TWI241278B - Article coated with aqueous dispersion of titanium oxide and particles of titanium oxide - 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

1241278 IX. Description of the Invention: [Technical Field of the Invention] Field of the Invention The present invention relates to a titanium oxide sol, a titanium oxide thin film formed on the surface of a substrate such as ceramics, 5 glue, and the like using the sol, and a method for manufacturing the titanium oxide sol. At the same time, it also relates to a method for producing titanium oxide particles with the sol. The titanium oxide film is transparent, has excellent photocatalytic activity, and has good adhesion to a substrate. [Prior Art 2 10 Background of the Invention Titanium dioxide (hereinafter referred to as "titanium oxide") is known to have 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 the stable titanium oxide is an anatase type. It can be heat treated and further calcined at 816 ~ 1,040. (: Obtaining brookite-type titanium oxide, and rutile-type titanium oxide can be obtained when the temperature range is further exceeded (Physical and Chemical Dictionary 3rd Edition, ρ 514 ~ 515). In addition, according to the liquid phase In the production of titanium oxide by the method, for example, Shogi Maki and others have reported in detail on the crystalline phase of titanium oxide 20 produced by the hydrolysis of titanium tetrachloride aqueous solution (Industrial Chemistry, Vol. 59, No. 11). Ρ · 1295 (1956)). According to the theory of the report, rutile titanium oxide is mainly generated from a high concentration solution, and anatase titanium oxide is generated from a low concentration side. It is impossible to generate brookite-type titanium oxide, even particulate titanium oxide in the phase. Since the raw material is titanium tetragas, 1241278, of course, gas ions coexist in the obtained titanium oxide. From these reports, Until now, it has been difficult to stably manufacture brookite-type titanium oxide by the liquid phase method. Although the titanium oxide was heat-treated at a high temperature to form a brookite-type titanium oxide by the vapor phase method as described above, this method 5 Adopted Therefore, it has been reported that it is difficult to obtain fine particles to produce banchite crystals. On the other hand, as for the method for generating a titanium oxide sol, crystalline or amorphous titanium oxide particles are generally dispersed in a dispersant, or Titanium alkoxide, titanium sulfate, titanium tetrachloride, and other titanium oxide precursors are added to / in the moon, and then formed into a sol by methods such as neutralization and hydrolysis. Sol can be used for the manufacture of titanium oxide powder on the one hand, or can be used to coat sol on glass and plastic, etc., to form a thin film of titanium oxide on the surface thereof. 15 Titanium is an optical semiconductor, which is known as When the particle diameter is small, transparency and photocatalytic function are improved. The photocatalytic function of titanium oxide has been actively researched and developed in recent years. Specific examples of the use of this photocatalyst include removing harmful substances to prevent Pollution, deodorization of malodorous gases such as ammonia, sterilization of field fungi, etc .: According to its purpose of use, the form of titanium oxide is a variety of large-volume particles, films and Sol. Adding transparency to such titanium oxide products using photocatalytic function is mostly used for thin films. To this end, emulsified titanium is used as a film-forming material in the form of a sol. I. Off, photocatalytic ability of titanium oxide The anatase type is considered to be greater than the% force of rutile. The reason is due to the energy interval between the two. The gold 1241278 redstone type is 3.02eV and the anatase type is 3 23eV approximately 0 ·. 2〇ν 的 差 # Xue 31 (1996) No. 10, ρ 817). Due to this energy difference, sharp-type ore-type titanium oxide with a soft interval of 2 is suitable to be used as a light semiconductor. :, With regard to the brookite type, the elemental substances that have been taken out so far are: 5: Moreover, because the conventional system is manufactured at high temperatures, particles may be burned to obtain a tool that can be used as an optical semiconductor (photocatalyst). The surface area of the particles is so invisible that they can be used as: touch = 10 15 In terms of the use of thin films, recent lighting appliances have proposed, for example, coating the glass tube of a camping lamp and its cover with an oxide demon The film is formed into a thin film, and when oil scale organic matter is attached to the uniform breaking tube: it is decomposed by photocatalysis to prevent the surface light tube and the cover. However, the dissolving knee obtained by the brief method is used to form a thin film: it is rarely able to become a highly transparent film; in particular, the conventional technique does not teach the titanium dioxide titanite-titanium titanate film as a sunlight photocatalyst. Xunzhi particles; and the nascent particles should be dispersed. In response to this kind of problem, the Department of Knowledge focuses on the use of oxidizing and refining anatase. When used to form titanium oxide films on glass, plastic, and other substrates as photocatalysts, the surface requires 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 fine particle having a high specific surface area. Further, when a film is formed on a lighting device or the like, the film must also have transparency. In order to form; good transparency, as in the case of catalyst activity, if the titanium oxide is micro 20! 241278 and when forming a titanium oxide film on the substrate, a good adhesion between the film and the substrate must be made Properties so that the film does not peel easily. In the conventional method of hydrolyzing titanium tetrachloride, it is difficult to obtain a titanium oxide sol having very small particles k, excellent crystallinity, and good transparency when forming a thin film. In the hydrolysis of titanium alkoxide compounds, although the titanium oxide in the core gum is excellent in the characteristics of forming powder objects such as very small particles, compared with titanium tetrachloride, titanium alkoxide compounds it's very expensive. C Ming Nai] Summary of the Invention: The above-mentioned conventional technology is provided. The purpose of the present invention is to provide a titanium oxide with a thickness of 15 Å to each county material to form an oxide on the surface of the substrate. Titanium oxide sol with excellent performance and good adhesion between the 4 film and the substrate, the ># film ' formed by using the sol, and a method for producing titanium oxide particles from the solvent. Mingming et al., With respect to the titanium oxide thin film formed of titanium oxide sol, with the result of nine, 'if chlorine is present in the titanium oxide sol, the thickness of the film is either or both. Some ions co-exist to obtain the characteristics of the modified osmium net, and the invention of the wide-type oxygen coffee. The above photocatalytic performance of Wei Ti_, thus completing this 1241278, is based on the present invention to provide chloride ions and other Bronsted test oxidized sols containing chloride ions. Here, the so-called "plant Bronsted test" means the proton acceptor in the Bronsted acid theory. Next, according to the present invention, there is provided a titanium oxide film formed by using the above-mentioned titanium oxide instead on the surface of a substrate. The surface is coated with the above-mentioned oxidation. Furthermore, an article of titanium sol provided on the surface of a substrate according to the present invention. Further steps-10 to 15 are provided according to the present invention.