WO2008047629A1 - Method for protecting base - Google Patents

Abstract

Disclosed is a novel method for preventing or reducing adhesion of contaminant to a base, while preventing or reducing color degradation or color change of the base over time. This method is characterized in that a water repellent agent or a water absorption-preventing agent and one or more positively charged substances selected from the group consisting of (1) cations, (2) positively charged conductive or dielectric bodies and (3) composite bodies of a conductive body and a dielectric or semiconductor body are arranged on the surface of the base or in the surface layer of the base.

Description

 Specification

 Substrate protection method

 Technical field

 [0001] The present invention provides a substrate surface with water repellency, in particular, water repellency that can be controlled to be hydrophilic, and positive charge, thereby achieving contamination prevention or reduction and protection of the surface. Regarding the law.

 Background art

 Conventionally, it is known that various colored substrates (for example, printed materials, building materials, fibers, organic polymer resin products, etc.) fade or discolor over time. These factors of fading or discoloration include deterioration by light, adhesion of contaminants to the substrate surface, and various methods are considered as countermeasures.

 [0003] For example, in order to prevent deterioration due to light, a method of mixing an ultraviolet absorber in the substrate has been adopted.

 [0004] On the other hand, a method for forming a film having an antifouling function or a self-cleaning function on the substrate surface has been developed in order to prevent and remove contaminants from the substrate surface. As this method, for example, there is a method of forming a photocatalyst layer using anatase-type titanium oxide described in JP-A-9-262481.

 Patent Document 1: JP-A-9 262481

 Disclosure of the invention

 Problems to be solved by the invention

However, when an ultraviolet absorber is mixed in the substrate, the ultraviolet absorber may be decomposed due to the action of components or the like in the substrate and may not exhibit a sufficient ultraviolet absorption effect.

[0006] When the photocatalytic function is imparted to the substrate surface, the substrate itself may be decomposed and deteriorated by the photocatalytic action depending on the type of the substrate. In addition, since it has a negative charge, there is a problem of electrostatically adsorbing contaminants having a positive charge.

[0007] An object of the present invention is to provide a new technique for preventing or reducing fading or discoloration of a substrate over time and at the same time preventing or reducing the adhesion of contaminants. Means for solving the problem

[0008] An object of the present invention is to provide a water repellent or a water absorption inhibitor in the substrate surface or substrate surface layer, and

 (1) Cation

 (2) Positively charged conductor or dielectric

 (3) Conductor and dielectric or semiconductor composite

 This is achieved by placing one or more positively charged substances selected from the group consisting of forces.

 [0009] The water repellent or water absorption inhibitor is preferably a silane, siliconate, silicone, silicone and silane composite, fluorine water repellent or water absorption inhibitor, or a mixture of at least two of these. In particular, a fluorine-based water repellent or water absorption inhibitor is preferred.

 [0010] It is preferable that the water repellent or water absorption inhibitor and the positively charged substance are disposed as a mixture on the substrate surface or the substrate surface layer. The mixture is composed of a noionic dispersant, an anionic dispersant, an amphoteric dispersant, a water-soluble resinous dispersant having an acid value of 50 to 250, and an emulsion resinous dispersant having an acid value of 50 to 250. One or more dispersants selected from the above, a pigment, and a pigment dispersion composed of a liquid can be contained. Furthermore, in the case where the mixture preferably forms a layer on the surface of the substrate, an intermediate layer may be formed between the surface of the substrate and the layer. A coating layer may be formed on the substrate.

 The invention's effect

 [0011] Contaminants suspended in the atmosphere and / or contaminants attached to the substrate are photooxidized by the action of sunlight or the like and are positively charged. However, the contaminants on the surface of the substrate to which the method of the present invention has been applied. However, since a positive charge is generated, the pollutant is repelled electrostatically and naturally leaves the substrate surface. Therefore, it becomes possible to self-clean the substrate surface.

[0012] Further, since not only positive charges but also water repellents or water absorption inhibitors exist on the surface of the substrate, a contamination preventing effect due to water repellency can be added to the substrate in the self-cleaning action. Therefore, it is possible to prevent or reduce the adhesion of contaminants to the substrate surface over a long period of time. In particular, when using a fluorine-based water repellent or water absorption inhibitor, By controlling the irradiation of electromagnetic waves to the surface, the characteristics of the substrate surface can be changed from water-repellent to hydrophilic, so that the protection mode of the substrate can be freely controlled.

[0013] Furthermore, the substrate treated by the method of the present invention has high resistance to the action itself of sunlight and the like, and can well protect the substrate from light deterioration caused by sunlight or the like.

 [0014] By these actions, the present invention is able to prevent or reduce the fading or discoloration of the substrate over a long period of time with a force S.

 Brief Description of Drawings

 FIG. 1 is a conceptual diagram showing an example of a positive charge imparting mechanism in the present invention.

 [FIG. 2] A diagram showing an outline of one embodiment of the method for producing a specific metal-doped titanium oxide of the present invention. [FIG. Conceptual diagram showing

 [Fig. 4] Conceptual diagram showing another mode of arrangement of a water repellent or water absorption inhibitor and a positively charged substance on a substrate surface.

 FIG. 5 is a conceptual diagram showing a mechanism for removing contaminants from a positively charged substrate surface. BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The pollutant that is one of the causes of fading or discoloration of the substrate surface is that inorganic substances such as carbon and / or organic substances such as oil that are floating in the atmosphere gradually accumulate on the substrate surface. To adhere to the substrate surface.

[0017] The present invention removes these contaminants from the substrate by electrostatic repulsion, or

Further, the present invention is characterized in that adhesion of these contaminants to the substrate is avoided or reduced.

[0018] It is said that pollutants, especially oil, which are mainly suspended in the outdoor air, are in an "oxidized" state due to the so-called photooxidation reaction caused by various electromagnetic waves including sunlight. .

 [0019] The photo-oxidation reaction is caused by the action of electromagnetic waves such as sunlight, and moisture (H ○) and oxygen (O) on the surface of organic or inorganic substances to hydroxyl radicals (· ΟΗ) and singlet oxygen ○).

2 2 2 Electron (e is extracted from the organic or inorganic matter when it is formed, and it is oxidized. This oxidation changes the molecular structure of the organic matter, causing discoloration or degradation called degradation. An embrittlement phenomenon is observed, and soot is generated in inorganic materials, particularly metals. These “oxidized” organic or inorganic surfaces are positively charged by extracting electrons (e−).

 In the present invention, by applying a positive charge to the surface of the substrate, the organic or inorganic material is naturally separated from the surface of the substrate using electrostatic repulsion. As a method for imparting a positive charge to the substrate surface, in the present invention, a cation; a conductor or dielectric having a positive charge; a composite of a conductor and a dielectric or semiconductor; or a mixture thereof is used. To do.

 [0021] The cation is not particularly limited, but alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium, aluminum, tin, cesium, indium, cerium, Ions of metal elements such as selenium, chromium, nickel, antimony, iron, copper, manganese, tungsten, zirconium and zinc are preferred, and copper ions are particularly preferred. Furthermore, cationic molecules such as methylene violet, bismarck brown, methylene blue, and malachite green, and organic molecules having cationic groups such as silicone modified with a quaternary nitrogen atom-containing group can be used. The valence of ions is not particularly limited. For example, !! to tetravalent cations can be used.

 [0022] A metal salt may be used as a source of the metal ions. Specifically, aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antimony chloride, 1st and 2nd iron chloride, cesium chloride, indium trichloride, 1st cerium chloride And various metal salts such as selenium tetrachloride, cupric chloride, manganese chloride, tungsten tetrachloride, tungsten dichloride, potassium tungstate, zirconium oxychloride, and zinc chloride. In addition, hydroxides such as indium hydroxide and key tungstic acid, or oxides such as fat oxides can also be used.

 [0023] Examples of positively charged conductors or dielectrics include conductors or dielectrics that generate positive charges other than the above-mentioned cations. For example, a battery made of various conductors described later. And positive dielectrics such as wool and nylon that are positively charged by friction.

 Next, the principle of imparting a positive charge by the composite is shown in FIG.

FIG. 1 is a conceptual diagram in which a combination of a conductor, a dielectric, or a semiconductor conductor is arranged on the surface of a substrate (not shown) or in a surface layer. Conductor moves freely inside The presence of a high concentration of free electrons that can be generated can have a positive charge state on the surface. It is also possible to use a conductive material containing cations as the conductor.

