JP4527112B2 - Laminated body and method for producing the same - Google Patents

Description

  This application claims priority with respect to Japanese Patent Application No. 2004-87345 for which it applied on March 24, 2004, and uses the content here.

  The present invention relates to a laminate having waterproofness and stain resistance, and also relates to a method for manufacturing the laminate.

  The surface of building materials used outdoors tends to be gradually polluted by pollutants in the air or rainwater, moss and mold spores, and microorganisms.

Moreover, in the concrete building material containing a reinforcing bar or a steel frame, since the concrete is porous, there is a possibility that the reinforcing bar or the steel frame will rust due to the penetration of rainwater, and the concrete may be damaged due to the volume increase of the reinforcing bar or the steel frame due to the rust. There is also a problem of neutralization of concrete due to acidic substances in rainwater. Further, there is a problem of deterioration due to CO _{2 in} rainwater in the building material made of marble.

  Therefore, in outdoor construction materials, conventionally, a water repellent substance such as a silicone compound and a fungicide or an antibacterial agent are applied to the surface of the building material in advance to prevent moisture from entering the building material and In order to reduce the adhesion of pollutants and the growth of moss and mold.

  On the other hand, a photocatalyst layer is recently formed on the building material surface as a simple method for preventing contamination of the building material surface. For example, Japanese Patent Laid-Open No. 2000-135442 proposes a method of forming a photocatalytic layer such as anatase-type titanium peroxide on a water-repellent layer made of an alkali metal silicate compound. Japanese Patent Application Laid-Open No. 2002-138243 proposes a method of forming a photocatalytic layer on a primer layer containing an acrylic resin having an alkoxysilyl group and a hydroxyl group.

Furthermore, in WO 2004/041723 pamphlet, a metal-doped titanium oxide layer having no photocatalytic function is formed on the surface of a substrate such as a building material, and the photo-oxidation function of the metal-doped titanium oxide layer It has been proposed to prevent surface contamination.
JP 2000-135442 A JP 2002-138243 A International Publication No. 2004/041723 Pamphlet

  By the way, in recent years, in order to improve the appearance while taking advantage of the texture of the building material itself, in addition to waterproofing and preventing contamination of the surface of the building material, it is required to color the surface of the building material in an arbitrary color.

  However, it is difficult to color the alkali metal silicate compound by the method described in JP-A-2000-135442. Furthermore, the photocatalyst layer may be hydrolyzed by the action of the alkali metal silicate compound.

  Further, in the method described in JP-A-2002-138243, the acrylic resin layer can be colored, but there is a problem that the acrylic resin layer is degraded by oxidative decomposition due to the action of the photocatalyst layer.

  The present invention is to solve the above problems. That is, an object of the present invention is to provide a laminate that can be arbitrarily colored while maintaining a good waterproof function and contamination prevention function, and a building material and a building including the laminate.

The purpose of the present invention is to
A substrate having pores on the surface,
A colorless, transparent or colored transparent, translucent or opaque water-absorptive layer comprising a silicon-containing compound formed on the substrate; and
A metal-doped titanium oxide-containing layer comprising titanium oxide doped with at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc, formed on the water absorption prevention layer This is achieved by the provided laminate.

  The laminate of the present invention is preferable as a building material, and particularly preferable as a decorative material. Therefore, the laminated body of this invention can be used suitably for a building.

  The metal-doped titanium oxide-containing layer is preferably made of amorphous titanium oxide. Moreover, it is preferable that the said metal dope titanium oxide content layer further contains silicone oil, especially polyether modified silicone oil.

  A photocatalytic function layer may be formed on the metal-doped titanium oxide-containing layer. The photocatalytic functional layer is preferably made of anatase type titanium oxide.

  The water absorption preventing layer containing the silicon-containing compound is preferably composed of a water absorption preventing agent comprising a silicon-containing compound and water.

The laminate of the present invention is
Forming a water-absorbing prevention layer containing a silicon-containing compound on a substrate having pores on the surface thereof, which is colorless and transparent, or colored, transparent, translucent or opaque; and
It can manufacture through the process of forming the said metal dope titanium oxide content layer on the said water absorption prevention layer.

The figure which shows the outline of an example of the 1st manufacturing method of metal dope titanium oxide.

  The substrate constituting the laminate of the present invention is an inorganic or organic substrate having pores on the surface. The substrate having pores on the surface includes, in addition to a porous substrate, a substrate having a porous coating layer on the substrate surface, and a substrate having essentially pore defects on the surface. Such a substrate has a rough surface and has a relatively high water absorption rate. Therefore, rainwater tends to enter the substrate together with contaminants such as pollutants in the atmosphere and dust and stay on the substrate surface.

  Examples of the inorganic base having pores on the surface include a base made of a material such as concrete, mortar, clay, stone, and a metal base on which a porous film such as a metal oxide or ceramic is formed on the surface. It is done. More specifically, concrete PC board, concrete member having exposed surface, ALC board, mortar member having finished surface, brick, tile, especially ceramic tile, tile, marble, granite, ceramic coated metal plate are exemplified. The

  Examples of the organic base having pores on the surface include a base made of a material such as wood or paper. The shape of the substrate is not particularly limited, and can be any shape such as a cube, a rectangular parallelepiped, a sphere, or a sheet.

