JP2017197695A - Film for surface protection of substrate and surface protection method of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a means for inhibiting adhesion or absorption of contaminant to a substrate surface by developing switching of an insulation state and a conductive state on the surface of the substrate even during no irradiation of light, neutralizing electrical properties such as charging obtained by a material which floats neighboring the substrate surface, and protecting the surface of the substrate by hydrophilizing the substrate surface at same time.SOLUTION: A surface protective film is a film containing particles or crystal bodies of a silicon compound to which at least one of alkali metals or alkali earth metals is doped or a film containing ions or particles or crystal bodies of metal high in conductivity and a silicon compound, and the film further contains at least one of a positive charge material and a negative charge material.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a technology for protecting a substrate surface.

  The inventors of the present application have proposed various methods for protecting (antifouling) the substrate surface. For example, Patent Literature 1, Patent Literature 2, and Patent Literature 3 relate to photocatalytic technology.

  On the other hand, the applicant, in Patent Document 4, generates a positive charge on the surface of the substrate by disposing a composite of a conductor and a dielectric or semiconductor on the surface of the substrate or the surface layer of the substrate. A technique for protecting a substrate surface by electrostatically attracting or repelling is disclosed. In addition, in the patent document 5, the applicant arranges a positively charged substance and a negatively charged substance on the substrate surface or the substrate surface layer, and positively and negatively charges the substrate surface, so that contaminants from the outside are introduced into the substrate. A technique for protecting a substrate surface by electrostatically attracting or repelling the surface is disclosed.

  Furthermore, in the patent document 6, the applicant has a substrate provided with a photosemiconductor-containing layer and a positively charged substance or a negatively charged substance-containing layer, or a single layer containing a photosemiconductor / positively charged substance and a negatively charged substance on the surface. Discloses a technique for protecting the substrate surface by irradiating the substrate with light and changing the conductive properties of the substrate surface.

  In particular, the technique disclosed in Patent Document 6 is an unprecedented new technique in that the surface of the substrate is protected by changing the surface of the substrate. However, when light was not irradiated, protection by other functions had to be relied upon.

Japanese Patent Laid-Open No. 9-262481 JP-A-10-235201 JP 11-333303 A International Publication WO2005 / 108056 International Publication No. WO2008 / 013148 International Publication WO2012 / 093632

  The present invention neutralizes the electrical characteristics such as charging of a substance floating near the substrate surface by causing the substrate surface to switch between an insulating state and a conductive state even when light is not irradiated. Accordingly, an object of the present invention is to provide a means for protecting the surface of the substrate by preventing the adhesion and adsorption of contaminants to the surface of the substrate and making the surface of the substrate hydrophilic.

  The surface protective film of the substrate according to the present invention is a film containing silicon compound particles or crystals doped with at least one of alkali metal and alkaline earth metal, or ions or particles or crystals of highly conductive metal And a silicon compound, wherein the film further contains at least one of a positively charged substance and a negatively charged substance, and the surface electrical resistance of the substrate is changed to a conductive state and an insulating state. It is characterized by periodically changing.

  Further, in the above-described embodiment of the surface protective film of the substrate, it is a film containing particles or crystals of a silicon compound doped with at least one of an alkali metal and an alkaline earth metal, and the film further includes a positively charged substance and In an embodiment containing at least one of the negatively charged substances, any one of the silicon compound particles or crystals, the positively charged substance, or the negatively charged substance can be at least an oxygen deficient substance.

  A film forming solution for a surface protective film of a substrate according to the present invention is a particle or crystal of a silicon compound doped with at least one of an alkali metal and an alkaline earth metal, or a highly conductive metal ion or particle or crystal. And a silicon compound, and further contains at least one of a positively charged substance and a negatively charged substance.

  The method for forming a surface protective film of a substrate according to the present invention comprises a particle or crystal of a silicon compound doped with at least one of an alkali metal and an alkaline earth metal, or a highly conductive metal ion or particle or crystal. A dispersion liquid containing silicon and a silicon compound is applied to a substrate, and heat treatment or non-heat treatment is performed.

  The surface protective film of the substrate according to the present invention is a substance that floats near the surface of the substrate by periodically changing the electrical resistance in the surface layer of the substrate or in the surface film between a conductive state and an insulating state in a short time. If the surface of the substrate is positively charged, electrons are applied, and if the surface of the substance existing near the surface of the substrate is negatively charged, the electrons are extracted, and the charged state of the surface of the suspended substance is electrically By neutralization, it is possible to prevent electrical adsorption of floating contaminants to the substrate. Furthermore, by generating oxygen deficiency in the substance contained in the surface protective film of the substrate, the hydrophilicity of the substrate surface can be maintained or developed, and contamination deterioration of the substrate surface can be further reduced or avoided.

It is a figure which shows an example of the preparation methods of the dispersion liquid of an alkali metal or alkaline-earth metal dope silicon oxide. It is a figure which shows an example of the preparation methods of the dispersion liquid of a metal (inorganic substance) dope titanium oxide. It is a figure which shows typically the function of the surface protection film by this invention. It is a figure which shows the implementation method of evaluation 2 in an Example.

Embodiments according to the present invention will be described below with reference to the drawings.
Outline The surface protective film of the substrate according to the present invention has the following aspect (1) or (2).
(1) A film containing silicon compound particles or crystals doped with at least one of an alkali metal and an alkaline earth metal, wherein the film further contains at least one of a positively charged substance and a negatively charged substance. Film.
(2) A film containing highly conductive metal ions or particles or crystals and a silicon compound, wherein the film further contains at least one of a positively charged substance and a negatively charged substance.

  By including the substance described in the above (1) or (2), the surface protective film of the above-described substrate periodically changes the surface electrical resistance of the substrate between a conductive state and an insulating state. Can be varied. The switching of the electrical resistance on the surface of the substrate does not require other conditions such as light irradiation.

In the film described in (1), any one of silicon compound particles or crystals, a positively charged substance, or a negatively charged substance can be used as an oxygen deficient substance.
There are many film forming methods such as a wet method and a dry method as a method for forming the surface protective film of the substrate on the substrate, and any of them may be used.

  Hereinafter, the substances contained in the surface protective film of the substrate according to the present invention, the method of forming the surface protective film of the substrate, the function of the surface protective film of the substrate, the intermediate layer other than the surface protective film formed on the substrate, Details of the target substrate will be described in order.

<Substances contained in the surface protective film of the substrate>
The substances contained in the surface protective film of the substrate according to the present invention will be described in <1> to <3> described below.

<1> Silicon Compound Particles or Crystals Doped with at least Any of Alkali Metal and Alkaline Earth Metal <1a> Silicon Compound Doped with at least Any of Alkali Metal and Alkaline Earth Metal Alkali used in the present invention Although the metal and the alkaline earth metal are not particularly limited, examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include calcium, strontium, barium, and radium. Can be mentioned. In addition, “alkaline earth metal” in this specification includes Group 11 elements beryllium and magnesium.

