JP3490012B2 - Method for producing crystalline titanium oxide particle dispersion liquid - Google Patents
Method for producing crystalline titanium oxide particle dispersion liquidInfo
- Publication number
- JP3490012B2 JP3490012B2 JP05086899A JP5086899A JP3490012B2 JP 3490012 B2 JP3490012 B2 JP 3490012B2 JP 05086899 A JP05086899 A JP 05086899A JP 5086899 A JP5086899 A JP 5086899A JP 3490012 B2 JP3490012 B2 JP 3490012B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- solution
- crystalline
- oxide particle
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【0001】[0001]
【発明の属する技術分野】本発明は、結晶性チタン酸化
物粒子分散液体の製造方法に関し、とくに基体上にチタ
ン酸化物膜を形成させるために使用するチタン酸化物塗
布剤として有用な結晶性チタン酸化物粒子分散液体を製
造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a crystalline titanium oxide particle-dispersed liquid, and particularly crystalline titanium useful as a titanium oxide coating agent used for forming a titanium oxide film on a substrate. The present invention relates to a method for producing an oxide particle-dispersed liquid.
【0002】[0002]
【従来の技術】チタン酸化物膜の形成方法は、酸化チタ
ン粉体スラリーあるいは塩化チタンや硫酸チタンの水溶
液を基体に塗布後焼成する塗布法、金属アルコキシドの
加水分解で作製したゾルを基体に塗布後焼成するゾルゲ
ル法、高真空中で酸化物のターゲットをスパッタリング
し基体上に成膜するスパッタリング法、有機金属化合物
やハロゲン化物を揮発させ加熱炉の中で分解して基体上
に膜を作製するCVD法、固体粒子を大気中で発生させ
たプラズマ中で溶融し基体表面に照射するプラズマ溶射
等がある。このうち、チタン酸化物膜の形成方法として
塗布液を用いる方法が簡便で実用性が高いとされてい
る。2. Description of the Related Art A titanium oxide film is formed by applying a titanium oxide powder slurry or an aqueous solution of titanium chloride or titanium sulfate to a substrate and then baking it, or applying a sol prepared by hydrolysis of a metal alkoxide to the substrate. Post-baking sol-gel method, sputtering method in which oxide target is sputtered in high vacuum to form film on substrate, organometallic compound or halide is volatilized and decomposed in heating furnace to form film on substrate There are a CVD method, plasma spraying in which solid particles are melted in plasma generated in the atmosphere, and the surface of the substrate is irradiated with the plasma. Among them, the method of using a coating liquid as a method of forming a titanium oxide film is said to be simple and highly practical.
【0003】酸化チタン粉末を用いる塗布法は簡単であ
るが、緻密で密着性良好な膜は得られ難く、チタン酸化
物膜の形成には、一般に高い合成温度を必要とするため
に合成温度に耐える耐熱性の基体を用いる必要があり、
適用できる基体の種類には制限がある。また、その酸化
チタンの微粒子の分散液体を得るために、一般に酸ある
いは適当な有機分散剤が用いられており、焼成によって
有害なハロゲン化合物等を生成する欠点があった。ま
た、塩化チタンや硫酸チタン等の水溶液を塗布焼成する
方法は有害なハロゲン化合物を生成し、また、焼成温度
も数百度以上を必要とした。Although the coating method using titanium oxide powder is simple, it is difficult to obtain a dense and good adhesive film, and a titanium oxide film generally requires a high synthesis temperature. It is necessary to use a heat resistant substrate that can withstand,
There are restrictions on the types of substrates that can be applied. Further, in order to obtain a dispersion liquid of the fine particles of titanium oxide, an acid or a suitable organic dispersant is generally used, and there is a defect that harmful compounds such as halogen compounds are produced by firing. Further, the method of coating and firing an aqueous solution of titanium chloride, titanium sulfate or the like produces a harmful halogen compound and requires a firing temperature of several hundred degrees or more.
