TWI230688B - Aqueous dispersion of Titanium oxide and preparation thereof - Google Patents

Abstract

An aqueous dispersion of titanium oxide comprising a chloride ion and at least one Bronsted base other than chloride ion, preferably at least one Bronsted base selected from a nitrate ion and a phosphate ion. Preferably, the titanium oxide contained in the aqueous dispersion is predominantly comprised of a Brookite type titanium oxide. The aqueous titanium oxide dispersion is prepared by hydrolyzing titanium tetrachloride in the presence of at least one Bronsted base. A titanium oxide film formed from the aqueous titanium oxide dispersion has excellent photocatalytic activity, transparency, and adhesion to a substrate.

Description

l23〇688

Technical Field (Please read the notes on the back before filling this page) a * This invention is about titanium oxide sol, titanium oxide thin film formed on the surface of ceramic, plastic and other substrates using this sol, and titanium oxide sol The manufacturing method also relates to a method for manufacturing titanium oxide particles using the sol. The titanium oxide film is transparent, has excellent photocatalytic activity, and has good adhesion to a substrate. BACKGROUND ART Titanium dioxide (hereinafter referred to as "titanium oxide") is known to exist in three crystalline phases: anatase, brookite, and rutile. In the gas phase method, which is produced by a mixed combustion method of titanium tetraoxide and oxygen, it is generated at the lowest temperature, and stable titanium oxide is an anatase type. It can be heat treated and further calcined to obtain brookite-type titanium oxide at 816 ~ 1,040. When it is further exceeded, it can obtain rutile-type titanium oxide (Physical and Chemical Dictionary) 3rd edition, ρ 514 ~ 515) 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the manufacture of titanium oxide based on the liquid phase method, for example, Zhou Muhaoyou Youmen had once mentioned The crystalline phase of titanium oxide produced by the hydrolysis of aqueous titanium oxide solution has been reported in detail (Industrial Chemistry, Vol. 59, No. ii, p. 1295 (1956)). According to the conclusion of the report, rutile-type titanium oxide is mainly produced from a high-concentration solution, and anatase-type titanium oxide is produced from a low-concentration side. This shows that it is impossible to generate brookite-type titanium oxide in the liquid phase, even particulate titanium oxide. Since the raw material is titanium tetraoxide, it is needless to say that chloride ions coexist in the obtained titanium oxide. From these reports, it has been judged that by now, the plate titanium has been stably manufactured by the liquid phase method. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). 4 1230688 A7 B7 V. Description of the invention (2 = titanium oxide still Difficult. Although "the above-mentioned method uses titanium dioxide to form brookite-type titanium dioxide at high temperature by using gas phase method", but because this method uses heat treatment, it is very difficult to record. " The product of 3L crystal of Qin Mine. Said another-Fang®, about the formation of titanium oxide sol 4, is generally the following: dispersed or amorphous titanium oxide particles in the dispersant or mixed in the dispersant Titanium alkGxide, titanium sulphate, titanium tetrachloride and other precursors of titanium oxide are used to form sols by means of hydrolysis and hydrolysis. Titanium oxide sols can be used in the manufacture of titanium oxide powders on the one hand, or on the other hand It can be used to coat sol on glass, plastic, etc. to form a thin film of oxidized fishing. Titanium oxide is an optical semiconductor. It is known that when the particle size is small, it will produce transparency and improve photocatalytic function. About The photocatalytic function of titanium oxide has been actively researched and developed in recent years. Specific examples of the use of this photocatalyst include removal of harmful substances to prevent pollution, deodorization of malodorous gases such as ammonia, and sterilization of bacteria According to the purpose of its use, titanium oxide is in the form of a variety of large-volume particles, films, and sols. Most of the time when transparency is added to such titanium oxide products using photocatalytic functions, it is exclusively used for films. To this end, Titanium oxide is used as a film-forming material in the form of a sol. Regarding the photocatalytic ability of titanium oxide, the anatase type is considered to have a greater capacity than the rutile type. The reason is due to the energy gap between the two. The difference between the rutile type is 3.02eV and the anatase type 3.23eV is about 0.2eV (Tao Yanxue 31 (1996) No. 10, P · 817). Due to this energy difference, it is suitable for the paper size China National Standard (CNS) A4 Specification (2) 0 X 297 mm (Please read the notes on the back before filling out this page) · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-T _ Intellectual Property Bureau of the Ministry of Economic Affairs Employee spending 1230688 A7 ____B7 _ printed by the company. V. Description of the invention (3) High-energy-interval anatase-type titanium oxide is suitable for use as an optical semiconductor. However, with regard to the brookite type, examples of elemental substances that have been taken out so far are very rare. And the particles are sintered because it is manufactured at a high temperature, and it is impossible to obtain microparticles with a specific surface area that can be used as an optical semiconductor (photocatalyst), so that it is completely impossible to see its use as a photocatalyst. In terms of the use of thin films, recent lighting appliances have proposed, for example, coating titanium oxide sol on the glass tube of a fluorescent lamp and its cover to form a thin film, and organic matter such as oil fume is attached to the glass lamp. When the tube and the cover are on, it is decomposed by photocatalysis to prevent the contamination of the glass tube and the cover. However, when the sol obtained in the aforementioned method is used to form a thin film, it is rarely able to become a highly transparent film; in particular, conventional techniques have not taught the use of a brookite-type oxide beverage film as a photocatalyst for lighting appliances and the like. When used to form a titanium oxide film on glass, plastic and other substrates as a photocatalyst, the film is required to have high catalyst activity. Since the photocatalysis is a reaction on the surface of the particle, in order to have high activity, the particle is preferably a particle having a south specific surface area. When a film is further formed on a lighting fixture or the like, the film must also have transparency. In order to form good transparency, as in the case of catalyst activity, titanium oxide is also required to be fine particles; and it is preferable that primary particles are dispersed. In response to this problem, the Department of Knowledge focuses on the use of miniaturization of anatase-type titanium oxide as a response. When forming a titanium oxide film on a substrate, it is necessary to make a good adhesion between the film and the substrate so that the film cannot be easily peeled off. (Please read the precautions on the back before filling out this page) Order VI -1.

