Visible-light-responsive titanium oxide microparticle dispersion, and process for production thereof

Visible light response type titanium oxide system particulate dispersion liquid and a manufacturing method for the same

0001The present invention relates to visible light response type titanium oxide system particulate dispersion liquid and a manufacturing method for the same, and also is in details, It is related with visible light response type titanium oxide system dispersion liquid which can produce the photocatalyst thin film with high transparency which is excellent in the dispersion stability of titanium oxide particulates, and has a visible light response simple, and a manufacturing method for the same.

0002Titanium oxide is used for the precursor of compound oxides, such as various uses, for example, paints, an ultraviolet-rays cover agent, a catalyst, a photocatalyst, a catalyst carrier, adsorbent, an ionic exchange agent, a bulking agent, a reinforcement agent, materials for ceramics, and a perovskite-type compound oxide, the lower coating agent of magnetic tape, etc.

0003Especially, since the light catalytic coating film which coated various the dispersion liquid on the surface of the substrate, and formed them disassembles an organic matter by photocatalyst operation of titanium oxide and makes the film surface hydrophilicity, light catalytic titanium oxide particulates are used abundantly at uses, such as sanctification on the surface of a substrate, deodorization, and antibacterial properties. In order to improve the photocatalyst activity, it is required to make large the contact surface product of photocatalyst particles and the quality of a decomposition subject, therefore it is required that the diameter of a primary particle of the particle should be 50 nm or less. Membranous transparency is also required so that the design nature of a substrate may not be lost.

0004The method (patent documents 1-3) of distributing 1 titanium-oxide fine powder in carrier fluid with a wet distribution machine, using distributed auxiliary agents, such as an organic polymers dispersing agent, as a manufacturing method of titanium oxide particulate dispersion liquid and the liquid phase method (patent documents 4) produced by hydrothermal processing of 2 titanium content compound solution are mentioned. It is a point which the problem of these processes needs a labor great [ in order that the ultrafine particle of 50 nm or less of mean particle sizes may tend to cause condensation ] in order to distribute to a primary particle, and cannot be distributed to a primary particle depending on the case.

0005Under irradiation of the light of ultraviolet regions where a wavelength is comparatively short, such as sunlight, although titanium oxide shows a good photocatalyst operation, it may be unable to reveal easily photocatalyst operation with visible light sufficient in the indoor space illuminated by the light source which occupies most like a fluorescent light. In recent years, although the tungstic oxide photocatalyst object (patent documents 4) attracts attention 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.

<p num="0006"><patcit num="1"><text>JP,01-003020,A</text></patcit><patcit num="2"><text>JP,06-279725,A</text></patcit><patcit num="3"><text>JP,07-247119,A</text></patcit><patcit num="4"><text>JP,2009-148700,A</text></patcit></p>

<p num="0007">It aims at providing visible light response type titanium oxide system dispersion liquid which can produce the photocatalyst thin film with high transparency which the present invention was made in view of the above-mentioned situation, and is excellent in the dispersion stability of titanium oxide particulates, and has a visible light response simple, and a manufacturing method for the same.</p>

