Laminate and method for production thereof

The present application claims priority over Japanese Patent Application No. 2004-87345 filed on March 24, 2004, the contents of which are incorporated herein by reference.

The present invention relates to a laminated body having waterproof and stain resistant properties, and also relates to a method for producing the laminated body.

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

Further, in a concrete building material containing a reinforcing bar or a steel frame, since the concrete is porous, the reinforcing bar or the steel frame may be rusted due to the permeation of rainwater, and the concrete may be damaged due to an increase in the volume of the reinforcing bar or the steel frame due to the rust. There is also the problem of neutralization of concrete due to acidic substances in rainwater. In addition, marble building materials have CO in rainwater.₂There is also the problem of deterioration due to.

Therefore, in outdoor building materials, conventionally, a water-repellent substance such as a silicone compound and a fungicide or an antibacterial agent are previously applied to the surface of the building material to prevent moisture from entering the building material and to prevent moisture from entering the building material surface. It is being carried out to reduce the adhesion of pollutants and the growth of moss and mold in the area.

On the other hand, recently, as a simple method for preventing contamination of the surface of a building material, a photocatalyst layer is formed on the surface of the building material. For example, Japanese Patent Application 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. Further, Japanese Patent Application Laid-Open No. 2002-138243 proposes a method of forming a photocatalyst layer on a primer layer containing an acrylic resin having an alkoxysilyl group and a hydroxyl group.

Furthermore, in International Publication No. 2004/041723, 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 photooxidation function of the metal-doped titanium oxide layer makes it applicable. It has been proposed to prevent surface contamination.<patcit num="1"><text>Japanese Unexamined Patent Publication No. 2000-135442</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 2002-138243</text></patcit><patcit num="3"><text>International Publication No. 2004/041723 Pamphlet</text></patcit>

<p> By the way, in recent years, in order to improve the appearance while making the best use of the texture of the building material itself, it is required to color the surface of the building material to an arbitrary color in addition to waterproofing and preventing contamination of the surface of the building material.</p><p> However, it is difficult to color the alkali metal silicate compound by the method described in JP-A-2000-135442. Furthermore, the photocatalytic layer may be hydrolyzed by the action of the alkali metal silicate compound.</p><p> Further, although the acrylic resin layer can be colored by the method described in JP-A-2002-138243, there is a problem that the acrylic resin layer is oxidatively decomposed and deteriorated by the action of the photocatalyst layer.</p><p> The present invention is for solving 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 an antifouling function, and a building material and a building provided with the laminate.</p>

<p> An object of the present invention is Hypokeimenon with pores on the surface, A colorless transparent or colored transparent, translucent or opaque, water absorption prevention layer containing a silicon-containing compound formed on the substrate, and A metal-doped titanium oxide-containing layer formed on the water-absorbing prevention layer and containing a titanium oxide doped with at least one of a metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron and zinc. Achieved by a laminate with.</p><p> The laminate of the present invention is preferable as a building material, and particularly preferably as a decorative material. Therefore, the laminate of the present invention can be suitably used for buildings.</p><p> The metal-doped titanium oxide-containing layer is preferably made of amorphous titanium oxide. Further, the metal-doped titanium oxide-containing layer preferably further contains a silicone oil, particularly a polyether-modified silicone oil.</p><p> A photocatalyst functional layer may be formed on the metal-doped titanium oxide-containing layer. The photocatalyst functional layer is preferably made of anatase-type titanium oxide.</p><p> The water absorption prevention layer containing the silicon-containing compound is preferably made of a water absorption prevention agent composed of the silicon-containing compound and water. </p><p> The laminate of the present invention A step of forming a colorless transparent or colored transparent, translucent or opaque water absorption prevention layer containing a silicon-containing compound on a substrate having pores on the surface, and Step of forming the metal-doped titanium oxide-containing layer on the water absorption prevention layer Can be manufactured via.</p>

<figref num="1">The figure which shows the outline of an example of the 1st manufacturing method of metal-doped titanium oxide.</figref>

The substrate constituting the laminate of the present invention is an inorganic or organic substrate having pores on its surface. The substrate having pores on the surface includes, in addition to the porous substrate, a substrate having a porous coating layer on the surface of the substrate, and a substrate having pore-like defects on the surface. Since such a substrate has a rough surface and a relatively high water absorption rate, rainwater tends to infiltrate into the substrate together with dirt such as pollutants and dust in the air, or stay on the surface of the substrate.