  In the laminate of the present invention, a water absorption preventing layer containing a silicon-containing compound is present on a substrate having pores on the surface. The water absorption preventing layer containing a silicon-containing compound has a function of preventing moisture from entering the substrate, and is particularly preferably composed of a water absorption preventing agent comprising a silicon-containing compound and water. Since the water absorption inhibitor composed of the silicon-containing compound and water can penetrate into the pores of the substrate to form a water absorption prevention layer, it is possible to effectively prevent moisture from entering the substrate.

Examples of the water absorption inhibitor comprising a silicon-containing compound and water include hydrolyzable silane, water, a silane water absorption inhibitor comprising a surfactant, and an aqueous solution of an alkyl metal salt of an alkyl siliconate. Of these, a silane-based water absorption inhibitor composed of hydrolyzable silane, water, and a surfactant is preferable because it has excellent permeability to the substrate, water absorption prevention performance, durability of the water absorption prevention layer, and handling workability.

  Various alkoxysilanes can be used as the hydrolyzable silane. Specific examples include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane. Of these, one type of hydrolyzable silane may be used alone, or two or more types of hydrolyzable silanes may be mixed and used as necessary. Moreover, you may mix | blend the hydrolyzate and various organopolysiloxane with these hydrolysable silanes.

  The surfactant is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a mixture thereof can be used.

  As such a silane-based water absorption inhibitor, compositions disclosed in JP-A Nos. 62-197369 and 6-313167 can be preferably used. Such a silane water absorption inhibitor is commercially available as Dry Seal S (manufactured by Toray Dow Corning Silicone Co., Ltd.).

  Examples of the aqueous solution of the alkali metal salt of the alkyl siliconate include an aqueous sodium methyl siliconate solution and an aqueous potassium methyl siliconate solution. Examples of such an aqueous solution of an alkali metal salt of an alkyl siliconate include dry seal C and dry seal E (manufactured by Toray Dow Corning Silicone Co., Ltd.).

  The water absorption preventing layer containing the silicon-containing compound may be colorless and transparent, or may be colored transparent, translucent or opaque. Coloring here includes not only red, blue, green, etc. but also white. In order to obtain a colored water absorption preventing layer, it is preferable to add various colorants such as inorganic or organic pigments or dyes to the water absorption preventing layer.

  Examples of the inorganic pigment include carbon black, graphite, yellow lead, iron oxide yellow, red lead, bengara, ultramarine blue, chromium oxide green, iron oxide and the like. As organic pigments, azo organic pigments, phthalocyanine organic pigments, selenium organic pigments, quinocridone organic pigments, dioxazine organic pigments, isoindolinone organic pigments, diketopyrrolopyrrole and various metal complexes can be used. Those having excellent light resistance are desirable. Examples of light-resistant organic pigments include Hansa Yellow, toluidine red, which are insoluble azo organic pigments, phthalocyanine blue B, phthalocyanine green, which are phthalocyanine organic pigments, and quinacridone red, which is a quinacridone organic pigment. It is done.

  Examples of the dye include basic dyes, direct dyes, acid dyes, vegetable dyes, and the like, but those having excellent light resistance are preferable. For example, direct scarlet for red, direct lorseline, azorubine, and orange for direct orange R For conch, acid orange and yellow, chrysophenine NS, methanol yellow, for brown, direct brown KGG, acid brown R, for blue, direct blue B, for black, direct black GX, nigrosine BHL, etc. are particularly preferred.

  When the water absorption preventing layer containing a silicon-containing compound is composed of a water absorption preventing agent comprising a silicon-containing compound and water, the mixing ratio (weight ratio) of the water-absorbing inhibitor comprising the silicon-containing compound, water and the pigment is 1: The range of 2 to 1: 0.05 is preferable, and the range of 1: 1 to 1: 0.1 is more preferable.

  In addition, additives such as a dispersant, a stabilizer, and a leveling agent may be further added to the water absorption preventing layer containing the silicon-containing compound. These additives have the function of facilitating the formation of the water absorption preventing layer. Further, when a colorant such as a pigment / dye is blended, it is also possible to add a binder for fixing the colorant. As the binder in this case, various paint binders mainly composed of an acrylic ester or an acrylic ester copolymer resin having excellent weather resistance can be used. For example, Polysol AP-3720 (Showa Polymer Co., Ltd.) And Polysol AP-609 (manufactured by Showa Polymer Co., Ltd.)

  The water absorption preventing layer containing a silicon-containing compound can be formed, for example, as follows. A water absorption inhibitor comprising a silicon-containing compound and water, and, if necessary, a solution containing the colorant, the additive and the binder so as to penetrate into the substrate surface layer to a depth of about 2 to 5 mm. Apply. Heating is performed as necessary, and the solvent is evaporated to form a water absorption preventing layer containing a silicon-containing compound on the substrate. The water absorption preventing layer containing a silicon-containing compound can impart water absorption preventing properties and colorability to the substrate by being integrated with the substrate.

  The thickness of the water absorption preventing layer containing the silicon-containing compound formed as described above is not particularly limited, but is preferably 0.01 to 1.0 μm, and more preferably 0.05 to 0.3 μm. Moreover, when a coloring agent, an additive, and a binder are added, 1.0 micrometer-100 micrometers are preferable, and 10 micrometers-50 micrometers are more preferable.