<p num="0008">In order that these artificers may achieve the above-mentioned object, as a result of inquiring wholeheartedly, after manufacturing the peroxotitanic acid which contained the tin compound using a materials titanium compound, a tin compound, and hydrogen peroxide, After carrying out the hydrothermal reaction of this under high pressure and obtaining titanium oxide particulate dispersion liquid, it adds and makes an iron compound and/or a copper compound react, The titanium oxide particulate dispersion liquid containing a Peroxo titanium ingredient, iron and/or a copper ingredient, and a tin ingredient is obtained, and it is these titanium oxide dispersion liquid, The knowledge of the photocatalyst thin film with high transparency which is excellent in the dispersion stability of titanium oxide particulates, and has a visible light response from these titanium oxide dispersion liquid being producible simple is carried out, and it came to make the present invention.</p><p num="0009">Therefore, the present invention provides following visible light response type titanium oxide system dispersion liquid and a manufacturing method for the same.<br />[1] Titanium oxide particulates are distributing in water carrier fluid, and it is a Peroxo titanium ingredient, Visible light response type titanium oxide system particulate dispersion liquid which a tin ingredient is contained in iron and/or a copper ingredient, and a row, and is characterized by the content of the Peroxo titanium ingredient being 0.1 to 20 mass % to titanium oxide.<br />[2] Visible light response type titanium oxide system particulate dispersion liquid given in [1] in which content in metallic iron conversion of the above-mentioned iron ingredient is characterized by being 0.01 to 5 mass % to titanium oxide.<br />[3] Visible light response type titanium oxide system particulate dispersion liquid given in [1] in which content in metal copper conversion of the above-mentioned copper ingredient is characterized by being 0.01 to 5 mass % to titanium oxide.<br />[4] Visible light response type titanium oxide system particulate dispersion liquid given in either of [1] - [3], wherein the content of the above-mentioned tin ingredient is 1-1000 in a molar ratio (Ti/Sn) with titanium oxide.<br />[5] The diameter (D) of 50% total distribution by which the above-mentioned titanium oxide particulates are measured by a dynamic scattering method₅₀Visible light response type titanium oxide system particulate dispersion liquid given in either of [1] - [4] being 50 nm or less.<br />[6] Process of manufacturing the peroxotitanic acid containing a tin compound from (1) materials titanium compound, a tin compound, and hydrogen peroxide,<br />(2) the process of obtaining the titanium oxide particulate dispersion liquid which heats peroxotitanic acid solution containing a tin compound at 80-250 under high pressure, and contains a Peroxo titanium ingredient and a tin ingredient -- and<br />(3) The process which makes an iron compound and/or a copper compound add and react to titanium oxide particulate dispersion liquid<br />A manufacturing method of visible light response type titanium oxide system particulate dispersion liquid given in either of With(ing) [1] - [5].</p>

<p num="0010">According to the present invention, visible light response type titanium oxide system dispersion liquid which can produce the photocatalyst thin film with high transparency which is excellent in the dispersion stability of titanium oxide particulates, and has a visible light response simple, and a manufacturing method for the same can be provided.</p>

0011Hereinafter, it explains still in detail about the present invention.<br />&lt;Visible light response type titanium oxide system particulate dispersion liquid&gt;<br />In the visible light response type titanium oxide system particulate dispersion liquid of the present invention, in the water solvent, titanium oxide particulates distribute highly, and also the tin ingredient is contained at the Peroxo titanium ingredient, an iron ingredient and/or a copper ingredient, and the row.

0012- Water carrier fluid:<br />A water solvent is used as water carrier fluid. A mixed solvent with the hydrophilic organic solvent mixed with water and water at an arbitrary rate as a water solvent is mentioned. As water, deionized water, distilled water, pure water, etc. are preferred, for example. As a hydrophilic organic solvent, alcohol, such as methanol, ethanol, and isopropanol, is preferred, for example. In this case, as for the mixed rate of a hydrophilic organic solvent, it is preferred that it is zero to 50 in water carrier fluid mass %.

0013- Titanium oxide particulates:<br />The diameter (D) of 50% cumulative distribution of the volume standard measured by the dynamic scattering method by which the laser beam was used for the titanium oxide particulates distributed by water carrier fluid₅₀(It is hereafter considered as a "mean particle size".) It is preferred that it is 50 nm or less, and more preferably it is 30 nm or less. Usually, although the lower limit in particular is not limited, it is preferred that it is 5 nm or more.

0014It is a point which is easy to produce the photocatalyst thin film of necessary thickness, the concentration of titanium oxide particulates has preferred 0.01 - 20 mass % among dispersion liquid, and especially its 0.5 - 10 mass % is preferred.

0015- Peroxo titanium ingredient:<br />Here, a "Peroxo titanium ingredient" means a titanium oxide system compound including Ti-O-O-Ti combination, and it includes the Peroxo titanium complex generated by the reaction of peroxotitanic acid, and Ti(VI) and hydrogen peroxide.

0016In the titanium oxide system particulate dispersion liquid of the present invention, a Peroxo titanium ingredient has the operation which distributes titanium oxide satisfactorily. Concentration of a Peroxo titanium ingredient is 0.1 to 20 mass % to titanium oxide particulates. Preferably it is 0.1 to 5 mass %. The concentration becomes easy to condense titanium oxide particulates with less than 0.1 mass %. On the other hand, when 20 mass % is exceeded, the photocatalyst effect of the photocatalyst thin film obtained from the dispersion liquid may become insufficient.

