Visible-light-responsive photocatalytic-titanium-oxide-particulate dispersion liquid, manufacturing method therefor, and member having thin photocatalytic film on surface thereof

Visible light response type photocatalytic oxidation titanium particulate dispersion liquid, its manufacturing method, and the member that has a photocatalyst thin film on the surface

0001The present invention relates to the member which has on the surface a photocatalyst thin film formed using visible light response type photocatalytic oxidation titanium particulate dispersion liquid, its manufacturing method, and the dispersion liquid, and also is in details, It is related with the member which has on the surface a photocatalyst thin film in which only visible light (400-800 nm) is formed using the visible light response type photocatalytic oxidation titanium particulate dispersion liquid which can produce the photocatalyst thin film with high transparency which reveals photocatalyst activity simple, its manufacturing method, and the dispersion liquid.

0002Light catalytic titanium oxide particulates have been used abundantly at uses, such as sanctification on the surface of a substrate, deodorization, and antibacterial properties. A photocatalytic reaction means the reaction which the excitation electron and electron hole which produced when titanium oxide absorbed light cause. It is thought that disassembly of an organic matter has occurred mainly by the following mechanisms. [1] The activated species which the excitation electron and electron hole which were generated performed oxygen and water which are sticking to the titanium oxide surface, and an oxidation-reduction reaction, and generated disassemble an organic matter. [2] Oxidize directly and the generated electron hole decomposes the organic matter which is sticking to the titanium oxide surface.

0003These days, examination which enables it to use application of the above photocatalyst operations not only in use on the outdoors which can use ultraviolet rays but in the indoor space illuminated by the light source for which the light (wavelength of 400-800 nm) of a visible region accounts most like a fluorescent light is performed. For example, although the tungstic oxide photocatalyst object (JP,2009-148700,A: patent documents 1) was developed as a visible light response type photocatalyst, since tungsten is a rare element, improvement in visible photoactive of a photocatalyst using titanium which is a general-purpose element is desired.

0004As the visible photoactive improvement method of a photocatalyst of having used titanium oxide, How to make the surface of the titanium oxide particulates which doped titanium oxide particulates and metal support iron and copper (For example, JP,2012-210632,A:patent documents 2, JP,2010-104913,A: Patent documents 3) Or After preparing tin, the titanium oxide particulates which dissolved the transition metal which improves visible light activity (dope), and the titanium oxide particulates which dissolved copper, respectively, the method (WO 2014/No. 045861: patent documents 4) of mixing and using, etc. are known.

0005How to mix and use after preparing the titanium oxide particulates which dissolved the transition metal which improves latter (patent documents 4) tin and visible light activity, and the titanium oxide particulates which dissolved copper, respectively, From each metal used in addition to titanium dissolving to titanium oxide particles, it is stable, and is hard to denature, and there is an advantage that a photocatalyst thin film with high endurance is obtained.

<p num="0006"><patcit num="1"><text>JP,2009-148700,A</text></patcit><patcit num="2"><text>JP,2012-210632,A</text></patcit><patcit num="3"><text>JP,2010-104913,A</text></patcit><patcit num="4"><text>WO 2014/No. 045861</text></patcit><patcit num="5"><text>JP,7-303835,A</text></patcit></p>

<p num="0007">The present invention combines the titanium oxide particulates which dissolved a different transition metal etc., and it mixes, It aims at providing the member which has on the surface visible light response type photocatalytic oxidation titanium particulate dispersion liquid which can obtain the high visible light activity of a different type from the former, its manufacturing method, and a photocatalyst thin film formed using the dispersion liquid.</p>

<p num="0008">The 2nd titanium oxide particulate combined to the titanium oxide particulates to which tin which is the 1st titanium oxide particulate used with patent documents 4 as one method for these artificers to achieve the above-mentioned object, and the transition metal which improves visible light activity dissolved is changed, It searched for a new material which shows high photocatalyst activity only on condition of visible light. Then, the titanium oxide particulates which dissolved the copper ingredient which is the 2nd titanium oxide particulate used with patent documents 4 are although it is what shows some photocatalyst activity only also on condition of visible light (400-800 nm), When the titanium oxide particulates which dissolved the iron ingredient which hardly shows photocatalyst activity only on condition of visible light if independent are blended with an unexpected thing as 2nd titanium oxide particulate, It turned out that the same high photocatalyst activity as the case where the titanium oxide particulates which dissolved the copper ingredient are combined only on condition of visible light is shown.</p><p num="0009">When are inquired in more detail about the case where the titanium oxide particulates which dissolved this iron ingredient are blended as 2nd titanium oxide particulate and the acetaldehyde gas contained in the air is made to decompose under visible light, With an old material, decomposition activity was obtained also in the low concentration field for which obtaining was difficult, and it was able to lower to 0.03 ppm or less which is an indoor concentration guideline value (acetaldehyde) of the chemical substance in indoor air upon which it was decided by the Ministry of Health, Labour and Welfare under visible light conditions within a time [ significant ]. That is, when the photocatalyst film which formed membranes using the visible light response type photocatalytic oxidation titanium particulate dispersion liquid containing tin, the 1st titanium oxide particulate in which the transition metal which improves visible light activity dissolved, and the 2nd titanium oxide particulate in which the iron-group ingredient dissolved is used, Under visible light conditions, when the decomposition substrate which was difficult until now is low concentration, it finds out that high decomposition activity is obtained, and it came to make the present invention.</p><p num="0010">Therefore, the present invention provides the member which has on the surface visible light response type photocatalytic oxidation titanium particulate dispersion liquid shown below, its manufacturing method, and a photocatalyst thin film formed using the dispersion liquid.<br />〔１〕<br />To the inside of water carrier fluid, Visible light response type photocatalytic oxidation titanium particulate dispersion liquid, wherein two kinds of titanium oxide particulates of the 1st titanium oxide particulate in which the transition metal ingredient (however, except for an iron-group ingredient) which improves a tin ingredient and a visible light response dissolved, and the 2nd titanium oxide particulate in which the iron-group ingredient dissolved are distributed.<br />〔２〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in [1] whose content of the tin ingredient contained to the 1st titanium oxide particulate is 1-1,000 in a molar ratio (Ti/Sn) with titanium.<br />〔３〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in [1] or [2] whose transition metal ingredient which dissolves to the 1st titanium oxide particulate is at least one chosen from vanadium, chromium, manganese, niobium, molybdenum, rhodium, antimony, tungsten, and cerium.<br />〔４〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in [1] or [2] whose transition metal ingredient which dissolves to the 1st titanium oxide particulate is at least one chosen from molybdenum and vanadium.<br />〔５〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in [4] whose content of a vanadium ingredient the content of the molybdenum component contained to the 1st titanium oxide particulate is 1-1,000 in a molar ratio (Ti/Mo) with titanium, and is 10-10,000 in a molar ratio (Ti/V) with titanium.<br />〔６〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in either of [1]- [5] whose content of the iron-group ingredient contained to the 2nd titanium oxide particulate is 1-1,000 in a molar ratio (Ti / iron-group ingredient) with titanium.<br />〔７〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in either of [1]- [6] whose iron-group ingredients which dissolved to the 2nd titanium oxide particulate are iron ingredients.<br />〔８〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in either of [1]- [7] whose mixture ratio of the 1st titanium oxide particulate and the 2nd titanium oxide particulate is 99-0.01 in each mass ratio [(1st titanium oxide particulate) /(2nd titanium oxide particulate)].<br />〔９〕<br />Visible light response type photocatalytic oxidation titanium dispersion liquid given in either of [1]- [8] containing a binder.<br />〔１０〕<br />Visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in [9] whose a binder is a silicon compound system binder.<br />〔１１〕<br />The member which has a photocatalyst thin film by visible light response type photocatalytic oxidation titanium particulate dispersion liquid given in either of [1]- [10] on the surface.<br />〔１２〕<br />(1) The process of manufacturing tin and transition metal content peroxotitanic acid solution from a materials titanium compound, a tin compound, a transition metal compound (however, except for an iron-group compound), a basic substance, hydrogen peroxide, and water carrier fluid,<br />(2) The process of heating tin and transition metal content peroxotitanic acid solution which were manufactured at the process of the above (1) at 80-250 under pressure control, and obtaining tin and transition metal content titanium oxide particulate dispersion liquid,<br />(3) The process of manufacturing iron-family-elements content peroxotitanic acid solution from a materials titanium compound, an iron-group compound, a basic substance, hydrogen peroxide, and water carrier fluid,<br />(4) The process of heating the iron-family-elements content peroxotitanic acid solution manufactured at the process of the above (3) at 80-250 under pressure control, and obtaining iron-family-elements content titanium oxide particulate dispersion liquid,<br />(5) The process of mixing two kinds of titanium oxide particulate dispersion liquid manufactured at the process of the above (2) and (4)<br />A manufacturing method of the With(ing) visible light response type photocatalytic oxidation titanium particulate dispersion liquid.</p>

<p num="0011">According to the present invention, only visible light (400-800 nm) reveals photocatalyst activity, The member which has on the surface visible light response type photocatalytic oxidation titanium particulate dispersion liquid which can produce a photocatalyst thin film with high transparency simple, its manufacturing method, and a photocatalyst thin film formed using the dispersion liquid can be provided.</p>

0012Hereinafter, the member which has the visible light response type photocatalytic oxidation titanium particulate dispersion liquid, its manufacturing method, and photocatalyst thin film of the present invention on the surface is explained in detail.