-A feature is a cloth that hydrolyzes titanium tetrachloride in the presence of at least one or more species selected from the group consisting of Brownsted Catalic Acid, and contains cloths other than chloride ions and random ions. At least __ the method of manufacturing titanium dissolves, especially the method for manufacturing titanium oxide by dispersing and dispersing oxide particles containing sheet-type titanium oxide, and is characterized by the oxidation produced by using this manufacturing method A method for producing a titanium oxide particle from titanium sol to obtain titanium oxide particles. More advanced, provided according to the present invention-a feature is that titanium tetrachloride is added to the hot water of 75 ~ 1 GGC 'and in the presence of Gu ion, acid ion ion single-phase or double-turn, in the machine ~ solvent The temperature at the puppet point makes — one or both of the titanium hydrolyzates containing chloride ions and “sharic acid ions and linoleic acid 1 隹 子”, and has brookite-type titanium oxide as the main limb. Titanium oxide conversion method; and 'Providing a simple illustration of a manufacturing pattern of titanium oxide particles characterized by dissolving titanium oxide produced by the manufacturing method to obtain plate-type titanium oxide oxide particles 20 1241278 The first diagram is a schematic cross-sectional view of an example of a reaction suit used in the manufacture of the “reversible” Ming Weiwei Titanium Transformer. [Implementing the cold type] Detailed description of the preferred embodiment + b. The sol contains chloride ions and is selected from other than chloride ions: at least one or more of the Stadt test, and the ytterbium film formed by the sol is not only a mouth A y Μ 4 疋 /, has excellent light Catalytic function, especially its properties, transparency and transparency 10 15 The Bronsted base contained in the titanium oxide / gluten is selected from the group consisting of nitrate ions, phosphoric acid ^ ^ ′, ... stone 4 acid ions, partial filling acid ions, polydisk acid ions, acetic acid Among the ions and organic acid ions, those that are particularly suitable are those selected from the group consisting of nitrate ions and ions. These Bronsted bases are included in a single group of ^ or more. Metaxanthoic acid, = cornerstone ?, acid, dodecalyl, and osmium acid are suitable. What is found in oxidized kinesol: The aforementioned Bronsted test is not just the amount that exists in solution in equilibrium. Means the absolute amount of the _existing ions. The total content of the plasma content called # is 5 () ~ 1 (), 100 ~ 4, _ah is more preferred. The dispersant of titanium oxide sol is usually Water, or a mixture of water and an organic solvent. In the method of hydrolyzing titanium tetrachloride to obtain oxidized amylol, hydrogen chloride is generated by reaction. In the obtained sol, almost all of the hydrogen chloride is dissociated into chloride ions and hydrogen. Ion. Most of the chlorinated gas will escape in the hydrolysis reaction under heating. Outside the system. Moreover, if the sol contains hydrogen chloride, titanium oxide powder can be obtained from the sol, or various obstacles will occur when manufacturing the oxide film 10 1241278; therefore, when the sol is left in the sol by a certain degree or more due to the hydrolysis reaction In the case of hydrogen chloride, it is very common to apply a dechlorination treatment to make the sol free of hydrogenated hydrogen as much as possible. However, the conventional technology does not take into account the effects of chloride ions in such sols on the properties of titanium oxide films. As a result, the technology of controlling chloride ions in the sol does not exist from this viewpoint. The inventors have found that if such chloride ions are contained in the sol, the light of the titanium oxide film formed by the sol It has high catalytic effect and excellent adhesion to the substrate. As a result, it was found that in addition to chloride ions, at least one of other Bronsted bases such as nitric acid 10 ions and phosphate ions coexist, the film is transparent. The invention has better properties, adhesion, and the like, and completed the present invention. Although the reason for this has not yet been determined, it is conceivable that a condensation reaction occurs on the surface of the titanium oxide particles due to the co-existence of acids such as trisolic acid and phosphoric acid, which improves the film-forming property of the coating film and the adhesion to the substrate. 15 In a titanium oxide sol, chloride ions and at least one ion of a Bronsted base other than chloride ions (hereinafter, chloride ions and other Bronsted bases are collectively referred to as "chlorine ions Etc.) If the coexistence is good, but in order to improve the adhesion between the titanium oxide film formed on the substrate and the substrate, the total amount of chloride ions and the like should be 50 ppm or more. In particular, when the film is fired, the adhesiveness is improved by containing chloride ion of 50 ppm or more. Conversely, when the amount of chloride ions and the like in the sol increases and the total amount exceeds 10,000 ppm, the transparency of the film is deteriorated. A particularly suitable range among the above ranges is 100 to 4,000 ppm. The ratio of Bronsted bases to chloride ions other than chloride ions is 1,241,278. There is no particular limitation, and their total amount can reach a wide range of 0.1 to 200 mols with respect to 1 mol of chloride ions. Also, surprisingly, by controlling the amount of Bronsted bases other than chloride ions and gas ions within the foregoing range, brookite type titanium oxide can be produced. The cause is uncertain. Compared with titanium oxide containing such brookite type crystals and hafnium oxide containing only rutile type crystals or anatase type crystals, or titanium oxide containing both rutile plastic crystals and anatase type crystals, The coating film has excellent transparency and photocatalysis. In particular, although the ratio of the content of the brookite-type crystal is not particularly limited, 10 to 100% by weight of 10 15 is used, and if the content is 50 to 100%, the effect will be more significant. Although the role of the above-mentioned chloride ions and the like is uncertain, it is inferred that due to the titanium oxide solution, the electrical repulsion between the particles of the oxygen secretion particles increases, so the particles have good dispersibility, resulting in transparency and peel strength. Such good results. The finer the titanium oxide particles that emulsify titanium, the higher the photocatalytic effect of the titanium oxide film, and the better the permeability. "Because there are manufacturing difficulties in obtaining fine oxygen: titanium particles, the average particle size of the titanium oxide particles in the sol is in the range of ~ 〇1㈣. In order to further improve the light and pure function and transparency of the solution, the titanium wipes are mainly formed of brookite-type titanium oxide with a surface area of 20 ^ or more. Sol is better. # «4 mixture of conventional methods to obtain brookite wide titanium oxide, not only 20 1241278 described by anatase-type oxidation k ... H physical method; and heat treatment compared to _ # 、 1 Ｍ 赖 日 r · Using heat treatment = radiation— ^ will grow greatly, so it is used in the formation of thin films. 5 10