On the other hand, the dielectric or semiconductor adjacent to the conductor is dielectrically polarized due to the influence of the surface charge state of the conductor. As a result, negative charges are generated in the dielectric or semiconductor on the side adjacent to the conductor and positive charges are generated on the non-adjacent side. By these actions, the surface of the combination of the conductor dielectric or the semiconductor conductor is positively charged, and a positive charge is imparted to the substrate surface. The size of the complex (which refers to the length of the longest axis passing through the complex) is lnm force, et al. 100 μm, preferably lnm to 10 μm, more preferably lnm to 1 m, more preferably lnm. It can be in the lOOnm range.

 [0027] The conductor constituting the composite used in the present invention is preferably a metal from the viewpoint of durability. Aluminum, tin, cesium, indium, cerium, selenium, chromium, nickel, antimony, iron, silver, Examples include metals such as copper, gold, manganese, platinum, tungsten, zirconium, and zinc. The shape of the conductor is not particularly limited, and can be any shape such as a particulate shape, a flake shape, or a fiber shape.

 [0028] As the conductor, metal salts of some metals can also be used. Specifically, aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antichloride, 1st and 2nd ferrous chloride, silver nitrate, cesium chloride, indium trichloride , Cerium chloride, selenium tetrachloride, cupric chloride, manganese chloride, platinum chloride, tungsten tetrachloride, tungsten oxychloride, potassium tungstate, gallium chloride, zirconium oxychloride, zinc chloride, etc. Various metal salts can be exemplified. In addition, as the conductor, indium hydroxide, key tungstic acid, and the like, hydroxides or oxides of the above metals, and the like can be used.

[0029] Conductors include polyaniline, polypyrrole, polythiophene, polythiophene vinylon, polyisothianaphthene, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly pphenylene, polyphenylene vinylone, polymethoxyphenol. Conductive polymers such as diylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, and polyazulene can also be used. [0030] Examples of the semiconductor include C, Si, Ge, Sn, GaAs, Inp, GeN, ZnSe, and PbSnTe. Semiconductor metal oxide, photo semiconductor metal, and photo semiconductor metal oxide can also be used. Preferably, besides titanium oxide (TiO 2), ZnO, SrTiOP, CdS, CdO, CaP, InP, In

 2 3 2

O, CaAs, BaTiO, K NbO, Fe O, Ta O, WO, NiO, Cu ² 0, SiC, SiO,

3 3 2 3 2 3 2 3 3 2

MoS, InSb, RuO, CeO, etc. are used.

3 2 2

 Is desirable.

 [0031] Dielectrics include ferroelectric barium titanate (PZT), so-called SBT, BLT, and PZT, PLZT— (Pb, La) (Zr, Ti) 0, SBT, SBTN— SrBi (Ta , Nb)

 3 2 2

O, BST— (Ba, Sr) TiO, LSCO— (La, Sr) CoO, BLT, BIT— (Bi, La) Ti

9 3 3 4 3

Composite metals such as O 2 and BSO—Bi 2 SiO can be used. Also water repellency or water absorption prevention

12 2 5

 Silane compounds, siliconate compounds, silicone compounds, silicone and silane composites, so-called organic modified silica compounds, organic polymer insulating films, arylene ether polymers, benzocyclobutenes, fluorine polymers Various low dielectric materials such as N or F, fluorinated amorphous carbon, and a fluorine-based water repellent or water absorption inhibitor described later can be used.

[0032] As a composite of a conductor and a dielectric or semiconductor, any combination of a conductor and a dielectric or semiconductor can be used as long as it can impart a positive charge to the surface of the base. From the viewpoint of self-cleaning of the surface, it is preferable to use metal-doped titanium oxide. As the metal, at least one metal element selected from the group consisting of copper, manganese, nickel, cobalt, iron and zinc is preferable.

 2

Various oxides and peroxides such as TiO, TiO, and TiO 2 / nH 2 O can be used. In particular

3 3 2

 Titanium peroxide having a peroxo group is preferred. The titanium oxide may be any of amorphous type, anatase type, brookite type and rutile type, and these may be mixed, but amorphous type titanium oxide is preferred.

[0033] Amorphous titanium oxide does not have a photocatalytic function! On the other hand, anatase, wurtzite, and rutile titanium oxides lose their photocatalytic function when they are combined with copper, manganese, nickel, nickel, cobalt, iron, or zinc, which have a photocatalytic function, at a certain concentration or more. Therefore, the metal-doped titanium oxide does not have a photocatalytic function. In addition, Amorphous titanium oxide can be converted to anatase titanium oxide over time by heating with sunlight, etc. When combined with copper, manganese, nickel, cobalt, iron, or zinc, anatase titanium oxide loses its photocatalytic function. However, the metal-doped titanium oxide does not exhibit a photocatalytic function over time.

 [0034] As the method for producing the metal-doped titanium oxide, a production method based on a hydrochloric acid method or a sulfuric acid method, which is a common method for producing titanium dioxide powder, may be employed, and various types of liquid dispersion may be employed. You may employ | adopt the manufacturing method of a titaure solution. The metal can be complexed with titanium oxide regardless of the production stage.

 [0035] For example, specific methods for producing the metal-doped titanium oxide include the following first to third production methods and conventionally known sol-gel methods.

 [0036] First manufacturing method

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

 [0037] The peroxidation oxidizing agent is not particularly limited, and is preferably a peroxygenated titanium, that is, a hydrogen peroxide capable of using various materials as long as it can form titanium peroxide. When hydrogen peroxide is used as the oxidizing agent, the concentration of hydrogen peroxide is not particularly limited, but 30 to 40% is preferable. It is preferable to cool the titanium hydroxide before peroxolation. The cooling temperature is preferably 1-5 ° C.

FIG. 2 shows an example of the first manufacturing method. In the illustrated production method, an aqueous solution of titanium tetrachloride and aqueous ammonia are mixed in the presence of at least one compound of copper, manganese, nickel, cobalt, iron, and zinc, and the hydroxide of the metal and titanium are mixed. This produces a mixture of hydroxides. The concentration and temperature of the reaction mixture at that time are not particularly limited. However, it is preferable that the temperature is dilute and at room temperature. This reaction is a neutralization reaction, and it is preferable that the pH of the reaction mixture is finally adjusted to around 7.

 [0039] The metal and titanium hydroxides thus obtained are washed with pure water, cooled to around 5 ° C, and then peroxolated with hydrogen peroxide. This makes it possible to produce an aqueous dispersion containing fine titanium oxide particles having amorphous peroxo groups doped with metal, that is, an aqueous dispersion containing metal-doped titanium oxide.

 [0040] Second manufacturing method

 A tetravalent titanium compound such as titanium tetrachloride is peroxolated with an oxidizing agent and reacted with a base such as ammonia to form ultrafine particles of amorphous titanium peroxide. This reaction is preferably carried out in an aqueous medium. Further, it can be transferred to anatase-type titanium peroxide by optionally heat-embedding. At least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed in each step.

 [0041] Third manufacturing method

 A tetravalent titanium compound such as titanium tetrachloride is reacted simultaneously with an oxidizing agent and a base to simultaneously form titanium hydroxide and peroxotate to form amorphous titanium peroxide with ultrafine particles. This reaction is preferably carried out in an aqueous medium. Further, it can be transferred to anatase-type titanium peroxide by optionally heat-treating. In any of the above steps, at least one of copper, manganese, nickel, cobalt, iron, zinc, or a compound thereof is mixed.

 [0042] In the first to third manufacturing methods, it goes without saying that a mixture of amorphous titanium peroxide and anatase titanium peroxide obtained by heating the same can be used as the metal-doped titanium oxide. .

 [0043] Manufacturing method by sol-gel method

The titanium alkoxide is mixed and stirred with a solvent such as water or alcohol, an acid or a base catalyst, and the titanium alkoxide is hydrolyzed to form a sol solution of ultrafine titanium oxide. Copper, manganese, nickel, cobalt, iron, zinc, either before or after this hydrolysis Or at least any one of these compounds is mixed. The titanium oxide thus obtained is an amorphous type having a peroxo group.

