JP2006321993A - Solution or dispersion for treating surface of base material, containing titanium oxide doped with metal element, method for treating surface of base material by using the liquid, and surface-treated material obtained by using the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface-treating agent for imparting water repellency or water absorption-preventing properties, and excellent antifouling properties to the surface of a material, especially the material used outdoors; and to provide the material surface-treated with the surface-treating agent. <P>SOLUTION: The method for treating the surface of the base material involves forming a layer containing a water repellent or a water absorption-preventing agent, and titanium oxide doped with at least one kind of a metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron and zinc on the surface of the base material and/or in the surface layer of the base material by using a solution or a dispersion containing the water repellent or water absorption-preventing agent, preferably the silane-based, siliconate-based, silicone-based, silicone and silane composite-based and/or fluorine-based water repellent or water absorption-preventing agent, and the titanium oxide doped with at least one kind of the metal element selected from the group consisting of the copper, the manganese, the nickel, the cobalt, the iron and the zinc, preferably, the amorphous titanium oxide or the amorphous titanium oxide at least a part of which is peroxidized. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a treatment solution used for producing a surface treatment material having excellent water absorption prevention and antifouling properties, a substrate surface treatment method using the treatment solution, and a surface obtained using the surface method. It relates to processing materials.

  For example, various materials used in buildings and the like and used outdoors are contaminated with various pollutants contained in the atmosphere and rainwater, organisms such as moss and mold, and microorganisms. There is a problem that the aesthetics of are damaged over time. In fact, in a building such as a building, regular surface cleaning is indispensable in order to keep the appearance beautiful.

  Further, in the building materials made of reinforcing steel and / or steel-containing concrete, there is a problem that rust is generated in the reinforcing steel and the steel frame due to the penetration of rainwater into the concrete, and the concrete is cracked by the volume expansion of the iron material due to the rust. In addition, concrete itself has a problem of strength reduction due to neutralization caused by acidic substances contained in rainwater. Similarly, marble building materials have a problem of deterioration due to acidic substances.

  In order to solve these problems, by applying a water repellent substance such as a silicone-based compound and / or a fungicide and / or an antibacterial agent to the surface of a material such as an outdoor building material, moisture can be prevented from entering the material. In addition, attempts have been made to suppress adhesion of contaminants on the surface of building materials and propagation on the surface of materials such as moss. However, even when a water-repellent substance is applied to the surface of the material, it is not possible to sufficiently prevent contamination of the surface of the material due to surface contamination due to the deposition of hydrophobic contaminants.

  In recent years, a method of forming a photocatalyst layer on the material surface has been used as a method for preventing contamination of the material surface. For example, a method of forming a photocatalyst layer such as anatase-type titanium peroxide on a water-repellent layer made of an alkali metal silicate compound formed on the substrate surface (see, for example, Patent Document 1), and forming on the substrate surface A method of further forming a photocatalyst layer on a primer layer containing an acrylic resin having an alkoxysilyl group and a hydroxyl group has been proposed (for example, see Patent Document 2). The inventor has also proposed a titania-metal composite as a material for forming an antifouling titania layer having excellent activity (see Patent Document 3).

Furthermore, the materials used for buildings and the like outdoors can be colored in order to enhance the design of the materials, and the color of the materials can be improved in combination with the excellent water absorption prevention and antifouling properties as described above. There is also a need for no change over time.
JP 2000-135442 A JP 2002-138243 A International Publication No. 2004/04173 Pamphlet

  Of the methods for preventing contamination of the material surface described above, in the method of further forming a photocatalyst on the water repellent layer made of an alkali metal silicate compound on the substrate surface (see Patent Document 1), the action of the alkali metal silicate compound The photocatalyst layer may be hydrolyzed, and it is difficult to color the alkali metal silicate compound.

  In the method of further forming a photocatalyst layer on the primer layer containing an acrylic resin having an alkoxysilyl group and a hydroxyl group formed on the surface of the substrate (see Patent Document 2), coloring the acrylic resin is relatively Although easy, there was a problem that the acrylic resin itself was decomposed and deteriorated by the action of the photocatalyst.

  The present invention provides a material for forming a surface layer that is excellent in water absorption prevention and antifouling properties and can be easily colored on the surface of a base material used outdoors such as for construction and civil engineering works, and the material. A surface treatment material having a surface layer which is surface-treated using the method, has excellent water absorption prevention and antifouling properties, and can be easily colored if desired. It is something to be offered.

  The material used for the surface treatment of the substrate in the present invention is doped with a water repellent or water absorption inhibitor and at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc. It is a solution or dispersion characterized by containing a titanium oxide.

  Furthermore, the water repellent or water absorption inhibitor used in the above solution or dispersion is a silane, siliconate, silicone, silicone and silane composite, and / or fluorine water repellent or water absorption inhibitor, and It is preferable that the titanium oxide doped with the metal element is amorphous titanium oxide or amorphous titanium oxide at least partially peroxolated.

  Furthermore, the above-mentioned solution or dispersion is further optionally a nonionic dispersant, an anionic dispersant, an amphoteric dispersant, a water-soluble resinous dispersant having an acid value of 50 to 250, and an emulsion having an acid value of 50 to 250. One or more dispersants selected from the group consisting of resinous dispersants, pigments, and aqueous pigment dispersions composed of water can be contained.

  Further, the solution or dispersion may further contain an organic resin binder as desired.

  In the substrate surface treatment method of the present invention, any one of the above solutions or dispersions is applied to the substrate, whereby the water repellent or water absorption inhibitor, and copper, manganese, nickel, cobalt, iron, and A layer containing titanium oxide doped with at least one metal element selected from the group consisting of zinc is formed on the substrate surface and / or in the substrate surface layer.

  The surface treatment material of the present invention is manufactured using the above surface treatment method, and is at least one selected from the group consisting of a water repellent or a water absorption inhibitor, and copper, manganese, nickel, cobalt, iron, and zinc. A layer containing titanium oxide doped with a metal element is formed on the surface of the base material and / or in the surface layer of the base material.

  The inventor uses a solution or dispersion containing a water repellent or a water absorption inhibitor together with the titanium oxide doped with the specific metal element, the titanium oxide on the surface or surface layer of the substrate, and By forming a layer containing a water repellent or a water absorption inhibitor, the surface of the substrate is hardly contaminated, water absorption to the substrate can be prevented, and it is easy to color the surface of the substrate. It has been found that the design of the substrate surface can be improved, and the present invention has been completed.

