patterned layer of the present invention preferably contains a chemical substance adsorbent (E). By including the component (E), it is effective in preventing adsorption and re-release of harmful gases (for example, formaldehyde, ammonia, hydrogen sulfide, methyl mercaptan, trimethylamine, etc.). Examples of the component (E) include amine compounds, urea compounds, amide compounds, imide compounds, hydrazide compounds, azole compounds, azine compounds, layered phosphate compounds, and aluminosilicates. Among these, at least one selected from a layered phosphate compound and an aluminosilicate is preferable, and an aluminosilicate is particularly preferable. The average particle size of such a chemical substance adsorbent is usually about 0.5 to 100 μm (preferably 1 to 50 μm).

Examples of the layered phosphate compound include layered zirconium phosphate, layered zinc phosphate, layered titanium phosphate, layered aluminum phosphate, layered magnesium phosphate, layered cerium phosphate, and the like. An amine compound is included in these layered phosphate compounds. Intercalated ones are preferred. Examples of the amine compound include methylamine, ethylamine, aniline, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, and tripropylenetetramine.
Examples of the aluminosilicate include a composite oxide of at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium, and aluminum and silicon.

(E) The compounding quantity of a component becomes like this. Preferably it is 0.1-100 weight part with respect to 100 weight part of solid content of (A) component, More preferably, it is 5-30 weight part. In such a range, it is effective for adsorption of toxic gas.

In the composition for a patterned layer of the present invention, an aggregate (F) (hereinafter referred to as “component (F)”) having an average particle diameter of more than 5 mm can be mixed for the purpose of improving the decorativeness of the patterned layer. The component (F) suitable for the present invention includes, for example, pulverized products such as natural stone, silica stone, and silica sand, ceramic pulverized products, ceramic pulverized products, mica, shells, glass pulverized products, glass beads, resin pulverized products, and resin beads. , Rubbers, plastics, plant fibers, plants such as plant pieces, metals such as alumina flakes, and those whose surfaces are colored and coated.

  Moreover, as long as the effect of this invention is not impaired remarkably, a well-known additive can also be mixed as needed. 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. The pattern phase composition of the present invention can be produced by uniformly mixing the above components by a conventional method.

The thickness of the pattern layer of the present invention is preferably 1.0 mm or greater and 5.0 mm or less. In such a case, since a deeply concavo-convex uneven pattern can be formed, it is possible to obtain excellent design with shadow and profound feeling.

In this invention, when shape | molding a laminated body, a base layer can also be laminated | stacked on the back surface of an antibacterial and antifungal layer. Such a base layer is not particularly limited, but a base layer having flexibility such as a woven fabric or a non-woven fabric is preferable. Such a woven or non-woven fabric has a thickness of 0.05 to 1.5 mm, (more preferably 0.1 to 1 mm, still more preferably 0.25 to 0.5 mm), and a basis weight of 5 to 300 g / m ^2. , (More preferably 10 to 200 g / m ² , still more preferably 20 to 100 g / m ² ) inorganic fibers are preferable. Examples thereof include woven fabrics and nonwoven fabrics made of inorganic fibers such as mineral fibers and glass fibers. Furthermore, a nonwoven fabric in which fibers are superposed and bonded in a three-dimensional structure by a resin component such as an adhesive is preferable. When the base layer in the above range is used, the contact interface with the antibacterial and antifungal layer becomes large, so that it has excellent adhesion, and when applied to a wall surface, the base layer can stably support the laminate by including inorganic fibers. it can. Furthermore, since the laminate can be prevented from turning over, warping, or falling off in the event of a fire, it is possible to exert an excellent effect in fireproofing and flameproofing.

Further, one or more kinds of glass mesh, glass cloth, ceramic paper, synthetic paper, non-combustible paper, etc. can be laminated and used on the woven fabric or non-woven fabric. When these are used, the strength of the laminate is improved, the fall-off prevention property at the time of fire is improved, and it is effective for fire resistance, flame resistance and the like.

(Laminate manufacturing method)
The laminate of the present invention is not particularly limited as long as the pattern layer is sequentially laminated on the antibacterial and antifungal layer, but for example, in the case of the following method, the effect is It is suitable in terms of expression.
(1) A method of pouring a composition for a pattern layer into a mold, drying and curing, then pouring the composition for an antibacterial and antifungal layer, drying, curing and demolding,
(2) A method of pouring a pattern layer composition into a mold, laminating a sheet impregnated with an antibacterial and antifungal agent, drying, curing, and demolding;
(3) A method of applying a pattern layer composition to a sheet impregnated with an antibacterial and antifungal agent, drying and curing,
(4) A method of applying a pre-formed pattern layer to the sheet impregnated with the antibacterial and antifungal agent via an adhesive,
Etc.