1230688

V. Description of the invention (4) In the conventional method for hydrolyzing titanium tetraoxide, it is difficult to obtain a titanium oxide sol having a very small particle diameter and having excellent crystallinity when forming a thin film. In the hydrolysis of titanium alkGxide compounds, although the titanium oxide in the sol lacks the characteristics of forming very small particles such as fine particles; it is quite excellent, but compared to titanium tetraoxide, titanium alkoxide compounds it's very expensive. Disclosure of Invention Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

In view of the above-mentioned conventional technology, the object of the present invention is to provide an excellent photocatalytic function and transparency when the titanium oxide sol is applied to various substrates to form an oxide film on the surface of the substrate. Titanium oxide, which has good adhesion between the film and the substrate, and a thin film formed by a sol, and a method for producing titanium oxide particles from the sol. The present inventors have conducted various studies on a titanium oxide thin film formed of a titanium oxide sol, and found that it is preferable that the titanium oxide sol has gas ions and other (bronsted base) other than gas ions;% acid Either one or both of ions and scaly acid ions are co-existed. At this time, properties such as transparency of the film, adhesion between the substrate and the film can be improved, and brookite The titanium oxide containing titanium oxide as a main component has a photocatalytic performance equal to or more than that of anatase titanium oxide, thereby completing the present invention. According to the present invention, a titanium oxide sol containing chloride ions and other Bronsted bases other than chloride ions is provided. Here, the so-called "Bronsted test" means the proton acceptor in the Bronsted acid theory. (Please read the precautions on the back before filling this page)-+ 1-This paper size is applicable to the national standard (CNSM4 specification⑵G X 297) 7 1230688 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5. DESCRIPTION OF THE INVENTION (5) Next, according to the present invention, a titanium oxide thin film formed on the surface of a substrate using the titanium oxide sol described above is provided. Furthermore, according to the present invention, there is provided an article coated with the above-mentioned titanium oxide sol on the surface of a substrate. Furthermore, according to the present invention, there is provided a feature that hydrolyzes titanium tetragas in the presence of at least one selected from the group consisting of Bronsted acids, and contains at least one Bronsted base other than gas ions and gas ions. The above titanium oxide sol manufacturing method, particularly a titanium oxide sol manufacturing method in which titanium oxide particles containing brookite-type titanium oxide are dispersed; and a method characterized by being obtained from a titanium oxide sol manufactured by such a manufacturing method Titanium oxide particle production method. Furthermore, according to the present invention, there is provided a feature in which titanium tetragas is added to hot water at 75 to 100 C, and in the presence of either one or both of nitrate ions and acid ions, at 75 〇c ~ The temperature range of the solution's boiling point is one or both of gaseous ions, nitrate ions, and phosphate ions hydrolyzed by tetrakisditanium, and titanium oxide particles mainly composed of brookite-type titanium oxide are dispersed. A method for producing the resulting titanium oxide sol; and a method for producing titanium oxide particles characterized by the titanium oxide sol produced by the production method to obtain titanium oxide particles containing brookite-type titanium oxide. Brief Description of the Drawings Fig. 1 is a schematic cross-sectional view of an example of a suitable reaction device used in the production of the titanium oxide sol of the present invention. -n. ^ 1 ϋ ϋ I ϋ ϋ fe I < ϋ I (Please read the notes on the back before filling this page) I.