  In the present invention, a solution or dispersion containing a water repellent or a water absorption inhibitor and a titanium oxide doped with the above-mentioned specific metal element is applied to the surface of the substrate, and the substrate surface and / or the substrate In the surface layer, a layer containing the water repellent or water absorption inhibitor and the titanium oxide is formed. When the base material is non-porous such as glass or metal, the above layer is formed on the surface of the base material, and when the base material is porous such as concrete, the above solution or dispersion is slightly from the base material surface to the inside. In order to penetrate, the layer is generally formed on and in the substrate surface layer. The substrate targeted by the present invention is not particularly limited. Examples of the non-porous substrate include stones, plastics, rubber, sealing materials, and glaze tiles in addition to the glass and metal described above. Examples of the porous substrate include wood, mortar, porous stone, and stoneware tiles in addition to the above-described concrete. The base material targeted by the present invention is particularly preferably concrete.

  The surface treatment agent for a substrate of the present invention contains a water repellent or water absorption inhibitor and titanium oxide doped with the specific metal element as essential components. Hereinafter, a titanium oxide doped with a specific metal element will be described, and then a water repellent or a water absorption inhibitor will be described.

A solution or dispersion containing the titanium oxide doped with the specific metal element (hereinafter also referred to as “specific metal-doped titanium oxide”) used in the present invention is disclosed in the pamphlet of International Patent Application Publication No. WO2004 / 041723. Can be used. More specifically, in the present specification, the specific metal-doped titanium oxide contained in the solution or dispersion is at least one selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc. Or a compound thereof, and a compound containing a titanium oxide or a titanium oxide at least partially peroxolated. As a titanium compound that becomes a base compound of at least a part of peroxo titanium oxide, various titanium oxides such as TiO ₂ , TiO ₃ , TiO, and TiO ₃ / nH ₂ O and titanium hydroxide are peroxidized. The thing made to react with a thing is mentioned. Furthermore, the crystal system of the titanium oxide may be any of amorphous type, anatase type, brookite type, rutile type, or a mixed type thereof, and is particularly excellent in film forming property and adhesion to a substrate. Therefore, the amorphous type is preferable.

Examples of a method for producing a solution or dispersion containing the specific metal-doped titanium oxide include the following methods.
(Production method 1)
A titanium hydroxide is synthesized by reacting a tetravalent titanium compound such as titanium tetrachloride with a base such as ammonia. Next, the obtained titanium hydroxide is oxidized with an oxidizing agent to peroxo to synthesize amorphous titanium oxide ultrafine particles at least partially peroxod (hereinafter, at least partly peroxodized). Titanium oxide is also referred to as peroxotitanium oxide). The above reaction is preferably performed in an aqueous medium. The obtained peroxo-amorphous titanium oxide can be transferred to peroxo-anatase-type titanium oxide by heating, if desired. In the present invention, as described above, it is particularly preferable to use amorphous titanium oxide. At any stage in the production process of the peroxotitanium oxide, at least one selected from copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is added to the reaction mixture. It is possible to obtain a specific metal-doped titanium oxide whose part is peroxo-ized.

  The oxidizing agent for peroxylating titanium hydroxide is not particularly limited as long as it is an oxidizing agent capable of producing a titanium peroxo compound, that is, titanium peroxide, but hydrogen peroxide is particularly preferable. In the present invention, it is particularly preferable to use hydrogen peroxide having a concentration of 30 to 40% by weight. Furthermore, when performing peroxo oxidation of titanium hydroxide, it is preferable to cool the solution containing titanium hydroxide in advance, and the temperature in that case is preferably 1 to 5 ° C.

  The said manufacturing method 1 is demonstrated based on FIG. FIG. 1 is a diagram showing an outline of one embodiment of the production method 1. First, as illustrated in FIG. 1, a titanium tetrachloride aqueous solution and an ammonia aqueous solution are mixed in the presence of at least one compound of copper, manganese, nickel, cobalt, iron, and zinc, and titanium tetrachloride and other metal compounds are mixed. To obtain 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 are not particularly limited as long as the desired reaction product can be obtained, but the stability of the dispersion is good. Therefore, it is preferable that the concentration of each raw material is low and the reaction temperature is room temperature. This reaction is a neutralization reaction, and the pH of the reaction mixture is preferably finally adjusted to about 7. The pH can be adjusted, for example, by adjusting the amount of the aqueous ammonia solution to be added. In this case, a metal compound other than titanium can be added before the start of the neutralization reaction performed by adding an aqueous ammonia solution and / or during the neutralization reaction.

  The metal hydroxide mixture obtained by the neutralization reaction is separated from the solution, washed with pure water and then cooled. The cooling temperature is preferably around 5 ° C., but is not particularly limited. Next, the aqueous dispersion of the metal hydroxide mixture is peroxoated with hydrogen peroxide. By this reaction, amorphous titanium oxide fine particles doped with at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc, and at least partially peroxolated A solution or dispersion containing is obtained. The obtained dispersion can be further ultrafiltered to obtain a dispersion containing ultrafine particles.

(Production method 2)
A tetravalent titanium compound such as titanium tetrachloride is first peroxolated using an oxidizing agent and then neutralized using a base such as ammonia, and is at least partially peroxolated. Synthesize ultrafine particles (ie amorphous titanium peroxide). This reaction is preferably carried out in an aqueous medium. Furthermore, the amorphous titanium peroxide can be transferred to anatase titanium peroxide by heat treatment if desired. In any one of the peroxolation step and the neutralization reaction, the specific metal dope of the present invention is mixed by mixing at least one selected from copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof. A solution or dispersion containing titanium oxide is obtained.

(Production method 3)
In the presence of at least one selected from copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof, a tetravalent titanium compound, for example, titanium tetrachloride, an oxidizing agent such as hydrogen peroxide and a base such as ammonia. By acting simultaneously, the hydrolysis of the metal compound and the tetravalent titanium compound and the peroxo conversion of the titanium compound are simultaneously performed, and the solution or dispersion containing the specific metal-doped titanium oxide of the present invention is obtained. Also in this case, if desired, amorphous titanium peroxide can be transferred to anatase titanium peroxide by heat treatment.

The tetravalent titanium compound used in the above production methods 1 to 3 may be any compound that can generate titanium hydroxide called orthotitanic acid (H ₄ TiO ₄ ) when reacted with a base. 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 acid salts such as titanium oxalate. Among these compounds, titanium tetrachloride is preferable because it is excellent in water solubility and can reduce the content of unnecessary impurities contained in the obtained specific metal-doped titanium oxide.