The silicon compound used in the present invention is not particularly limited, but silicon oxide (including silicon oxide compounds) is preferable, and various kinds of materials such as SiO ₂ , SiO ₃ , SiO, and SiO ₃ / nH ₂ O are used. Oxides and peroxides can be used.

  The silicon compound doped with at least one of alkali metal and alkaline earth metal is preferably fine particles or crystals.

<1b> Method for Producing Alkali Metal or Alkaline Earth Metal Doped Silicon Oxide Here, as a preferred example of a silicon compound doped with at least one of alkali metal and alkaline earth metal that can be used in the present invention, an alkali metal is used. Alternatively, a method for producing silicon oxide doped with alkaline earth metal will be described.

  Many types of products are commercially available as materials containing silicon oxide. For example, the following can be cited as a binding material (composite material) of an organic material and an inorganic material.

・ Water-soluble coating agent with methoxy group or ethoxy group due to hydrolyzability in silane coupling agent that improves mechanical strength, bondability and surface hydrophilicity of composite materials ・ Organic functional group and alkoxy group Silicone oligomer used as a resin modification or functional coating agent by compounding various substances as an oligomer type coupling agent in the molecule. Alkoxylanes or alkoxylazanes with methyl groups, long-chain alkyl groups, or phenyl groups ・ Organic or organic materials that have an origanosilyl group that protects active hydrogen in inorganic materials or that are controlled by controlling the reaction position of alkyl groups Silylating agents that can make synthetic members, etc. Using the above-mentioned materials containing silicon oxide, Can make a film-forming solution containing alkaline earth metal doped silicon oxide. Hereinafter, an example of a method for producing a dispersion of alkali metal or alkaline earth metal-doped silicon oxide will be described with reference to FIG.

  First, alcohol, pure water and a predetermined amount of catalyst are mixed with methyl silicate and hydrolyzed. When stirred until it is transparent, a silica sol is produced. This silica sol is diluted with pure water. The solid content concentration in the silica sol dilution is preferably 10% to 0.2%, more preferably 4% to 0.85%. This silica sol diluted solution and an alkali metal or alkaline earth metal compound adjusted to a concentration of 1% are preferably in a molar concentration ratio to silica of 1: 0.03 to 1: 2.7, more preferably 1 : 0.03 to 1: 0.27. Then, the silica sol diluted solution mixed with the alkali metal or alkaline earth metal compound thus obtained is heated at a predetermined temperature for a predetermined time (for example, at 50 ° C. for 20 hours) to thereby obtain an alkali metal or an alkali. A solution in which fine particles or crystals of silicon oxide doped with earth metal are dispersed is obtained.

  In addition, as shown in FIG. 1, lithium, sodium, potassium, rubidium, strontium, barium, calcium mixed in order to obtain the alkali metal and alkaline earth metal which can be complexed with silicon oxide in the preparation of the above dispersion liquid As examples of the compounds of, radium, beryllium, magnesium and cesium, the following can be exemplified.

Li compound: LiOH, Li ₂ CO ₃ , LiCl, etc. Na compound: NaOH, NaCl, Na ₂ CO ₂ etc. K compound: KOH, K ₂ O, KCl etc. Rb compound: RbO ₂ , RbOH etc. Sr compound: SrO ₂ , SrCl ₂ etc. Ba compound: BaCl ₂ etc. Ca compound: Ca (OH) ₂ , CaCl ₂ etc. Ra compound: Ra (OH) ₂ , [Ra (H ₂ Ox)] ²⁺ etc. Be compound: Be (OH) ₂ , BeCl ₂ Mg compound: Mg (OH) ₂ , MgCl ₂ etc. Cs compound: CsOH, CsCl, etc. In addition to the method for producing the alkali metal or alkaline earth metal doped silicon oxide dispersion described with reference to FIG. There are many methods for compounding metal or alkaline earth metal and silicon oxide, and any of them may be used. For example, silicon oxide particles such as colloidal silica and alkali metal or alkaline earth metal particles to be combined may be separately prepared, and the powder or the solvent dispersion may be mixed.

<2> Highly conductive metal ions or particles or crystals and silicon compound <2a> Mixture of highly conductive metal ions or particles or crystals and silicon compound Highly conductive metal used in the present invention For example, silver, copper, gold, aluminum, magnesium, zinc and the like are used, and copper is particularly preferable. The metal mixed with the silicon compound is preferably particles or crystals.

Further, the silicon compound mixed with the metal having high conductivity is not particularly limited, but silicon oxide (including a silicon oxide compound) is preferable, and SiO ₂ , SiO ₃ , SiO, SiO ₃ / nH ₂ Various oxides and peroxides such as O can be used.

<2b> Method for producing film-forming solution containing highly conductive metal ions or particles or crystals and silicon compound Film-forming solution containing highly conductive metal ions or particles or crystals and silicon compound Select, for example, the type of substance to be compounded from the compatibility of the solvates of the substance to be compounded, and the silicon compound solution and conductivity for compounding the substance contained in the target film-forming solution. In order to accelerate the catalyst addition and the composite one-component solution after mixing with a high metal solution, it can be produced by stirring while heating at a room temperature to 90 ° C.

<3> Positively Charged Substance and Negatively Charged Substance In the following, in the surface protective film of the substrate according to the present invention, a silicon compound particle or crystal doped with at least one of alkali metal and alkaline earth metal, or conductive A positively charged substance and a negatively charged substance that are further included in a mixture of high metal ions or particles or crystals and a silicon compound will be described. In the present specification, a positively charged substance refers to a substance that positively charges the surface of the substrate, and a negatively charged substance refers to a substance that negatively charges the surface of the substrate.

<3a> A substance that can be used as a positively charged substance or a negatively charged substance The positively charged substance described above is a substance having one or more positive charges selected from the group consisting of the following (i) and (ii) It is.

(I) a cation (ii) a conductor having a positive charge, a composite of a conductor having a positive charge and a dielectric or semiconductor, a composite comprising two or more kinds of dielectrics or semiconductors having a positive charge The negatively charged substance is a substance having one or more negative charges selected from the group consisting of the following (iii) to (v).
(Iii) anion (iv) a conductor having a negative charge, a composite of a conductor having a negative charge and a dielectric or a semiconductor, a composite comprising two or more kinds of dielectrics or semiconductors having a negative charge (v) Substance having a photocatalytic function The cation used as the positively charged substance is not particularly limited, but alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium; aluminum, tin, cesium, Ions of other metal elements such as indium, cerium, selenium, chromium, cobalt, nickel, antimony, iron, copper, manganese, tungsten, zirconium, and zinc are preferable, and copper ions are particularly preferable. Furthermore, cationic molecules such as methyl violet, bismarck brown, methylene blue and malachite green, and organic molecules having a cationic group such as silicone modified with a quaternary nitrogen atom-containing group can also be used. The valence of ions is not particularly limited, and for example, a cation having 1 to 4 valences can be used.