l23〇688 _____B7_____ 5. Description of the invention (6) The best mode for implementing the present invention (please read the precautions on the back before filling out this page) The titanium oxide sol of the present invention contains aerosols and is selected from other than chloride ions At least one type of Bronsted base, and the thin film formed by the sol not only has excellent photocatalytic function, but also has excellent adhesion and transparency to the substrate. The Bronsted base contained in the titanium oxide sol of the present invention is preferably selected from the group consisting of nitrate ion, phosphate ion, pyrophosphate ion, metaphosphate ion, polyphosphate ion, acetate ion, and organic acid ion, and particularly suitable It is selected from the group consisting of nitrate ion and phosphate ion. These Bronsted bases are included alone or in combination of two or more. As the organic acid, metasulfonic acid, ethylsulfonic acid, dodecylbenzenesulfonic acid, propanesulfonic acid and the like are suitable. The amount of the aforementioned Bronsted base contained in the titanium oxide sol is not just the amount existing in equilibrium in the solution 'but it means the absolute amount of ions present in the system. The amount of this 4-ion g is preferably 50 to 10,000 ppm, and more preferably 100 to 4,000 ppm. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The dispersant of titanium oxide sol is usually water or a mixture of water and organic solvents. In the method of hydrolyzing titanium tetragas to obtain a titanium oxide sol, hydrogen chloride is generated through a reaction. In the obtained sol, almost all gaseous hydrogen was dissociated into gas ions and hydrogen ions. Most of the hydrogenated gas will escape from the system during the hydrolysis reaction under heating. Furthermore, if the sol contains vaporized hydrogen, titanium oxide powder can be produced from the sol or various obstacles can occur in the manufacture of the titanium oxide film; therefore, when a certain degree of gasification remains in the sol due to the hydrolysis reaction, In the case of hydrogen, it is very common to apply a degassing treatment to make the sol free of vaporized hydrogen as much as possible. However, the paper size in the conventional technology is applicable to the Chinese National Standard (CNS) A4 specification (21〇X 297g t)-" " ---- l23〇688 A7 V. The invention description (7) is not considered The influence of the gas ions in such a sol on the characteristics of the titanium oxide film (please read the precautions on the back before filling this page). Therefore, from this point of view, the technology to control the gas ions in the sol does not exist. The inventors have found that if such chloride ions are contained in the sol, the titanium oxide film formed by the core gel has a high photocatalytic effect and excellent adhesion to the substrate; as a result, it has been found that In addition, when at least one of other Bronsted bases such as nitrate ions and phosphate ions coexist, the transparency and adhesion of the film are better, thereby completing the present invention. Although the reason for this has not yet been determined, it is conceivable that the condensation reaction occurs on the surface of the titanium oxide particles due to the co-existence of the acid catalytic effects of nitric acid and phosphoric acid, which improves the film-forming property of the coating film and the adhesion to the substrate. In a titanium oxide sol, chloride ions and at least one or more ions selected from the Bronsted test other than chloride ions (hereinafter, gas ions and other Bronsted bases are collectively referred to as "gas ions and the like" ") If the coexistence is good, but in order to improve the adhesion of the titanium oxide film formed on the substrate to the substrate, the total amount of gas ions and the like should be more than 50% melon. When forming a thin film, the adhesion is improved by containing gas ions of 50 ppm or more. Conversely, if the amount of gas ions and the like in the sol increases and the total I printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs exceeds 10,000 ppm, the transparency of the film will deteriorate. Among the above ranges, a particularly suitable range is from 10,000 to 4,000,000 ppm. The ratio of Bronsted bases to chloride ions other than chloride ions is not particularly limited, and their total amount can reach a wide range of 0.1 to 200 mols with respect to moore ions. Also, surprisingly, by controlling the chloride ions within the aforementioned range and the application of this paper size_CNS A4 size ⑵G x 297 issued) ------ A7 B7 Description of the invention (8 The amount of Bronsted base other than chloride ion can form brookite type titanium oxide. The reason is not certain. Titanium oxide containing this type of ocher crystal and rutile m anatase only The coating film has excellent transparency and photocatalytic activity compared with the oxide of the crystalline type or titanium oxide containing both the rutile type crystal and the anatase type crystal. In particular, the content ratio of the brookite type crystal Although it is not particularly limited, it is preferably 10 to 100% by weight, and the effect will be more significant if it contains 50 to 100%. Although the effects of the above-mentioned gas ions and the like are uncertain, the reasoning is that In the titanium oxide sol, the electrical repulsion between the particles of the titanium oxide particles is increased, so that the particle has a good knife property, which results in such good results as transparency and peel strength. Photocatalysis of thin, titanium oxide films The higher the effect, the better the transparency. However, due to the manufacturing difficulties associated with obtaining fine titanium oxide particles, the titanium oxide particles in the sol are, in terms of the average particle diameter of the primary particles, 0.001. The range of ~ 〇 丨 is in the above-mentioned titanium oxide sol. In order to further improve the photocatalytic function and transparency of the thin film formed by the sol, the average particle diameter is 0.001 ~ 0.1 / zm and the specific surface area is 20 A sol formed by dispersing a titanium oxide particle composed mainly of brookite-type titanium oxide having a mass of m2 / g or more in a mixture of water and an organic solvent is preferred. The conventional method for obtaining brookite-type titanium oxide is not Only the heat treatment method by anatase-type titanium oxide as described above; and when the brookite-type titanium oxide particles obtained by the heat treatment are used as the thin film, because of the heat treatment, the paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) ------- *-、 —— (Please read the notes on the back before filling out this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11 1230688 V. Description of the invention (9 ratio (Using sintered particle control will be larger than 4 & 1, ㈣ is completely unusable. T curved in the emulsified titanium sol of Ben Sheming, if the oxide particles in the sol = :, then the particles will agglomerate, and the sol will not The stability of titanium oxide particles is too low, for example, when forming a thin film, problems such as the time-consuming process of coating the sol will occur. Due to various conditions, the concentration of rolled titanium particles in the titanium oxide sol (containing The amount is suitably from 0.05 to 10 moles. The titanium oxide sol of the present invention can be obtained by general methods such as filtering, washing, drying, and the like. The average particle diameter of the particles is based on the primary particles. 0.01 ~ 〇 .. The particles obtained from a titanium oxide sol composed mainly of brookite-type titanium oxide have an average particle diameter of 〇〇 丨 ~ 〇. ^ # M, and a specific surface area of 20 m2 / g or more is preferable. . When a titanium oxide sol is used for the formation of a thin film, a small amount of a water-soluble polymer, for example, about 10 to 100,000 () ppm may be added to the sol in order to improve the film-forming property of the thin film. Suitable as water-soluble polymers are polyvinyl alcohol, methyl cellulose, ethyl cellulose, CMC, and starch. The hafnium oxide sol of the present invention can be coated on a substrate of various materials, shaped bodies, and the like to form a titanium oxide film on the surface of the substrate. Ceramics, glass, metals, plastics, wood, paper, etc. are used as the substrate, and they can be used without any restrictions. These substrates may be painted articles. A catalyst carrier made of alumina, oxidized oxide, or the like may be used as the base material, and a catalyst carrying a titanium oxide film may be used as the catalyst. In addition, if the paper size such as fluorescent lamp is applicable to the Chinese National Standard (CNS) A4 (210x297 mm) -------------- (Please read the precautions on the back before filling in this Page) Order ---