0017- Iron ingredient:<br />An iron ingredient has the operation which improves the decomposition activity of the photocatalyst thin film obtained. A this iron ingredient's existence state may not be limited, for example, may be any of metallic iron, an oxide, hydroxide, a nitrate, sulfate, a halogenation thing, and a complex compound. As for this iron ingredient, it is preferred that the part is supported by the titanium oxide particulate surface at least, and it is dissolving and/or distributing other portions in dispersion liquid.

0018The content of metallic iron conversion of this iron ingredient has preferred 0.01 - 5 mass % to titanium oxide particulates, and its 0.1 - 2 mass % is especially preferred. If there is too much content of an iron ingredient, photocatalyst activity may not fully be demonstrated.

0019- Copper ingredient:<br />It has the operation which improves the decomposition activity of the photocatalyst thin film from which a copper ingredient is also obtained. A this copper ingredient's existence state may not be limited, for example, may be any of metal copper, an oxide, hydroxide, a nitrate, sulfate, a halogenation thing, and a complex compound. As for this copper ingredient, it is preferred that the part is supported by the titanium oxide particulate surface at least, and, as for other portions, dissolving and/or distributing in dispersion liquid is preferred.

0020The content of metal copper conversion of this copper ingredient has preferred 0.01 - 5 mass % to titanium oxide particulates, and its 0.1 - 2 mass % is especially preferred. If there is too much content of a copper ingredient, photocatalyst activity may not fully be demonstrated.

0021- Tin ingredient:<br />A tin ingredient has the operation which improves the visible light response of the photocatalyst thin film obtained. The tin ingredient's existence state may not be limited, for example, may be any of a metallic tin, an oxide, hydroxide, a nitrate, sulfate, a halogenation thing, and a complex compound. As for the tin ingredient, it is preferred that the part is supported by a dope or the titanium oxide particulate surface inside titanium oxide particulates at least, and, as for other portions, dissolving and/or distributing in dispersion liquid is preferred.

0022As for the tin ingredient, it is preferred to contain 1-1000 times by the molar ratio (Ti/Sn) with titanium oxide, and 5-200 are especially preferred, and more preferably they are 10-100. If the molar ratio exceeds 1000, the content effect of a tin compound is insufficient. On the other hand, if smaller than 1, a titanium oxide content rate falls and a photocatalyst effect may not be demonstrated enough.

0023&lt;A manufacturing method of visible light response type titanium oxide system particulate dispersion liquid&gt;<br />The above-mentioned titanium oxide system particulate dispersion liquid,<br />(1) The process of manufacturing the peroxotitanic acid containing a tin compound from a materials titanium compound, a tin compound, and hydrogen peroxide,<br />(2) the process which heats peroxotitanic acid solution containing a tin compound at 80-250 under high pressure, and it converts into titanium oxide particulate dispersion liquid -- and<br />(3) The process which makes an iron compound and/or a copper compound add and react to titanium oxide particulate dispersion liquid<br />It can manufacture with the manufacturing method which With.

0024- Process (1):<br />In a process (1), the peroxotitanic acid which contained the tin compound by making a materials titanium compound, a tin compound, and hydrogen peroxide react is manufactured. As a reaction method, a basic substance is added to a materials titanium compound, it is considered as titanium hydroxide and the impurities ion to contain is removed, and a tin compound is added, after adding hydrogen peroxide to make peroxotitanic acid, The method of considering it as tin content titanium hydroxide, and removing the impurities ion to contain, adding [ adds a basic substance, and ] hydrogen peroxide, and using as tin content peroxotitanic acid also by the method of using as tin content peroxotitanic acid, after adding a tin compound to a materials titanium compound may be used.

0025As the materials titanium compound used as materials at a process (1), For example, inorganic acid salt, such as chloride salt of titanium, a nitrate, and sulfate, formic acid, citrate, The titanium hydroxide etc. which were deposited by adding alkali in organic acid salt, such as oxalic acid, lactic acid, and glycolic acid, and these solution, and hydrolyzing into them are mentioned, and it may be used combining two or more kinds among these. As for especially the concentration of solution of this materials titanium compound, 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 more than 1 mass %.