  It is also possible to use a metal salt as a source of the metal ion as the cation described above. Specifically, aluminum chloride, first and second tin chloride, chromium chloride, nickel chloride, first and second antimony chloride, first and second iron chloride, cesium chloride, indium trichloride, first cerium chloride, Examples include various metal salts such as selenium tetrachloride, cupric chloride, manganese chloride, tungsten tetrachloride, tungsten oxychloride, potassium tungstate, zirconium oxychloride, zinc chloride, and barium carbonate. Furthermore, metal hydroxides such as aluminum hydroxide, iron hydroxide, chromium hydroxide, and indium hydroxide, hydroxides such as silicotungstic acid, and oxides such as oil and fat oxides can be used.

  Examples of the positively charged conductor include conductors in which a positive charge other than the above-mentioned cation is generated. For example, a positive electrode of a battery made of various conductors described later, and positively by friction. Examples thereof include dielectric materials such as charged wool and nylon.

  The anion used as the negatively charged substance is not particularly limited, but halide ions such as fluoride ion, chloride ion and iodide ion; hydroxide ion, sulfate ion, nitrate ion, carbonate ion, etc. Inorganic ions; organic ions such as acetate ions. The valence of ions is not particularly limited, and for example, a 1 to 4 valent anion can be used.

  Examples of the conductor having a negative charge include conductors having a negative charge other than the above anions, such as metals such as gold, silver and platinum; metal oxides; graphite, sulfur, selenium, Elements such as tellurium; sulfides such as arsenic sulfide, antimony sulfide, mercury sulfide; clay, glass powder, quartz powder, asbestos, starch, cotton, silk, wool, etc .; conger, indigo, aniline blue, eosin, naphthol yellow Examples include dye colloids. Of these, colloids of metals such as gold, silver and platinum and metal oxides are preferred, and silver colloids are more preferred. In addition, the negative electrode of the battery which consists of the various conductors mentioned later, dielectric materials, such as negatively charged halogen, a fluororesin, vinyl chloride, polyethylene, polyester, and these compounds and composites are mentioned. .

As a substance having a photocatalytic function used as a negatively charged substance, a substance containing a specific metal compound and having a function of oxidizing and decomposing organic and / or inorganic compounds on the surface of the layer by photoexcitation can be used. The principle of photocatalyst by photoexcitation specific metal compounds, from the water or oxygen in the air OH ^- or O ₂ ^- radical species is generated in, that the radical species oxidize reductive decomposition of organic and / or inorganic compound It is generally understood that there is.

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

  The substance having a photocatalytic function may contain a metal (Ag, Pt) that improves the photocatalytic performance. Moreover, various substances, such as a metal salt, can be included in a range that does not deactivate the photocatalytic function. Examples of the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, and zinc. In addition, hydroxides or oxides can be used for some metals or nonmetals. Specifically, aluminum chloride, stannous chloride and stannic chloride, chromium chloride, nickel chloride, primary and secondary antimony chloride, ferrous chloride, silver nitrate, cesium chloride, indium trichloride, selenium tetrachloride And various metal salts such as cupric chloride, manganese chloride, calcium chloride, platinum chloride, tungsten tetrachloride, tungsten oxychloride, potassium tungstate, cupric chloride, zirconium oxychloride, and zinc chloride. Examples of compounds other than metal salts include indium hydroxide, silicotungstic acid, silica sol, potassium hydroxide, calcium hydroxide and the like.

  The conductor used in the present invention is preferably a metal from the viewpoint of durability, and is a metal such as aluminum, tin, indium, cerium, selenium, chromium, nickel, antimony, iron, silver, copper, manganese, platinum, tungsten, or zinc. Is mentioned. Also, oxides, composites or alloys of these metals can be used. The shape of the conductor is not particularly limited, and may be any shape such as a particle shape, a flake shape, or a fiber shape.

  As the above-described conductor, a metal salt of a part of metal can also be used. Specifically, aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antimony chloride, 1st and 2nd iron chloride, silver nitrate, cesium chloride, indium trichloride, selenium tetrachloride And various metal salts such as cupric chloride, manganese chloride, second platinum chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, second gold chloride, and zinc chloride. Also, hydroxides or oxides such as indium hydroxide and silicotungstic acid can be used.

  Furthermore, the above conductors include polyaniline, polypyrrole, polythiophene, polythiophene vinylon, polyisothianaphthene, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly-p-phenylene, polyphenylene vinylon, polymethoxyphenylene, polyphenylene sulfide, Conductive polymers such as polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, and polyazulene can also be used.

Examples of the semiconductor constituting the composite with the conductor used in the present invention include C, Si, Ge, Sn, GaAs, Inp, GeN, ZnSe, PbSnTe, and the like. An optical semiconductor metal oxide can also be used. Preferably, besides titanium oxide (TiO ₂ ), ZnO, SrTiOP ₃ , CdS, CdO, CaP, InP, In ₂ O ₃ , CaAs, BaTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₃ , WO ₃ , NiO, Cu ² O, SiC, SiO ₂ , MoS ₃ , InSb, RuO ₂ , CeO _2, etc. are used. When used as a semiconductor, the photocatalytic ability is deactivated with Na or the like. Is preferred.

Examples of the dielectric constituting the composite with the conductor used in the present invention include ferroelectric barium titanate (PZT), so-called SBT, BLT and the following PZT, PLZT- (Pb, La) (Zr). , Ti) O ₃ , SBT, SBTN-SrBi ₂ (Ta, Nb) ₂ O ₉ , BST- (Ba, Sr) TiO ₃ , LSCO- (La, Sr) CoO ₃ , BLT, BIT- (Bi, La) ₄ Ti ₃ O ₁₂ , BSO—Bi ₂ SiO _{5 and} other composite metals can be used. Also, silane compounds, silicone compounds, so-called organic modified silica compounds, which are organosilicon compounds, organic polymer insulating films, arylene ether-based polymers, benzocyclobutene, fluorine-based polymer parylene N, or F, fluorinated amorphous carbon, etc. Various low dielectric materials can also be used.

  The dielectrics and semiconductors excluding titanium oxide and / or silicon oxide (including titanium oxide and / or silicon oxide compounds) used as positively charged substances and / or negatively charged substances in the present invention are described above. In addition, a semiconductor or a dielectric (except for titanium oxide, silicon oxide, and these compounds) constituting a composite with a conductor can be used.