0013&lt;Visible light response type photocatalytic oxidation titanium particle dispersion liquid&gt;<br />The 1st titanium oxide particulate and the 2nd titanium oxide particulate whose visible light response type photocatalytic oxidation titanium particulate dispersion liquid of the present invention is titanium oxide particulates from which composition differs in water carrier fluid are distributed. The 1st titanium oxide particulate is titanium oxide particulates to which a tin ingredient and a transition metal ingredient (however, except for an iron-group ingredient) dissolved, and the 2nd titanium oxide particulate is titanium oxide particulates to which an iron-group ingredient dissolved.

0014The phase to which it replaced by atom with an another atom which is in the lattice point of one certain crystal phase with a solid solution here, or another atom entered the lattice gap, i.e., the mixed phase regarded as other substances having melted into a certain crystal phase, is said, and what is a uniform phase as a crystal phase is said. Although that by which the Solute atom went into the substitution solid solution and the lattice gap what the solvent atom in a lattice point replaced by the Solute atom is called interstitial solid solution, these all shall be pointed out here.

0015The titanium oxide particulates of the present invention are characterized by forming tin and a transition metal atom (however, except for an iron-group ingredient), and a solid solution, and forming the iron-group ingredient and the solid solution by the 2nd titanium oxide particulate by the 1st titanium oxide particulate. As a solid solution, it may be a replaced type or may be an invaded type. A titanium site of a titanium oxide crystal is replaced by various metal atoms, and a substitution solid solution is formed. Various metal atoms go into a lattice gap of a titanium oxide crystal, and an interstitial solid solution is formed in it. When various metal atoms dissolved to titanium oxide and a crystal phase is measured according to an X diffraction etc., only the peak of the crystal phase of titanium oxide is observed and the peak of the compound of the added various metal atom origin is not observed.

0016Although the method in particular of dissolving different-species metal into a metal oxide crystal is not limited, it can mention gaseous phase methods (a CVD method, the PVD method, etc.), liquid phase methods (a hydrothermal method, a sol-gel method, etc.), solid phase synthesis (the high temperature calcinating method etc.), etc.

0017As a crystal phase of titanium oxide particulates, although a rutile type, a Anatase type, and brookite type three are known, also in any of the 1st above-mentioned titanium oxide particulate and the 2nd above-mentioned titanium oxide particulate, it is usually preferred to mainly use a rutile type and a Anatase type. The rutile type of the 1st titanium oxide particulate is mainly more preferred among a rutile type and a Anatase type, and the 2nd titanium oxide particulate mainly has a preferred Anatase type. As for here "mainly concerning", more than 50 mass %, preferably more than 70 mass % may usually mean that more than 90 mass % contains still more preferably among the whole titanium oxide particulate crystal, and it may be 100 mass %.

0018A water solvent is usually used, and although it is preferred to use water as for the carrier fluid of dispersion liquid, the mixed solvent of the hydrophilic organic solvent and water which are mixed with water at an arbitrary rate may be used for it. As water, deionized water, distilled water, pure water, etc. are preferred, for example. As a hydrophilic organic solvent, they are methanol and ethanol, for example, Glycol ether, such as glycols, such as alcohol, such as isopropanol, and ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol n-propyl ether, is preferred. When using a mixed solvent, there are more rates of the hydrophilic organic solvent in a mixed solvent than zero, it is preferred that it is below 50 mass %, and below 20 mass % is below 10 mass % still more preferably more preferably.

0019Although the 1st titanium oxide particulate is titanium oxide particulates which dissolved transition metal ingredients other than a tin ingredient and the iron-group ingredient which improves visible light activity, As a transition metal ingredient which improves visible light activity, although it can choose from vanadium, chromium, manganese, niobium, molybdenum, rhodium, antimony, tungsten, cerium, etc., it is preferred that molybdenum and/or vanadium are chosen also in it.

0020Although it is for improving the visible light response of a photocatalyst thin film, it may be guided from a tin compound, and the tin ingredients which dissolve to the 1st titanium oxide particulate may be the metal (Sn) of tin, and an oxide (SnO, SnO).₂Hydroxide, a chloride (SnCl)₂SnCl₄Nitrate (Sn (NO))₃）₂Sulfate (SnSO)₄What a halogenation thing, a complex compound, etc. were mentioned and was used combining these one sort or two kinds or more may be used. It is an oxide (SnO, SnO) also in it.₂Chloride (SnCl)₂SnCl₄Sulfate (SnSO)₄It is preferred to use it.

0021The content of the tin ingredient in the 1st titanium oxide particulate is 1-1,000, preferably 5-500, more preferably 5-100 in a molar ratio (Ti/Sn) with titanium. This is because the content rate of titanium oxide falls, a photocatalyst effect may not be demonstrated enough, when a molar ratio is less than one, and a visible light response may become insufficient when it is 1,000 excess.

0022The transition metal ingredient which dissolves to the 1st titanium oxide particulate is guided from the transition metal compound concerned, metal, an oxide, hydroxide, a chloride, a nitrate, sulfate, a halogenation thing, various complex compounds, etc. should just be mentioned, and these one sort or two kinds or more are used.

0023Although the content of the transition metal ingredient in the 1st titanium oxide particulate can be suitably selected according to the kind of transition metal ingredient, it is preferred the range of 1-10,000 and that it is especially the range of 5-1,000 at a molar ratio (Ti/transition metal) with titanium.

0024In this case, when choosing molybdenum as the transition metal ingredient which dissolves to the 1st titanium oxide particulate, a molybdenum component may be guided from a molybdenum compound, and they may be the metal (Mo) of molybdenum, and an oxide (MoO).₂MoO₃Hydroxide, a chloride (MoCl)₃MoCl₅What a nitrate, sulfate, a halogenation thing, a complex compound, etc. were mentioned, and was used combining these one sort or two kinds or more may be used. Also in it, it is an oxide (MoO).₂MoO₃Chloride (MoCl)₃MoCl₅It is preferred to use it.

0025The content of the molybdenum component in the 1st titanium oxide particulate is 1-1,000, preferably 2-100, more preferably 2-50 in a molar ratio (Ti/Mo) with titanium. When a molar ratio is less than one, the content rate of titanium oxide falls, a photocatalyst effect may not be demonstrated enough, and this is because a visible light response becomes insufficient and the low concentration of acetaldehyde and high decomposition activity may not be obtained, when it is 1,000 excess.

0026When choosing vanadium as the transition metal ingredient which dissolves to the 1st titanium oxide particulate, a vanadium ingredient may be guided from a vanadium compound, and they may be metal (V) of vanadium, and an oxide (VO, V).₂O₃VO₂V₂O₅Hydroxide, a chloride (VCl)₅Oxy-salts ghost (VOCl)₃A nitrate, sulfate, Oxy sulfate (VOSO)₄What a halogenation thing, a complex compound, etc. were mentioned and was used combining these one sort or two kinds or more may be used. Also in it, it is an oxide (V).₂O₃V₂O₅Chloride (VCl)₅Oxy-salts ghost (VOCl)₃Oxy sulfate (VOSO)₄It is preferred to use it.

0027The content of the vanadium ingredient in the 1st titanium oxide particulate is 10-10,000, preferably 100-10,000, more preferably 100-5,000 in a molar ratio (Ti/V) with titanium. When a molar ratio is less than ten, the content rate of a titanium oxide crystal falls, a photocatalyst effect may not be demonstrated enough, and this is because a visible light response becomes insufficient and the low concentration of acetaldehyde and high decomposition activity may not be obtained, when it is 10,000 excess.

0028The both sides of molybdenum and vanadium can also be chosen as a transition metal ingredient which dissolves to the 1st titanium oxide particulate. Each amount of ingredients in that case can be chosen from a mentioned range, however the molar ratio [Ti/(Mo+V)] of the sum total of each amount of ingredients and titanium is smaller than 10,000 at one or more.