  In the above production methods 1 to 3, the concentration of the tetravalent titanium compound when reacted with the base is not particularly limited as long as the titanium hydroxide to be formed is a concentration capable of forming a gel, but avoids the remaining unreacted substances. Therefore, a relatively dilute solution is preferable. Specifically, the concentration of the tetravalent titanium compound in the solution is preferably 5 to 0.01% by mass, and more preferably 0.9 to 0.3% by mass. By reacting the tetravalent titanium compound and the base in this concentration range, a titanium hydroxide dispersion or gel having good dispersibility can be obtained.

  The base used in the said manufacturing methods 1-3 should just be a thing which can produce | generate a titanium hydroxide gel from the tetravalent titanium compound to be used, and is not specifically limited. Examples of the base include ammonia, caustic soda, sodium carbonate, and caustic potash, but ammonia is particularly preferable. The base is usually added as a solution, for example, an aqueous solution, to the tetravalent titanium compound solution or dispersion. In this case, the concentration of the base solution is not particularly limited as long as the titanium hydroxide gel can be formed, but it is preferably a relatively dilute solution. Specifically, the concentration of the base solution used is preferably It is 10-0.01 mass%, More preferably, it is 1.0-0.1 mass%. When ammonia water is used as the base solution, the ammonia concentration is preferably 10 to 0.01% by mass, and more preferably 1.0 to 0.1% by mass in order to avoid excessive ammonium ions remaining.

The compounds of copper, manganese, nickel, cobalt, iron, or zinc used in the above production methods 1 to 3 are as follows:
Ni compound: Ni (OH) ₂ , NiCl ₂ ;
Co compound: Co (OH) NO ₃ , Co (OH) ₂ , CoSO ₄ , CoCl ₂ ;
Cu compound: Cu (OH) ₂ , Cu (NO ₃ ) ₂ , CoSO ₄ , CoCl ₂ , Cu (CH ₃ COO) ₂ ;
Mn compound: MnNO ₃ , MnSO ₄ , MnCl ₂ ;
Fe compounds: Fe (OH) ₂ , Fe (OH) ₃ , FeCl ₃ ;
Zn compound: Zn (NO ₃ ) ₂ , ZnSO ₄ , ZnCl ₂ ;
Can be illustrated.

  The solid content concentration (total concentration of titanium compound and specific metal compound contained in the liquid) of the solution or dispersion of the specific metal-doped titanium oxide of the present invention obtained by the above production methods 1 to 3 has good stability. In order to obtain a solution or a dispersion, 0.05 to 15% by mass is preferable, and 0.1 to 5% by mass is more preferable. Furthermore, the molar ratio of titanium and other specific metals contained in the solution or dispersion is good because the antifouling performance and the like of the substrate surface-treated with these solutions or dispersions becomes good. 0.01-1: 0.5 are preferable and 1: 0.03-1: 0.1 are more preferable.

(Production method 4: Production method by sol-gel method)
A solution containing titanium alkoxide, a solvent such as water and alcohol, and an acid or base catalyst is mixed and stirred to hydrolyze the titanium alkoxide to prepare an ultrafine titanium oxide sol solution. At least one selected from copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is added to the above solution or sol solution before, during, or after the hydrolysis reaction. To obtain a solution or dispersion containing the specific metal-doped titanium oxide of the present invention.

The titanium alkoxide used in the production method 4 is a compound represented by the general formula: Ti (OR ′) ₄ (wherein R ′ is an alkyl group), or one or two OR ′ in the general formula. A compound in which the group is substituted with a carboxyl group or a β-dicarbonyl-containing group, or a mixture thereof is preferred. Examples of the titanium alkoxide include Ti (O—isoC ₃ H ₇ ) ₄ , Ti (O—nC ₄ H ₉ ) ₄ , Ti (O—CH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ) ₄ , Ti (O—C ₁₇ H ₃₅ ) ₄ , Ti (O—isoC ₃ H ₇ ) ₂ [CO (CH ₃ ) CHCOCH ₃ ] ₂ , Ti (O—nC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C _{2 H 4 OH) 2] 2} , Ti (OH) 2 [OCH (CH 3) COOH] 2, Ti (OCH 2 CH (C 2 H 5) CH (OH) C 3 H 7) 4, and Ti (O _{-nC 4 H 9) 2 (OCOC} 17 H 35) 2 and the like.

The sol-gel method of production method 4 is known as a method for synthesizing metal oxides. When producing the specific metal-doped titanium oxide of the present invention, a commonly used method and necessary compounds such as acids or bases are used. Can be implemented.
Moreover, the compound of copper, manganese, nickel, cobalt, iron, or zinc used when manufacturing the specific metal dope titanium oxide of this invention by a sol-gel method is the same as the compound used by the said manufacturing methods 1-3. . Furthermore, preferred solid content concentration (total concentration of titanium compound and specific metal compound contained in the liquid) of the specific metal doped titanium oxide solution or dispersion of the present invention prepared by the sol-gel method, and in the solution or dispersion liquid The preferable molar ratio of titanium and other specific metals contained in the above is the same as those concentrations and molar ratios described in the production methods 1 to 3.

  In addition, the specific metal-doped titanium oxide of the present invention is obtained by mixing and dissolving the “organic titanium peroxy compound” described in JP 2000-159786 A and the specific metal compound in water, and concentrating the obtained solution. It can also be produced by a method of gelling. It is also possible to prepare a water-soluble mixture composed of a “titanium complex” described in JP-A No. 2001-10816 and a “metal complex” other than titanium as a starting material.

(Water repellent or water absorption inhibitor)
The substrate surface treatment solution or dispersion of the present invention includes a water repellent or a water absorption inhibitor together with the specific metal-doped titanium oxide. The water repellent or water absorption inhibitor used in the present invention is preferably a silane, siliconate, silicone, silicone and silane composite, or fluorine water repellent or water absorption inhibitor. Such a material is called a water repellent when applied to a non-porous substrate surface, and can prevent water absorption to the substrate when applied to a porous substrate surface. It is called a water absorption inhibitor.