【0004】また、ゾルゲル法で作製された市販の酸化
チタンゾルは塗布や含浸処理が可能で、大面積コーティ
ング、低温合成が可能で工業的な利点が多いが、チタン
テトライソプロポキサイドやテトラブチルチタネートな
どの有機金属を利用して合成しなければならなかったた
め、原料が高価であるとともに、原料が化学的に不安定
で温度制御や雰囲気に影響されやすく取り扱い難いとい
う問題があった。また、ゾルゲル法は原料ゾル中に酸や
有機物質を含むので焼成除去するのに400℃以上の加
熱が必要であり、酸に侵されやすい材料には不向きであ
り、低温焼成では多孔質になりやすいという問題点があ
った。Commercially available titanium oxide sol prepared by the sol-gel method can be applied and impregnated, and can be coated on a large area and can be synthesized at low temperature, which has many industrial advantages, but titanium tetraisopropoxide and tetrabutyl titanate are available. Since it has to be synthesized by using such an organic metal, there is a problem that the raw material is expensive, and the raw material is chemically unstable and easily affected by temperature control and atmosphere and is difficult to handle. Further, the sol-gel method requires heating at 400 ° C. or higher to remove by burning because the raw material sol contains an acid or an organic substance, and is not suitable for a material that is easily attacked by an acid. There was a problem that it was easy.
【0005】また、ゾルゲル法は工程が煩雑で、有機溶
媒を使用しなければならないず、ゾルゲル法によって作
製した酸化チタンゾル中には酸やアルカリ、あるいは有
機物が加えられており、被塗布材の腐蝕の問題があっ
た。また、有機物を分解するために400℃以上の温度
が必要であり、加熱焼成中に有害なハロゲン化物や窒素
酸化物などが副成する等の欠点があった。In the sol-gel method, the steps are complicated, and an organic solvent must be used. Acids, alkalis, or organic substances are added to the titanium oxide sol produced by the sol-gel method, which causes corrosion of the material to be coated. There was a problem. Further, a temperature of 400 ° C. or higher is required for decomposing organic substances, and there is a drawback that harmful halides, nitrogen oxides, and the like are by-produced during heating and firing.
【0006】このように、従来の方法では密度の高い結
晶性チタニア膜を低温で作製することが困難であり、比
較的低温で作製できるゾルゲル法では有機物質や酸等を
熱処理で分解消失させることが必要で、そのことが多孔
質化しやすくする原因にもなり、密度の高い膜を作製す
るには熱処理温度を比較的高くしなければならなかっ
た。また、それらの助剤が熱処理によって窒素酸化物や
有機物気体等の有害物質を生成する欠点もあった。As described above, it is difficult to form a crystalline titania film having a high density at a low temperature by the conventional method, and the sol-gel method, which can be formed at a relatively low temperature, decomposes and eliminates an organic substance, an acid and the like by heat treatment. However, this also causes the porous layer to be easily made porous, and the heat treatment temperature had to be relatively high in order to form a film having a high density. In addition, there is a drawback that these auxiliary agents generate harmful substances such as nitrogen oxides and organic gas by heat treatment.
【0007】こうした方法に対して、ペルオキソチタン
水和物からチタン酸化物膜を形成する場合には、特性の
良好な膜を比較的低い温度で形成可能なことが知られて
いる。ペルオキソチタン水和物は、四塩化チタン、硫酸
チタンなどの溶液に直接、過酸化水素水を添加すると、
ペルオキソチタン水和物イオンを生成し、それが縮合し
て固体析出物の形で生成されることが知られている。ま
た、ペルオキソチタン水和物イオンはpHが1以上では
チタン原子を2個以上含む多核イオンなどとして生成
し、常温では除々に縮合し、析出沈殿する。したがっ
て、pHが1以上で酸化チタンの塗布剤として使用する
ことは困難であるので、pHが1以下の強酸性の塗布剤
を適用可能な基体の種類は限定された。また、含まれる
ハロゲンや硫黄等が熱処理によってハロゲン化水素や硫
黄酸化物等の有害物質を生成するという問題点もあっ
た。In contrast to such a method, when a titanium oxide film is formed from peroxotitanium hydrate, it is known that a film having good characteristics can be formed at a relatively low temperature. Peroxotitanium hydrate can be obtained by adding hydrogen peroxide solution directly to a solution of titanium tetrachloride, titanium sulfate, etc.
It is known to produce peroxotitanium hydrate ions, which condense and form in the form of solid precipitates. Further, peroxotitanium hydrate ion is generated as a polynuclear ion containing two or more titanium atoms at a pH of 1 or more, and gradually condenses and precipitates at room temperature. Therefore, since it is difficult to use it as a titanium oxide coating agent having a pH of 1 or more, the types of substrates to which a strongly acidic coating agent having a pH of 1 or less can be applied are limited. Further, there is a problem that the contained halogen, sulfur, etc. generate harmful substances such as hydrogen halide, sulfur oxide, etc. by heat treatment.
