TWI344448B - Fibrous titanium oxide particles, production method thereof and uses of particles - Google Patents

Description

1344448 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to novel fibrous titanium oxide particles, and a method and use for the same. [Prior Art] Oxide particles and oxide particles mainly composed of titanium oxide have been widely used by their chemical properties. For example, oxidized sulphur has an appropriate bonding strength for oxygen and has a good acidity of 'senior' and thus can be used as an oxidation and reduction catalyst or carrier. Further, titanium oxide itself has a high uv shielding property, and thus can be used for a cosmetic material or a plastic surface coating agent. X, due to its high refractive index, can be used for anti-reflective coating materials to prevent light reflection. Titanium oxide, particularly non-stoichiometric titanium oxide (semi-titanium oxide), is often electrically conductive and found to be useful as an antistatic material. The use as a functional hard coat material in combination with these aforementioned properties is provided. Further, titanium oxide has other applications for antibacterial agents, antifouling agents and superhydrophilic coatings. Meanwhile, titanium oxide has a high energy band gap, and has been suitably used in recent years as a so-called photoelectric conversion material which is a photocatalyst or capable of converting light energy into electric energy. The use is further extended to, for example, a solid electrolyte of a secondary battery such as a chain battery, an argon storage material, and a proton conductive material. As described in 2, oxygenated oxygen and oxygen-doped complex oxides have a wide variety of applications and require many functions in any application. For example, 'the use of titanium oxide as a catalyst is not only required and active for the main reaction' but also exhibits selectivity, mechanical strength, heat resistance, acidity and durability of 316110 5 1344448. When used as a cosmetic material, titanium oxide needs to exhibit smoothness, soft texture and transparency, and provide UV shielding. In the case where titanium oxide is used as the material of the A t coating, it is required to include high transparency and refractive index ' and the film contains excellent film formability f, adhesion, film hardness, mechanical strength and abrasion resistance. In the above case, the applicant's patent document 1 (JP A S62-283817) discloses titanium dioxide particles and a process for preparing the same. The particles are different from the conventional titanium oxide particles in that they have a large axis L of 2 or more. Rod-shaped titanium dioxide particles having an axial D t 匕 rate (L/D length ratio). This patent document also states that such titanium dioxide particles are suitably used for hard coating films and the like. The problem to be solved by the present invention is that it is difficult to stably obtain fibrous-like particles having a L/D ratio extending in the longitudinal direction and :: or more, particularly 20 or more, by the known method. Further, even if the fibrous titanium oxide particles are produced = the specific surface area and crystallinity of the particles are liable to be lowered to cause catalytic activity or insufficient photoelectric conversion efficiency. Therefore, it is required that the fibrous titanium oxide particles have sufficient fiber length / crystallinity and can be efficiently produced. Means to solve the problem = In the case of ^, the inventor of the case studied the new _ crystallization method: really. As a result, it was found that the tubular titanium oxide particles were prepared by treating the titanium oxide sol by the heart to a night, and the heat treatment was performed to close the tubular titanium oxide particles to obtain a fibrous titanium oxide particle having a sufficiently long and 曰 property. This method has high efficiency and reproduction; 316110 6 1344448 and it is easy to control the thickness and length of the fibrous titanium oxide particles. The present invention has been accomplished based on these findings. SUMMARY OF THE INVENTION A fiber-coated titanium oxide particle according to the present invention has an average minor axis width (W) of 5 to 4 〇 nm 'average major axis length of 25 to 1000 nm 1), and an average aspect ratio of $ to 200 (L/). w). s Mysterious fibrous titanium oxide particles can be used as a catalyst, a catalyst carrier, an adsorbent, a photocatalyst, a cosmetic material, an optical material, and a photoelectric conversion material. This fibrous titanium oxide particle includes anatase type titanium oxide. Anatase has South Photocatalyst activity and excellent photoelectric conversion efficiency. In the fibrous titanium oxide particles, the sodium content is 5% by weight or less. This sodium content results in excellent catalyst properties, catalyst properties and photocatalytic properties. Μ Explosion is not known ~ General 哗 礼 铱 铱 铱 铱 铱 铱 铱 铱 铱 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在Titanium particles; made of 胶^ glue. The tubular oxidized particles are washed, followed by drying; and the particles are calcined at the temperature of coffee C. The average particle size, and the particles which are effective as titanium oxide, preferably have a diameter of 2 to i 〇〇 nm. This average particle diameter enables the particles to be stably dispersed in water to produce fibrous titanium oxide particles. The ammonium hydroxide and the organic base are preferably at least one selected from the group consisting of alkali metal hydroxides. 316]] 〇7 1344448 The oxide other than titanium oxide is preferably selected from the group Ia servant, na group, Hb group, ma group, ffib group, iVa group, lvb group two group, Vb group, Via group of the periodic table. An oxide of at least one of the elements vib, vib, VIIa and VIII*. In particular, at least one of the oxides is suitably selected from the group consisting of species Si〇2, Zr02, ZnO, Al2〇3, Ce〇2, γ2〇3, then 2〇3, w〇3, Fe^〇3, and Sb2〇5. The group of people. When such an oxide is contained, 3, obtained in a yield of 纤维), fibrous titanium oxide particles. Further, the presence of such an oxide in the fibrous oxidized particles can control the UV absorption range, dielectric constant, photocatalytic activity, proton conductivity, and solid acid properties, and can also control the thermal and chemical stability of the particles. The titanium oxide-based particles preferably contain from 5% to 50% by weight of oxides other than titanium oxide. The titanium oxide-based particles are preferably obtained by hydrolysis of peroxotitanic acid. Titanium oxide particles derived from peroxotitanic acid have a uniform particle size when dispersed

A very stable sol is obtained in water. Therefore, the fibrous titanium oxide particles β X having a thickness I and a length average can be obtained by hydrothermal treatment in the presence of a base, followed by hydrothermal treatment of the scored dispersion in the presence of an acid. The hydrothermal treatment in the presence of an acid neutralizes the test used and can also neutralize and remove the infiltrated human particles, and the resulting fibrous titanium oxide particles contain a small amount of alkali metal. The photovoltaic cell according to the present invention contains fibrous titanium oxide particles as a semiconductor film component. The catalyst according to the present invention contains fibrous titanium oxide particles. Effect of the Invention 316110 8 ^344448 : Only UV shielding effect and smoothness, texture and transparency Rong 2! Ming's fibrous titanium oxide particles are superior to the conventional oxidation. In the case of the coating material, it is excellent in film formability = formation of a coating film having high transparency and refractive index, and excellent adhesion, film mechanical strength and abrasion resistance. Therefore, the fiber emulsified particles of the present invention can be used as a catalyst, a catalyst carrier, an adsorbent, a photocatalyst, a cosmetic material, an optical material, and (4) conversion (4). In the present invention, a sol comprising water-dispersed cerium oxide particles and/or oxidized oxidized particles is used as a source of titanium oxide having a specific particle diameter within a specific range. Therefore, it is not necessary to calcine at a high temperature to crystallize the titanium oxide source. The fibrous titanium oxide particles produced according to the present invention are obtained in a high yield, - having a small aggregate of ' and having a particle shape. Fibrous oxidized t-batch often contains oxides other than oxidized oxime and also has a small amount of residual genus. Therefore, the present invention provides a high aspect ratio and can be used as a functional material such as a catalyst, a catalyst carrier, and an adsorbent 'photocatalyst. Method for Producing Fibrous Titanium Oxide Particles of Cosmetic Materials, Optical Materials, and Photoelectric Conversion Materials [Embodiment] Preferred Embodiments of the Invention Hereinafter, fibrous titanium oxide particles, a method for producing the same, and use of particles will be described in detail. First, fibrous