0026The above-mentioned tin compound content peroxotitanic acid solution may contain alkalinity or acid things for pH control etc. As an alkaline substance, ammonia, sodium hydroxide, calcium hydroxide, etc. are mentioned and 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 as acid things.<br />In this process (1), as for the amount of the hydrogen peroxide used, although the amount of the tin compound used is as having mentioned above, it is preferred that it takes 1.5 of the number of sum total Mol of Ti and Sn - 5 times for mol. As for the reaction temperature in the reaction which adds this hydrogen peroxide and uses a materials titanium compound thru/or titanium hydroxide as peroxotitanic acid, it is preferred to consider it as 5-60 , and, as for reaction time, it is preferred to consider it as 30 minutes - 24 hours.<br />As the basic substance added in order to use a materials titanium compound as titanium hydroxide, Hydroxide of alkaline metals, such as sodium hydroxide and a potassium hydrate, or alkaline-earth metals, ammonia, alkanol amine, alkylamine, etc. are mentioned, and it is added and used in quantity which becomes seven or more about the pH of solution of a materials titanium compound.<br />As for the pH of the obtained tin compound content peroxotitanic acid solution, it is preferred 1-7, and that it is especially 4-7 in respect of the safety of handling.

0027- Process (2):<br />In a process (2), a hydrothermal reaction is presented with peroxotitanic acid solution containing a tin compound under high pressure at the temperature of 80-250 , preferably 120-250 . 80-250 is suitable for reaction temperature from a controllable viewpoint of reaction efficiency and a reaction. As a result, peroxotitanic acid is changed into titanium oxide particulates.<br />In this case, as for pressure, it is preferred the high pressure of about 0.01-4.5 MPa and that it is the high pressure of about 0.15-4.5 MPa especially, and, as for reaction time, it is preferred that they are 1 minute - 24 hours.<br />By this process (2), the titanium oxide particulate dispersion liquid containing a Peroxo titanium ingredient and a tin ingredient is obtained.

0028- Process (3):<br />An iron compound and/or a copper compound are made to add and react to the titanium oxide particulate dispersion liquid obtained at the process (2) in a process (3). The method of adding an iron compound and/or a copper compound to titanium oxide particulate dispersion liquid, and carrying out hydrothermal processing at the temperature of 80-250 also by the method of adding an iron compound and/or a copper compound to titanium oxide particulate dispersion liquid, and agitating at normal temperature as a reaction method, may be used. In this case, as for reaction time, it is preferred that they are 1 minute - 3 hours.

0029As the iron compound used as materials at a process (3), For example, inorganic acid salt, such as iron chloride salt, a nitrate, and sulfate, formic acid, citrate, Complexes, such as organic acid salt, such as oxalic acid, lactic acid, and glycolic acid, iron hydroxide deposited by adding alkali in these solution and hydrolyzing into it, and an iron tetra ammine complex, are mentioned, and it may be used combining two or more kinds among these.<br />As the copper compound used as materials at a process (3) on the other hand, For example, inorganic acid salt, such as copper chloride salt, a nitrate, and sulfate, formic acid, citrate, Complexes deposited by adding alkali in organic acid salt, such as oxalic acid, lactic acid, and glycolic acid, and these solution, and hydrolyzing into them, such as copper hydroxide and a copper tetra ammine complex, are mentioned, and it may be used combining two or more kinds among these.

0030Thus, the titanium oxide system particulate dispersion liquid obtained can be used in order to make a photocatalyst film form in the surfaces, such as various substrates, for example, an inorganic substrate like glass, and organic group material like a polyester film. In this case, a publicly known method is adopted as a formation method of a photocatalyst film, and although it may apply, it may dry and various thickness of a photocatalyst film is also selected, it is usually the range of 50 nm - 10 micrometers. In an ultraviolet region, the formed photocatalyst film has a good photocatalyst operation like [ it is transparent and ] before, and it is excellent also in a visible light response.