  As a method for forming a water absorption preventing layer containing a silicon-containing compound on a substrate having pores on the surface, any known method can be used. For example, spray coating, dip coating, flow coating, spin coating Coating methods, roll coating methods, brush coating, sponge coating, and the like are possible. In order to improve the physical performance such as the hardness of the water absorption preventing layer and the adhesion to the substrate, it is preferable to heat them at a temperature within an allowable range after the water absorption preventing layer is formed on the substrate.

In the laminate of the present invention, a titanium oxide doped with at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron and zinc is formed on the water absorption preventing layer containing the silicon-containing compound. There is a metal-doped titanium oxide containing layer. Titanium oxide includes various oxides and peroxides such as TiO ₂ , TiO ₃ , TiO, and TiO ₃ / nH ₂ O, and may be any of amorphous type, anatase type, brookite type, and rutile type. .

  The metal-doped titanium oxide comprises a titanium oxide comprising one or more metal elements selected from the group consisting of copper, manganese, nickel, cobalt, iron and zinc, preferably having a peroxo group, The property is fine particles or powder. The titanium oxide having a peroxo group may be any of amorphous type, anatase type, brookite type, rutile type, or a mixture thereof.

  Amorphous titanium oxide does not have a photocatalytic function. On the other hand, anatase type, brookite type, and rutile type titanium oxides have a photocatalytic function. However, when copper, manganese, nickel, cobalt, iron, or zinc is combined at a certain concentration or more, the photocatalytic function is lost. Therefore, the metal-doped titanium oxide used in the present invention does not have a photocatalytic function. Amorphous titanium oxide is converted to anatase titanium oxide over time by heating with sunlight, etc., but as described above, when combined with copper, manganese, nickel, cobalt, iron or zinc, anatase titanium oxide Loses its photocatalytic function, so that, ultimately, the metal-doped titanium oxide does not exhibit a photocatalytic function over time.

  On the other hand, the metal-doped titanium oxide exhibits a unique anti-catalytic antifouling action. Thereby, deterioration and contamination of the surface of the metal-doped titanium oxide-containing layer are prevented or reduced. Although the mechanism of this action is unknown, it is thought to be due to a complex action based on a photo-oxidation reaction caused by short-wave electromagnetic waves such as ultraviolet rays (sunlight).

The photo-oxidation reaction here means that active oxygen such as hydroxyl radical (.OH), ¹ O ₂ (singlet oxygen) is generated from oxygen and / or moisture in the air or organic matter by a short wavelength electromagnetic wave. It is a concept including reacting with an organic substance and / or an inorganic substance attached to the surface of the layer. It is considered that a positive charge is generated in the organic substance and / or the inorganic substance.

  The metal-doped titanium oxide layer according to the present invention is positively charged as a whole because the doped metal has a positive charge. Therefore, the metal-doped titanium oxide layer having a positive charge as well as the organic substance and / or inorganic substance having a positive charge is electrically repelled, and the organic substance and / or the inorganic substance is relatively easy due to the action of an external force such as running water or wind and rain. To be removed from the surface of the metal-doped titanium oxide layer. Thereby, it is considered that contamination on the surface of the metal-doped titanium oxide layer can be suppressed or reduced.

  As a method for producing a metal-doped titanium oxide according to the present invention, a production method based on a hydrochloric acid method or a sulfuric acid method, which is a common method for producing titanium dioxide powder, may be adopted, and various liquid-dispersed titanias may be used. You may employ | adopt the manufacturing method of a solution. And the said metal can be compounded with a titanium oxide regardless of a manufacturing stage.

  For example, specific methods for producing the metal-doped titanium oxide include the following first to third production methods and conventionally known sol-gel methods.

First Production Method First, a titanium hydroxide is formed by reacting a tetravalent titanium compound such as titanium tetrachloride with a base such as ammonia. Next, this titanium hydroxide is peroxo-oxidized with an oxidizing agent to form ultrafine particles of amorphous titanium peroxide. This reaction is preferably carried out in an aqueous medium. Furthermore, it is also possible to transfer to anatase-type titanium peroxide by arbitrary heat treatment. In any of the above steps, at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed.

  The peroxidation oxidizing agent is not particularly limited, and various agents can be used as long as they can form a titanium peroxo compound, that is, titanium peroxide, but hydrogen peroxide is preferred. When hydrogen peroxide is used as the oxidizing agent, the concentration of hydrogen peroxide is not particularly limited, but is preferably 30 to 40%. It is preferred to cool the titanium hydroxide before peroxolation. The cooling temperature at that time is preferably 1 to 5 ° C.

  FIG. 1 shows an example of the first manufacturing method. In the illustrated production method, an aqueous titanium tetrachloride solution and aqueous ammonia are mixed in the presence of at least one compound of copper, manganese, nickel, cobalt, iron, and zinc, and the metal hydroxide and titanium water are mixed. An oxide mixture is formed. The concentration and temperature of the reaction mixture at that time are not particularly limited, but are preferably diluted and at room temperature. This reaction is a neutralization reaction, and it is preferable that the pH of the reaction mixture is finally adjusted to around 7.