titanium oxide particles are discussed. [Fibrous Titanium Oxide Particles] The fibrous titanium oxide particles have an average small axial width (w) of 5 to 40 nm, preferably 8 to 30 nm, 316110 9 "344448". The average small axis width refers to the average fiber thickness of the fibrous oxidized granules. In the fibrous titanium oxide particles, the small axis (W) is in the range of the average small axis width ± 〇 2 ', preferably ± 〇, for the entire particle length. That is, the small axis width of the particles is uniform. The specific surface area of the fibrous titanium oxide particles having the above small axis is suitable as a catalyst carrier or an adsorbent. When the small axial width (trade) of the fibrous titanium oxide particles falls below the above range, the production of such particles becomes difficult. On the other hand, although the fibrous titanium oxide particles can be produced in a small axial width (w) larger than the above range, the fibrous titanium oxide particles cannot sufficiently exhibit their properties. For example, the L-list area becomes so low that the particles may not be able to be replenished when used as a catalyst or a catalyst carrier. Further, a film made of fibrous titanium oxide particles having a large small draw width may easily cause voids, and the film may have low adhesion to the substrate and poor transparency. The fibrous titanium oxide particles have an average major axis length of from 25 to 1 〇〇〇 nm, preferably from % to _nm (1 〇. The major axis length refers to the longitudinal length of the fibrous oxygen. 1 fibrous titanium oxide particles have 5 to 2 〇〇, preferably 1 〇 to the aspect ratio (L/W). = All-purity (in the above range, the fibrous oxidized granules) has sufficient fiber length to achieve the substrate A smooth film with high adhesion and high strength. In addition, it can prevent cracking when forming a film with a large thickness. 316110 IT344448 If the average major axis length (L) falls below the above range, then fibrous oxidation...; The fiber length exhibits a reduced adhesion to the substrate and a low degree of film. Further, 'the crack may occur when the film is formed with a large thickness. When the average major axis length (L) exceeds the above range, the fibrous oxidation When granulating, a film having poor surface smoothness is obtained, and depending on the coating technique, for example, 'in screen printing' sometimes causes poor coating properties. Therefore, it is based on (4) Sex, transparency, strength and thickness uniformity The titanium oxide particles having an aspect ratio falling within the above range have a fiber shape. The particles having the vertical rank ratio exhibit high adhesion to the substrate and obtain a film having high strength. ° ▲ When the aspect ratio (L/W) When it exceeds the above range, the production of such particles may become difficult. Even if it is obtained, the fibrous titanium oxide particles are excessively long and entangled in the formation of secrets, resulting in an increase in the number of filaments and poor coating. Properties (depending on the coating technique). Therefore, the formed film becomes insufficient in adhesion to the substrate, transparency, strength, and thickness uniformity. Titanium oxide having a length ratio (L/W) of less than 5 The particles are too short to have a fiber shape. The film produced from the particles causes a decrease in adhesion to the substrate and a decrease in film strength. The average small axis width (W) and the average large axis length (L) are averaged by transmissive The data of the (9) particles obtained by the electron micrograph are determined separately. The crystal form of the fibrous titanium oxide particles may be in the form of 316110 1344448 which may be used for the titanium oxide. Specific examples include amorphous, sharp , rutile and slab mineral shape. Titanium oxide is not limited to Ti 〇 2 and may be a non-stoichiometric (sub-oxide type or reduced type) titanium oxide having the formula Ti 〇 n (where n is less than 2). Part of the oxygen atom may be replaced by nitrogen. In the present invention, it is particularly preferred to be anatase titanium oxide. Compared with amorphous, rutile and brookite titanium oxide, the sharp titanium oxide has superior catalytic properties. , catalyst carrier properties, adsorption properties, photocatalytic properties, and photoelectric conversion properties. The sodium content in the fibrous oxidized granules may vary depending on the application, but is, usually, (M wt% or less, preferably 〇〇 1% by weight or for photoelectric conversion such as photocells, the nano content is preferably 0.001% by weight or less. When the nano content of titanium exceeds °, 1% by weight, the fibrous oxidation = sub-display Reduced Catalyst Performance, Catalyst Carrier Performance, Photocatalyst Depression Fig. 1 is a micrograph illustrating the invention in accordance with the present invention. The electron of the fibrous titanium oxide particles of the present invention is produced by the fibrous titanium oxide particles of the present invention. j is explained by the method described below to describe the method according to the present invention. [Production method of fibrous titanium oxide particles] [Method for producing fibrous titanium oxide particles] The method for producing fibrous titanium oxide particles according to the present invention includes 3J6J10 12 ΙΓ 344448 ^ Preparing a tubular oxidized particle of titanium oxide or titanium oxide and another oxide dispersion of the oxide of the oxide as the main particle; washing the tubular titanium oxide particles, followed by drying; and at 3 50 to 9 〇〇 The particles were calcined at a temperature of °C. Preparation of particles mainly composed of cerium oxide In the present description, first, particles mainly composed of titanium oxide as a raw material of tubular titanium oxide particles are produced. The official titanium oxide particles are prepared by hydrothermal treatment of an aqueous dispersion of particles mainly composed of titanium oxide in the presence of a base. In the present invention, the raw material may include a single titanium oxide particle 'a complex oxide oxide particle mainly composed of oxidized and another oxide, or a combination of the two. · " In this Qiming, the oxide oxide particles and the titanium oxide-based complex oxide particles are collectively referred to as titanium oxide-based particles. The particles mainly composed of the raw material titanium oxide preferably have an average particle diameter of 2 to 1 Å, preferably 5 to 80 nm. When the titanium oxide-based particles have the above-mentioned diameter, a stable dispersion can be obtained when dispersed in water. Therefore, a higher yield can be obtained by producing tubular titanium oxide particles (precursors of fibrillar cerium oxide particles) from particles of bismuth-deposited titanium. Further, the obtained tubular titanium halide particles have excellent dispersion properties. The average particle size of 2 nm is difficult to obtain the scatter of water-dispersed particles. The average particle size of iGGnm is not able to further increase the yield of tubular yttrium titanium and to monodisperse to a higher degree of tubular oxidation. 316110 F^44448 2 does not provide better wire. Conversely, the average particle size of the excessive dance is prolonged by the time required to produce the particles of the raw material titanium oxide. The present invention generally uses a dispersion of the aforementioned particles in water. An organic solvent such as an alcohol may be added as needed. The concentration of the titanium oxide-based particles in the aqueous dispersion is not particularly limited to 1 ', but is preferably from 2 to 5 % by weight based on the oxide. Further, it is 5 to - when the particles mainly composed of titanium oxide have the above concentrations, the titanium oxide particles can be prepared in a high yield and in a state of being stably dispersed. When the concentration is less than the above range, the amount of the base added is also decreased, so that the synthesis of the tubular titanium oxide is prolonged to cause a decrease in the yield, resulting in inefficiency. The same concentration as in the above range tends to cause water-dispersed titanium oxide-based particles to be unstable or aggregate in the sol. The raw material may include a single titanium oxide particle, a titanium oxide-containing oxide oxide particle containing titanium oxide and another oxide, or a combination of the two. The oxide other than oxidized oxime is preferably selected from the group consisting of la, Ib, Π a, π b, gua a, mb, IVa, IVb, %, Vb, Via, An oxide of at least one element of the group consisting of VIb, vna, and νιπ. Specific examples thereof include SiO 2 , ZrO 2 , ZnO, Al 2 〇 3, Ce 02, Y 2 〇 3, Nd 2 〇 3, W 〇 3, Fe 203, Sb 205, Cu 〇, AgO, AuO, Li 20 , SrO, BaO and pu 〇 2 . The use of such additional oxides promotes the synthesis of tubular titanium oxide particles. The theory of this promotion is not well understood but can be assumed to be due to the fact that 14 316110 IT344448 can inhibit the specific knot of titanium oxide particles when the other oxide is alkali soluble.

