Solution or dispersion for substarate surface treatment comprising titanium oxide doped with metallic element, method for substrate surface treatment using the same, and surface-treated material obtained therefrom

A substrate surface treatment solution or dispersion liquid containing titanium oxide doped with a metal element, a substrate surface treatment method using the solution, and a surface treatment material obtained by the method

The present invention relates to a treatment solution for manufacturing a surface treatment material with excellent water absorption and antifouling properties, a substrate surface treatment method using the treatment solution, and a surface treatment material obtained by using the method.

This application claims priority based on Japanese Patent Application No. 2005-125152 filed in Japan on April 22, 2005, and its content is quoted here.

For example, various materials used in buildings are equivalent to those used outdoors. Because their surfaces are contaminated by various pollutants in the atmosphere and rainwater, organisms such as moss and mold, and microorganisms, the beauty of the materials changes with the passage of time. The problem of damage. In fact, in order to maintain the beautiful appearance of buildings and other buildings, the surface must be cleaned regularly.

In addition, there are also the following problems: in concrete building materials containing steel bars and/or steel frames, the steel bars and steel frames rust due to rainwater soaking through the concrete, and the volumetric expansion of the steel caused by the rust will cause turtles in the concrete. Crack and so on. Furthermore, there is a problem that the concrete itself will be neutralized due to the acidic substances contained in the rainwater, resulting in a decrease in strength. In addition, there is also the problem of deterioration due to acidic substances in marble building materials.

In order to solve these problems, the industry has tried to coat the surface of outdoor building materials and other materials with water-repellent substances such as silicone compounds and/or anti-fungal agents and/or antibacterial agents, thereby preventing moisture intrusion into the materials and suppressing pollutants Attaching to the surface of building materials and moss is equivalent to reproduction on the surface of the material. However, even when the water-repellent substance is applied to the surface of the material, it cannot completely prevent the surface contamination of the material caused by the accumulation of hydrophobic contaminants to contaminate the surface.

In addition, in recent years, as a method of preventing material surface contamination, a method of forming a photocatalyst layer on the surface of a material has been used. For example, the following method is currently proposed: forming a photocatalyst layer such as anatase-type titanium peroxide on the water-repellent layer containing an alkali metal silicate compound formed on the surface of the substrate (for example, refer to Patent Document 1); And, a photocatalyst layer is further formed on an undercoat layer containing an acrylic resin having an alkoxysilyl group and a hydroxyl group formed on the surface of the substrate (for example, refer to Patent Document 2). In addition, the inventor proposed the use of a titanium dioxide-metal composite as a material for forming an antifouling titanium dioxide layer with excellent activity (refer to Patent Document 3).

Furthermore, the industry also seeks for materials used in outdoor buildings and the like to have the above-mentioned excellent water absorption and antifouling properties, and in order to improve the ingenuity of the materials, the surface can be colored and its color will last for a long time.

[Patent Document 1] Japanese Patent Laid-Open No. 2000-135442 [Patent Document 2] Japanese Patent Laid-Open No. 2002-138243 [Patent Document 3] International Publication No. WO2004/04173

<p>In the above-mentioned method of preventing material surface contamination, a photocatalyst is formed on a water-repellent layer containing an alkali metal silicate compound on the surface of a substrate (refer to Patent Document 1). The effect of this causes the photocatalyst layer to be hydrolyzed, which makes it difficult to color the alkali metal silicate compound.</p><p>In the method of forming a photocatalyst layer on a primer layer containing an acrylic resin having an alkoxysilyl group and a hydroxyl group formed on the surface of a substrate (refer to Patent Document 2), it is easier to color the acrylic resin, but acrylic The resin itself decomposes and deteriorates due to the action of the photocatalyst.</p><p>The object of the present invention is to provide the following: a material used for the surface of a base material used outdoors in construction, civil engineering, etc., to form a surface layer with excellent water absorption and antifouling properties and easy to color Material; and a method that uses the material to treat the surface of the substrate; a surface treatment material that uses the method for surface treatment, and has excellent water absorption and antifouling properties, and has the desired ease of coloring Of the surface.</p><p>The material used for the surface treatment of the substrate in the present invention is a solution or dispersion, which is characterized by comprising: a water repellent or an anti-absorbent, and a titanium oxide doped with at least one metal element, the metal element being selected Freedom from the group consisting of copper, manganese, nickel, cobalt, iron and zinc.</p><p>Furthermore, the water-repellent or water-absorption agent used in the above-mentioned solution or dispersion is: silane-based, silicate-based, polysiloxane-based, polysiloxane and silane composite system, and/or fluorine-based water-repellent or water-repellent The water absorbing agent and the above-mentioned titanium oxide doped with metal elements are preferably amorphous titanium oxide or amorphous titanium oxide in which at least a part of peroxide is oxidized.</p><p>Furthermore, the above-mentioned solution or dispersion may further contain an aqueous pigment dispersion as required. The aqueous pigment dispersion contains a dispersant selected from the group consisting of nonionic dispersant, anionic dispersant, amphoteric dispersant, and acid value. One or more of the group consisting of 50-250 water-soluble resin-based dispersants and latex resin-based dispersants with acid values of 50-250; pigments; and water.</p><p>Furthermore, the said solution or dispersion liquid may further contain an organic resin binder as needed.</p><p>The substrate surface treatment method of the present invention is characterized in that by applying any of the above-mentioned solutions or dispersions to the substrate, a layer containing the following compound is formed on the surface of the substrate and/or in the surface layer of the substrate: Water repellent or water absorption inhibitor, and titanium oxide doped with at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc.</p><p>The surface treatment material of the present invention is characterized in that it is manufactured by the above-mentioned surface treatment method, and a layer containing the following compounds is formed on the surface of the substrate and/or in the surface layer of the substrate: Titanium oxide of at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc.</p><p>The inventor found that a solution or dispersion containing titanium oxide doped with the above-mentioned specific metal element and containing a water-repellent or water-absorbing agent is used to form the above-mentioned titanium oxide on the surface or on the surface layer of the substrate, and The layer of the water repellent or water-absorbent agent can make the surface of the substrate difficult to be contaminated, and can prevent the substrate from absorbing water, and can be easily colored on the substrate surface to improve the originality of the substrate surface, thereby completing the present invention.</p>

In the present invention, a solution or dispersion containing a water repellent or anti-absorbent and titanium oxide doped with the above-mentioned specific metal elements is applied to the surface of the substrate, on the surface of the substrate and/or on the surface of the substrate In the process, a layer containing the following compound is formed: the above-mentioned water-repellent agent or anti-absorption agent and the above-mentioned titanium oxide. When the substrate is non-porous such as glass or metal, the above-mentioned layer is formed on the surface of the substrate; when the substrate is porous, such as concrete, the solution or dispersion slightly penetrates from the surface of the substrate to the inside. The above-mentioned layers are usually formed on the surface layer of the substrate and in the surface layer of the substrate. The substrate that is the object of the present invention is not particularly limited. As the non-porous substrate, in addition to the above-mentioned glass and metal, stone, plastic, rubber, sealing material, and glazed tile can be cited. As the above-mentioned porous base material, in addition to the above-mentioned concrete, wood, mortar, porous stone, stone tile, etc. may be mentioned. As the substrate of the present invention, concrete is particularly preferred.