  The metal and titanium hydroxides thus obtained are washed with pure water, cooled to around 5 ° C., and then peroxoated with hydrogen peroxide. As a result, an aqueous dispersion containing titanium oxide fine particles having amorphous peroxo groups doped with metal, that is, an aqueous dispersion containing the metal-doped titanium oxide according to the present invention can be produced. .

Second Production Method A tetravalent titanium compound such as titanium tetrachloride is peroxo-oxidized with an oxidizing agent, and this is reacted with a base such as ammonia to form amorphous fine titanium peroxide. This reaction is preferably carried out in an aqueous medium. Furthermore, it is possible to transfer to anatase-type titanium peroxide by arbitrarily heat-treating. In any of the above steps, at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed.

Third production method A tetravalent titanium compound such as titanium tetrachloride is reacted simultaneously with an oxidizing agent and a base to simultaneously form titanium hydroxide and peroxidize it, thereby producing amorphous fine titanium peroxide particles. Form. This reaction is preferably carried out in an aqueous medium. Furthermore, it is possible to transfer to anatase-type titanium peroxide by arbitrarily heat-treating. In any of the above steps, at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed.

  In the first to third manufacturing methods, it goes without saying that a mixture of amorphous titanium peroxide and anatase titanium peroxide obtained by heating the same can be used as the metal-doped titanium oxide of the present invention.

Manufacturing method by sol-gel method A titanium alkoxide is mixed and stirred with a solvent such as water or alcohol, an acid or a base catalyst, and the titanium alkoxide is hydrolyzed to produce a sol solution of ultrafine titanium oxide. Before or after the hydrolysis, at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed. The titanium oxide thus obtained is an amorphous type having a peroxo group.

As the titanium alkoxide, a compound represented by the general formula: Ti (OR ′) ₄ (where R ′ is an alkyl group), or one or two alkoxide groups (OR ′) in the general formula is a carboxyl group. Alternatively, a compound substituted with a β-dicarbonyl group or a mixture thereof is preferable.

Specific examples of the titanium alkoxide include Ti (O—isoC ₃ H ₇ ) ₄ , Ti (O—nC ₄ H ₉ ) ₄ , Ti (O—CH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ) _4. , Ti (O—C ₁₇ H ₃₅ ) ₄ , Ti (O—isoC ₃ H ₇ ) ₂ [CO (CH ₃ ) CHCOCH ₃ ] ₂ , Ti (O—nC ₄ H ₉ ) ₂ [OC ₂ H ₄ N ( _{C 2 H 4 OH) 2]} 2, Ti (OH) 2 [OCH (CH 3) COOH] 2, Ti (OCH 2 CH (C 2 H 5) CH (OH) C 3 H 7) 4, Ti (O _{-nC 4 H 9) 2 (OCOC} 17 H 35) , and the like.

Tetravalent Titanium Compound As a tetravalent titanium compound used in the production of the metal-doped titanium oxide according to the present invention, hydroxylation, which is also called orthotitanic acid (H ₄ TiO ₄ ), when reacted with a base. Various titanium compounds can be used as long as they can form titanium, and examples thereof include water-soluble inorganic acid salts of titanium such as titanium tetrachloride, titanium sulfate, titanium nitrate, and titanium phosphate. In addition, water-soluble organic acid salts of titanium such as titanium oxalate can be used. Of these various titanium compounds, titanium tetrachloride is preferred because it is particularly excellent in water solubility and no components other than titanium remain in the dispersion of metal-doped titanium oxide.

  When a solution of a tetravalent titanium compound is used, the concentration of the solution is not particularly limited as long as a titanium hydroxide gel can be formed, but a relatively dilute solution is preferable. Specifically, the solution concentration of the tetravalent titanium compound is preferably 5 to 0.01 wt%, and more preferably 0.9 to 0.3 wt%.

As the base to be reacted with the tetravalent titanium compound, various substances can be used as long as they can react with the tetravalent titanium compound to form titanium hydroxide. For example, ammonia, caustic soda, sodium carbonate Examples thereof include caustic potash, and ammonia is preferable.

  When the above base solution is used, the concentration of the solution is not particularly limited as long as a titanium hydroxide gel can be formed, but a relatively dilute solution is preferable. Specifically, the concentration of the base solution is preferably 10 to 0.01 wt%, and more preferably 1.0 to 0.1 wt%. In particular, the concentration of ammonia when ammonia water is used as the base solution is preferably 10 to 0.01 wt%, and more preferably 1.0 to 0.1 wt%.

Metal compound Examples of the compound of copper, manganese, nickel, cobalt, iron, or zinc are as follows.
Ni compound: Ni (OH) ₂ , NiCl ₂
Co compound: Co (OH) NO ₃ , Co (OH) ₂ , CoSO ₄ , CoCl ₂
Cu compound: Cu (OH) ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , CuCl ₂ , Cu (CH ₃ COO) ₂
Mn compound: MnNO ₃ , MnSO ₄ , MnCl ₂
Fe compound: Fe (OH) ₂ , Fe (OH) ₃ , FeCl ₃
Zn compound: Zn (NO ₃ ) ₂ , ZnSO ₄ , ZnCl ₂

  The titanium peroxide concentration (total amount including coexisting copper, manganese, nickel, cobalt, iron or zinc) in the aqueous dispersion obtained by the first to third production methods is preferably 0.05 to 15 wt%, 0.1-5 wt% is more preferable. Moreover, about the compounding quantity of copper, manganese, nickel, cobalt, iron, and zinc, 1: 0.01-1: 0.5 are preferable at the molar ratio of titanium and a metal component, and 1: 0.03-1 : 0.1 is more preferable.