In the titanium oxide sol with a handle, if the titanium oxide particles in the sericin are too large, the particles will agglomerate, and the sol becomes prostitute. On the other hand, when the oxidized particles are too low, for example, when a thin film is formed, the coating process of the sol occurs, which takes a lot of time. Due to various conditions, the concentration (content) of emulsified titanium particles in the titanium oxide sol is mm mol / liter. B The titanium oxide sol of the present invention can be obtained by adopting general methods such as shouting, washing, and drying to obtain oxidation. Titanium particles. The average particle size of the particles is preferably a primary particle. It is preferable that the particles obtained from the titanium titan gum which is composed of plate titanium and titanium oxide as the main body have an average particle size of 0 ″ # 15 m and a specific surface area of 20 m 2 / g or more.

In addition, 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 10, 000 PPn, may be added to the sol in order to improve the film forming property of the thin film. Suitable water-soluble polymers include polyvinyl alcohol, methylcellulose, ethylcellulose, CMC, and starch. The titanium oxide sol of the present invention can be applied to substrates of various materials, shaped bodies, and the like to form a titanium oxide film on the surface of the substrate. Pottery materials, glass, metal, plastic, wood, paper, etc. can be used as the substrate. They can be used without any restrictions. These substrates may be painted articles. The substrate can also be a catalyst carrier composed of 13 1 ^ 41278 load = ::: Shao, thorium oxide, etc., so that it can be used as a catalyst. In addition, if the surface of a fluorescent lamp, such as a fluorescent lamp, and the titanium film of its plastic lampshade, the film not only penetrates through two materials and forms an effect thereon: Decomposes organic matter such as oil fume to prevent it from being broken happily. Titanium oxide film is formed on the glass and lampshade materials. Similarly, the second reading of building glass and walls is used to prevent pollution in the building. Therefore, the building materials and wall materials can be used.

It is not necessary to call for low building management costs. In order to make Xinyeye a vocational school, the method of coating titanium oxide can be immersed in a substrate and dissolved in a solvent === sol sprayed on the substrate, and the method of brushing with bristles. The application amount of the sol is made liquid thickness 15 = appropriate. After coating, it can be dried by removing moisture to obtain a thin film, and it can also be used as it is for applications such as catalysts. In Japan, when the base material is made of heat-resistant materials such as f, y, and glass, t can be sintered after forming an emulsified titanium film.