 The titanium alkoxide has a general formula: Ti (OR ′) (where R ′ is an alkyl group)

 Four

 A compound represented by the above formula, a compound in which one or two alkoxide groups (OR ′) in the above general formula are substituted with a carboxyl group or a / 3-dicarbonyl group, or a mixture thereof is preferable.

 [0045] Specific examples of the titanium alkoxide include Ti (〇—isoC H), Ti (〇—nC H),

 3 7 4 4 9 4

Ti (〇1 CH CH (C H) C H), Ti (〇1 C H), Ti (〇1 isoC H) [CO (CH

 2 2 5 4 9 4 17 35 4 3 7 2 3

) CHCOCH], Ti (○ — nC H) [OC H N (C H OH)], Ti (OH) [OCH (CH

 3 2 4 9 2 2 4 2 4 2 2 2

 ) COOH], Ti (OCH CH (C H) CH (OH) C H), Ti (OiC H) (OCOC

3 2 2 2 5 3 7 4 4 9 2 17

H) and the like.

 35

 [0046] Tetravalent titanium compound

 The tetravalent titanium compound used in the production of metal-doped titanium oxide can form titanium hydroxide, also called orthotitanic acid (H TiO), when reacted with a base.

 4 4

 In this case, various titanium compounds can be used, for example, water-soluble inorganic acid salts of titanium such as titanium tetrachloride, titanium sulfate, titanium nitrate, and titanium phosphate. In addition, water-soluble organic acid salts of titanium such as titanium oxalate can be used. Of these various titanium compounds, titanium tetrachloride is preferred because it is particularly excellent in water-solubility and no components other than titanium remain in the dispersion of metal-doped titanium oxide.

 [0047] When a tetravalent titanium compound solution is used, the concentration of the solution is not particularly limited as long as a titanium hydroxide gel can be formed, but it is relatively dilute. A solution is preferred. Specifically, the solution concentration of the tetravalent titanium compound is preferably 5 to 0. Olw t%, more preferably 0.9 to 0.3 wt%.

 [0048] base

As the base to be reacted with the tetravalent titanium compound, various bases can be used as long as they can react with the tetravalent titanium compound to form titanium hydroxide, such as ammonia, caustic soda, sodium carbonate. , Power that can be exemplified by caustic potash, etc. S, ammonia is preferred [0049] Further, when the above-mentioned base solution is used, the concentration of the solution is not particularly limited as long as a titanium hydroxide gel can be formed, but a relatively dilute solution is preferable. . Specifically, the concentration of the base solution is preferably 10-0.01 wt%, more preferably 1.0 to 0.1 wt%. In particular, when ammonia water is used as the base solution, the ammonia concentration is preferably 10-0.01 wt%, more preferably 1.0 to 0.1 wt%.

 [0050] Metal compounds

 Examples of the compound of copper, manganese, nickel, cobalt, iron or zinc are as follows.

 Ni compounds: Ni (OH), NiCl

 twenty two

 Co compounds: Co (OH) NO, Co (OH), CoSO, CoCl

 3 2 4 2

 Cu compounds: Cu (OH), Cu (NO), CuSO, CuCl,

 2 3 2 4 2

 Cu (CH COO)

 3 2

 Mn compounds: MnNO, MnSO, MnCl

 3 4 2

 Fe compounds: Fe (OH), Fe (OH), FeCl

 2 3 3

 Zn compounds: Zn (NO), ZnSO, ZnCl

 3 2 4 2

 [0051] The concentration of titanium peroxide in the aqueous dispersion obtained by the first to third production methods (total amount including coexisting copper, manganese, nickel, cobalt, iron, or zinc) is 0.05 to 15 wt%. Is preferred 0.;! ~ 5wt% is more preferred. In addition, regarding the blending amount of copper, manganese, nickel, cobalt, iron, and zinc, 1: 1 is preferable from the present invention in terms of the molar ratio of titanium to the metal component, but it is 1 from the stability of the aqueous dispersion. : 0. 01 ~; 1: 0. 5 is preferable, 1: 0. 03 ~; 1: 0. 1 is more preferable.

 [0052] The substrate to which the present invention is applied is not particularly limited, and various inorganic substrates and organic substrates, or combinations thereof can be used.

[0053] Examples of the inorganic substrate include a substrate made of a material such as transparent or opaque glass, metal, metal oxide, ceramics, concrete, mortar, and stone. Examples of the organic base include a base made of a substance such as an organic resin, wood, and paper. More specific examples of the organic resin include, for example, polyethylene, polypropylene, polycarbonate, polyacrylate, polyesterolate, polyamide, polyurethane, ABS tree, and polysalt. Examples include bur, silicone, melamine resin, urea resin, silicone resin, fluororesin, cellulose, and epoxy-modified resin. The shape of the substrate is not particularly limited, and may be any shape such as a cube, a rectangular parallelepiped, a sphere, a sheet, and a fiber. The substrate may be porous. As the substrate, a water-absorbing construction / civil engineering substrate, a device, a device transport body, and a display screen are suitable.

 [0054] The coating material on which the surface of the substrate may be painted is alkyd resin, acrylic resin, amino resin, polyurethane resin, epoxy resin, silicone resin, fluororesin, acrylic silicon resin, unsaturated polyester resin, ultraviolet ray It contains a synthetic resin such as a curable resin, phenol resin, vinyl chloride resin, component resin emulsion, and coloring agent.

 [0055] The thickness of the coating film is preferably from 0.01 to 100 m force S, more preferably from 0 to 50 m force S, and particularly preferably from 0.5 m to 10 m.

 [0056] Further, as the painting means, for example, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a brush coating, a sponge coating or the like can be applied. In order to improve physical properties such as the hardness of the coating film and adhesion to the substrate, it is desirable to heat within the allowable range of the substrate and the coating film.

 [0057] In the present invention, one or more positively charged substances selected from the group consisting of the cation; a positively charged conductor or dielectric; a conductor dielectric or semiconductor composite, It is disposed on the surface of the substrate together with a water repellent or water absorption preventing agent that is a dielectric.

 [0058] Examples of the water repellent or water absorption inhibitor used in the present invention include silane-based, siliconate-based, silicone-based, silicone and silane composite-based, fluorine-based water repellent or water-absorbing inhibitor, or at least of these. A mixture of the two is preferred, and a fluorine-based water repellent or water absorption inhibitor is particularly preferred. Such a material is called a water repellent when applied to the surface of a non-porous substrate, and when applied to the surface of a porous substrate, it can prevent water absorption to the substrate. It is called an inhibitor.

[0059] The silane-based, siliconate-based, silicone-based, and silicone-silane-based water-repellent agent or water-absorbing agent used in the present invention is a water-repellent agent or water-absorbing agent after being applied to the substrate surface. Can react with the substrate to form a chemical bond or chemical A material that can form a film with a certain degree of durability by cross-linking 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. The water repellent or water absorption inhibitor has the above-described cation in its chemical structure.

 [0060] Various silane-based, silicone and silane composite-based, siliconate-based, silicone-based, and fluorine-based water repellents or water absorption inhibitors are known, and any one is used in the present invention. Two or more types can be used in combination. Of the silane, siliconate, silicone, and silicone and silane composite water repellents or water absorption inhibitors, they are preferred as the water repellents or water absorption inhibitors used in the present invention. A silane-based water repellent or water-absorbing agent composed of degradable silane, water, and a surfactant, and further selected from hydrolyzate and / or partial hydrolyzate of hydrolyzable silane and various organopolysiloxanes. Silicone-containing silane-based water repellent or water absorption inhibitor, and siliconate-based water repellent or water absorption inhibitor composed of an aqueous solution of an alkali metal salt of an organosiliconate.

 [0061] Various known hydrolyzable silanes used in the silane-based water repellent or water absorption inhibitor include, for example, tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkyl. One or two or more selected from these forces can be used. The surfactant is not particularly limited, and any of a cationic surfactant, a cationic surfactant, a nonionic surfactant, and a mixture thereof can be used.

[0062] The silicone and silane composite water repellent or water absorption inhibitor includes the hydrolyzable silane, a surfactant, and a hydrolyzate and / or partial hydrolyzate of the hydrolyzable silane. And those comprising a compound selected from hydrolyzable silanes, surfactants, and various organopolysiloxanes. As the various organopolysiloxanes, organopolysiloxanes having hydrolyzable groups selected from alkoxy groups, alkenoxy groups, amino groups, amide groups, acetoxy groups, ketoxime groups, and the like bonded to a silicon atom may be used. it can. Silico Specific examples of water and silane composite water repellents or water absorption inhibitors include, for example, Dry Seal S (trade name, manufactured by Toray “Dow Cowing” Silicone Co., Ltd.).