<3b> Method for Producing Metal or Other Inorganic Doped Titanium Dioxide Dispersion Here, as a preferred example of a positively charged substance or a negatively charged substance that can be used in the present invention, a film containing metal or other inorganic doped titanium dioxide is used. The manufacturing method of the dispersion liquid of a metal or other inorganic substance dope titanium oxide for forming is demonstrated.

Various oxides and peroxides such as TiO ₂ , TiO ₃ , TiO, TiO ₃ / nH ₂ O are used as titanium oxide (including titanium oxide compounds) to be combined with the above-described metals and inorganic substances other than metals. Is possible.

  The above-mentioned metal or other inorganic-doped titanium oxide may adopt a production method based on a hydrochloric acid method or a sulfuric acid method, which is a general production method of titanium dioxide powder, or production of various liquid-dispersed titania solutions. A method may be adopted. The metal to be combined with titanium oxide and some inorganic substances other than the metal can be combined with titanium oxide regardless of the manufacturing stage.

  Hereinafter, an example of a method for producing a dispersion of a metal or other inorganic-doped titanium oxide will be described with reference to FIG. First, an inorganic compound or a metal compound (compound having crystal water) illustrated on the left side of FIG. 1 is added at a molar ratio of 1:50 to a solution obtained by diluting 50% titanium tetrachloride (commercially available product) with pure water 80 to 100 times. Mix at a ratio of 0.05.

  A plurality of types of inorganic compounds and metal compounds can be mixed. The mixing ratio of titanium tetrachloride and the inorganic compound or metal compound is preferably 1: 0.01 to 1: 0.3, more preferably 1: 0.02 to 1: 0.1 in terms of molar ratio. To this, 2.5% ammonia water prepared by diluting 25% ammonia water (commercially available product) 10 times with pure water is added dropwise to adjust the pH to around 7 to precipitate titanium and inorganic or metal hydroxides. . The precipitated hydroxide is washed with pure water until the supernatant has a conductivity of 0.9 mS / m or less. Mixing the washed hydroxide with hydrogen peroxide solution with a concentration of 35%, reacting for several hours and performing ultrafiltration, the composite inorganic substance and the modified amorphous titanium peroxide modified with metal A solution in which fine amorphous material is dispersed is obtained. In addition, after mixing and reacting hydrogen peroxide with the above-mentioned hydroxide, heating and ultrafiltration, the fine structure of anatase-type titanium peroxide modified with complex inorganic substances and metals is achieved. A solution in which particles or crystals are dispersed is obtained.

  The concentration of titanium peroxide in the aqueous dispersion obtained by the above-described production method (total amount including coexisting metals such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, and zinc) was 0.00. 05-15 wt% is preferable and 0.1-5 wt% is more preferable.

  Gold mixed to obtain inorganic materials and metals (including alkali metals and alkaline earth metals) combined with titanium oxide (including its compounds) in the manufacturing process of the above metal or other inorganic-doped titanium oxide Examples of compounds of silver, platinum, nickel, cobalt, copper, manganese, iron, zinc, lithium, sodium, silicon, potassium, zirconium, cerium, hafnium, rubidium, strontium, yttrium, niobium, molybdenum, palladium, barium The following can be exemplified.

Au compound: AuCl, AuCl ₃ , AuOH, Au (OH) ₄ , Au ₂ O, Au ₂ O _3, etc. Ag compound: AgNO ₃ , AgF, AgClO ₃ , AgOH, Ag (NH ₃ ) OH, Ag ₂ SO _4, etc. Pt compound: PtCl ₂ , PtO, Pt (NH ₃ ) Cl ₂ , PtO ₂ , PtCl ₄ , [Pt (OH) ₆ ] ²⁻ etc. Ni compound: Ni (OH) ₂ , NiCl ₂ etc. Co compound: Co (OH ) NO ₃ , Co (OH) ₂ , CoSO ₄ , CoCl ₂ etc. Cu compound: Cu (OH) ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , CuCl ₂ etc. Mn compound: MnNO ₄ , MnSO ₄ , MnCl ₂ etc. Fe compound: Fe (OH) ₂ , Fe (OH) ₃ , FeCl ₃ etc. Zn compound: Zn (NO ₃ ) ₂ , ZnSO ₄ , ZnCl ₂ etc. Li Compound: LiOH, Li ₂ CO ₃ , LiCl etc. Na compound: NaOH, NaCl, Na ₂ CO ₂ etc. Si compound: SiO ₂ , SiH ₄ , SiCl ₄ etc. K compound: KOH, K ₂ O, KCl etc. Zr compound: Zr ₂ O, Zr (OH) ₂ , ZrCl, etc. Ce compound: CeO ₂ , CeCl ₂ etc. Hf compound: HfCl ₂ , Hf (OH) ₂ etc. Rb compound: RbO ₂ , RbOH etc. Sr compound: SrO ₂ , SrCl ₂ etc. Y Compound: Y ₂ O ₃ , Y (OH) ₂ etc. Nb compound: NbCl ₄ , NbO etc. Mo compound: MoO ₂ , MoCl ₄ etc. Pd compound: PdCl ₄ , Pd ₂ O ₄ etc. Ba compound: BaCl ₂ etc. In addition to the method for producing a metal-doped titanium oxide dispersion described with reference to 2, an inorganic substance or a metal and titanium oxide are combined. Law are numerous, for example, particles of pre-oxidized titanium and an inorganic substance or metal particle to composite produced separately, they may be mixed, respectively. In the present invention, in order to produce titanium oxide doped with metal or the like, in addition to the above-described production method, there are various methods for producing fine amorphous materials of titanium oxide and dispersions thereof. Also good.

<Method for Forming Surface Protective Film of Substrate>
Examples of the method for forming the surface protective film of the substrate on the surface or surface layer of the substrate according to the present invention include the methods <a> to <c> described below. However, a film containing silicon compound particles or crystals doped with at least one of alkali metal and alkaline earth metal, or a film containing highly conductive metal ions or particles or crystals and a silicon compound The method is not limited to <a> to <c> as long as it is a method for forming a surface protective film containing at least one of a positively charged substance and a negatively charged substance on the substrate. Any method may be used.

<A> Wet construction method The substrate is immersed in a film-forming solution containing a substance contained in the surface protective film of the substrate to perform dip coating, or the film-forming solution is sprayed or rolled onto the surface or surface layer of the substrate. A surface protective film can be formed on the surface or surface layer of the substrate by performing at least one step of drying or heating to remove the solvent after applying with a brush, sponge, or the like.

<A> Dry construction method A component containing a substance contained in the surface protective film of the substrate is ionized by a dry construction method including sputtering and ion plating, and sprayed onto the surface or surface layer of the substrate to obtain the surface or surface of the substrate. A surface protective film can be formed on the layer.