The surface treatment agent of the substrate of the present invention must contain a water-repellent agent or a water-absorbing agent, and titanium oxide doped with the above-mentioned specific metal elements as essential components. Hereinafter, the titanium oxide doped with a specific metal element will be described, and then the water-repellent agent or water-absorption agent will be described.

As used in the present invention, a solution or dispersion containing titanium oxide doped with the above-mentioned specific metal element (hereinafter referred to as "titanium oxide doped with specific metal") can be used in the International Patent Application Publication No. Revealed in the WO 2004/041723 case. More specifically, in this specification, the so-called titanium oxide doped with a specific metal contained in the above-mentioned solution or dispersion includes the following substances: selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc At least one metal or compound of the group consisting of; a compound containing titanium oxide or at least a part of titanium oxide that has been peroxide. As the titanium compound, it becomes the matrix compound of the above-mentioned at least a part of the peroxide titanium oxide, such as TiO₂, TiO₃, TiO, and TiO₃/nH₂O and other titanium oxides and titanium hydroxide and peroxide reactants. Furthermore, the crystal system of titanium oxide may be any of amorphous, anatase, brookite, and rutile, or a mixed type of these. The amorphous type has excellent properties. The film-forming properties and adhesion to the substrate are particularly good.

As a method of producing a solution or dispersion containing a titanium oxide doped with a specific metal, the following methods can be cited.

(Manufacturing method 1)

A tetravalent titanium compound such as titanium tetrachloride is reacted with a base such as ammonia to synthesize titanium hydroxide. Then, the obtained titanium hydroxide is oxidized with an oxidizing agent and then peroxidized to synthesize at least a part of the super-oxidized amorphous titanium oxide ultrafine particles (hereinafter referred to as: obtained by peroxidizing at least a part of the peroxidized titanium oxide Titanium oxide). Preferably, the above reaction is carried out in an aqueous medium. The obtained amorphous peroxide type titanium oxide can be converted into anatase peroxide type titanium oxide by heating as required. In the present invention, as described above, it is particularly preferable to use amorphous titanium oxide. At any stage of the manufacturing steps of the titanium peroxide, at least one selected from copper, manganese, nickel, cobalt, iron, zinc, or these compounds is added to the reaction mixture, thereby obtaining at least a part of the Peroxidized titanium oxide doped with a specific metal.

The oxidizing agent used to peroxidize the titanium hydroxide may be an oxidizing agent that can produce titanium peroxide, which is a peroxide of titanium, and is not limited to a specific oxidizing agent, and hydrogen peroxide is particularly preferred. In the present invention, it is particularly preferable to use hydrogen peroxide with a concentration of 30-40% by weight. Furthermore, in the case of peroxidizing titanium hydroxide, it is preferable to cool the solution containing titanium hydroxide in advance, and the temperature in this case is preferably 1 to 5°C.

The above-mentioned manufacturing method 1 is explained based on FIG. 1. Fig. 1 is a diagram showing an overview of a mode of manufacturing method 1. First, as shown in Figure 1, in the presence of at least one compound of copper, manganese, nickel, cobalt, iron, and zinc, an aqueous solution of titanium tetrachloride and an aqueous ammonia solution are mixed to hydrolyze titanium tetrachloride and other metal compounds , Thereby obtaining titanium and other metal hydroxides. In this case, the concentration of each raw material contained in the reaction mixture and the temperature of the reaction mixture should be within the range in which the desired reaction product can be obtained, and there is no particular limitation. It is preferred that the dispersion is stable The performance should be good, so the concentration of each raw material is low, and the reaction temperature is normal temperature. This reaction is a neutralization reaction, and it is preferable to finally adjust the pH of the reaction mixture to about 7. The adjustment of the pH can be carried out, for example, by adjusting the addition amount of an aqueous ammonia solution. In this case, metal compounds other than titanium may be added before the start of the neutralization reaction and/or during the neutralization reaction by adding the aqueous ammonia solution.

The metal hydroxide mixture obtained by the above neutralization reaction is separated from the solution, washed with pure water, and then cooled. The cooling temperature is preferably about 5°C, but it is not particularly limited. Then, the aqueous dispersion of the metal hydroxide mixture is peroxidized with hydrogen peroxide. Through this reaction, it is doped with at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc, and an amorphous titanium oxide containing at least a part of peroxide can be obtained A solution or dispersion of fine particles. The obtained dispersion liquid can be further exceeded, thereby obtaining a dispersion liquid containing superparticles.

(Manufacturing Method 2)

First, the tetravalent titanium compound, such as titanium tetrachloride, is peroxidized with an oxidizing agent, and then a base such as ammonia is used for neutralization to synthesize at least a part of the peroxidized amorphous titanium oxide (ie, amorphous titanium peroxide). ) Of ultra-fine particles. The reaction is preferably carried out in an aqueous medium. Furthermore, if necessary, the amorphous type titanium peroxide may be converted into anatase type titanium peroxide by heat treatment. In any one of the above-mentioned peroxidation step and the above-mentioned neutralization reaction, at least one selected from copper, manganese, nickel, cobalt, iron, zinc, or these compounds can be mixed, thereby obtaining the dopant comprising the present invention There are solutions or dispersions of titanium oxides of specific metals.

(Manufacturing Method 3)

In the presence of at least one selected from copper, manganese, nickel, cobalt, iron, zinc, or these compounds, an oxidizing agent such as hydrogen peroxide and a base such as ammonia are simultaneously applied to a tetravalent titanium compound such as titanium tetrachloride By this, the hydrolysis of the metal compound and the tetravalent titanium compound and the peroxidation of the titanium compound are carried out simultaneously, and a solution or dispersion containing the titanium oxide doped with a specific metal of the present invention can be obtained. In this case, if necessary, the amorphous titanium peroxide may be converted into anatase titanium peroxide by heat treatment.

As the tetravalent titanium compound used in the above-mentioned manufacturing methods 1 to 3, if it reacts with a base, it can produce what is called ortho titanic acid (H₄TiO₄) Of titanium hydroxide. Examples of such tetravalent titanium compounds include water-soluble titanium inorganic salts such as titanium tetrachloride, titanium sulfate, titanium nitrate, and titanium phosphate, and water-soluble titanium organic salts such as titanium oxalate. Among these compounds, titanium tetrachloride has excellent water solubility and can reduce the content of useless impurities contained in the obtained titanium oxide doped with a specific metal. Therefore, titanium tetrachloride is preferred.

In the above-mentioned manufacturing methods 1 to 3, the concentration of the tetravalent titanium compound when reacting with the base can be the concentration at which the produced titanium hydroxide can form a gel. There is no special restriction, but it is to avoid the residue of unreacted substances. , Preferably a thinner solution. Specifically, the concentration of the tetravalent titanium compound in the solution is preferably 5 to 0.01% by mass, more preferably 0.9 to 0.3% by mass. Within this concentration range, the tetravalent titanium compound reacts with the base, thereby obtaining a titanium hydroxide dispersion or gel with good dispersibility.

