Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles
Abstract
The invention provides a process of producing a titanium oxide-forming solution, wherein a hydrogen peroxide solution is added to a titanium- containing starting agueous solution toform a peroxotitanium complex, a basic substance is then added to the peroxotitanium complex to obtain a solution which isin turnlet stand or heated, thereby forming a precipitate of a peroxotitanium hydrate polymer, at least a dissolved component derived from the titanium-containing starting aqueous solution, except water, is then removed from the precipitate, and a hydroxide peroxide solution is finally allowed to act on a dissolved component-free precipitate. The invention also provides a dispersion with titanium oxide dispersed therein.

Term
No projected expiry on record.
- Priority
- Filed
- Granted
- Today
1 claim: 1 independent, 0 dependent
- 11 _ 一種欽 係在含有 成過氧化鈦 入鹽基性物 合物之沉殿 液中之水以 作用。 2. 如申請 方法,其中 基性物質之 3. 如申請 方法,其中 成分之除去 4. 如申請 方法,其中 成分之除去 5. 如申請 方法,其中 物之聚合物 6. 如申請 方法,其中 物之聚合物 7. 如申請 方法,其中 專利範 係除去 水以外 專利範 係藉由 處理。 專利範 儀藉由 處理。 專利範 係在40 之沉澱 專利範 係在40 之沉澱 專利範 係在40 氧化物形成用溶液之製造方法,其特徵為: 鈦之原料水溶液中,添加入過氧化氫水,而形 錯合物之後’接著’藉由放置或者加熱該添加 質之所得到之溶液而形成過氧化鈦水合物之聚 物’然後’至少除去該來自含有鈦之原料水溶 外之溶解成分’接著’使得過氧化氫水,發生 圍第1項之鈦氧化物形成用溶液之製造 該來自添加於水合物形成用溶液中之趟 之溶解成分。 圍第1項之鈦氧化物形成用溶液之製造 水洗或者離子交換反應’而進行著溶解 圍第2項之鈦氧化物形成用溶液之製造 水洗或者離子交換反應,而進行著溶解 圍第1項之鈦氧化物形成用溶液之製造 C以下之溫度下,進行著過氧化鈦水合 物和過氧化氫水之間之反應。 圍第2項之鈦氧化物形成用溶液之製造 C以下,溫度了’進行f過氧化欽水合 物和過氧化氫水之間之反應。 圍第3項之鈦氧化物形成用^容液之製造 C以下之溫度下,進行著過氧化鈦水合 S910293I.ptd 第63頁 460416 六、申請專利範圍 物之聚合物之沉澱物和過氧化氫水之 8.如申請專利範圍第4項 氳 物之聚合物之沉澱物和過氧化氫水之間之反應。 σ 9_ 一種鈦氧化物形成用溶液,其特徵為:, 屬L、3戈者含有氧和氫中之至少二種之固體狀鈦化 ::中光:加:該具有對於鈦含量呈過剩之羥基之鹽基性 人:成盔二還添加入過氧化氫水’而使得該固體狀鈦化 液化狀態…’溶液中之欽離子、含欽之 :子以及氫離子以外之陽離子濃度,係為鈦濃度之i /2以 Γ ° 二’二種®鈦氧化物形成用溶液之製造方法,其特徵為: ^ ,鈦、或者含有氧和氫中之至少一種之固體狀鈦 2 # ,添加入該具有對於鈦含量呈過剩之羥基之鹽基 ’並且’在溶液之pH值(酸驗度)保持在3〜1〇之 ’二下,進行著許多次之添加入過氧化氫水之所生成之溶 液中之鈦離子、含鈦之離子以及氳離子以外之陽離子之除 去和過剩之過氧化氫水之分解作業。 土 11.如申請專利範圍第10項之鈦氧化物形成用溶液之製 造方法’其中固體狀鈦化合物,係為在鈦化合物中,添加 入鹽基性物質而生成之鈦水合物。 1 2.如申請專利範圍第丨〇項之鈦氧化物形成用溶液之製 造方法’其中係添加入羥基量對於鈦含量昱2倍以上之鹽 基性物質。 六、申請專利範圍 、」么如申甘清專利範圍第1】項之鈦氧化物形成用溶液之製 ;,:;:質其中係添加入經基量對於欽含量呈2倍以上之鹽 造1 方4、去如申其清中專圍第1〇項之鈦氧化物形成用溶液之製 ':法,其中係在溶液令’含有過氧化鈦。 ▲方、:專利範圍第11項之鈦氧化物形成用溶液之製 、方法’其中係在溶液中,含有過氧…-… 造1 方6:、:,申二專二範圍第12項之敍氧化物形成用溶液之製 方法其中係在溶液令,含有過氧化鈦。 造1 方7 :Λ請範圍第13項之鈦氧化物形成用溶液之製 '其中係在溶液中,含有過氧化鈦。 造1 方8 申Λ專//圍第14項之鈦氧化物形成用溶液之製 坆方法,其中_係在溶液令,含有過氧化鈦。 1 9 · 一種鈦氧化物塗敷劑之製造方法,其 係藉由在金屬鈦、或者含有氧和氫中之至少一種之固體 中並!加ΐ該具有對於钦含量呈過剩之經基之 鹽基]·生物冑並且,在溶液之ΡΗ值(酸鹼度)保持在3〜 10 =狀態下’進行著許多次之添加入過氧化氫水之所生成 之浴液中之鈦離子、含鈦之離子以及氫離子以外之陽離子 之除去和過剩之過氧化氫水之分解作業,以便於在使得鈦 離子'含鈦之離子以及氫離子以外之陽離子濃度,成為欽 濃度之1/2以下之後,接著,在8〇t;以上之溫度下,進行 著加熱處理’而析出銳鈦礦(anatase )粒子。 20, 一種結晶性鈦氧化物粒子分散液體之製造方法,其 89102931.ptd 第65頁 460416 六、申請專利範圍 特徵為: 而形 添加 之聚 水溶 之狀 '係f含有鈦之原料水溶液中,添加入過氧化氫水, 成過氧化鈦錯合物之後,接著,藉由放置或者加熱該 人孤基座物質之所得到之溶液而形成過氧化鈦水合物 合物之沉澱物,然後,至少除去該來自含有鈦之原料 液中之水以外之溶解成分,接著,在並無分離出水分 態下’於70 °C以上之溫度中,進行著加熱。 2 1,如申請專利範圍第2 〇項之結晶性鈦氧化物粒子分散 液體之製造方法,其中係也除去該來自添加於水合物形成 用溶液中之鹽基性物質之水以外之溶解成分。 22·如申請專利範圍第20項之結晶性鈦氧化物粒子分散 液體之製造方法’其中係藉由水洗或者離子交換反應,而 進行著溶解成分之除去處理。 2 3.如申請專利範圍第21項之結晶性鈦氧化物粒子分散 液體之製造方法’其中係藉由水洗或者離子交換反應,而 進行著溶解成分之除去處理。 第66頁
235 paragraphs, as filed
Solution for forming titanium oxide and method for producing crystalline titanium oxide particle dispersion liquid
[Detailed Description of the Invention] [Background of the Invention]
The present invention relates to a method for producing a titanium oxide forming solution and a crystalline titanium oxide particle dispersed liquid; that is, the present invention relates to a titanium oxide having a titanium oxide film formed thereon as a substrate. A method for producing a coating agent and a titanium oxide film covering produced by using the titanium oxide coating agent.
The method for forming the titanium oxide film is as follows:
a coating method in which a titanium oxide powdery slurry, an aqueous solution of titanium chloride or titanium sulfate is applied onto a substrate, followed by sintering treatment;
a sol-gel method in which a sol produced by hydrolysis of a metal alkoxide is applied to a substrate, followed by sintering; and
Sputtering method in which a sputtering method is performed on a target of an oxide in a high vacuum, and a film is formed on a substrate; and a CVD (Chemical Vapor Phase) method is used. The CVD (Chemical Vapor Deposition) method is a method of producing a thin film on a substrate by volatilizing and decomposing an organometallic compound or a halide in a heating furnace;
A plasma spray method in which a solid particle is melted in a plasma generated in the atmosphere, and the molten solid particles are irradiated onto a surface of a substrate. In the above method, the method of using the coating liquid as a method of forming a titanium oxide film is relatively simple and has considerable practicality.
The coating method using titanium oxide powder is relatively simple, but it is not easy to obtain a film which is dense and has good adhesion. Therefore, in order to form a titanium oxide film, it is generally necessary to use the synthetic temperature which can withstand. A substrate having heat resistance so as to be required to be blended with a relatively high synthesis temperature, and as a result, the type of the substrate which can be used is limited.
Further, in order to obtain the dispersion liquid of the fine particles of titanium oxide described above, an acid or a suitable organic dispersant is generally used, so that there is a disadvantage that a harmful halogen compound or the like is formed by the sintering treatment. Further, the method of applying and sintering an aqueous solution of titanium chloride or titanium sulfate produces a harmful halogen compound, and the sintering temperature of the method must be several hundred degrees or more.
In addition, the commercially available titanium oxide sol produced by the sol-gel method can be used for coating or impregnation treatment, and can also be used for large-area coating and low-temperature synthesis treatment. There are quite a few industrial advantages. However, the commercially available titanium oxide sol produced by the sol-gel method must utilize an organic metal such as titanium tetraisopropoxide or tetrabutyl titanate. The synthesis is carried out, and therefore, the price of the raw material is quite expensive, and the chemical nature of the raw material is rather unstable and is susceptible to temperature control or the atmosphere, so that there is a problem of so-called handling.
Further, since the sol-gel method contains an acid or an organic substance in the raw material sol, it is necessary to heat to 400 ° C or higher in order to perform sintering and removal treatment, and as a result, the sol-gel method is Not suitable for materials that are easily attacked by acids, and the melt-gel method is At the time of low-temperature sintering treatment, there is a problem that it is easy to become porous.
In addition, the operation of the sol-gel method is quite complicated, and it is also necessary to use an organic solvent, and an acid or a base or an organic substance is added to the titanium oxide sol produced by the sol-gel method. There is a problem that the material to be coated is corroded. Further, the sol-gel method is required to be heated to a temperature of 400 ° C or more in order to decompose the organic matter, and therefore, various disadvantages such as generation of harmful halogen compounds or nitrogen oxides in the heat-sintering treatment may occur. .
As described above, in the prior art method, it is not easy to produce a crystalline titanium dioxide film having a relatively high density in a low temperature state, and a relatively high density can be produced in a relatively low temperature state. In the sol-gel method of the crystalline titanium dioxide film, it is necessary to decompose and eliminate organic substances or acids by heat treatment, and as a result, the phenomenon of being easily porous is caused by the above phenomenon. A relatively high heat treatment temperature is employed in order to produce a film of relatively high density. Further, in the sol-gel method, there are also disadvantages in that these additives cause harmful substances such as nitrogen oxides or organic substances due to heat treatment.
It is known that a film having a relatively good characteristic can be formed at a relatively low temperature in a state in which a titanium oxide film is formed from a titanium peroxide hydrate in a method as described above. It is known that when hydrogen peroxide water is directly added to a solution of titanium tetrachloride, titanium sulfate or the like, ions of titanium peroxide hydrate are formed, and for the titanium peroxide The ions of the hydrate are subjected to a condensation treatment to form a solid precipitate to form titanium peroxide hydrate.
In addition, in the state where the pH (pH) is 1 or more, ions of the titanium peroxide hydrate are formed in the form of a multinuclear ion or the like containing two or more titanium atoms, and in a state of normal temperature, The ions of the titanium peroxide hydrate are gradually subjected to a condensation treatment to precipitate and precipitate the titanium peroxide hydrate. Therefore, when the pH (pH) is 1 or more, it is not easy to use titanium oxide as a coating agent, and as a result, the type of the substrate is limited to a strong acid having a pH (pH) of 1 or less. The base of the coating agent. Further, there is a problem that harmful substances such as hydrogen halide or sulfur oxide are generated by halogen or sulfur contained in the heat treatment.