<C> Method for Forming Surface Protective Film Containing Oxygen Deficient Substance In the surface protective film of the substrate according to the present invention, among the substances contained in the surface protective film, particles or crystals of silicon compounds, positively charged substances, or negatively charged substances Any one of these can be used as an oxygen-deficient substance. In order to form a surface protective film containing these oxygen-deficient substances, a dispersion liquid containing the surface protective film-containing substance and carbon and / or a thermally decomposable organic compound to be used as an oxygen-deficient substance in advance is added. After mixing with a dispersion liquid containing a substance to be contained in the surface protective film to form a film-forming liquid, the film-forming liquid is applied on the surface or surface layer of the substrate, and then heated at a high temperature to produce carbon and / or Alternatively, a film in which an oxygen deficient substance is generated can be formed by ejecting a thermally decomposable organic compound as carbon dioxide gas.

<Switching of conductive properties on surface of substrate and surface protection function>
The surface protective film of the substrate according to the present invention is a film containing silicon compound particles or crystals doped with at least one of alkali metal and alkaline earth metal, or highly conductive metal ions or particles or crystals. And a silicon compound, and by adding at least one of a positively charged substance and a negatively charged substance to the film, the surface electrical resistance of the substrate can be made to have an electrically conductive surface state and an insulating property. The surface state can be periodically changed. Hereinafter, how this surface protective film functions to protect the substrate surface will be described with reference to FIG.

  FIG. 3 is a diagram schematically showing an insulating state and a conductive state of the surface of the substrate on which the surface protective film of the substrate according to the present invention is formed. The surface protective film is a positive charge substance and a negative charge. An embodiment containing a substance is shown.

As shown in FIG. 3, when the surface protective film contains a positively charged substance and a negatively charged substance, the surface of the base is positively and negatively charged when the surface protective film is in an insulating state. As for the substance (substrate / solid / liquid), both a positively charged substance and a negatively charged substance are electrostatically attracted to the substrate surface. On the other hand, when the substrate surface is in a conductive state, the surface protective film takes electrons (e ⁻ ) from a negatively charged substance attached to or near the substrate surface, and is attached to or near the substrate surface. By imparting electrons (e ⁻ ) to a positively charged substance, the electrical state of the substance that is in contact with or near the substrate surface is neutralized. And since the surface state having conductivity and the surface state having insulation in this surface protective film are switched in a short cycle, the adsorption to the substrate surface is prevented or the substance adhering to the substrate surface is released, thereby It is thought to protect the surface.

  In addition, although the mechanism of the surface protection demonstrated above is not completely clarified at present, as shown in an Example, the surface electrical resistance of a base | substrate is made into the surface state which has electroconductivity, and the surface state which has insulation. By periodically varying them, it is possible to reliably prevent or suppress the adhesion and adsorption of contaminants to the substrate surface.

<About the intermediate layer>
An intermediate layer can be provided between the surface protective film and the substrate. For this intermediate layer, for example, various organic or inorganic substances capable of imparting hydrophilicity or hydrophobicity or water repellency or oil repellency to the substrate can be used.

  Among organic or inorganic substances that can be used for the intermediate layer, hydrophilic organic substances include polyethers such as polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol block copolymers; polyvinyl alcohol; polyacrylic acid (alkali metal salts) , Including salts such as 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; polyvinylpyrrolidone; hydrophilic celluloses such as carboxymethylcellulose (CMC) and methylcellulose (MC); and natural hydrophilic polymer compounds such as polysaccharides. It is also possible to use a composite material obtained by blending these polymer materials with an inorganic dielectric such as glass fiber, carbon fiber or silica. It is also possible to use a paint as the polymer material.

Among organic or inorganic substances that can be used for the intermediate layer, examples of hydrophilic inorganic materials include silane coupling agents, SiO _{2, and} other silicon compounds.

  Among organic or inorganic substances that can be used in the intermediate layer, water-repellent organic substances include polyolefins such as polyethylene, polypropylene, and polystyrene; polyacrylates, acrylonitrile / styrene copolymers (AS), acrylonitrile / butadiene / styrene copolymers Acrylic resins such as (ABS); polyacrylonitrile; polyvinyl halides such as polyvinyl chloride and polyvinylidene chloride; polytetrafluoroethylene, fluoroethylene / propylene copolymer, polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride Fluororesin such as Ride (PVDF) and vinylidene fluoride / trifluoroethylene copolymer; Polyester such as polyethylene terephthalate and polycarbonate; Phenol resin; Urea resin; Melamine resin; Polyimide resin; polyamide resins such as nylon, epoxy resins, polyurethanes, and the like.

  Of the above water-repellent organic substances, fluororesins are preferable, and in particular, vinylidene fluoride / trifluoroethylene copolymer having ferroelectricity and water repellency, β-type crystals of polyvinylidene fluoride and the like are contained. Those that do are preferred. A commercially available fluororesin can be used, and examples of the commercially available product include HIREC 1550 manufactured by NTT-AT Corporation.

  Furthermore, a copolymer comprising two or more kinds of olefins containing fluorine atoms, a copolymer of an olefin containing fluorine atoms and a hydrocarbon monomer, and a copolymer comprising two or more kinds of olefins containing fluorine atoms A fluororesin emulsion comprising a surfactant and at least one fluororesin selected from the group consisting of a mixture of an acrylic resin and a thermoplastic acrylic resin, and a curing agent (JP-A-5-124880, JP-A-5-117578) JP-A-5-179191) and / or a composition comprising the above-mentioned silicone resin water repellent (see JP2000-121543A and JP2003-26461A) can also be used. 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.

  Among organic or inorganic substances that can be used for the intermediate layer, examples of water-repellent inorganic materials include silane-based, siliconate-based, silicone-based and silane composite-based, or fluorine-based water repellents or water absorption inhibitors. Can be mentioned. In particular, fluorine-based water repellents are preferable, and examples include fluorine-containing compounds such as perfluoroalkyl group-containing compounds or fluorine-containing compound-containing compositions. In addition, when the intermediate layer contains a fluorine-containing compound having high adsorptivity to the substrate surface, the chemical component of the intermediate layer 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 of the intermediate layer and the substrate to be cross-linked.

  The fluorine-containing compound that can be used as such a fluorine-based water repellent preferably has a molecular weight of 1,000 to 20,000 containing a perfluoroalkyl group in the molecule, and specifically, perfluorosulfonic acid. Salt, perfluorosulfonic acid ammonium salt, perfluorocarboxylate, perfluoroalkyl betaine, perfluoroalkylethylene oxide adduct, perfluoroalkylamine oxide, perfluoroalkyl phosphate ester, perfluoroalkyltrimethylammonium salt, etc. Is 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 a material, Surflon S-112 and Surflon S-121 (both trade names, manufactured by Seimi Chemical Co., Ltd.) are commercially available.

  In the case of a water-absorbing substrate, it is preferable that an intermediate layer containing a silane compound is formed on the substrate in advance under the surface protective film. Since this intermediate layer contains a large amount of Si—O bonds, it is possible to improve the strength of the surface protective film and the adhesion to the substrate. In addition, the intermediate layer also has a function of preventing moisture from entering the substrate.