Additives The aqueous dispersion of the metal-doped titanium oxide according to the present invention obtained by the first to third production methods preferably contains an additive such as a leveling agent or a dispersant that facilitates layer formation. .

  Silicone oil is preferable as the leveling agent, and various types can be used. Of these, polyether-modified silicone oil is preferable. Specifically, at the molecular chain terminal or side chain, polyethylene oxide, polypropylene oxide, polybutylene oxide, polyethylene oxide-polypropylene oxide copolymer block, polyethylene oxide-polybutylene oxide copolymer block, polypropylene oxide-polybutylene oxide copolymer An organopolysiloxane having a structure such as a block may be mentioned. Among these, an organopolysiloxane in which a polyethylene oxide, polypropylene oxide, or polyethylene oxide-polypropylene oxide copolymer block is bonded to a silicon atom via an alkylene group is preferable. Such a polyether-modified silicone oil can be produced by a known method, for example, by the method described in JP-A-9-165318. Examples of such polyether-modified silicone oils include TSF4445, TSF4446 (manufactured by GE Toshiba Silicone Co., Ltd.), KF-352, KF-353 (manufactured by Shin-Etsu Chemical Co., Ltd.), and SH3746 (Toray Dow). Corning Silicone Co., Ltd.).

    In addition, it is effective to improve the stability of the aqueous dispersion by blending a mixture of a dispersant mainly composed of an anionic surfactant and sodium tripolyphosphate.

  Moreover, it is also possible to mix | blend the silane compound which has an amino group, an epoxy group, and a methacryloxy group, and what is called a silane coupling agent. This coupling agent makes it possible to improve the hardness of the metal-doped titanium oxide-containing layer and the adhesion with an adjacent layer. In addition, silicone rubber, silicone powder, silicone resin, and the like may be blended.

  The mixing ratio (wt%) of the metal-doped titanium oxide according to the present invention and additives such as leveling agents and dispersants is preferably 1: 0.02 to 1:20, and 1: 0.05 to 1: 10 is more preferable.

  The metal-doped titanium oxide-containing layer in the laminate of the present invention can be produced by applying an aqueous dispersion containing a metal-doped titanium oxide on the water absorption preventing layer and then drying it. The thickness of the metal-doped titanium oxide-containing layer is preferably 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.0 μm. As the coating method, a general-purpose film forming method such as brush coating, roller coating, spray coating or the like can be used.

  In addition, when a metal dope titanium oxide layer contains a silicone oil as a leveling agent, it is preferable that the mixing ratio of a metal dope titanium oxide and a silicone oil will be 1: 0.002-1: 20. 0.05-1: 10 is more preferable. In this case, the thickness of the metal-doped titanium oxide-containing layer is preferably 0.01 to 1.0 μm, and more preferably 0.05 to 0.3 μm.

  Since the metal-doped titanium oxide-containing layer does not have a photocatalytic function, even if it receives light energy such as ultraviolet rays, the constituent materials of adjacent layers, particularly organic substances, are not deteriorated by the photocatalytic function. Moreover, organic resin, such as an acrylic resin, a polyester resin, a polycarbonate resin, can also be mixed with the metal dope titanium oxide containing layer itself as needed.

  In addition, when the metal-doped titanium oxide-containing layer contains silicone oil, particularly polyether-modified silicone oil, the metal-doped titanium oxide-containing layer is deteriorated, color is deteriorated (fading), or the layer surface is made of an organic or inorganic substance. In particular, the effect of suppressing or reducing the contamination is enhanced.

  A photocatalytic function layer can be further provided on the metal-doped titanium oxide layer in the laminate of the present invention.

The photocatalytic functional layer is a layer having a function in which a specific metal compound oxidizes and decomposes organic and / or inorganic compounds on the surface of the layer by photoexcitation. The principle of photocatalyst by photoexcitation specific metal compounds, from the water or oxygen in the air OH ^- or O ₂ ^- radical species is generated in, that the radical species oxidize reductive decomposition of organic and / or inorganic compounds It is generally understood that there is.

  However, since a negative charge is generated instead of a positive charge on the surface of the photocatalytic functional layer, organic and / or inorganic compounds having a positive charge generated by the reaction with the radical species adhere to the surface of the photocatalytic functional layer by electrostatic force. Then, the organic and / or inorganic compound is further decomposed by the radical species, and the decomposed product is removed by an external force such as running water or wind and rain at the stage where the electrostatic force of the decomposed product is reduced by its action.

Examples of the metal compound include typical titanium oxide (TiO ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O _3. , Ta ₂ O ₅ , WO ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO _{2 and the} like are known.