= It is firmly adhered to the substrate, and the hardness of the film is preferably 200t or more at a time. The place,, w, AA, L,,,, and mouth are extremely difficult according to the material-there are no particular restrictions. Although it is appropriate to know the heat resistance of ..., the substrate can be excessively upgraded. Further increase the hardness of the film and its adhesion to the substrate, ^ ㈣ until _C. In addition, when the crystal shape is maintained by brookite-type oxygen, it is 7 or more. . . . The following temperature: = In the presence of wall acid ions, oxidized amyl sol containing «acid ions due to hydrolysis of ammonium tetrachloride, without the addition of dead junction = = 14 1441278 10 15 20, 0 C or more With a low sintering temperature of 500 C, it is possible to form a thin film having excellent adhesion to the surface of a financially heat-resistant substrate such as glass stainless steel. The atmosphere during the sintering of the taxi is not particularly limited, and it may be in the atmosphere. The sintering is not limited in time ', for example, it may be performed in the range of one minute. When the thickness of the oxide film is the coating amount described in M, it is 0.05 to 1.0 / zm. Furthermore, 'the transparent film formed by the titanium oxide sol of the present invention is used as the winter's mouth, and the mouth of the mouth is opened.' In order to improve the adhesion of the surface to the substrate, a suitable dwelling agent can be added to the titanium oxide sol. . As an adjuvant, for example, organic dioxin compounds such as alky succinate (alky 丨 silieate) are added. Although there is no particular limitation, it is relative to the oxidation-soluble Γ of the present invention. In the case of titanium, silk sulphate, converted to ⑽2 at about 1 ~ 50% / and the right addition is insufficient! For weight force, the effect of the meter-adding agent is very high. If it exceeds 50% by weight, the adhesion strength of the substrate will obviously be promoted, but the oxygen storage particles will be completely covered, which will cause the photocatalytic force to change. weak. The method of adding an anticulum is based on the nature of the reducing agent, or it is selected to be mixed immediately before film formation. A, A off, / work +-forming a mixed state in the gluten in advance =, eight '-for the present invention The effect will not have any problems. ^ The film of the dead agent is not sintered, and sintering is also acceptable. == The titanium oxide film produced by the invention of the oxygen domain sol = 物 ^ Titanium oxide particle shirt is very fine, contains all, and the material is not limited, so the photocatalytic ,,, The particles and particles are close to humans and have a high degree of transparency. In particular, the oxides are mainly composed of titanium (e.g., 50% by weight or more) and have a wide range of titanium emulsified titanium. Its catalytic ability

] 5 1241278 is higher. Next, the manufacturing method of the titanium oxide sol of this invention is demonstrated. The titanium oxide sol of the present invention is not particularly limited as long as it contains gas ions and the like as described above. For example, titanium alkoxide compound 5 is hydrolyzed to obtain a titanium oxide sol containing a small amount of alcohol; HC1 and the like are added thereto, and at least one of nitrate ions and phosphate ions is further added to make the concentration of chloride ions and the like into the aforementioned range. . However, it is preferable to use titanium tetrachloride for the production of hydrogen chloride by hydrolysis. A method for producing a titanium oxide sol in the case of using titanium tetrachloride will be described below. 10 It is advisable to prevent the hydrogen chloride generated during the hydrolysis of titanium tetrachloride from escaping from the reaction tank and to leave it in the sol as much as possible. If titanium tetrachloride is hydrolyzed while the generated hydrogen chloride is allowed to escape, the particle size of the titanium oxide in the sol is difficult to be reduced, and the crystallinity is not good. Even if the escape of hydrogen chloride due to hydrolysis cannot be completely prevented, it is advisable to suppress it. This method is not particularly limited as long as it can be suppressed. For example, pressurization can be used, or the easiest and most effective method is to use a reaction tank equipped with a reflux cooler for hydrolysis. An example of such a device is shown in FIG. In the figure, a reaction tank 1 filled with a titanium tetrachloride aqueous solution 2 is provided with a reflux cooler 3, a stirrer 4, 20 thermometer 5, and a device 6 for heating the reaction tank. Although the steam of water and hydrogen chloride is generated by the hydrolysis reaction, most of them are condensed by the reflux cooler 3 and returned to the reaction tank 1. Therefore, almost no hydrogen chloride escapes from the reaction tank 1. If the concentration of titanium tetrachloride in the hydrolyzed aqueous solution of titanium tetrachloride is too low 16 1241278, the productivity will be poor, and the resulting & rate will be low; if the concentration of titanium sol is reduced, the effective titanium particles will be difficult to rely on. It is a transparent film-forming material. It is also not suitable for making liters, so it is not suitable for liters.钛 · Titanium water; fine g._mol / particles are dispersed in the water towel, and then turn into titanium oxide (™ 2) amine. If the hydrolysis is added to the reflux cooler and enters I, the oxygen cut concentration of the obtained sol is roughly ㈣5 ~ Shi Er / male 10