0029The 1st titanium oxide particulate may be used by one sort, and may be used combining two or more kinds. When two or more kinds with a different visible light response are combined, the effect that visible light activity increases may be acquired.

0030It has different composition from the 1st titanium oxide particulate, an iron-group ingredient dissolves characteristically, and the 2nd titanium oxide particulate does not contain transition metals or tin other than an iron-group ingredient like the 1st titanium oxide particulate as a general form.

0031The iron-group metal which dissolves to the 2nd titanium oxide particulate has a preferred iron element also in it, although iron, cobalt, and nickel are mentioned.

0032It may be guided from an iron-group compound and the iron-group ingredients which dissolve to the 2nd titanium oxide particulate may be an iron metal (Fe) and an oxide (Fe).₂O₃Fe₃O₄Hydroxide (FeO (OH)), a chloride (FeCl)₂FeCl₃Nitrate (Fe (NO))₃Sulfate (FeSO)₄Fe₂(SO₄）₃A halogenation thing, a complex compound, etc. are mentioned and it may be used combining these one sort or two kinds or more. Also in it, it is an oxide (Fe).₂O₃Fe₃O₄Hydroxide (FeO (OH)), a chloride (FeCl)₂FeCl₃Nitrate (Fe (NO))₃Sulfate (FeSO)₄Fe₂(SO₄）₃It is preferred to use it.

0033The content of the iron-group ingredient in the 2nd titanium oxide particulate is 1-1,000, preferably 2-200, more preferably 5-100 in a molar ratio (Ti / iron-group ingredient) with titanium. This is because the content rate of titanium oxide falls, a photocatalyst effect may not be demonstrated enough, when a molar ratio is less than one, and a visible light response may become insufficient when it is 1,000 excess.

0034The diameter (D) of 50% cumulative distribution of the volume standard measured by the dynamic-light-scattering method by which the laser beam was used for the 1st titanium oxide particulate in visible light response type photocatalytic oxidation titanium particulate dispersion liquid, and the 2nd titanium oxide particulate₅₀(It may be hereafter called a "mean particle size".) It is preferred that it is 5-30 nm, and more preferably it is 5-20 nm. This is because photocatalyst activity may become insufficient when a mean particle size is less than 5 nm, and dispersion liquid may become opaque when it is an excess of 30 nm. As a device which measures a mean particle size, nano track UPA-EX150 (made by Nikkiso Co., Ltd.), LA-910 (made by Horiba, Ltd.), etc. can be used, for example.

0035The mixture ratio of the 1st titanium oxide particulate contained in visible light response type photocatalytic oxidation titanium particulate dispersion liquid, and the 2nd titanium oxide particulate, it is preferred that it is 99-0.01 in each mass ratio [(1st titanium oxide particulate) /(2nd titanium oxide particulate)] -- more -- desirable -- 19 to 0.05 -- still more preferably it is 9-1. This is because visible light activity may become insufficient, when the above-mentioned mass ratios are 99 excess or less than 0.01.

0036It is a point of the ease of producing of the photocatalyst thin film of necessary thickness, the concentration of the sum total of the 1st titanium oxide particulate in visible light response type photocatalytic oxidation titanium particulate dispersion liquid and the 2nd titanium oxide particulate has preferred 0.01 - 20 mass %, and especially its 0.5 - 10 mass % is preferred.

0037A binder may be added in order to make the dispersion liquid easy to apply to the various member surfaces mentioned below and to be easy to paste up the particulate on visible light response type photocatalytic oxidation titanium particulate dispersion liquid. As a binder, organic resin system binders, such as metallic-compounds system binders, such as silicon, aluminum, titanium, and zirconium, fluororesin, acrylic resin, and urethane system resin, etc. are mentioned, for example.

0038As a mass ratio [binder/titanium oxide] of a binder and titanium oxide, it is preferred 0.01-99 more preferably 0.1-9, and to add and use it in 0.4-2.5 still more preferably. This is because it becomes insufficient pasting up of the titanium oxide particulates on the various surface of a member when the above-mentioned mass ratio is less than 0.01, and visible light activity may become insufficient when it is 99 excess.

0039Especially in order to obtain a photocatalyst operation and the outstanding photocatalyst thin film with high transparency, It is especially preferred compounding ratios (mass ratio of a silicon compound and titanium oxide) 1:99-99:1 more preferably 10:90-90:10, and to use a silicon compound system binder in 30:70-70:30 still more preferably, adding. The silicon compound which contains the silicon compound of the shape of a solid, or the shape of a fluid in water carrier fluid with a silicon compound system binder here, It is colloidal dispersion liquid, solution, or emulsion, and is in a concrete target, Colloidal silica (1-150 nm of desirable particle diameter); silicate solution, such as silicate; Silang, The Shiroki Sun hydrolysis thing emulsion; silicone resin emulsion; the emulsion of the copolymer of silicone resin, such as a silicone acrylic resin copolymer and a silicone urethane resin copolymer, and other resin, etc. can be mentioned.

0040&lt;A manufacturing method of visible light response type photocatalytic oxidation titanium particulate dispersion liquid&gt;<br />The manufacturing method of the visible light response type photocatalytic oxidation titanium particulate dispersion liquid of the present invention manufactures the 1st titanium oxide particulate dispersion liquid and the 2nd titanium oxide particulate dispersion liquid, respectively, and is prepared by mixing the 1st titanium oxide particulate dispersion liquid and the 2nd titanium oxide particulate dispersion liquid.

0041Specifically, the manufacturing method which has a process of following the (1) - (5) can be mentioned.<br />(1) The process of manufacturing tin and transition metal content peroxotitanic acid solution from a materials titanium compound, a tin compound, a transition metal compound (however, except for an iron-group compound), a basic substance, hydrogen peroxide, and water carrier fluid,<br />(2) The process of heating tin and transition metal content peroxotitanic acid solution which were manufactured at the process of the above (1) at 80-250 under pressure control, and obtaining tin and transition metal content titanium oxide particulate dispersion liquid,<br />(3) The process of manufacturing iron-family-elements content peroxotitanic acid solution from a materials titanium compound, an iron-group compound, a basic substance, hydrogen peroxide, and water carrier fluid,<br />(4) The process of heating the iron-family-elements content peroxotitanic acid solution manufactured at the process of the above (3) at 80-250 under pressure control, and obtaining iron-family-elements content titanium oxide particulate dispersion liquid,<br />(5) The process of mixing two kinds of titanium oxide particulate dispersion liquid manufactured at the process of the above (2) and (4).

0042Process (1) - (2) is the process of obtaining the 1st titanium oxide particulate dispersion liquid, process (3) (4) - is a process of obtaining the 2nd titanium oxide particulate dispersion liquid, and it is the process of obtaining the dispersion liquid in which (5) finally contains the 1st titanium oxide particulate and the 2nd titanium oxide particulate.<br />Since it is preferred to use a molybdenum compound and/or a vanadium compound as a transition metal compound used at a process (1) as already stated, the premise explains each process in detail below.

0043- Process (1):<br />In a process (1), a transition metal and tin content peroxotitanic acid solution are manufactured by making a materials titanium compound, a transition metal compound, a tin compound, a basic substance, and hydrogen peroxide react in water carrier fluid.

0044As a reaction method, a basic substance is added to the materials titanium compound in water carrier fluid, and it is considered as titanium hydroxide, Impurities ion other than the metal ion to contain is removed, and after adding hydrogen peroxide to make peroxotitanic acid, a transition metal compound and a tin compound are added, Also by the method of using as a transition metal and tin content peroxotitanic acid, the materials titanium compound and the basic substance in water carrier fluid are received, After adding a transition metal compound and a tin compound and making it dissolve, the method of considering it as a transition metal and tin content titanium hydroxide, removing impurities ion other than the metal ion to contain, adding hydrogen peroxide, and using as a transition metal and tin content peroxotitanic acid may be used.<br />In the latter preceding paragraph, it is the materials titanium compound and the basic substance in water carrier fluid, It divides into the water carrier fluid of 2 liquid like the water carrier fluid which distributed the materials titanium compound, and the water carrier fluid which distributed the basic substance, Both may be mixed after dissolving each compound in either or both of the 2 liquid concerned according to the solubility to the 2 liquid concerned of each compound of a transition metal compound and a tin compound.

0045Thus, after obtaining a transition metal and tin content peroxotitanic acid, the titanium oxide particulates which dissolved the various metal concerned to titanium oxide can be obtained by presenting the hydrothermal reaction of the below-mentioned process (2).