nnn ϋ I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 12 1230688 A7 V. Description of the invention (10) The glass and its plastic lampshade printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are oxidized as the base material and oxidized Converging the film, the film is not only transparent, but also has photocatalytic properties. This can effectively prevent the pollution of glass and lampshades by preventing organic matter such as oil fume. Furthermore, if a titanium oxide film is formed on the building glass and glass, it can also prevent pollution. Therefore, it can be used for window materials and wall materials of high-rise buildings, making cleaning operations unnecessary and reducing building management costs. . — When coating titanium oxide sol on the substrate, the method of immersing the substrate in the sol, the method of misting the solvent, and the method of applying the sol to the substrate by bristles can be used. It is appropriate that the application amount of the sol is made into a liquid thickness of 0 to 0 to 0.2 mm. After coating, the film can be obtained by drying and removing moisture, and it can also be used as it is for applications such as catalysts. When the substrate is made of a heat-resistant substance such as metal, ceramic, glass, etc., it can be sintered after the titanium oxide film is formed, thereby making the film more firmly adhere to the substrate and increasing the hardness of the film. . The sintering temperature is preferably 200 C or higher. The upper limit of the sintering temperature is not particularly limited. Although it is appropriate to set it according to the heat resistance of the substrate, an excessively high temperature can no longer improve the hardness of the film and its adhesion to the substrate. Therefore, the appropriate one is Up to 800 ° C. When a brookite-type titanium oxide is used as the main material, the crystal size is 700 to maintain the crystal shape. (: Sintering at the following temperature is preferred. Particularly suitable is a titanium oxide sol containing chloride ions and phosphate ions due to the hydrolysis of titanium tetragas in the presence of phosphate ions, and 200 Å without adding a binder. Low sintering temperature above 500 ° C but less than 500 ° C, which can form excellent adhesion to the surface of heat-resistant substrates such as glass and stainless steel. This paper applies Chinese National Standard (CNS) A4 (210 X 297). %) (Please read the notes on the back before filling this page) Order ----- s'. -1 · 13 1230688 A7

V. Description of the invention (11) The film of hardness and hardness printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The atmosphere during sintering is not particularly limited, and it may be in the atmosphere. There is no limitation on the sintering time, for example, it may be performed in the range of 丨 to ⑼ minutes. In the case where the thickness of the titanium oxide film is the aforementioned coating amount, it is 0.05 to 10 mm. Furthermore, the transparent film formed of the titanium oxide sol of the present invention is used to make a stronger article. In order to improve the adhesion to the substrate, an appropriate adhesive can be added to the titanium oxide sol. As the adhesive, for example, an organic silicon dioxide compound such as alkyl sincate is suitable. Although the amount to be added is not particularly limited, the case of an alkyl silicate is converted to g in% of the titanic acid sol in the titanium oxide sol of the present invention. If the added amount is less than the working weight, ^, the effect of the addition of a deadening agent is very low. On the other hand, if it exceeds 50% by weight, the adhesion strength to the substrate becomes very strong, but the titanium oxide particles are completely covered with the elixirs, which weakens the photocatalytic ability. The method of adding the binder is based on the nature of the binder, it is appropriate to select or mix it immediately before film formation, or to form a mixed state in the sol in advance, and there is no problem with the effect of the present invention. The adhesive-containing film is preferably not sintered, and sintering is also acceptable. The titanium oxide thin film produced by using the titanium oxide sol according to the present invention is crystalline, and the titanium oxide fine particles are very fine particles and contain no impurities, and the titanium oxide fine particles are not limited to the primary particles being nearly dispersed, so light The catalytic ability and transparency are high, and especially titanium oxide mainly contains (for example, 50% by weight or more) brookite-type titanium oxide, and its catalytic ability is higher. Next, the manufacturing method of the titanium oxide sol of this invention is demonstrated. (Please read the notes on the back before filling this page) --------— Order-: -----

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This paper size is in accordance with Chinese National Standard (CNS) A4 specification (2) χ 297 mm 1230688 A7 V. Description of the invention (l2) If the titanium oxide sol of the present invention contains the foregoing amount, it is better to manufacture it The method is not particularly limited. For example, the titanium alkoxide compound is hydrolyzed to obtain a small amount of alcohol-containing ammonium oxide; adding at least one of them, and further adding at least one of nitrate ion and phosphate ion, etc., can make gas ions, etc. The concentration is within the range described above. However, it is preferable to use a titanium tetrachloride produced by hydrolysis to generate hydrogen chloride. The following will describe a method for producing a titanium oxide sol in the case of using titanium tetragas. The vaporized chlorine generated during the hydrolysis of titanium oxide escapes from the reaction tank, and it is better to leave it in the sol as much as possible. If the generated hydrogen gas is allowed to escape, the hydrolysis of the tetra-gasified titanium is performed , The particle size of the titanium oxide in the sol is difficult to be reduced, and the crystallinity is not good. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Customs, even if it cannot be completely prevented. It is advisable to suppress the escape of hydrogenated hydrogen gas generated by hydrolysis, and this method is not particularly limited as long as it can be suppressed. For example, pressurization can also be used, or the easiest to implement and effective method In order to perform the hydrolysis, a reaction tank equipped with a reflux cooler is used. An example of such a device is shown in Fig. 丨. In the figure, a reaction tank filled with a tetrakisdized titanium aqueous solution 2 is provided with a reflux cooler 3 , Stirrer 4, thermometer 5, and device 6 for heating the reaction tank. Although the steam of water and hydrogen chloride is generated by the hydrolysis reaction, most of it is condensed by the reflux cooler 3 and returned to the reaction tank. There is almost no case where hydrogen chloride escapes from the reaction tank 1. If the concentration of the titanium tetraoxide in the hydrolyzed titanium tetrahydrate solution is too low, the productivity is poor, and the efficiency when forming a thin film from the generated titanium oxide sol Low; if the concentration is too high, the reaction becomes fierce. The size of the obtained oxidized paper conforms to the Chinese National Standard (CNS) A4 (210 X 297 mm 15-