[0063] As the siliconate-based water repellent or water absorption inhibitor, known ones can be used. Strength Sodium methyl siliconate aqueous solution, sodium probil siliconate aqueous solution, strength sodium methylsilicone aqueous solution, and potassium propyl Examples include aqueous solutions of alkali metal salts of alkyl siliconates such as aqueous siliconate solutions; and aqueous alkali metal aminoorganofunctional siliconates described in JP-A-5-214251. Examples of such commercially available silicone-based water repellents or water absorption inhibitors include Dry Seal C and Dry Seal E (V, trade name: Toray Dow Co., Ltd.).

[0064] Examples of the silicone-based water repellent or water absorption inhibitor include silicone resins having hydrolyzable groups such as hydroxyl groups or alkoxy groups, such as silicone aqueous emulsion resin compositions, and hydroxysilyl group-containing diorganopolyesters. Examples thereof include room temperature curable silicone resin water repellents or water absorption inhibitors made of siloxane and hydrolyzable group-containing silane or hydrolyzable group (excluding hydroxyl group) -containing organopolysiloxane.

[0065] The fluorine-based water repellent or water absorption inhibitor used in the present invention is a fluorine-containing compound or a fluorine-containing compound-containing composition such as a perfluoroalkyl group-containing compound. When a fluorine-containing compound having high adsorptivity to the substrate surface is selected, after being applied to the substrate surface, the chemical component of the water repellent or water absorption inhibitor reacts with the substrate to form a chemical bond, or It is not always necessary for the chemical components to be cross-linked.

[0066] 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. Specifically, perfluorosulfonic acid salt, perfluorosulfonic acid ammonium salt, perfluorocarboxylic acid salt, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide adduct, perfluoro Examples include cycloalkylamine oxides, perfluoroalkyl phosphate esters, and perfluoroalkyltrimethylammonium salts. Of these, perfluoroalkyl phosphate ester and perfluoroalkyltrimethyl ammonium salt are preferred because of their excellent adsorptivity to the substrate surface! Such materials include Surflon S-112 and Surflon S-121 (both trade names, Seimi Chemical Co., Ltd.) is commercially available!

 [0067] Other fluorine-based water repellents or water absorption inhibitors include copolymers of two or more kinds of olefins containing fluorine atoms, copolymers of olefins containing fluorine atoms and hydrocarbon monomers. And fluorine resin emulsion composed of at least one fluorine resin selected from the group consisting of a mixture of two or more kinds of olefins containing fluorine atoms and a thermoplastic acrylic resin, and a surfactant, and Examples include a curing agent (see JP-A-5-124880, JP-A-5-117578, JP-A-5-179191) and / or a silane-based water repellent or water absorption inhibitor. (Refer to Unexamined-Japanese-Patent No. 2000-1 21543, Unexamined-Japanese-Patent No. 2003-26461). As this fluororesin emulsion, commercially available products can be used, which can be purchased from Daikin Industries Co., Ltd. as a jeffle series and from Asahi Glass Co., Ltd. as a Lumiflon series. 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.

 [0068] In particular, when a fluorine-based water repellent or water absorption inhibitor is used, by controlling the irradiation of electromagnetic waves such as ultraviolet rays and sunlight (particularly ultraviolet rays) onto the substrate surface, the surface of the substrate surface is characterized. The property can be changed from water repellency to hydrophilicity. As a result, the protection mode can be freely changed according to the characteristics required of the substrate, so that both the contact angle characteristics of water and oil and the surface positive charge characteristics are used as vitality. Is particularly preferred to use fluorine-based water repellents or water absorption inhibitors.

 [0069] In a preferred embodiment of the present invention, the water repellent or water absorption inhibitor and a cation; a positively charged conductor or dielectric; a conductor dielectric or semiconductor composite; or two or more of these The positively charged substance that is a combination is mixed and disposed on the substrate surface as a mixture. The mixture can be obtained by mixing the water repellent or water absorption inhibitor and the positively charged substance in an appropriate medium such as water, an aqueous medium such as alcohol, or an organic solvent such as acetone. Can take the form of solutions, suspensions or emulsions.

[0070] The mixture is preferably applied and placed on the substrate surface. How to apply to substrate As a method, it is possible to use a known method such as brush coating, roller coating, and spray coating. After the mixture is applied to the substrate surface, it is preferably dried. On the other hand, for example, during casting of the substrate, a predetermined amount of the mixture having a higher or lower specific gravity than the liquid is mixed into an uncured liquid of the substance constituting the substrate, and the liquid is cured after being left for a predetermined time. In this way, the water repellent or water absorption inhibitor and the positively charged substance can be arranged in the surface layer of the substrate. As a result, a layer excellent in water repellency or water absorption resistance and antifouling property can be formed on the substrate surface and / or in the substrate surface layer, thereby reducing contamination of the substrate surface and making it porous. In the case of a porous substrate, water can be prevented from entering the substrate. When the substrate is coated, the water repellent or water absorption inhibitor and the positively charged substance may be included in the paint.

 FIG. 3 is a conceptual diagram showing one embodiment of the arrangement of the water repellent or water absorption inhibitor and the positively charged substance on the surface of the substrate, and a layer made of a mixture of the water repellent or water absorption inhibitor and the positively charged substance. An embodiment formed on the surface of the substrate is shown. The thickness of the membrane is preferably from 0 · 01 to; lOO ^ m force S, more preferably from 0.;! To 5 C ^ m force S, and particularly preferably from 0.5 m to 10 m. Any positively charged material may be present in the membrane, not necessarily exposed on the surface of the membrane. Further, the layer need not be a continuous layer but may be a discontinuous layer. Although illustration is omitted, in the layer, due to dielectric polarization, a negative charge is generated on the side of the water repellent or water absorption inhibitor that is in contact with the positively charged substance, and the layer on the side separated from the positively charged substance. A positive charge is generated on the surface. This positive charge can prevent contamination of the substrate surface as will be described later. Moreover, since the water repellent can be imparted to the layer itself by the action of the water repellent or the water absorption preventive agent, it is possible to further improve the prevention of contamination by the characteristics.

 [0072] If desired, a pigment dispersion for enhancing the design of the substrate surface can be added to the mixture. 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.

Even when organic pigments and / or dyes are used as the pigments and / or dyes, surprisingly, in the method of the present invention, the fading of the organic pigments and / or dyes is suppressed. This is particularly effective for those having a negative charge. [0073] The pigment dispersion is not particularly limited as long as the pigment is uniformly and stably dispersed. As the pigment dispersion, a dispersion in which a pigment is dispersed in a liquid such as water using a dispersing agent can be used according to a known method.

 [0074] Among the pigments, inorganic pigments include metal oxide, composite oxide, chromate, sulfide, phosphate, and metal complex pigments, carbon black, metal powder, Indicating pigments, luminous pigments, pearl pigments, basic pigments, lead white and the like. Organic pigments include azo, phthalocyanine, anthraquinone, quinacridone, indigo, dioxazine, perylene, perinone, isoindolinone, isoindoline, metal complex, quinophthalone, and Examples thereof include diketopyrrolopyrrole pigments, anole strength ribanol, aniline black, and fluorescent pigments. These pigments can be used alone or in combination of two or more.

 [0075] For example, as a dispersant used when an aqueous pigment dispersion is obtained by dispersing a pigment in water, a nooionic dispersant, an ayuonic dispersant, an amphoteric dispersant, a water-soluble resin having an acid value of 50 to 250 And an emulsion resinous dispersant having an acid value of 50 to 250. These dispersants can be used alone or in combination of two or more.

 [0076] 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 ester, and polyoxyethylene fatty acid ester.

[0077] Examples of the anionic dispersant include fatty acid salt, alkyl sulfate ester salt, alkyl aryl sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl dialyl ether disulfonate, alkyl phosphate, polyoxy Ethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, polyoxyethylene glycerol fatty acid ester salt, glycerol pore fatty acid ester salt, and Examples include sodium tripolyphosphate. Among them, it is possible to stabilize the aqueous pigment dispersion by blending a mixture of the sodium tripolyphosphate and the other cation dispersant. This is preferable because it is effective in improving the properties.