The alkali used in the above-mentioned production methods 1 to 3 is not particularly limited as long as it can generate a titanium hydroxide gel from the tetravalent titanium compound used. As the alkali, ammonia, caustic soda, sodium carbonate, and caustic potassium can be exemplified, and ammonia is particularly preferred. The above-mentioned base is usually a solution, for example, an aqueous solution, which is added to the above-mentioned tetravalent titanium compound solution or dispersion. In this case, the concentration of the alkali solution is not particularly limited as long as it can form a titanium hydroxide gel. It is preferably a thinner solution. Specifically, the concentration of the alkali solution used is preferably It is 10~0.01% by mass, more preferably 1.0~0.1% by mass. When ammonia water is used as the alkaline solution, in order to avoid excess ammonium ion remaining, the ammonia concentration is preferably 10 to 0.01% by mass, more preferably 1.0 to 0.1% by mass.

As the compounds of copper, manganese, nickel, cobalt, iron, or zinc used in the above-mentioned manufacturing methods 1 to 3, the following can be exemplified respectively: Ni compound: Ni(OH)₂, NiCl₂; Co compound: Co(OH)NO₃, Co(OH)₂, CoSO₄, CoCl₂; Cu compound: Cu(OH)₂, Cu(NO₃)₂, CuSO₄, CuCl₂, Cu(CH₃COO)₂; Mn compound: MnNO₃, MnSO₄, MnCl₂; Fe compound: Fe(OH)₂, Fe(OH)₃, FeCl₃; Zn compound: Zn(NO₃)₂, ZnSO₄, ZnCl₂。

The solution or dispersion liquid of the titanium oxide doped with the specific metal of the present invention is obtained by the above-mentioned manufacturing methods 1 to 3. The solid content concentration (the total concentration of the titanium compound and the specific metal compound contained in the solution) is better It is 0.05 to 15% by mass, and more preferably 0.1 to 5% by mass, in order to obtain a stable solution or dispersion. In addition, the molar ratio of titanium to other specific metals contained in the above-mentioned solution or dispersion is preferably 1:0.01~1:0.5, more preferably 1:0.03~1:0.1, so as to use them The antifouling performance of the substrate after surface treatment of the solution or dispersion is good.

(Manufacturing method 4: Manufacturing method by sol-gel method)

The solution containing titanium alkoxide, water, ethanol and other solvents, and acid or alkali catalyst is mixed and stirred, and the titanium alkoxide is hydrolyzed to prepare a colloidal solution of ultrafine particles of titanium oxide. At any stage before, during or after the hydrolysis reaction, at least one of copper, manganese, nickel, cobalt, iron, zinc, or these compounds is selected and added to the above solution or colloidal solution, by This can obtain a solution or dispersion containing the titanium oxide doped with a specific metal of the present invention.

The titanium alkoxide used in the above-mentioned production method 4 preferably has the general formula: Ti(OR')₄(In the formula, R'is an alkyl group) represented by a compound; or a compound in which one or two OR' groups in the general formula are substituted by a carboxyl group or a group containing a β-dicarbonyl group; or a mixture of these. As the above-mentioned titanium alkoxide, for example, Ti(O-isoC₃H₇)₄, Ti(O-nC₄H₉)₄, Ti(O-CH₂CH(C₂H₅)C₄H₉)₄, Ti(O-C₁₇H₃₅)₄, Ti(O-isoC₃H₇)₂[CO(CH₃)CHCOCH₃]₂, Ti(O-nC₄H₉)₂[OC₂H₄N(C₂H₄OH)₂]₂, Ti(OH)₂[OCH(CH₃)COOH]₂, Ti(OCH₂CH(C₂H₅)CH(OH)C₃H₇)₄, And Ti(O-nC₄H₉)₂(OCOC₁₇H₃₅)₂。

The sol-gel method of the above-mentioned manufacturing method 4 is well-known as a method for synthesizing metal oxides. When manufacturing the titanium oxide doped with a specific metal of the present invention, the commonly used method and acid or alkali can also be used. Wait for the necessary compounds to proceed.

In addition, when the titanium oxide doped with a specific metal of the present invention is manufactured by the sol-gel method, the compound of copper, manganese, nickel, cobalt, iron, or zinc used is the same as the above-mentioned manufacturing method 1~ The compounds used in 3 are the same. Furthermore, the solution or dispersion of the titanium oxide doped with the specific metal of the present invention prepared by the sol-gel method has a good solid content concentration (the titanium oxide contained in the solution and the specific metal oxide The total concentration of the substance), and the better molar ratio of titanium to other specific metals contained in the solution or dispersion, are the same as the concentration and molar ratio of the modifications described in manufacturing methods 1 to 3.

In addition, the titanium oxide doped with a specific metal of the present invention can also be manufactured by the following method: The "organic titanium peroxide compound" disclosed in the specification of Japanese Patent Laid-Open No. 2000-159786 is mixed with the above-mentioned specific metal compound and dissolved in water , The resulting solution is concentrated, and then gelatinized. In addition, a water-soluble mixture containing the "titanium complex" disclosed in the specification of Japanese Patent Laid-Open No. 2001-10816 and a "metal complex" other than titanium can also be prepared as a starting material.

(Water repellent or anti-absorbent)

The solution or dispersion for surface treatment of a substrate of the present invention is characterized in that it contains not only the aforementioned titanium oxide doped with a specific metal, but also a water-repellent agent or a water-absorbent agent. As the water-repellent or water-absorption agent used in the present invention, silane-based, silicate-based, polysiloxane-based, polysiloxane and silane composite systems, or fluorine-based water-repellent or water-absorption agents are preferred Agent. When such a material is applied to the surface of a non-porous substrate, it is called a water repellent; when applied to the surface of a porous substrate, it can prevent water from being absorbed into the substrate. It is called anti-absorbent.

The so-called silane-based, silicate-based, polysiloxane-based, and polysiloxane and silane composite water-repellent or anti-absorbent materials used in the present invention are as follows: After being applied to the surface of the substrate, the water repellent The chemical components of the agent or the water-absorbent agent can react with the substrate to generate chemical bonds, or cross-link between the chemical components, thereby forming a film with a certain degree of durability. Such a material is advantageous because it can quickly express water repellency or water absorption resistance, can maintain the water repellency or water absorption resistance of the substrate for a long time, and has excellent weather resistance.

Various silane-based, silicate-based, polysiloxane-based, polysiloxane and silane composite systems, and fluorine-based water-repellent agents or water-absorbent agents are known, and any of them can be used in the present invention. Use two or more kinds in combination. In the present invention, it is preferable to use a silane-based, silicate-based, polysiloxane-based, or a combination of polysiloxane and silane water-repellent or water-absorbing agent. Even among these, as the water-repellent or water-absorbing agent used in the present invention, particularly good ones include: a silane-based water-repellent or water-absorbing agent, which includes hydrolyzable silane, water, and a surfactant; Polysiloxane and silane composite water repellent or anti-absorbent, which further contains hydrolyzate and/or partial hydrolyzate selected from hydrolyzable silane, and various organopolysiloxane compounds; and, silicate-based repellent Aqueous agent or anti-absorbent agent, which contains an alkali metal aqueous solution of organosilicate.