  Examples of the silane compound include hydrolyzable silanes, hydrolysates thereof, and mixtures thereof. Various alkoxysilanes can be used as the hydrolyzable silane, and specific examples include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and trialkylalkoxysilane. Among these, one type of hydrolyzable silane may be used alone, or two or more types of hydrolyzable silanes may be confused and used as necessary. Moreover, you may mix | blend various organopolysiloxane with these silane compounds. As a constituent material of the intermediate layer containing such a silane compound, for example, there is Dry Seal S (manufactured by Toray Dow Corning Co., Ltd.).

  Moreover, as a constituent material of the intermediate layer, room temperature curable silicone resins such as methyl silicone resin and methyl phenyl silicone resin may be used. Examples of such room temperature curable silicone resins include AY42-170, SR2510, SR2406, SR2410, SR2405, SR2411 (manufactured by Toray Dow Corning Co., Ltd.).

<About the substrate>
The material of the substrate that is the subject of the present invention is not particularly limited, and various hydrophilic or hydrophobic inorganic and organic substrates, or a combination thereof can be used.

  Examples of the inorganic substrate include a substrate made of a material such as transparent or opaque glass such as soda lime glass, metal oxide such as zirconia, ceramics, concrete, mortar, stone, and metal. Examples of the organic base include a base made of a substance such as an organic resin, wood, paper, and cloth. More specific examples of the organic resin include, for example, polyethylene, polypropylene, polycarbonate, acrylic resin, polyester such as PET, polyamide, polyurethane, ABS resin, polyvinyl chloride, silicone, melamine resin, urea resin, silicone resin, fluorine resin. , Cellulose, epoxy-modified resin and the like.

  The shape of the substrate that is the subject of the present invention is not particularly limited, and can be any shape such as a cube, a rectangular parallelepiped, a sphere, a sheet, and a fiber. The substrate may be porous. The surface of the substrate may be made hydrophilic by corona discharge treatment or ultraviolet irradiation treatment. The substrate is preferably used for a construction / civil engineering substrate or a sealing material, a device, a body for conveying an apparatus, a display screen, or the like.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. Evaluation substrates 1 to 6 were prepared using the film-forming solutions described in Examples 1 to 6 below, and evaluated with a comparative substrate. In addition, it describes below which each Example is an example of the film forming liquid of the film | membrane containing which substance of the surface protective film of the base | substrate by this invention.

Example 1: Silicon compound doped with alkali metal + negatively charged substance + positively charged substance Example 2: Silicon compound doped with alkali metal + negatively charged substance (oxygen deficiency generation) + positively charged substance Example 3: Alkali metal added Doped silicon compound + positively charged substance + negatively charged substance Example 4: Alkali metal doped silicon compound + negatively charged substance Example 5: Alkali metal doped silicon compound + positively charged substance Example 6: Alkali metal doped Silicon compound + positively charged substance

Example 1: Solution for indium-doped anatase-type titanium peroxide and copper-silicon-doped anatase-type titanium peroxide and potassium-doped polysilicate composite film [A: Preparation of indium-doped anatase-type titanium peroxide aqueous solution]
A solution is prepared by adding 10 g of a 50% titanium tetrachloride solution (manufactured by Osaka Titanium Technologies Co., Ltd.) to a solution obtained by completely dissolving 0.772 g of InCl ₃ × H ₂ O (indium chloride) in 1000 g of pure water. Ammonia water diluted 10 times with 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was added dropwise thereto to precipitate a mixture of indium hydroxide and titanium hydroxide m having a pH of 7.0. This precipitate is washed with pure water until the conductivity of the supernatant becomes 0.9 mS / m or less. Since the electrical conductivity reached 0.865 mS / m, when cleaning was completed, 350 g of 0.73 wt% hydroxide was produced. Next, 56 g of 35% hydrogen peroxide water (manufactured by Taiki Pharmaceutical Co., Ltd.) was added at room temperature and stirred for 16 hours to obtain 403 g of an amorphous titanium peroxide solution modified with yellow transparent indium. . Furthermore, when 100 g of this amorphous titanium peroxide solution modified with indium was heated at 90 ° C. for 5 hours, an anatase-type titanium oxide aqueous dispersion modified with indium was obtained.
[B: Preparation of copper and silicon-doped anatase-type titanium peroxide aqueous dispersion]
A solution is prepared by adding 10 g of a 50% titanium tetrachloride solution (manufactured by Osaka Titanium Technologies Co., Ltd.) and 2.5 g of 30 wt% silica sol to 1000 g of pure water.
Ammonia water diluted 10-fold with 25% aqueous ammonia (manufactured by Takasugi Pharmaceutical Co., Ltd.) was added dropwise thereto to precipitate pH 7.0 titanium hydroxide. This precipitate is washed with pure water until the conductivity of the supernatant becomes 0.9 mS / m or less. Since the electrical conductivity reached 0.809 mS / m, when cleaning was completed, 350 g of 0.77 wt% hydroxide was produced. Next, 20 g of 35% hydrogen peroxide (Taiki Pharmaceutical Co., Ltd.) was added at room temperature and stirred for 16 hours to obtain 370 g of an amorphous titanium peroxide solution modified with yellow transparent silica. . Furthermore, when 100 g of the amorphous titanium peroxide solution modified with silica was heated at 90 ° C. for 5 hours, an anatase-type titanium peroxide aqueous dispersion modified with silica was obtained. Further, 1 g of 35% hydrogen peroxide water, 1 g of 2.5% ammonia water and 0.16 g of copper powder (Mitsui Metal Mining Co., Ltd.) were added to this silica-modified anatase type titanium peroxide aqueous dispersion. After stirring for 20 hours, an anatase-type titanium peroxide aqueous dispersion in which 1600 ppm of copper ions and silica were modified was obtained.
[C: potassium-doped polysilicate solution]
When 30 g of methyl silicate 51 (Mitsubishi Chemical Corporation) is stirred with 60 g of meta-modified alcohol, 5.7 g of pure water, and 0.3 g of acetylacetone aluminum, 96 g of polysilicate is produced. Further, the prepared liquid is adjusted to a solid content concentration of 4 wt% with pure water to prepare a polysilicate liquid. Next, 100 g of this diluted polysilicate solution and 20 g of potassium hydroxide adjusted to 1% concentration were mixed and heated at 50 ° C. for 20 hours.
[Indium-doped anatase-type titanium peroxide and copper-silicon-doped anatase-type titanium peroxide and potassium-doped polysilicate composite film solution]
A composite membrane solution prepared by mixing the liquid obtained in A and B at 1: 1 and the liquid obtained in C at 2: 8 was used as Example 1.