Examples of the inorganic substrate having pores on the surface include a substrate made of a substance such as concrete, mortar, clay, and stone, and a metal substrate having a porous film such as a metal oxide or ceramic formed on the surface. Be done. More specifically, concrete PC boards, concrete members with exposed surfaces, ALC boards, mortar members with finished surfaces, bricks, tiles, especially ceramic tiles, tiles, marble, granite, ceramic coated metal plates are exemplified. To.

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

In the laminate of the present invention, a water absorption prevention layer containing a silicon-containing compound is present on a substrate having pores on its surface. The water absorption prevention layer containing the silicon-containing compound has a function of preventing the infiltration of water into the substrate, and is particularly preferably composed of a water absorption prevention agent composed of the 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 the water absorption prevention layer, it is possible to effectively prevent the infiltration of water into the substrate.

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

As the hydrolyzable silane, various alkoxysilanes can be used. Specific examples thereof include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane. Of these, one type of hydrolyzable silane may be used alone, or two or more types of hydrolyzable silane may be mixed and used as required. Further, these hydrolyzable silanes may be mixed with the hydrolyzate and various organopolysiloxanes.

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

As such a silane-based water absorption inhibitor, the compositions disclosed in JP-A-62-197369 and JP-A-6-313167 can be preferably used. Further, such a silane-based 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 alkyl silicate include an aqueous solution of sodium methyl silicate and an aqueous solution of potassium methyl silicate. Examples of such an aqueous solution of an alkali metal salt of alkyl silicate include Dry Seal C and Dry Seal E (manufactured by Toray Dow Corning Silicone Co., Ltd.).

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

Examples of the inorganic pigment include carbon black, graphite, yellow lead, iron oxide yellow, lead tan, red iron oxide, ultramarine blue, chromium oxide green, iron oxide and the like. As the organic pigment, azo-based organic pigment, phthalocyanine-based organic pigment, slene-based organic pigment, quinocridone-based organic pigment, dioxazine-based organic pigment, isoindolinone-based organic pigment, diketopyrrolopyrrole and various metal complexes can be used. Those with excellent light resistance are desirable. Examples of the light-resistant organic pigment include Hansa ello, which is an insoluble azo organic pigment, toluidin red, phthalocyanine blue B, which is a phthalocyanine organic pigment, phthalocyanine green, and quinacridone red, which is a quinacridone organic pigment. Be done.

Examples of the dye include basic dyes, direct dyes, acidic dyes, vegetable dyes, etc., and those having excellent light resistance are preferable. For example, in red, direct scarlet, roxelin, azorbin, and in orange, direct orange R Chrysophenin NS and Metanil Yellow for conch, acid orange and yellow, direct brown KGG and acid brown R for brown, direct blue B for blue, direct black GX and nigrocin BHL for black are particularly preferable.

When the water absorption prevention layer containing the silicon-containing compound is composed of the water absorption inhibitor composed of the silicon-containing compound and water, the mixing ratio (weight ratio) of the water absorption inhibitor composed of the silicon-containing compound and water and the pigment is 1: 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 prevention layer containing the silicon-containing compound. These additives have an action of facilitating the formation of a water absorption prevention layer. Further, when a colorant such as a pigment or a dye is blended, it is also possible to add a binder for assisting the fixing of the colorant. As the binder in this case, a binder for various paints containing an acrylic acid ester or an acrylic acid ester copolymer resin having excellent weather resistance as a main component can be used. For example, Polysol AP-3720 (Showa High Polymer Co., Ltd.) ), Polysol AP-609 (manufactured by Showa High Polymer Co., Ltd.) and the like.

The water absorption prevention layer containing the silicon-containing compound can be formed, for example, as follows. A water absorption inhibitor composed of a silicon-containing compound and water, and a solution containing the colorant, the additive, and the binder, if necessary, are allowed to penetrate into the surface layer of the substrate to a depth of about 2 to 5 mm. Apply. If necessary, it is heated to evaporate the solvent to form a water absorption prevention layer containing a silicon-containing compound on the substrate. The water absorption prevention layer containing the silicon-containing compound can impart water absorption prevention property and coloring property to the substrate by integrating with the substrate.