  The silane-based, siliconate-based, silicone-based, and silicone and silane composite-based water repellent or water absorption inhibitor used in the present invention is based on the chemical components of the water repellent or water absorption inhibitor after being applied to the substrate surface. It refers to a material that can form a chemical bond by reacting with the material, or can form a film having a certain degree of durability by cross-linking chemical components. Such a material is advantageous because it quickly develops water repellency or water absorption resistance, maintains water repellency or water absorption resistance to the substrate for a long period of time, and is excellent in weather resistance.

  Various types of silane-based, siliconate-based, silicone-based, silicone and silane composite-based, and fluorine-based water repellents or water absorption inhibitors are known, and any of them can be used in the present invention. Two or more kinds can be used in combination. In the present invention, it is preferable to use a silane, siliconate, silicone, or silicone and silane composite water repellent or water absorption inhibitor. Among these, particularly preferable as the water repellent or water absorption inhibitor used in the present invention is a silane-based water repellent or water absorption inhibitor comprising a hydrolyzable silane, water and a surfactant, and further water added thereto. Hydrolyzate and / or partial hydrolyzate of degradable silane and silicone and silane composite water repellent or water absorption inhibitor containing compounds selected from various organopolysiloxanes, and alkali metal salts of organosiliconate Examples thereof include a siliconate-based water repellent or a water absorption inhibitor made of an aqueous solution.

  Various hydrolyzable silanes used for the silane-based water repellent or water absorption inhibitor are known. For example, tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane include 1 type, or 2 or more types selected from these can be used. The surfactant is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a mixture thereof can be used.

  Examples of the silicone and silane composite water repellent or water absorption inhibitor include the hydrolyzable silane, surfactant, hydrolyzate and / or partial hydrolyzate of the hydrolyzable silane, and And those comprising a compound selected from the above hydrolyzable silanes, surfactants, and various organopolysiloxanes. As the above various organopolysiloxanes, organopolysiloxanes having hydrolyzable groups selected from alkoxy groups bonded to silicon atoms, alkenoxy groups, amino groups, amide groups, acetoxy groups, and ketoxime groups can be used. .

Specific examples of the silicone and silane composite water repellent or water absorption inhibitor include the compositions disclosed in JP-A-62-2197369 or JP-A-6-313167. A particularly preferred silane-based water repellent or water absorption inhibitor used in the present invention is an aqueous composition, and (A) general formula R ¹ _a Si (OR ² ) _4-a (wherein R ¹ has ¹ carbon atom) -20 identical or different monovalent hydrocarbon groups, R ² is a monovalent hydrocarbon group having 1 to 3 carbon atoms, and a is 1 or 2.) 100 parts by weight, (B) Formula bonded to a silicon atom: —R ³ —Si (R ⁴ ) _b (OR ² ) _3-b (wherein R ² is a monovalent hydrocarbon having 1 to 3 carbon atoms) R ³ is a divalent hydrocarbon group, R ⁴ is the same or different monovalent hydrocarbon group, and b is 0, 1, or 2). 1 to 200 parts by weight of an organosiloxane having (C) an anionic surfactant, and (D) water. Is shall.

Specific examples of R ¹ of the organoalkoxysilane as the component (A) include methyl, ethyl, propyl, tert-butyl, pentyl, n-hexyl, heptyl, and 2-ethylhexyl. Group, octyl group, dodecyl group, octadecyl group and other alkyl groups; phenyl group, tolyl group, xylyl group, naphthyl group and other aryl groups; benzyl group, phenethyl group and other aralkyl groups; fluoromethyl group, 3, 3, 3 -Substituted alkyl groups such as trifluoropropyl group, 3,3,4,4,5,5-heptafluoropentyl group and difluoromonochloropropyl group. Among these, an alkyl group having 4 to 10 carbon atoms is particularly preferable. When the number of carbon atoms is 4 or more, water repellency as a water repellent can be increased, and by setting the number of carbon atoms to 10 or less, the permeability to the porous substrate can be increased. Specific examples of R ² of the organoalkoxysilane include a methyl group, an ethyl group, and a propyl group. The organoalkoxysilane can be used alone or in combination of two or more. When this component (A) is applied to the surface of an inorganic base material (specifically, a building material such as concrete) as a porous base material, it penetrates into the base material and chemically bonds with the base material surface layer. A water repellent layer can be formed therein.

The aspect of the substituent in the organic group bonded to the organosiloxane of the component (B) is as follows. R ² is the same as ^{R 2} in component (A). R ³ is a divalent hydrocarbon group, and specifically includes an alkylene group such as an ethylene group, an n-propylene group, an isopropylene group, and an isobutylene group. R ⁴ is the same or different monovalent hydrocarbon group, for example, alkyl group such as methyl group, ethyl group, propyl group, octyl group, decyl group, dodecyl group; phenyl group, naphthyl group, tolyl group, etc. Aryl groups; aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group; and halogenated alkyl groups such as 3,3,3-trifluoropropyl group. b is preferably 0 or 1. The organic group can be present only at the molecular chain end of the organosiloxane, only at the side chain, or both. In addition to the organic group represented by the above structural formula, the organic group that the organosiloxane of the component (B) has is preferably the same or different monovalent hydrocarbon group, particularly a methyl group and a carbon number of 4 or more. It preferably has an alkyl group. The organosiloxane of component (B) can be linear, branched, and / or cyclic, and is preferably linear. Further, the component (B) may be any of a homopolymer, a block copolymer, and a random copolymer.

  Examples of the formula (B) component include the following formula:

  (Wherein, m is a number of 0 or more, n is a number of 1 or more, and m + n is a number of 1 to 50). By setting m + n in the formula to 1 to 50, the permeability into the porous substrate can be enhanced. The component (B) is preferably used in an amount of 1 to 200 parts by weight, more preferably 10 to 100 parts by weight, relative to 100 parts by weight of the component (A). The storage stability of the mixture can be increased by using the component (B) in an amount of 1 part by weight or more, and the content of the component (A) can be increased by reducing the content of the component (A) to 200 parts by weight or less. The water repellency of the surface layer formed when applied to the material can be increased.

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

  The component (C) is preferably used in the range of 0.1 to 50 parts by weight, and in the range of 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B) More preferably. The water of component (D) is preferably used in such an amount that the total amount of component (A) and component (B) is 5 to 60% by weight of the total amount of (A) to (D). . The aqueous water repellent or water absorption inhibitor obtained by emulsifying these mixtures is particularly preferable as the water repellent or water absorption inhibitor used in the present invention. Examples of the commercially available water repellent or water absorption inhibitor include Dry Seal S (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.).