<p num="0031">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="0032">(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-EX" and Nikkiso Co., Ltd.).</p><p num="0033">(2) Transparency of a photocatalyst thin film<br />The HAZE value (%) of the glass board which is a substrate is measured. Next, the HAZE value of the glass board in the state where produced the photocatalyst thin film by applying dispersion liquid on the glass and drying, and it produced the thin film is measured. The HAZE value of a photocatalyst thin film is calculated from the difference. Measurement of the HAZE value used HAZE meter (a brand name "digital Haze meter NDH-200" and Nippon Denshoku Industries Co., Ltd.). The following standard estimated from the difference of the HAZE value which was able to search for the transparency of the photocatalyst thin film.</p><p num="0034">Good (O and display) .... A difference is +1% or less.<br />He is a defect ( and display) a little.... A difference exceeds +1% and it is +3% or less.<br />Defect (x and display) .... A difference exceeds +3%.</p><p num="0035">(3) Acetaldehyde gas decomposition system performance testing of a photocatalyst thin film (under visible light 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 circulation type gas decomposition quality assessment method. Specifically, it is a capacity of 12.5 cm.³It is acetaldehyde gas with a concentration of 250 ppm which installed the sample for evaluation in which the photocatalyst thin film was formed, on the substrate which consists of glass of a 5-cm square in Quartz glass cells and whose humidity it controlled in the cell at 50% of humidity Flow 5 mL-s^-1It came out, and making it circulate, it irradiated with light so that it might be set to illumination 8000LUX by the fluorescent light installed in the cell upper part. If acetaldehyde gas decomposes with the photocatalyst on a thin film, the acetaldehyde gas concentration in the gas which flows out of the cell will fall. Then, the amount of acetaldehyde gas decomposition can be calculated by measuring the concentration. Acetaldehyde gas concentration was measured using the gas chromatograph (a brand name "GC-8A", Shimadzu Corp.).</p><p num="0036">(4) Self cleaning system performance testing of a photocatalyst thin film (under visible light irradiation)<br />The decomposition reaction of oleic acid estimated the activity of the photocatalyst thin film produced by applying dispersion liquid and drying on slide glass.</p><p num="0037">The thin film surface is made to apply and dry 0.5 mass % oleic acid by a dip coater, and, specifically, the sample for photocatalyst activity evaluation is obtained. The sample is irradiated with the light of a fluorescent light by illumination 10,000LUX. If oleic acid on the thin film surface decomposes, in connection with it, hydrophilicity-ization on the surface of a thin film will take place, and a water angle of contact will become small gradually. Then, the water angle of contact on the surface of a sample is measured every other hour. The water angle of contact was measured using the angle-of-contact meter (a brand name "CA-A" and Harmony Interface Science).</p><p num="0038">[Example 1]<br />(1) After having added tin chloride (IV) in titanium chloride (IV) solution of 36 mass % so that Ti/Sn (molar ratio) might be set to 20, and diluting this with pure water 10 times, the sediment of titanium hydroxide 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 9. Addition and Decantation of pure water were repeated and deionization processing of the sediment of the obtained titanium hydroxide was carried out. 30 mass % hydrogen peroxide solution is added so that hydrogen peroxide/titanium hydroxide (molar ratio) may become 2.5 or more at the titanium hydroxide sediment after this deionization processing, and it agitated one whole day and night, and made it fully react at room temperature after that. then, the thing for which pure water is added and concentration adjustment is performed -- yellow -- transparent tin content peroxotitanic acid solution (a) and (solid content concentration 1 mass %) were obtained.</p><p num="0039">(2) Ferrous sulfate was dissolved with pure water and ferrous sulfate solution (b) of 1 mass % was obtained.</p><p num="0040">(3) teaching tin content peroxotitanic acid solution (a) 400mL obtained by (1) to the autoclave of capacity 500mL -- this -- pressure -- 200 carried out hydrothermal processing for 120 minutes 1.6 MPa. Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0041">Addition mixture of the ferrous sulfate solution (b) obtained by (2) by the titanium oxide system particulate dispersion liquid obtained by (3) is carried out so that metallic iron may serve as 0.2 mass % to titanium oxide, and hydrothermal processing is carried out at 150 for 30 minutes, The visible light response type titanium oxide system particulate dispersion liquid (A) of the present invention which 1 mass % Contains titanium oxide and 1 mass % Contains a Peroxo titanium ingredient to titanium oxide was obtained. It was 20 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0042">[Example 2]<br />(4) After having added tin chloride (IV) in titanium chloride (IV) solution of 36 mass % so that Ti/Sn (molar ratio) might be set to five, and diluting this with pure water 10 times, the sediment of titanium hydroxide 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 9. Addition and Decantation of pure water were repeated and deionization processing of the sediment of the obtained titanium hydroxide was carried out. 30 mass % hydrogen peroxide solution is added so that hydrogen peroxide/titanium hydroxide (molar ratio) may become 2.5 or more at the titanium hydroxide sediment after this deionization processing, and it agitated one whole day and night, and made it fully react at room temperature after that. then, the thing for which pure water is added and concentration adjustment is performed -- yellow -- transparent tin content peroxotitanic acid solution (c) and (solid content concentration 1 mass %) were obtained.</p><p num="0043">(5) Iron nitrate was dissolved with pure water and iron nitrate solution (d) of 1 mass % was obtained.</p><p num="0044">(6) teaching tin content peroxotitanic acid solution (c) 400mL obtained by (4) to the autoclave of capacity 500mL -- this -- pressure -- 150 carried out hydrothermal processing for 120 minutes 0.5 MPa. Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0045">The ferrous sulfate solution (d) obtained by (5) by the titanium oxide system particulate dispersion liquid obtained by (6) is added so that metallic iron may serve as 0.25 mass % to titanium oxide, The visible light response type titanium oxide system particulate dispersion liquid (B) of the present invention which is mixed, 1 mass % Contains titanium oxide, and 2 mass % Contains a Peroxo titanium ingredient to titanium oxide was obtained. It was 24 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0046">[Example 3]<br />(7) After diluting titanium chloride (IV) solution of 36 mass % with pure water 10 times, the sediment of titanium hydroxide 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 10. Addition and Decantation of pure water were repeated and deionization processing of the sediment of the obtained titanium hydroxide was carried out. 30 mass % hydrogen peroxide solution is added so that hydrogen peroxide/titanium hydroxide (molar ratio) may become 2.5 or more at the titanium hydroxide sediment after this deionization processing, and it agitated one whole day and night, and made it fully react at room temperature after that. then, the thing for which pure water is added and concentration adjustment is performed -- yellow -- transparent peroxotitanic acid solution (e) and (solid content concentration 1 mass %) were obtained.</p><p num="0047">(8) Tin chloride 5 hydrate was dissolved with pure water, and tin chloride solution (f) of 10 mass % was obtained.</p><p num="0048">(9) Peroxotitanic acid solution (e) 350mL obtained by (7) and tin chloride solution (f) 10mL obtained by (8) were taught to the autoclave of capacity 500mL, and hydrothermal processing of this was carried out for 120 minutes 150 . Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0049">The ferrous sulfate solution (d) obtained by (5) by the titanium oxide system particulate dispersion liquid obtained by (9) is added so that metallic iron may serve as 0.3 mass % to titanium oxide, The visible light response type titanium oxide system particulate dispersion liquid (C) of the present invention which is mixed, 1 mass % Contains titanium oxide, and 2 mass % Contains a Peroxo titanium ingredient to titanium oxide was obtained. It was 31 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0050">[Comparative example 1]<br />(10) Titanium oxide system particulate dispersion liquid (D) was obtained like Example 1 except not having added ferrous sulfate solution. It was 9 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0051">[Comparative example 2]<br />(11) Peroxotitanic acid solution (e) 400mL obtained by the autoclave of capacity 500mL in Example 3 was taught, and hydrothermal processing of this was carried out for 120 minutes 150 . Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0052">The ferrous sulfate solution (d) obtained by (5) by the titanium oxide system particulate dispersion liquid obtained by (11) was added so that metallic iron might serve as 0.25 mass % to titanium oxide, and it mixed, and obtained titanium oxide system particulate dispersion liquid (E). It was 30 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0053">[Comparative example 3]<br />Titanium oxide particulate dispersion liquid (F) was obtained like Example 1 except hydrothermal treatment temperature having been 60 . Since there were few amounts of creation of particles, the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was not able to be measured. In this comparative example, since the amount of generation of titanium oxide particulates was little very much, measurement of the other characteristics was not performed.</p><p num="0054">It is TiO about the binder (colloidal silica, a brand name: SNOWTEX 20 (made by Nissan Chemical Industries, Ltd.)) of a silica system to the dispersion liquid produced by Examples 1-3 and comparative examples 1 and 2.₂/SiO₂After adding by ratio 1.5, by the dip coater, it applied to glass tabular and it was dried, and film thickness formed the photocatalyst thin film which is 150 nm, and obtained the sample for evaluation.