Various hydrolyzable silanes used in the above-mentioned silane-based water repellents or anti-absorbents are known, for example, tetraalkoxy silanes, alkyl trialkoxy silanes, dialkyl dialkoxy silanes, and As for the trialkylalkoxysilane, one kind or two or more kinds selected from these can be used. The surfactant is not particularly limited, and anionic surfactants, cationic surfactants, nonionic surfactants, and mixtures thereof can be used.

Examples of the above-mentioned polysiloxane and silane composite water repellent or water-absorbing agent include the following: those containing the above-mentioned hydrolyzable silane, a surfactant, and the hydrolyzate and/or partial hydrolyzate of the above-mentioned hydrolyzable silane, and those containing Those selected from the above-mentioned hydrolyzable silanes, surfactants, and various organopolysiloxane compounds. As the aforementioned various organopolysiloxanes, there can be used organopolysiloxanes containing hydrolyzable groups selected from alkoxy groups, alkenyloxy groups, amino groups, and amide groups bonded to silicon atoms. Group, acetoxy group, and ketoxime group.

Specific examples of the polysiloxane and silane composite water-repellent agent or water-absorbing agent include the composition disclosed in Japanese Patent Laid-Open No. 62-197369 or Japanese Patent Laid-Open No. 6-313167. The silane-based water-repellent or anti-absorbent-based water-based composition used in the present invention contains the following: (A) Organoalkoxysilanes, which are represented by the general formula: R¹_aSi(OR²)₄_－_a(In the formula, R¹It is the same or different monovalent hydrocarbon group with 1-20 carbon atoms, R²It is a monovalent hydrocarbon group with 1 to 3 carbon atoms, and a is 1 or 2. ) 100 parts by weight; (B) Organosiloxane, which contains at least one silicon atom in its molecule, with the general formula: -R³-Si(R⁴)_b(OR²)₃_－_b(In the formula, R²It is a monovalent hydrocarbon group with 1 to 3 carbon atoms, R³It is a divalent hydrocarbon group, R⁴It is a monovalent hydrocarbon group of the same or different species, and b is 0, 1, or 2. 1 to 200 parts by weight of the organic group represented by ); (C) anionic surfactant; and (D) water.

R of the organic alkoxysilane of the above (A) component¹Specific examples include: methyl, ethyl, propyl, tertiary butyl, pentyl, n-hexyl, heptyl, 2-ethylhexyl, octyl, dodecyl, octadecyl, etc. Alkyl, phenyl, methylbenzene, dimethylbenzene, naphthyl and other aryl groups, benzyl, phenethyl and other aralkyl groups, fluoromethyl, 3,3,3-trifluoropropyl, 3,3 ,4,4,5,5-Heptafluoropentyl, difluoromonochloropropyl and other substituted alkyl groups. Among these, the alkyl group having 4 to 10 carbon atoms is particularly preferred. A carbon number greater than 4 can improve the water repellency of the water repellent; a carbon number less than 10 can improve the permeability of the porous substrate. As the R of the above organic alkoxysilane²Specific examples include methyl, ethyl, and propyl. Organoalkoxysilanes can be used singly or in combination of two or more. When the component (A) is applied to the surface of a porous substrate, such as an inorganic substrate (specifically, building materials such as concrete), it penetrates into the interior of the substrate and combines with the substrate, thereby forming water resistance in the surface layer of the substrate. Floor.

The form of the substituent in the organic group bonded to the organosiloxane of the component (B) is as follows. R²R with the above (A) component²same. R³It is a divalent hydrocarbon group, and specific examples include alkylene groups such as vinyl, n-propenyl, isopropenyl, and isobutenyl. R⁴It is a monovalent hydrocarbon group of the same or different kind, for example, alkyl groups such as methyl, ethyl, propyl, octyl, decyl, dodecyl, aryl groups such as phenyl, naphthyl, and tolyl, 2- Aralkyl groups such as phenylethyl and 2-phenylpropyl groups, and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups. b is preferably 0 or 1. The above-mentioned organic group may exist only in the molecular chain end, side chain, or both of the organosiloxane. In addition to the organic group represented by the above structural formula, as the organic group having the component (B) organosiloxane, preferably the same or different monovalent hydrocarbon groups, particularly preferably having a methyl group and a carbon number of 4 Those of the above alkyl groups. The organosiloxane of the component (B) may be linear, branched, and/or cyclic, and is particularly preferably linear. Furthermore, (B) component may be any of a homopolymer, a block copolymer, and a random copolymer.

As the above-mentioned general formula (B) component, for example, the following general formula:<chemistry general="n"><img file="TW200704593A_D0001.tif" /></chemistry>

(In the formula, m is a number greater than 0, n is a number greater than 1, and m+n is a number from 1 to 50) represented by organosiloxane. By setting m+n in the formula to 1-50, the permeability into the porous substrate can be improved. The component (B) is preferably used in the range of 1 to 200 parts by weight, and more preferably used in the range of 10 to 100 parts by weight relative to 100 parts by weight of the above-mentioned (A) component. By setting the use amount of (B) component to 1 part by weight or more, the storage stability of the mixture can be improved; setting it to 200 parts by weight or less can increase the content of (A) component and increase the application to porous substrates. Under the circumstances, the water repellency of the formed surface layer.

The anionic surfactant of the component (C) is a component for emulsifying the components (A) and (B). Examples of preferred anionic surfactants include alkyl benzene sulfonic acids such as octyl benzene sulfonic acid, dodecyl benzene sulfonic acid and cetyl benzene sulfonic acid, higher alcohol sulfates, and polyoxyethylene Alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, and sodium, potassium, lithium, or ammonium salts of selected acids of alkyl naphthyl sulfonic acid.

The component (C) is preferably used in the range of 0.1 to 50 parts by weight, and more preferably in the range of 0.1 to 10 parts by weight, relative to 100 parts by weight of the total amount of the above-mentioned (A) component and (B) component Used within. The water of the above-mentioned (D) component is preferably used in such an amount that the total amount of the above-mentioned (A) component and (B) component becomes 5 to 60% by weight of the total amount of (A) to (D). The water-repellent agent or water-absorbing agent obtained by emulsifying these mixtures is particularly preferably the water-repellent agent or water-absorbing agent used in the present invention. As the preferable water-repellent or water-absorbent agent, a commercially available one can cite DrySeal S (trade name, manufactured by Dow Corning Toray Silicone Co., Ltd.).