0046Here, if it is considered as a materials titanium compound, they are a chloride of titanium, and a nitrate, for example, The titanium hydroxide etc. which were deposited by adding alkali in organic acid salt, such as inorganic acid salt, such as sulfate, formic acid, citrate, oxalic acid, lactic acid, and glycolic acid, and these solution, and hydrolyzing into them are mentioned, and it may be used combining these one sort or two kinds or more. Also in it, it is a chloride (TiCl) of titanium.₃TiCl₄It is preferred to use it.

0047As a transition metal compound, a tin compound, and water carrier fluid, the above-mentioned thing is used, respectively so that it may become the above-mentioned combination. As for especially the concentration of the materials titanium compound solution formed from a materials titanium compound and water carrier fluid, it is [ below 60 mass % ] preferred that it is below 30 mass %. Although the minimum of concentration is selected suitably, it is preferred that it is usually more than 1 mass %.

0048It is for a basic substance using a materials titanium compound as titanium hydroxide smoothly, For example, hydroxide of alkaline metals, such as sodium hydroxide and a potassium hydrate, or alkaline-earth metals, Amine compounds, such as ammonia, alkanol amine, and alkylamine, are mentioned, and the pH of materials titanium compound solution is used, adding seven or more in quantity which is especially set to pH 7-10. A basic substance may be used with the above-mentioned water carrier fluid, making it into solution of suitable concentration.

0049Hydrogen peroxide is for transforming the above-mentioned materials titanium compound or titanium hydroxide to Peroxo titanium, i.e., a titanium oxide compound including Ti-O-O-Ti combination. Usually, it is used with a form of hydrogen peroxide solution. As for the amount of addition of hydrogen peroxide, it is preferred that it takes 1.5 to 20 times as much as a transition metal and the number of sum total Mol of V and Sn for mol. In the reaction which adds hydrogen peroxide and uses a materials titanium compound or titanium hydroxide as peroxotitanic acid, as for reaction temperature, it is preferred to consider it as 5-80 , and, as for reaction time, it is preferred to consider it as 30 minutes - 24 hours.

0050The peroxotitanic acid solution containing the transition metal and tin which are obtained in this way may contain an alkaline substance or acid things for pH control etc. As an alkaline substance here, ammonia, sodium hydroxide, calcium hydroxide, etc. are mentioned and it is as acid things, for example, For example, organic acid, such as inorganic acid, such as sulfuric acid, nitric acid, chloride, a carbonic acid, phosphoric acid, and hydrogen peroxide, formic acid, citrate, oxalic acid, lactic acid, and glycolic acid, is mentioned. In this case, as for the pH of the peroxotitanic acid solution containing the transition metal and tin which were obtained, it is preferred 1-9, and that it is especially 4-7 in respect of the safety of handling.

0051- Process (2):<br />In a process (2), 0.01 - a 24-hour hydrothermal reaction are presented with the transition metal and tin content peroxotitanic acid solution which were obtained at the above-mentioned process (1) under pressure control at the temperature of 80-250 , preferably 100-250 . 80-250 is suitable for reaction temperature from a controllable viewpoint of reaction efficiency and a reaction, and, as a result, a transition metal and tin content peroxotitanic acid are changed into a transition metal and tin content titanium oxide particulates. The bottom of pressure control here includes the case where it controls by atmospheric pressure, when pressurizing suitably, saying maintaining reaction temperature and making it into the temperature below the boiling point of carrier fluid so that reaction temperature can be maintained, when reaction temperature exceeds the boiling point of carrier fluid. The pressure used here is usually about 0.12-4.5 MPa, preferably about 0.15-4.5 MPa, more preferably 0.20 - 4.5MPa. As for reaction time, it is preferred that they are 1 minute - 24 hours. By this process (2), the transition metal and tin content titanium oxide particulate dispersion liquid which are the 1st titanium oxide particulate are obtained.

0052Although the diameter of a particle of the titanium oxide particulates obtained here has a preferred thing of the range as already stated, it can control the diameter of a particle by adjusting reaction conditions, for example, can make the diameter of a particle small by shortening reaction time.

0053- Process (3):<br />In a process (3), iron-family-elements content peroxotitanic acid solution is manufactured aside from the process of above-mentioned (1) - (2) by making a materials titanium compound, an iron-group compound, a basic substance, and hydrogen peroxide react in water carrier fluid. It can replace with the transition metal compound and tin compound in the above-mentioned process (1) as a reaction method, and can completely carry out in a similar way except using an iron-group compound.

0054That is, an above-mentioned thing is used so that it may become above-mentioned combination, and a reaction is presented with the materials titanium compound, the iron-group compound, the water carrier fluid, the basic substance, and hydrogen peroxide as a start material under an above-mentioned temperature and time, respectively.

0055For pH control etc., the iron-family-elements content peroxotitanic acid solution obtained in this way may also contain an alkaline substance or acid things, and can deal with them like [ an alkaline substance here, acid things, and pH control ] the above-mentioned.

0056- Process (4):<br />In a process (4), 0.01 - a 24-hour hydrothermal reaction are presented with the iron-family-elements content peroxotitanic acid solution obtained at the above-mentioned process (3) under pressure control at the temperature of 80-250 , preferably 100-250 . 80-250 is suitable for reaction temperature from a controllable viewpoint of reaction efficiency and a reaction, and, as a result, iron-family-elements content peroxotitanic acid is changed into iron-family-elements content titanium oxide particulates. The bottom of pressure control here includes the case where it controls by atmospheric pressure, when pressurizing suitably, saying maintaining reaction temperature and making it into the temperature below the boiling point of carrier fluid so that reaction temperature can be maintained, when reaction temperature exceeds the boiling point of carrier fluid. The pressure used here is usually about 0.12-4.5 MPa, preferably about 0.15-4.5 MPa, more preferably 0.20 - 4.5MPa. As for reaction time, it is preferred that they are 1 minute - 24 hours. By this process (4), the iron-family-elements content titanium oxide particulate dispersion liquid which is the 2nd titanium oxide particulate is obtained.

0057Although the diameter of a particle of the titanium oxide particulates obtained here also has a preferred thing of the range as already stated, it is possible to control the diameter of a particle by adjusting reaction conditions, for example, it can make the diameter of a particle small by shortening reaction time.

0058- Process (5):<br />In a process (5), the 2nd titanium oxide particulate dispersion liquid obtained at process (1) the 1st titanium oxide particulate dispersion liquid obtained by - (2) and process (3) - (4) is mixed. The method of distributing with an ultrasonic dispersion machine also by the method which is not limited but is agitated with a stirrer may be sufficient as especially a mixing method. It is preferred that the temperature at the time of mixture is 20-100 , and time is 1 minute - 3 hours. About the mixture ratio, the mass ratio of the titanium oxide particulates in each titanium oxide particulate dispersion liquid should just be mixed so that it may become a mass ratio as already stated.

0059The mass of the titanium oxide particulates contained in titanium oxide particulate dispersion liquid is computable from the quantity and concentration of titanium oxide particulate dispersion liquid. The measuring method of concentration can sample some titanium oxide particulate dispersion liquid, and can compute it according to a following formula from the mass of the non-volatile matter content (titanium oxide particulates) after heating at 105 for 3 hours and volatilizing a solvent, and the mass of the sampled titanium oxide particulate dispersion liquid.<br />Concentration (%) = non-volatile-matter-content mass (g) of titanium oxide particulate dispersion liquid / titanium oxide particulate dispersion liquid mass (g) x100

0060In this way, it is a point of the ease of producing of the photocatalyst thin film of necessary thickness, its 0.01 - 20 mass % is preferred, and especially 0.5 - 10 mass % is preferred [ concentration ] as the concentration of the sum total of the 1st titanium oxide particulate in the prepared visible light response type photocatalytic oxidation titanium particulate dispersion liquid and the 2nd titanium oxide particulate was mentioned above. About concentration adjustment, when concentration is higher than the concentration of a request, concentration can be lowered by adding and diluting a water solvent, and when lower than the concentration of a request, concentration can be raised by volatilizing or filtering a water solvent. Concentration is computable as mentioned above.

0061When adding the binder which improves the film formation nature mentioned above, it is preferred to add to the visible light response type photocatalytic oxidation titanium particulate dispersion liquid which performed concentration adjustment as mentioned above so that it may become the concentration of a request after mixing the water binder solution to add.

0062&lt;The member which has a photocatalyst thin film on the surface&gt;<br />The visible light response type photocatalytic oxidation titanium particulate dispersion liquid of the present invention can be used in order to make a photocatalyst film form in the surface of various members. Here, although various members in particular are not restricted, as a material of a member, organic materials and the charge of non-equipment are mentioned, for example. These can have various shape according to each object and a use.