  As the above-mentioned siliconate water repellent or water absorption inhibitor, known ones can be used, but alkyl such as sodium methyl siliconate aqueous solution, sodium propyl siliconate aqueous solution, potassium methyl siliconate aqueous solution, and potassium propyl siliconate aqueous solution. An aqueous solution of an alkali metal salt of a siliconate; and an aqueous solution of an alkali metal aminoorganofunctional siliconate described in JP-A-5-214251. Examples of commercially available siliconate-based water repellents or water absorption inhibitors include dry seal C and dry seal E (both trade names: manufactured by Toray Dow Corning).

Examples of the silicone-based water repellent or water absorption inhibitor include an anionically stabilized hydroxyl group-containing diorganopolypolyol described in JP-A No. 58-118853 or JP-A No. 60-96650. A silicone emulsion comprising siloxane, colloidal silica, and a curing catalyst, or an ionic or non-ionically stabilized alkoxy group-containing diorganopolysiloxane and a titanium catalyst described in JP-A-7-150045 A room temperature curable aqueous silicone emulsion composition that cures at room temperature by removal of moisture to give an elastomeric cured product, such as a silicone emulsion; described in JP-A-55-48245;
(A) Average unit formula R ′ _l SiO ₍ 4-1k _{) / 2} (OH) _k (wherein R ′ is a substituted or unsubstituted monovalent hydrocarbon group, and l is 0.80 to 1. And k is a value such that the proportion of hydroxyl groups bonded to silicon atoms in the compound is 0.01% by mass or more.)
(B) α represented by the general formula HO— (R ⁵ ₂ SiO) _q —H (wherein R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group, and q is an integer of 2 or more). , Ω-dihydroxydiorganopolysiloxane; and (c) a silicon compound represented by the general formula R ⁶ _c SiX _4-c (where c is 0, 1 or 2 and X is a hydrolyzable group) or Its partially hydrolyzed condensate,
A room temperature curable silicone resin composition characterized in that, and described in JP-A-6-73291,
(A) an organopolysiloxane containing SiO _4/2 units or R ⁷ SiO _3/2 units and having a silicon atom-bonded hydroxyl group or silicon atom-bonded alkoxy group content of 0.1% by mass or more in the molecule;
(B) a diorganopolysiloxane represented by the general formula HO (R ⁸ ₂ SiO) _p H (wherein R ⁸ is a monovalent hydrocarbon group and p is an integer of 2 or more);
(C) Aminoxy represented by the general formula R ⁹ ₂ NO (R ¹⁰ SiO) _r NR ⁹ (wherein R ⁹ and R ¹⁰ are monovalent hydrocarbon groups, and r is an integer of 1 or more). Group-containing organosilicon compounds;
(D) a surfactant; and (E) water,
A silicone resin having a hydrolyzable group such as a hydroxyl group or an alkoxy group, a hydrosilyl group-containing diorganopolysiloxane, and a hydrolyzable group-containing silane or hydrolyzable, such as an aqueous silicone emulsion resin composition comprising Examples include room temperature curable silicone resin water repellents or water absorption inhibitors composed of a group (excluding hydroxyl groups) -containing organopolysiloxane.

  The fluorine-based water repellent or water absorption inhibitor used in the present invention is a fluorine-containing compound such as a perfluoroalkyl group-containing compound or a fluorine-containing compound-containing composition. In addition, when a fluorine-containing compound having high adsorptivity to the substrate surface is selected, the chemical component of the water repellent or water absorption inhibitor reacts with the substrate to form a chemical bond after being applied to the substrate surface. It is not always necessary for the chemical components to be cross-linked.

  The fluorine-containing compound that can be used as such a fluorine-based water repellent or water absorption inhibitor preferably has a molecular weight of 1,000 to 20,000 containing a perfluoroalkyl group in the molecule. Perfluorosulfonate, ammonium perfluorosulfonate, perfluorocarboxylate, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoroalkylamine oxide, perfluoroalkyl phosphate ester, and perfluoroalkyltrimethyl An ammonium salt etc. are mentioned. Especially, since it is excellent in the adsorptivity to the base-material surface, perfluoroalkyl phosphate ester and perfluoroalkyl trimethyl ammonium salt are preferable. As such materials, Surflon S-112, Surflon S-121 (both trade names, manufactured by Seimi Chemical Co., Ltd.) and the like are commercially available.

  Other fluorine-based water repellents or water absorption inhibitors include copolymers of two or more olefins containing fluorine atoms, copolymers of olefins containing fluorine atoms and hydrocarbon monomers, and fluorine atoms. A fluororesin emulsion comprising at least one fluororesin selected from the group consisting of a mixture of a copolymer of two or more olefins and a thermoplastic acrylic resin and a surfactant, and a curing agent -124880, JP-A-5-117578, JP-A-5-179191) and / or a composition comprising the above silane-based water repellent or water-absorbing agent (JP-A-2000-121543). JP 2003-26461 A). As this fluororesin emulsion, what is marketed can be used, and it can be purchased as a Zaffle series from Daikin Industries, Ltd. and as a Lumiflon series from Asahi Glass Co., Ltd. As the curing agent, a melamine curing agent, an amine curing agent, a polyvalent isocyanate curing agent, and a block polyvalent isocyanate curing agent are preferably used. Of these, polyisocyanate-based curing agents are preferred because they can be cured at room temperature and can be applied on site.

  As described above, the first object of the present invention is to provide a solution or dispersion liquid used for treating a substrate surface in order to impart excellent water repellency or water absorption resistance and antifouling property to the substrate surface ( Hereinafter, it is intended to provide a simple substrate surface treatment liquid). The substrate surface treatment liquid is a solution or dispersion containing the water repellent or water absorption inhibitor and the specific metal-doped titanium oxide. This solution or dispersion can be obtained by mixing the above-described solution or dispersion containing the specific metal-doped titanium oxide and the above water repellent or water absorption inhibitor.

  If desired, an aqueous pigment dispersion for enhancing the design of the substrate surface can be added to the substrate surface treatment liquid of the present invention. The pigment used in the present invention is not particularly limited, and inorganic pigments and organic pigments can be used. One of these can be used, or both can be used in combination. The layer formed on the substrate surface or substrate surface layer using the substrate surface treatment liquid of the present invention to which a pigment and / or dye is added is surprising even when organic pigments and / or dyes are used. It has been discovered that there is an effect that the fading of dyes and / or pigments can be suppressed.