The above-mentioned silicate water repellent or anti-water absorption agent can be used well-known ones, including: sodium methyl silicate aqueous solution, propyl sodium silicate aqueous solution, potassium methyl silicate aqueous solution, and propyl potassium silicate aqueous solution, etc. An aqueous solution of an alkali metal salt of an acid alkyl ester, and an alkali metal amine organic functional silicate aqueous solution disclosed in Japanese Patent Laid-Open No. 5-214251. As such silicate-based water repellent or anti-absorbent agents, DrySeal C and DrySeal E (both are trade names, manufactured by Dow Corning Toray Silicone Co., Ltd.) are commercially available. .

In addition, as the silicone water repellent or water absorption inhibitor, the following can be cited: a room temperature curable water-based silicone emulsion composition, which is described in Japanese Patent Laid-Open No. 58-118853 or Japanese Patent As disclosed in Kokai No. 60-9650, a polysiloxane emulsion containing hydroxyl-containing organopolysiloxane, colloidal silica, and hardening catalyst stabilized by anion, or disclosed in Japanese Patent Laid-Open No. 7- Bulletin 150045 contains a polysiloxane emulsion containing alkoxy-containing diorganopolysiloxanes stabilized by ions or non-ions, and a titanium catalyst. These emulsions are cured at room temperature by removing water to impart elasticity Body-shaped hardening material; room temperature hardening type silicone resin water repellent or anti-absorbent agent, such as the following: the room temperature hardening silicone resin combination disclosed in Japanese Patent Laid-Open No. 55-48245Object, characterized in that it contains: (A) in the average unit formula R'_lSiO₍₄_－_l_－_k₎_/₂(OH)_k(In the formula, R'is a substituted or unsubstituted monovalent hydrocarbon group, l is a number ranging from 0.80 to 1.80, and k is a value such that the ratio of hydroxyl groups bonded to silicon atoms in the compound is 0.01% by mass or more. ) Represents the organopolysiloxane resin, (B) is represented by the general formula HO-(R⁵₂SiO)_q-H (where, R⁵It is a substituted or unsubstituted monovalent hydrocarbon group, and q is an integer of 2 or more. ) Represented by α,ω-dihydroxydiorganopolysiloxane, and (C) are represented by the general formula R⁶cSiX₄_－_c(Wherein c is 0, 1, or 2, X is a hydrolyzable group) represented by a silicon compound or a partial hydrolysis condensate thereof, and a polysiloxane aqueous emulsion disclosed in Japanese Patent Laid-Open No. 6-73291 A resin composition characterized by comprising: (A) containing SiO₄_/₂Unit or R⁷SiO₃_/₂Unit, and the content of the hydroxyl group bonded to the silicon atom or the alkoxy group bonded to the silicon atom in the molecule is 0.1% by mass or more of organopolysiloxane; (B) is represented by the general formula HO(R⁸₂SiO)_pH (where R⁸It is a monovalent hydrocarbon group, and p is an integer of 2 or more. ) Represents the second organopolysiloxane; (C) is represented by the general formula R⁹₂NO(R¹⁰SiO)_rNR⁹(In the formula, R⁹And R¹⁰It is a monovalent hydrocarbon group, and r is an integer of 1 or more. ) Represents an organosilicon compound containing an aminooxy group; (D) a surfactant; and (E) water.

Etc., which include: polysiloxane resins containing hydrolyzable groups such as hydroxyl or alkoxy, diorganopolysiloxanes containing hydroxysilyl groups, and silanes containing hydrolyzable groups or hydrolyzable groups (but hydroxyl Except) organopolysiloxane.

In addition, the fluorine-based water repellent or water-absorbing agent used in the present invention is a fluorine-containing compound such as a perfluoroalkyl group-containing compound or a composition containing a fluorine-containing compound. Furthermore, when selecting a fluorine-containing compound with a higher absorbency to the surface of the substrate, after being applied to the surface of the substrate, the chemical components of the water repellent or anti-absorbent do not necessarily have to react with the substrate to form a chemical bond Junction, or cross-linking between chemical components.

The fluorine-containing compound that can be used as such a fluorine-based water repellent or water-absorbing agent preferably has a molecular weight of 1,000 to 20,000 containing a perfluoroalkyl group. Specific examples include: perfluorosulfonate, all perfluorosulfonic acid ammonium salt, perfluorocarboxylate, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl amine oxide compounds, perfluoroalkyl phosphate, perfluoroalkyl group and three Methyl ammonium salt and so on. Among them, in terms of the adsorption properties from the surface of the substrate, perfluoroalkyl phosphate and perfluoroalkyl trimethylammonium salt are preferred. As such materials, Surflon S-112, Surflon S-121 (both are trade names, manufactured by SEIMI CHEMICAL Co., Ltd.) and the like are commercially available.

As other fluorine-based water repellents or anti-absorbents, a composition containing the following compounds can be cited: fluororesin latex, which contains at least one fluororesin and a surfactant, wherein the fluororesin is selected from two or more types containing fluorine atoms Copolymers of olefins, copolymers of olefins containing fluorine atoms and hydrocarbon monomers, and mixtures of copolymers containing two or more olefins containing fluorine atoms and thermoplastic acrylic resins; and hardeners (see Japanese Patent Laid-Open No. 5-124880, Japanese Patent Laid-Open No. 5-117578, Japanese Patent Laid-Open No. 5-179191) and/or the above-mentioned silane-based water repellent or anti-absorbent (refer to Japanese Patent Laid-Open 2000-121543, Japanese Patent Laid-Open No. 2003-26461). As the fluororesin emulsion, commercially available ones can be used, and the zeffuru series can be purchased from Daikin Industry (Stock) and the lumiflon series can be purchased from Asahi Glass (Stock). As for the above-mentioned curing agent, it is preferable to use a melamine-based curing agent, an amine-based curing agent, a polyvalent isocyanate-based curing agent, and a blocked polyvalent isocyanate-based curing agent. Among them, a polyvalent isocyanate-based curing agent is preferable in terms of being able to be cured at room temperature and then on-site.

The first object of the present invention is to provide a solution or dispersion (hereinafter, only referred to as substrate surface treatment liquid), which is as described above, in order to impart excellent water repellency or water absorption resistance, and water resistance to the surface of the substrate. Staining, used to treat the surface of the substrate. In addition, the substrate surface treatment liquid includes a solution or dispersion of the above-mentioned water-repellent agent or water-absorbing agent and the above-mentioned titanium oxide doped with a specific metal. This solution or dispersion liquid is obtained by mixing the above-mentioned solution or dispersion liquid containing the titanium oxide doped with the specific metal with the above-mentioned water-repellent agent or water-absorbent agent.

In the substrate surface treatment liquid of the present invention, an aqueous pigment dispersion for improving the ingenuity of the substrate surface can be further added as needed. The pigment used in the present invention is not particularly limited, and inorganic pigments and organic pigments can be used, and one of these or both can be used in combination. It has been found that the substrate surface treatment liquid of the present invention added with pigments and/or dyes is surprisingly used in the layer formed on the surface of the substrate or in the surface layer of the substrate, even when organic pigments and/or dyes are used. It has the effect of inhibiting the fading of dyes and/or pigments.

The above-mentioned aqueous pigment dispersion is not particularly limited as long as the pigment is uniformly and stably dispersed in water. As the aqueous dispersion, a pigment can be dispersed in water with a dispersing agent using a dispersing machine according to a well-known method.