0063As organic materials, they are vinyl chloride resin (PVC) and polyethylene (PE), for example, Polypropylene (PP), polycarbonate (PC), an acrylic resin, Polyace tar, a fluoro-resin, silicone resin, an ethylene-vinyl acetate copolymer (EVA), Acrylonitrile butadiene rubber (NBR), polyethylene terephthalate (PET), Polyethylenenaphthalate (PEN), polyvinyl butyral (PVB), An ethylene vinyl alcohol copolymer (EVOH), polyimide resin, A polyphenylene sulfide (PPS), polyether imide (PEI), Polyether ether imide (PEEI), a polyether ether ketone (PEEK), The semisynthesis material of natural materials, such as synthetic resin materials, such as melamine resin, phenol resin, and acrylonitrile butadiene styrene (ABS) resin, and crude rubber, or the above-mentioned synthetic resin material and natural material is mentioned. These may be produced commercially by necessary shape, such as a film, a sheet, textile materials, textiles, other casts, and a layered product, and composition.

0064As a charge of non-equipment, the charge of nonmetallic non-equipment and metal inorganic matter material are included, for example.<br />As a charge of nonmetallic non-equipment, glass, ceramics, a stone, etc. are mentioned, for example. These may be produced commercially by various forms, such as a tile, glass, a mirror, a wall, and design material.<br />As a metal inorganic matter material, cast iron, steel materials, iron, an iron alloy, aluminum, an aluminium alloy, nickel, a nickel alloy, zinc die-casting, etc. are mentioned, for example. These may be plating which plating of the above-mentioned metal inorganic matter material may be given, and the above-mentioned organic materials may be applied, and is given to the surface of the above-mentioned organic materials or the charge of nonmetallic non-equipment.

0065Also in the various above-mentioned members, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid of the present invention is useful, although a transparent photocatalyst thin film is especially produced on high polymer films, such as PET.

0066As the formation method of the photocatalyst film on the various surface of a member, About visible light response type photocatalytic oxidation titanium particulate dispersion liquid, it is on the above-mentioned member surface, for example, After applying with publicly known coating methods, such as a spray coat and a dip coat, it may be made to dry with publicly known drying methods, such as far-infrared dryness, IH dryness, and hot air drying, and various thickness of a photocatalyst film may also be selected, but the range of 10 nm - 10 micrometers is usually preferred.

0067Thus, not only having a good photocatalyst operation but the photocatalyst film formed is [ in / like / it is transparent and / before / the light (10-400 nm) of an ultraviolet region ], The photocatalyst operation which is the visible region which was not able to obtain photocatalyst operation sufficient in the conventional photocatalyst and which was excellent only in light (400-800 nm) is obtained, Since the various members in which the photocatalyst film was formed disassemble the organic matter which stuck to the surface by photocatalyst operation of titanium oxide, they can demonstrate effects, such as sanctification on the surface of a member, deodorization, and antibacterial properties.