If the material is coated with the appropriate titanium oxide concentration directly, it can be read as needed. Add water to the solution obtained in the hydrolysis, or concentrate as needed, so that the titanium oxide indifference becomes the aforementioned. Range. The temperature is from above the machine to the stagnation point of the titanium tetrachloride aqueous solution. If the temperature is not reached, the hydrolysis will take a long time. Hydrolysis is performed at the upper phase temperature 'for 10 minutes to 12 hours. The process of maintaining the% solution temperature at a high temperature is preferred. 15 enthusiasts, the light hydrolysis of Titanium is in the boiling of the solution

Point temperature range. At this time, the mixed solution of titanium tetrachloride and water may be heated to a predetermined temperature in the reaction tank, or water may be heated in the reaction tank in advance, and titanium tetrachloride may be added to the predetermined temperature to make it a predetermined temperature. Temperature is OK. By this kind of hydrolysis, in general, it is possible to obtain 20 2 components with a banqin type, and an anatase type and / or a rutile type titanium oxide are mixed therein. To specifically increase the content of brookite-type titanium oxide, the water is heated in the reaction tank to 75 ~ 10 {rc, preferably 85 ~ 95t, and titanium tetrachloride is added to it. In the temperature range of 75t to the boiling point of the solution, when the pre-heating temperature is 85 to 95t, the method at the temperature range of 85t to the Buddha's point of the solution] 7 1241278 is suitable. According to this method, all of the produced plate-type titanium oxide can reach 7 (%) by weight or more. Although the reason for the formation of titanium oxide is still to be determined, but because it contains mixtures other than Bronsted's test, the sub-hunting hydrolysis temperature from § to 5 (rc to ^-matter, J: # & It is possible to make the titanium tetrahydrate solution fresh, and it is possible to make 1% of cloth_Tade acid to be the ratio of || to the boiling point of nitric acid and phosphoric acid. 10

: = The faster the temperature rise of the titanium tetrachloride solution in solution, the faster the temperature is, so it is better to be / 1 fine, more preferably, it is more than / 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 0.1 to 0.1, which is a good crystallinity. The manufacturing method of the titanium oxide is not limited to the batch method; the reaction can also be sighed into a continuous tank, while tetrachloromethane and water are continuously input, and 15-the reaction is performed on the opposite side of the input π Continuous method of taking out the liquid and continuously performing dechlorination.