【0008】また、高純度の酸化チタン膜を作製するた
めに、水素化チタンあるいはアルコキシチタンに直接に
過酸化水素水を添加して溶解して過酸化水素化チタン、
すなわちペルオキソチタン水和物と思われる物質を製造
することが特開昭62−252319号公報において提
案されている。しかしながら、これらのチタン原料は安
定ではなく、過酸化水素水を作用させた場合にかなりの
発熱反応が起こって、原料や生成物の熱分解などの悪影
響を生じるという欠点があった。したがって、大量に生
産しようとする場合には、十分に冷却ができないため
に、生成するペルオキソチタン酸が重合して非常に増粘
し、甚だしい場合には光の透過を遮る程度にまで粒子が
成長して濁ってくるので、塗布剤として使用した場合に
は膜の密着性や密度が低下する原因となる。Further, in order to produce a high-purity titanium oxide film, titanium hydrogen peroxide is obtained by directly adding hydrogen peroxide water to titanium hydride or alkoxy titanium to dissolve it.
That is, it has been proposed in JP-A-62-252319 to produce a substance considered to be peroxotitanium hydrate. However, these titanium raw materials are not stable, and have a drawback that a considerable exothermic reaction occurs when hydrogen peroxide solution is allowed to act, resulting in adverse effects such as thermal decomposition of the raw materials and products. Therefore, in the case of large-scale production, the peroxotitanic acid that is produced polymerizes and becomes extremely thick because it cannot be sufficiently cooled, and in extreme cases, particles grow to such an extent that light transmission is blocked. When it is used as a coating agent, it causes a decrease in the adhesion and density of the film.
【0009】また、含水酸化チタンのゲルあるいはゾル
に、過酸化水素水を添加してチタニルイオン過酸化水素
錯体あるいはチタン酸と記載されているされるペルオキ
ソチタン水和物と考えられる水溶液の製造方法が特開昭
63−35419号公報、および特開平1−22422
0号公報に記載されている。ところが、水酸化チタンに
直接過酸化水素水を添加するとペルオキソ化と溶液化が
同時に起こるため発熱が大きく、十分に攪拌冷却する必
要があるが、製造量が多くなると温度調整が非常に難し
くなり、十分に冷却できないと、増粘し、縮合が起こっ
てポリマーが粒子として成長し、さらには濁ってくるこ
とがあるという問題点があった。Further, a method for producing an aqueous solution considered to be peroxotitanium hydrate described as titanyl ion hydrogen peroxide complex or titanic acid by adding hydrogen peroxide water to a gel or sol of hydrous titanium oxide. JP-A-63-35419 and JP-A-1-224422.
No. 0 publication. However, when hydrogen peroxide solution is directly added to titanium hydroxide, since peroxo oxidation and solution formation occur at the same time, a large amount of heat is generated and it is necessary to sufficiently stir and cool, but when the production amount increases, it becomes very difficult to control the temperature. If it cannot be cooled sufficiently, there is a problem that the viscosity increases, condensation occurs, the polymer grows as particles, and it may become cloudy.
【0010】また、含水酸化チタンのゲルまたはゾルを
作製する場合に、アンモニアなどの塩基性物質を添加す
るが、瞬間的に含水酸化チタンの析出が起こるので不純
物であるアンモニウムイオンなどの陽イオンや塩素イオ
ンなどの陰イオンを取り込んで吸着しやすくなる。とく
に、塩素イオンや硫酸イオンなどの陰イオン不純物の存
在は、過酸化水素水を添加した後に生成するペルオキソ
チタン水和物の縮合を促進し、透明な水溶液が得られな
い場合がある。また、含水酸化チタンを蒸留水で洗浄し
ても完全に不純物を除くことは難しく、ペルオキソチタ
ン水和物の安定的な生産のためには大きな問題となって
いた。In addition, when a gel or sol of hydrous titanium oxide is prepared, a basic substance such as ammonia is added, but since the hydrous titanium oxide precipitates instantaneously, cations such as ammonium ions which are impurities and Incorporates anions such as chlorine ions to facilitate adsorption. In particular, the presence of anionic impurities such as chlorine ions and sulfate ions accelerates the condensation of peroxotitanium hydrate formed after the addition of hydrogen peroxide solution, and a transparent aqueous solution may not be obtained in some cases. Further, it is difficult to completely remove impurities even if the hydrous titanium oxide is washed with distilled water, which is a big problem for stable production of peroxotitanium hydrate.