Among the above-mentioned pigments, inorganic pigments include: metal oxide-based, composite oxide-based, chromate-based, sulfide-based, phosphate-based, and metal double-salt-based pigments, carbon black, metal powder, and temperature indicator Pigments, light-storing pigments, pearl pigments, alkaline pigments, lead white, etc. In addition, as organic pigments, azo, phthalocyanine, anthraquinone, quinacridone, indigo, dioxazine, perylene, perinone, iso Indolinone series, isoindoline series, metal double salt series, quinophthalone series, and diketopyrrolopyrrole series pigments, alkali blue, nigrosine, fluorescent pigments, etc. These pigments can be used alone or in combination of two or more kinds.

As a dispersant used when the pigment is dispersed in water to obtain an aqueous pigment dispersion, there can be mentioned; nonionic dispersant, anionic dispersant, amphoteric dispersant, water-soluble resin with an acid value of 50-250 Dispersant and emulsion resin dispersant with acid value of 50~250. These dispersants can be used alone or in combination of two or more kinds.

Examples of the aforementioned nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block polymers, sorbitan fatty acid esters, and polyoxyethylene sorbitans. Alkyd fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, etc.

Examples of the above-mentioned anionic dispersants include fatty acid salts, alkyl sulfate ester salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, and alkyl diaryl ethers. Sulfonate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalenesulfonate formalin condensate, polyoxyethylene alkyl phosphate salt, polyoxyethylene glycerin Fatty acid ester salt, glycerol boolaide fatty acid ester salt, and soda tripolyphosphate, etc. Among them, adding the mixture of the above-mentioned soda tripolyphosphate and the above-mentioned other anionic dispersants can effectively improve the stability of the aqueous pigment dispersion, so it is preferred.

Examples of the amphoteric dispersant include alkyl betaine, alkyl amine oxide, and lecithin.

Examples of the water-soluble resin dispersant with an acid value of 50 to 250 include acrylic resin, acrylic styrene resin, and styrene maleic acid resin; as an emulsion resin dispersant with an acid value of 50 to 250, Examples include acrylic emulsion resins, acrylic styrene emulsion resins, and the like.

The above-mentioned dispersant is preferably used in the range of 0.1-100 parts by mass, and more preferably used in the range of 0.1-60 parts by mass relative to 100 parts by mass of the pigment.

In the above-mentioned water-based pigment dispersion, in addition to the above-mentioned pigment, the above-mentioned dispersant, and water, one or two or more self-soluble solvents, wetting agents, tackifiers, defoamers, and preservatives may be contained as needed. The materials selected among the others.

In the above-mentioned substrate surface treatment liquid, a binder resin for facilitating the formation of a coating film on the surface of the substrate can be further added as necessary. The binder resin may be directly added to the above-mentioned substrate surface treatment liquid, or may be added in advance to the above-mentioned aqueous pigment dispersion. As such a binder resin, natural resins and various synthetic resin emulsions can be exemplified. Examples of natural resin-based binder resins include rosin, shellac, casein, cellulose derivatives, and starch. As synthetic resin emulsions, emulsions containing the following compounds can be exemplified: polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl acetate-acrylate copolymer, vinyl acetate-acrylic acid copolymer, ethylene-acrylic acid copolymer , Polyvinyl alcohol, acrylic resin, acrylate resin containing methyl acrylate, acrylate resin containing ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and other acrylates, styrene-acrylate copolymer, methacrylate resin , Acrylic methacrylic copolymer, silicone modified acrylic resin, epoxy resin, fluororesin, polyurethane resin, and mixtures or copolymers of these. In view of the excellent durability of the obtained coating film, an acrylic resin or methacrylate resin emulsion is preferred, and an acrylic silicone emulsion with acrylate or methacrylate as the main component is particularly preferred. Furthermore, the acid value of the binder resin is preferably less than 50, more preferably less than 30, and particularly preferably 10 or less. As a better commercially available adhesive resin, one can cite: Polysol A-609L (trade name, acrylic resin emulsion manufactured by Showa Polymer Co., Ltd.), Polysol AP-3900 (trade name, acrylic silicone emulsion manufactured by Showa Polymer Co., Ltd.).

In the above-mentioned substrate surface treatment liquid, additives such as a leveling agent and a silane coupling agent can be further added as necessary.

As the leveling agent, silicone oil is preferred, and various silicone oils can be used. Among them, polyether-modified silicone oil is preferred. Specific examples include organopolysiloxanes containing the following structures at the molecular chain end or side chain: polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene-polyoxyethylene Butylene oxide block copolymer, polyoxypropylene-polyoxybutylene block copolymer, etc. Among them, polyoxyethylene, polyoxypropylene, or polyoxyethylene-polyoxypropylene copolymer block is preferably an organopolysiloxane bonded to a silicon atom through an alkylene group. Such polyether-modified silicone oil can be produced by a well-known method, for example, by the method disclosed in Japanese Patent Laid-Open No. 9-165318. As such polyether modified silicone oils, there are TSF4445, TSF4446 (both trade names) (the above are manufactured by GE Toshiba Polysiloxane Co., Ltd.), KF-352, KF-353 (both are trade names) (the above are Shin-Etsu Chemical Industry Manufacturing), SH3746 (trade name, manufactured by Dow Corning Toray Silicone Co., Ltd.).

In addition, a silane compound containing an amine group, an epoxy group, or a methacryloxy group, that is, a silane coupling agent may be added. The coupling agent can improve the hardness of the layer containing the metal-doped titanium oxide and the adhesion with the adjacent layer. In addition, materials selected from silicone rubber, silicone powder, and silicone resin can also be added to the substrate surface treatment solution of the present invention.

Therefore, as the substrate surface treatment liquid of the present invention, there are the following forms: (1) a liquid containing the above-mentioned titanium oxide doped with a specific metal and a silane-based water repellent or anti-absorbent; (2) in the above ( 1) Liquid containing pigments and/or dyes; (3) Liquid containing the above-mentioned titanium oxide doped with specific metals and silicate water repellent or anti-absorbent; (4) In the above (3) A liquid containing pigments and/or dyes; (5) A liquid containing the above-mentioned titanium oxide doped with a specific metal and a polysiloxane and silane composite water repellent or water-absorbing agent; (6) In the above (5) (7) A liquid containing the above-mentioned titanium oxide doped with a specific metal and a polysiloxane-based water repellent or anti-absorbent agent; (8) In the above (7) A liquid containing pigments and/or dyes; (9) A liquid containing a binder resin in the above (2), (4), (6), and (8); (10) A liquid containing the above-mentioned specific metal doped The liquid of titanium oxide and fluorine-based water repellent or anti-absorbent; (11) In the above (10), the liquid further contains pigments and/or dyes and binder resin.