  The aqueous pigment dispersion is not particularly limited as long as the pigment is uniformly and stably dispersed in water. As the aqueous pigment dispersion, a dispersion of a pigment in water using a dispersing agent can be used according to a known method.

  Among the above pigments, inorganic pigments include metal oxide, complex oxide, chromate, sulfide, phosphate, and metal complex pigments, carbon black, metal powder, temperature pigments, Examples thereof include phosphorescent pigments, pearl pigments, basic pigments, and lead white. Organic pigments include azo, phthalocyanine, anthraquinone, quinacridone, indigo, dioxazine, perylene, perinone, isoindolinone, isoindoline, metal complex, quinophthalone, and diketo. Examples include pyrrolopyrrole pigments, alkali blue, aniline black, and fluorescent pigments. These pigments can be used alone or in combination of two or more.

  Examples of the dispersant used when the pigment is dispersed in water to obtain an aqueous pigment dispersion include nonionic dispersants, anionic dispersants, amphoteric dispersants, water-soluble resinous dispersants having an acid value of 50 to 250, and An emulsion resinous dispersant having an acid value of 50 to 250 can be mentioned. These dispersants can be used alone or in combination of two or more.

  Examples of the nonionic dispersant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid Examples include esters and polyoxyethylene fatty acid esters.

  Examples of the anionic dispersant include fatty acid salts, alkyl sulfate esters, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl ether sulfates. , Polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, polyoxyethylene glycerol fatty acid ester salt, glycerol borate fatty acid ester salt, and sodium tripolyphosphate. Among these, it is preferable to add a mixture of the above-mentioned sodium tripolyphosphate and the other anionic dispersant because it is effective for improving the stability of the aqueous pigment dispersion.

  Examples of the amphoteric dispersant include alkylbetaines, alkylamine oxides, and lecithin.

  Examples of the water-soluble resinous dispersant having an acid value of 50 to 250 include an acrylic resin, an acrylic styrene resin, and a styrenemaleic acid resin. An emulsion resinous dispersant having an acid value of 50 to 250 is an acrylic resin. An emulsion resin, an acrylic styrene emulsion resin, etc. are mentioned.

  The dispersant is preferably used in the range of 0.1 to 100 parts by mass and preferably in the range of 0.1 to 60 parts by mass with respect to 100 parts by mass of the pigment.

  In addition to the pigment, the dispersant, and water, the aqueous pigment dispersion further includes a material selected from a water-soluble solvent, a wetting agent, a thickener, an antifoaming agent, an antiseptic, and the like as necessary. One kind or two or more kinds can be contained.

  A binder resin for facilitating the formation of a coating film on the surface of the substrate can be further added to the substrate surface treatment liquid as desired. The binder resin may be blended directly into the substrate surface treatment liquid or may be blended in advance with the aqueous pigment dispersion. Examples of such a binder resin include natural resins and various synthetic resin emulsions. Examples of the natural resin binder resin include rosin, shellac, casein, cellulose derivatives, and starch. Synthetic resin emulsions include: polyvinyl acetate; ethylene / vinyl acetate copolymer; vinyl acetate / acrylic acid ester copolymer; vinyl acetate / acrylic acid copolymer; ethylene / acrylic acid copolymer; Acrylic resin; Acrylic ester resin composed of acrylic ester such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; styrene / acrylic ester copolymer; methacrylic ester resin; acrylic methacrylic acid Examples of the emulsion include a copolymer; a silicone-modified acrylic resin; an epoxy resin; a fluororesin; a polyurethane resin, and a mixture or copolymer thereof. In particular, an acrylic ester resin or methacrylic ester resin emulsion is preferred, and an acrylic silicon emulsion mainly composed of an acrylic ester or methacrylic ester is preferred because the resulting coating film has excellent durability. Further, 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 commercially available binder resin, Polysol A-609L (trade name, emulsion of acrylic ester resin manufactured by Showa Polymer Co., Ltd.), Polysol AP-3900 (trade name, acrylic manufactured by Showa Polymer Co., Ltd.) Silicone emulsion).

  If desired, additives such as a leveling agent and a silane coupling agent can be added to the substrate surface treatment liquid.

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

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

Therefore, as the substrate surface treatment liquid of the present invention, the following embodiments:
(1) A liquid containing the specific metal-doped titanium oxide and a silane-based water repellent or water absorption inhibitor;
(2) A liquid further containing a pigment and / or dye in (1) above;
(3) A liquid containing the specific metal-doped titanium oxide and the siliconate-based water repellent or water absorption inhibitor;
(4) A liquid further containing a pigment and / or dye in (3) above;
(5) A liquid containing the specific metal-doped titanium oxide and silicone and a silane composite water repellent or water absorption inhibitor;
(6) A liquid further containing a pigment and / or a dye in (5) above;
(7) A liquid containing the specific metal-doped titanium oxide and the silicone-based water repellent or water absorption inhibitor;
(8) A liquid further containing a pigment and / or dye in (7) above;
(9) A liquid further containing a binder resin in the above (2), (4), (6) and (8);
(10) a liquid containing the specific metal-doped titanium oxide and a fluorine-based water repellent or a water absorption inhibitor; and (11) a liquid further containing a pigment and / or dye and a binder resin in (10) above,
There is. One of these liquids (solution or dispersion) is applied to the substrate surface to treat the substrate surface. As a method for application to the substrate, 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 having excellent water repellency or water absorption resistance and antifouling property on the surface of the substrate and / or in the surface of the substrate. Thus, contamination of the substrate surface can be reduced, and in the case of a porous substrate, water can be prevented from entering the substrate.

Hereinafter, the present invention will be described based on specific examples.
(Reference Example 1: Preparation of copper-doped amorphous titanium oxide)
To a solution in which 0.463 g of 97% CuCl ₂ · 2H ₂ O (cupric chloride, manufactured by Nippon Chemical Industry Co., Ltd.) is completely dissolved in 500 ml of pure water, a 50% titanium tetrachloride solution (manufactured by Sumitomo Sitix Corporation) is further added. 10 g was added, and pure water was added to make the total volume 1000 ml.
A mixture of copper hydroxide and titanium hydroxide is added to the above solution by dropwise addition of 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) diluted 10 times with pure water to adjust the pH to 7.0. Precipitated.
The precipitate was repeatedly washed with pure water until the conductivity of the supernatant of the precipitate was 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 was obtained.
Next, while cooling the aqueous dispersion to 1 to 5 ° C., 25 g of 35% by mass hydrogen peroxide (manufactured by Taiki Pharmaceutical Co., Ltd.) was added, and the mixture was further stirred for 16 hours. As a result, 365 g of a dispersion containing 0.9% by mass of copper-doped amorphous titanium peroxide was obtained as a transparent green liquid.

