JP2012017217A - Cured object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cured object excellent not only in designing property and antibacterial activity but also in anti-mold and antibacterial activities within the same.SOLUTION: The cured object contains, as essential components, a synthetic resin (A) which forms a film having a reflection region in which reflectance becomes ≥10% at a wavelength of 300-500 nm, a photocatalytic metal oxide (B) which exhibits photocatalytic action in the reflection region, a humidity conditioning powder (C), and a colored aggregate (D) having an average particle size of 0.01-5 mm, wherein the colored aggregate (D) contains at least an aggregate (E) having antibacterial activity.

Description

  The present invention relates to a novel cured product.

  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 reinforcing layer made of a synthetic resin fabric is laminated on one surface of a plate of a spray material in which an aggregate is mixed with a 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, 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 it contains a lot of aggregate, there is a possibility that the photocatalytic action cannot be efficiently exhibited up to the inside of the building material. 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 hardening body which is excellent also in the antifungal property and antibacterial property inside while being excellent in the designability and antibacterial property.

In the present invention, as a result of intensive studies to achieve the above object, the synthetic resin (A), the photocatalytic metal oxide (B), the humidity control powder (C), and the colored particles having an average particle diameter of 0.01 to 5 mm are obtained. A hardened body containing the aggregate (D) as an essential component was conceived and the present invention was completed.
That is, the cured body of the present invention has the following characteristics.

1. A synthetic resin (A), a photocatalytic metal oxide (B), a humidity-controlling powder (C), and a colored aggregate (D) having an average particle diameter of 0.01 to 5 mm as essential components, and the above-mentioned synthesis The resin (A) forms a film having a reflection region having a reflectance of 10% or more at a wavelength of 300 to 500 nm, and the photocatalytic metal oxide (B) exhibits a photocatalytic action in the reflection region. And the colored aggregate (D) contains at least an antibacterial aggregate (E).
2. 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. Cured product according to 3. The antibacterial aggregate (E) is characterized in that an antibacterial agent is attached to the aggregate surface. ~ 2. 3. Hardened | cured material in any one of 4. 1. The antibacterial aggregate (E) is embedded so as to be exposed on the surface of the cured body. ~ 3. The cured product according to any one of

The cured product of the present invention comprises a specific synthetic resin emulsion, a photocatalytic metal oxide, a humidity-controlling powder, and a specific colored aggregate as essential components, and includes those having antibacterial properties as a colored aggregate. Therefore, it has excellent design properties, and has excellent performance in photocatalytic action such as decomposability of organic matter, antibacterial and antifungal properties.

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

The hardened body of the present invention contains, as essential components, a synthetic resin (A), a photocatalytic metal oxide (B), a humidity control powder (C), and a colored aggregate (D) having an average particle diameter of 0.01 to 5 mm, The colored aggregate (D) includes at least an aggregate (E) having antibacterial properties.
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 cured body of the present invention is diffused and reflected in the cured body, reaches the inside of the cured body, and is dispersed in the cured body. And the photocatalytic activity is increased, whereby antibacterial properties can be enhanced.
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 becomes possible to obtain a cured body excellent in 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 cured body 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. As a result, various physical properties of the cured body 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 with a normal synthetic resin emulsion, a cured product having various physical properties such as flexibility, fire resistance, and adhesion to a substrate with a smaller amount of resin. 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 cured body 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 cured body 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, the photocatalytic metal oxide (B) (hereinafter referred to as “component (B)”) is an essential component. The component (B) 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 the component (A) of wavelengths 300 to 500 nm is 10% or more. It is. By including such a component (B), 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 component (B) 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. (B) 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 cured body.
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 (B) 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 (B), the photocatalytic action is excellent, and the total calorific value at the time of a 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 blending amount of the component (B) is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and further preferably 2 to 20 parts by weight with respect to 100 parts by weight of the solid content of the 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 cured body.

  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 cured body. 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.

Further, in the present invention, a colored aggregate (D) (hereinafter referred to as “component (D)”) having an average particle diameter of 0.01 to 5 mm is an essential component. This (D) component can give a fine unevenness | corrugation to the hardening body 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 (D) 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 (D) 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.

(D) 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 (D) component with respect to (A) component like the said range, the outstanding designability which utilized the texture of the aggregate can be obtained, and fireproofing can be improved further.