1230688 V. Description of the invention (13) It is difficult to make Jinzi fine, and its dispersibility is also poor, so it is not suitable as a transparent film forming material. A suitable sol of titanium tetraoxide having a concentration of 0.05 to 10 mol / a liter can be obtained by heating and hydrolyzing the aqueous solution of titanium tetrahydrate to obtain titanium oxide (T2O) particles dispersed in water. If the hydrolysis is carried out under reflux cooling, the titanium oxide concentration of the obtained sol is generally from 0.05 to 10, ear / a liter, so it can be directly used as a suitable titanium oxide / agrochemical coating. Covering material. Further, water may be added to the gelatin obtained during the hydrolysis, or the sol may be concentrated so that the concentration of titanium oxide falls within the aforementioned range, as necessary. The hydrolysis temperature ranges from 50 ° C or more to the boiling point of the titanium tetrachloride aqueous solution. If it does not reach 5 ° C, the hydrolysis takes a long time. The hydrolysis is carried out by increasing the temperature to the above-mentioned temperature and holding it for about 10 minutes to 12 hours. The holding time is preferably a short time period in which the hydrolysis temperature is high temperature. Preferably, The water-soluble hydrolysis of titanium tetrachloride is carried out at a temperature ranging from 75 <t to the boiling point of the aqueous solution. At this time, the mixed solution of titanium tetrachloride and water can be heated to a predetermined temperature in the reaction tank, or water can be used. It can be heated in the reaction tank in advance, and titanium tetragas can be added to it, and then it can be brought to a predetermined temperature. By this hydrolysis, generally, a brookite type main component can be obtained, in which Anatase-type and / or rutile-type titanium oxide is mixed. In order to increase the content of brookite-type titanium oxide in particular, water is heated in the reaction tank to 75 to 100 in advance. It is preferably 85 ~ 95 ° C, and titanium tetrachloride is added to the temperature range of 75t: ~ the boiling point of the solution, and the pre-heating temperature is 85 ~ ". When it is, the temperature range is 85 ~~ the boiling point of the solution. The method of carrying out hydrolysis is suitable. ---------- r-AW --------- Order -------- MW. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 specifications 〇〇 297 公 发 _

123,0688 5. Description of the invention (14) Among the total titanium oxides formed, brookite-type titanium oxide can reach 70% by weight or more. Although the reason for the formation of mainly brookite-type titanium oxide has not been determined, but because it contains a mixture of Bronsted bases other than gas ions and chloride ions, and the hydrolysis temperature is adjusted to above 5 acryl to titanium tetrachloride The boiling point of the aqueous solution is up to |, and its production is possible. The good Bronsted acid is nitric acid and scaly acid which have higher boiling points than hydrochloric acid. The faster the temperature rising rate of the titanium tetrachloride aqueous solution during the hydrolysis, the finer the particles obtained, so it is preferably at least 0_2 t / min, more preferably at least 0 ° C / min. According to this method, it is preferable that the average particle diameter of the titanium oxide particles in the sol is in the range of 0.001 to 0.1 #m and that the crystallinity is good. The manufacturing method of the oxidative convergence of the present invention is not limited to the batch type. It is also possible to set the reaction tank as a continuous tank, while continuously feeding titanium tetragas and water, and taking out the reaction solution on the opposite side of the charging port, Continuous mode for continuous degassing. The generated sol is subjected to dechlorination treatment, or water, dehydration, etc. are added in a range that does not hinder, so as to adjust the gas ions to less than 10,000 ppm. The dechlorination treatment can be carried out by a generally known means such as electrodialysis, ion exchange resin, electrolysis, and the like. Either one or both of nitric acid and phosphoric acid is added to the sol whose gas ions are adjusted to less than 10,000. The total amount of these ions is preferably adjusted to 50 to 10,000 ppm. Nitric acid and phosphoric acid can also be added during the hydrolysis of titanium tetrachloride. The dispersant of the saponified titanium sol of the present invention is generally water or a mixture of water and an organic solvent. Organic solvent or added to the sol after the hydrolysis of titanium tetraoxide. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----------- rlM ^ W (please first Read the notes on the back and fill in this page again} Order --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 17 1230688 A7 V. Description of the invention (l5) Force: Enter the aqueous solution of tetrachloromethane to dissolve it. Disperse Included in the agent: When the agent is used, the suitable concentration of the oxidizing agent of the sol used as the coating material is also 0.05 / H) mol / liter. When adding an organic solvent after conversion, i can concentrate the conversion according to the material, such as hemp and high oxidized organic solvents: ^ Add an organic solvent to it to make the inertness of titanium oxide in the sol into the range described. . The organic solvent is preferably a hydrophilic one, and examples thereof include monovalent or polyvalent alcohols such as methanol, ethanol, and ethylene glycol, such as ketones such as acetone, and esters such as ethyl acetate, and ethylene glycol-ethyl_hyl. eell_lve) and other cellosolve. These may be used alone or as a mixture thereof. The organic binder can be mixed in any amount with respect to the cold glue ', but it is appropriate that it is 2,000 parts by weight or less based on 100 parts by weight of water in the sol. When a titanium oxide thin film is formed from the titanium oxide sol according to the present invention, it is preferable to directly use the sol generated by hydrolysis ^; the titanium oxide powder is produced from the sol, dispersed in water, and then made into a sol instead of using Better method. Titanium oxide particles have high surface activity, and their activity will indeed increase if they are formed into fine particles. Therefore, it becomes very difficult to disperse into water, that is, aggregates are formed, and the film made from this has poor transparency and photocatalytic activity. . Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following examples, the identification of the titanium oxide crystal structure and the content rate of the identified titanium oxide with the crystal structure were measured as described below. The main crystal system of titanium oxide is brookite type, anatase. The paper size is applicable to Chinese National Standard (CNS) A4 specification (2) × 297 mm. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 1230688 A7 __Β7 ____ 5. Description of the invention (16) (Anatase) type and Rutile type. The three X-ray peak positions are shown in Table 1 (JCPDS (Joint Committe Powder Diffraction Standards) data), and there are many overlapping parts. In particular, the d values of the main peaks (intensity ratio 100) of the brookite type and anatase type are 3.52 (crystal plane 12) and 3 · 5 1 (crystal plane 101). In the tube, 20 is near 28 · Γ. This angle difference is 20 °. In the following, due to the overlap, the content ratio cannot be obtained from the main peak intensity ratio of either one. Moreover, the brookite type also has a peak at a d value of 3.47 (crystal plane 111). Among these three peaks, '2 0 is 2 8 · 1 to 2 8.5. Nearby, substantially overlap. As described above, since the intensity ratio of the main peaks of the anatase type and the anatase type cannot be obtained, here the peaks of the 121 surface of the anatase type that do not overlap with the anatase type peaks are used here. Find the intensity ratio of the peaks overlapping with the above three peaks (wave intensity of the 121 brookite type) / (three overlapping peak intensities), and then obtain the brookite type and anatase type. The content of titanium oxide. Also, the rutile-type oxide is determined by the ratio of the intensity of its main peak (110 plane) to the three overlapping peaks (the intensity of the rutile main peak) / (the intensity of the three overlapping peaks).得 量 量。 Get the content rate. The actual measurement was carried out using an X-ray diffraction device (manufactured by Rigaku Electric Co., Ltd., RAD-B Mouth, 7k, and 7k), and the quantitative analysis based on data processing was performed at the same time as the X-ray diffraction identification. This paper size applies to China National Standard (CNS) A4 specification (210 χ 297 mm) ---------- f -------.-- Order · '-------- ^ 9— (Please read the precautions on the back before filling this page) 19 1230688 A7 B7 V. Description of the invention (17) Table 1 brookite (29-1360) d value 3.51 2.90 3.47 f ^ 'No.' Crystal surface 120 面 21 111 Strength ratio 100 90 80 (21-1272) d value 3.52 1.89 2.38 Rutile (21-1276) Crystal surface 101 200 004 Strength ratio 100 35 20 d value 3.25 1.69 2.49 Crystal surface 110 211 101 Strength More than 100 60 50 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the following examples, the following evaluations of the physical properties of the films were performed as the characteristics of the titanium oxide sol of the present invention. Evaluation of the physical properties of the film 2 ml of the coating solution prepared in the example or the comparative example was coated on a soda-lime-glass (substrate) of 76 X 26 mm, and kept in the vertical direction for 10 minutes to remove excess coating. Cover the liquid and form a surface layer. After the surface layer is formed, it is dried or fired at a predetermined temperature (hereinafter referred to as "film-forming temperature", but means heating and firing temperature) described in the examples or comparative examples to obtain oxin; 4 films (Film thickness is about 0.2 m). The transparency, photocatalytic energy, adhesion, adhesion and pencil hardness of this film were measured. Transparency was measured with (H) East; 7. Hazemeter (JIS K6718 standard) manufactured by Denso Technology Center Co., Ltd., and evaluated in the following three stages. ◎ · · · The haze rate is less than 2.0% ○ · · · The haze rate is 2.0% or more and less than 500 / 〇X · · · The haze of 5.0% or more is determined by coating a few drops of red on the substrate The ink was irradiated with a black light at an ultraviolet intensity of 2.i mW / cm2 for 30 minutes, and the discoloration of the red ink was judged in 3 stages according to visual inspection. This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 20 1230688 A7 B7 V. Description of the invention (18)