In addition, in order to produce a high-purity titanium oxide film, JP-A-62-252319 (A) is proposed, and it is proposed to directly add hydrogen peroxide water to titanium hydride or titanium alkoxide to dissolve. The titanium hydride or titanium alkoxide is used to produce titanium hydrogen peroxide, that is, a substance which is considered to be a titanium oxide hydrate.
However, the above-mentioned titanium raw materials are not stable, and in the state in which hydrogen peroxide water acts, a considerable heat generation reaction is caused, so that there is a disadvantage that the raw material or the thermal decomposition of the product is adversely affected. occur. Therefore, in the state of attempting mass production, since the system is not sufficiently cooled, the generated perovskite acid undergoes polymerization, which increases considerable viscosity, and, in a relatively severe state, The particles grow and become turbid, until they block the light. As a result of the degree of penetration, in the state in which the above-mentioned raw materials are used as a coating agent, the above-described phenomenon causes a decrease in the adhesion or density of the film.
In addition, Japanese Laid-Open Patent Publication No. 63-35419 (A) and Japanese Patent No. JP 01-224220 (A) disclose a method for producing an aqueous solution of titanium peroxide hydrate described below: In the sol or gel of titanium hydroxide, hydrogen peroxide water is added to form an aqueous solution of a hydroperoxide complex of titanium dioxide ions or a titanium peroxide hydrate of titanic acid.
However, when hydrogen peroxide water is directly added to the titanium hydroxide, the effects of so-called peroxidation and solubilization are caused at the same time, and as a result, considerable heat generation occurs, and it must be carried out quite sufficiently. Stirring and cooling treatment, but when the amount of the solution is considerably increased, it is very difficult to adjust the temperature, and when the cooling is not sufficiently performed, the solution may have a viscosity-increasing and condensation reaction, resulting in The problem that the polymer grows into a particle or even becomes a turbid state occurs.
In addition, in the state in which the above-described sol or gel containing titanium hydroxide is produced, a salt-based substance such as ammonia is added, but since the phenomenon of precipitation of the so-called titanium hydroxide-containing particles is instantaneously caused, It is quite easy to put in and adsorb the cation such as an ammonium ion or an anion such as a chloride ion which is an impurity. In particular, the presence of an impurity anion such as a chloride ion or a sulfate ion promotes a condensation reaction of a hydrate of titanium hydroxide formed after the addition of hydrogen peroxide water, so that there is a so-called transparent aqueous solution. The state occurs. In addition, even with distilled water, Also, it is not possible to wash the solution containing titanium hydroxide, and it is not easy to completely remove the impurities, and therefore, there is a considerable problem in terms of stable productivity of the titanium hydroxide hydrate.
In addition, the present inventors proposed in Japanese Patent No. 2875993 and Japanese Patent No. 2938376 that the precipitation of anatase ultrafine particles can be obtained by heating titanium peroxide hydrate. Further, by the coating agent, a coating agent having an anatase ultrafine particle deposited thereon can be used to form a crystalline titanium dioxide film having a relatively good adhesion.
In the above-mentioned methods, a titanium dioxide film having a relatively good crystallinity can be formed as compared with the prior art method, but in a state where the residual amount of the cation of the ammonium ion or the like is relatively large and during heating In the state in which an aqueous solution of titanium oxide hydrate is used to produce an anatase sol, the decomposition of the peroxy group is not easily caused, and the size of the particles is also made so large that In the state in which an anatase sol is used as a coating agent, adhesion or density is deteriorated.
In particular, when the residual amount of the impurity anion such as chloride ion or sulfate ion becomes considerable, the polymerization of the perovskite acid formed after the addition of hydrogen peroxide water is promoted, so that there is The state in which the transparent aqueous solution cannot be obtained occurs, or the so-called thickening phenomenon is caused. Further, the impurity ions adsorbed on the titanium hydrate can be repeatedly washed by the purified water in order to reduce the concentration of the impurity ions, and also by causing the hydrogen peroxide water to function. system A transparent perovskite solution is produced. However, when the concentration of the impurities becomes relatively small, the titanium hydrate is not easily precipitated. Therefore, it takes a relatively long time for the cleaning of the impurities to be washed.
In addition, the inventors of the present invention are required to provide a manufacturing method more easily, and even in a large amount, in comparison with the method of using a liquid for forming a titanium dioxide film as proposed in Japanese Patent No. 2875993 and Japanese Patent No. 2938376. It is also possible to produce a liquid for forming a titanium dioxide film which has a relatively good characteristic and is stable.
The present invention has been made in order to improve the conventional problems of the prior art; the present invention provides a novel method of producing an aqueous solution of titanium peroxide hydrate. In other words, the above-mentioned problem is to prevent condensation caused by heat influence in the manufacturing process in a state where an aqueous solution of titanium peroxide hydrate is produced by hydrogen peroxide water, or due to particles It is necessary to use a growth agent or the like as a result of the use of the coating agent as a coating agent, and the adhesion or density is lowered. Further, the problem of the present invention is to obtain a film which is excellent in adhesion. And a solution for forming a titanium oxide of a titanium oxide coated film having a relatively large density.
Further, the present invention provides a novel method for producing crystalline titanium oxide particles which are useful as a coating agent for a solution for forming a titanium oxide film. In other words, the above-mentioned problem is to prevent condensation caused by heat influence in the manufacturing process in a state where an aqueous solution of titanium peroxide hydrate is produced by hydrogen peroxide water, or due to particles It is necessary to use a growth agent or the like as a result of the use of the coating agent as a coating agent, and the adhesion or density is lowered. Further, the lesson of the present invention The problem is to obtain a crystalline titanium oxide particle which can form a titanium oxide coating film having a relatively good adhesion and a relatively high density.
Further, an object of the present invention is to provide a solution for forming a titanium oxide used in a titanium oxide coating agent or the like, and a method for producing the same, and an object of the present invention is to provide a titanium which can solve the conventional prior art. A solution for forming a titanium oxide which is a relatively stable problem in the production method for forming an oxide, and a dispersion of anatase fine particles obtained by the above-described solution for forming a titanium oxide A novel manufacturing method for a sol. Further, an object of the present invention is to provide a production method for promoting solubilization by adjusting impurity ions during a reaction from a raw material to a solution for forming a titanium oxide.
[Overview of the invention]
In the method for producing a solution for forming a titanium oxide according to the present invention, after adding hydrogen peroxide water to an aqueous solution containing titanium, a titanium peroxide complex is formed, and then the salt is added by placing or heating. Forming a solution of the polymer of the titanium peroxide hydrate by the solution obtained from the basic substance, and then removing at least the dissolved component other than the water in the aqueous solution containing the titanium, and then causing the hydrogen peroxide to occur. effect.
Further, in the method for producing a solution for forming a titanium oxide according to the present invention, the dissolved component other than the water derived from the salt-based substance added to the solution for forming a hydrate is also removed.
The method for producing a solution for forming a titanium oxide according to the present invention is a method of removing a dissolved component by a water washing or an ion exchange reaction.
The method for producing a solution for forming a titanium oxide according to the present invention is a reaction between a precipitate of a polymer of titanium peroxide hydrate and hydrogen peroxide at a temperature of 40 ° C or lower.
Further, the titanium oxide forming solution of the present invention is added to the solid titanium compound containing at least one of oxygen and hydrogen, and a salt-based substance having a hydroxyl group which is excessive in titanium content is added. Further, hydrogen peroxide water is added to make the solid titanium compound in a solubilized state, and the concentration of cations other than titanium ions, titanium-containing ions, and hydrogen ions in the solution is 1/% of the titanium concentration. 2 or less.
Further, the method for producing a solution for forming a titanium oxide according to the present invention is characterized in that a titanium metal or a solid titanium compound containing at least one of oxygen and hydrogen is added to the salt group having a hydroxyl group which is excessive in titanium content. a substance, and a titanium ion, a titanium-containing ion, and a hydrogen ion in a solution formed by adding hydrogen peroxide water many times while maintaining the pH value (pH-base) of the solution at 3 to 10. Removal of cations other than cations and decomposition of excess hydrogen peroxide water.
The method for producing a solution for forming a titanium oxide according to the present invention, wherein the solid titanium compound is a titanium hydrate formed by adding a salt-based substance to a titanium compound.
The method for producing a solution for forming a titanium oxide according to the present invention is a salt-based substance in which the amount of the hydroxyl group is twice or more the titanium content.
Further, the method for producing a solution for forming a titanium oxide according to the present invention is characterized in that a titanium metal or a solid titanium compound containing at least one of oxygen and hydrogen is added to the salt group having a hydroxyl group which is excessive in titanium content. Sex After the titanium compound is precipitated and separated, the cleaning process is performed to remove the cations other than the titanium ions, the titanium-containing ions, and the hydrogen ions, and then the hydrogen peroxide water is added thereto. Dissolving treatment.
In the above-described method for producing a solution for forming a titanium oxide according to the present invention, the concentration of the cation other than the titanium ion, the titanium-containing ion, and the hydrogen ion in the solution is 1/2 or less of the titanium concentration.
The method for producing a titanium oxide forming solution of the present invention described above contains titanium peroxide in a solution.
Further, the method for producing a titanium oxide coating agent of the present invention is carried out by adding a hydroxyl group having an excessive content to titanium in a titanium metal or a solid titanium compound containing at least one of oxygen and hydrogen. a salt-based substance, and a titanium ion, a titanium-containing ion, and a solution obtained by adding the hydrogen peroxide water to the solution in a state in which the pH (pH) of the solution is maintained at 3 to 10 Removal of cations other than hydrogen ions and decomposition of excess hydrogen peroxide water so that the concentration of cations other than titanium ions, titanium-containing ions, and hydrogen ions becomes 1/2 or less of the titanium concentration, and then At an temperature of 80 ° C or higher, heat treatment is performed to precipitate anatase particles.
Further, in the method for producing a crystalline titanium oxide particle-dispersed liquid of the present invention, hydrogen peroxide water is added to an aqueous solution containing titanium to form a titanium peroxide complex, followed by standing or heating. Adding the obtained solution of the salt-based substance to form a precipitate of the polymer of the titanium peroxide hydrate, and then removing at least the raw material water containing titanium The dissolved component other than the water in the solution is then heated at a temperature of 70 ° C or higher without separating the water.
In the method for producing a crystalline titanium oxide particle-dispersed liquid of the present invention, the dissolved component other than the water derived from the salt-based substance added to the hydrate-forming solution is also removed.
In the above-described method for producing a crystalline titanium oxide particle-dispersed liquid of the present invention, the removal treatment of the dissolved component is carried out by water washing or ion exchange reaction.
[Description of a preferred embodiment]
In the present invention, it has been found that in the production process of a solution for forming a titanium oxide via titanium oxide hydrate, it is possible to obtain a titanium oxide having a relatively good characteristic by removing the cause of the condensation reaction or the like. The solution is used so that the present invention can be completed.
A: Method for producing titanium oxide forming solution 1
In other words, in the course of the reaction, the reaction product which is a factor contributing to the condensation reaction or the like or the impurity which is mixed by the raw material is separated in an early stage, so as to prevent the occurrence of the condensation reaction or the like. Further, the exothermic reaction is carried out discontinuously, and at the same time, the first exothermic reaction and the second exothermic reaction are separated by the operation of the exothermic reaction caused by the reaction between the raw material and the hydrogen peroxide water. The problem caused by the exothermic reaction is solved; the method 1 for producing a titanium oxide forming solution is constituted by the following operations:
(1) Precipitation of a polymer of titanium peroxide hydrate
It is possible to dilute a soluble titanium compound such as titanium tetrachloride by water. Further, an excessive amount of hydrogen peroxide water is added to form a brown peroxy complex, and then a salt-based substance such as ammonia is added to prepare an aqueous solution of yellow titanium peroxide hydrate, and The aqueous solution of the above-mentioned yellow perovskite hydrate is placed at a normal temperature or an aqueous solution of the yellow perovskite hydrate to heat and precipitate a polymer of the titanium oxide hydrate.