The generated sol is dechlorinated, or added with water, dehydration, etc. within the range not to hinder the chloride ions to less than 10,000 ppm. The degassing treatment can be performed by well-known methods, such as electrodialysis, resin replacement, electrolysis, and the like. Add one or both of nitric acid and phosphoric acid to the sol whose gas ions are adjusted to less than 10,000 ppm, the combination of these ions. Ten miles is better when it is made from 50 to 10, 000 ppm in η week. Lutetic acid and linoleic 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. The organic solvent is added to the sol after the hydrolysis of titanium tetrachloride, or it is added to the aqueous solution of titanium tetrachloride to hydrolyze it. When the dispersant contains an organic solvent, the suitable concentration of titanium oxide as the sol of the coating material is also 0.05 to 10 mol / liter. When an organic solvent is added after the sol is formed, 5 the sol may be concentrated, dehydrated, etc. as needed to increase the titanium oxide concentration, or an organic solvent may be added to the sol to make the concentration of titanium oxide in the sol into the aforementioned range. The organic solvent is preferably a hydrophilic one, and examples thereof include monovalent or polyvalent alcohols such as methanol, ethanol, and ethylene glycol, ketones such as acetone, 10 types of ethyl acetate, and ethylene glycol monoethyl ether. (Ethyl cellosolve), etc. These may be used alone or as a mixture thereof. Although the organic solvent may be mixed in any amount with respect to the sol, it is appropriate that it is 2,000 parts by weight or less with respect to 100 parts by weight of water in the sol. When a titanium oxide thin film is formed from the titanium oxide sol of the present invention, the sol generated by hydrolysis 15 is preferably used directly; a titanium oxide powder is produced from the sol, dispersed in water, and used as a sol. Not the better way. Titanium oxide particles have a high surface activity. If they form microparticles, their activity will indeed increase, so it becomes very difficult to disperse in water, that is, aggregates will be formed. The film made from this has poor transparency and photocatalytic activity. decline. 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. 19 1241278 The main crystalline systems of oxan are brookite, Anatase, and Rutile. These three ray peak position systems are shown in Table 1 (JCPDS ( Joint Committe Powder Diffractioin plus Qin butterfly data), there are a lot of overlapping parts. In particular, the 5 main peaks of the brookite type and sharp ore type (intensity ratio ⑺ ... are respectively 3.52 (crystal plane) 120) and 3.51 (crystal plane 101). Among the 011 tube bulbs in the X-ray diffraction, 20 is near the M plant. This angle difference is W (U. Below, due to overlap, it cannot be controlled by- The content ratio is calculated from the peak intensity ratio. In addition, the Banqin type also has a peak at a value of 3.47 (crystal plane 111). Among the three peaks, 20 is Lu 10 28 · 1 ~ 28.5. Nearby, the essence As described above, since the intensity ratio of the main peaks of the anatase type and the anatase type cannot be obtained, the 121 surface of the anatase type that does not overlap with the anatase type peaks is used here. Wave peaks to find the intensity ratio of the 15 peaks (wave intensity of brookite type 12 丨 plane) which overlaps with the above three peaks // Overlap = wave-peak intensity), and then the content ratios of brookite-type and anatase-type titanium oxides are obtained. Moreover, the rutile-type titanium oxide is replaced by the main peak surface The ratio of the intensity of the three overlapping peaks (the main peak intensity of the rutile type) / (the intensity of the three overlapping peaks) is used to determine the content rate. The actual measurement is performed using a χ-ray diffraction device (manufactured by Rigaku Corporation) , RAEKB 20 7 7 P 7 again) And the X-ray diffraction identification is performed at the same time based on the analysis of data processing volume. &Amp; 20 1241278 Table 1 (card number) plate titanium $ wide (29-1360) a 1272) / 1 JT) Redstone (21-1276) d-value crystal plane strength ratio d-value crystal plane strength ratio d-value crystal plane strength ratio 3.51 120 100 3.52 101 __100 3.25 110 100 2.90 121 90 1.89 200 ^ 35 1.69 211 1 60 3.47 111 80 2.38 ^ οαΓί 20 2.49 101 50 In the following examples, the following physical properties of the film were evaluated, and 5 was used as the properties of the titanium oxide sol of the present invention. The evaluation of the physical properties of the film was prepared in the examples or comparative examples. The coating solution 2 m 丨 coated on 7 6 X 2 On a 6 mm soda-lime glass (soda glass) (substrate), it is held in the vertical direction for 10 minutes to remove excess coating liquid and form a surface layer. After forming the surface layer 10, it is described in the examples or comparative examples. The predetermined temperature (hereinafter referred to as the "film-forming temperature", but meaning the heating and firing temperature) is dried or fired to obtain a titanium oxide gadolinium film (film thickness of about 0.2 "m). The film was measured for transparency, photocatalytic energy, adhesion, adhesion, and pencil hardness. Transparency was measured with a Hazemeter 15 (JIS K6718 standard) manufactured by the East Hall and Denso Technology Center, and was evaluated in the following three stages. ◎ ···· Haze rate is less than 2.0% ○ ···· Haze rate is 2.0% or more and less than 5.0% X ···· Haze rate is 5.0% or more 20 The photocatalytic energy is determined by coating a few drops of red ink on the substrate. The black light was irradiated with an ultraviolet intensity of 2] mW / cm2 for 30 minutes, and the discoloration of the red ink was judged in 3 stages according to visual observation. 21 1241278 ◎ ···· fading is in good condition .. ·····································································································································································酉 Fine> Wet tissue paper (Feng A 7 Y 7. (Successive batch), manufactured by Yuki 7 Moss) After wiping the soda-lime glass substrate ten times, then wipe it again with a dry, koji, and ten After that, the state of the coating film was visually evaluated in the following three stages. ◎ ··· No damage on the coating film ···························--------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- . The cuts are spaced 1 mm apart and the number of divisions is 100. The yttrium pen hardness is based on the pencil hardness test method (JIS K5400). 15 Example 1 Water was added to titanium tetrachloride (purity: 99.9%), and the solution was prepared so that the titanium tetrachloride / Chen degree was 0.25 mole / liter (equivalent to 2% by weight of titanium oxide). Therefore, the temperature of the aqueous solution will not rise to 50 ° C or more by ice-cooling. Next, 1 liter of this aqueous solution was charged into a 20 reaction tank with a reflux cooler as shown in the figure, and heated to the vicinity of the boiling point (1. 0), and kept for 60 minutes to hydrolyze to cool the obtained sol. After that, the residual gas generated in the reaction was removed by electrodialysis to make the chloride ion (C1 ion) become 0.001 ppm. Electrodialysis, using an electrodialysis device type manufactured by Asahi Kasei Corporation The implementer is monitoring the pH value of the sol solution. Next, nitric acid is added to the sol 22 1241278 so that NO is 3,000 ppm. Titanium oxide prepared by chloride and nitrate ions as described above / Gum is added with water-soluble south molecular weight polyvinyl alcohol of 〇, 0 μm relative to the weight of the sol solution as a film-forming aid. Even if the sol passes 5 or more days, the generated titanium oxide particles cannot be used. Deposition was detected. A part of the particles in the sol was taken out and observed with a transmission electron microscope. The average particle size of the particles was ㈣18 // m. Then, the crystal structure of the emulsified titanium was investigated by X-ray diffraction. As a result, The X-ray peak intensity ratio (the peak intensity of the 121-type plate / three overlapping peak intensity) is 0.35, while the peaks in the rutile 10 stone are not visible. Titanium oxide, under crystallinity, according to the foregoing The peak intensity ratio is composed of about 40% by weight of anatase type and rhenium-based brookite type. For the fire, tetraethyl orthosilicate (ethanol / valley) is prepared. Liquid (changed to SiO2: 0.25 wt.%) Was used as an adhesive. 15 The above sol aqueous solution and this adhesive solution were mixed at a weight ratio of 1: 1 to prepare a coating agent for a titanium oxide sol. The composition of the coating agent is shown in Table 2. The physical properties of this coating agent solution were evaluated in accordance with the evaluation method of the film described in Rain. However, the application temperature of the coating film was adjusted to 100 ° C. Obtained here The evaluation results of the thin films are shown in Table 3. / 20 Example 纟 —The titanium oxide sol was prepared in the same manner as in Example 1 and further formed this material. The composition of the coating agent and its manufacturing method are the same as before ..., same as in Example 1, except that the heating (firing) temperature is changed to 400 ° C. The composition of osmium is not shown in Table 2, and the evaluation results of the film material are shown in Table 3. 23 25 1241278 Comparative Example 1! // 2! ”3 // 4 Example 1 // 2 // 3” 4 // 5 " 6 // 7 // 8 9 //!. () // 11 η 12 // 13 // 14 Example and comparative example numbers-^ ^ έ 1φ 六 49 氺 1 // //: 49 氺1 // /; // // // η " " // // 49 氺 2 ethanol 氺 1 or methanol 氺 2 wt% 〇 >. Of > · 〇 & 々-¾ ☆ 々々 > A >. I polyvinyl alcohol weight% 1 1 0/125 /; 0/125 // // // // // " η η if η // West ethyl orthosilicate converted to Si02 weight % 1000 // 1000 // 500; η 1000 // 100 ί // 2000 n 1. () () () // 1500 600 600 i gas ion (Ci) ppm (weight) Μ Μ. 1500 // 50. // 10 () () " 1000 // 1000 nitrate ion (N03) ppm (weight)! 1! I 200! 100 // 100 // 500 /; 200 600: phosphate ion (ρα!) Ppm (weight) 0.125 " 0.125 // 0.125 // //, " // // // // // // // // π (L25 0.125 Oxidation deficiency: (Ti〇2); Moi / L Kill 24 1241278 丄 ~ Xibian comparative example and real Correction was performed similarly to prepare a titanium oxide sol, and its physical properties were evaluated. However, nitrate was not added as early as possible — and the values in Table 2 were replaced with chloride ions. In Comparative Examples 丨 and 2, the "detergent" is shown in detail. The composition of the coating agent is shown in detail (continued in Table 2), and the physical properties are shown in Table 3. Examples 3 to 12 10