<p num="0068">Although an example and a comparative example are shown below and the present invention is concretely explained to it, the present invention is not limited to the following examples. Various kinds of measurement in the present invention was performed as follows.</p><p num="0069">(1) The mean particle size (D) of the titanium oxide particulates in dispersion liquid₅₀）<br />The mean particle size (D) of the titanium oxide particulates in dispersion liquid₅₀It measured using the size distribution measuring device (a brand name "nano track grading analysis meter UPA-EX150" and Nikkiso Co., Ltd.).</p><p num="0070">(2) Acetaldehyde gas decomposition system performance testing of a photocatalyst thin film (under LED irradiation)<br />The decomposition reaction of acetaldehyde gas estimated the activity of the photocatalyst thin film which produced dispersion liquid by applying and drying. Evaluation was performed by the batch type gas decomposition quality assessment method.<br />After installing the sample for evaluation which specifically formed the photocatalyst thin film which contains the photocatalyst particulates for about 50 mg as dry mass the whole surface on the PET film of A4 size (210 mm x 297 mm) in the cell made from stainless steel with a silica glass window of capacity 5L, The cell was filled with acetaldehyde gas with a concentration of 5 ppm whose humidity was controlled to 50% of humidity, and it irradiated with light so that it might be set to illumination 30,000Lx by LED (a goods part number "TH-211x200SW", CCS, Inc., spectral distribution: 400-800 nm) installed in the cell upper part. If acetaldehyde gas decomposes with the photocatalyst on a thin film, the acetaldehyde gas concentration in the cell will fall. Then, the amount of acetaldehyde gas decomposition can be calculated by measuring the concentration. Acetaldehyde gas concentration is an optical sound multi-gas monitor (brand name "INNOVA1412"). It measured using the product made by LumaSense, the time taken to reduce acetaldehyde gas concentration to 5 ppm to [1]1ppm of the first stage and [2]0.03ppm was compared, and the following standard estimated. The examination was carried out till 20 hours.<br />- Very good (O and display) ... It decreases within 10 hours.<br />- Good (O and display) ... It decreases within 20 hours.<br />- He is a defect ( and display) a little... Although the reduction from initial concentration (5 ppm) is seen, a standard value (1 ppm and 0.03 ppm) cannot be reduced within 20 hours.<br />- Defect (x and display) ... The reduction from initial concentration (5 ppm) is not seen (it does not decrease at all).</p><p num="0071">(3) Identification of the crystal phase of titanium oxide particulates<br />The crystal phase of titanium oxide particulates was identified by measuring the powder X diffraction (a brand name "table type X diffraction device D2 PHASER" and Bruker AXS, Inc.) of the titanium oxide particulate powder which made it dry for 3 hours and collected the dispersion liquid of the obtained titanium oxide particulates 105 .</p><p num="0072">[Example 1]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and molybdenum dissolved&gt;<br />It adds and dissolves so that Ti/Sn (molar ratio) may be set to 20 in tin chloride (IV) at titanium chloride (IV) solution of 36 mass %, After diluting this with pure water 10 times, to Ti ingredient of above-mentioned titanium chloride (IV) solution Naka, Ti/Mo (molar ratio) adds gradually the ammonia solution of 10 mass % which added and dissolved so that it might be set to 20 in this solution, and molybdenum oxide (VI) neutralizes and hydrolyzes into it, The sediment of titanium hydroxide containing tin and molybdenum was obtained. The pH of the solution at this time was 8. Addition and Decantation of pure water were repeated and deionization processing of the obtained sediment was carried out. It is H to the titanium hydroxide sediment containing tin and molybdenum after this deionization processing.₂O₂adding 35 mass % hydrogen peroxide solution so that / (Ti+Sn+Mo) (molar ratio) may be set to 10, agitating for 3 hours and making it fully react at 50 after that -- orange -- transparent tin and molybdenum content peroxotitanic acid solution (a) were obtained.</p><p num="0073">Tin and molybdenum content peroxotitanic acid solution (a) 400mL is taught, hydrothermal processing of this is carried out for 90 minutes under a 150 condition, pure water is added to the autoclave of capacity 500mL after that, and concentration adjustment is performed to it, The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (A) in which tin and molybdenum dissolved were obtained. When powder X diffraction measurement of titanium oxide particulates (A) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin and molybdenum are dissolving to titanium oxide.</p><p num="0074">&lt;Manufacture of the titanium oxide particulate dispersion liquid in which iron dissolved&gt;<br />In titanium chloride (IV) solution of 36 mass %, ferric chloride (III) is added so that Ti/Fe (molar ratio) may be set to ten, After diluting this with pure water 10 times, the sediment of titanium hydroxide containing iron was obtained by adding the ammonia solution of 10 mass % gradually, neutralizing and hydrolyzing into this solution. The pH of the solution at this time was 8. Addition and Decantation of pure water were repeated and deionization processing of the obtained sediment was carried out. It is H to the titanium hydroxide sediment containing iron after this deionization processing.₂O₂adding 35 mass % hydrogen peroxide solution so that / (Ti+Fe) (molar ratio) may be set to 8, agitating for 2 hours and making it fully react at 40 after that -- orange -- transparent iron content peroxotitanic acid solution (b) was obtained.</p><p num="0075">Iron content peroxotitanic acid solution (b) 400mL is taught, hydrothermal processing of this is carried out for 90 minutes under a 130 condition, pure water is added to the autoclave of capacity 500mL after that, and concentration adjustment is performed to it, The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (B) in which iron dissolved were obtained. When powder X diffraction measurement of titanium oxide particulates (B) was performed, the peak observed is only a thing of Anatase type titanium oxide, and it turned out that iron is dissolving to titanium oxide.</p><p num="0076">By mixing each dispersion liquid so that titanium oxide particulates (A) and titanium oxide particulates (B) may be set to (A):(B) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-1) of the present invention was obtained.</p><p num="0077">It is a binder (colloidal silica, a brand name: SNOWTEX 20, the Nissan Chemical Industries, Ltd. make, 10-20 nm of mean particle sizes, SiO) of a silica system to photocatalytic oxidation titanium particulate dispersion liquid (E-1).₂It is TiO about concentration 20 mass % solution.₂/SiO₂It added so that a (mass ratio) might be set to 1.5, and the coating fluid for evaluation was produced.</p><p num="0078">It Coating so that the photocatalyst thin film (about 0.2 micrometer in thickness) which contains a 50-mg photocatalytic oxidation titanium particulate in the PET film of A4 size for the coating fluid for evaluation with the wire bar coater of #7 may be formed, It was made to dry for 1 hour in the oven set as 80 , and the sample member for acetaldehyde gas decomposition quality assessments was obtained. The place which measured the acetaldehyde gas decomposition performance of this photocatalyst thin film by the batch type gas decomposition quality assessment method, 1 ppm (very much good : O) fell in 2.5 hours after LED (wavelength of 400-800 nm) irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (very much good : O) in 6.1 hours.</p><p num="0079">[Example 2]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and molybdenum dissolved&gt;<br />The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (C) in which tin and molybdenum dissolved were obtained like Example 1 except having added molybdenum oxide (VI) so that Ti/Mo (molar ratio) might be set to 3.3, and having carried out hydrothermal processing time for 120 minutes. When powder X diffraction measurement of titanium oxide particulates (C) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin and molybdenum are dissolving to titanium oxide.</p><p num="0080">By mixing each dispersion liquid so that titanium oxide particulates (C) and titanium oxide particulates (B) may be set to (C):(B) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-2) of the present invention was obtained.</p><p num="0081">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-2) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 2.3 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (very much good : O) in 4.1 hours.</p><p num="0082">[Example 3]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and molybdenum dissolved&gt;<br />The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (D) in which tin and molybdenum dissolved were obtained like Example 1 except having added molybdenum oxide (VI) so that Ti/Mo (molar ratio) might be set to 100. When powder X diffraction measurement of titanium oxide particulates (D) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin and molybdenum are dissolving to titanium oxide.</p><p num="0083">By mixing each dispersion liquid so that titanium oxide particulates (D) and titanium oxide particulates (B) may be set to (D):(B) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-3) of the present invention was obtained.</p><p num="0084">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-3) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (good : O) fell in 10.4 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (good : O) in 19.0 hours.</p><p num="0085">[Example 4]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and molybdenum dissolved&gt;<br />The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (E) in which tin and molybdenum dissolved were obtained like Example 1 except having added titanium chloride (IV) solution so that Ti/Sn (molar ratio) might be set to five, and hydrothermal treatment temperature having been 180 . When powder X diffraction measurement of titanium oxide particulates (E) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin and molybdenum are dissolving to titanium oxide.</p><p num="0086">By mixing each dispersion liquid so that titanium oxide particulates (E) and titanium oxide particulates (B) may be set to (E):(B) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-4) of the present invention was obtained.</p><p num="0087">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-4) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 4.1 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (very much good : O) in 7.6 hours.</p><p num="0088">[Example 5]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and molybdenum dissolved&gt;<br />The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (F) in which tin and molybdenum dissolved were obtained like Example 1 except having added titanium chloride (IV) solution so that Ti/Sn (molar ratio) might be set to 33, and hydrothermal treatment temperature having been 140 . When powder X diffraction measurement of titanium oxide particulates (F) was performed, the peak observed is only a thing of Anatase type titanium oxide and a rutile type titanium dioxide, and it turned out that tin and molybdenum are dissolving to titanium oxide.</p><p num="0089">By mixing each dispersion liquid so that titanium oxide particulates (F) and titanium oxide particulates (B) may be set to (F):(B) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-5) of the present invention was obtained.</p><p num="0090">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-5) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 7.5 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (good : O) in 12.5 hours.</p><p num="0091">[Example 6]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and molybdenum dissolved&gt;<br />The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (G) in which tin and molybdenum dissolved were obtained like Example 1 except having added molybdenum oxide (VI) so that Ti/Mo (molar ratio) might be set to 12.5. When powder X diffraction measurement of titanium oxide particulates (G) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin and molybdenum are dissolving to titanium oxide.