The thickness of the water absorption prevention layer containing the silicon-containing compound formed as described above is not particularly limited, but is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.3 μm. When a colorant, an additive, or a binder is added, 1.0 μm to 100 μm is preferable, and 10 μm to 50 μm is more preferable.

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

In the laminate of the present invention, a titanium oxide doped with at least one of a metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron and zinc is provided on the water absorption prevention layer containing the silicon-containing compound. There is a metal-doped titanium oxide-containing layer containing. What is Titanium Oxide?₂, TiO₃, TiO, TiO₃/ nH₂It contains various oxides such as O and peroxides, 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 properties are fine particles or powder. The titanium oxide having a peroxo group may be an amorphous type, an anatase type, a brookite type, a 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 oxide have a photocatalytic function, but when copper, manganese, nickel, cobalt, iron or zinc are combined at a certain concentration or higher, 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-type titanium oxide over time by heating with sunlight, etc., but as described above, when combined with copper, manganese, nickel, cobalt, iron or zinc, anatase-type titanium oxide is converted. After all, the metal-doped titanium oxide does not exhibit photocatalytic function over time because it loses its photocatalytic function.

On the other hand, the metal-doped titanium oxide exhibits a unique non-photocatalytic pollution-preventing effect. As a result, deterioration / contamination of the surface of the metal-doped titanium oxide-containing layer is prevented or reduced. The mechanism of action is unknown, but it is thought to be due to a complex action based on the photooxidation reaction caused by short-wavelength electromagnetic waves such as ultraviolet rays (sunlight).

The photooxidation reaction here refers to hydroxyl radicals ( OH) from oxygen and / or moisture in the air or organic matter by short-wavelength electromagnetic waves.¹O₂It is a concept that includes the generation of active oxygen such as (single term oxygen), which reacts with organic substances and / or inorganic substances adhering to the layer surface, and by the reaction. It is believed that positive charges are generated in organic and / or inorganic substances.

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 like the organic substance and / or the 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 external forces such as running water and wind and rain. Is removed from the surface of the metal-doped titanium oxide layer. It is considered that this makes it possible to suppress or reduce contamination on the surface of the metal-doped titanium oxide layer.

As a method for producing the metal-doped titanium oxide according to the present invention, a production method based on the hydrochloric acid method or the sulfuric acid method, which is a general method for producing titanium dioxide powder, may be adopted, or various liquid-dispersed titanias may be produced. A method for producing a solution may be adopted. Then, the metal can be composited with titanium oxide regardless of the production 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 manufacturing method First, a compound of tetravalent titanium such as titanium tetrachloride is reacted with a base such as ammonia to form titanium hydroxide. Next, this titanium hydroxide is peroxozized 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. At least one of copper, manganese, nickel, cobalt, iron, zinc or a compound thereof is mixed in any of the above steps.

The oxidizing agent for peroxolation is not particularly limited, and various types of peroxoized titanium, that is, those capable of forming titanium peroxide can be used, but hydrogen peroxide is preferable. When a hydrogen peroxide solution is used as the oxidizing agent, the concentration of hydrogen peroxide is not particularly limited, but 30 to 40% is preferable. It is preferable to cool the titanium hydroxide before peroxoification. 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 solution of titanium tetrachloride and water of ammonia are mixed in the presence of at least one compound of copper, manganese, nickel, cobalt, iron and zinc, and the hydroxide of the metal and water of titanium are mixed. It produces a mixture of oxides. 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 peroxozylated with hydrogen peroxide solution. Thereby, a metal-doped aqueous dispersion containing titanium oxide fine particles having an amorphous peroxo group, that is, an aqueous dispersion containing the metal-doped titanium oxide according to the present invention can be produced. ..

Second manufacturing method A compound of tetravalent titanium such as titanium tetrachloride is peroxozized with an oxidizing agent, and this is reacted with a base such as ammonia 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 optionally heating and embedding. At least one of copper, manganese, nickel, cobalt, iron, zinc or a compound thereof is mixed in any of the above steps.