【0011】また、本発明者は特開平9−71418号
公報、および特開平10−67516号公報において、
ペルオキソチタン水和物を加熱することによってアナタ
ーゼ超微粒子が析出した塗布剤が得られ、これによって
密着性が良好な結晶性のチタニア膜の形成が可能である
ことを提案している。これらの方法では、従来の方法に
比べて密着性が良好な結晶性のチタニア膜を形成するこ
とが可能であるが、アンモニウムイオンなどの陽イオン
の残存量が多い場合には、ペルオキソチタン水和物の水
溶液を加熱してアナターゼゾルを作製する場合に、ペル
オキソ基の分解が起こり難くなり、粒子の大きさが大き
くなって、塗布剤として使用した場合に密着性、あるい
は密度に劣る場合があった。The inventor of the present invention discloses in Japanese Patent Laid-Open Nos. 9-71418 and 10-67516,
It is proposed that a coating agent in which anatase ultrafine particles are deposited can be obtained by heating peroxotitanium hydrate, and by this, a crystalline titania film having good adhesion can be formed. By these methods, it is possible to form a crystalline titania film having better adhesion than conventional methods. However, when the residual amount of cations such as ammonium ions is large, peroxotitanium hydrate is hydrated. When an anatase sol is produced by heating an aqueous solution of a substance, decomposition of the peroxo group is less likely to occur, the particle size becomes large, and the adhesiveness or density when used as a coating agent may be poor. It was
【0012】[0012]
【発明が解決しようとする課題】本発明は、従来の問題
点を改善するものであり、チタン酸化物膜形成用の塗布
剤としても有用な、結晶性チタン酸化物粒子の新しい作
成方法を提供するものである。すなわち、過酸化水素水
によってペルオキソチタン水和物の水溶液を作製する場
合に、製造過程における熱的な影響による縮合、あるい
は粒子の必要以上の成長等によって塗布剤として使用し
た場合に生じる密着性や密度の低下を防止することを課
題とするものであり、密着性が良好で、密度が大きなチ
タン酸化物塗布膜が形成可能な結晶性チタン酸化物粒子
を得ることを課題とするものである。DISCLOSURE OF THE INVENTION The present invention solves the conventional problems and provides a new method of producing crystalline titanium oxide particles, which is also useful as a coating agent for forming a titanium oxide film. To do. That is, when an aqueous solution of peroxotitanium hydrate is prepared with hydrogen peroxide solution, the adhesion and the adhesiveness caused when it is used as a coating agent due to condensation due to thermal influence in the manufacturing process, or excessive growth of particles, etc. It is an object to prevent a decrease in density, and an object is to obtain crystalline titanium oxide particles which have good adhesion and can form a titanium oxide coating film having a high density.
【0013】[0013]
【課題を解決するための手段】本発明は、結晶性チタン
酸化物粒子の製造方法において、チタン含有原料水溶液
に過酸化水素水を加えてペルオキソチタン錯体を形成さ
せた後に、塩基性物質を添加して得られた溶液を放置す
ることによってペルオキソチタン水和物の重合体の沈殿
物を形成した後に、少なくともチタン含有原料水溶液に
由来する水以外の溶解成分を除去した後に、水分を分離
しない状態で70℃以上の温度において加熱する結晶性
チタン酸化物粒子分散液体の製造方法である。水和物形
成用に添加した塩基性物質に由来する水以外の溶解成分
も除去する前記の結晶性チタン酸化物粒子分散液体の製
造方法である。溶解成分の除去を水洗、もしくはイオン
交換反応によって行う前記の結晶性チタン酸化物粒子分
散液体の製造方法である。The present invention provides a method for producing crystalline titanium oxide particles, wherein hydrogen peroxide is added to a titanium-containing raw material aqueous solution to form a peroxotitanium complex, and then a basic substance is added. After forming a precipitate of a polymer of peroxotitanium hydrate by allowing the solution obtained by leaving to stand, at least after removing dissolved components other than water derived from the titanium-containing raw material aqueous solution, water is not separated Is a method for producing a crystalline titanium oxide particle-dispersed liquid which is heated at a temperature of 70 ° C. or higher. The method for producing a crystalline titanium oxide particle-dispersed liquid as described above, wherein dissolved components other than water derived from the basic substance added for forming a hydrate is also removed. The method for producing a crystalline titanium oxide particle-dispersed liquid as described above, wherein the dissolved components are removed by washing with water or an ion exchange reaction.