◎ 〇X • ·· Fading is good (please read the precautions on the back before filling in this page) • •• There is no fading part • ·· The adhesion between the non fading and the substrate is evaluated based on the water rubbing test . Wet with water or alcohol to wipe the Nadine glass substrate ten times, and then wipe it with a dry paper towel. After wiping back and forth ten times, 'the state of the coating film was visually evaluated in the following three stages. ◎ · · · · No damage on the coating film …… ·· · Damaged part of the coating film X · · · · Coating film The peel adhesion test was performed using the m K5400 standard grid tape method. The cut interval was 1 mm with a pitch of 100. The pencil hardness was based on the pencil hardness test method (JIS K5400). Example 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, adding water to titanium tetrachloride (purity 99.9%), and preparing the solution into titanium tetrachloride. The degree is 0.25 mol / liter (converted to 2% by weight). Titanium oxide). At this time, the temperature of the aqueous solution will not rise to more than 50 ° C by ice-cooling treatment. Next, 1 liter of this aqueous solution is charged into a reaction tank with a reflux cooler as shown in the figure, and Heat to near the boiling point (104t) and hold for 60 minutes to hydrolyze. The obtained sol After that, the residual gas generated during the reaction was removed by electrodialysis to make the chloride ions (C1 ions) become claws. The electrodialysis system used one side of the electrodialysis device G3 manufactured by Asahi Kasei Corporation. Monitor the pH value of the sol solution while implementing it. Then add nitric acid to the aforementioned paper size applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 21 1230688 A7 B7 V. Description of the invention (l9) No. 3 becomes 3,000 ppm. (Please read the precautions on the back before filling out this page.) To the titanium oxide sol prepared by chloride and nitrate ions as described above, add 1 to the weight of the sol. 〇OOppm of water-soluble high-molecular-weight polyvinyl alcohol is used as a film-forming aid. Even if the sol has passed for more than one day, the generated titanium oxide fine particles cannot detect the sedimentation. Take out a part of the particles in the sol to penetrate The average particle diameter of the particles observed by a type electron microscope was 0_〇18 # m. The X-ray diffraction was used to investigate the crystal structure of titanium oxide. As a result, the X-ray peak intensity ratio (Banqin type 1) The peak intensity of the 21 plane / three overlapping peak intensity) is 0.35, while the rutile peaks are not visible. Titanium oxide, under crystallinity, is about 40% by weight based on the aforementioned peak intensity ratio. It is composed of anatase type and 60% by weight brookite type. Next, 'tetraethylorthoxate (tetraethyl in ethanol solution (equivalent to 0.02% by weight) is used as an adhesive. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the above sol aqueous solution and this adhesive solution in a weight ratio of 1: 1 to form a coating agent for the withered titanium oxide sol. The composition of the coating agent is shown in Table 2. The coating agent solution was evaluated for physical properties in accordance with the aforementioned film evaluation method. However, the application temperature of the coating film was adjusted to 10 (rc.) The evaluation results of the rhenium film obtained here are shown in Table 3. Implementation Example 2 A titanium oxide sol was prepared in the same manner as in Example 1, and further shaped. The film was evaluated for this material. Although the composition of the coating agent and its manufacturing method were the same as those in Example 1 described above, the heating (firing) temperature was changed to that of the bucket. The composition of the coating agent is shown in Table 2, The evaluation results of the film material are shown in Table 3. This paper is based on the standard _ 雑 准 (CNS) A4 彳 ^^] ----, 22 1230688 A7