Third manufacturing method A compound of tetravalent titanium such as titanium tetrachloride is reacted at the same time as an oxidizing agent and a base to form titanium hydroxide and peroxoization thereof at the same time 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 optionally heating and embedding. At least one of copper, manganese, nickel, cobalt, iron, zinc or a compound thereof is mixed in any of the above steps.

Needless to say, in the first to third production methods, a mixture of amorphous titanium peroxide and anatase-type titanium peroxide obtained by heating the amorphous titanium peroxide can be used as the metal-doped titanium oxide of the present invention.

Manufacturing method by sol-gel method A solvent such as water or alcohol, an acid or a base catalyst is mixed and stirred with the titanium alkoxide to hydrolyze the titanium alkoxide to produce a sol solution of ultrafine titanium oxide. Before or after this 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 above titanium alkoxide, the general formula: Ti (OR ́)₄(However, R ́ is an alkyl group), or a compound in which one or two alkoxide groups (OR ́) in the above general formula are substituted with a carboxyl group or a β-dicarbonyl group, or those. Is preferred.

As a specific example of the above titanium alkoxide, Ti (O-isoC)₃H₇)₄, Ti (O-nC₄H₉)₄, Ti (O-CH₂CH (C₂H₅) C₄H₉)₄, Ti (OC₁₇H₃₅)₄, Ti (O-isoC₃H₇)₂[CO (CH)₃) CHCOCH₃]₂, Ti (O-nC₄H₉)₂[OC₂H₄N (C₂H₄OH)₂]₂, Ti (OH)₂[OCH (CH)₃) COOH]₂, Ti (OCH₂CH (C₂H₅) CH (OH) C₃H₇)₄, Ti (O-nC₄H₉)₂(OCOC₁₇H₃₅) Etc. can be mentioned.

Compound of tetravalent titanium The tetravalent titanium compound used in the production of the metal-doped titanium oxide according to the present invention includes orthotitanium acid (H) when reacted with a base.₄TiO₄), Various titanium compounds can be used as long as they can form titanium hydroxide, and examples thereof include water-soluble inorganic acid salts of titanium such as titanium tetrachloride, titanium sulfate, titanium nitrate, and titanium phosphate. In addition, a water-soluble organic acid salt of titanium such as titanium oxalate can also be used. Among these various titanium compounds, titanium tetrachloride is preferable because it is particularly excellent in water solubility and components other than titanium do not remain in the dispersion liquid of the 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%, more preferably 0.9 to 0.3 wt%.

base As the base to be reacted with the above-mentioned tetravalent titanium compound, various bases can be used as long as they can react with the tetravalent titanium compound to form titanium hydroxide, such as ammonia, caustic soda, sodium carbonate, and the like. Caustic potash and the like can be exemplified, but ammonia is preferable.

When the above-mentioned 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%, more preferably 1.0 to 0.1 wt%. In particular, when aqueous ammonia is used as the base solution, the concentration of ammonia is preferably 10 to 0.01 wt%, more preferably 1.0 to 0.1 wt%.

Metal compound Examples of the compounds of copper, manganese, nickel, cobalt, iron or zinc include the following. Ni compound: Ni (OH)₂, NiCl₂ Co compound: Co (OH) NO₃, Co (OH)₂, CoSO₄, CoCl₂ Cu compound: Cu (OH)₂, Cu (NO)₃)₂, CuSO₄, CuCl₂, Cu (CH)₃COO)₂ Mn compound: MnNO₃, MnSO₄, MnCl₂ Fe compound: Fe (OH)₂, Fe (OH)₃, FeCl₃ Zn compound: Zn (NO)₃)₂, ZnSO₄, ZnCl₂

The concentration of titanium peroxide (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%, preferably 0.1 to 0.1 to 5 wt% is more preferred. Regarding the blending amount of copper, manganese, nickel, cobalt, iron, and zinc, the molar ratio of titanium to the metal component is preferably 1: 0.01 to 1: 0.5, more preferably 1: 0.03 to 1: 0.1.

Additive It is preferable to add an additive such as a leveling agent or a dispersant that facilitates layer formation to the aqueous dispersion of the metal-doped titanium oxide according to the present invention obtained by the first to third production methods.