(2) Removal of ionic substances or impurities Washing the liquid containing the precipitation precipitate of the polymer of the titanium peroxide hydrate or filtering and washing the liquid containing the precipitate of the polymer containing the titanium peroxide hydrate. The treatment is performed to remove the ammonium ion or chloride ion contained in the liquid or the impurity derived from the raw material.
(3) Formation of an aqueous solution of titanium peroxide hydrate
The titanium oxide hydrate which removes the ionic substance or the impurity by the washing treatment is cooled to room temperature or below, and hydrogen peroxide water is further added to make yellow transparent and A quasi-stable aqueous solution of titanium oxide hydrate.
A solution for forming a titanium oxide can be produced by the above operation, so that a solution for forming a titanium oxide capable of suppressing the occurrence of a condensation reaction can be obtained.
In the method of the present invention, the soluble titanium compound used as a raw material may, for example, be titanium tetrachloride, titanium sulfate, titanium nitrate or titanium alkoxide.
Further, the hydrogen peroxide added to the aqueous solution of the soluble titanium compound The amount of water is such that the molar ratio of hydrogen peroxide to titanium is 1 or more, and in the state where the number of moles of hydrogen peroxide/titanium is 1 or less, the peroxidation reaction cannot be completely completed. Further, since the hydrogen peroxide water to be added is decomposed regardless of the reaction, it is preferable to add excess hydrogen peroxide water so that the hydrogen peroxide/titanium molar ratio is more than 1.
When hydrogen peroxide water is added to the solution containing soluble titanium, the peroxidation reaction occurs almost instantaneously. When the pH (pH) is 3 or less, the titanium in the solution mainly dissolves into a cation. In addition, when the pH (pH) is 3 or more, the titanium in the solution mainly exists in the state of being an anion of the titanium peroxide hydrate. As described above, it is considered that the higher the pH (pH), the more the condensation reaction occurs as early as possible, and the polymer of the amorphous titanium peroxide hydrate is precipitated. Even when the pH value (pH) is lowered in the state where the salt-based substance is added, the time required for the precipitation of the polymer of the titanium peroxide hydrate becomes long, and therefore, the most It is preferable to add a salt-based substance until the pH (pH) is 3 or more. If it is more preferable, the pH (pH) may be adjusted to the neutral region.
In the state in which a yellow precipitate is formed from the yellow transparent liquid of the titanium peroxide hydrate formed by adding a salt-based substance, the titanium peroxide hydrate can be placed at room temperature. A yellow transparent liquid, however, it is also possible to promote the precipitation of the yellow precipitate by warming the liquid. When the liquid is stirred, the yellow precipitate can be precipitated as early as possible. However, when the warming liquid is above 80 ° C, it will be generated. Since the state of the anatase crystal particles occurs, it is preferable to carry out the liquid warming treatment at a temperature of 80 ° C or lower.
In the operation of removing the ammonium ion or chloride ion contained in the liquid from the liquid containing the precipitated precipitate, or the impurities derived from the raw material, the so-called decantation, filtration washing can be used in common. A method such as centrifugation or an ion exchange reaction or a reverse osmosis method, and a method for removing an ionic substance can also be used.
In the state where the residual amount of the impurities is relatively large, the impurities may cause adverse effects to the stability or property state of the finally obtained aqueous solution of the titanium peroxide hydrate, and therefore, it is preferable to treat the impurities sufficiently well. . In particular, an anion such as a chloride ion is considered to promote the condensation reaction of the titanium peroxide hydrate. However, in the state in which the anion such as the chloride ion is not completely removed, the aqueous solution cannot be completely transparent. A turbid state occurs. On the other hand, even if an cation such as ammonium ion remains, when the anion is completely removed, the yellow transparent aqueous solution containing the titanium peroxide hydrate can be obtained.
Further, in the treatment of the precipitate, when the precipitate is dried, the precipitate is dehydrated and solidified, which may cause an adverse effect to the subsequent solubilization operation, and therefore, the precipitate must not be dried.
Next, in the formation operation of the aqueous solution of the titanium peroxide hydrate, the amount of the hydrogen peroxide water added is added in the state where the hydrogen peroxide water is added to the liquid containing the precipitated precipitate by the washing treatment, It is preferable that the molar ratio of hydrogen peroxide/titanium is 1 or more, and when the number of moles of hydrogen peroxide/titanium is 1 or less, the solution may not be completely dissolved. The status takes place.
Further, when the liquid is previously cooled to 40 ° C or lower, it is possible to prevent the excessive temperature rise of the liquid caused by the so-called reaction heat or the like, and also prevent the recondensation of the so-called solubilized titanium peroxide hydrate. The phenomenon occurs. When the temperature of the liquid in the reaction becomes 40 ° C or more, the liquid will have a relatively large viscosity increasing effect. Therefore, the liquid temperature must be 40 ° C or lower, preferably cooling liquid to 20 ° C or lower.
In the prior art method of directly adding hydrogen peroxide water to titanium hydride or titanium oxide hydrate, the peroxidation and dissolution processes are continuously caused, and therefore, a considerable amount of heat is emitted, but, When the polymer which has been subjected to the oxidized titanium peroxide hydrate is in a solution state, the heat generation phenomenon as described above is not caused, and the reaction can be carried out relatively gently, so that the quality can be obtained. A good aqueous solution of titanium oxide hydrate.
In the above-mentioned solubilization process, when the aqueous solution is heated to room temperature or higher, the solubilized titanium peroxide hydrate undergoes re-condensation, and therefore, due to the viscosity of the liquid, the formation of fine particles, The solution is opaque or the like, and a state in which the desired titanium oxide coating agent is not obtained is generated. As a result, it is preferred to add hydrogen peroxide water after cooling the liquid containing the precipitate in advance, or Hydrogen peroxide water is added while cooling the liquid containing the precipitate.
After the coating treatment is performed using the titanium oxide forming solution of the present invention as a coating agent, the amorphous titanium oxide film can be formed by heat treatment at less than 200 ° C, and it is also possible to borrow From 200 ° C or more The heat treatment is carried out to form a relatively dense titanium oxide film having crystallinity. The foregoing films have relatively good acid resistance and can be utilized as various anti-corrosion coatings.
In addition, since an anatase melt liquid which has been subjected to heat treatment at 80 ° C or higher can be applied to form a crystalline titanium oxide film, the anatase sol liquid is It is quite advantageous as a coating agent for the material which cannot be heat-treated. In the method as described above, it can be used in various applications such as a protective coating film or a light-touch coal, and a coating having a relatively high density and good adhesion can be obtained at a relatively low temperature. Dressing.
The titanium oxide coating agent of the present invention has a function of dispersing various fine particles, and the titanium oxide coating agent and the solid fine particles may be mixed together, and the titanium oxide is dispersed by an ultrasonic wave or a ball mill or the like. The coating agent and the solid fine particles may be formed or dispersed in the titanium oxide film obtained by subjecting the titanium oxide coating agent as described above to drying and sintering. a complex of other substances. In addition, the substrate for coating may be any material that can withstand the heat treatment of ceramic materials, ceramics, metals, plastics, fibers, and building materials, and The titanium oxide coating agent of the present invention may be subjected to surface treatment of the inside of the porous body or powder, and the titanium oxide coating agent produced by the present invention may be utilized in various material products. The protective coating film, photocatalyst film, coating film for ultraviolet blocking, coating film for coloring, dielectric film, film type sensor, and production of titanium oxide sol.
B: Method for producing titanium oxide forming solution 2
The present invention provides a more excellent solution for forming a titanium oxide and a method for producing the same, and the titanium oxide forming solution and the method for producing the same are used as a raw material for producing a titanium compound by using a specific raw material. The solubilization of a novel titanium compound and the formation of a titanium oxide in a solution are also combined so as to be able to be used in the formation of titanium oxide having a relatively good characteristic.
That is, it has been found that a salt-based substance having a hydroxyl group which is excessive in titanium content is added to titanium metal or a titanium compound containing at least one of oxygen and hydrogen, and Hydrogen peroxide water acts to dissolve the titanium compound, and then it is in a solubilized state, and the salt-based substance is lowered from the above solution to a predetermined state without lowering the titanium recovery rate. The concentration is below the concentration in order to obtain a solution for forming a titanium oxide which is preferably used as a titanium oxide coating agent having a stable peroxy group.
In particular, it has been conventionally not to use a dispersant composed of a titanium oxide coating agent as a raw material, but the present invention provides a relatively useful method for producing an aqueous solution of titanic acid, which is a titanium oxide. The method for producing an aqueous acid solution is a relatively stable titanium oxide coating agent or the like by using titanium such as titanium metal, titanium hydride, or titanium oxide, or a compound between at least one of oxygen and hydrogen and titanium.
The solution in which a salt-based substance and hydrogen peroxide water are added to titanium, titanium hydride, and titanium oxide to be in a dissolved state is a type and amount of a salt-based substance used for dissolution, or hydrogen peroxide water. Different amount of addition, Further, after the solution is formed, the solution is kept in a state of a transparent solution from a few minutes until a few days, but as time passes, there is a so-called solution that becomes cloudy or causes Unstable phenomena such as gelation occur. Further, although the liquid can be stored by cooling, there is a problem in terms of long-term preservation of the surface.
For the reason of the instability of the titanium-containing solution as described above, attention is paid to the remaining salt-based substance and hydrogen peroxide, and the salt-based substance is removed to a predetermined concentration or lower, and at the same time, The decomposition reaction of hydrogen peroxide is carried out in order to obtain a relatively stable titanium-containing compound.
In the form of an anion composed of a complex compound having a hydroxyl group, the dissolved titanium in the titanium-containing solution produced by adding the excess salt-based substance and hydrogen peroxide to titanium . Therefore, if the substance for exchanging or supplementing the cation of the cation exchange resin and the zeolite is added to the solution to remove the above substances, the titanium can be removed without affecting the dissolved titanium. A cation produced by a salt-based substance present in a solution.
However, when the cation derived from the salt-based substance is removed by a cation exchange resin or the like, the pH of the solution is caused by the ion exchange reaction between the cation derived from the salt-based substance and the hydrogen ion. The value (pH) changes. Then, when the pH value (pH-base) of the solution is less than a certain value, the titanium-containing ions such as perovskite ions in the solution become cations such as titanium ions, and are supplemented by the cation exchange resin, so that they are lost. Titanium in solution. Therefore, the system must be at pH (acid and alkali In the state where the degree is 3 or more, the removal of the cation from the salt-based substance in the solution is carried out, and it is preferable that the pH (pH) is 4 or more.
In addition, it is necessary to decompose the hydrogen peroxide which is excessively added to the solution, but when the hydrogen peroxide is rapidly decomposed, the pH (pH) is increased or the dissolved titanium compound is present. Problems such as precipitation occur. The pH (pH) must not rise to 10 or more, and more preferably, it is preferable not to rise to 9 or more.
Therefore, in the method of the present invention, it is characterized in that the pH value (pH-base) of the solution for removing the salt-based substance and the decomposition process of hydrogen peroxide is kept within a certain range, and therefore, In many cases, the removal treatment of the cation from the salt-based substance and the decomposition treatment of hydrogen peroxide are performed.
Further, in the present invention, the concentration of the cation in the solution does not mean the concentration of the dissociated cation in the solution, but means that the cation having no dissociation and the cation in a coordinated state are analyzed. The concentration of all of the cations determined. Even in the case of the same titanium concentration, the so-called titanium concentration in the solution means that the total amount of titanium present in the solution is not considered in consideration of the existence state of titanium in the solution.
Hereinafter, a certain example of the method of removing the cation from the salt-based substance and the method of decomposing hydrogen peroxide will be described.
1. Adding a salt-based substance and hydrogen peroxide water to titanium metal or a titanium compound containing at least one of titanium, hydrogen and oxygen and forming a solution The titanium-containing solution in the state is added to the cation exchange resin and kept in a range of a weak acid or a neutral region having a pH (pH) of about 3 to 6, in order to remove the cation derived from the salt-based substance.