Example 2: Solution for strontium-doped anatase-type titanium peroxide and copper and silicon-doped anatase-type titanium peroxide and potassium-doped polysilicate composite film [Preparation of film- forming solution for strontium-doped anatase-type titanium peroxide oxygen-deficient film]
Of pure water 1000g SrCl ₃ · _6H 2 O to prepare the solution addition of 50% titanium tetrachloride solution to a solution complete (strontium chloride) 0.167 g (manufactured by Osaka Titanium Technologies) 10 g. Ammonia water diluted 10 times with 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was added dropwise thereto to precipitate a mixture of strontium hydroxide and titanium hydroxide having a pH of 7.0. This precipitate is washed with pure water until the conductivity of the supernatant becomes 0.9 mS / m or less. Since the electrical conductivity was 0.825 mS / m, 350 g of 0.75 wt% hydroxide was produced when the cleaning was completed. Next, 56 g of 35% hydrogen peroxide (Taiki Pharmaceutical Co., Ltd.) was added at room temperature and stirred for 16 hours to obtain 405 g of an amorphous titanium peroxide solution modified with yellow transparent strontium. . When 100 g of the amorphous titanium peroxide solution modified with strontium was heated at 90 ° C. for 5 hours, an anatase titanium peroxide dispersion modified with strontium was obtained. This strontium-modified anatase-type titanium peroxide dispersion was mixed with 2% disaccharide to obtain a strontium-doped anatase-type titanium peroxide oxygen-deficient film-forming solution. This strontium-doped anatase-type titanium peroxide-deficient A film-forming solution for membrane, a solution prepared by mixing copper and silicon-doped anatase-type titanium peroxide dispersion prepared in Example 1 at 1: 1, and a potassium-doped polysilicate solution prepared in Example 1 at 2: 8 The mixed membrane solution prepared by mixing was designated as Example 2.

Example 3: Solution for copper-doped amorphous titanium peroxide and tin-doped amorphous titanium peroxide and potassium-doped polysilicate composite film [A: Preparation of copper-doped amorphous titanium peroxide solution]
A solution obtained by further adding 10 g of 50% titanium tetrachloride solution (manufactured by Osaka Titanium Technologies Co., Ltd.) to a solution obtained by completely dissolving 0.926 g of 97% CuCl ₂ .2H ₂ O (cupric chloride) in 1000 g of pure water prepare. Ammonia water diluted 10 times with 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was added dropwise thereto to precipitate a mixture of copper hydroxide and titanium hydroxide having a pH of 7.0. This precipitate is washed with pure water until the conductivity of the supernatant becomes 0.9 mS / m or less. Since the electrical conductivity reached 0.855 mS / m, 345 g of 0.82 wt% hydroxide was produced when the cleaning was completed. Next, when 50 g of 35% hydrogen peroxide (Taiki Pharmaceutical Co., Ltd.) was added at room temperature and stirred for 16 hours, a 0.91 wt% amorphous titanium peroxide solution modified with green transparent copper 390 g was obtained. Furthermore, 0.12g of 35% hydrogen peroxide solution 1g, 2.5% ammonia solution 1 and copper powder (Mitsui Metal Mining Co., Ltd.) was added to 100g of the amorphous titanium peroxide solution modified with copper obtained above. After stirring for 20 hours at room temperature, an amorphous titanium peroxide solution modified with 1600 ppm of copper ions was obtained.
[B: Preparation of tin-doped amorphous titanium peroxide solution]
Prepare a solution in which 10 g of 50% titanium tetrachloride solution (manufactured by Osaka Titanium Technologies Co., Ltd.) is further added to a solution in which 0.594 g of SnCl ₂ · 2H ₂ O (stannic chloride) is completely dissolved in 1000 g of pure water. . Ammonia water diluted 10-fold with 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was added dropwise to this solution to precipitate a mixture of tin hydroxide and titanium hydroxide having a pH of 7.0. This precipitate is washed with pure water until the conductivity of the supernatant becomes 0.9 mS / m or less. Since the electrical conductivity reached 0.713 mS / m, 333 g of 0.80 wt% hydroxide was produced when the cleaning was completed. Next, 56 g of 35% hydrogen peroxide solution (manufactured by Taiki Pharmaceutical Co., Ltd.) was added at room temperature and stirred for 16 hours to obtain 389 g of an amorphous titanium peroxide solution modified with tan transparent tin. It was.
[Copper-doped amorphous titanium peroxide, tin-doped amorphous titanium peroxide and potassium-doped polysilicate composite film solution]
The liquid obtained by mixing the liquids obtained in A and B with 1: 1 and the potassium-doped polysilicate liquid prepared in Example 1 were mixed and adjusted in 2: 8 to obtain Example 3.

Example 4: Liquid for cerium-doped amorphous titanium peroxide and potassium-doped polysilicate composite film [A: Preparation of cerium-doped amorphous titanium peroxide solution]
A solution is prepared by adding 10 g of a 50% titanium tetrachloride solution (manufactured by Osaka Titanium Technologies Co., Ltd.) to a solution obtained by completely dissolving 0.649 g of CeCl ₃ · 7H ₂ O (first cerium chloride) in 1000 g of pure water. Ammonia water diluted 10 times with 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was added dropwise to this solution to precipitate a mixture of cerium hydroxide and titanium hydroxide having a pH of 7.0. This precipitate is washed with pure water until the conductivity of the supernatant becomes 0.9 mS / m or less. When cleaning was completed when the electrical conductivity reached 0.679 mS / m, 340 g of a 0.79 wt% hydroxide dispersion was produced. Next, when 56 g of 35% hydrogen peroxide (Taiki Pharmaceutical Co., Ltd.) was added to this solution at room temperature and stirred for 16 hours, 0.82 wt% amorphous peroxidation modified with tan transparent cerium was added. 396 g of titanium solution was obtained.
[Cerium-doped amorphous titanium peroxide and potassium-doped polysilicate composite membrane solution]
Example 4 was prepared by mixing the liquid obtained in A with the potassium-doped polysilicate solution prepared in Example 1 at 2: 8.

Example 5: Liquid for tin-doped amorphous titanium peroxide and potassium-doped polysilicate composite film 2 of the tin-doped amorphous titanium peroxide solution prepared in Example 3 and the potassium-doped polysilicate liquid prepared in Example 1 8 was mixed and adjusted to give Example 5.

Example 6: Copper Doped Amorphous Titanium Peroxide and Potassium Doped Polysilicate Composite Film Solution Two copper doped amorphous titanium peroxide solutions prepared in Example 3 and two potassium doped polysilicate solutions prepared in Example 1 were used. 8 was mixed and adjusted to give Example 6.