In the present invention, the colored aggregate (D) includes at least an aggregate (E) having antibacterial properties (hereinafter referred to as “component (E)”). By disperse | distributing this (E) component to a hardening body, the outstanding antimicrobial property can be exhibited. As such a component (E), one having an antibacterial agent attached to the surface of the component (D) can be used.
As the antibacterial agent, a known antibacterial agent can be used, but in the present invention, it is particularly preferable to use an inorganic antibacterial agent. For example, a metal or metal ion centered on silver, copper, or zinc is substituted or used. Examples include supported inorganic compounds. Examples of the inorganic compound include activated carbon, activated alumina, silica gel, zeolite, hydroxyapatite, zirconium phosphate, zinc phosphate, titanium phosphate, aluminum phosphate, magnesium phosphate, cerium phosphate, potassium titanate, hydrous bismuth hydroxide , Hydrous zirconium oxide, hydrotalcite and the like.

The method for attaching the antibacterial agent to the surface of the component (D) is not particularly limited, but it is preferable to use a binder. The binder is not particularly limited. For example, organic binders include various binders such as water-soluble resins, water-dispersible resins, solvent-soluble resins, solvent-free resins, non-water-dispersed resins, and powder resins. Alternatively, a binding material obtained by combining these can be used. 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 silicone resin, fluorine Examples thereof include resins and the like, and composites thereof. In addition, examples of the inorganic binder include glassy powder, water glass, metal alkoxide compounds, and the like, and heat treatment can be performed as necessary. Moreover, the blending amount of the antibacterial agent is preferably 0.01 to 5% by weight with respect to the component (D).

The amount of component (E) is preferably at least 5% by weight, more preferably 10 to 90% by weight, of component (D). By including the component (E) with respect to the component (D) as in the above range, it is possible to obtain an excellent design utilizing the texture of the aggregate and to exhibit an excellent antibacterial property.

In the present invention, aggregate (F) (hereinafter referred to as “component (F)”) having an average particle diameter of more than 5 mm can be mixed or dispersed for the purpose of improving the decorativeness of the cured body. 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 cured product of the present invention has an average particle size of 0.01 including the above-mentioned synthetic resin (A), photocatalytic metal oxide (B), humidity-controlling powder (C), and at least an antibacterial aggregate (E). A composition for cured body (hereinafter also referred to as “cured body composition”) in which colored aggregate (D) of ˜5 mm is mixed is molded into a film shape, a plate shape, or the like. The thickness 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.

The structure of the cured body may be a cured body in which the above components (A) to (E) are mixed and dispersed. However, from the viewpoint of the effects of the present invention, the (E) component is exposed on the surface of the cured body. It is preferable that it is buried so as to. In such a case, the antibacterial property can be efficiently exhibited on the surface of the cured body, and a sufficient effect can be obtained even if the amount of the component (E) is relatively small. For example, when the cured product of the present invention is used as a building material for interiors, the anti-bacterial property is effective against splashes caused by hand contact, coughing, and sneezing due to the exposed component (E). Can be demonstrated.
As a manufacturing method of the cured body embedded so that the (E) component is exposed on the surface of the cured body, for example,
(A) When molding the composition for a cured body, a method of spraying (E) component on the surface, drying and curing,
(B) A method of demolding the composition after the component (E) is dispersed in a formwork and the like, then applying the composition for a cured body, drying the composition,
Etc.
In the above (a) and (b), the amount of the component (E) to be dispersed or scattered is preferably about 10 to 500 g / m ² , more preferably about ²⁰ to 400 g / m ² . In (A) above, for example, a mold made of silicone resin, urethane resin, metal, or a mold provided with release paper can be used as the mold used.

In this invention, a base layer can also be laminated | stacked on a hardening body. 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 cured body becomes large, so that the adhesiveness is excellent. Further, when applied to a wall surface or the like, the cured body can be stably supported by including the inorganic fiber in the base layer. . Further, since the cured body can be prevented from turning over, warping, or falling off during a fire, it is possible to exhibit excellent effects in fire resistance and flame resistance.

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.
In addition, when laminating the base layer on the cured body, it may be laminated on one side of the cured body, and in the case of a cured body embedded so that the component (E) is exposed, it is laminated on the opposite side of the exposed surface of (E). do it.

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 design of the cured body can be utilized as it is, and antibacterial properties and photocatalytic activity 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.