B V. Description of the invention (20) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Π &quot; Private U) K) A »—k I— * ►—a η- ^ ^ 〇〇 '·« J On Lai ^ K) 1 private u &gt; κ) — o Li Khan public Η ^ ^ ^ 妄 妄 & 妄 妄 &gt; &gt; &gt; &gt; &gt; &gt; &gt; &gt; &gt; &gt; &gt; Golifrili νψ 1 φ incompatible ^ ^ ^ * Ό-Κ)-L ^ u -¾ C ^ _ 势 势 骤 No 〇-X- °° K) Η ^ Ρ 1— ^ hfflK efficacy W W 丨 1 1 LT \ 14 枘 0 0 Φ potential Ε »Ρ N) Η— ^ -§-§ Ο Ο ►— ^ Η- * 1—k οο ～ 〇 &quot; * 〇 &gt; 〇 &gt; 〇〜〇〜〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇¾¾ 14 ^ ! _ G 1 1 1 1 § 卜卜 § 丨 卜 ^ 丨 卜 g Ο Ο Ο Ο ο Once received Miao wg disk (Φ w + 1 1 1 1 ^ to LT \ Κ- *,, Κ), ι ΟΟ ^ Ο ^ Ο ^ Ο ^ Ο Ο Ο Ο Ο Ο Ο 1 1 Ο 1 1 Μ ^ β tantan luTiU 4 ^ 1 * 1 pt〇p ㈣ 田 ^ p ο ο Κ) Κ) LT \ LT \ Ο Ο Ο • · · To to Οι Lh 2: 0 ^ ------------------- Order --------- ^ 9— (Please read the precautions on the back first (Fill in this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 23 123〇688 A7

----- I --------- {Please read the note on the back? (Please fill in this page again for details.) A titanium oxide sol was prepared in the same manner as in Example 1, and a thin film was further formed to evaluate its physical properties. However, no nitric acid was added, but radon ions were substituted according to the values shown in Table 2. In Comparative Examples 丨 and 2, no tetraethylorthoester (adhesive) was added. The coating agent component composition is shown in Table 2 in detail, and the evaluation results of the film physical properties are shown in Table 3. ^ Example 3 to Example Ί A titanium oxide sol was prepared in the same manner as in Example 1, and a thin film was further formed to evaluate its physical properties. However, the amounts of phosphoric acid and nitrate ions were changed. The coating agent component composition is shown in Table 2 in detail, and the evaluation results of the film physical properties are shown in Table 3. Furthermore, the particle diameters and crystal forms of the titanium oxides of Comparative Examples 1, 2 and Examples 3 to 12 are the same as those of Example 1. 2 is almost the same. 954 ml of distilled water was charged into a reaction tank with a reflux cooler as shown in Fig. I and heated to 95 ° C. Phosphoric acid was added thereto so that the Po4 ion became 200 ppm. While maintaining the stirring speed at about 200 rpm, an aqueous solution of titanium tetragas (a content of 16% by weight, 163% by weight, and a specific gravity of 159 printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, purity 99.9%) in this aqueous solution 46 ml was dripped into the reaction tank at a rate of about 5 ml / min. At this time, care must be taken not to lower the temperature of the reaction solution. As a result, the concentration of titanium tetrachloride was 0.25 mol / liter (converted to 2 weight of titanium oxide 0 / 〇) 〇 Although the reaction solution began to become white turbid immediately after dropping from the reaction solution, the temperature was maintained continuously until After it is finished, it will be further heated to make the paper size suitable for the Chinese National Standard (CNS) A4 specification [210 X 297 Public Love] 24 V. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 123〇688 Description of invention (22) Wen Zhi Near the Buddha's point (104 ° c), keep in this state for 60 minutes to complete the reaction. After cooling, the residual chlorine generated during the reaction was removed by electrodialysis to adjust to ρΗ = 1 · 9 (chlorine ion 600 ppm, phosphate ion 200 ppm), and then added to the titanium oxide content at a weight of 丨 weight. /. The water-soluble polymer, polyethylene glycol, was used as a film-forming aid to make a titanium oxide sol (Ti02 about 0.25 mol / liter). The sol is stable, and the sedimentation of the oxidized microparticles formed over 30 days is still undetectable. After filtering a part of the sol, a vacuum dryer was used at 60 ° C to make a powder, and the result of "the same quantitative analysis as in the previous example" was taken out. The peak intensity) ratio was 0.38, and the (rutile-type main peak intensity) / (three overlapping peak intensity) was 0.05. Based on this, it was found that the titanium oxide was crystalline brookite type at about 700 wt.%, Rutile type at about 1.2% by weight, and anatase type at about 28.8% by weight. The microparticles were observed with a transmission electron microscope, and the average particle diameter of the primary particles was 0.015. When further measured by the bet method, the specific surface area of the fine particles was 14 m2 / g. Table 3 shows the evaluation results of the coating agent component composition and the film physical properties. Example 14 Under the same hydrolysis conditions as in Example 1, titanium tetrachloride was hydrolyzed to obtain a sol containing 0.25 mol / liter of titanium oxide. Prior to electrodialysis, 'the sol was first concentrated by evaporation to a titanium oxide concentration of 2.5 moles / liter (20% by weight of titanium oxide), and then the residual gas was removed by electrodialysis to make the gas ions approximately 1,200 ppm. Secondly, add nitric acid and phosphoric acid to the aforementioned sol to form NO. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) ---------- 1 ------- -• —Order ---------- (Please read the notes on the back before filling in this page) 25 1230688 A7 B7 V. Description of the invention (23 ions 2,00 ppm, P04 ions It is 1000 ppm. To the titanium oxide sol adjusted with gas ions, nitrate ions, and phosphate ions as described above, methanol is added as a solvent, and water-soluble polymer polyvinyl alcohol in an amount shown in Table 2 is mixed. To prepare a titanium oxide sol (Ti0 2 about 0.5 mol / liter). Using this sol, a thin film was prepared in the same manner as described above to evaluate the physical properties of the thin film. The results are shown in Table 3. Furthermore, The average particle size, ratio of crystalline form, and specific surface area of the titanium oxide particles are all substantially the same as those in Examples i and 2 .---------------------------- Order ------- --- (Please read the precautions on the back before filling out this page) The paper printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 26 1230688 A7 B7 V. Description of the invention (24) Comparative Example 1 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 // 2 // 3 // 4 Example 1 // 2 // 3 // 4 // 5 // 6 // 7 // 8 // 9 // 10 // 11 // 12 // 13 // 14 100 400 100 400 100 400 100 400 100 400 100 400 100 400 100 400 400 400 Temperature (° C) 〇〇〇〇〇 ◎◎◎◎◎ 〇〇 ◎ ◎ 〇 ◎◎ Transparency 〇 ◎ 〇 ◎ Photocatalytic energy 〇〇X ◎◎◎◎◎◎◎◎◎◎◎ Adhesion (water wipe) XXXX ◎◎◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇 Adhesion (alcohol) 90 // // // η 11 95 // // // // // 100 100 ί # ®, X dd pencil hardness secret tf ¢ ----------- 1 ------- i order ---------- (Please read the Note: Please fill in this page again) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 27