(Reference Example 2: Preparation of zinc-doped amorphous titanium oxide)
To a solution in which 0.3359 g of 97% ZnCl ₂ (zinc chloride) is completely dissolved in 500 ml of pure water, 10 g of 50% titanium tetrachloride solution (manufactured by Sumitomo Sitix Co., Ltd.) is added, and pure water is added to make the total volume. The volume was 1000 ml.
A mixture of zinc hydroxide and titanium hydroxide was added to the above solution by dropwise addition of ammonia water diluted 10-fold with 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) with pure water to adjust the pH to 7.0. Precipitated.
The precipitate was repeatedly washed with pure water until the conductivity of the supernatant of the precipitate was 0.713 mS / m (target value was 0.8 mS / m or less). 409 g of an aqueous dispersion containing 0.48% by mass of copper hydroxide and titanium hydroxide in total was obtained.
Next, while cooling the aqueous dispersion to 1 to 5 ° C., 25 g of 35% by mass hydrogen peroxide (manufactured by Taiki Pharmaceutical Co., Ltd.) was added, and the mixture was further stirred for 16 hours. As a result, 434 g of an aqueous solution containing zinc-doped amorphous titanium peroxide was obtained as a yellowish brown transparent liquid.

(Reference Example 3: Preparation of water absorption inhibitor S)
20 parts by weight of n-hexyltriethoxysilane, the following formula:

10 parts by weight of an organosiloxane having 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-exchanged water Were mixed. This mixed solution was put into a homogenizer and passed through the homogenizer twice at a pressure of 300 kg / cm ² to obtain a milky white water absorption inhibitor S having a pH of 6.9.

(Reference Example 4: Preparation of water absorption inhibitor 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 this mixture, the produced methanol was removed by distillation, and distilled water was further added to adjust the amount of solids, thereby adding a water absorption inhibitor C containing 30% by mass of sodium methylsiliconate. Obtained.

Example 1
The copper-doped amorphous titanium peroxide dispersion having a concentration of 0.85% by mass prepared in Reference Example 1 and the water absorption inhibitor S prepared in Reference Example 3 were mixed at a volume ratio of 4: 1 and stirred. A substrate surface treatment solution 1 was obtained.

(Example 2)
The copper-doped amorphous titanium peroxide dispersion having a concentration of 0.85% by mass prepared in Reference Example 1 and the water absorption inhibitor C prepared in Reference Example 4 were mixed at a volume ratio of 6: 1 and stirred. A substrate surface treatment liquid 2 was obtained.

(Example 3)
To the substrate surface treatment liquid 1 (85 parts by mass) prepared in Example 1 above, a titanium oxide-containing aqueous pigment dispersion as a pigment (65 parts by mass of titanium oxide, 19.5 parts by mass of an acrylic styrene resin having an acid value of 195) , 15.5 parts by mass of water) (8 parts by mass), Polysol A-609L (trade name) (made by Showa Polymer Co., Ltd.) (10 parts by mass) which is an emulsion of an acrylate resin as a binder resin, The substrate surface treatment liquid 3 was obtained by stirring.

Example 4
In the same manner as in Example 3, a substrate surface treatment liquid 4 containing a pigment and a binder resin was obtained. However, in this case, the substrate surface treatment liquid 2 prepared in Example 2 was used instead of the substrate surface treatment liquid 1 used in Example 3.

(Example 5)
The dispersion containing the zinc-doped amorphous titanium peroxide prepared in Reference Example 2 and the water absorption inhibitor S prepared in Reference Example 3 were mixed at a volume ratio of 4: 1 and stirred to obtain a substrate surface treatment solution. 5 was obtained.

〔Evaluation test〕
Using the substrate surface treatment liquids 1 to 5 as examples, the copper-doped amorphous titanium peroxide dispersion prepared in Reference Example 1 was used as Comparative Solution 1, and the water absorption inhibitor S prepared in Reference Examples 3 and 4 above. The following evaluation tests were conducted using Comparative Solutions 2 and 3 as C and C, respectively.

(Evaluation Test 1)
A commercially available PC concrete paving block (300 mm × 300 mm × 50 mm) was used as the substrate. Each of the substrate surface treatment liquids 1 to 5 and the comparative liquids 1 to 3 was brushed onto one half of the surface of the paving stone block and then dried at room temperature to prepare an evaluation sample. The material for evaluation was exposed outdoors toward the south surface inclined at 75 degrees with the surface coated with the substrate surface treatment liquid or the comparison liquid facing upward. Exposure was conducted in Fujitsu-gun, Saga, and exposure was conducted from April 2004 to December 2004.

  The sample surface for evaluation after exposure was visually observed to evaluate the antifouling performance of each sample. In addition, after the exposure, the sample surface for evaluation is sufficiently sprayed with a sprayer and allowed to stand for about 10 minutes, and then each sample is cut, and the penetration of water from the sample surface to the inside in the cross section is visually observed. Observing and evaluating the water absorption preventing performance of each sample for evaluation. The evaluation results were determined based on the following criteria, and the results obtained are summarized in Table 1.

Antifouling performance: Antifouling performance is based on the test results of PC concrete paving blocks that were not exposed to the outdoors.
A indicates that no difference was observed with the sample for evaluation. ○ indicates that slight discoloration was observed in the sample for evaluation, but no adhesion of dirt was observed. Δ indicates that discoloration and slight adhesion of dirt were observed in the sample for evaluation. X shows that discoloration was recognized by the sample for evaluation and adhesion of dirt was remarkable. Here, “discoloration” means that the surface of the PC concrete paving block repeats water absorption and drying during outdoor exposure, resulting in a slightly reddish white color (beige to cream) due to deterioration of the bluish gray surface. It means to present.
Water absorption prevention performance: A indicates that no penetration of water from the surface of the sample for evaluation was observed. O indicates that slight water intrusion was observed in the extreme surface layer portion of the sample for evaluation. X indicates that clear water intrusion was observed from the surface of the sample for evaluation.

  From the results shown in Table 1, when the substrate is treated with a surface treatment solution containing a water absorption inhibitor or water repellent and copper or zinc-doped titanium oxide, water absorption prevention performance and antifouling performance are simultaneously imparted to the substrate. I understand that

(Example 6: Red ink fading test)
The substrate surface-treated with the substrate surface treatment solution was colored with an organic dye, and the fading rate of the organic dye by photooxidation was measured. The test was conducted as follows.