</p><p num="0055">The water angle-of-contact measurement result 5 hours after [ of irradiation ] by the fluorescent light in transparency evaluation of the reaction conditions of an example and a comparative example, a mean particle size, and a photocatalyst thin film and self cleaning system performance testing and the gas decomposition rate 90 minutes after [ of fluorescent light irradiation ] in an acetaldehyde gas decomposition examination are collectively shown in Table 1.</p><p num="0056">Unless it adds an iron ingredient so that the result of comparative example 1 may show, sufficient visible light activity is not obtained.</p><p num="0057">Unless it adds a tin ingredient so that the result of comparative example 2 may show, sufficient visible light activity is not obtained.</p><p num="0058">If reaction temperature is too low so that the result of comparative example 3 may show, the conversion to titanium oxide will become very slow.</p><p num="0059">As the result of Examples 1-3 shows, by containing an iron ingredient and a tin ingredient in dispersion liquid shows that the acetaldehyde under fluorescent light irradiation and decomposition (namely, photocatalyst activity) of oleic acid become good.</p><p num="0060"><tables num="1"><img file="WO2011145385A1_D0001.tif" /></tables></p><p num="0061">[Example 4]<br />(12) In titanium chloride (IV) solution of 36 mass %, tin chloride (IV) is added so that Ti/Sn (molar ratio) may be set to 20, After diluting this with pure water 10 times, the sediment of titanium hydroxide 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 9. Addition and Decantation of pure water were repeated and deionization processing of the sediment of the obtained titanium hydroxide was carried out. 30 mass % hydrogen peroxide solution is added so that hydrogen peroxide/titanium hydroxide (molar ratio) may become 2.5 or more at the titanium hydroxide sediment after this deionization processing, and it agitated one whole day and night, and made it fully react at room temperature after that. then, the thing for which pure water is added and concentration adjustment is performed -- yellow -- transparent tin content peroxotitanic acid solution (g) and (solid content concentration 1 mass %) were obtained.</p><p num="0062">(13) Copper sulfate was dissolved with pure water and copper sulfate solution (h) of 1 mass % was obtained.</p><p num="0063">(14) teaching tin content peroxotitanic acid solution (g) 400mL obtained by (12) to the autoclave of capacity 500mL -- this -- pressure -- 200 carried out hydrothermal processing for 120 minutes 1.6 MPa. Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0064">Addition mixture of the copper sulfate solution (h) obtained by (13) by the titanium oxide system particulate dispersion liquid obtained by (14) is carried out so that metal copper may serve as 0.2 mass % to titanium oxide, and hydrothermal processing is carried out at 150 for 30 minutes, The visible light response type titanium oxide system particulate dispersion liquid (G) of the present invention which 1 mass % Contains titanium oxide and 1 mass % Contains a Peroxo titanium ingredient to titanium oxide was obtained. It was 12 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0065">[Example 5]<br />(15) After having added tin chloride (IV) in titanium chloride (IV) solution of 36 mass % so that Ti/Sn (molar ratio) might be set to five, and diluting this with pure water 10 times, the sediment of titanium hydroxide 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 9. Addition and Decantation of pure water were repeated and deionization processing of the sediment of the obtained titanium hydroxide was carried out. 30 mass % hydrogen peroxide solution is added so that hydrogen peroxide/titanium hydroxide (molar ratio) may become 2.5 or more at the titanium hydroxide sediment after this deionization processing, and it agitated one whole day and night, and made it fully react at room temperature after that. then, the thing for which pure water is added and concentration adjustment is performed -- yellow -- transparent tin content peroxotitanic acid solution (i) (solid content concentration 1 mass %) was obtained.</p><p num="0066">(16) The cupric nitrate was dissolved with pure water and cupric nitrate solution (j) of 1 mass % was obtained.</p><p num="0067">(17) teaching tin content peroxotitanic acid solution (i)400mL obtained by (15) to the autoclave of capacity 500mL -- this -- pressure -- 150 carried out hydrothermal processing for 120 minutes 0.5 MPa. Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0068">The copper sulfate solution (j) obtained by (16) by the titanium oxide system particulate dispersion liquid obtained by (17) is added so that metal copper may serve as 0.25 mass % to titanium oxide, The visible light response type titanium oxide system particulate dispersion liquid (H) of the present invention which is mixed, 1 mass % Contains titanium oxide, and 2 mass % Contains a Peroxo titanium ingredient to titanium oxide was obtained. It was 10 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0069">[Example 6]<br />(18) After diluting titanium chloride (IV) solution of 36 mass % with pure water 10 times, the sediment of titanium hydroxide 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 10. Addition and Decantation of pure water were repeated and deionization processing of the sediment of the obtained titanium hydroxide was carried out. 30 mass % hydrogen peroxide solution is added so that hydrogen peroxide/titanium hydroxide (molar ratio) may become 2.5 or more at the titanium hydroxide sediment after this deionization processing, and it agitated one whole day and night, and made it fully react at room temperature after that. then, the thing for which pure water is added and concentration adjustment is performed -- yellow -- transparent peroxotitanic acid solution (k) and (solid content concentration 1 mass %) were obtained.