The growth of the Ba surface causes the dissolved oxide to adsorb to the titanium oxide particles. Even if the other oxide is insoluble in alkali, the titanium oxide dissolves and sinks as described above; I can synthesize the official titanium oxide particles. The insoluble oxide remains in the most, as the obtained fibrous titanium oxide particles. Thus, a complex oxide comprising fibrous oxidized particles having a solid acid catalytic functionality and ion exchange performance can be obtained. At least one oxide other than titanium oxide is suitably selected from the group consisting of SiO 2 ,

Zr02 ZnO, Al2〇3, Ce02, γ2〇3, Nd2〇3, w〇3, 0 and Sb>2〇5 group. When such an additional oxide is used, the fiber can be obtained in high yield.

Titanium oxide particles. Further, the presence of the remaining oxide can control the UV absorption range 'dielectric constant, photocatalytic activity, proton conductivity, and solid acid property', and can also control the enthalpy and chemical properties of the obtained fibrous titanium oxide particles. The complex oxide particles used in the present invention preferably contain from i to 50% by weight, preferably from 2 to 25% by weight, of the oxide (8) other than the titanium oxide. Having any smaller amount of additional oxides and the use of separate oxidations and the difference between '', ', and shell' use of oxides other than titanium oxide has no effect. When the amount is larger, the amount of titanium oxide is relatively decreased to lower the rate of the fibrous titanium oxide particles, which sometimes leads to the failure of the production of the fibrous titanium oxide particles. The preparation method of the dispersion is particularly limited. However, it is advantageous to use the titanium oxide sol and titanium oxide disclosed in the applicant's 316110 15 '1344448 JP-A-S62-283817 > JP-A-S63-185820 ^ JP-A-H02-255532 The complex oxide sol. An exemplary manufacturing method is as follows. Hydrogen peroxide is added to the dioxin, or 4 rubber towels are used to make the material. The obtained material is mixed with a titanium oxide sol, a oxychloride gel, an inorganic oxide sol other than cerium oxide or an inorganic hydroxide sol other than nitrous oxide, followed by heating. In the present invention, the particles mainly composed of the raw material titanium oxide are preferably derived from peroxygen (iv). The particles derived from titanium oxide of peroxotitanic acid have a particle size of a uniform sentence and form a stable sol when dispersed in water. For example, an aqueous dispersion (sol) of titanium oxide-based particles can be prepared by the following steps (a) and (b). (a) a step of preparing a titanic acid gel or a sol; or first, hydrolyzing a compound by a conventional method to form a titanic acid sol orthotitanate gel can be obtained by U(IV), such as a titanium salt such as titanium cyanide, Titanium sulphate or titanyl sulphate is dissolved in the "liquid" and then washed. Dissolved in water, and then added to neutralize the water-soluble ortho-titanic acid. By dissolving the water of the titanium salt to remove the anion, the smog is caused by six s. The eagle is replaced by the water in the middle of the day to obtain the water and the organic solvent ==: titanium tetraethoxide, tetraethanol or titanium tetraisopropoxide in water to obtain the water. The above neutralization or hydrolysis bamboo

Preferably, the pH of the 7 to H servant 仏 化合物 compound solution is ~, * 钦 compound solution has a pH outside this range, m (four) becomes pure and insoluble in the hydrogen peroxide solution towel. Therefore, 316110 16 1344448 oxygen, the synthesis of titanium particles becomes difficult, and the yield of fibrous titanium oxide particles, particularly crystalline fibrous titanium oxide particles, may be lowered. , "neutralization or hydrolysis is preferably carried out at a temperature of from 〇 to 4〇〇c, particularly preferably from 〇 to 3〇t. Neutralization or hydrolysis at a temperature outside this la is liable to cause the fibrous titanium oxide particles to be 'specially 疋The yield of the crystalline fibrous oxidized chin particles is lowered. The gel or the ruthenium acid particles in the melt are preferably amorphous. (b) preparation step of sol of titanium oxide fine particles of water knife θ, '', 'man', adding ortho titanate gel or sol, or a mixture thereof with hydrogen peroxide to dissolve orthotitanic acid, thereby preparing peroxygen An aqueous solution of titanic acid. The aqueous peroxotitanic acid solution is then aged at a high temperature to obtain a sol of water-dispersed titanium oxide fine particles. In the preparation of an aqueous solution of peroxotitanic acid, it is preferred to heat the ortho-titanate or the sol, or a mixture thereof, at about 5 (rc or above or with stirring as needed). When ortho-titanic acid has a too high concentration It is often the case that ortho-titanic acid needs to be dissolved for a long time to become a precipitate of an insoluble gel; or the obtained titanium peroxide is viscous in an aqueous solution. Therefore, the Ti〇2 concentration is preferably about ι 重量% or more. Smaller, more preferably about 5% by weight or less. The amount of hydrogen peroxide added is such that the weight ratio of H2〇2/Ti〇2 (positive titanic acid in terms of Ti〇2) becomes 1 or more. When hydrogen peroxide is added, the orthotitanic acid can be completely dissolved. The weight ratio of hOVTiO2 becomes less than}, and the unreacted gel or sol remains without completely dissolving the orthotitanic acid. The larger the ratio of H2〇2/Ti〇2 The faster the dissolution rate of orthotitanic acid and the shorter the reaction time. However, the excessive use of hydrogen peroxide will only cause the unreacted portion to remain in the reaction system, which is uneconomical. When using hydrogen peroxide in the aforementioned amount When, 316110 rhino 344448 orthotitanic acid dissolves in about 0.5 to 20 hours The sol of the titanium peroxide aqueous solution is aged at a temperature not lower than that of the thief to serve the sol of the water-dispersed titanium oxide fine particles. The aging may be in the presence of a hydrogen peroxide and/or an organic test at 5 g to 3 At the temperature of the soil = ^ 2 thief, the titanium oxide fine-grain phase of the water-dispersed water is applied by hydrothermal treatment. The organic test used here is better than the hydrazine hydroxide and/or the organic test. The dispersion has a normal temperature of 8 to 14', more preferably 10 to 13.5. (4) When the hydrothermal treatment is carried out at the above temperature and the pH of the dispersion, the fibrous titanium oxide particles of the final coating are easily higher. In the crystallinity and production, in the production of Γ) and (b), titanium hydride fine particles can be used as the titanium compound 2 to prepare an aqueous solution of peroxotitanic acid, followed by formation of a water-dispersed oxidized zirconia sol. In the above examples, the titanium hydride fine particles are simply dispersed in water to take the formation method of the orthotitanate gel or sol in the step (a). The titanium hydride fine particles are preferably dispersed in water at a concentration of about 1% by weight or less, more preferably about 5% by weight or less, based on Ti〇2. In the case where titanium hydride and 'field particles are used in place of orthotitanic acid, hydrogen peroxide is added in an amount such that the weight ratio (calcium hydroxide based on Ti 〇 2) becomes ??? or more. In this case, the aqueous dispersion of the titanium hydride fine particles may be about 5 Torr. 