/ Example 1 A titanium oxide sol was prepared in the same manner, and was further formed into a thin film, and its physical properties were evaluated. However, the amount of meta-acid and nitrate added. Coating agent composition group scale * material 2, _pure evaluation storage fruit ㈣ = s: the three particles of titanium oxide and the crystal structure of titanium oxide of Comparative Examples 1, 2 and Examples 3 to 12 are roughly the same as those of Examples i and 2. On the same. 1 Example 13 Filled with 954 ml of disease and pseudo water! As shown in the figure, in a 15 reaction tank with a reflux cooler, it is heated to 95t. Add dishic acid to it to make the tritium ions into

It was 200 PPm. While maintaining the stirring speed at about 200 rpm, in this aqueous solution, titanium tetrachloride (Ti content · 16 3% by weight, specific gravity 159, purity 99.9 weight 畺 / 〇), a water solution of 46 mi at about 5 mi / Drop into the reaction tank at a rate of min. At this time, care must be taken not to lower the temperature of the reaction solution. As a result, the concentration of tetrachloromethane was 0.25 mol / liter (converted to 2 weight of titanium oxide / 0). Although white turbidity started to occur immediately after the reaction solution was dropped in the reaction tank, the temperature was maintained continuously. After the dropping was completed, further heating was performed to raise the temperature to near the boiling point (104.0.0, and kept in this state for 60 minutes to make The reaction was complete and completed. After cooling, the residual gas generated in the reaction was removed by electrodialysis for 25 1241278 weeks to pH-1.9 (chloride ion 600 ppm, phosphate ion 2000 ppm). A water-soluble high-molecular-weight polyethylene gardenia having a content of 0.01% by weight is used as a film-forming aid to prepare a titanium oxide sol (Ti0 2 about 0.25 mole / liter. Liter). This sol is stable, The sedimentation of the oxidatively deficient micro-particles produced by the above 30-degree is still undetectable. After filtering a part of the above-mentioned bath gel, use a 60.degree vacuum dryer to make Zhimoya and take it out. The results obtained by applying the same quantitative analysis as in the previous example, "(the peak intensity of the 121 brookite type) / (the three overlapping peak intensities) 10 ratio is 0.38, (the main peak intensity of the rutile type) ) / (Three overlapping peak intensities · degrees) is 0.05. According to The titanium oxide was found to be about 7000 wt. In brookite type. The crystalline titanium oxide was about 1.2 wt.% In gold, 'workstone' type, and about M '% in anatase type, and a transmission electron microscope was used. When the microparticles were observed, the average particle diameter of the primary particles was 0.015 / zm. When further measured by the Beta method, the specific surface area of the microparticles was 140 m2 / g. The results of the evaluation of the composition of the coating composition and the physical properties of the film are shown in Table 3. Column 14 was subjected to the same hydrolysis conditions as in Example 1. Titanium tetrachloride was hydrolyzed to obtain a sol having a titanium oxide of 0.25 mol / litre. After performing electrodialysis, the sol was first After evaporation, it is concentrated to a titanium oxide concentration of 2.5 mol · 0 / liter (20% by weight of titanium oxide), and then the residual chlorine is removed by electrodialysis, so that the chloride ion becomes approximately 1,200 ppm. Next, Lithic acid and wall acid are added to the sol to open 2,000 ppm of 30% NO ions, and PA ions are "⑻ 卯!". As mentioned above-perchloride, nitrate and phosphate TiO Add sol =-26 1241278 to the sol as solvent, then A water-soluble polymer polyvinyl alcohol in an amount as shown in Table 2 was combined to prepare a titanium oxide sol (but 0.5 mol / liter). Using this sol, a film was prepared in the same manner as described above to perform a film. Evaluation of physical properties. The results are shown in Table 3. In addition, the average particle diameter, the ratio of the crystal form, and the specific surface area of the titanium oxide particles were almost the same as those of Examples 1 and 2.