2. Next, by directly placing, stirring, ultrasonically irradiating, or heat-treating the solution containing titanium to decompose hydrogen peroxide, thereby making the pH of the solution containing titanium at this time ( The increase in pH is in the range of pH 7 (pH) 7 to 10.
3. Again, the same as the above 1, and in the titanium-containing solution, a small amount of a cation exchange resin is added to become a deionized state, so as to be a weak acid having a pH (pH) of about 3 to 6. Alternatively, the cation derived from the salt-based substance is removed in the neutral range, and then the same treatment as in the above 2 is carried out.
In the above operation, in the initial removal operation of the cation derived from the first salt-based substance, a large amount of hydrogen peroxide is present in the solution, so that the cation is not sufficiently performed. As a result of the removal treatment, as a result, the pH value (pH) is in the range of about 3 to 6, preferably in the range of about 4 to 6 pH (pH), and the initial salt-based substance is used. The initial removal of the cations. Then, in the decomposition operation of hydrogen peroxide, when a large amount of hydrogen peroxide is decomposed, precipitates of titanium peroxide hydrate may be precipitated, and therefore, it is necessary to have a pH value (pH) of about 7 to 9. Inside, decomposition treatment of hydrogen peroxide is performed.
Further, when the removal treatment of the cation derived from the salt-based substance and the decomposition treatment of hydrogen peroxide are performed, it is necessary to avoid In the removal operation of the cation, titanium in the solution for forming titanium oxide is lost, or a precipitate is formed by avoiding formation of a polymer in the titanium oxide.
The concentration of the cation derived from the salt-based substance in the obtained titanium oxide-forming solution is preferably lower than the titanium concentration, and preferably is 1/2 or less of the titanium concentration. The solution for forming a titanium oxide as a coating agent can be stably present by a cation concentration as described above.
As the salt-based substance used for the dissolution treatment of the titanium or the titanium compound in the present invention, aqueous ammonia, an aqueous alkali metal hydroxide solution, an aqueous solution of a tetraalkylammonium or the like can be used, but titanium oxide is used. When a coating film for forming a titanium oxide is formed as a coating agent, the titanium oxide forming solution preferably does not contain the ammonia water and tetraoxane which are relatively easily removed by volatilization and decomposition treatment. The metal element such as a amide group, in particular, preferably does not contain ammonia water.
Further, the amount of the salt-based substance used for dissolving the titanium or titanium compound is preferably twice or more the molar number of titanium, and more preferably, it is preferably 4 times the number of moles of titanium. The number above. Further, in the state of the titanium compound not containing a hydroxyl group, the amount of the salt-based substance used for dissolving the titanium or the titanium compound is preferably four times or more the number of moles of titanium, and more preferably Yes, it is best to use more than 6 times the number of moles of titanium.
The dissolution treatment by the salt-based substance and the hydrogen peroxide water may be carried out at normal temperature, but heating may be performed to promote the dissolution reaction caused by the salt-based substance and hydrogen peroxide water. . The titanium metal obtained from the titanium mineral or the like or the titanium compound containing at least one of hydrogen and oxygen may be used as the titanium-containing material which is a raw material for the titanium oxide forming solution. A substance described below can be used. After adding hydrogen peroxide water to an aqueous solution of a soluble titanium compound such as titanium tetrachloride, a salt-based substance such as ammonia water is added to obtain a titanium hydrate, and An anion such as a chloride oxide or the like, and a chloride ion or the like is removed from the titanium oxide or the like to obtain a substance.
In the present invention, in addition to the method of removing a cation derived from a salt-based substance, in addition to a method using a cation exchange resin or a zeolite, or by electrodialysis using the ion exchange membrane, The removal of the cation from the salt-based substance is carried out by a method such as dialysis or reverse osmosis.
The method for producing a solution for forming a titanium oxide of the present invention is capable of producing not only a solution for the purpose described below: a metal-based titanium or a compound containing titanium is added to a salt-based substance, and is also added thereto. Hydrogen peroxide water dissolves the metal titanium or a compound containing titanium and a salt-based substance to obtain a solution for forming a titanium oxide, so that the titanium obtained by the foregoing can be obtained without performing an operation such as precipitation or the like. The solution for forming an oxide is used to produce a solution for the purpose; and the method for producing a solution for forming a titanium oxide of the present invention can also be carried out by continuously placing a solution in which titanium or a compound containing titanium is dissolved. Alternatively, by heating the solution in which titanium or a compound containing titanium is dissolved, a precipitate of the titanium compound is precipitated, and then washed, and the salt is washed away. The cation of the base material is such that the concentration of the cation is reduced to less than the desired concentration, and then, the hydrogen peroxide water is caused to act to produce a solution for forming a titanium oxide.
Further, the cation concentration of the salt-based substance in the titanium oxide-forming solution produced by the above method may be subjected to a decationization treatment so that the cation concentration becomes a titanium concentration 1/2 or less, preferably 1/4 or less of the titanium concentration, and then heated by heating to a temperature of 80 ° C or higher, or by an autoclave under pressure The treatment is carried out to facilitate the production of a titanium oxide coating agent composed of the anatase sol in which anatase particles are dispersed.
Further, after the titanium compound is precipitated from the titanium oxide forming solution, the amount of hydrogen peroxide water added to the operation of the titanium compound which once again makes the titanium compound into a solubilized state is The ratio of hydrogen peroxide to titanium must be 1 or more; when the ratio of hydrogen peroxide to titanium is 1 or less, it is not easy to cause a complete peroxidation reaction, and it is not possible to add the added Hydrogen peroxide water reacts without causing decomposition of the hydrogen peroxide water. Therefore, it is preferable to add hydrogen peroxide water having a ratio of hydrogen peroxide/titanium of more than one. The reaction temperature may be either normal temperature or heating. However, in the state where a relatively stable raw material such as an oxide is used, the higher the temperature, the more the reaction can be carried out as quickly as possible. However, when the temperature is raised, the volatile salt-based substance such as ammonia is easily dissipated, and the added hydrogen peroxide itself is easily decomposed, and the raw material is completely Before the ground is in a solubilized state, the raw material is in a state of turbidity, or the raw material is in a sol-form state, or a precipitate is formed.
When a large amount of the salt-based substance is contained, even if the reaction temperature is raised, only a small amount of titanium oxide such as anatase is in a crystallized state. Therefore, it is preferably carried out at 80 ° C or lower. Reaction. Further, the reaction can be promoted by stirring.
The titanium oxide film can be produced by applying a solution for forming a titanium oxide of the present invention to a substrate and then heating it at a temperature of less than 200 ° C to produce an amorphous titanium oxide film. Further, if it is heated to 200 ° C or more, a relatively dense titanium oxide film can be produced. These titanium oxide films have relatively good acid resistance and can be utilized as various corrosion-resistant coatings. Further, since the crystalline titanium dioxide film can be formed only by coating the dispersion of the anatase sol produced from the titanium oxide forming solution of the present invention, the present invention A dispersion of an anatase sol produced by a solution for forming a titanium oxide is a coating agent which is a material which is not heat-treated. Further, it is also possible to mix an anatase sol dispersion and a relatively stable titanium oxide forming solution of the present invention in an arbitrary ratio so as to be utilized as a coating agent, and An anatase film having a relatively good adhesion is formed by a coating agent as described above. Further, after using a solution of a titanium oxide forming solution and an anatase sol which are relatively stable, a solution for forming a titanium oxide of the present invention is applied onto a substrate of a synthetic resin or the like, followed by , When a dispersion of an anatase sol is applied to a substrate of the synthetic resin or the like to form a layered body, the phenomenon described below can be prevented from occurring:
The decomposition of the organic matter of the substrate occurs due to the photocatalytic action of the titanium oxide layer on the surface; and
The coated titanium oxide layer is peeled off from the substrate.
The solution for forming a titanium oxide of the present invention can be used for the purpose of forming a protective coating film or a photocatalyst layer, and can obtain a film having high density and good adhesion at a relatively low temperature.
Further, the titanium oxide fine particles obtained by the solution for forming a titanium oxide of the present invention have a relatively good dispersibility, and the titanium oxide fine particles may be mixed with various solid fine particles in advance. The titanium oxide fine particles and various solid fine particles are dispersed by a device for ultrasonic dispersion, a ball mill, or the like, and then the titanium oxide fine particles and various solid fine particles are coated, and dried and sintered. The treatment is carried out to obtain a titanium oxide film, and in addition, in the obtained titanium oxide film, a composite in which other fine particles are carried or dispersed can be produced.
Further, as the substrate to be coated, a ceramic material, a ceramics, a metal, a plastic, a fiber, a building material, or the like can be used, and the inside of the porous body or the powder may be subjected to surface treatment.
C: Method for producing titanium oxide forming solution
In the present invention, it has been found that during the production process of the crystalline titanium oxide particles via the titanium oxide hydrate, the factor of promoting condensation and the like is removed, and at the same time, the hydrate is precipitated, and directly Get the characteristic phase When it is a good crystalline particle; therefore, the present invention can be completed.
In other words, in the course of the reaction, the reaction product which is a factor contributing to the condensation reaction or the like or the impurity which is mixed by the raw material is separated in an early stage so as to prevent the occurrence of the condensation reaction or the like; The method for producing a solution for forming a titanium oxide is constituted by the operation described below.
(1) Precipitation of a polymer of titanium peroxide hydrate
A soluble titanium compound such as titanium tetrachloride may be diluted by water, and an excess amount of hydrogen peroxide water may be added to form a brown peroxy complex, followed by addition of a salt-based substance such as ammonia. In order to produce an aqueous solution of the yellow titanium peroxide hydrate, and the aqueous solution of the yellow titanium peroxide hydrate described above is placed at a normal temperature or an aqueous solution of the yellow titanium peroxide hydrate is heated. A polymer of precipitated and precipitated titanium oxide hydrate.
(2) Removal of ionic substances or impurities
Washing the liquid containing the precipitation precipitate of the polymer of the titanium peroxide hydrate or filtering and washing the liquid containing the precipitate of the polymer containing the titanium peroxide hydrate. The treatment is performed to remove the ammonium ion or chloride ion contained in the liquid or the impurity derived from the raw material.
(3) Shape of crystalline titanium oxide particles, work
The ionic substance or the impurity is removed by the washing treatment at 80 ° C or higher, normal pressure, or autoclave in a state where the moisture or the dispersion is not separated. Peroxide The precipitate of the hydrate is subjected to heat treatment to form crystalline titanium oxide particles.
A solution for forming a titanium oxide can be produced by the above operation to form crystalline titanium oxide particles, and a dispersion of relatively useful crystalline titanium oxide particles can be obtained, and the crystalline titanium can be obtained. The dispersion of the oxide particles is advantageous for the formation of a titanium oxide film having a good property at a low temperature.
The titanium peroxide hydrate used in the method of the present invention is exemplified by the production method 1 of the solution for forming a titanium oxide, and the production method 2 for the solution for forming a titanium oxide. A solution for forming a titanium oxide.
In the following description, the method of the method for producing A solution for forming titanium oxide is described. However, the use of B: a solution for forming a titanium oxide may be employed. The solution for forming a titanium oxide produced by the method 2 is described.
Examples of the soluble titanium compound used as a raw material include titanium tetrachloride, titanium sulfate, titanium nitrate, and titanium alkoxide.
Further, the amount of the hydrogen peroxide water added to the aqueous solution of the soluble titanium compound is such that the molar ratio of hydrogen peroxide to titanium is 1 or more, and the number of moles of hydrogen peroxide/titanium is 1 or less. In this state, the peroxidation reaction cannot be completely completed. Further, since the hydrogen peroxide water to be added is decomposed regardless of the reaction, it is preferable to add excess hydrogen peroxide water so that the hydrogen peroxide/titanium molar ratio is more than 1.