After applying any of these liquids (solutions or dispersions) to the surface of the substrate, the surface of the substrate is treated. As a method of application to the substrate, well-known methods such as brush coating, roller coating, and spray coating can be used. After the treatment liquid of the present invention is applied to the surface of the substrate, it is dried to form a layer with excellent water repellency or water absorption resistance and antifouling properties on the surface of the substrate and/or in the surface layer of the substrate, thereby , Can reduce the pollution of the substrate surface, in the case of a porous substrate, can prevent water from entering the interior of the substrate.

The present invention will be described based on the following specific examples.

(Reference example 1: Preparation of copper-doped amorphous titanium oxide)

0.463 g97% CuCl₂. 2H₂O (copper chloride, manufactured by Nippon Chemical Industry Co., Ltd.) is completely dissolved in 500 ml of pure water, and 10 g of a 50% titanium tetrachloride solution (manufactured by Sumitomo Sitix Co., Ltd.) is added to the solution, and then pure water is added Make the total volume up to 1000 ml.

To the above solution, 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) diluted 10 times with pure water was added dropwise to adjust the pH to 7.0, thereby precipitating a mixture of copper hydroxide and titanium hydroxide.

Wash the precipitate repeatedly with pure water until the conductivity of the supernatant of the precipitate reaches 0.8 mS/m or less. 340 g of an aqueous dispersion containing 0.85% by mass of copper hydroxide and titanium hydroxide in total can be obtained.

Then, while cooling the above aqueous dispersion to 1 to 5°C, 25 g of hydrogen peroxide water (manufactured by Taiki Chemical Industries Co., Ltd.) with a concentration of 35% by mass was added, and then stirred 16 hours. As a result, 365 g of a dispersion liquid as a green transparent liquid containing a concentration of 0.9% by mass of copper-doped amorphous titanium peroxide can be obtained.

(Reference example 2: Preparation of amorphous titanium oxide doped with zinc)

0.3359 g 97% ZnCl₂(Zinc chloride) is completely dissolved in 500 ml of pure water, and 10 g of a 50% titanium tetrachloride solution (manufactured by Sumitomo Sitix) is added to the solution, and then pure water is added to make the total volume 1000 ml.

To the above solution, 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) diluted 10 times with pure water was added dropwise to adjust the pH to 7.0, thereby precipitating a mixture of zinc hydroxide and titanium hydroxide.

Wash the above-mentioned sediment repeatedly with pure water until the conductivity of the clear liquid layer of the sediment reaches 0.713 mS/m (the target value is below 0.8 mS/m). 409 g of an aqueous dispersion containing a total of 0.48% by mass of copper hydroxide and titanium hydroxide can be obtained.

Then, while cooling the aqueous dispersion to 1 to 5°C, 25 g of hydrogen peroxide water (manufactured by Taiki Chemical Industries Co., Ltd.) with a concentration of 35% by mass was added, and then stirred 16 hours. As a result, 434 g of an aqueous solution as a yellow-brown transparent liquid containing amorphous titanium peroxide doped with zinc can be obtained.

(Reference example 3: Preparation of anti-absorbent agent S)

Mix the following materials: 20 parts by weight of n-hexyltriethoxysilane, with the following formula:<chemistry general="n"><img file="TW200704593A_D0002.tif" /></chemistry>

As indicated, 10 parts by weight of organosiloxane with a viscosity of 21 cS, 0.5 parts by weight of polyoxyethylene (2 mol) sodium lauryl ether sulfate, 0.05 parts by weight of sodium oleate, and 69.45 parts by weight of ion exchange water. Pour the mixture into a homogenizer, at 300 kg/cm²Under the pressure, make it pass through the homogenizer twice to obtain milky white water-absorbent agent S with a pH value of 6.9.

(Reference Example 4: Preparation of Water-absorbing Agent C)

To 350 parts by mass of methyltrimethoxysilane, 200 parts by mass of a 50% by mass aqueous solution of sodium hydroxide was slowly added. After adding 450 parts by mass of distilled water to the mixture, the generated methanol was removed by distillation, and then distilled water was added to adjust the solid content to obtain a water-absorbing agent C containing 30% by mass of sodium methyl silicate.

(Example 1)

The 0.85 mass% copper-doped amorphous titanium peroxide dispersion prepared in Reference Example 1 above and the water-absorbent agent S prepared in Reference Example 3 described above are in a volume ratio of 4:1 Mix and stir to obtain substrate surface treatment liquid 1.

(Example 2)

The 0.85 mass% copper-doped amorphous titanium peroxide dispersion prepared in Reference Example 1 above, and the water-absorbent agent C prepared in Reference Example 4 above, will have a volume ratio of 6:1 Mix and stir to obtain substrate surface treatment liquid 2.

(Example 3)

In the substrate surface treatment solution 1 (85 parts by mass) prepared in the above Example 1, mixed with an aqueous pigment dispersion containing pigment titanium oxide (65 parts by mass of titanium oxide, 19.5 parts by mass of acrylic styrene resin with an acid value of 195) Parts, water 15.5 parts by mass) (8 parts by mass), an emulsion of acrylic resin as a binder resin, namely Polysol A-609L (trade name) (manufactured by Showa Polymer Co., Ltd.) (10 parts by mass), and Stir to obtain a substrate surface treatment liquid 3.

(Example 4)

The operation was carried out in the same manner as in the above-mentioned Example 3 to obtain a substrate surface treatment liquid 4 containing a pigment and a binder resin. Wherein, in this case, the substrate surface treatment liquid 2 prepared in the above-mentioned Example 2 was used instead of the substrate surface treatment liquid 1 used in the above-mentioned Example 3.

(Example 5)

The dispersion liquid containing the amorphous titanium peroxide doped with zinc prepared in Reference Example 2 and the water-absorbing agent S prepared in Reference Example 3 were mixed and stirred at a volume ratio of 4:1 to obtain substrate surface treatmentliquid5.

[Evaluation Test]

Using the above substrate surface treatment solutions 1 to 5 as examples, the copper-doped amorphous titanium peroxide dispersion prepared in the above reference example 1 was used as the comparison solution 1, and the above reference examples 3 and 4 were prepared. The anti-absorbent agents S and C were used as comparative solutions 2 and 3, respectively, and the following evaluation tests were carried out.

(Evaluation test 1)

Use commercially available PC concrete paving stones (300 mm×300 mm×50 mm) as the base material. The substrate surface treatment liquids 1 to 5 and the comparative liquids 1 to 3 were respectively brushed on 1/2 of the surface of the paving stones, and dried at room temperature to prepare samples for evaluation. Place the surface of the evaluation material coated with the substrate surface treatment liquid or the comparison liquid upward, tilt it to the south by 75 degrees, and expose it to the outdoors. The exposure was carried out in Fujitsu County, Saga Prefecture from April 2004 to December 2004.

Visually observe the surface of the evaluation sample after exposure to evaluate the antifouling performance of each sample. In addition, use a sprayer to fully spread pure water on the surface of the evaluation sample after exposure. After leaving it for about 10 minutes, cut each sample and visually observe the penetration of water from the surface to the inside of the section to evaluate each evaluation sample. Anti-water absorption performance. The evaluation was based on the following benchmarks, and the results obtained are summarized in Table 1.