Preparation of Evaluation Substrate and Comparative Substrate Each of the film- forming solutions described in Examples 1 to 6 is about 100 nm in dry film by using SS method (sponge squeegee method) on soda lime glass having a thickness of 3 mm. After applying and drying, evaluation substrates 1 to 6 were obtained by heating and baking at 500 ° C. for 15 minutes (peak holding temperature).

  In order to contrast with these evaluation substrates 1 to 6, a substrate in which an anatase-type titanium oxide film that does not become an oxygen-deficient film is formed in the same manner as the evaluation substrate is a comparative substrate 1, and amorphous-type titanium oxide that does not become an oxygen-deficient film A substrate on which a film was formed in the same manner as the evaluation substrate was used as a comparative substrate 2.

The following evaluation 1 was implemented using said evaluation board | substrates 1-6 and the comparison board | substrates 1-2.
<Evaluation 1>
“Dark place (UV-A light amount 0 μw / cm ² )”, “Under fluorescent lamp (UV-A light amount 10 μw / cm ² )”, “Outdoor / sunlight ( The volume resistance value (conductivity) evaluation in “UV-A light quantity 1800 μw / cm ² )” was performed under the following evaluation apparatus, evaluation conditions, and evaluation time.

・ Evaluation equipment: Lorester GP manufactured by Mitsubishi Chemical Corporation
Evaluation conditions: film thickness (100 nm), voltage: (90 V)
・ Evaluation time: 30 seconds / sheet (energization time)
The results of Evaluation 1 are shown in Table 1 below.

表示導電性：絶縁性（×１０^１５以上：ＯＶ．ＬＤ）
半導電性（×１０^３〜×１０^７：ＯＶ．ＲＧ）
導電性（０．０×１０^０）
絶縁性⇔（スイッチング）導電性（ＯＶ．ＬＤ⇔０．０×１０^０）
絶縁性⇔導電性スイッチング状態：ＯＶ．ＬＤ⇔０．０×１０^０
のスイッチングが約１秒〜数秒
毎に切り替わる
≪表示数値は体積抵抗値：Ω・ｃｍ≫

＜評価１による結果＞
表１に示すように、光照射の有無に関わらず、評価基板１〜６は、「絶縁性⇔導電性」のスイッチング現象を確認することが出来た。また、比較基板１〜２は、造膜組成分の各々の電気的特性を表示しているが、スイッチング現象が生じることはない。

Display conductivity: insulation (× 10 ¹⁵ or more: OV.LD)
Semiconductive (× 10 ³ to × 10 ⁷ : OV.RG)
Conductivity (0.0 × 10 ⁰ )
Insulation ⇔ (switching) conductivity (OV.LD ⇔ 0.0 × 10 ⁰ )
Insulating / conducting switching state: OV. LD ⇔ 0.0 × 10 ⁰
Switching is about 1 second to several seconds
Switch every time
≪Displayed value is volume resistance: Ω ・ cm≫

<Results of evaluation 1>
As shown in Table 1, regardless of the presence or absence of light irradiation, the evaluation substrates 1 to 6 were able to confirm the “insulating and conductive” switching phenomenon. Moreover, although the comparison board | substrates 1-2 are displaying the electrical property of each part for film forming composition, a switching phenomenon does not arise.

<Evaluation 2>
In order to confirm the function to prevent and reduce adhesion by changing the charge of contaminants adhering to the surface as a function to protect the substrate, evaluation of adhesion reduction performance for silicone sealing material for glass fixing and maintenance of surface hydrophilicity The long-term outdoor exposure evaluation of the evaluation board | substrates 1-6 and the comparison board | substrates 1-2 was implemented.
The evaluation substrate and the comparative substrate are under the same prototype conditions as in Evaluation 1 (however, the film fixing temperature is 500 ° C. for 15 minutes).

As shown in FIG. 4, a silicone sealant (SE960: manufactured by Toray Dow Corning Co., Ltd.) is attached to each surface of the evaluation substrates 1 to 6 and the comparison substrates 1 to 2, and each substrate is fixed vertically, and under the rain conditions. evaluated.
Implementation period: 2014 / 08-2015 / 08
Location: Saga Evaluation 2 results are shown in Table 2 below.

＜評価２による結果＞
土木・建築・工作分野での外部器材の汚染の原因で最も高度な対応が必要なシリコーンシール材の可塑部材の油分流出拡大による撥水性分の拡大を低減するのは大変難しいとされてきた。その中で、表２に示すように、長期間にわたる評価（２０１４／０８〜２０１５／０８）において、評価基板１〜６は、シール撥水成分の拡大を抑える効果があることが分かる。
これに対し、比較基板１（光触媒機能）及び比較基板２は、シール撥水成分の拡大を抑える効果が小さいことがわかる。

<Results from evaluation 2>
It has been considered extremely difficult to reduce the expansion of the water repellency due to the increased oil spillage of the plastic material of the silicone sealant, which requires the most advanced measures due to contamination of external equipment in the civil engineering, construction and construction fields. Among them, as shown in Table 2, in the evaluation over a long period (2014/08 to 2015/08), it can be seen that the evaluation substrates 1 to 6 have an effect of suppressing the expansion of the seal water-repellent component.
On the other hand, it can be seen that the comparative substrate 1 (photocatalytic function) and the comparative substrate 2 have a small effect of suppressing the expansion of the seal water repellent component.

Claims (5)

A film containing silicon compound particles or crystals doped with at least one of an alkali metal and an alkaline earth metal, or a film containing highly conductive metal ions or particles or crystals and a silicon compound. The film further contains at least one of a positively charged substance and a negatively charged substance, and the surface electrical resistance of the substrate is periodically changed between a conductive state and an insulating state. , Surface protective film of substrate. A film containing silicon compound particles or crystals at least doped with either an alkali metal or an alkaline earth metal, wherein the film further contains at least one of a positively charged substance and a negatively charged substance A surface protective film of a substrate, wherein the surface electrical resistance of the substrate is periodically changed between a conductive state and an insulating state, wherein the silicon compound particles or crystals, or a positively charged substance The surface protective film for a substrate according to claim 1, wherein any one of the negatively charged substances is at least an oxygen deficient substance. A particle or crystal of a silicon compound doped with at least one of an alkali metal and an alkaline earth metal, or an ion or particle or crystal of a highly conductive metal and a silicon compound, and a positively charged substance and A film-forming solution for a surface protective film of a substrate, which contains at least one of negatively charged substances and periodically varies the surface electrical resistance of the substrate between a conductive state and an insulating state. A silicon compound particle or crystal at least doped with either an alkali metal or an alkaline earth metal, or a dispersion containing a highly conductive metal ion or particle or crystal and a silicon compound is applied to a substrate. A method for forming a surface protective film on a substrate, wherein the surface electrical resistance of the substrate is periodically changed between a conductive state and an insulating state, characterized by performing a heat treatment or a non-heat treatment. A substrate provided with the surface protective film of the substrate according to claim 1.

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