When adding hydrogen peroxide water to the solution containing soluble titanium, then The peroxidation reaction occurs almost instantaneously, and when the pH (pH) is 3 or less, the titanium in the solution is mainly dissolved into a cation, and when the pH (pH) is 3 or more, the solution is obtained. Titanium is mainly present in a state of being an anion of titanium peroxide hydrate. As described above, it is considered that the higher the pH (pH), the more the condensation reaction occurs as early as possible, and the polymer of the amorphous titanium peroxide hydrate is precipitated. Even when the pH value (pH) is lowered in the state where the salt-based substance is added, the time required for the precipitation of the polymer of the titanium peroxide hydrate becomes long, and therefore, the most It is preferable to add a salt-based substance until the pH (pH) is 3 or more. If it is more preferable, the pH (pH) may be adjusted to the neutral region.
In the state in which a yellow precipitate is formed from the yellow transparent liquid of the titanium peroxide hydrate formed by adding a salt-based substance, the titanium peroxide hydrate can be placed at room temperature. A yellow transparent liquid, however, it is also possible to promote the precipitation of the yellow precipitate by heating the liquid. When the liquid is stirred, the yellow precipitate can be precipitated as early as possible.
In the operation of removing the ammonium ion or chloride ion contained in the liquid from the liquid containing the precipitated precipitate or the impurity derived from the raw material, so-called decantation, filtration washing can be applied. A method such as centrifugation or an ion exchange reaction or a reverse osmosis method, and a method for removing an ionic substance can also be used.
In the state where the residual amount of the impurity is quite large, due to the impurity, The adverse effect is caused to the stability or property state of the finally obtained aqueous solution of the titanium oxide hydrate, and therefore, the impurities are preferably treated fairly well. In particular, an anion such as a chloride ion is considered to promote the condensation reaction of the titanium peroxide hydrate. However, in the state in which the anion such as the chloride ion is not completely removed, the aqueous solution cannot be completely transparent. A turbid state occurs. On the other hand, even if an cation such as ammonium ion remains, when the anion is completely removed, the yellow transparent aqueous solution containing the titanium peroxide hydrate can be obtained.
Next, the dispersion or the slurry containing the precipitated precipitate is subjected to heat treatment. The heating temperature is preferably 70 ° C or higher; at a low temperature lower than 70 ° C, the crystalline titanium oxide particles of anatase are not sufficiently formed. Further, the heating temperature is preferably 80 to 200 °C. When the heating temperature is 200 ° C or more, the precipitation reaction of anatase is caused in a relatively short period of time, and therefore, it is not easy to adjust the treatment time. Further, the heating time is preferably from 5 hours to 20 hours. The heat treatment can be carried out in an autoclave to produce crystalline titanium oxide particles in a relatively short period of time. It is preferably heated at 100 to 200 ° C in an autoclave.
Further, in the treatment of the precipitate, when the precipitate is dried, the precipitate is dehydrated and solidified, which adversely affects the production operation of the dispersed liquid of the crystalline titanium oxide particles, and therefore, it is necessary to dry the precipitate. Precipitate.
In the method of the present invention, when the precipitate is heated, a knot is formed Crystalline particles, at the same time, also generate dispersed liquid of particles
In addition, since the crystalline titanium oxide film can be formed only by coating the crystalline titanium oxide particle dispersion liquid of the present invention, the crystalline titanium oxide particles of the present invention disperse the liquid, which is quite helpful as the A coating agent for a material that cannot be heat treated. Further, the crystalline titanium oxide particle-dispersing liquid of the present invention may be used in various applications such as a protective coating film, a photocatalyst, or a gas for preventing penetration of a synthetic resin film, and may be used. At a relatively low temperature, a film having a relatively high density and a relatively good adhesion is obtained.
In addition, the liquid in which the crystalline titanium oxide particles of the present invention are dispersed is a mixture of various solid fine particles, and the various solid particles are dispersed by an ultrasonic wave dispersing device and a ball mill. Further, the coating treatment of the liquid of the crystalline titanium oxide particles of the present invention is carried out, and the dry sintering treatment is performed to obtain a titanium oxide film, and the obtained titanium oxide film can also be produced. A composite in which other substances are carried or dispersed. Further, as the substrate to be coated, a ceramic material, a ceramics, a metal, a plastic, a fiber, a building material, or the like can be used, that is, as long as it can withstand the heat treatment material for the different purposes, All of them can be used as the substrate to be coated, and the surface of the porous body or the powder can be surface-treated; in addition, the titanium oxide coating agent produced by the present invention can be utilized. In the fields of protective coatings, photocatalyst films, coating films for ultraviolet blocking, coating films for coloring, dielectric films, model sensors, and production of titanium oxide sols for various material products.
Hereinafter, the embodiment will be described in series, and the present invention will be described.
<u style="single">Example 1-1</u>
In a solution in which 5 ml of a 60% aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, 20 ml of a 30% aqueous hydrogen peroxide solution was added thereto, and the mixture was stirred to prepare a brown transparent liquid, and ammonia water was dropped (1). :9) To the above solution, the pH (pH) was made 7 to facilitate the production of a yellow transparent solution. The solution obtained as described above was placed at 25 ° C for a day and night to form a yellow precipitate.
After the filtration and washing treatment of the precipitated yellow precipitate obtained as described above, the precipitation of the yellow precipitate is increased to about 150 ml by adding distilled water, and 25 g is separately charged. The cation exchange resin and the anion exchange resin were placed in a solution of the aforementioned yellow precipitation precipitate, and left for 30 minutes to remove the cationic substance and the anionic substance.
As the cation exchange resin, a so-called hydrochloric acid having a concentration of 2N and a phenol formaldehyde ion exchange resin IR120B (Na) made of organic matter is used.<sup>+</sup>Substituted type), after one hour of treatment, and then washed again, becomes H<sup>+</sup>A substitution type cation exchange resin; further, as an anion exchange resin, a so-called sodium hydroxide having a concentration of 1 N is used, and a phenol formaldehyde ion exchange resin IRA410 (Cl-substituted type) made of an organic substance is treated for 1 hour. Then, it is washed again and becomes OH.<sup>-</sup>Substituted anion exchange resin.
By X-ray diffraction device (made by Rigaku Motor Co., Ltd., RAD-B), The copper target was used, and the powder obtained by drying the obtained yellow precipitate at 25 ° C was measured under the measurement conditions of an acceleration voltage of 30 kV and a current of 15 mA, and the measurement result was performed. , is shown in Figure 1. The precipitate obtained in this manner is in an amorphous state.
Further, a tablet method in which a powder obtained by drying at 25 ° C and a potassium bromide powder are mixed together to form a tablet, and a multi-leaf conversion infrared absorption spectrum measuring device (Japan) is also used. The measurement was carried out by a penetrating method, and the measurement results are shown in Fig. 2 . The number of waves in Figure 2 is 900cm.<sup>-</sup><sup>1</sup>Nearby, it is considered that absorption occurs, that is, it is considered to have a peroxy group.
Then, after the ion exchange resin was removed by the filtration treatment, distilled water was added thereto to be about 180 ml, and further cooled with ice water, and 20 ml of a 30% aqueous hydrogen peroxide solution was added, followed by addition of 20 ml of a 30% aqueous hydrogen peroxide solution. Further, cooling was carried out so that after 1 hour, 200 ml of a transparent yellow liquid containing titanium was obtained.
In the storage treatment of the refrigerator at 7 ° C, even if one month or more, the transparent yellow liquid containing titanium did not undergo any change.
Further, the pH (pH) of the transparent yellow liquid after 5 days of the preparation treatment was 5.1. Even at normal temperature, the transparent yellow liquid was subjected to a drying treatment to be in a powder state, and similarly, it was measured by an X-ray diffraction apparatus, and the measurement results are shown in Fig. 3 . The result of X-ray diffraction is not found to show The peak of crystallinity, that is, the powder of the transparent yellow liquid, is amorphous. Further, the results obtained by the FT-IR infrared spectroscopy analyzer are also shown in Fig. 4. The number of waves in Figure 4 is 900cm.<sup>-</sup><sup>1</sup>In the vicinity, it is considered that absorption occurs, that is, it can be confirmed that there are many peroxy groups present.
<u style="single">Example 1-2</u>
The yellow transparent liquid obtained in Example 1-1 was sealed in a glass container, and heat-treated at 100 ° C for 5 hours to obtain a pale yellow translucent liquid. The pH (pH) of the pale yellow translucent liquid was 8.8. The powder obtained by drying the above-mentioned pale yellow translucent liquid at normal temperature was the same as in Example 1-1, and was measured by an X-ray diffraction apparatus. To: a crystalline anatase is formed, and the obtained liquid is an anatase melt.
<u style="single">Examples 1-3</u>
The liquid obtained in Example 1-1 was applied and dried four times on a glass slide, and heat-treated at various temperatures to produce a film having a thickness of about 1 μm. It is confirmed by X-ray diffraction that the film is amorphous when the heat treatment temperature is less than 200 ° C, but the film is present in a state where the heat treatment temperature is 200 ° C or higher. There is anatase. Further, the film which was dried or heat-treated at a normal temperature or higher was not peeled off by the glass tape peeling test.
The so-called glass tape peeling test is performed on the formed film at 1 mm. At the interval, after the scratch is scored by the cutter, and then the glass tape (manufactured by NICHIBAN Co., Ltd.) is bonded, and then, at a speed of 1 cm/sec, it is perpendicular to the formed film. In the direction, the glass tape was peeled off, and the film surface and the glass tape surface were observed to investigate whether or not film peeling occurred.
<u style="single">Examples 1-4</u>
In a solution in which 5 ml of a 60% aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, 20 ml of a 30% aqueous hydrogen peroxide solution was added and stirred to prepare a brown transparent liquid, and ammonia water was dropped (1). :9) Into the above solution, such that the pH (pH) is 7, and a yellow transparent solution is produced, and then, at 50 ° C, heat treatment is performed for 2 hours to produce a yellow color. Precipitate precipitated. Then, the precipitated yellow precipitate obtained as described above was subjected to filtration and washing treatment. The liquid containing the precipitated precipitate of yellow was made into 130 ml, and 20 ml of a 30% aqueous hydrogen peroxide solution was added at 15 ° C, and then the solution was allowed to stand, and after 12 hours passed, 150 ml of transparency was obtained. Yellow liquid. The temperature of the liquid after the addition of hydrogen peroxide water was raised to a maximum of 20 °C. The pH value (pH) of the liquid after a few days was 5.0, and the viscosity of the liquid was 8 cp.
<u style="single">Comparative Example 1-1</u>
In a solution in which 5 ml of a 60% aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, ammonia water (1:9) was dropped, so that the pH (pH) became 7, and a white gel-like hydrogen was also precipitated. Titanium oxide is subjected to filtration and washing treatment, and distilled water is used to make the solution 130ml. Next, the liquid temperature was changed to 15 ° C, and 20 ml of a 30% aqueous hydrogen peroxide solution was added, and then the solution was allowed to stand, and after 12 hours passed, 150 ml of a yellow liquid containing titanium was obtained. The liquid temperature during this period rose to a maximum of 41 °C. The pH (pH) of the liquid after 5 days of the preparation treatment was 5.0. The liquid system is gelatinized to have a jelly shape, and the viscosity of the liquid is about 28,000 cp. Therefore, the liquid system is not easily used as a coating agent.
<u style="single">Example 2-1</u>
Titanium dioxide is used as a titanium raw material. Weighed 0.8 g of titanium dioxide (titanium dioxide P25 manufactured by AEROZIL Co., Ltd., Japan), and further added 15 ml of a 2% dilution of ammonia water having a concentration of 25% by weight and 40 ml of 30% by weight of hydrogen peroxide water. The solution was also made to be 100 ml by distilled water, and further subjected to a stirring treatment so that the solution was allowed to stand for 2 days at 25 ° C, and dissolution treatment was carried out to obtain a yellow transparent solution. . The titanium concentration was 0.1 mol/l, and the ammonium concentration was 1.1 mol/l.
Next, in the obtained solution, gradually add 30 g of the washed water by the distilled water.<sup>+</sup>A substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic material) was stirred to have a pH (pH) of 5.0. After the cation exchange resin to be added is separated, the solution is irradiated with ultrasonic waves so that the decomposition of hydrogen peroxide is performed until the pH (pH) of the solution becomes 8.0. Further, the decomposition of the hydrogen peroxide can be confirmed by the generation of bubbles from the solution.