[0078] Examples of the amphoteric dispersant include alkylbetaines, alkylamine oxides, and lecithin.

 [0079] 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 styrene maleic acid resin, and an emulsion resinous dispersant having an acid value of 50 to 250. Examples thereof include acrylic emulsion resins and acrylic styrene emulsion resins.

 [0080] The dispersant is preferably used in the range of 0 .;! To 100 parts by weight with respect to 100 parts by weight of the pigment, and preferably used in the range of 0 .;! To 60 parts by weight.

 [0081] The pigment dispersion includes, in addition to the pigment and the dispersant, water and various organic solvents, and if necessary, a water-soluble solvent, a wetting agent, a thickener, an antifoaming agent, and an antiseptic. One or two or more selected materials can be contained.

[0082] Further, a binder resin for facilitating formation of a layer on the surface of the substrate may be further added to the mixture as desired. The binder resin may be blended directly into the mixture or may be blended in advance with the aqueous pigment dispersion. Examples of such binder resins include natural resins and various synthetic resin emulsions. Examples of natural resin binder resins include rosin, shellac, casein, cellulose derivatives, and starch. Synthetic resin emulsions include poly (ethylene acetate); ethylene 'vinyl acetate copolymer; acetate acetate' acrylate ester copolymer; acetate acetate · acrylic acid copolymer; ethylene · acrylic acid copolymer; Alcohol; Acrylic resin; Methyl acrylate, Ethyl acrylate, Butyl acrylate, Acrylate ester resin consisting of acrylate such as 2-ethylhexyl acrylate; Styrene. Acrylate ester copolymer; Methacrylate Examples thereof include an emulsion made of a resin; an acrylic acid / methacrylic acid copolymer; a silicone-modified talyl resin; an epoxy resin; a fluororesin; a polyurethane resin, and a mixture or copolymer thereof. In particular, an emulsion of an acrylate 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 less than 10. [0083] If desired, the mixture may further contain an additive such as a leveling agent or a silane coupling agent.

[0084] As the leveling agent, various types of silicone oil can be used. Of these, polyether-modified silicone oil is preferable. Specifically, at the molecular chain end 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. Of 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-9 165 318. Such polyether-modified silicone oils include TSF4445 and TSF4446 (both trade names) (named GE Toshiba Silicone Co., Ltd.), _KF 352, KF-353 (both trade names) (named Shin-Etsu Chemical Co., Ltd.) And SH3746 (trade name, manufactured by Toray 'Dowcoung' Silicone Co., Ltd.).

 [0085] A silane compound having an amino group, an epoxy group, or a methacryloxy group, that is, a so-called silane coupling agent may be blended. This coupling agent makes it possible to improve the hardness of the layer containing the water repellent or water absorption inhibitor and the positively charged substance and the adhesion between adjacent layers. In addition, a material selected from silicone rubber, silicone powder, silicone resin, and the like may be added to the mixture.

 [0086] The water repellent or water absorption inhibitor and the positively charged substance may be arranged on the substrate in other modes. FIG. 4 shows a mode in which a positively charged substance is arranged on the surface of a substrate, and a water repellent material or a water absorption inhibitor is arranged on the surface of the positively charged substance in a non-film form. Due to dielectric polarization in the insulating water repellent or water absorption inhibitor film, negative charges are generated on the side in contact with the positively charged substance, and positive charges are generated on the surface of the film on the side separated from the positively charged substance. Occurs.

[0087] As a method of arranging the water repellent or the water absorption inhibitor in a non-film form, for example, chemical modification is performed by grafting organic or inorganic substance atoms or atomic groups onto the surface of the positively charged substance. The method of decorating is mentioned. As the atom or atomic group to be chemically modified, those containing a fluorine atom are preferable. As the fluorine compound for chemical modification, for example, a fluoroalkyl acrylate copolymer is preferred. For example, FT-tone GM 101 and GM-105 are commercially available from Daikin Industries, Ltd. The chemical modification described above can be produced by performing at least one step of drying after applying the solution of the fluorinated compound to the substrate surface. As the coating method, methods such as brush coating, roller coating, and spray coating can be used.

 In the present invention, a cover layer may be further formed on the layer containing the water repellent or water absorption inhibitor and the positively charged substance. The thickness of the coating layer (from 0 · 01 to 100 μm force << preferably, more preferably from 0 · 05 to 50 µm, particularly preferably from 0 ·; to 10 to 10 m.

 [0089] The material of the coating layer is not particularly limited, and any organic or inorganic substance can be used.

 [0090] As the organic substance, a water-repellent or hydrophilic polymer material is preferred! Examples of water-repellent polymer materials include polyolefins such as polyethylene, polypropylene and polystyrene; acrylic resins such as polyacrylate, acrylonitrile 'styrene copolymer (AS), and acrylonitrile' butadiene 'styrene copolymer (ABS); Rononitrile; Polyhalogenated vinylols such as poly (vinyl chloride) and poly (vinylidene chloride); Polytetrafluoroethylene, Fluorethylene (propylene) copolymer, Polychlorinated trifluoroethylene (PCTFE), Polyvinylidene fluoride (PVDF) Fluorine resin such as vinylidene fluoride 'trifluoroethylene copolymer; Polyester such as polyethylene terephthalate and polycarbonate; Phenolic resin; Urea resin; Melamine resin; Polyimide resin; Polyamide resin such as nylon; Epoxy resin; Urethane, and the like.

[0091] Fluororesin is preferred as the water-repellent polymer material, in particular, vinylidene fluoride 'trifluoroethylene copolymer having ferroelectricity and water repellency, β-type crystals of polyvinylidene fluoride and Those that contain it are preferred. Commercially available products can be used as the fluororesin, and examples of commercially available products include HIREC1550 manufactured by NTT-AT Corporation.

[0092] Further, a copolymer comprising two or more olefins containing fluorine atoms, fluorine atoms At least one selected from the group consisting of a copolymer of a olefin containing hydrocarbon monomer and a mixture of two or more of a fluorine atom-containing copolymer and a thermoplastic acrylic resin. Fluororesin emulsion composed of a fluororesin and a surfactant, and a curing agent (see JP-A-5-124880, JP-A-5-117578, JP-A-5-179191) and / or the silicone resin water repellent It is also possible to use a composition comprising these (see JP 2000-121543 A and JP 2003-26461 A). As this fluororesin emulsion, commercially available products can be used, which can be purchased from Daikin Industries, Ltd. as the Zeffle series, and from Asahi Glass Co., Ltd., as the Lumiflon series. 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.

[0093] Examples of the hydrophilic polymer material include polyethylene glycol, polypropylene glycol, polyethylene glycol such as a polypropylene glycol block copolymer; polybulu alcohol; polyacrylic acid (including salts such as alkali metal salts and ammonium salts) ), Polymethacrylic acid (including salts such as alkali metal salts and ammonium salts), polyacrylic acid-polymethacrylic acid (including salts such as alkali metal salts and ammonium salts) copolymers; polyacrylamide; polybutyropyrrolidone; carboxy Examples include hydrophilic celluloses such as methyl cellulose (CMC) and methyl cellulose (MC); natural hydrophilic polymer compounds such as polysaccharides.

 [0094] These polymer materials may be combined with an inorganic dielectric such as glass fiber, carbon fiber, silica, and the like, and combined. It is also possible to use a paint as the polymer material.

 [0095] The inorganic substance is preferably made of a water-repellent or hydrophilic inorganic compound.

[0096] Examples of the water repellent inorganic material include silane water repellents, fluorine water repellents, and the like. Particularly preferred examples of fluorine-based water repellents include fluorine-containing compounds or fluorine-containing compound-containing compositions such as perfluoroalkyl group-containing compounds. When a fluorine-containing compound with high adsorptivity to the substrate surface is selected, after application to the substrate surface, the chemical component of the water repellent or water absorption inhibitor reacts with the substrate to form a chemical bond or It is not always necessary to cross-link academic components.