When laminating the base layer,
(5) After (1) above, a method of laminating the base layer with an adhesive or the like,
(6) A method of laminating a base layer before the composition for antibacterial / antifungal layer of (1) is dried,
(7) A method of applying a composition for a bacteriostatic / antifungal layer to a base layer, drying and curing, then applying a composition for a pattern layer, drying and curing,
(8) A method of applying a pattern layer formed in advance via an adhesive, after applying a composition for an antibacterial / antifungal layer to a base layer, drying and curing,
(9) Applying a composition for antibacterial / antifungal layer to the base layer and applying a pre-formed pattern layer before curing,
Etc.

As the mold used in the above (1) and (2), for example, a mold made of silicone resin, urethane resin, metal or the like, or a mold provided with release paper can be used. Moreover, you may use a mold release agent as needed.

In the above (1) to (3) and (5) to (9), when the antibacterial / antifungal layer composition and the pattern layer composition are poured or applied, for example, spray, roller, trowel, etc. A method using means such as brush coating, reciprocation, coater, pouring, etc. can be employed.

In the above (1) to (3) and (5) to (9), when the antibacterial / antifungal layer composition and the pattern layer composition are dried, they may usually be carried out at room temperature. It can also be heated.

In the above (4), (8), and (9), as a method of forming the pattern layer in advance, for example, a formwork may be used, and the same formwork as in the above (1) and (2) may be used. it can.

In addition, as long as the effect of the present invention is not hindered, for example, a reinforcing material (ceramic paper, synthetic paper, glass cloth, mesh, etc.) is laminated between pattern layers, etc. It can also be formed or sprayed with decorative materials. Examples of the decorative material include colored aggregates, mica, shells, plants, alumina flakes, glass flakes, metals, rubbers, plastics, and the like.
For example, when manufacturing by the method of said (1), (2), (4)-(6), (8), (9), since formation of a concavo-convex pattern becomes the pattern layer surface on the mold side, The pattern layer composition can be applied by adjusting the shape of the inside of the mold, and when the decoration material is dispersed, the decoration material is scattered on the bottom of the mold using a known or commercially available spreader. Just pour things. In the case of producing by the above methods (3) and (7), the formation of the concavo-convex pattern and the spraying of the decoration material may be performed before the pattern layer composition is cured. In addition, a method using embossing, a roller, or the like can be adopted, and the decoration material can be sprayed using a known or commercially available sprayer.

It does not specifically limit as said adhesive agent, What is necessary is just to use a well-known thing. For example, the synthetic resin used for the adhesive is not particularly limited, but ethylene resin, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, phenol resin, melamine resin, amino resin , Polycarbonate resin, acrylic silicon resin, acrylic vinyl acetate resin, acrylic styrene resin, acrylic urethane resin, silicone resin, water-soluble type such as fluorine resin, water dispersion type, etc. Can be used.
In addition, powder components, hollow particles, porous particles, fibers, etc. may be added to give various performances such as workability, finish, adhesive strength, fire resistance, etc., and coloring materials and extender pigments may be added as necessary. Commonly used additives such as dispersants, viscosity modifiers, antifoaming agents, antifungal agents, preservatives, and algaeproofing agents can be added as appropriate.

  Furthermore, an overcoat layer can be laminated for the purpose of enhancing surface protection and the like within a range that does not significantly impair the effects of the present invention. The topcoat layer only needs to have air permeability. In this case, the hue of the pattern layer can be utilized as it is, and a photocatalytic action can also be exhibited. The overcoat layer may be a color clear layer to which various pigments are added within a range having transparency. Such an overcoating layer can be formed by applying a known aqueous or solvent-type overcoating material.

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

<Anti-bacterial and anti-fungal layer>
(Antibacterial and antifungal layer composition 1)
A composition 1 for an antibacterial / antifungal layer was prepared by mixing 600 parts by weight of the extender pigment 1 and 0.4 parts by weight of the antibacterial / antifungal agent 1 with respect to 100 parts by weight of the binder 1 (solid content). The raw materials shown below were used.
Binder 1: Acrylic styrene resin emulsion (Tg 5 ° C., solid content 50% by weight)
・ Body pigment 1: Heavy calcium carbonate (average particle size 3μm)
Antibacterial and antifungal agent 1: isothiazoline compound (water solubility: 1 to 500 ppm)