〇 or above or can be heated under stirring as required. When an aqueous dispersion 3161J0 1344448 (sol) of titanium oxide-based complex oxide particles is to be obtained, it can be manufactured by a series of steps, including: adding a titanic acid gel or a sol, or a mixture thereof Mixing hydrogen peroxide to dissolve orthotitanic acid; mixing the obtained aqueous solution of peroxotitanic acid with inorganic compound particles other than titanium (such as cerium oxide particles, cerium oxide sol, alumina particles or zirconia particles) or alkoxy decane a metal alkoxide or a salt of a salt such as zirconium chloride or magnesium hydride, followed by heating; and, as in step (b), in the presence of ammonium hydroxide and/or an organic base at 50 to 300 ° C, preferably At a temperature of 80 to 250 ° C, hydrothermal treatment of the mixture is carried out as needed. Preparation of Tubular Titanium Oxide Particles The sol of the above-prepared water-dispersed titanium oxide-based particles was then subjected to hydrothermal treatment in the presence of a base to synthesize tubular titanium oxide particles. The synthesis mechanism of the tubular titanium oxide particles has not been fully clarified, but it can be assumed that the titanium oxide is repeatedly dissolved and precipitated in the presence of a base to cause selective growth of the crystal in one direction. An exemplary test consists of a metal hydroxide, a hydrogen peroxide, and an organic test. The alkali metal hydroxide comprises LiOH, NaOH, KOH, RbOH, CsOH, and mixtures thereof. Particularly suitable are NaOH, KOH and mixtures thereof due to the high yield of tubular titanium oxide particles. The amount of the metal hydroxide to be used is preferably such that the alkali metal hydroxide (AM) in the dispersed oxide oxide particles (TM) is a molar ratio of TiO2 to the TiO2 (AM). ) / (TM) becomes 1 to 30, more preferably 2 to 15. 19 316110 1344448 In the case of molar ratio, it is effective to produce tubular titanium oxide particles when the alkali metal hydroxide contained therein satisfies the above ratio. When the molar ratio (AM)/(TM) is less than 1, the crystallization of the oxide particles of the titanium oxide particles or the cerium oxide-based complex is caused (it is too difficult. The production of the SU匕' fibrous titanium oxide particles is sometimes Conversely, when the molar ratio (AM) / (tm) exceeds 3 Q, the excessive increase of the plate-like titanium oxide particles tends to lower the yield of the precursor crystalline titanium oxide particles. The alkali metal hydroxide emulsified ammonium and/or organic base is substituted or used together in the hydrothermal treatment. Examples of the organic base include a quaternary ammonium salt such as a tetramethylammonium salt, a hydroxide, and an amine. Such as monoethanolamine 'diethanolamine and triethanolamine. When replacing metal oxychloride, 'the amount of substitution material is the same as alkali metal hydroxide. When ammonium hydroxide and / or organic base is combined with alkali metal hydroxide, The preferred amount of these is such that the total amount of alkali metal hydroxide (AM) and ammonium hydroxide and/or organic base (OBM) is Tier 2 (TM) molar ratio (AM) + (〇BM) / (TM) becomes 1 to 30, more preferably 2 to 15. Mobi (AM): (OBM) should be 0: 1 to 1: 1, 〇: i to 0.5 : 1. ^ The combined use of ammonium hydroxide and/or an organic base tends to result in a decrease in the alkali metal content of the finally obtained fibrous titanium oxide particles. Therefore, the fibrous titanium oxide particles may suitably It is used as a catalyst or a photocatalyst. In the present invention, the hydrothermal treatment of the sol of the water-dispersed titanium oxide-based particles 316110 20 ^ 344448 in the presence of the test is carried out at 5 Torr to 35 Torr, preferably at a temperature. The above temperature of 8 〇 to 25 〇t enables the hydrothermal treatment to synthesize tubular titanium oxide particles with sub-efficiency of less than 5 (the hydrothermal treatment temperature of TC causes the human-to-length extension of the f-shaped titanium oxide particles, and the yield is lowered. m more than 3 catching liquid treatment temperature can not further increase the crystalline tubular rate or yield and the material is caused by (four) heat energy. 1 sub-amplifier. If necessary, can be washed and dried as described above. The particle cleaning method is not particularly limited as long as it can reduce the content of the metal, etc.: The exemplary cleaning method includes a conventional filter cake, ultrafiltration, ion father resin replacement, electrodialysis and reading, and Cleaning. Money. It is possible to use tubular oxidized granules which have been treated with an acid such as hydrochloric acid or hydrothermal solution to have a content of 5% by weight or less, preferably 〇. 〇5, by weight, or less, in terms of Na2 。. ΰ or less, particularly preferably (10), the aqueous dispersion of the official titanium oxide particles thus prepared is preferably subjected to hydrothermal treatment in the presence of an acid. The acid used herein may be selected from inorganic acids such as hydrochloric acid and stone. Chamoic acid, a mixture of organic acids such as acetic acid, oxalic acid, citric acid, r-butyric acid, glycidic acid, malonic acid and maleic acid, and the like. Hydrothermal treatment in the presence of acid can significantly reduce the content of the test. At the same time maintain a high degree of crystallinity. Gate 316110 21 1344448 The amount of acid used is preferably such that the acid (PM) in the oxide particles (TM) of the titanium oxide particles or the oxidized complex is the molar ratio (ρΜ) / (τΜ) of the butyl group. It becomes 1 to 30, more preferably 2 to 15. Also, the amount of acid used is preferably a dispersion? 11 becomes about 2 to 6, more preferably about 3 to 5. The hydrothermal treatment temperature is the same as in the first example. The hydrothermal treatment can be repeated as needed. The tubular titanium oxide particles which have been subjected to hydrothermal treatment in the presence of an acid have a Na2〇 content of 100 ppm or less. The tubular titanium oxide particles produced as described above generally have a tube diameter (D〇ut) of 5 to 5 〇 _, a tube diameter (Din) of 4 to 30 nm, a tube thickness of 〇 5 to 2 〇 nm, 25 to 〗 The tube length (L) of 〇〇〇(10), and the tube length (L) of 5 to 2 (9) to the outer tube diameter (Dout). The outer tube diameter (D〇Ut), the inner tube diameter (Din), and the tube length (l) are obtained by averaging the data of one particle obtained by a transmission electron microscope image. The inner tube diameter (Din) can be determined based on a circle inside the circle defining the diameter of the outer tube and a circle having a boundary with respect to the apparent portion (which is hollow inside). The thickness of the tubular titanium oxide particles depends on the size of the titanium oxide particles used, the degree of solidity, the amount of the test, the temperature, the reaction time, and the like. These conditions can be appropriately controlled to obtain a desired thickness. Field Calcination Step Next, the tubular titanium oxide particles are washed and dried as required, and then at 350 to 900. (:, preferably 5 〇〇 to 75 〇χ: the temperature is calcined. The calcination at this temperature causes the tubular and hollow titanium oxide particles to be closed, thereby forming fibrous titanium oxide particles. 316Π0 22 Ϊ 344448 when decompressed When calcination is preferably carried out under vacuum, a titanium oxide having a higher crystallinity can be obtained at a lower temperature. A calcination temperature lower than 350 ° C may not convert the tubular oxide particles into a fibrous shape. Particles. Even if the conversion occurs, the obtained fibrous oxidized granules may not have sufficient catalytic ability and semiconductor properties. The calcination at a temperature exceeding 900 C causes sintering, and the obtained fibrous titanium oxide particles become non- It is porous and has a low specific surface area. The calcination time is not particularly limited as long as the tubular oxidized particles are converted into fibrous titanium oxide particles. Usually, the calcination time is from 〇5 to the calcination temperature. 