Further, after the pH (pH) of the solution is 5.0 by the operation of the removal treatment of the cation by the same cation exchange resin as before, the decomposition and cation of hydrogen peroxide are performed twice separately. The operation of removing the cation by the resin was carried out to obtain a solution for forming a titanium oxide having a pH (pH) of 5.0. The ammonium concentration in the solution for forming titanium oxide obtained was 0.01 mol/l.
By using an X-ray diffraction device (manufactured by Rigaku Corporation, RAD-B), a copper target is used, and under the conditions of acceleration voltage of 30 kV and current of 15 mA, for the titanium obtained at 25 ° C. The powder obtained by drying the solution for forming an oxide was measured, and the measurement results are shown in Fig. 5 . The liquid obtained in this manner is in an amorphous state.
Further, a tablet method in which a powder obtained by drying at 25 ° C and a potassium bromide powder are mixed together to form a tablet, and a multi-leaf conversion infrared absorption spectrum measuring device (Japan) is also used. The measurement was carried out by a penetrating method, manufactured by Spectrum Co., Ltd., FT/IR-5300), and the measurement results are shown in Fig. 6. The number of waves in Figure 6 is 900cm.<sup>-</sup><sup>1</sup>In the vicinity, it is considered that absorption occurs, that is, it is confirmed that there is a peroxy group.
Further, in the state of 25 ° C, even if the solution was left for 30 days, no precipitate was precipitated, and no change in the nature of the solution occurred.
Further, in all of the examples and comparative examples, the measurement process of the titanium concentration and the ammonium concentration was measured by the measurement method described below. Determine the titanium concentration and the ammonium concentration.
(Method for measuring the concentration of titanium) The sample was diluted in an amount of 200 times by using distilled water, and an ICP emission spectrometer (ICPS-2000, manufactured by Shimadzu Corporation) was used, and the titanium standard solution was used. A calibration curve prepared by a standard solution having a concentration of 10 ppm, 20 ppm, and 40 ppm prepared by Wako Pure Chemical Industries, Ltd. and having a concentration of 1000 ppm) was used to determine the titanium concentration.
(Method for measuring ammonium concentration)
Taking any number of samples, and completely decomposing the hydrogen peroxide in the state containing hydrogen peroxide, and then diluting the solution to 10 times, and taking 10 ml of the diluted solution to the container To the vessel, 20 ml of distilled water and 1 ml of a 0.35 mol/l zinc sulfate aqueous solution were added, and further, the alkalinity of 30 g of sodium hydroxide and 25 g of sodium carbonate dissolved in 200 ml of distilled water was added. The solution was placed in the container so that the pH (pH) of the solution became 10.5.
Next, 10 ml of a 1.3 mol/l sodium benzene solution and 1 ml of a 0.15 mol/l ethylene diamine tetraacetic acid disodium solution were added, followed by stirring, and 5 ml of a 1% by volume sodium hypochlorite was further added. The saline solution and distilled water were used to make the solution 50 ml, and the mixture was stirred. Further, after 30 minutes passed, the solution was subjected to filtration treatment. The absorbance at 630 nm of the obtained filtrate was measured by a spectrophotometer (UV-2100, manufactured by Shimadzu Corporation).
In addition, it dissolves and dilutes ammonium chloride (special grade reagent), and prepares the standard The quasi-liquid is measured by the same method as the test liquid, and a calibration curve is prepared to determine the concentration of the test liquid.
<u style="single">Example 2-2</u>
Metal titanium is used as a titanium raw material. 0.48 g of metal titanium powder (manufactured by Wako Pure Chemical Industries, Ltd., titanium metal powder) was weighed, and 7 ml of a 2% dilution of ammonia water having a concentration of 25% by weight and 20 ml of 30% by weight of hydrogen peroxide were added. Water, at the same time, the solution was made to be 100 ml by distillation of water, and further, a stirring treatment was carried out so that the solution was allowed to stand at 25 ° C for 24 hours to be dissolved. Yellow transparent solution. The titanium concentration was 0.1 mol/l, and the ammonium concentration was 0.6 mol/l.
Next, in the obtained solution, gradually add 30 g of the washed water by the distilled water.<sup>+</sup>a substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic material) is stirred, and after the pH value (pH) of the solution reaches 5.0, the added cation exchange resin is separated, and then, Ultrasonic, the solution is irradiated to facilitate the decomposition treatment of hydrogen peroxide, and when the pH value (pH-base) of the solution becomes 8, 5 g of the cation exchange resin is again charged to make the pH of the solution The value (pH) becomes 4.
Further, the operation of the above-described decomposition treatment of hydrogen peroxide and the removal of the cation by the cation exchange resin are performed twice, respectively, to obtain a solution for forming a titanium oxide having a pH (pH) of 5.0. .
Titanium concentration is 0.1 mol/l, and ammonium concentration is 0.01 mol/ 1.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 1 is measured by an X-ray diffraction apparatus, it can be known that the obtained powder, It is in an amorphous state.
In addition, in the same manner as in the first embodiment, the measurement was carried out by a Fourier transform infrared absorption spectrum measuring apparatus (FT/IR-5300, manufactured by Nippon Spectrum Co., Ltd.), and it was found that the number of waves was 900 cm.<sup>-</sup><sup>1</sup>In the vicinity, it is considered that absorption occurs, that is, it is confirmed that there is a peroxy group.
<u style="single">Example 2-3</u>
Titanium tetrachloride is used as a raw material for titanium. In a solution in which 5 ml of a 60% by weight aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, a 10-fold dilution of ammonia water having a concentration of 25% by weight was dropped, so that the pH (pH) of the solution became 7, and Further, a white gelatinous titanium hydroxide was precipitated, and subjected to filtration and washing treatment, and distilled water was used to make the total amount of the residue after filtration into 150 ml.
Next, 25 ml of a 4% dilution of ammonia water having a concentration of 25% by weight and 20 ml of 30% by weight of hydrogen peroxide water, and distilled water were added, and the solution was allowed to stand, and after 12 hours passed, 250 ml was obtained. A yellow liquid containing titanium.
The titanium concentration of the obtained titanium-containing solution was 0.1 mol/l, the ammonium concentration was 0.38 mol/l, and the chlorine concentration was 0.0086 mol/l.
Next, in the obtained solution, 50 g of distilled water is charged. Washing treatment H<sup>+</sup>a substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic matter), and the solution is allowed to stand for 1 hour, and the cation exchange resin added after removal of the ammonium ion is separated and removed, and While maintaining the solution at 7 ° C, 10 ml of a 30% by weight aqueous hydrogen peroxide solution was added to the solution to obtain a yellow transparent aqueous solution of titania. The ammonium concentration in the yellow transparent perovskite aqueous solution was 0.011 mol/l.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 2-1 was measured by an X-ray diffraction apparatus, it was found that the obtained powder was obtained. The powder is in an amorphous state.
Further, in the same manner as in Example 2-1, when the measurement was carried out by the multiplex-leaf conversion infrared absorption spectrum measuring apparatus, it was found that the number of waves was 900 cm.<sup>-</sup><sup>1</sup>In the vicinity, it is considered that absorption occurs, that is, it is confirmed that there is a peroxy group.
<u style="single">Example 2-4</u>
Titanium tetrachloride is used as a raw material for titanium. In a solution in which 5 ml of a 60% by weight aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, a 10-fold dilution of ammonia water having a concentration of 25% by weight was dropped, so that the pH (pH) of the solution became 7, and Further, a white gelatinous titanium hydroxide is precipitated, which is subjected to filtration and washing treatment, and distilled water is used to make the total amount of the residue after filtration into 150 ml, and the above solution is also used as ice water. , cooled to below 10 ° C, while adding 20 ml of 30% by weight of ammonia water in hydrogen peroxide, after 12 hours In order to obtain a yellow translucent titanium oxide forming solution.
Into the obtained solution for forming titanium oxide, 30 g of OH was charged.<sup>-</sup>Substituted anion exchange resin, and the OH<sup>-</sup>The substituted anion exchange resin is treated with sodium hydroxide at a concentration of 1 N, and an anion exchange resin (phenol formaldehyde ion exchange resin IRA410 made of organic material) is treated for 1 hour, and then washed, and then washed. After the titanium oxide forming solution was allowed to stand for 3 hours, and then the anion exchange resin was separated, then, a 25-fold dilution of 25 wt% aqueous ammonia and a concentration of 10 ml of 30% by weight were added. Hydrogen peroxide water was added to the solution, and after the solution was allowed to stand for 12 hours, it was allowed to obtain 250 ml of a yellow liquid containing titanium. The yellow liquid had a titanium concentration of 0.1 mol/l, an ammonium concentration of 0.39 mol/l, and a chlorine concentration of 0.0039 mol/l.
Next, in the obtained solution, 50 g of distilled water treated with distilled water is charged.<sup>+</sup>a substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic matter), and the solution is allowed to stand for 1 hour to separate and remove the cation exchange resin added after removing the residual ammonium ions. Further, while cooling the solution to maintain the solution at 7 ° C, 10 ml of a 30% by weight hydrogen peroxide water solution was added to the solution to obtain a yellow transparent solution. The ammonium concentration in the yellow transparent solution was 0.013 mol/l.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 2-1 was measured by an X-ray diffraction apparatus, it was found that the obtained powder was obtained. Powder, is a non-knot Crystal state.
Further, in the same manner as in Example 2-1, when the measurement was carried out by the FT-IR infrared absorption spectrum measuring apparatus, it was found that an absorption phenomenon occurred in the vicinity of the wave number of 900 cm-1, that is, Say, it can be confirmed that there is a peroxy group.
<u style="single">Example 2-5</u>
Titanium tetrachloride is used as a raw material for titanium. In a solution in which 5 ml of a 60% by weight aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, 20 ml of 30% by weight of hydrogen peroxide water was added thereto, and the mixture was stirred to produce a transparent brown color. a liquid, and a 10-fold dilution of a 25 wt% aqueous ammonia solution is dropped into the above solution, so that the pH value (pH) of the solution becomes 7, in order to produce a yellow transparent solution, and at 25 ° C The yellow transparent solution was placed for a day and night to precipitate a yellow precipitate. After the filtration and washing treatment of the yellow transparent solution described above, the residue after filtration was made into 150 ml of distilled water.
Next, in the solution for forming titanium oxide obtained, 30 g of OH was charged.<sup>-</sup>Substituted anion exchange resin, and the OH<sup>-</sup>The substituted anion exchange resin is treated with sodium hydroxide at a concentration of 1 N, and an anion exchange resin (phenol formaldehyde ion exchange resin IRA410 made of organic material) is treated for 1 hour, and then washed, and then washed. After the titanium oxide forming solution was allowed to stand for 30 minutes, the added anion exchange resin was separated by using a synthetic resin net and the chlorine ions were removed, and then the solution was made to be distilled water. 180 ml, and added to 25 ml of a 4-fold dilution of ammonia water having a concentration of ammonia concentration of 25% by weight and 20 ml of hydrogen peroxide water having a concentration of 30% by weight, and distilled water to the solution, after 12 hours, to facilitate A clear yellow liquid of 250 ml of the titanium compound was obtained.
The titanium concentration of the solution obtained was 0.1 mol/l, the ammonium concentration was 0.41 mol/l, and the chlorine concentration was 0.005 mol/l.
Next, in the obtained solution, 50 g of distilled water treated with distilled water is charged.<sup>+</sup>a substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic matter), and the solution is allowed to stand for 1 hour to separate and remove the cation exchange resin added after removing the residual ammonium ions. Further, while cooling the solution to maintain the solution at 7 ° C, 10 ml of a 30% by weight hydrogen peroxide water solution was added to the solution to obtain a yellow transparent solution. The ammonium ion concentration in the yellow transparent solution was 0.011 mol/l.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 2-1 was measured by an X-ray diffraction apparatus, it was found that the obtained powder was obtained. The powder is in an amorphous state.