<Pattern layer>
(Production of synthetic resin A)
・ Synthetic resin 1-4
The following acrylic resin and silicone resin were mixed to obtain resins 1 to 4.
Acrylic resin emulsion; (Tg 21 ° C., component; t-butyl methacrylate: n-butyl acrylate: 2-ethylhexyl acrylate: methyl methacrylate = 30: 6: 24: 40), solid content 50% by weight.
Silicone resin emulsion (Tg-130 ° C., emulsified dispersion of dimethylsiloxane compound), solid content 50% by weight
Synthetic resin 1; acrylic resin emulsion: silicone resin emulsion (solid content weight ratio) = 99: 1
Synthetic resin 2; acrylic resin emulsion: silicone resin emulsion (solid content weight ratio) = 93: 7
-Synthetic resin 3; acrylic resin emulsion: silicone resin emulsion (solid content weight ratio) = 70:30,
Synthetic resin 4; acrylic resin emulsion: silicone resin emulsion (solid weight ratio) = 50: 50

・ Synthetic resin 5
Outer layer: acrylic resin (Tg 31 ° C., component: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, deca Methylcyclopentasiloxane)
Inner layer: acrylic resin (Tg-33 ° C., component: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane) , Decamethylcyclopentasiloxane),
Weight ratio of outer layer to inner layer 46:54, weight ratio of acrylic resin to silicone resin 80:20, acrylic resin constituent in emulsion; t-butyl methacrylate: n-butyl acrylate: 2-ethylhexyl acrylate: methyl methacrylate = 19 : 25:24:32, solid content 50% by weight, Tg-46 ° C.

・ Synthetic resin 6
Outer layer: acrylic resin (Tg 49 ° C., component: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, deca Methylcyclopentasiloxane),
Inner layer: acrylic resin (Tg-32 ° C., component: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane) , Decamethylcyclopentasiloxane),
Weight ratio of outer layer to inner layer 53:47, weight ratio of acrylic resin to silicone resin 80:20, acrylic resin constituent in emulsion; t-butyl methacrylate: n-butyl acrylate: 2-ethylhexyl acrylate: methyl methacrylate = 27 : 33:12:28, solid content 50% by weight, Tg-39 ° C.

・ Synthetic resin 7
Outer layer: acrylic resin (Tg 58 ° C., constituent components: t-butyl methacrylate, n-butyl acrylate, methyl methacrylate), silicone resin (constituent components: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane) ,
Inner layer: Acrylic resin (Tg-36 ° C., component: t-butyl methacrylate, n-butyl acrylate, methyl methacrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopenta Siloxane),
Weight ratio of outer layer to inner layer 45:55, weight ratio of acrylic resin to silicone resin 80:20, acrylic resin constituent in emulsion; t-butyl methacrylate: n-butyl acrylate: 2-ethylhexyl acrylate: methyl methacrylate = 25 : 52: 2: 21, solid content 50% by weight, Tg-43 ° C.

・ Synthetic resin 8
Outer layer: Acrylic resin (Tg 39 ° C, component: t-butyl methacrylate, n-butyl acrylate, methyl methacrylate)
Inner layer: acrylic resin (Tg-30 ° C., component: t-butyl methacrylate, n-butyl acrylate, methyl methacrylate), silicone resin (component: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopenta Siloxane),
Weight ratio of outer layer to inner layer 45:55, weight ratio of acrylic resin to silicone resin 90:10, acrylic resin component in emulsion; t-butyl methacrylate: n-butyl acrylate: 2-ethylhexyl acrylate: methyl methacrylate = 29 : 29:19:23, solid content 50% by weight, Tg-25 ° C.

・ Synthetic resin 9
Outer layer: acrylic resin (Tg 55 ° C., component: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate),
Inner layer: acrylic resin (Tg-50 ° C., constituent components: t-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate),
Weight ratio of outer layer to inner layer: 50:50, acrylic resin component in emulsion; t-butyl methacrylate: n-butyl acrylate: 2-ethylhexyl acrylate: methyl methacrylate = 25: 25: 24: 26, solid content 50% by weight , Tg-7.3 ° C.

The above synthetic resins 1 to 9 were applied to a release paper and dried to prepare a film having a film thickness of 0.1 mm, and the reflectance of the film was measured. In addition, the reflectance of the film was performed using the spectrophotometer (the Shimadzu Corporation make, UV-3100). The results are shown in Table 1.
As a result, the synthetic resins 2 to 7 had a reflection region in which the ultraviolet reflectance was 10% or more in the wavelength region of 300 nm to 500 nm. In addition, the synthetic resin 8 has a region where the ultraviolet reflectance is 10% or less in a region having a wavelength of 400 nm or more, and the ultraviolet reflectance is 10% or more in a region having a wavelength of less than 400 nm. On the other hand, the synthetic resins 1 and 9 had an ultraviolet reflectance of less than 10% in the reflection region. Table 1 shows the ultraviolet reflectance at wavelengths of 380 nm, 400 nm, and 500 nm as typical values.