'When the calcination temperature is within the above range, the fibrous titanium oxide particles of Ruiqin = will be obtained. Usually, the k-type is converted to rutile by forging k at a temperature higher than the temperature of Saki or higher. Titanium oxide. However, the titanium oxide prepared by the above method is calcined in a selective manner to form anatase titanium oxide particles having a south crystallinity. In the calcination, the tubular titanium oxide particles shrink and the inner cavity is hollow. The diameter of the outer tube of the granules is also strongly contracted (but the shrinkage occurs throughout the particles). The fibrous titanium oxide particles can be used as functional materials such as materials and photoelectric conversion materials. Catalysts, decant materials, Optical material [Use] The photovoltaic cell according to the present invention has a titanium oxide particle. The structure of the photovoltaic cell is the same as that of the fiber structure of the two-conductor film component, but the semiconductor film 316110 23 1344448 contains fibrous titanium oxide particles. For example, in the fibrous titanium oxide of the present invention, the particles may be suitably used in place of the anatase titanium oxide particles or in a mixture with the ruthenium oxide granules. For example, the inventors of the present invention, JP, Hi i-339867 and JP_A_2〇 〇〇_77691 The gold of the exposed light battery belongs to the oxide semiconductor. In addition to the semiconductor film, the aforementioned fibrous titanium oxide particles can also be suitable. It is used in a film for white or titanium oxide particles. Examples of such a film include a thin film photocatalyst and a polarizing film. The fibrous titanium oxide particles of the present invention have high aspect ratio and high crystallinity, so that they can be formed with high strength and A film that is excellent in the properties of the semiconductor and the semiconductor. The film usually includes fibrous titanium oxide particles and a binder component. For example, it can be obtained by mixing fibrous titanium oxide particles, binder components, dispersion, mussels and selection. The film forming aid is formed to form a coating liquid, and then the coating liquid is applied and then dried, and the resulting film is heated to cure. Examples of the binder component include colloidal particle dispersions such as cerium oxide sol, alumina sol and titania sol, resin binders, and hydrolysis products of organic hydrazine compounds. Exemplary coating methods include conventional dip coating, spin coating, spray coating, roller coating, fast drying printing, screen printing, and spray spraying. After the application, the coating film is cured by heat, UV irradiation or the like to form a film. Further, the fibrous titanium oxide particles may be used as a catalyst carrier as they are or formed into pellets, spherical 'plates or honeycombs. The fibrous titanium oxide particles have the catalytic activity inherent in titanium oxide. 316110 24 1344448 Particles, spheres, and energy. In this case, the particles may be used as a catalyst either by themselves or in the form of a sheet or honeycomb. High photocatalytic activity. However, the VIIA of the periodic table, the metal and/or the metal oxide, and the fibrous titanium oxide particles themselves are also suitable for supporting at least one of the group, the group IB and the group b and the rare earth element. An active ingredient.

Specific examples of Ru La active ingredients include Mn, Tc, Rp c 〇 n, Ke, Fe, Co, Ni

Metals and/or metal oxides of Rh, Pd, 〇s, Ir, Pt, Cu, A s u Zn, Cd, Hg, e, Pr, Nd and Pm. The catalyst according to the present invention can be used to catalyze various reactions including partial oxidation of oxygen, desulfurization, denitrification, and photocatalytic reaction. The present invention will be described in more detail by the following examples, and the invention is not limited to the embodiments. [Example 1] Preparation of dispersion of titanium oxide particles (T-1) The aqueous solution of titanium oxide was diluted with pure water to a concentration of 5% by weight based on Ti〇2. This aqueous solution was added to ammonia water having a temperature controlled at a concentration of 5 2 to 15% by weight to be neutralized and hydrolyzed. The pH after the addition of the aqueous solution of titanium oxide was 10.5. Next, the gel formed was filtered and washed to obtain a titanic acid gel having a concentration of 9% by weight based on butyl phthalate. 100 g of orthotitanate gel was dispersed in 2900 g of pure water' and 8 g of a 35 wt% hydrogen peroxide solution was added to the suspension. This mixture was heated at 85 ° C for 3 hours under a mixture to form an aqueous solution of peroxotitanic acid. The concentration of TiO 2 in the aqueous solution of peroxotitanic acid was 0.5% by weight. 316110 25 1344448 The dispersion of this aqueous solution was then heated at 95 °C. Next, the dispersion liquid is oxidized to the oxidized granules, 149.2) and mixed to make oxygen; ^ tetramethyl hydrazine (the temperate, the molar ratio becomes _. The score == treatment -: two: post-titanium oxide The average particle size of the particles (T-1) is shown in the table. The titanium oxide bismuth cold liquid makes the molar ratio (AMVCTM) of the alkaloid metal hydroxide (AM) to Ti〇2(TM) 1 ( Then, it was hydrothermally treated for 2 hours in the 15th generation. The obtained particles were then thoroughly washed with pure water. The residual % 2% by weight. Then the particles were passed through a cation exchange resin to reduce the octabase 3. Thus, the precursor was prepared. (Through titanium oxide particles (ρτ_ 1 shows residual content of tubular titanium oxide particles (ΡΤ·!), average particle, length 'average outer tube diameter, average inner tube diameter, average particle length / average outer tube diameter ratio, and ratio Surface area. _ After the TC, the precursor tubular titanium oxide particles (ρτ_υ dried for 1 hr) and then at 65 (TC 椴 for 3 hours to obtain fibrous oxidation (FT-1). Analysis of fibrous titanium oxide particles ( FT-1) to determine the average small axis width, average large axis length, aspect ratio And the specific surface area, and also analyzed by a 1 ray detector to determine the crystallinity. The results are shown in Table 1. 