Claims (1)

T230688 6. Scope of patent application . ^^ 部 智慧 财 屋 ^ Employee elimination cooperation ^^, No. 7864 patent application application patent scope amendment 1 _ ^ date L ~ T on U six | Z 0㈡. A titanium reduction converter, which is characterized by containing chlorine Bronsted test other than ions and chloride ions, and the aforementioned cloth test is selected from the group consisting of nitrate ions, ions, gallate ions, partial ions, polyisocyanates, acetate ions, and organic acid ions. The average particle size of at least, upper, and lower is 0.01 ~ 0.1 # m. 2. The oxidation demon sol according to item 1 of the patent application scope, wherein the aforementioned Bronsted test contains either one or both of nitrate ion and dish acid ion. 3. The titanium oxide sol according to the scope of the patent application] or 2, wherein the total amount of chloride ions and Bronsted's test other than chloride ions as anions is 50 to 10,000 ppm. 4. The titanium oxide sol as claimed in item No.} or 2 of the patent scope, which is mainly composed of banqin-type titanium oxide on an average particle size of 〇 !! ~ G.Um and a specific surface area of 2Qm2 / ga. A dispersion of the composed titanium oxide particles. 5 · If the scope of patent application is the first! Or 2 items of oxidized kinesol, wherein the content of oxidized kinesol is 0.05 to 10 mol / liter. 6. If the titanium oxide sol according to the scope of the patent application is No. 2 or 2, it further contains 10 to 10,000 ppm of water-soluble polymer. 7. The titanium oxide sol according to item 1 or 2 of the patent application scope further contains a binder. 8. If the titanium oxide dissolved in item 7 of the patent application is successful, the adhesive agent is a catalyzed salt. _9. For example, the titanium oxide sol in the first or second scope of the patent application, in which the titanium oxide, the date of the month is October 28th, J3. If the first MU back © 之. ^ #. ¥ 1 | --- _fill Scolded Ben Ϊ) Order --- Clear profit range The dispersant of the gum is water, or a mixture of hydrazone 10 _ one organic solvent. • A method for producing a titanium sol containing at least one type of Bronsted's test other than chloride ion ^ heavy, from nitric acid, phosphoric acid, pyrophosphoric acid, metaxoic acid, polyphosphoric acid, metasulfonic acid Rhenium tetrachloride is hydrolyzed in the presence of a selected Bronsted acid from the group consisting of acid, ethylsalic acid, dodecylbenzenesulfonic acid and propanesulfonic acid. The method for manufacturing a titanium oxide sol according to claim 10 of the patent application, wherein the total amount of Bronsted's test other than ions and gas ions as anions is adjusted to 5 (Μ Μ⑼ppm. 12 = patent application The method for producing a titanium oxide sol according to the nth item, wherein the Bronsted material described in the month J contains one or both of a nitrate ion and a scale acid ion. The manufacturing method of titanium oxide sol is the one that hydrolyzes titanium tetrachloride in a reaction tank equipped with a reflux cooler. Page) K The Ministry of Economic Affairs, the 1st Bureau of Intellectual Property, Consumer Affairs Cooperation: '仁 印 3 ___ 』Ι_ -30