(Manufacture of pattern layer composition)
(Composition 1 for pattern layer)
According to the formulation shown in Tables 2 and 3, compositions for pattern layer (simply abbreviated as “composition” in the table) 1 to 20 were prepared by mixing and stirring the respective raw materials by a conventional method. In addition, the following were used as a raw material.

(B) Component / Aggregate 1: Colored silica sand (light yellow, average particle size of 80 to 120 μm)
-Aggregate 2: Heavy calcium carbonate (average particle size 50-150 μm)
(C) Component / Humidity-controlling powder 1: Silica gel (average particle size 20 μm)
Component (D): Photocatalytic oxide 1: UV-responsive anatase-type titanium oxide (excitation wavelength: 200 to 380 nm, average particle size 0.2 μm)
Photocatalytic oxide 2: Visible light-responsive anatase-type titanium oxide (excitation wavelength: 400 to 650 nm, average particle diameter of 15 nm)
・ Metal oxide: Alumina (average particle size 1.0 μm)
・ Chemical adsorbent: Zinc aluminosilicate (average particle size 3μm)
・ Additives: Thickener (hydroxyethylcellulose, urethane associative thickener), film-forming aid, water

(Test Example 1A)
Pour the pattern layer composition 1 into the inner surface of a silicone mold (150 mm long x 70 mm wide x 5 mm deep) coated with a release agent so that the thickness of the patterned layer after drying is 2.5 mm, Smoothed with a trowel. After drying at 23 ° C. for 24 hours, the antibacterial / antifungal layer composition 1 is poured so that the thickness after drying is 0.4 mm, smoothed using a trowel, and then dried at 23 ° C. for 24 hours. After drying, the mold was removed. Next, the laminate 1 was obtained by curing at 23 ° C. for 14 days. The design property (texture by aggregate and hiding property of the pattern layer) of the pattern layer of the laminate was good.
The following tests were performed on the obtained laminate 1. The results are shown in Table 4.

<Bacterial and fungicidal test>
The antibacterial and antifungal test was performed by a film adhesion method based on JIS Z 2801 (2000). Escherichia coli and Staphylococcus aureus were used as test bacteria. The evaluation criteria of the antibacterial and antifungal test are as follows.
A: Antibacterial activity 2.0 or more B: Antibacterial activity less than 2.0

<Photocatalytic test>
After applying a solution obtained by adding 2% sodium hydroxide to an ethanol solution of 1.0 wt% phenolphthalein on the surface of the test body 1, sunlight (wavelength region: 305 to 4045 nm) was irradiated for 72 hours. The color difference of was measured. The decomposition of phenolphthalein by the action of the photocatalyst was evaluated based on the color difference ΔE. The color difference was measured using a color difference meter (CM-3700d, manufactured by Minolta Co., Ltd.).
The evaluation criteria for the photocatalytic test are as follows.
A: 6 ≦ ΔE
B: 5 <ΔE <6
C: ΔE ≦ 5

(Test Examples 2A to 13A, Test Examples 17A to 23A)
Instead of the pattern layer composition 1 of Test Example 1A, laminates 2 to 13 and 17 to 23 were obtained in the same manner as Test Example 1A, except that the pattern layer compositions shown in Tables 2 to 3 were used. . Each laminate was evaluated in the same manner as the laminate 1, and the results are shown in Tables 4 and 6.

(Test Example 14A)
A glass nonwoven fabric (thickness 0.4 mm, basis weight 50 g / m ² ) was impregnated with a mixed solution of the binder 1 and the antibacterial / antifungal agent 1 to prepare an antibacterial / antifungal sheet.
Next, the pattern layer composition 7 was applied onto the antibacterial / antifungal sheet so that the thickness of the pattern layer after drying was 2.5 mm and dried to obtain a laminate 14. The obtained laminate 14 was evaluated in the same manner as the laminate 1, and the results are shown in Table 5.

(Test Example 15A)
On the glass nonwoven fabric (thickness 0.4 mm, basis weight 50 g / m ² ), the antibacterial / antifungal layer composition 1 was applied so that the thickness after drying was 0.4 mm, and the composition was 24 at 24 ° C. Then, the pattern layer composition 7 was applied so that the thickness of the pattern layer after drying was 2.5 mm, and dried and cured at 24 ° C. for 14 days to produce a laminate 15. The obtained laminate 15 was evaluated in the same manner as the laminate 1, and the results are shown in Table 5.