316110 26 1344448 Fig. 2 is a set of fibrous titanium oxide particles obtained in the examples of the present invention. High-resolution transmission electron micrograph (FT-1) and electron beam diffraction pattern. As shown by the electron beam diffraction pattern, titanium oxide is highly crystalline. The third layer is used as a group of the present invention. High-resolution transmission electron micrograph and electron beam diffraction pattern of tubular titanium oxide particles (PT·) of the precursor of the fibrous oxidized granule (FT)), as shown by the electron beam diffraction pattern, oxidized Titanium is an anatase with poor crystallinity. For the photocell (C-1U竿), 10g of titanium oxide fine particles are suspended in 2L of pure water. The suspension is added with 800 § of 5 wt% hydrogen peroxide solution for 30 minutes. Then, the mixture was heated to 80 ° C to produce a peroxotitanic acid solution. The fibrous titanium oxide particles (FT-1) were dispersed in a dispersion medium to a concentration of 1 G% based on the oxide. Titanium particles (ft•(10) dispersion and bonding The above-prepared peroxyacid solution of the precursor of the component component is mixed to make the weight ratio of the perovskite (tetra) fibrous titanium oxide particles (the peroxytitanic acid/fibrous titanium oxide particles (FT_1}) to 〇ι Further, a coating solution for forming a semiconductor crucible is prepared by adding a propyl methacrylate having an amount of 3% by weight of an oxide as a film-forming auxiliary agent. Next, the coating solution is applied to have a transparent glass plate of an electrode layer formed by fluorine-doped tin oxide. After the coating layer is naturally dried, a low-pressure mercury lamp (4) v of 6 mm/cm 2 is used, and peroxytitanic acid is decomposed and solidified to decompose the hydroxypropyl fiber. The coated film was annealed at 3001 for 30 minutes at 316110 27 1344448 to form a metal oxide semi-V body film (sc-ι) having a thickness of 15 mm. The pore volume and average pore diameter of the metal oxide semiconductor film (SC-1) were determined by nitrogen adsorption. The results are shown in Table 2. Then 'make the photo-sensitive complex, specifically cis (2,2-double D-biti-4,4'-dihydro acid) 钌(n) dissolved in ethanol to 3x l (T4mol Concentration of /L.... The photosensitizer solution was applied to a metal oxide semiconductor film (SCM) by an rpml rotator and dried. The step of drying after coating was repeated five times. Adsorption on a metal oxide semiconductor The amount of the photosensitizer on the film is shown in Table 1. (1) The syrup is mixed with acetonitrile and ethylene carbonate in a volume ratio of 1.4 to acetonitrile to form a solvent. And 峨 are dissolved in the solvent by "〇.46m〇1/L and 0.06m〇1/L (4) to obtain an electric solution. The transparent glass plate with electrodes prepared as above is configured to face with gas-doped tin oxide The transparent glass plate supporting the electrode is sealed with the resin and the electrolyte solution prepared above is sealed between the electrodes, and the electrode is connected to the electrode to prepare a photovoltaic cell (c_丨). The solar simulator is 100W/ M2 intensity light illuminates the photocell (called measurement I (open circuit voltage short circuit current density), ff (filled) Number) and (conversion efficiency). The results are not shown in Table 2. [Example 2], the sub-slave fibrous titanium oxide (FT ·)) prepared Xi ^ \

Preparation of precursor tubular oxidized particles I 1 316110 28 ^44448 in the same manner as in Example 1.

The stem of Ti〇 is made to have a ratio of 0 to 1 with respect to the ear and the ear. The pH measured at this stage is 3.0, at 190. (: The dispersion was subjected to hydrothermal treatment of the tubular titanium oxide particles (PT_2). The results of Table 1 show that the residual titanium oxide particles (ΡΤ_2) are called 〇 content, the average particle length is 'average outer tube diameter, and the average Tube diameter, average particle length / average outer tube diameter ratio, and specific surface area. Thereafter, the precursor tubular titanium oxide particles (1 > D 2 ) were calcined at 8 rc for 1 hr and then calcined at 650 C for 3 hours. The fibrous titanium oxide particles (FT-2) were obtained to analyze the fibrous titanium oxide particles (FT_2) to determine the average small axis width, the average major axis length, the aspect ratio and the specific surface area, and were also obtained by a χ-light diffractometer. The crystallinity was measured by the analysis. The results are shown in Table 1. The photocell (C-2) was prepared and evaluated according to the procedure described in Example 1, but the fibrous titanium oxide particles (FT-2) were used instead. The results are shown in Table 2. [Example 3] Preparation of fibrous titanium oxide particles (FT-3) Disperse titanium oxide particles (P25, Degussa 'average particle diameter: 3 〇 nm;) in dispersion medium In order to reach a concentration of 5% by weight of Ti〇2. Combine 112g of dispersion with 7〇g of 40% by weight of 1^<:^ aqueous solution such that the molar ratio (AM)/(TM) of the alkali metal hydroxide (AM) to Ti〇2(TM) becomes 10, followed by 29 316110 1344448 150 The solution was hydrothermally treated for 2 hours. The resulting particles were then thoroughly washed with pure water. The residual NaaO concentration was % by weight. Next, the particles were passed through a cation exchange resin to lower the alkali content thereof. Thus, the precursor tubular titanium oxide was prepared. Particles (PT-3). Table 1 shows residual Na2〇 content of tubular titanium oxide particles (ρτ_3), average particle length, average outer tube diameter, average inner tube diameter, average particle length/average outer tube diameter ratio, and specific surface area. Thereafter, the precursor tubular titanium oxide particles (PT-3) were dried at 80 ° C for 1 〇 small 4, and then calcined at 650 C for 3 hours to obtain fibrous cerium oxide particles (FT-3). The titanium oxide particles (FT-3) were measured for the average minor axis width, the average major axis length 'aspect ratio and the specific surface area, and were also analyzed by a χ-light diffractometer to determine the crystallinity. The results are shown in Table 1. Preparation of light K (C-3) Preparation and evaluation of light by the procedure described in Example 1 Pool (C-3), but using fibrous titanium oxide particles (FT-3). The results are shown in Table 2. [Example 4] Preparation of the material particles (T-4V> liquid by the example 1 The procedure described is to prepare a 380 〇g aqueous solution of peroxotitanic acid. The concentration of TiO2 in an aqueous solution of peroxotitanic acid is 〇.5% by weight. Then the aqueous solution is combined with 7.0 g of cerium oxide sol (SI-350, catalyst and Chemical Industry Co., Ltd., Si〇2 concentration: 30% by weight, average particle size: 8 nm). 30 316110 1344448 = 'When this mixture is heated at 95 ° C for 3 * to obtain a knives of titanium oxide and cerium oxide composite particles (T-4) having a concentration of * 0.56 liters of 〇 1 〇 2 and Si 〇 2 Political liquid. The average particle diameter of the composite oxide particles (τ_4) is shown in Table 1. Titanium tablets are prepared early. a dispersion of the composite oxide particles (T-4) and 70 g of a 40% by weight aqueous solution of Ν_, such that the metal hydroxide (AM) is trained to 2 (top) Mo Er ratio (AM) / (TM) Become 1〇, then 15〇. 〇 Treat with hydrothermal fluid for 2 hours. The resulting particles were then thoroughly washed with pure water. The residual sputum concentration is 1.5 weight %. Then, the particles were passed through a cation exchange resin to reduce the low, and the alkali 3 was used. Thus, tubular titanium oxide particles were prepared. The & titanium oxide particles (pT_4_I) were dispersed in water to achieve a weight of 5 wt··〇ι〇2 ′. Next, citric acid as an organic acid is added to the dispersion so that its molar ratio with respect to Ti〇2 becomes 〇1. At this stage, the pH was measured to be 3.0. Thereafter, the dispersion was subjected to hydrothermal treatment for 5 hours at 丨9〇乞 to obtain tubular titanium oxide particles (ρτ_4_2). Table 1 shows the residual Na2〇 content of the tubular titanium oxide particles (ρτ_4_2), the average particle length 'average outer tube diameter, the average inner tube diameter, the average particle length / the average outer tube diameter ratio, and the specific surface area. Thereafter, the official titanium oxide particles (?τ_4_2) were dried for 8 hours and then at 700. (: Forging for 3 hours to obtain fibrous titanium oxide particles (FT-4). The fibrous titanium oxide particles (FT_4) were analyzed to determine the average small-axis width, and the average large-axis length 'aspect ratio and specific surface area' were also The crystallinity was measured by χ_light diffractometer. 316110 31 1344448 The results are shown in Table 1.