Antifouling performance: The antifouling performance is based on the test results of PC concrete paving stones that have not been exposed to outdoor exposure. means that there is no difference between the sample and the evaluation sample. means that although it was confirmed that the sample for evaluation was slightly discolored, no dirt adhesion was observed. means that the sample for confirmation evaluation has discoloration and slight dirt adhesion. × means that the color of the sample for confirmation grading has changed, and the adhesion of dirt is remarkable. The so-called "discoloration" here means that when the surface of the PC concrete paving stone is exposed to the outdoors, it repeatedly absorbs water and dries, thereby deteriorating the greenish gray surface initially and presenting a reddish white (pink ocher yellow ~ cream).

Water absorption resistance: means that it has not been confirmed that water has penetrated into the interior from the surface of the sample for evaluation. means that it is confirmed that a little water has penetrated into the extreme surface part of the evaluation sample. × means that water was seen to penetrate into the interior from the surface of the sample for evaluation.

<tables><img file="TW200704593A_D0003.tif" /></tables>

From the results shown in Table 1, it can be seen that when the substrate is treated with a surface treatment solution containing a water-absorbing agent or a water-repellent agent, and titanium oxide doped with copper or zinc, the substrate can be simultaneously provided with water-absorbing properties and Antifouling performance.

(Example 6: Red ink fading test)

Color the substrate that has been surface-treated with the substrate surface treatment liquid with organic dyes, and measure the fading rate of the organic dyes produced by photooxidation. The test is carried out as follows.

Use 100 mm×100 mm white ceramic tiles (manufactured by Danto Co., Ltd.) as the substrate. Evaluate the following 7 samples.

(1) The surface of the untreated substrate (2) The surface of the substrate has been treated with B56 (Sustainable Titania Technology Inc., photocatalyst). (3) Compared to the copper-doped amorphous titanium oxide in Reference Example 1 above 100 parts by mass of the dispersion liquid, 0.1 parts by mass of the leveling agent SH3746M (trade name, manufactured by Toray Dow Corning Co., Ltd.) is added, and the surface of the substrate is treated with this solution (4) The copper-doped substance in the above reference example 1 The surface of the substrate is treated with the amorphous titanium oxide dispersion liquid (5) The surface of the substrate is treated with the water-absorbent agent S of Reference Example 3 (6) The substrate is treated with the substrate surface treatment solution 1 of Example 1 (7) The surface treatment of the substrate surface treated with the substrate surface treatment liquid 3 of the above-mentioned Example 3 The surface treatment of the above-mentioned substrate is carried out as follows: Use a spray gun (Meiji Machinery

Co., Ltd.), each treatment liquid is 15 g/cm²~20 g/cm²Spray on the surface of the substrate, and then heat it in a constant temperature and humidity room at 80°C for 15 minutes after drying.

Then on the surface-treated substrate (above (1) ~ (7)), the red ink made by pilot company is diluted with ethanol 10 times at 0.001 g/100 cm each time²The amount was sprayed 7 times and then dried, and evaluated by the following method.

(assessment method)

Arrange the above surface-treated substrate samples (1)~(7) whose surface is colored with red ink on a straight line, and place a 20 W black lamp (manufactured by Toshiba Optoelectronics) on the sample, on the sample colored with red ink The surface is irradiated with ultraviolet rays. The amount of ultraviolet light is 1100 μW/cm². Using a colorimeter (manufactured by Minolta, CR-200), the fading rate of the red ink on the surface of the sample was measured over time.

Use the following formula to calculate the fading rate (%) of the red ink.

<b>The color data of the sample surface before the surface is colored with red ink: L0, a0, b0 The color data of the sample surface colored with the red ink (initial value): L1, a1, b1 The color data of the sample surface after ultraviolet radiation: L2, a2 b2 fading rate</b>＝<img file="TW200704593A_D0004.tif" />

The resulting fade rate results are shown in Table 2. In the table, the value (%) represents the UV exposure time after the test and the red ink fading rate on the surface of the sample. The larger the fading rate in the table, the more obvious the fading of the red ink.

<tables><img file="TW200704593A_D0005.tif" /></tables>

From the results shown in the table, it can be seen that, compared with samples (1) to (5), the red ink fading rate of samples (6) and (7) is low, and the degradation of red ink pigment caused by ultraviolet light is low.

(Example 7)

32.1 parts by mass of the copper-doped amorphous titanium oxide dispersion prepared in Reference Example 1 with a concentration of 0.85% by mass, and 7.6 parts by mass of the water-absorbing agent S prepared in Reference Example 3 above, containing as a pigment Monoazo Red is an aqueous pigment dispersion of organic pigments (pigment red 1725 parts by mass, polyoxyethylene nonylphenyl ether HLB 14.1 7.5 parts by mass, water 67.5 parts by mass) 1.2 parts by mass, and acrylic resin emulsion as a binder resin Polysol A-609L (trade name) (manufactured by Showa Polymer Co., Ltd.) (10 parts by mass) was mixed and stirred to obtain a substrate surface treatment liquid 6.

(Comparative Example 4)

Using 32.1 parts by mass of pure water instead of 32.1 parts by mass of the copper-doped amorphous titanium peroxide dispersion prepared in Reference Example 1 with a concentration of 0.85% by mass, the same operation as in Example 7 was carried out to obtain Substrate surface treatment liquid 7.

(Comparative Example 5)

Except that 7.6 parts by mass of pure water was used instead of 7.6 parts by mass of the water-absorbing agent S prepared in Reference Example 3, the same operation as in Example 8 was carried out to obtain a substrate surface treatment liquid 8.

(Evaluation test 3)

Use 100 mm×100 mm white ceramic tiles (manufactured by Danto Co., Ltd.) as the substrate. After brushing the above-mentioned substrate surface treatment liquids 6 to 8 on the surface of the tile, it is dried at room temperature to prepare a sample for evaluation. For the evaluation material, after covering a part of the surface coated with the substrate surface treatment liquid and setting the non-irradiated part, use the WEL-SUN-HCH of Suga Test Instruments Co. Ltd. (Suga Test Instruments. Co. Ltd). B-type sunshine weather meter (black panel temperature 63°C), 600 hours of accelerated weather resistance test.

Use a macbeth color eye CE-7000A spectrophotometer on the surface of the evaluation sample after the accelerated weathering test, and measure the color difference of the irradiated part with the masked unirradiated part as the standard. The results obtained are summarized in Table 3.

<tables><img file="TW200704593A_D0006.tif" /></tables>

From the results shown in Table 3, it can be seen that when the substrate is treated with a substrate surface treatment solution containing a water-repellent or an anti-absorbent, copper-doped titanium oxide, and a pigment, it is compared with the case where the substrate is doped with copper. When the substrate surface treatment solution of titanium oxide and pigment is used to treat the substrate, and the substrate surface treatment solution containing only the pigment is used to treat the substrate, the pigment contained in the substrate surface treatment solution is fading due to ultraviolet rays reduce.

FIG. 1 is a schematic diagram showing an aspect of the method for producing a titanium oxide doped with a specific metal of the present invention.