As a base material, a white ceramic tile of 100 mm × 100 mm (manufactured by Danto Co., Ltd.) was used. Evaluation was performed on the following seven samples.
(1) No surface treatment of the substrate (2) Surface treatment of the substrate with B56 (manufactured by Sustainable Technology Co., Ltd., photocatalyst) (3) 100 mass of the copper-doped amorphous titanium oxide dispersion of Reference Example 1 above The surface of the substrate was treated with a solution obtained by adding 0.1 part by mass of SH3746M (trade name, manufactured by Toray Dow Corning) as a leveling agent to the part. (4) Copper-doped amorphous titanium of Reference Example 1 above A substrate surface treated with an oxide dispersion (5) A substrate surface treated with the water absorption inhibitor S of Reference Example 3 above (6) A substrate surface with the substrate surface treatment solution 1 of Example 1 above (7) The substrate surface treated with the substrate surface treatment solution 3 of Example 3 above

Surface treatment of the substrate, using a spray gun (Meijikikai Co.), each processing solution ^15g / cm ^{2 ~20g} / cm 2 spray painted on the surface of the substrate, after further drying, thermostatic It was performed by heating to 80 ° C. for 15 minutes in a constant humidity chamber.

Next, on the surface-treated substrate (above (1) to (7)), a 10-fold diluted ethanol solution of red ink manufactured by Pilot Company was used seven times in an amount of 0.001 g / 100 cm ² per time. And then dried and evaluated using the following method.

(Evaluation methods)
The surface-treated substrate samples (1) to (7) whose surfaces are colored with red ink are arranged on a straight line, and a 20 W black light (manufactured by Toshiba Lighting & Technology Corp.) is placed on the sample and colored with red ink. The sample surface was irradiated with ultraviolet rays. The amount of ultraviolet light was 1100 μW / cm ² . Using a color difference meter (Minolta Co., Ltd., CR-200), the fading rate of the red ink on the sample surface was measured over time.

  The fading rate (%) of the red ink was obtained by calculation using the following formula.

  The results of the obtained fading rate are shown in Table 2. In the table, the ultraviolet irradiation time after the test and the fading rate of the red ink on the sample surface are shown as numerical values (%). The larger the numerical value of the fading rate in the table, the more fading the red ink.

  From the results shown in the table, compared with samples (1) to (5), samples (6) and (7) have a lower fading rate of red ink and a lower degree of deterioration of red ink pigment due to ultraviolet rays. Recognize.

(Example 7)
The copper-doped amorphous titanium oxide dispersion having a concentration of 0.85% by mass prepared in Reference Example 1 above, 32.1 parts by mass, the water absorption inhibitor S 7.6 parts by mass prepared in Reference Example 3 above, and monoazo red as a pigment -Based organic pigment-containing aqueous pigment dispersion (Pigment Red 17 25 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, acrylic acid as binder resin Polysol A-609L (trade name) (manufactured by Showa Polymer Co., Ltd.) (10 parts by mass) which is an emulsion of an ester resin was mixed and stirred to obtain a substrate surface treatment liquid 6.

(Comparative Example 4)
Except for using 32.1 parts by mass of pure water instead of 32.1 parts by mass of the copper-doped amorphous titanium peroxide dispersion having a concentration of 0.85% by mass prepared in Reference Example 1, A substrate surface treatment liquid 7 was obtained.

(Comparative Example 5)
A substrate surface treatment liquid 8 was obtained in the same manner as in Example 8 except that 7.6 parts by mass of pure water was used instead of 7.6 parts by mass of the water absorption inhibitor S prepared in Reference Example 3.

(Evaluation Test 3)
As a base material, a white ceramic tile of 100 mm × 100 mm (manufactured by Danto Co., Ltd.) was used. The substrate surface treatment liquids 6 to 8 were brushed on the tile surface and then dried at room temperature to prepare an evaluation sample. The material for evaluation was masked on a part of the surface coated with the substrate surface treatment liquid to provide an unirradiated part, and then a SWE Tester Co., Ltd. WEL-SUN-HCH / B type sunshine weather meter (black panel) The accelerated weathering test was conducted for 600 hours using a temperature of 63 ° C.).

  The sample surface for evaluation after the accelerated weathering test was measured using a Macbeth Color Eye CE-7000A spectrophotometer, and the color difference of the irradiated part was measured with the masked non-irradiated part as a standard. The results obtained are summarized in Table 3.

  From the results shown in Table 3, when the substrate was treated with a substrate surface treatment solution containing a water repellent or water absorption inhibitor, copper-doped titanium oxide, and pigment, a group containing copper-doped titanium oxide and pigment Compared to the case where the substrate is treated with the material surface treatment solution and the case where the substrate is treated with the substrate surface treatment solution containing only the pigment, the fading of the pigment contained in the substrate surface treatment solution due to ultraviolet rays is reduced. I understand that

It is the figure which showed the outline of the one aspect | mode of the manufacturing method of the specific metal dope titanium oxide of this invention.

Claims (5)

  A solution comprising a water repellent or a water absorption inhibitor, and a titanium oxide doped with at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc Or dispersion.   Titanium in which the water repellent or water absorption inhibitor is a silane, siliconate, silicone, silicone and silane composite, and / or fluorine water repellent or water absorption inhibitor and doped with the metal element The solution or dispersion according to claim 1, wherein the oxide is amorphous titanium oxide or amorphous titanium oxide at least partially peroxolated.   The aqueous pigment dispersion further comprises at least one dispersant selected from the group consisting of a nonionic dispersant, an anionic dispersant, an amphoteric dispersant, and a resinous dispersant, a pigment, and water. Or the solution or dispersion liquid of 2.   By applying the solution or dispersion according to any one of claims 1 to 3 to a substrate, from the water repellent or water absorption inhibitor, and copper, manganese, nickel, cobalt, iron, and zinc. Surface treatment of a base material characterized in that a layer containing titanium oxide doped with at least one metal element selected from the group consisting of is formed on the base material surface and / or in the base material surface layer Method. A water repellent or water absorption inhibitor, and at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron, and zinc, manufactured using the surface treatment method according to claim 4. A surface treatment material, wherein a layer containing a doped titanium oxide is formed on a surface of a base material and / or in a surface layer of the base material.

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