  The photocatalytic functional layer is formed by applying an aqueous dispersion containing fine particles (about 2 nm to 20 nm) of these metal compounds together with various additives as necessary on the metal-doped titanium oxide-containing layer and drying. Can be formed. The thickness of the photocatalytic functional layer is preferably 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.0 μm. For the formation of the photocatalytic functional layer, it is preferable to use an aqueous dispersion, but alcohol can also be used as a solvent.

  The aqueous dispersion for forming a photocatalytic functional layer can be produced, for example, by the following method. Titanium peroxide in the aqueous dispersion can be changed to titanium oxide in a dry film-forming state.

First Production Method Titanium hydroxide is formed by reacting the tetravalent titanium compound described above with a base such as ammonia. Next, this titanium hydroxide is peroxo-oxidized with an oxidizing agent such as hydrogen peroxide to form amorphous fine titanium peroxide particles. Further, it is transferred to anatase type titanium peroxide by heat treatment.

Second Production Method The tetravalent titanium compound described above is peroxoated with an oxidizing agent such as hydrogen peroxide and then reacted with a base such as ammonia to form ultrafine particles of amorphous titanium peroxide. Further, it is transferred to anatase type titanium peroxide by heat treatment.

Third production method The tetravalent titanium compound described above is reacted with an oxidizing agent such as hydrogen peroxide and a base such as ammonia to simultaneously form titanium hydroxide and peroxo to produce amorphous peroxidation of ultrafine particles. Titanium is formed. Further, it is transferred to anatase type titanium peroxide by heat treatment.

  Metals (Ag, Pt) that improve the photocatalytic performance may be added to the photocatalytic functional layer. In order to reduce the electrostatic adhesion of organic and / or inorganic compounds to the surface, various substances such as metal salts can be added in a range that does not deactivate the photocatalytic function. Examples of the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, and zinc. In addition, hydroxides or oxides can be used for some metals or nonmetals. Specifically, aluminum chloride, stannous chloride and stannic chloride, chromium chloride, nickel chloride, ferrous chloride and ferric chloride, ferrous and ferric chloride, silver nitrate, cesium chloride, indium trichloride, ferrous chloride Various metals such as cerium, selenium tetrachloride, cupric chloride, manganese chloride, calcium chloride, platinum chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, gold chloride, zirconium oxychloride, zinc chloride A salt can be illustrated. Examples of compounds other than metal salts include indium hydroxide, silicotungstic acid, silica sol, and calcium hydroxide. In addition, in order to improve the sticking property of a photocatalyst functional layer, it is also possible to mix | blend amorphous type titanium oxide.

  Since the contaminants on the surface of the laminate of the present invention are decomposed by the action of the photocatalytic functional layer, contamination of the laminate surface can be prevented and the appearance of the laminate can be maintained well over time. If the photocatalytic functional layer is formed directly on the substrate, the photocatalytic functional layer may be peeled off from the substrate over time, but the photocatalytic functional layer is integrated well with the substrate by interposing a metal-doped titanium oxide-containing layer. Can be

  Further, when the photocatalytic functional layer is formed directly on the water absorption preventing layer, a silicon-containing compound or the like that is a water absorption preventing agent deteriorates due to the oxidative decomposition action of the photocatalytic functional layer. Since the metal-doped titanium oxide-containing layer having no photocatalytic function is interposed between the photocatalytic function layer, the water absorption preventing layer does not deteriorate.

  The laminate of the present invention can be used in various fields where various design properties and high waterproofness and contamination resistance are required, such as glass, metal, ceramics, concrete, wood, stone, sealing agent, etc. It is suitably used for the production of artifacts used outdoors such as building materials, air-conditioning outdoor units, kitchen equipment, sanitary equipment, lighting equipment, automobiles, bicycles, motorcycles, airplanes, trains, and ships. In particular, the laminate of the present invention is suitable as a building material, and a building constructed using the building material, a building such as a building, and a civil engineering work such as a road and a tunnel have a high waterproofing effect and contamination over time. The antifouling effect can be demonstrated.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to an Example.

Reference Example 1-1
A mixture of 100 parts by weight of red-brown bengara fine powder (average particle size 100 μm) and 5 parts by weight of water as an inorganic pigment, and 10 of dry seal S (silicone water absorption inhibitor manufactured by Toray Dow Corning Silicone Co., Ltd.) The double water diluted solution was mixed and stirred at a weight ratio of 1:10 to obtain a water absorption preventing coloring solution.

Reference Example 1-2
A mixture of 100 parts by weight of Pollux White (PC-CRH: manufactured by Sumika Color Co., Ltd.) as an inorganic pigment and 5 parts by weight of Pollux binder (PM-FD: manufactured by Sumika Color Co., Ltd.) as a binder, and dry seal A 10-fold water dilution of S (silicone water absorption inhibitor manufactured by Toray Dow Corning Silicone Co., Ltd.) was mixed and stirred at a weight ratio of 1:10 to obtain a water absorption preventing coloring solution.

Reference Example 1-3
A mixture of 100 parts by weight of Pollux Royal Blue (PM-R1: Sumika Color Co., Ltd.) as an organic pigment and 5 parts by weight of Pollux binder (PM-FD: Sumika Color Co., Ltd.) as a binder, and dry seal A 10-fold water dilution of S (silicone water absorption inhibitor manufactured by Toray Dow Corning Silicone Co., Ltd.) was mixed and stirred at a weight ratio of 1:10 to obtain a water absorption preventing coloring solution.