27 1241278 Comparative example 1 j ”2 // 3 /; 4 embodiment 1, 7 2 // 3 // 4 // 5 // 6 // 7 // 8 " 9 '' 10 // 11 // 12 / / 13 // 14 [V cf 蛑 100 400 100 400 100 400 100 400 100 400 100 400 100 400 100 400 400 400 Film forming temperature Γ〇 〇〇〇〇 ◎ ◎◎◎ _〇〇 ◎◎ 〇 ◎◎ Transparency 〇 @ 〇 @ © ◎◎◎◎◎◎◎◎◎◎ 〇 © Photocatalytic energy 〇 〇 〇 X Adhesiveness (water wiping) XXXX @ © @ 〇 @ 〇 @ 〇 @ 〇 @ 〇 @ 〇丨 (Alcohol) 1 ^ S 〇0 0 ¾ ^ ^ >, bi > ^ ^ 々: ¾ guest > 5 1 \ jj \ 1 ^ ^ ^ ^ ^) · > ** »· ί tmW | Pencil Hardness 28 1241278 Industrial applicability ★ In addition to gas ions, the titanium oxide sol of this example also contains ^ ions, other than Bronsted Gamma 3 to 1 gas containing side ions and human ions ; = = When a titanium oxide film is formed, the film becomes transparent and has a chemical effect. In particular, titanium oxide is a brookite-type catalyst: excellent rigidity and fibrous properties 10 The use of two =? Film has durability, if the film, such as D. /, Glass lamp officials and covers of lighting appliances, etc .; in the case of light interruption, the light can be maintained after a long period of time: chemical: 15 20 to in chemical 1_ due to the use of tetrachloromethane as a raw material, but _ For the shape film, the economic aspect is also favorable. In order to easily form a thin film formed by titanium dioxide containing nitrate, it is also possible to prevent photocatalysis during firing in order to cause Hajj to break glass veneer. It can be lowered and maintain the 'c diagram. Simple explanation] This is a schematic cross-sectional view of an example of clothing and clothing used in the manufacture of the oxidized cyanosol according to the present invention. [Description of symbols of main components] l · reaction tank; 3. ·· reflux cooler; 2. ·· titanium tetrachloride aqueous solution; 5 ··, thermometer; 4 ··· mixer; 6. ·· for heating reaction tank Device 29

Claims (1)

1241278 Announcement X. Scope of Patent Application: ~ Patent No. 93132721 Patent Application Amendment of Patent Scope June 17, 1994 1. An article coated with a titanium oxide sol on the surface of a substrate, wherein the titanium oxide sol contains chloride ions and other Bronsted tests other than chloride ions, and the foregoing Bronsted test is selected from the group consisting of bowl acid ions, At least one or more of acid ions, pyrophosphate ions, metaphosphate ions, polyphosphate ions, acetic acid ions, and organic acid ions are filled. The average particle diameter of titanium oxide is 0.01 to 0.1 // m. 2. For the article in the scope of patent application, the substrate is at least one selected from the group consisting of ceramics, metal, glass, plastic, paper and wood. 3. A titanium oxide particle, which is produced by drying a titanium oxide sol, the titanium oxide sol containing chloride ions and other Bronsted bases other than chloride ions, and the foregoing Bronsted bases are selected from the group consisting of nitric acid At least one or more of ions, phosphate ions, pyro-acid ions, meta-acid ions, multi-wall acid ions, acetic acid ions, and organic acid ions. The titanium oxide has an average particle size of 0.01 to 0.1 // m. 30