As the leveling agent, silicone oil is preferable, and various kinds can be used. Of these, polyether-modified silicone oil is preferable. Specifically, polyethylene oxide, polypropylene oxide, polybutylene oxide, polyethylene oxide-polypropylene oxide copolymer block, polyethylene oxide-polybutylene oxide copolymer block, polypropylene oxide-polybutylene oxide copolymerization at the end or side chain of the molecular chain. Examples thereof include an organopolysiloxane having a structure such as a block. Among them, an organopolysiloxane in which a polyethylene oxide, a polypropylene oxide or a 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, and for example, it can be produced by the method described in JP-A-9-165318. Examples of such polyether-modified silicone oils include TSF4445, TSF4446 (above, manufactured by GE Toshiba Silicone Co., Ltd.), KF-352, KF-353 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), SH3746 (Toray Dow). (Made by Corning Silicone Co., Ltd.).

Further, blending a dispersant containing an anionic surfactant as a main component and a mixture of sodium tripolyphosphate is effective in improving the stability of the aqueous dispersion.

It is also possible to blend a silane compound having an amino group, an epoxy group and a methacryloxy group, a so-called silane coupling agent. This coupling agent makes it possible to improve the hardness of the metal-doped titanium oxide-containing layer and the adhesion to the 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 to additives such as leveling agents and dispersants is preferably 1: 0.02 to 1:20, more preferably 1: 0.05 to 1:10. ..

The metal-doped titanium oxide-containing layer in the laminate of the present invention can be produced by applying an aqueous dispersion containing the metal-doped titanium oxide on the water absorption prevention layer and then drying the layer. 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, or spray coating can be used.

When the metal-doped titanium oxide layer contains silicone oil as a leveling agent, the mixing ratio of the metal-doped titanium oxide and the silicone oil is preferably 1: 0.002 to 1:20, preferably 1: 0.05 to. 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, more preferably 0.05 to 0.3 μm.

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

When the metal-doped titanium oxide-containing layer contains silicone oil, particularly a polyether-modified silicone oil, the metal-doped titanium oxide-containing layer is deteriorated, color deteriorated (faded), or the surface of the layer is caused by an organic substance or an inorganic substance. The effect of suppressing or reducing the contamination of silicon is particularly enhanced.

A photocatalytic functional 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 of oxidatively decomposing an organic and / or inorganic compound on the surface of a specific metal compound by photoexcitation. The principle of photocatalyst is that a specific metal compound is photoexcited to OH from water or oxygen in the air.^-And O₂^-It is generally understood that the radical species of the above are generated and that the radical species redox-decompose organic and / or inorganic compounds.

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

Typical metal compounds include titanium oxide (TiO).₂), ZnO, SrTiOP₃, CdS, CdO, CaP, InP, In₂O₃, CaAs, BaTiO₃, K₂NbO₃, Fe₂O₃, Ta₂O₅, WO₃, NiO, Cu₂O, SiC, SiO₂, MoS₃, InSb, RuO₂, CeO₂Etc. are known.

The photocatalyst 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 the photocatalyst functional layer. Can be formed. The thickness of the photocatalyst functional layer is preferably 0.01 μm to 2.0 μm, more preferably 0.1 μm to 1.0 μm. An aqueous dispersion is preferably used for forming the photocatalytic functional layer, but alcohol can also be used as a solvent.

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

First manufacturing method Titanium hydroxide is formed by reacting the above-mentioned tetravalent titanium compound with a base such as ammonia. Next, this titanium hydroxide is peroxozized with an oxidizing agent such as hydrogen peroxide to form ultrafine particles of amorphous titanium peroxide. Further heat treatment is performed to transfer to anatase-type titanium peroxide.

Second manufacturing method The above-mentioned tetravalent titanium compound is peroxozized 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 heat treatment is performed to transfer to anatase-type titanium peroxide.

Third manufacturing method The above-mentioned tetravalent titanium compound is reacted with an oxidizing agent such as hydrogen peroxide and a base such as ammonia to form titanium hydroxide and peroxoization at the same time to form ultrafine particles of amorphous titanium peroxide. Further heat treatment is performed to transfer to anatase-type titanium peroxide.