Reference Example 1-4
Dry seal S, a mixture of 100 parts by weight of Pollux Yellow (PC-LD: manufactured by Sumika Color Co., Ltd.) as an organic pigment and 5 parts by weight of Pollux binder (PM-FD: manufactured by Sumika Color Co., Ltd.) as a binder A 10-fold water dilution of Toray Dow Corning Silicone Co., Ltd. (silicone water absorption inhibitor) was mixed and stirred at a weight ratio of 1:10 to obtain a water absorption preventing coloring solution.

Reference Example 2-1
To a solution in which 0.463 g of 97% CuCl ₂ · 2H ₂ O (cupric chloride: manufactured by Nippon Chemical Industry Co., Ltd.) is completely dissolved in 500 ml of pure water, a 50% titanium tetrachloride solution (manufactured by Sumitomo Sitix Corporation) is further added. 10 g was added, pure water was added, and the total volume was 1000 ml.

  A mixture of copper hydroxide and titanium hydroxide was precipitated by dropwise addition of dilute ammonia water obtained by diluting 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) 10 times into this solution to pH 7.0.

  This precipitate was washed with pure water until the conductivity of the supernatant liquid became 0.8 mS / m or less, and the washing was terminated when the conductivity became 0.80 mS / m. Thereby, 340 g of a hydroxide-containing liquid having a concentration of 0.81 wt% was produced.

  Next, 25 g of 35% aqueous hydrogen peroxide (manufactured by Taiki Pharmaceutical Co., Ltd.) was added while cooling the hydroxide-containing liquid to 1 to 5 ° C., and the mixture was stirred for 16 hours. As a result, 365 g of a transparent green 0.90 wt% copper-doped amorphous titanium peroxide dispersion was obtained. This was diluted with pure water to prepare 385 g of a 0.85 wt% copper-doped amorphous titanium peroxide dispersion.

Reference Example 3-1
An anatase type titanium peroxide aqueous dispersion (B56 manufactured by Sustainable Technology Co., Ltd.) was used as a photocatalyst function-imparting liquid.

Example 1
The water-absorptive coloring liquid of Reference Example 1-1 was applied twice to a commercially available plexcast concrete substrate (width 300 mm, length 300 mm, thickness 30 mm) with a paint brush and dried well at room temperature.

Next, the copper-doped amorphous titanium peroxide dispersion of Reference Example 2-1 was applied on it with an air pressure of 2 kg / m ² in an amount of 10 g / m ² using a spray gun for coating, and dried at room temperature. It was.

Furthermore, the photocatalyst function-providing liquid of Reference Example 3-1 was applied in an amount of 30 g / m ^{2 in} the same manner as in Reference Example 2-1, and dried at room temperature to obtain an evaluation substrate.

Example 2
An evaluation substrate was obtained by the same method as in Example 1 except that Reference Example 1-2 was used instead of Reference Example 1-1.

Example 3
An evaluation substrate was obtained by the same method as in Example 1 except that Reference Example 1-3 was used instead of Reference Example 1-1.

Example 4
An evaluation substrate was obtained by the same method as in Example 1 except that Reference Example 1-4 was used instead of Reference Example 1-1.

Comparative Examples 1-4
Of Examples 1 to 4, only the water-absorptive coloring liquid was applied and dried, and the copper-doped amorphous titanium peroxide dispersion and the photocatalyst function-imparting liquid were not used.

Comparative Example 5
The copper-doped amorphous titanium peroxide dispersion prepared in Reference Example 2-1 was applied to the same substrate as in Example 1 using a coating spray gun at an air pressure of 2 kg / m ² and an amount of 10 g / m ^2. It dried and it was set as the comparative example 5.

Evaluation 1
The evaluation substrates of Examples 1 to 4 and Comparative Examples 1 to 5 were exposed outdoors from mid-May to early October in Chiba and Saga Prefectures, and the contamination status of the evaluation substrate was visually evaluated. did. The results are shown in Table 1.

Reference Example 1-5
Only the dry seal S was used as a transparent water absorption preventing liquid.

Reference Example 1-6
A mixture of 9.5 g of Brown PC-RB (manufactured by Sumika Color Co., Ltd.) as a coloring pigment and 0.5 g of Polysol AP-3720 (manufactured by Showa Polymer Co., Ltd.) as a pigment fixing auxiliary agent 40 g of the double water diluted solution was mixed and stirred to obtain a water absorption preventing coloring solution.

Reference Example 2-3
Polyether-modified silicone oil SH3746 (manufactured by Toray Dow Corning Silicone Co., Ltd.) 0.4 wt% was added to 0.85 wt% of the copper-doped amorphous titanium peroxide dispersion prepared in Reference Example 2-1, and mixed and stirred. A copper-doped amorphous titanium peroxide-polyether-modified silicone mixed dispersion was obtained.

Example 5
The water absorption preventing liquid of Reference Example 1-5 was applied twice to a commercially available plexicast concrete substrate (width 300 mm, length 300 mm, thickness 30 mm) with a coating brush and dried well at room temperature.