</p><p num="0092">&lt;Manufacture of the titanium oxide particulate dispersion liquid in which iron dissolved&gt;<br />The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (H) in which iron dissolved were obtained like Example 1 except having added ferric chloride (III) so that Ti/Fe (molar ratio) might be set to 20, and having carried out hydrothermal processing time for 120 minutes. When powder X diffraction measurement of titanium oxide particulates (H) was performed, the peak observed is only a thing of Anatase type titanium oxide, and it turned out that iron is dissolving to titanium oxide.</p><p num="0093">By mixing each dispersion liquid so that titanium oxide particulates (G) and titanium oxide particulates (H) may be set to (G):(H) =90:10 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-6) of the present invention was obtained.</p><p num="0094">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-6) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 8.8 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (good : O) in 19.8 hours.</p><p num="0095">[Example 7]<br />By mixing each dispersion liquid so that titanium oxide particulates (G) and titanium oxide particulates (H) may be set to (G):(H) =60:40 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-7) of the present invention was obtained.</p><p num="0096">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-7) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 2.4 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (very much good : O) in 7.8 hours.</p><p num="0097">[Example 8]<br />By mixing each dispersion liquid so that titanium oxide particulates (A) and titanium oxide particulates (H) may be set to (A):(H) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-8) of the present invention was obtained.</p><p num="0098">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-8) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 6.3 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (good : O) in 15.3 hours.</p><p num="0099">[Example 9]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and vanadium dissolved&gt;<br />It adds and dissolves so that 20 may become 2000 about tin chloride (IV) in Ti/Sn (molar ratio) and Ti/V (molar ratio) may become titanium chloride (IV) solution of 36 mass % about vanadyl sulfate (IV), After diluting this with pure water 10 times, the ammonia solution of 10 mass % was added gradually, and the sediment of titanium hydroxide containing tin and vanadium was obtained by neutralizing and hydrolyzing. The pH of the solution at this time was 8.5. Addition and Decantation of pure water were repeated and deionization processing of the obtained sediment was carried out. It is H to the titanium hydroxide sediment containing tin and vanadium after this deionization processing.₂O₂adding 35 mass % hydrogen peroxide solution so that / (Ti+Sn+V) (molar ratio) may be set to 10, agitating for 3 hours and making it fully react at 50 after that -- orange -- transparent tin and vanadium content peroxotitanic acid solution (i) were obtained.</p><p num="0100">Tin and vanadium content peroxotitanic acid solution (i)400mL are taught, hydrothermal processing of this is carried out for 90 minutes under a 150 condition, pure water is added to the autoclave of capacity 500mL after that, and concentration adjustment is performed to it, The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulate (I) in which tin and vanadium dissolved were obtained. When powder X diffraction measurement of titanium oxide particulate (I) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin and molybdenum are dissolving to titanium oxide.</p><p num="0101">By mixing each dispersion liquid so that titanium oxide particulate (I) and titanium oxide particulates (B) may be set to (I):(B) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-9) of the present invention was obtained.</p><p num="0102">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-9) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 6.5 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (good : O) in 13.8 hours.</p><p num="0103">[Example 10]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin and vanadium dissolved&gt;<br />The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (J) in which tin and vanadium dissolved were obtained like Example 9 except to have added vanadyl sulfate (IV) and hydrothermal treatment temperature having been 180 as [ set / to 500 / Ti/V (molar ratio) ], and having made hydrothermal processing time into 20 minutes. When powder X diffraction measurement of titanium oxide particulates (J) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin and vanadium are dissolving to titanium oxide.</p><p num="0104">By mixing each dispersion liquid so that titanium oxide particulates (J) and titanium oxide particulates (H) may be set to (J):(H) =50:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-10) of the present invention was obtained.</p><p num="0105">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-10) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 7.2 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (good : O) in 14.6 hours.</p><p num="0106">[Example 11]<br />By mixing each dispersion liquid so that titanium oxide particulate (A) and titanium oxide particulate (I) and titanium oxide particulates (B) may be set to (A):(I):(B) =25:25:50 by a mass ratio, the visible light response type photocatalytic oxidation titanium particulate dispersion liquid (E-11) of the present invention was obtained.</p><p num="0107">Hereinafter, it is from photocatalytic oxidation titanium particulate dispersion liquid (E-11) like Example 1, When the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured, 1 ppm (very much good : O) fell in 2.0 hours after LED irradiation, and acetaldehyde gas concentration fell to 0.03 ppm (very much good : O) in 3.5 hours.</p><p num="0108">[Comparative example 1]<br />Titanium oxide particulate dispersion liquid (C-1) was obtained only from the dispersion liquid of titanium oxide particulates (A).</p><p num="0109">Hereinafter, when the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured from titanium oxide particulate dispersion liquid (C-1) like Example 1, acetaldehyde gas concentration fell to 3.7 ppm (a little defect : ) in 20 hours after LED irradiation.</p><p num="0110">[Comparative example 2]<br />Titanium oxide particulate dispersion liquid (C-2) was obtained only from the dispersion liquid of titanium oxide particulates (B).</p><p num="0111">Hereinafter, when the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured from titanium oxide particulate dispersion liquid (C-2) like Example 1, even if 20 hours passed after LED irradiation, the fall of acetaldehyde gas concentration was not observed (defect: x).</p><p num="0112">[Comparative example 3]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which copper dissolved&gt;<br />After having added and dissolved so that Ti/Cu (molar ratio) might become titanium chloride (IV) solution of 36 mass % with 20 about copper chloride (II), and diluting this with pure water 10 times, the ammonia solution of 10 mass % was added gradually, and the sediment of titanium hydroxide containing copper was obtained by neutralizing and hydrolyzing. The pH of the solution at this time was 7.5. Addition and Decantation of pure water were repeated and deionization processing of the obtained sediment was carried out. It is H to the titanium hydroxide sediment containing copper after this deionization processing.₂O₂Added 35 mass % hydrogen peroxide solution so that / (Ti+Cu) (molar ratio) might be set to 12, and agitated at 40 after that for 3 hours, it was made to fully react, and transparent green copper content peroxotitanic acid solution (k) was obtained.</p><p num="0113">Copper content peroxotitanic acid solution (k) 400mL is taught, hydrothermal processing of this is carried out for 90 minutes under a 130 condition, pure water is added to the autoclave of capacity 500mL after that, and concentration adjustment is performed to it, The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (K) in which copper dissolved were obtained. When powder X diffraction measurement was performed, the peak observed is only a thing of Anatase type titanium oxide, and it turned out that copper is dissolving to titanium oxide.</p><p num="0114">Titanium oxide particulate dispersion liquid (C-3) was obtained only from the dispersion liquid of titanium oxide particulates (K).</p><p num="0115">Hereinafter, when the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured from titanium oxide particulate dispersion liquid (C-3) like Example 1, acetaldehyde gas concentration fell to 3.2 ppm (a little defect : ) in 20 hours after LED irradiation.</p><p num="0116">[Comparative example 4]<br />By mixing each dispersion liquid so that titanium oxide particulates (G) and titanium oxide particulates (K) may be set to (G):(K) =90:10 by a mass ratio, titanium oxide particulate dispersion liquid (C-4) was obtained.</p><p num="0117">Hereinafter, it is from titanium oxide particulate dispersion liquid (C-4) like Example 1, The place which produced the coating fluid for evaluation, and a photocatalyst thin film, and measured the acetaldehyde gas decomposition performance, Although acetaldehyde gas concentration fell to 1 ppm (very much good : O) in 2.0 hours after LED irradiation, acetaldehyde gas concentration fell only to 0.16 ppm (a little defect : ) in 20 hours.</p><p num="0118">[Comparative example 5]<br />By mixing each dispersion liquid so that titanium oxide particulates (G) and titanium oxide particulates (K) may be set to (G):(K) =60:40 by a mass ratio, titanium oxide particulate dispersion liquid (C-5) was obtained.</p><p num="0119">Hereinafter, it is from titanium oxide particulate dispersion liquid (C-5) like Example 1, The place which produced the coating fluid for evaluation, and a photocatalyst thin film, and measured the acetaldehyde gas decomposition performance, Although acetaldehyde gas concentration fell to 1 ppm (very much good : O) in 6.8 hours after LED irradiation, acetaldehyde gas concentration fell only to 0.20 ppm (a little defect : ) in 20 hours.</p><p num="0120">[Comparative example 6]<br />By mixing each dispersion liquid so that titanium oxide particulate (I) and titanium oxide particulates (K) may be set to (I):(K) =50:50 by a mass ratio, titanium oxide particulate dispersion liquid (C-6) was obtained.</p><p num="0121">Hereinafter, it is from titanium oxide particulate dispersion liquid (C-6) like Example 1, The place which produced the coating fluid for evaluation, and a photocatalyst thin film, and measured the acetaldehyde gas decomposition performance, Although acetaldehyde gas concentration fell to 1 ppm (very much good : O) in 6.0 hours after LED irradiation, acetaldehyde gas concentration fell only to 0.13 ppm (a little defect : ) in 20 hours.</p><p num="0122">[Comparative example 7]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which tin dissolved&gt;<br />It adds and dissolves so that Ti/Sn (molar ratio) may be set to 20 in tin chloride (IV) at titanium chloride (IV) solution of 36 mass %, After diluting this with pure water 10 times, the ammonia solution of 10 mass % was added gradually, and the sediment of titanium hydroxide containing tin was obtained by neutralizing and hydrolyzing. The pH of the solution at this time was 9. Addition and Decantation of pure water were repeated and deionization processing of the obtained sediment was carried out. It is H to the titanium hydroxide sediment containing tin after this deionization processing.₂O₂adding 35 mass % hydrogen peroxide solution so that / (Ti+Sn) (molar ratio) may be set to 6, agitating one whole day and night and making it fully react at room temperature after that -- orange -- transparent tin content peroxotitanic acid solution (l) was obtained.</p><p num="0123">Tin content peroxotitanic acid solution (l) 400mL is taught, hydrothermal processing of this is carried out for 90 minutes under a 150 condition, pure water is added to the autoclave of capacity 500mL after that, and concentration adjustment is performed to it, The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (L) in which tin dissolved were obtained. When powder X diffraction measurement of titanium oxide particulates (L) was performed, the peak observed is only a thing of a rutile type titanium dioxide, and it turned out that tin is dissolving to titanium oxide.</p><p num="0124">By mixing each dispersion liquid so that titanium oxide particulates (L) and titanium oxide particulates (B) may be set to (L):(B) =50:50 by a mass ratio, titanium oxide particulate dispersion liquid (C-7) was obtained.</p><p num="0125">Hereinafter, it is from titanium oxide particulate dispersion liquid (C-7) like Example 1, The place which produced the coating fluid for evaluation, and a photocatalyst thin film, and measured the acetaldehyde gas decomposition performance, Although acetaldehyde gas concentration fell to 1 ppm (good : O) in 18.6 hours after LED irradiation, acetaldehyde gas concentration fell only to 0.80 ppm (a little defect : ) in 20 hours.