#. Ray Pool (C-4) Process A Photocell (c_4) was prepared and evaluated by the procedure described in Example 1, but using fibrous titanium oxide particles (FT-4). The results are shown in Table 2. [Example 5] A composite oxide particle (T-5) dispersion was prepared, and 38 g of an aqueous solution of peroxotitanic acid was prepared by the procedure described in Example 1. The concentration of Ti〇2 in the aqueous solution of peroxotitanic acid was 0.55% by weight. This aqueous solution was combined with 15.8 g of cerium oxide sol (SI_35 〇, catalyst and chemical industry company σσ, SiO 2 concentration: 30% by weight, average particle diameter: 8 nm). Thereafter, the mixture was brought to 95. (: heating for 3 hours to obtain a dispersion of titanium oxide and cerium oxide composite particles (τ_5) having a concentration of 〇62% by weight of Ti〇2 and si〇2. The average particle diameter of the composite oxide particles (Τ_5) is shown in In the table, the turtle JUL titanium oxide particles rFT-su y is combined with the composite oxide particles (τ_5) dispersion and 70g of 40 weight ° / 〇 NaOH aqueous solution to make the alkali metal hydroxide (A) ^) to Ti 〇 ^ TM The molar ratio becomes 10, followed by 15 (rc is hydrothermally treated for 2 hours. Then the resulting particles are thoroughly washed thoroughly, and the residual concentration is 2 〇 weight / 〇, then the particles are passed through the cation exchange resin. The alkali content is lowered. The tubular titanium oxide particles (PT-5-1) are prepared in this manner. The official titanium oxide particles (PT-5-1) are dispersed in water to achieve a 浪2 wave of 5% by weight. Adding the citric acid as the organic acid to the dispersion "mole ratio relative to Tl 〇 2 becomes 〇. 1. The pH of 316110 32 1344448 measured at this stage is 3 〇. After that, the dispersion is made at 19 〇〇c was treated with hydrothermal fluid for $hour to obtain tubular titanium oxide particles (PT-5-2). Table 1 shows tubular Residual Na2〇 content of titanium particles (PT-5-2), average particle length, average outer tube diameter, average inner tube diameter, average particle length/average outer tube diameter ratio, and specific surface area. The particles (PT-5-2) were dried at 80 ° C for 10 hours, and then calcined at 75 (TC for 3 hours to obtain fibrous titanium oxide particles (FT-5). The fibrous titanium oxide particles (FT-5) were analyzed to The average small axis width, the average major axis length, the aspect ratio and the specific surface area were measured, and the crystallinity was also measured by a χ-light diffractometer. The results are shown in Table 1. [Comparative Example 1] Shame titanium tweezers (RT-1) After the mashing, the titanium oxide particles prepared by the procedure described in Example 1 were dried overnight, and then calcined at 6,000 C for 2 hours. The titanium oxide particles were finely ground to an average particle diameter of 20 nm. Then, fine titanium oxide particles were dispersed in water to obtain a dispersion of titanium oxide particles (RT-1) having a Ti〇2 concentration of 10% by weight. Fibrous titanium telluride particles (RFT-η y monument combined with titanium oxide particles (RT-1) dispersion and 7〇g of 40% by weight NaOH 7 The jc solution is such that the molar ratio (AM) / (TM) of the metal hydroquinone (am) to Ti02 (TM) becomes 10, followed by hydrothermal treatment for 2 hours at i5 ° C. Then fully with pure water The obtained particles were washed, and the residual Na2〇 concentration was 2.5% by weight. Then, the particles were passed through a cation exchange resin to reduce the amount of the titanium oxide particles (RPT-ll) by decreasing the amount of 316110 1344448. 吏B ^Oxide The particles (PRT_ 1 -1) were dispersed in water to achieve 5% by weight of Tl〇e2 ♦ degrees. Then, citric acid as an organic acid is added to the dispersion so that the molar ratio of / to Tl 〇 2 becomes 〇". The pH measured at this stage was 3, 〇. Thereafter, the dispersion was allowed to stand at 19 Torr. The crucible was treated with hydrothermal fluid for $hour to obtain tubular titanium oxide particles (RPT-1-2). Table 1 shows the residual Na2〇 residual average particle length, average outer tube diameter, average inner tube diameter, average particle length/average outer tube diameter ratio, and specific surface area of the tubular titanium oxide particles (RPPU). Thereafter, the precursor tubular titanium oxide particles (Rpn _2) were calcined at 8 (Γ (1: dry for 1 hr) and then calcined at 650 ° C for 3 hours to obtain fibrous titanium oxide particles (RFT-1). The particles (rFT_丨) were measured for the average minor axis width 'average large axis length' aspect ratio and specific surface area, and the crystallinity was also measured by an x-ray diffractometer. The results are shown in Table 1, and the crystallinity was Amorphous 'that is, 'this titanium oxide is low crystalline anatase titanium oxide. Preparation of photocell (RC-1) According to the procedure described in Example 1, the photovoltaic cell (RC-1) was prepared and evaluated, but the fiber was changed. Titanium oxide particles (RFT-1). The results are shown in Table 2. [Comparative Example 2] Preparation of composite vaporized particle (RT-2) dispersion. Composite oxide particles prepared according to the procedure described in Example 4 ( Τ-4) The dispersion was dried, and then calcined at 600 ° C for 2 hours. The obtained composite oxide particles were finely ground to an average particle diameter of 300 nm, and 34 316110 1344448 was used to disperse the composite oxide fine particles.水中ι〇2 and Si〇2 with a weight of 1% by weight in water a dispersion of composite oxide particles (RT_2). The fibrous titanium oxide is mixed with a composite oxide particle (foot _2) dispersion and 7 〇g of a 4% by weight aqueous NaOH solution to cause alkali metal hydroxide The molar ratio (AM)/(TM) of the material (AM) to Ti〇2 (TM) was 1 Torr, followed by treatment with 15 (rc for 2 hours in hot liquid), and then the obtained particles were sufficiently washed with pure water. The concentration is then 5,0% by weight. Next, the particles are passed through a cation exchange resin to lower the alkali content thereof. Thus, the tubular titanium oxide particles (RPm) are prepared ^ Disperse the official titanium oxide particles (PRT_2_丨) The concentration of Ti 〇 2 in water is up to 5% by weight. Then, the citric acid as the organic acid is added to the dispersion, so that the molar ratio to Tih becomes 〇. The pH measured at this stage is 3.0. Thereafter, the dispersion was subjected to 19 (Γ: treatment with hydrothermal fluid for 1 hour to obtain tubular titanium oxide particles (RpT_2_2). 