  Next, the copper-doped amorphous titanium peroxide-polyether-modified silicone mixed dispersion of Reference Example 2-3 was applied twice with a coating brush and dried well at room temperature to obtain an evaluation substrate.

Example 6
An evaluation substrate was obtained in the same manner as in Example 5 except that the water absorption preventing coloring liquid of Reference Example 1-6 was used instead of Reference Example 1-5.

Example 7
The photocatalyst function-imparting liquid of Reference Example 3-1 was applied three times with a coating brush on the evaluation substrate of Example 5 and dried at room temperature.

Example 8
The photocatalyst function-imparting solution of Reference Example 3-1 was applied three times with a coating brush on the evaluation substrate of Example 6 and dried at room temperature.

Comparative Example 6
An evaluation substrate was obtained by the same method as in Example 5 except that the copper-doped amorphous type titanium peroxide-polyether-modified silicone mixed dispersion of Reference Example 2-3 was not used.

Comparative Example 7
An evaluation substrate was obtained by the same method as in Example 6 except that the copper-doped amorphous type titanium peroxide-polyether-modified silicone mixed dispersion in Reference Example 2-3 was not used.

Evaluation 2
The evaluation substrates of Examples 5 to 8 and Comparative Examples 6 to 7 were exposed outdoors in Saga Prefecture from October 2003 to late January 2004, and the evaluation of contamination of the evaluation substrate with the naked eye, the following tape (Registered trademark) Adhesiveness evaluation by peel test, hydrophilicity evaluation by the naked eye, and water absorption evaluation by the naked eye were performed. Absorption evaluation evaluated the water absorption state of the cross section visually by cutting a part of the evaluation board after spraying tap water on the surface of each evaluation board. The results are shown in Table 2.

* Sellotape (registered trademark) peel test method Commercially available sellotape (registered trademark) is applied to the evaluation substrate surface in a grid pattern so that an opening of 10 mm square can be formed, and peeled at the same time. It was visually evaluated whether or not a doped titanium oxide film was adhered.

  In the laminate of the present invention, the water absorption preventing layer containing a silicon-containing compound can be arbitrarily colored to give a free design while taking advantage of the texture of the substrate itself.

  Moreover, contamination of the laminate surface can be prevented by the unique contamination prevention function exhibited by the metal-doped titanium oxide-containing layer itself. And the said antifouling effect can be further improved by mix | blending a silicone oil, especially polyether modified silicone oil with the said metal dope titanium oxide content layer. In addition, since the said metal dope titanium oxide content layer does not have a photocatalytic function, it does not oxidatively decompose the water absorption prevention layer containing a silicon containing compound.

  Therefore, the laminate of the present invention can provide an arbitrary design while maintaining good waterproofness and stain resistance with time, and is particularly suitable as a building material for outdoor buildings.

Furthermore, in the laminate of the present invention in which a photocatalytic functional layer is formed on the metal-doped titanium oxide-containing layer, the water absorption preventing layer is not oxidized and degraded by the action of the photocatalytic functional layer, and the photocatalytic functional layer Is not hydrolyzed. Thus, the laminate can provide any design while maintaining good waterproof and stain resistance over time, for example, houses (including exterior walls, bathrooms, kitchens, toilets), buildings It is preferably used as a building material for outdoor buildings such as waterways, dams, roads, tunnels, bridges, airports, and harbor facilities.

Claims (10)

A substrate having pores on the surface;
On the colorless and transparent or colored transparent, translucent or opaque water-absorbing prevention layer containing a silicon-containing compound and a water-absorbing prevention layer containing the silicon-containing compound formed on the substrate having pores on the surface formed, with copper, manganese, nickel, cobalt, and including metal-doped titanium oxide layer containing an amorphous type titanium oxide at least one doped metal element selected from the group consisting of iron and zinc laminate body.   The laminate according to claim 1, wherein the water absorption preventing layer containing the silicon-containing compound comprises a water absorption preventing agent containing a silicon-containing compound and water.   The laminate according to claim 2, wherein the silicon-containing compound is hydrolyzable silane, and the water absorption inhibitor further contains a surfactant. The laminate according to any one of claims 1 to 3 , wherein the metal-doped titanium oxide-containing layer further contains silicone oil. The laminate according to claim 4 , wherein the silicone oil is a polyether-modified silicone oil. Wherein the photocatalytic functional layer is formed on the metal-doped titanium oxide-containing layer, the laminate according to any one of claims 1 to 5. The laminate according to claim 6 , wherein the photocatalytic functional layer is made of a film containing anatase-type titanium oxide. A building comprising the laminate according to any one of claims 1 to 7 . A building material comprising the laminate according to any one of claims 1 to 7 . A method for producing a laminate,
Forming a water-absorbing prevention layer containing a silicon-containing compound on a substrate having pores on the surface thereof, which is colorless and transparent, or colored, transparent, translucent or opaque; and
The water absorption preventing layer comprising a silicon-containing compound, copper, manganese, nickel, cobalt, at least one including metal-doped titanium oxide amorphous-type titanium oxide which is doped with metal elements selected from the group consisting of iron and zinc A manufacturing method comprising a step of forming a material-containing layer.

Images