  The cured product of the present invention can be applied mainly as an interior building material for buildings. That is, interior finishing can be performed by pasting on each part of the building interior surface. Specifically, it can be applied to walls, partitions, doors, ceilings, etc. in houses, condominiums, schools, hospitals, stores, offices, factories, warehouses, restaurants, etc. Examples of the base constituting such a part include gypsum board, plywood, concrete, mortar, tile, fiber-mixed cement board, cement calcium silicate board, and slag cement pearlite board. These bases may be those having an existing coating film on the surface thereof, or those already having wallpaper attached thereto.

Moreover, what is necessary is just to stick to a base | substrate using an adhesive agent, an adhesive, an adhesive tape, a nail, a wrinkle, etc. when constructing this invention hardening body. In addition, it can also be fixed using pins, fasteners, rails or the like. Especially, it is preferable to stick the hardening body of this invention to a base | substrate using an adhesive agent.
It does not specifically limit as an 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 silicone 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 appropriately added.

When a cured body is affixed with an adhesive, adjacent cured bodies can be abutted and affixed, or joints can be provided between the cured bodies. When affixing and affixing, it is preferable that the adhesive does not protrude. Moreover, when providing a joint, the space | interval at the time of sticking a hardening body is not specifically limited, What is necessary is just about 1 mm-30 mm. If it is such a range, interior finishing which makes use of a joint pattern can be performed. Moreover, you may smooth the adhesive of a joint part with a spatula etc. as needed. The ambient temperature at which the adhesive is cured can be set as appropriate, but is usually room temperature.

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

(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.

Component (B): 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)
(C) Component / Humidity-controlling powder 1: Silica gel (average particle size 20 μm)
(D) Component / Aggregate 1: Colored silica sand (light yellow, average particle size 80-120 μm)
-Aggregate 2: Heavy calcium carbonate (average particle size 50-150 μm)
(E) Component / Aggregate 3: Silver-supported phosphate-coated silica sand (average particle size 200 μm, content of antibacterial agent 1% by weight)
Other components / Metal oxide: Alumina (average particle size 1.0 μm)
・ Additives: Thickener (hydroxyethylcellulose, urethane associative thickener), water

(Production of composition for cured body)
(Compositions for cured body 1-20)
In accordance with the formulation shown in Tables 2 and 3, each raw material (excluding aggregate 3) is uniformly mixed and stirred by a conventional method to obtain a composition for cured body (simply abbreviated as “composition” in the table) 1 to 20 Manufactured.

(Test Example 1A)
On the glass nonwoven fabric (thickness 0.4 mm, basis weight 50 g / m ² ), the composition 1 for cured body is applied so that the thickness of the cured body after drying is 2.5 mm, and 50 g of the aggregate 3 is applied. After spraying / m ² , the cured product 1 was produced by drying and curing at 60 ° C. for 120 minutes. The following tests were performed on the obtained cured body 1. The results are shown in Table 4.

<Antimicrobial test>
The antibacterial 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 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 cured body 1, irradiation with sunlight (wavelength region 305 to 4045 nm) was performed 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 20A)
It replaced with the composition 1 for hardening bodies of Test Example 1A, and obtained the hardening bodies 2-20 similarly to Test Example 1A except having used the composition for hardening bodies shown in Tables 2-3. Each cured body was evaluated in the same manner as the cured body 1, and the results are shown in Tables 4 and 5.

(Test Examples 1B to 13B)
Subsequently, the following evaluation was implemented about the hardening bodies 1-14. The results are shown in Table 6.
<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.

Claims (4)

A synthetic resin (A), a photocatalytic metal oxide (B), a humidity-controlling powder (C), and a colored aggregate (D) having an average particle diameter of 0.01 to 5 mm as essential components,
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 (B) exhibits a photocatalytic action in the reflection region,
The said colored aggregate (D) contains the aggregate (E) which has an antibacterial property at least, The hardening body characterized by the above-mentioned. The said synthetic resin (A) contains the acrylic resin derived from the (meth) acrylic-acid alkylester, and a silicone resin by the solid content weight ratio 95: 5-30: 70, It is characterized by the above-mentioned. Cured body   The cured body according to any one of claims 1 to 2, wherein the antibacterial aggregate (E) has an antibacterial agent attached to the surface of the aggregate.   The hardened body according to any one of claims 1 to 3, wherein the aggregate (E) having antibacterial properties is embedded so as to be exposed on the surface of the hardened body.