 [0097] The fluorine-containing compound that can be used as such a fluorine-based water repellent is preferably one having a molecular weight of 1,000 to 20,000 containing a perfluoroalkyl group in the molecule. Perfluorosulfonic acid salt, perfluorosulfonic acid ammonium salt, perfluorocarboxylic acid salt, perfluoroalkyl betaine, perfluoroalkylethylene oxide adduct, perfluoroalkylamine oxide Perfluoroalkyl phosphate ester, perfluoroalkyltrimethylammonium salt, and the like. Of these, perfluoroalkyl phosphate ester and perfluoroalkyltrimethylammonium salt are preferred because of their excellent adsorptivity to the substrate surface. As such materials, Surflon S-112 and Surflon S-121 (both trade names, manufactured by Seimi Chemical Co., Ltd.) are commercially available!

 [0098] Examples of the hydrophilic inorganic material include SiO, a silicon compound, and a photocatalytic function.

 2

 And materials such as titanium oxide.

[0099] The photocatalytic substance contains a specific metal compound and has a function of oxidizing and decomposing organic and / or inorganic compounds on the surface of the layer by photoexcitation. The principle of photocatalysis is that certain metal compounds generate radical species such as OH— and O— from water or oxygen in the air by photoexcitation.

 2

 It is generally understood that this radical species is a redox degradation of organic and / or inorganic compounds.

[0100] As the metal compound, in addition to typical titanium oxide (TiO 2), ZnO, SrTiOP, Cd

 twenty three

S, CdO, CaP, InP, In O, CaAs, BaTiO, K NbO, Fe O, Ta O, WO, N

 2 3 3 2 3 2 3 2 5 3 iO, Cu 0, SiC, SiO, MoS, InSb, RuO, CeO, etc. are known.

 2 2 3 2 2

 [0101] A film made of a photocatalytic substance is prepared by converting an aqueous dispersion containing fine particles (about 2 nm to 20 nm) of these metal compounds together with various additives as required, into the water repellent or water absorbing inhibitor. And it can form by apply | coating and drying on the layer containing the said positively charged substance. The thickness of the membrane is preferably from 0.01 μm to 2. O ^ m, more preferably from 0.1 μm to ί · Οπι. An aqueous dispersion is preferably used for forming the photocatalytic substance film, but alcohol can also be used as a solvent.

[0102] The aqueous dispersion for forming a photocatalytic substance film can be produced, for example, by the following method. it can. Titanium peroxide in the aqueous dispersion can be changed to titanium oxide in the dry film-forming state.

 [0103] First manufacturing method

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

[0104] Second manufacturing method

 The tetravalent titanium compound described above is peroxoated with an oxidizing agent such as hydrogen peroxide, and then reacted with a base such as ammonia to form ultrafine particles of amorphous titanium peroxide.

. Further, it is transferred to anatase type titanium peroxide by heat treatment.

[0105] Third manufacturing method

 The tetravalent titanium compound described above is reacted with an oxidizing agent such as hydrogen peroxide and a base such as ammonia to form titanium hydroxide and peroxo at the same time to form ultrafine particles of amorphous titanium peroxide. To do. Further, it is transferred to anatase-type titanium peroxide by heat treatment.

[0106] Metals (Ag, Pt) that improve the photocatalytic performance may be added to the photocatalytic material film. In addition, various substances such as metal salts can be added to the extent that they do not deactivate the photocatalytic function. Examples of the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tandastene, zirconium, and zinc. In addition, hydroxides or oxides can be used for some metals or non-metals. Specifically, aluminum chloride, stannous chloride and stannic chloride, chromium chloride, nickel chloride, primary and secondary antimony chloride, ferrous and ferric chloride, silver nitrate, cesium chloride, indium trichloride , Cerium chloride, selenium tetrachloride, cupric chloride, manganese chloride, calcium chloride, platinum chloride, tungsten tetrachloride, tungsten oxytungsten chloride, potassium tungstate, gold chloride, zirconium oxychloride, chloride Various metal salts such as zinc can be exemplified. Other compounds than metal salts include indium hydroxide, key tungstic acid, silica sol, hydroxide Examples include calcium. Amorphous titanium peroxide can be added to improve the adhesion of the photocatalytic material film.

[0107] Since the contaminant on the substrate surface is decomposed by the action of the photocatalytic substance film, contamination of the substrate surface can be prevented and the cosmetic properties of the substrate can be maintained over time. If the photocatalytic material film is formed directly on the substrate, the photocatalytic material film may be peeled off from the substrate over time. However, the ability to integrate the photocatalytic material film with the substrate satisfactorily by interposing a positively charged material. Touch with S.

 [0108] When the positively charged substance is coated with the insulating organic or inorganic substance film in this manner, the side in contact with the layer containing the positively charged substance is caused by dielectric polarization in the insulating organic or inorganic substance film. A negative charge is generated, and a positive charge is generated on the surface of the film on the side separated from the layer containing the positively charged substance. This positive charge can be used to prevent contamination of the substrate surface as will be described later. In addition, the water repellency or hydrophilicity and the chemical properties of the insulating organic or inorganic film itself are maintained, so that the prevention of contamination by the chemical properties can be further improved.

 In the present invention, when the water repellent or water absorption inhibitor and the positively charged substance form a layer, an intermediate layer may exist between the surface of the substrate and the layer. In particular, when the layer containing the water repellent or water absorption inhibitor and the positive charge substance further contains an organic silicon compound, it is preferable to form an intermediate layer containing a silane compound on the substrate in advance. Since this intermediate layer contains a large amount of Si—O bonds, the strength of the layer and the adhesion to the substrate can be improved. The intermediate layer also has a function of preventing moisture from entering the substrate.

[0110] Examples of the silane compounds include hydrolyzable silanes, hydrolysates thereof, and mixtures thereof. As the hydrolyzable silane, various alkoxysilanes can be used. Specific examples include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldianoloxysilane, and trialkylalkoxysilane. Of these, one type of hydrolyzable silane may be used alone, or two or more types of hydrolyzable silanes may be mixed and used as necessary. Various organopolysiloxanes may be blended with these silane compounds. As an intermediate layer forming agent containing such a silane compound, there is Dry Seal S (manufactured by Toray 'Dowcoung' Silicone Co., Ltd.). [0111] Further, as the intermediate layer forming agent, a room temperature curable silicone resin such as methyl silicone resin and methyl phenyl silicone resin may be used. Examples of such room-temperature-curing silicone trees include AY42-170, SR2510, SR2406, SR2410, SR2405, and SR2411 (manufactured by Toray 'Dowcoung' Silicone Co., Ltd.).

[0112] The intermediate layer may be colorless and transparent, or may be colored transparent, translucent or opaque. Coloring here includes not only red, blue, green, etc. but also white. In order to obtain a colored intermediate layer, it is preferable to mix various colorants such as inorganic or organic pigments or dyes in the intermediate layer.

 [0113] Examples of inorganic pigments include carbon black, graphite, yellow lead, iron oxide yellow, red lead, red rose, ultramarine, chromium oxide green, iron oxide and the like. As organic pigments, azo organic pigments, phthalocyanine organic pigments, selenium organic pigments, quinotalidone organic pigments, dioxazine organic pigments, isoindolinone organic pigments, diketopyrrolopyrrole and various metal complexes are used. Although it is possible, it should have excellent light resistance. Examples of light-resistant organic pigments include, for example, Hansa Yellow, toluidine red, which is an insoluble azo organic pigment, phthalocyanine blue B, which is a phthalocyanine organic pigment, quinacridone red, which is a quinacridone organic pigment, and the like. Is mentioned.

 [0114] Examples of the dye include basic dyes, direct dyes, acid dyes, vegetable dyes, etc., but those having excellent light resistance are preferred. For example, in red, direct scarlet, loxelin, azolbin, orange , Direct Orange R Conch, Acid Orange, and Yellow are particularly preferably Chrysophenine NS, Methanil Yellow, Brown is Direct Brown KGG, Acid Brown R, Blue is Direct Blue B, Black is Direct Black GX, and Nigguchi Shin BHL.

 [0115] When the intermediate layer is composed of a silane compound or silicone resin, the mixing ratio (weight ratio) of these silane compound or silicone resin and pigment is preferably in the range of 1: 2 to 1: 0.05. The range of 1: 1 to; 1: 0 · 1 is more preferable.