(Test Example 16A)
Pour the pattern layer composition 7 into the inner surface of a silicone mold (150 mm long x 70 mm wide x 5 mm deep) coated with a release agent so that the thickness of the patterned layer after drying is 2.5 mm, Smoothed with a trowel. The pattern layer 7 was produced by drying and curing at 60 ° C. for 120 minutes.
On a glass nonwoven fabric (thickness 0.4 mm, basis weight 50 g / m ² ), the antibacterial / antifungal layer composition 1 is applied so that the thickness after drying is 0.4 mm, and in an undried state The said pattern layer 7 was laminated | stacked and the laminated body 16 was produced. The obtained laminate 16 was evaluated in the same manner as the laminate 1, and the results are shown in Table 5.

(Test Example 24A)
The pattern layer 7 was evaluated in the same manner as the laminate 1 and the results are shown in Table 6.

(Test Example 25A)
A pattern layer 20 was produced in the same manner as in Test Example 24A, except that the pattern layer composition 20 was used instead of the pattern layer composition 7 in Test Example 24A, and the same evaluation as in the laminate 1 was performed. The results are shown in Table 6.

(Test Examples 1B to 16B)
Next, the following evaluation was performed on the stacked bodies 1 to 16. The results are shown in Tables 7-8.
<Fireproof test 1>
A 100 mm x 100 mm x 12.5 mm gypsum board was used as a base material for the test, an adhesive was applied to the base material, each laminate was affixed, and cured at 23 ° C and 50 ± 10% RH for 240 hours. This was used as a test specimen.
The total calorific value of the test specimen after 20 minutes was measured with a cone calorimeter defined by ISO 5660. As the corn calorimeter, “CONE2A” (manufactured by Atlas) was used, and the heating intensity was 50 kW / m ² .
The evaluation criteria for the exothermic test are as follows.
A: The total amount of heat generated at the heating time of 20 minutes is 6.0 mJ / m ² or less B: the total amount of heat generated at the heating time of 20 minutes exceeds ^{6.0MJ / m 2, 8.0MJ / m} 2 or less C: the heating exceeds the total calorific value 8.0MJ / m ² at time 20 minutes, 12.0MJ / m ² or less D: the total amount of heat generated at the heating time of 20 minutes exceeds 10.0MJ / m ^2, 12.0MJ / m ² or less E: Total calorific value after heating time of 20 minutes exceeds 12.0 MJ / m ² Note that the adhesive comprises synthetic resin emulsion 5, titanium oxide, heavy calcium carbonate, dispersant, thickener, An antifoaming agent and water produced by uniformly stirring and mixing were used.

<Contamination resistance test>
Set each laminate as a test body, place the test body horizontally, spread the dirt component (black cinnabar sand) on the surface of the coating film, leave it for 2 hours, and then stand the test plate vertically, The degree was confirmed. The evaluation criteria were a four-step evaluation (excellent: A>B>C> D: poor), where “A” is the one from which the dirt has been removed and “D” is the one from which the dirt remains significantly.

  Moreover, about the laminated bodies 14-16, the adhesive agent similar to the fireproof test 1 is apply | coated to the slate of 70 mm x 150 mmx6mm as a base material for a test, the laminated bodies 14-16 are affixed, and 23 degreeC Test specimens were cured under 50 ± 10% RH for 24 hours. The test specimen was set up vertically and burned with a burner from a distance of 10 cm for 3 minutes, and then the surface properties were evaluated. All the laminates were held on the slate, which was a good result.

Claims (3)

A laminate in which a pattern layer is laminated on an antibacterial and antifungal layer,
The antibacterial / antifungal layer contains an antibacterial / antifungal agent,
The pattern layer has as essential components a synthetic resin (A), a colored aggregate (B) having an average particle diameter of 0.01 to 5 mm, a humidity control powder (C), and a photocatalytic metal oxide (D),
The synthetic resin (A) forms a film having a reflective region with a reflectance of 10% or more at a wavelength of 300 to 500 nm,
The photocatalytic metal oxide (D) exhibits a photocatalytic action in the reflection region. The antibacterial and antifungal layer is
The laminate according to claim 1, wherein the laminate is formed from a film of a composition containing an antibacterial / antifungal agent and / or a sheet impregnated with the antibacterial / antifungal agent. The synthetic resin (A) contains an acrylic resin derived from a (meth) acrylic acid alkyl ester, and a silicone resin in a solid content weight ratio of 95: 5 to 30:70. The laminated body in any one of 2