Metals (Ag, Pt) that improve photocatalytic performance may be added to the photocatalytic functional layer. Further, in order to reduce electrostatic adhesion of organic and / or inorganic compounds to the surface, various substances such as metal salts can be added to the extent that the photocatalytic function is not deactivated. 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 non-metals. Specifically, aluminum chloride, first and second tin chloride, chromium chloride, nickel chloride, first and second antimony chloride, first and second iron chloride, silver nitrate, cesium chloride, indium trichloride, first 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, etc. Salt can be exemplified. Examples of the compound other than the metal salt include indium hydroxide, silicotungstic acid, silica sol, calcium hydroxide and the like. It is also possible to add amorphous titanium oxide in order to improve the adhesiveness of the photocatalyst functional layer.

Since the pollutants on the surface of the laminate of the present invention are decomposed by the action of the photocatalytic functional layer, it is possible to prevent contamination of the surface of the laminate and maintain a good appearance of the laminate over time. If the photocatalyst functional layer is directly formed on the substrate, the photocatalyst functional layer may be peeled off from the substrate over time. However, by interposing a metal-doped titanium oxide-containing layer, the photocatalyst functional layer is well integrated with the substrate. Can be transformed into.

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

The laminate of the present invention can be used in any field where various designs, high waterproofness and stain resistance are required, and glass, metal, ceramics, concrete, wood, stone, sealant, etc. or these. It is suitable for manufacturing artificial objects used outdoors such as building materials; air-conditioning outdoor units; kitchen equipment; sanitary equipment; lighting equipment; automobiles; bicycles; motorcycles; aircraft; trains; ships and the like. In particular, the laminate of the present invention is suitable as a building material, and buildings such as houses and buildings constructed using the building material, and civil engineering works such as roads and tunnels have a high waterproof effect and contamination over time. It can exert a preventive stain effect.

Hereinafter, the present invention will be illustrated in more detail by way of examples, but the present invention is not limited to the examples.

Reference example 1-1 Mixture of 100 parts by weight of reddish brown red-brown red powder (average grain diameter 100 μm) and 5 parts by weight of water as an inorganic pigment, and 10 of Dryseal S (silicone-based water absorption inhibitor manufactured by Toray Dow Corning Silicone Co., Ltd.) The diluted solution of double water was mixed and stirred at a weight ratio of 1:10 to obtain a water absorption prevention coloring solution.

Reference example 1-2 A mixture of 100 parts by weight of Polx White (PC-CRH: manufactured by Sumika Color Co., Ltd.) as an inorganic pigment and 5 parts by weight of Polx Binder (PM-FD: manufactured by Sumika Color Co., Ltd.) as a binder, and a dry seal. A 10-fold water-diluted solution of S (silicone-based 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 Polx Royal Blue (PM-R1: manufactured by Sumika Color Co., Ltd.) as an organic pigment and 5 parts by weight of Polx Binder (PM-FD: manufactured by Sumika Color Co., Ltd.) as a binder, and a dry seal. A 10-fold water-diluted solution of S (silicone-based 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 A mixture of 100 parts by weight of Polx Yellow (PC-LD: manufactured by Sumika Color Co., Ltd.) as an organic pigment and 5 parts by weight of Polx Binder (PM-FD: manufactured by Sumika Color Co., Ltd.) as a binder, and Dry Seal S A 10-fold water-diluted solution of (silicone-based 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 2-1 97% CuCl in 500 ml of pure water₂ 2H₂Add 10 g of 50% titanium tetrachloride solution (manufactured by Sumitomo Citix Co., Ltd.) to a solution in which 0.463 g of O (copper chloride: manufactured by Nippon Kagaku Sangyo Co., Ltd.) is completely dissolved, and add pure water to add total volume. Was 1000 ml.

A mixture of copper hydroxide and titanium hydroxide was precipitated by dropping dilute ammonia water diluted 10-fold with 25% aqueous ammonia (manufactured by Takasugi Pharmaceutical Co., Ltd.) into this solution to adjust the pH to 7.0.

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

Next, while cooling this hydroxide-containing liquid to 1 to 5 ° C, 25 g of 35% hydrogen peroxide solution (manufactured by Taiki Yakuhin Kogyo Co., Ltd.) was added, 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 Anatase-type titanium peroxide aqueous dispersion (B56 manufactured by Sustainable Technology Co., Ltd.) was used as a photocatalytic function-imparting solution.