Further, in the same manner as in Example 2-1, when the measurement was carried out by the multiplex-leaf conversion infrared absorption spectrum measuring apparatus, it was found that the number of waves was 900 cm.<sup>-</sup><sup>1</sup>In the vicinity, it is considered that absorption occurs, that is, it is confirmed that there is a peroxy group.
<u style="single">Example 2-6</u>
50 ml of the liquid obtained in Example 2-2 was sealed in a glass container And, at 100 ° C, heat treatment was carried out for 5 hours to obtain a pale yellow translucent liquid. The powder obtained by subjecting the above-mentioned pale yellow translucent liquid to a drying treatment was the same as in Example 2-1, and when it was measured by an X-ray diffraction apparatus, it was found that: Crystalline anatase, and it was confirmed that the obtained liquid was an anatase sol.
<u style="single">Example 2-7</u>
Metal titanium is used as a titanium raw material. Weigh 0.48 g of metal titanium powder (manufactured by Wako Pure Chemical Industries, Ltd.) into four containers, and separately add 4 ml dilutions of 5 ml, 10 ml, and 15 ml of ammonia water at a concentration of 25% by weight to Three of the four containers were added, and 40 ml of 30% by weight of hydrogen peroxide water and distilled water were added to all the containers, and the solution was made into 100 ml, followed by stirring, followed by The solution was allowed to stand at 25 ° C for 20 hours.
The titanium concentration is 0.1 mol/l, and the ammonium concentration is 0, 0.18, 0.37, and 0.55 mol/l, respectively. The sample having an ammonium concentration of 0.18 mol/l or less cannot be completely dissolved, and some insoluble matter remains. In the state where the ammonium concentration is 0.37 mol/l or more, the sample can be completely dissolved and becomes transparent.
Next, in the obtained solution, gradually add 30 g of the washed water by the distilled water.<sup>+</sup>A substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic material) was stirred to have a pH (pH) of 5.0. Then, in the separation of the added After the addition of the cation exchange resin, the ultrasonic wave is irradiated by the ultrasonic irradiation device to decompose the hydrogen peroxide, and with the decomposition of hydrogen peroxide, the pH value (pH) of the solution is also raised. When the pH (pH) of the solution became 8, another 5 g of the cation exchange resin was further introduced, and the stirring treatment was performed to adjust the pH (pH) of the solution to 5, and then the cation exchange resin was separated. Subsequently, the decomposition of hydrogen peroxide and the removal of the cation by the cation exchange resin caused by the ultrasonic irradiation twice were repeated, and a yellow transparent aqueous solution having a pH (pH) of 5.0 was obtained. The ammonium concentration in the obtained yellow transparent aqueous solution was 0.01 mol/l.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 3-1 was measured by an X-ray diffraction apparatus, it was found that the obtained one was obtained. The powder is in an amorphous state.
Further, in the same manner as in Example 2-1, when the measurement was carried out by the multiplex-leaf conversion infrared absorption spectrum measuring apparatus, it was found that the number of waves was 900 cm.<sup>-</sup><sup>1</sup>In the vicinity, it is considered that absorption occurs, that is, it is confirmed that there is a peroxy group.
<u style="single">Example 2-8</u>
Titanium dioxide is used as a titanium raw material. Weigh 0.8 g of titanium dioxide (titanium dioxide P25 manufactured by AEROZIL Co., Ltd., Japan) into three containers, and separately add 4 ml of dilution solution of 5 ml, 10 ml, and 15 ml of ammonia water at a concentration of 25 wt% to the foregoing. In 3 containers, in addition, 40 ml of 30% by weight of hydrogen peroxide was added to all the containers. The water was distilled water to make the solution 100 ml, and the mixture was stirred. Next, the solution was subjected to a heat treatment for 5 minutes at 60 ° C, and then the solution was allowed to stand at 25 ° C for 30 hours to carry out a dissolution treatment. The titanium concentration is 0.1 mol/1, and the ammonium concentration is 0, 0.18, 0.37, and 0.55 mol/1, respectively. The sample having an ammonium ion concentration of 0.37 mol/l or less was not completely dissolved, and the solution containing no aqueous ammonia was used, and the powder of titanium oxide was hardly dissolved, and only a white opaque suspension was obtained.
In the solution obtained, gradually add 30 g of washed water by distilled water.<sup>+</sup>A substituted cation exchange resin (phenol formaldehyde ion exchange resin IR118 made of organic material) was stirred so that the pH (pH) of the solution became 5.0, and then the cation exchange resin was separated. Then, the ultrasonic wave is irradiated by the ultrasonic irradiation device to decompose a part of the hydrogen peroxide. With the decomposition of hydrogen peroxide, the pH value (pH) of the solution is also raised, and when the pH value (pH-base) of the solution becomes 8, another 5 g of the cation exchange resin is charged and stirred. After the pH (pH) of the solution was changed to 5, then the cation exchange resin was separated. Subsequently, the decomposition of hydrogen peroxide and the removal of the cation by the cation exchange resin caused by the ultrasonic irradiation twice were repeated, and a yellow transparent aqueous solution having a pH (pH) of 5.0 was obtained. The ammonium concentration in the obtained yellow transparent aqueous solution was 0.01 mol/l.
<u style="single">Example 2-9</u>
Take 20ml of the same transparency as that obtained in Example 2-2. a solution, and adding ammonia water to the transparent solution, so that the ammonium ion concentration in the solution becomes 0.0136, 0.021, 0.0284, 0.0358, 0.0423, and 0.055 mol/l, and then, the solution is placed in a closed container, and The heat treatment was carried out for 6 hours at 100 °C.
Further, the powder obtained by subjecting the above solution to drying treatment at 25 ° C in the same manner as in Example 1 was measured by an X-ray diffraction apparatus, and the measurement results are shown in the figure. 7 in. It can be known that the powder obtained is in an amorphous state.
Further, in Fig. 8, it is shown that, similarly to Example 2-1, the same powder was measured by a multiplexed-leaf conversion infrared absorption spectrometry apparatus. According to the results of the X-ray diffraction, it is known that the powder having an ammonium concentration of 0.0284 mol/l or more is in an amorphous state, and the results of the investigation by the infrared absorption spectrum of the complex ray are known. : The number of waves is 900cm<sup>-</sup><sup>l</sup>In the vicinity, it is considered that absorption occurs, that is, it is confirmed that there is a peroxy group.
On the other hand, according to the result of the X-ray diffraction, it was judged that the powder having an ammonium concentration of 0.021 mol/l or less contained an anatase crystal and became a sol state. That is, in the state where the ammonium concentration is lower than the titanium concentration, only an anatase sol can be obtained.
Further, in the solution which is not subjected to heat treatment at 100 ° C and is added with ammonia, the solution having an ammonium concentration of 0.0423 mol/l or less is transparent at a normal temperature for one month or longer, and does not have any The change occurred, however, the solution with an ammonium concentration of 0.055 mol/l was turbid. Born, and become unstable. In addition, in the state in which the ammonium concentration is 1/2 or less of the titanium concentration, a relatively stable aqueous solution of titania is obtained. However, in the state where the concentration of ammonium is 1/2 or more of the concentration of titanium, This aqueous solution of titania acid does not provide long-term stability.
<u style="single">Example 2-10</u>
The yellow transparent solution having the titanium concentration of 0.1 mol/l obtained in the same manner as in Example 2-2 was heat-treated at 70 ° C for 3 hours to precipitate a yellow gel-like precipitate. . After the yellow gelatinous precipitate was washed with distilled water, the yellow gelatinous precipitate was made into a solution of 80 ml in distilled water, and the solution was further cooled, and the solution was dried. While maintaining the temperature at 7 ° C, 20 ml of 30% by weight aqueous ammonia water of hydrogen peroxide was added to obtain a yellow transparent titanium compound solution. The ammonium concentration in the yellow transparent titanium compound solution was 0.02 mol/l.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 2-1 was measured by an X-ray diffraction apparatus, it was found that the obtained powder was obtained. The powder is in an amorphous state.
Further, in the same manner as in Example 2-1, when the measurement was carried out by the multiplex-leaf conversion infrared absorption spectrum measuring apparatus, it was found that the number of waves was 900 cm.<sup>-</sup><sup>1</sup>In the vicinity, it is considered that absorption occurs, that is, it is confirmed that there is a peroxy group.
Metal titanium is used as a titanium raw material. 0.48 g of titanium metal powder (manufactured by Wako Pure Chemical Industries, Ltd., titanium metal powder) was added, and 7 ml of a 2% dilution of ammonia water having a concentration of 25% by weight was added, and further, a concentration of 30% by weight of 30 ml was further added. The hydrogen peroxide water was added to distilled water to make the solution 100 ml, and the mixture was stirred. Then, the solution was allowed to stand at 25 ° C for 24 hours to be dissolved. Yellow transparent solution. The titanium concentration was 0.1 mol/l, and the ammonium ion concentration was 0.6 mol/l.
Next, 30 g of the H+-substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic material) was gradually added to the obtained solution, and the mixture was stirred, and the pH (pH) of the solution reached 5.0. At the time point, after the cation exchange resin to be added is separated, ultrasonic irradiation is performed to decompose hydrogen peroxide to obtain a solution 1. Next, 2 g of the cation exchange resin was again introduced into the solution 1, and after the pH (pH) of the solution 1 reached 5.0, the added cation exchange resin was separated, and ultrasonication was performed. Irradiation to facilitate decomposition of hydrogen peroxide gives solution 2. Further, 2 g of the cation exchange resin was again introduced into the solution 2, and after the pH (pH) of the solution 2 reached 5.0, the added cation exchange resin was separated, and ultrasonication was performed. Irradiation to facilitate decomposition of hydrogen peroxide gives solution 3.
Each of the above solutions is yellow transparent, and the ammonium ion concentration of solution 1 is 0.058 mol/1, the ammonium ion concentration of solution 2 is 0.043 mol/1, and the ammonium ion concentration of solution 3 is 0.020. Mol/ 1. In the solution 2 and the solution 3, even after one month or more, no change occurred. However, when the solution 1 was placed at 25 ° C, the solution 1 was turbid from the second day. Precipitate solids.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 2-1 was measured by an X-ray diffraction apparatus, it was found that the obtained powder was obtained. The powder is in an amorphous state.
Further, in the same manner as in Example 2-1, when the measurement was carried out by the FT-IR infrared absorption spectrum measuring apparatus, it was found that an absorption phenomenon occurred in the vicinity of the wave number of 900 cm-1, that is, Say, it can be confirmed that there is a peroxy group.
<u style="single">Example 2-12</u>
Metal titanium is used as a titanium raw material. Weighed 0.48g of titanium metal powder (manufactured by Wako Pure Chemical Industries, Ltd., metal titanium powder), and put it into 50g of distilled water to dissolve 4g of sodium hydroxide (produced by Wako Pure Chemical Industries Co., Ltd., special grade reagent) In the solution, 20 ml of 30% by weight of hydrogen peroxide water was further added, and distilled water was added to make the solution 100 ml, and the mixture was stirred, and then, at 25 ° C, the solution was placed. After 15 hours, a dissolution treatment was carried out to obtain a yellow transparent solution. The titanium concentration is 0.1 mol/l, and the sodium ammonium concentration is 1.0 mol/l.
Next, 60 g of a H+-substituted cation exchange resin (phenolic formaldehyde ion exchange resin IR118 made of organic material) was gradually introduced into the obtained solution, and the mixture was stirred to reach the pH (pH) of the solution. At a time point of 5.0, after the cation exchange resin was separated, ultrasonic irradiation was performed to decompose hydrogen peroxide, and at a time point when the pH (pH) of the solution became 8, another 4 g of cation exchange was introduced. Resin, and after the pH value (pH) of the solution reaches 5, after the added cation exchange resin is separated, ultrasonic irradiation is performed to facilitate decomposition of hydrogen peroxide, and at the pH of the solution When the pH was 8, the 4 g of the cation exchange resin was further charged, and the ultrasonic irradiation treatment was further performed so that the pH (pH) of the solution became 5. After the cation exchange resin is separated, the decomposition of hydrogen peroxide caused by the ultrasonic irradiation three times and the removal of the cation by the cation exchange resin are repeatedly performed to obtain a yellow transparent titanium oxide. Use a solution. The sodium concentration in the solution for forming a yellow transparent titanium oxide was 0.01 mol/l.