</p><p num="0070">(19) Tin chloride 5 hydrate was dissolved with pure water, and tin chloride solution (m) of 10 mass % was obtained.</p><p num="0071">(20) Peroxotitanic acid solution (k) 350mL obtained by (18) and tin chloride solution (m) 10mL obtained by (19) were taught to the autoclave of capacity 500mL, and hydrothermal processing of this was carried out for 120 minutes 150 . Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0072">The copper sulfate solution (j) obtained by (16) by the titanium oxide system particulate dispersion liquid obtained by (20) is added so that metal copper may serve as 0.3 mass % to titanium oxide, Visible light response type titanium oxide system particulate dispersion liquid (I) of the present invention which is mixed, 1 mass % Contains titanium oxide, and 2 mass % Contains a Peroxo titanium ingredient to titanium oxide was obtained. It was 25 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0073">[Comparative example 4]<br />(21) Titanium oxide system particulate dispersion liquid (J) was obtained like Example 4 except not having added copper sulfate solution. It was 9 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0074">[Comparative example 5]<br />(22) Peroxotitanic acid solution (k) 400mL obtained by the autoclave of capacity 500mL in Example 6 was taught, and hydrothermal processing of this was carried out for 120 minutes 150 . Then, the reaction mixture in autoclave was discharged via the sampling pipe in the container held during 25 bathing, the reaction was stopped by cooling quickly, and titanium oxide system particulate dispersion liquid was obtained.</p><p num="0075">The copper sulfate solution (j) obtained by (16) by the titanium oxide system particulate dispersion liquid obtained by (22) was added so that metal copper might serve as 0.25 mass % to titanium oxide, and it mixed, and obtained titanium oxide system particulate dispersion liquid (K). It was 25 nm when the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was measured.</p><p num="0076">[Comparative example 6]<br />Titanium oxide particulate dispersion liquid (L) was obtained like Example 4 except hydrothermal treatment temperature having been 60 . Since there were few amounts of creation of particles, the mean particle size of the titanium oxide particulates in the obtained dispersion liquid was not able to be measured. In this comparative example, since the amount of generation of titanium oxide particulates was little very much, measurement of the other characteristics was not performed.</p><p num="0077">It is TiO about the binder (colloidal silica, a brand name: SNOWTEX 20 (made by Nissan Chemical Industries, Ltd.)) of a silica system to the dispersion liquid produced by Examples 4-6 and comparative examples 4 and 5.₂/SiO₂After adding by ratio 1.5, by the dip coater, it applied to glass tabular and it was dried, and film thickness formed the photocatalyst thin film which is 150 nm, and obtained the sample for evaluation.</p><p num="0078">The water angle-of-contact measurement result 5 hours after [ of irradiation ] by the fluorescent light in transparency evaluation of the reaction conditions of an example and a comparative example, a mean particle size, and a photocatalyst thin film and self cleaning system performance testing and the gas decomposition rate 90 minutes after [ of fluorescent light irradiation ] in an acetaldehyde gas decomposition examination are collectively shown in Table 2.</p><p num="0079">Unless it adds a copper ingredient so that the result of comparative example 4 may show, sufficient visible light activity is not obtained.</p><p num="0080">Unless it adds a tin ingredient so that the result of comparative example 5 may show, sufficient visible light activity is not obtained.</p><p num="0081">If reaction temperature is too low so that the result of comparative example 6 may show, the conversion to titanium oxide will become very slow.</p><p num="0082">As the result of Examples 4-6 shows, by containing a copper ingredient and a tin ingredient in dispersion liquid shows that the acetaldehyde under fluorescent light irradiation and decomposition (namely, photocatalyst activity) of oleic acid become good.</p><p num="0083"><tables num="2"><img file="WO2011145385A1_D0002.tif" /></tables></p>

0084The titanium oxide system particulate dispersion liquid of the present invention is adding a binder, 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, it is useful, and it is useful although a transparent photocatalyst thin film is produced especially on a high polymer film.