[0116] The intermediate layer may further contain additives such as a dispersant, a stabilizer, and a leveling agent. These additives have an effect of facilitating the formation of the intermediate layer. Furthermore, when blending a colorant such as a pigment 'dye, a binder for fixing the colorant may be added. Is possible. As the binder in this case, various paint binders mainly composed of an acrylic ester or an acrylic ester copolymer resin having excellent weather resistance can be used. For example, Polysol AP-3720 (Showa Polymer Co., Ltd.) And Polysol AP-609 (manufactured by Showa Polymer Co., Ltd.).

 [0117] The intermediate layer can be formed, for example, as follows. An intermediate layer forming agent composed of a silane compound or a silicone resin in a volatile solvent, and a solution containing the colorant, the additive and the binder, if necessary, having a thickness of about 2 to 5 mm on the surface of the substrate. Apply so that If necessary, the intermediate layer is formed on the substrate by heating and evaporating the volatile solvent. The colored intermediate layer can be imparted with a colored cosmetic by being integrated with the substrate.

 [0118] The thickness of the intermediate layer formed as described above is not particularly limited, but is preferably 0.01 to 1.0 111 force << preferably, more preferably 0.05 to 0.33 force. In addition, when coloring is added IJ, added calorie IJ, and the strength of the cylinder is added, 1.0 to 111 to 100 to 111 is preferable, and 10 to 111 to 50 to 111 is more preferable.

 [0119] As the method for forming the intermediate layer on the substrate, any known method can be used. For example, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, Brush painting, sponge painting, etc. are possible. In order to improve the physical performance such as the hardness of the intermediate layer and the adhesion to the substrate, it is preferable to heat them at a temperature within an allowable range after the formation of the intermediate layer on the substrate. ,.

 Next, FIG. 5 shows a mechanism for removing contaminants from a positively charged substrate surface.

 First, a positive charge is applied to the substrate surface (FIG. 5 (1)).

 [0122] Contaminants accumulate on the substrate surface and are photooxidized by the action of electromagnetic waves such as sunlight. In this way, a positive charge is also given to the pollutant (Fig. 5 (2)).

[0123] An electrostatic repulsion of positive charges occurs between the substrate surface and the contaminant, and a repulsion and separation force is generated in the contaminant. This reduces the adherence of contaminants to the substrate surface (Figure 5).

(3)).

 [0124] Contaminants are easily removed from the substrate by physical action such as wind and rain (Fig. 5 (4)).

Thereby, the substrate is self-cleaned. [0125] Therefore, in the present invention, the water repellency by the water repellent or the water absorption inhibitor is utilized, and at the same time, the positive charge imparted to the surface of the substrate is utilized to exhibit a continuous "antifouling / antifogging function". This makes it possible to obtain products that will This technology can be applied to any substrate, but in particular, it can maintain the function for a long time by applying a positive charge to the surface of the substrate having excellent water repellency. Is preferred. This makes “dirty V, plastic” possible.

 [0126] Further, the positive charge on the substrate surface can reduce the oxidative degradation of the substrate due to electromagnetic waves. That is, oxidative degradation of the substrate is caused by generation of radicals such as' θ, ···, etc. due to electromagnetic waves such as ultraviolet rays on the surface of the substrate or in the substrate to cause an oxidative decomposition reaction.

 2

 Of course, the positively charged surface of the substrate makes these radicals stable molecules. Therefore, it is considered that the oxidative deterioration of the substrate is prevented or reduced. When the substrate is made of metal, it is possible to reduce the generation of soot from the same process.

[0127] The present invention can be used in various fields where various design properties and high waterproof / antifouling performance are required. Glass, metal, ceramics, concrete, wood, stone, polymer resin cover, polymer Resin sheets, textiles (clothing, curtains, etc.), sealants, etc., or a combination of these materials; building materials; air conditioning outdoor units; kitchen equipment; sanitary equipment; lighting equipment; automobiles; bicycles; It is preferably used for articles used indoors and outdoors such as, and face panels of various machines, electronic devices, televisions and the like. In particular, according to the present invention, a building such as a house, building, road, or tunnel constructed using the building material preferred for a building material having high water absorption can exhibit a high waterproof / antifouling effect over time. Can

[0128] In the present invention, the combination of the water repellent or the water absorption inhibitor and the positively charged substance is used alone as a contamination preventing or reducing agent for the substrate surface including the combination, or as a protective agent. Can be distributed in the market.

 Example

 [0129] Hereinafter, the present invention will be described based on specific examples.

[0130] (Production Example 1)

97% CuCl · 2Η 0 (cupric chloride) (manufactured by Nippon Chemical Industry Co., Ltd.) 0.4 g 2.5% Ammoni A solution of 10 Og of a deep blue positively charged metal solution having a copper concentration of about 800 ppm was completely dissolved in 99.6 g of water.

[0131] (Production Example 2)

 97% CuCl · 2Η 0 (cupric chloride) (manufactured by Nippon Chemical Industry Co., Ltd.) 0.8g to pure water 199.2g

 twenty two

 Dissolve completely to prepare 200 g of light blue positively charged metal solution with a copper concentration of about 800 ppm.

[0132] (Production Example 3)

 A water-repellent dispersion (100 g) was prepared by mixing a water-repellent agent (Dry Seal S: manufactured by Toray Industries, Inc.) and pure water at a weight ratio of 20:80.

[0133] (Production Example 4)

 A water repellent (dry seal S: manufactured by Toray Dow Coung Co., Ltd.) and pure water were mixed at a weight ratio of 40:60 to prepare 100 g of a water repellent dispersion.

[0134] (Production Example 5)

 The solution prepared in Production Example 2 and the dispersion prepared in Production Example 3 were mixed at a weight ratio of 1: 1 to prepare 100 g of a positively charged metal-containing water-repellent dispersion.

[0135] (Production Example 6)

 The solution prepared in Production Example 2 and the dispersion prepared in Production Example 4 were mixed at a weight ratio of 1: 1 to prepare 100 g of a positively charged metal-containing water-repellent dispersion.

[0136] (Production Example 7)

 90 g of the positively charged metal-containing water-repellent dispersion prepared in Production Example 5 is mixed with 10 g of a white pigment (Polx White PC—CRH (manufactured by Sumika Color Co., Ltd.)), and Polysol AP—609L (as a binder) Showa Polymer Co., Ltd. (5 g) was mixed to prepare 105 g of a positively charged water-repellent white dispersion.

[Example 1]

Spray the positively-charged metal-containing water-repellent dispersion prepared in Production Example 5 onto the surface of a ceramic tile (97mm x 97mm) at a coating weight of 2.0g / 100cm ² and heat it at 70 ° C for 1 hour. A substrate was obtained.

[0138] (Example 2) Spray the positively charged water-repellent white dispersion prepared in Production Example 7 on the back of a ceramic tile (97mm X 97mm) at a coating weight of 2.0g / 100cm ² and heat at 70 ° C for 1 hour for evaluation. A substrate was obtained.

[0139] (Comparative Example 1)

Spray the photocatalyst solution (B56: Sustainable Technology Co., Ltd.) on the back of the ceramic tile (97mm X 97mm) with a coating amount of 2. Og / 1 OOcm ² and heat at 70 ° C for 1 hour. An evaluation substrate was obtained.

[0140] (Comparative Example 2)

Spray the surface of porcelain tile (97mm x 97mm) with a water repellent (Dry Seal S: manufactured by Toray 'Dauco Ninging Co., Ltd.) 10 times diluted with pure water at a coating amount of 2.0g / 100cm ² Then, the substrate for evaluation was obtained by heating at 70 ° C. for 1 hour.

[0141] (Evaluation 1)

Red ink containing Indico dye, which is a negatively charged dye (manufactured by Pilot Co., Ltd.) is diluted with ethanol to give a 10-fold diluted solution, with an application amount of 0.007 g / 100 cm ² , Examples 1 and 2 and Spot coating was performed on the surface of each evaluation substrate of Comparative Examples 1 and 2. Each substrate;! ~ 4 was arranged on a straight line, 20W black light (manufactured by Toshiba Lighting & Technology Co., Ltd.) was placed on each substrate, and the surface of each substrate was irradiated with ultraviolet rays at a rate of 1100 W / cm ² . A color difference meter (manufactured by Minolta Co., Ltd., CR 200) was used to measure the fading rate of the red ink on each evaluation substrate surface over time.

[0142] The fading rate (%) of the red ink was obtained by calculation using the following equation.