Further, when the powder obtained by subjecting the obtained solution to a drying treatment in the same manner as in Example 1 is measured by an X-ray diffraction apparatus, it can be known that the obtained powder, It is in an amorphous state.
Further, in the same manner as in Example 2-1, when the measurement was carried out by the FT-IR infrared absorption spectrum measuring apparatus, it was found that an absorption phenomenon occurred in the vicinity of the wave number of 900 cm-1, that is, Say, it can be confirmed that there is a peroxy group.
<u style="single"></u>
<u style="single">Example 2-13 and Comparative Example 2-1</u>
Metal titanium is used as a titanium raw material. 0.48 g of titanium metal powder (manufactured by Wako Pure Chemical Industries, Ltd., titanium metal powder) was added and added to 7 ml. 2 times dilution of ammonia water having a concentration of 25% by weight, and further adding 20 ml of 30% by weight of hydrogen peroxide water, and distilling water to make the solution 100 ml, and stirring treatment, followed by stirring The solution was allowed to stand at 25 ° C for 24 hours to be dissolved to obtain a yellow transparent solution. The titanium concentration is 0.1 mol/l, and the ammonium ion concentration is 0.6 mol/l.
Next, the solution is stirred after changing the amount of the H + substituted cation exchange resin (phenol formaldehyde ion exchange resin IR118 made of organic material), and then, after 10 minutes, the added cation exchange resin is removed. In the case of the above solution, the pH (pH), the titanium concentration, and the ammonium ion concentration of the solution were measured, and the results of the measurement are shown in Table 1.
Regardless of any of the above-mentioned samples, hydrogen peroxide remains, and foaming occurs continuously, and after the third day, the foaming phenomenon is stopped, and the pH value (pH) of the solution rises. No matter in any of the above samples, turbidity and precipitation occur.<tables><img file="TW460416B_D0001.tif" /></tables>
<u style="single">Comparative Example 2-2</u>
In the example 2-1, the titanium oxide-forming solution produced by the removal of the cation by the cation exchange resin was placed at 25 ° C for 5 days. Then, the solution for forming a titanium oxide is in a yellowish white turbid state. The liquid obtained in Example 2-1 did not undergo any change even after being left for 30 days.
<u style="single">Example 3-1</u>
In a solution in which 5 ml of a 60% aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, 20 ml of a 30% aqueous hydrogen peroxide solution was added and stirred to prepare a brown transparent liquid, and ammonia water was dropped (1). :9) To the above solution, the pH (pH) was made 7 to facilitate the production of a yellow transparent solution. The solution obtained as described above was also left to stand overnight at 25 ° C to form a yellow precipitate.
After the filtration and washing treatment of the precipitated yellow precipitate obtained as described above, the precipitation of the yellow precipitate is increased to about 150 ml by adding distilled water, and 25 g is separately charged. The cation exchange resin and the anion exchange resin were placed in a solution of the aforementioned yellow precipitation precipitate, and left for 30 minutes to remove the cationic substance and the anionic substance.
As the cation exchange resin, a so-called hydrochloric acid having a concentration of 2N and a phenol formaldehyde ion exchange resin IR120B made of an organic substance are used. Substitute), after 1 hour of treatment, and then washed, then become H<sup>+</sup>A substitution type cation exchange resin; in addition, as an anion exchange resin, a so-called sodium hydroxide having a concentration of 1 N is used, and a phenol formaldehyde ion exchange resin IRA410 (C1-substituted type) made of an organic substance is treated for one hour. Then, it is further subjected to a washing treatment to form an OH-substituted anion exchange resin.
The liquid obtained by the above-mentioned yellow precipitate-containing liquid was 150 ml, and was sealed in a glass container, and a light yellow translucent liquid was formed at a temperature of 100 ° C for 5 hours. . By using an X-ray diffraction device (manufactured by Rigaku Corporation, RAD-B), a copper target is used, and under the measurement conditions of an acceleration voltage of 30 kV and a current of 15 mA, in order to make the resulting pale yellow translucent The powder obtained by drying the liquid was measured and measured, and the measurement results are shown in Fig. 9 . In Fig. 9, it was confirmed that there was a peak of anatase showing crystallinity, and it was also confirmed that there was a crystalline anatase in a dry substance of a pale yellow translucent liquid. Mine (anatase). The crystallite diameter determined from the half width of the diffraction peak was 8 nm.
Further, the liquid generated as described above was applied onto a glass slide, and dried and heat-treated at 60 ° C to obtain a titanium oxide film.
<u style="single">Example 3-2</u>
In a solution of 5 ml of a 60% aqueous solution of titanium tetrachloride diluted to 500 ml with distilled water, 20 ml of a 30% aqueous solution of hydrogen peroxide was added thereto. With stirring, a brown transparent liquid was produced, and ammonia water (1:9) was dropped into the above solution to bring the pH (pH) to 7, in order to produce a yellow transparent solution. The solution obtained as described above was placed at 25 ° C for a day and night to form a yellow precipitate.
After the filtration and washing treatment were carried out on the yellow transparent solution described above, the yellow transparent solution was added to about 150 ml by adding distilled water, and the solution was sealed in a glass container. In the same manner as in Example 1, except that the heat treatment was carried out for 5 hours at 100 ° C, the anatase containing the same as Example 3-1 was obtained. a dispersion of crystalline titanium oxide.
<u style="single">Example 3-3</u>
In a solution in which 5 ml of a 60% aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, 20 ml of a 30% aqueous hydrogen peroxide solution was added and stirred to prepare a brown transparent liquid, and ammonia water was dropped (1). :9) to the above solution, so that the pH (pH) is 7 to facilitate the production of a yellow transparent solution, and further, for 60 hours, the solution obtained for the above is carried out for 2 hours. Heat treatment to produce a yellow transparent solution, and then, at 60 ° C, the yellow transparent solution obtained above was heat-treated for 2 hours to form a yellow precipitate, and Further, the liquid containing the yellow precipitate was made into 150 ml, and then the liquid was sealed in a glass container, and at 75 ° C, 12 was carried out. Heat treatment in an hour to obtain a yellow translucent liquid. The measurement result of the measurement of the powder obtained by drying the liquid produced by the X-ray diffraction apparatus is shown in FIG. In Fig. 10, it was confirmed that there was a peak of anatase showing crystallinity, and it was also confirmed that there was a crystalline anatase in a dry substance of a pale yellow translucent liquid. Mine (anatase).
<u style="single">Comparative Example 3-1</u>
In a solution in which 5 ml of a 60% aqueous solution of titanium tetrachloride was diluted to 500 ml with distilled water, 20 ml of a 30% aqueous hydrogen peroxide solution was added and stirred to prepare a brown transparent liquid, and ammonia water was dropped (1). :9) to the above solution, so that the pH (pH) is 7 to facilitate the production of a yellow transparent solution, and also heated at 60 ° C for 2 hours, and for the obtained yellow precipitate The material is sufficiently filtered and washed.
In addition, the liquid containing the yellow precipitate described above was made 150 ml, and the liquid of the yellow precipitate was sealed in a glass container, and heated at 60 ° C for 12 hours, and the rest was carried out. The same treatment as in Example 3 was carried out to obtain a yellow opaque liquid. In Fig. 11, the result of measuring the powder obtained by drying the aforementioned yellow opaque liquid by an X-ray diffraction apparatus is shown. In Fig. 11, it was not confirmed that a clear peak for indicating the presence of a crystalline substance was observed, that is, it was confirmed that there was no crystalline anatase in the liquid.
Fig. 1 is a view for explaining the results of X-ray diffraction of the precipitate obtained in Example 1-1 of the present invention. Fig. 2 is a view showing the results of measurement performed by the apparatus for measuring the Fourier transform infrared absorption spectrum of the precipitate obtained in Example 1-1 of the present invention. Fig. 3 is a view for explaining the results of X-ray diffraction of the transparent yellow liquid obtained in Example 1-2 of the present invention. Fig. 4 is a view showing the results of measurement performed by the multi-leaf converted infrared absorption spectrometry apparatus for the transparent yellow liquid obtained in Example 1-2 of the present invention. Fig. 5 is a view for explaining the results of X-ray diffraction of a dry powder of the titanium oxide forming solution obtained in Example 2-1 of the present invention. Fig. 6 is a view showing the results of measurement performed by a multi-leaf converted infrared absorption spectrum measuring apparatus for a titanium oxide forming solution obtained in Example 2-1 of the present invention. Fig. 7 is a view for explaining the results of X-ray diffraction of the dried titanium oxide powder obtained in Example 2-2 of the present invention. Fig. 8 is a view showing the measurement results of the multiplexed-leaf converted infrared absorption spectrometry apparatus for the titanium oxide forming solution obtained in Example 2-2 of the present invention. Fig. 9 is a view for explaining the results of X-ray diffraction of the dried product of the pale yellow translucent liquid obtained in Example 3-1 of the present invention. Fig. 10 is a view for explaining the results of X-ray diffraction of a dried yellowish translucent liquid obtained in Example 3-2 of the present invention. Fig. 11 is a view for explaining the results of X-ray diffraction of the dried product of the pale yellow opaque liquid obtained in Comparative Example 3-1 of the present invention.
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Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| CN110833826A | Cited by | China | Search report |
14 members in 7 offices
Priority claims12
| Document | Office | Kind | Date |
|---|---|---|---|
| 11050868 | Japan | – | |
| 11050869 | Japan | – | |
| 5086899 | Japan | A | |
| 5086999 | Japan | A | |
| 11224190 | Japan | – | |
| 22419099 | Japan | A | |
| 19990050868 | – | – | – |
| 19990050869 | – | – | – |
| 19990224190 | – | – | – |
| JP19990050868 | – | – | – |
| JP19990050869 | – | – | – |
| JP19990224190 | – | – | – |
Members14
| Document | Office | Kind | |
|---|---|---|---|
| CA2299187A1 | Canada | A1 | |
| EP1031538A1 | European Patent Office (EPO) | A1 | |
| JP2000247638A | Japan | A | |
| JP2000247639A | Japan | A | |
| JP3122658B1 | Japan | B1 | |
| KR20010006681A | Republic of Korea | A | |
| JP2001048538A | Japan | A | |
| TW460416BThis record | Taiwan Province of China | B | |
| US6602918B1 | United States of America | B1 | |
| JP3490012B2 | Japan | B2 | |
| JP3490013B2 | Japan | B2 | |
| CA2299187C | Canada | C | |
| EP1031538B1 | European Patent Office (EPO) | B1 | |
| DE60041997D1 | Germany | D1 |
2 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
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|---|---|---|
| Expiration of patent term of an invention patentMK4A | MK4A | |
| Issue of patent certificate for granted invention patentGrantedGD4A | GD4A |
Numbers
- Publication
- 460416
- Publication, DOCDB
- 460416
- Publication, EPODOC
- TW460416B
- Application
- 89102931
- Application, DOCDB
- 89102931
- Application, EPODOC
- TW20000102931
Titles4
- Chinese
- 鈦氧化物形成用溶液及結晶性鈦氧化物粒子分散液體之製造方法
- English
- PROCESSES OF PRODUCING A TITANIUM OXIDE-FORMING SOLUTION AND A DISPERSION WITH CRYSTALLINE TITANIUM OXIDE PARTICLES
- Unlabeled
- 鈦氧化物形成用溶液及結晶性鈦氧化物粒子分散液體之製造方法
- Unlabeled
- Solution for forming titanium oxide and method for producing crystalline titanium oxide particle dispersion liquid
Classification
- CPC, 6
- C09D17/008
- C01G23/047
- C01P2002/72
- C01P2002/84
- C01P2006/60
- C09D17/00
- IPC, 2
- C01G23 047
- C09D17 00