</p><p num="0126">[Comparative example 8]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid in which molybdenum dissolved&gt;<br />After diluting titanium chloride (IV) solution of 36 mass % with pure water 10 times, In this solution, molybdenum oxide (VI) adds gradually the ammonia solution of 10 mass % which added and dissolved so that Ti/Mo (molar ratio) might be set to 20 to Ti ingredient of above-mentioned titanium chloride (IV) solution Naka, and neutralizes in it, The sediment of titanium hydroxide containing molybdenum was obtained by hydrolyzing. The pH of the solution at this time was 8. Addition and Decantation of pure water were repeated and deionization processing of the obtained sediment was carried out. It is H to the titanium hydroxide sediment containing molybdenum after this deionization processing.₂O₂adding 35 mass % hydrogen peroxide solution so that / (Ti+Mo) (molar ratio) may be set to 8, agitating one whole day and night and making it fully react at room temperature after that -- orange -- transparent molybdenum content peroxotitanic acid solution (m) was obtained.</p><p num="0127">Molybdenum content peroxotitanic acid solution (m) 400mL is taught, hydrothermal processing of this is carried out for 120 minutes under a 130 condition, pure water is added to the autoclave of capacity 500mL after that, and concentration adjustment is performed to it, The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (M) in which molybdenum dissolved were obtained. When powder X diffraction measurement of titanium oxide particulates (M) was performed, the peak observed is only a thing of Anatase type titanium oxide, and it turned out that molybdenum is dissolving to titanium oxide.</p><p num="0128">By mixing each dispersion liquid so that titanium oxide particulates (M) and titanium oxide particulates (B) may be set to (M):(B) =50:50 by a mass ratio, titanium oxide particulate dispersion liquid (C-8) was obtained.</p><p num="0129">Hereinafter, when the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured from titanium oxide particulate dispersion liquid (C-8) like Example 1, acetaldehyde gas concentration fell to 4.1 ppm (a little defect : ) in 20 hours after LED irradiation.</p><p num="0130">[Comparative example 9]<br />&lt;Manufacture of titanium oxide particulate dispersion liquid&gt;<br />After diluting titanium chloride (IV) solution of 36 mass % with pure water 10 times, the ammonia solution of 10 mass % was added gradually, and the sediment of titanium hydroxide was obtained by neutralizing and hydrolyzing. The pH of the solution at this time was 9. Addition and Decantation of pure water were repeated and deionization processing of the obtained sediment was carried out. It is H to the titanium hydroxide sediment after this deionization processing.₂O₂adding 35 mass % hydrogen peroxide solution so that /Ti (molar ratio) may be set to five, agitating one whole day and night and making it fully react at room temperature after that -- yellow -- transparent peroxotitanic acid solution (n) was obtained.</p><p num="0131">The dispersion liquid (solid content concentration 1 mass %) of titanium oxide particulates (N) were obtained by teaching peroxotitanic acid solution (n) 400mL, carrying out hydrothermal processing of this for 90 minutes under a 130 condition, adding pure water to the autoclave of capacity 500mL after that, and performing concentration adjustment to it. When powder X diffraction measurement of titanium oxide particulates (N) was performed, the peak observed was a thing of Anatase type titanium oxide.</p><p num="0132">Titanium oxide particulate dispersion liquid (C-9) was obtained only from the dispersion liquid of titanium oxide particulates (N).</p><p num="0133">Hereinafter, when the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured from titanium oxide particulate dispersion liquid (C-9) like Example 1, even if 20 hours passed after LED irradiation, the fall of acetaldehyde gas concentration was not observed (defect: x).</p><p num="0134">[Comparative example 10]<br />&lt;Recovery of the dissolution component from the titanium oxide particulate dispersion liquid in which iron dissolved&gt;<br />By centrifuging by 210,000xg with a small size super-centrifugal machine (a brand name "himacCS150NX", the Hitachi Koki Co., Ltd. make), the dispersion liquid of titanium oxide particulates (B) in which iron dissolved were divided into the titanium oxide particulates (B) to which iron dissolved, and a solvent and a dissolution component. It is an ICP optical-emission-spectrometry device (brand name "ICP issue analysis device IRIS 1000") about the iron dissolution component concentration in a solvent. thermostat Fisher -- scientific -- Co., Ltd. -- when measured, it turned out that it is an insoluble element -- are 2.2 ppm and most is dissolving to titanium oxide particulates among the added iron ingredients.</p><p num="0135">The solvent and dissolution component which separated titanium oxide particulates (B) from the dispersion liquid of titanium oxide particulates (A) and titanium oxide particulates (B) with the super-centrifugal machine, By mixing each dispersion liquid and solvent, and a dissolution component so that it may be set to (A):(B dissolution component) =50:50 by a mass ratio, titanium oxide particulate dispersion liquid (C-10) was obtained.</p><p num="0136">Hereinafter, when the coating fluid for evaluation and a photocatalyst thin film were produced and the acetaldehyde gas decomposition performance was measured from titanium oxide particulate dispersion liquid (C-10) like Example 1, acetaldehyde gas concentration fell to 4.0 ppm (a little defect : ) in 20 hours after LED irradiation.</p><p num="0137">[Comparative example 11]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid adsorbed on the surface in the iron ingredient (= support)&gt;<br />The iron ingredient obtained the titanium oxide particulate dispersion liquid (C-11) by which the surface was adsorbed by mixing the dispersion liquid of titanium oxide particulates (G), and the ferric chloride (III) solution which dissolved ferric chloride (III) with pure water so that the mass ratio of titanium oxide particulates (G) and iron may be set to 100:0.05.</p><p num="0138">Hereinafter, it is from titanium oxide particulate dispersion liquid (C-11) like Example 1, The place which produced the coating fluid for evaluation, and a photocatalyst thin film, and measured the acetaldehyde gas decomposition performance, Although acetaldehyde gas concentration fell to 1 ppm (very much good : O) in 4.6 hours after LED irradiation, acetaldehyde gas concentration fell only to 0.09 ppm (a little defect : ) in 20 hours.</p><p num="0139">[Comparative example 12]<br />&lt;Manufacture of the titanium oxide particulate dispersion liquid adsorbed on the surface in the iron ingredient (= support)&gt;<br />Since the titanium oxide particulates in dispersion liquid (C-12) condensed and precipitated when the dispersion liquid of titanium oxide particulates (G) and the ferric chloride (III) solution which dissolved ferric chloride (III) with pure water were mixed so that the mass ratio of titanium oxide particulates (G) and iron might be set to 100:0.5, evaluation was stopped. Thus, the amount of addition is extremely restricted to a small quantity, and the method of adding an iron-group compound to dispersion liquid has the problem that the stability of liquid also worsens in order to worsen the dispersion state of the titanium oxide particulates in dispersion liquid.</p><p num="0140">The materials ratio of the titanium oxide particulates used for Examples 1-11 and comparative examples 1-12 in Table 1, hydrothermal processing conditions, a mean particle size (D)₅₀It is shown collectively.</p><p num="0141"><tables num="1"><img file="WO2016152487A1_D0001.tif" /></tables></p><p num="0142">The mixture ratio of the visible light response type photocatalyst-particulates dispersion liquid of Examples 1-11 and comparative examples 1-12, a mean particle size, and an acetaldehyde gas decomposition test result are collectively shown in Table 2.</p><p num="0143"><tables num="2"><img file="WO2016152487A1_D0002.tif" /></tables></p><p num="0144">The 1st titanium oxide particulate in which the transition metal ingredient (a molybdenum component and/or a vanadium ingredient) which improves a tin ingredient and a visible light response dissolved so that the result of Examples 1-11 might show, The 2nd titanium oxide particulate in which the iron ingredient dissolved is mixed, Decomposition of acetaldehyde gas becomes good also under the LED irradiation in which only the light of a visible region emits light, It is acetaldehyde gas concentration to 0.03 ppm or less which is an indoor concentration guideline value (acetaldehyde) of the chemical substance in indoor air upon which it was decided by the Ministry of Health, Labour and Welfare, It can be made to fall within 5 hours in a still more desirable thing within a time [ effective / less than ], for example, 20 hours, for less than 10 hours in a desirable thing.</p><p num="0145">the result of comparative examples 1 and 2 shows -- as -- the 1st titanium oxide particulate and the 2nd titanium oxide particulate -- if independent [ each ], sufficient photocatalyst activity under visible light irradiation is not acquired.</p><p num="0146">When not iron but copper is chosen as a metal which dissolves to the 2nd titanium oxide particulate so that the result of comparative examples 4, 5, and 6 may show, the early decomposition with high acetaldehyde gas concentration is good under visible light irradiation, but sufficient photocatalyst activity over low concentration acetaldehyde gas is not acquired. On the other hand, when iron was chosen as a metal which dissolves to the 2nd titanium oxide particulate as shown in each example of the example, even if acetaldehyde gas concentration turned into low concentration, activity was obtained, and the result of the ability to make it falling to 0.03 ppm or less was obtained.</p><p num="0147">If the metal which dissolves to the 1st titanium oxide particulate becomes one of tin and the transition metals so that the result of comparative examples 7 and 8 may show, sufficient photocatalyst activity under visible light irradiation will not be acquired. Therefore, in order to obtain high activity under visible light irradiation, it is necessary to add the transition metal ingredient which improves tin and a visible light response to the 1st titanium oxide particulate.</p><p num="0148">When the titanium oxide particulates which made iron dissolve, or the titanium oxide particulates which do not make different-species metal dissolve are alone used so that the result of comparative examples 3 and 9 may show, the activity under visible light irradiation is not obtained at all. This is an action from which the titanium oxide particles which made copper dissolve differ.</p><p num="0149">The iron ingredient which is dissolving into dispersion liquid without the 2nd titanium oxide particulate being indispensable for the improvement in visible photoactive, and dissolving to the 2nd titanium oxide particulate has not contributed to the improvement in active so that the result of comparative example 10 may show. That is, the key factor of the visible photoactive improvement effect is not an iron ingredient which begins to leak from the 2nd titanium oxide particulate, and is based on the combination of the 1st titanium oxide particulate that made the transition metal ingredient which improves the 2nd titanium oxide particulates, tin, and visible light response that made iron dissolve dissolve.</p><p num="0150">A dissolution iron ingredient contributes to the improvement in visible photoactive to some extent so that the result of comparative examples 11 and 12 may show, but sufficient visible light activity to low concentration acetaldehyde gas is not obtained. When it adds so much, condensation and precipitation of the titanium oxide particulates in dispersion liquid may be caused.</p>

0151The visible light response type photocatalyst-particulates dispersion liquid of the present invention are useful, although it gives to various substrates consisting of organic substances, such as inorganic matters, such as glass and metal, and high polymer films (PET film etc.), and a photocatalyst thin film is produced, and although a transparent photocatalyst thin film is produced especially on a high polymer film, they are useful.