曰 Table 1 shows residual Na2〇 of the tubular titanium oxide particles (RPT-2-2) , average particle length, average outer tube diameter, average inner tube diameter, average particle length / average outer tube After the diameter ratio ' and the specific surface area. After drying, the tubular titanium oxide particles (RPT-2-2) were dried at 8 Torr for 10 hours, and then calcined at 65 (TC for 3 hours to obtain fibrous titanium oxide particles (RFT-2). The fibrous titanium oxide particles (RFT_2) were analyzed to determine the average small axis width, the average major axis length 'aspect ratio and specific surface area, and the crystallinity was also measured by a χ-light diffractometer. The results are shown in Table 1. The crystallinity is amorphous, that is, the cerium oxide is low crystalline anatase 316110 35 1344448 titanium oxide. [Comparative Example 3] Fibrous titanium oxide particles were produced by the method disclosed in Example 1 of JP-A-S62-283817. More specifically, titanium sulfate was dissolved in ion-exchanged water to obtain an aqueous solution having a concentration of 0.4% by weight based on Ti〇2. To the aqueous solution, 15% by weight of aqueous ammonia was gradually added under stirring to give a white aqueous solution having a pH of 8.5. Over; consider the slurry to clean the filter, cake. As a result, a titania cake having a solid concentration of 9% by weight was obtained. A mixture of 5.55 kg of cake and 60 6 kg of 33% hydrogen peroxide solution and 13.4 kg of water was combined. The resulting mixture was heated at 8 〇. To get 254 containing 2. 4% by weight plus 2 titanium dioxide solution. This titanium oxide solution was brownish yellow and had a pH of 8". Next, 9 kg of a titanium oxide solution, 13 〇g of a silica gel having a particle size of 7 #m and a particle concentration of 15% by weight, mixed with 19 water, and then heated at 6 C for 6 G hours to obtain a milky white transparent Colloidal solution. The colloidal solution was concentrated by vacuum evaporation, and then calcined at 801 for 10 hours and then calcined at 650 C for 3 hours to obtain titanium oxide particles (RFT-3). The titanium oxide particles (RFT_3) produced, precipitated, cut, and quasi-shaped were measured for crystallinity by measuring the average minor axis width, aspect ratio, and specific surface area by X-ray diffractometry. The results are shown in the table! in. Like olive; Τίΐ ί 显 7 ^ fibrous titanium oxide particles (RFT · 3) are long and SiO shape and ancient, fibrous titanium oxide particles (RFT-3) containing 9.8 wt% 1 brother Qin mine, crystal structure, However, compared with the first embodiment, the junction 316110 36 1344448 has a low crystallinity. The photovoltaic cell (RC_3) was prepared and evaluated according to the procedure described in Example 1, but the fibrous titanium oxide particles (RFT_3) were used instead. The results are shown in Table 2. [Simple description of the diagram] Figure 1 is a set of transmission electron microscope images. Fig. 2 is a high-resolution transmission electron micrograph and electron beam diffraction pattern of a group of fibrous titanium oxide particles obtained in Example i. Fig. 3 is a diagram showing the paleo-resolution transmission electron micrograph and electron beam diffraction pattern of a tube of the **^ s-shaped porous titanium particles obtained in Example 1. <Net 316110 37 1344448 Comparative Example 3 Comparative Example 2 Comparative Example 1 Example 5 Example 4 Example 31_i Example 2 Example 1 CO β Η· 〇〇ΙΟ Ν; CO Η Η* Η· 〇ο Ν) ru Η······················· ΚΩ Ο Ο Ι-* 00 cp cn ♦-* Ο ο ND 00 〇〇h-* Ο ο l·-· Ο Ο μ-&gt; 〇〇h-» 〇〇 Composition LO ο ο Ο Ο 1-* ro UJ CJ CO 1 i Average 1 particle size i nm h-* »-* 〇CP ο Ln Ο Ln 0 (_n 〇cn concentration weight % 1 1 NaOH NaOH NaOH NaOH j NaOH NaOH ; 1 NaOH 瘃ίΆ Γ*0 1 t —· η M ι~· μ-* Ι-» 1 Am/Tm Moore ratio 1 14 or more 14 or more 14 or more Ό X 1 I—» o »-» tn Ο h-» CP 〇μ-* Ln ο fj cn 0 h-* Cji 〇f—» LT 〇1 temperature °c 1 ro h〇ro ro N) ro 03 nr life 1 cn o ro LP ro o «—» (J1 H-1 »—&gt;〇&gt;X) 0 VD 1 Na 2〇% by weight after washing 1 oo 〇o 〇o ο 〇1 0 ro cn 0 0 h-1 CJ1 IE 1 Resin Na2〇% by weight 1 1600 1 1100 en Ln CJ U&gt; 1 'Chloric acid treated Na2〇 ppm , 1 1 00 1 CTi to 1 1 1 M〇x Weight % 38 3)6110 1344448 ss^. ^效窆一

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Claims (1)

Patent Application No. 93,322,862, April 18, 100, revised, replacement page, April, next day, revision of the tenth, application for patent garden: L A fibrous titanium oxide particle, which has a closed internal cavity, "to 4 - Average minor axis width (w), 25 phantom _(10) $ average major axis length (L), and an average aspect ratio of 5 to 200 (0), as in the patented scope item 1, fibrous titanium oxide particles, wherein The particles include anatase type titanium oxide. /, 3. The fibrous titanium oxide particles according to claim 1 or 2, wherein: the content of sodium is 〇"% by weight or more 4. A method of producing fibrous titanium oxide particles having a closed internal cavity. The method comprises: dispersing a water containing titanium oxide or a complex of another compound of oxide in a hydrothermal solution in the presence of a hydrothermal solution. a sol of the main particles of titanium oxide to prepare tubular titanium oxide particles; washing the tubular titanium oxide particles, followed by drying; and calcining the tubular titanium oxide particles at a temperature of 350 to 9 Torr to shrink the tubular titanium oxide particles To close its internal space 5. The method of claim 4, wherein the oxidized capsule-based particles have an average particle diameter of 2 to 1 〇〇 nm. 6. The method of claim 4 or 5, wherein The test system is selected from the group consisting of alkali metal rolled products, ammonium hydroxide and organic bases. 7. As in the method of claim 4 to 6 &quot; The oxide system is at least one selected from the group consisting of the group of the periodic table, the ib group, the na group, the nb group, the ma group, the mb group, the group IVa, and the 316110 (revision) 41 1344448 Patent No. 93,922,862, filed Apr. Correcting the oxides of the elements of the group consisting of the Vila and IVb, Va, Vb, Via, and v and Vin families. The method of items 4 to 7 wherein the =2 oxidation The system is selected from the group consisting of _, ring, Sh η 2 3 e〇2, Υ2〇3, Nd2〇3, W03, Fe203, and Sb2〇5. 9. In the scope of claims 4 to 8 = the particle contains .... weight, two = 卜, the method of the oxygen per 4th 9.5th item - wherein the particle of u is hydrolyzed by peroxotitanic acid The winners of the second and fourth paragraphs of the fourth to the tenth, after the treatment, the resulting dispersion is then treated with hydrothermal solution under acid storage. 12 kinds of it batteries, including the patent scope The fibrous titanium oxide particles according to any one of items 3 to 3 are those having a semiconductor film component. The type of the catalyst is a fibrous titanium oxide particle according to any one of the above claims. Revised version) 42