Example 1 A commercially available plexicast concrete substrate (width 300 mm, length 300 mm, thickness 30 mm) was coated with the water absorption prevention coloring liquid of Reference Example 1-1 twice with a painting brush and dried well at room temperature.

Next, on top of that, the copper-doped amorphous titanium peroxide dispersion of Reference Example 2-1 was applied with an air pressure of 2 kg / m using a spray gun for painting.²At 10g / m²Was applied and dried at room temperature.

On top of that, the photocatalyst function-imparting solution of Reference Example 3-1 was added at 30 g / m in the same manner as in Reference Example 2-1.²Was applied 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 to 4 Of Examples 1 to 4, those obtained by applying and drying only the water absorption prevention coloring liquid and not using the copper-doped amorphous titanium peroxide dispersion liquid and the photocatalyst function-imparting liquid were designated as Comparative Examples 1 to 4.

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 spray gun for painting, and the air pressure was 2 kg / m.²At 10g / m²And dried at room temperature to give Comparative Example 5.

Evaluation 1 The evaluation boards of Examples 1 to 4 and Comparative Examples 1 to 5 were exposed outdoors in Chiba and Saga prefectures from mid-May to early October 2003, and the contamination status of the evaluation boards was visually evaluated. did. The results are shown in Table 1.

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Reference example 1-5 Only Dry Seal S was used as the transparent water absorption prevention 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 aid, and 10 times more water than dry seal S. 40 g of the diluted solution was mixed and stirred to obtain a water absorption prevention coloring solution.

Reference example 2-3 0.4 wt% of polyether-modified silicone oil SH3746 (manufactured by Toray Dow Corning Silicone Co., Ltd.) 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 used.

Example 5 A commercially available plexicast concrete substrate (width 300 mm, length 300 mm, thickness 30 mm) was coated twice with the water absorption prevention liquid of Reference Example 1-5 with a painting 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 by the same method as in Example 5 except that the water absorption prevention coloring liquid of Reference Example 1-6 was used instead of Reference Example 1-5.

Example 7 The photocatalytic 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 photocatalytic function-imparting liquid 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 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 titanium peroxide-polyether-modified silicone mixed dispersion of 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 the end of January 2004, and the evaluation substrate contamination status was evaluated with the naked eye. (Registered trademark) Adhesion evaluation by peeling test, hydrophilicity evaluation with the naked eye, and water absorption evaluation with the naked eye were performed. In the absorbability evaluation, after tap water was sprayed on the surface of each evaluation substrate, a part of the evaluation substrate was cut and the water absorption state of the cross section was visually evaluated. The results are shown in Table 2.

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* Cellotape (registered trademark) peeling test method A commercially available cellophane tape (registered trademark) is attached to the surface of the evaluation substrate in a lattice pattern so as to have an opening of 10 mm square, and at the same time, the cellophane tape (registered trademark) is peeled off, and the pigment and the metal-doped titanium oxide film adhere to the surface of the cellophane tape (registered trademark). It was visually evaluated whether or not it was present.

In the laminate of the present invention, by arbitrarily coloring the water absorption prevention layer containing the silicon-containing compound, a free design can be applied while making the best use of the texture of the substrate itself.

In addition, the unique contamination prevention function exhibited by the metal-doped titanium oxide-containing layer itself can prevent contamination on the surface of the laminate. Then, by blending a silicone oil, particularly a polyether-modified silicone oil, with the metal-doped titanium oxide-containing layer, the antifouling effect can be further improved. Since the metal-doped titanium oxide-containing layer does not have a photocatalyst function, the water absorption prevention layer containing the silicon-containing compound is not oxidatively decomposed.

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

Further, in the laminate of the present invention in which the photocatalyst functional layer is formed on the metal-doped titanium oxide-containing layer, the water absorption prevention layer does not oxidize and decompose due to the action of the photocatalyst functional layer, and the photocatalyst functional layer does not deteriorate. Is not hydrolyzed. Therefore, the laminate can provide any design while maintaining good waterproofness and stain resistance over time, such as houses (including exterior walls, bathrooms, kitchens, washrooms), buildings. , Waterways, dams, roads, tunnels, bridges, airports, harbor facilities and other outdoor structures.