 Decoloration rate = 100—

— L) ² + (a -a) ² + (b — b) ² )) / ^ ((L — L) ² + (aa) ² + (b — b) ²

2 0 2 0 2 0 1 0 1 0 1 0

)) xioo

 L, a, b: Color data of substrate surface before applying red ink

 0 0 0

 L, a, b: Color data of substrate surface immediately after application of red ink

 L, a, b: Color data of substrate surface after UV irradiation

 2 2 2

 [0143] The results of the obtained fading rate are shown in Table 1. The higher the fading rate in Table 1, the more pronounced the red ink fading.

[0144] [Table 1] table 1

 [0145] From the results shown in Table 1, it can be seen that in Comparative Example 2, the red ink disappears rapidly due to oxidative decomposition and negative charge generation on the substrate surface due to photocatalysis. Comparative Example 1 also has a high final decoloration rate due to oxidative decomposition of black light by ultraviolet rays. On the other hand, in Examples 1 and 2, it can be seen that the release of red ink is suppressed by the positive charge on the substrate surface, and the oxidative decomposition due to ultraviolet rays is reduced. As a result, it can be seen that the anti-fouling property against environmental pollutants having a positive charge is excellent as in the case of Examples 1 and 2 having a positive charge on the surface.

[0146] (Production Example 8)

 90 g of the water-repellent dispersion prepared in Production Example 3 is mixed with 10 g of a white pigment (Polx White PC—CRH (manufactured by Sumika Color Co., Ltd.)), and Polysol AP—609L (Showa Polymer Co., Ltd.) as a binder. 5 g) was mixed to prepare 105 g of a water-repellent white dispersion. 50 g of this water-repellent white dispersion and 50 g of the positively charged metal solution of Production Example 1 were mixed at a weight ratio of 1: 1 to prepare 100 g of a positively charged metal-containing water-repellent white dispersion.

[0147] (Production Example 9)

 90 g of the water-repellent dispersion prepared in Production Example 3 is mixed with 10 g of a white pigment (Polx White PC—CRH (manufactured by Sumika Color Co., Ltd.)), and Polysol AP—609L (Showa Polymer Co., Ltd.) as a binder. 5 g) was mixed to prepare 105 g of a water-repellent white dispersion. 50 g of this water-repellent white dispersion and 50 g of the positively charged metal solution of Production Example 2 were mixed at a weight ratio of 1: 1 to prepare 100 g of a positively charged metal-containing water-repellent white dispersion.

[0148] (Production Example 10)

90 g of the water-repellent dispersion prepared in Production Example 3 is mixed with 10 g of a white pigment (Polx White PC—CRH (manufactured by Sumika Color Co., Ltd.)), and Polysol AP—609L (Showa Polymer Co., Ltd.) as a binder. 5 g) was mixed to prepare 105 g of a water-repellent white dispersion. [Example 3]

Spray the positively charged water-repellent white dispersion prepared in Production Example 8 on the back of a paving concrete block (300mm X 300mm X 30mm) at a coating amount of 20g / l 00cm ² and dry it at room temperature. Got.

[0150] (Example 4)

Spray the positively charged water-repellent white dispersion prepared in Production Example 9 on the back of a paving concrete block (300mm X 300mm X 30mm) at a coating amount of 20gZ 100cm ² and dry at room temperature to obtain a substrate for evaluation It was.

[0151] (Comparative Example 3)

The evaluation substrate was obtained by spray-coating the water-repellent white dispersion of Production Example 10 at a coating amount of 20 g / 100 cm ² on the back of a paving concrete block (300 mm X 300 mm X 30 mm) and drying at room temperature.

[0152] (Evaluation 2)

 Each of the evaluation substrates of Examples 3 and 4 and Comparative Example 3 was subjected to an exposure test for 5 months in Saga Prefecture, and the surface contamination of each substrate was visually observed. The results are shown in Table 2. “Water repellency” in Table 2 indicates that the contact angle with water is 95 °.

[0153] [Table 2]

 Table 2

 [0154] From the results shown in Table 2, the degree of surface contamination is relatively small in the substrate coated with not only the water repellent but also the positively charged substance as compared with the substrate coated with the water repellent. . Therefore, it can be seen that a substrate provided with a positively charged substance on the surface together with a water repellent is excellent in antifouling performance.

 [Example 5]

Porcelain tile (97mm x 97mm) surface with fluorine water repellent (GM-105: Daikin Kogyo Co., Ltd.) and the positively charged metal solution of Production Example 2 were mixed at a weight ratio of 1: 1, and the resulting mixture was brushed at a coating weight of 5 g / 100 cm ² and then 130 ° C for 30 minutes. The substrate for evaluation was obtained by heating.

 [0156] (Comparative Example 4)

Brush the porcelain tile (97mm x 97mm) with a fluorine-based water repellent (GM-105: manufactured by Daikin Industries Co., Ltd.) at a coating weight of 5g / 100cm ² and heat at 130 ° C for 30 minutes. A substrate for evaluation was obtained.

[0157] (Evaluation 3)

 An exposure test was performed on each evaluation substrate in Example 3 and Comparative Example 4 in Tesaga Prefecture, and the contamination state on the surface of each substrate was visually observed. Specifically, each evaluation board was exposed to sunlight outside a wholesaler on the 18th, and then left for 2 days in a certain place. The results are shown in Table 3. In Table 3, “strong water repellency” means that the contact angle with water is 100 ° or less, and “water repellency” means that the contact angle with water is around 95 °. “Hydrophilic” means that the contact angle with water is 20 ° or less. The contact angle was visually measured with a manual goniometer.

[0158] [Table 3]

Table 3

 As shown in Table 3, Comparative Example 4 is water repellent regardless of exposure conditions. Example 5 becomes hydrophilic when exposed to sunlight, while it becomes water repellent when not exposed to sunlight. Therefore, the results shown in Table 3 indicate that the water repellency and hydrophilicity of the substrate surface can be controlled by arranging a positively charged substance on the substrate surface together with the water repellent. Evaluation 3 was performed twice, but the results were the same for both.

Claims

Claims [1] A water-repellent agent or a water absorption inhibitor in the substrate surface or substrate surface layer, and (1) a cation (2) a conductor or dielectric having a positive charge (3) a conductor and dielectric A method for generating a positive charge on the surface of a substrate, comprising arranging one or more positively charged substances selected from the group consisting of: [2] A water-repellent agent or a water-absorption inhibitor in the substrate surface or substrate surface layer, and (1) a cation (2) a conductor or dielectric having a positive charge (3) a conductor and a dielectric or semiconductor A method for preventing or reducing contamination of a substrate surface, characterized in that one or more positively charged substances selected from the group consisting of: [3] In the substrate surface or substrate surface layer, a water repellent or water absorption inhibitor, and

 (1) Cation

 (2) Positively charged conductor or dielectric

 (3) Conductor and dielectric or semiconductor composite

 A method for protecting a substrate surface, comprising arranging one or more positively charged substances selected from the group consisting of:

[4] The water repellent or water absorption inhibitor is a silane, siliconate, silicone, silicone and silane composite, fluorine-based water repellent or water absorption inhibitor, or at least one of these

The method according to claim 1, which is a mixture of two kinds.

5. The method according to any one of claims 1 to 4, wherein the mixture of the water repellent or the water absorption inhibitor and the positively charged substance is disposed in a substrate surface or a substrate surface layer.

[6] The mixture further comprises: Selected from the group consisting of noon dispersants, ayuon dispersants, amphoteric dispersants, water-soluble resinous dispersants having an acid value of 50 to 250, and emulsion resinous dispersants having an acid value of 50 to 250. 6. A process according to claim 5, characterized in that it comprises a pigment dispersion consisting of one or more dispersants; a pigment; and a liquid.

7. The method according to claim 5 or 6, wherein the mixture forms a layer.

8. The method according to claim 7, wherein an intermediate layer is formed between the substrate surface and the mixture layer.

 [9] The method according to claim 7 or 8, wherein a coating layer is further formed on the mixture layer.

 [10] An article provided with the substrate, the surface of which is prevented or reduced in the air or water by the method according to any one of claims 1 to 9, or the surface is protected.

[11] A contamination preventing or reducing agent for a substrate surface, comprising a water repellent or a water absorption inhibitor and a positively charged substance.

 [12] A substrate surface protective agent comprising a water repellent or water absorption inhibitor and a positively charged substance.