【0014】[0014]
【発明の実施の形態】本発明は、ペルオキソチタン水和
物を経由した結晶性チタン酸化物粒子の製造過程におい
て、縮合等を促進する要因を除去するとともに、沈殿状
態の水和物から直接的に特性の優れた結晶性粒子が得ら
れることを見いだし本発明をなし得たものである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention eliminates a factor that promotes condensation and the like in the process of producing crystalline titanium oxide particles via peroxotitanium hydrate, and at the same time, directly removes the precipitated hydrate. It was found that crystalline particles having excellent characteristics can be obtained, and the present invention has been accomplished.
【0015】すなわち、反応過程において縮合等を促進
する要因となる反応生成物、あるいは原料から混入する
不純物を早期に分離することによって縮合等を防止した
ものであり、以下の工程から構成されている。
(1)ペルオキソチタン水和物の重合体の析出工程
四塩化チタン等の可溶性チタン化合物を水で希釈し、適
量の過酸化水素水を添加して褐色のペルオキソ錯体を生
成せしめ、次に、アンモニア等の塩基性物質を添加し、
黄色のペルオキソチタン水和物の水溶液を作製し、この
水溶液を常温放置、あるいは加熱してペルオキソチタン
水和物の重合体を析出沈殿させる。
(2)イオン性物質や不純物の除去工程
ペルオキソチタン水和物の重合体の析出沈殿物を含む液
体を洗浄、あるいはろ過と洗浄等の処理を行って、液体
中に含まれているアンモニウムイオンや塩素イオン、あ
るいは原料に由来する不純物を取り除く。
(3)結晶性チタン酸化物粒子の形成工程
洗浄処理によってイオン性物質や不純物を除去したペル
オキソチタン水和物の沈殿物を水分を分離しない泥状
物、あるいは分散液の状態で80℃以上において、常
圧、あるいはオートクレーブ中において加熱することに
よって、結晶性チタン酸化物粒子を形成する。That is, the condensation product is prevented by early separating the reaction product, which is a factor that promotes the condensation product in the reaction process, or the impurities mixed in from the raw materials, and is composed of the following steps. . (1) Step of Precipitating Polymer of Peroxotitanium Hydrate A soluble titanium compound such as titanium tetrachloride is diluted with water, and an appropriate amount of hydrogen peroxide solution is added to form a brown peroxo complex. Basic substance such as
An aqueous solution of yellow peroxotitanium hydrate is prepared, and the aqueous solution is left standing at room temperature or heated to precipitate and precipitate a polymer of peroxotitanium hydrate. (2) Step of removing ionic substances and impurities The liquid containing the precipitate of the peroxotitanium hydrate polymer is washed or subjected to treatments such as filtration and washing to remove ammonium ions and the like contained in the liquid. Remove chlorine ions or impurities derived from raw materials. (3) Step of forming crystalline titanium oxide particles At 80 ° C or higher, a precipitate of peroxotitanium hydrate from which ionic substances and impurities have been removed by a washing treatment does not separate water into a muddy substance or a dispersion liquid. The crystalline titanium oxide particles are formed by heating at normal pressure or in an autoclave.
【0016】以上の工程によって作製することによっ
て、結晶性チタン酸化物粒子を形成することができ、特
性の優れた酸化チタン膜の低温での形成等に有用な結晶
性チタン酸化物粒子の分散体を得ることができる。A crystalline titanium oxide particle dispersion capable of forming crystalline titanium oxide particles by the above steps and useful for forming a titanium oxide film having excellent characteristics at low temperatures, etc. Can be obtained.
【0017】本発明の方法において原料として使用され
る可溶性チタン化合物は、四塩化チタン、硫酸チタン、
硝酸チタン、アルコキシチタンなどを挙げることができ
る。また、可溶性チタン化合物の水溶液へ添加する過酸
化水素水の量は過酸化水素/チタンのモル比は1以上が
必要で、それ以下の量では、完全にペルオキソ化が完了
しない。しかも、添加した過酸化水素水には反応に関与
することなく分解するものがあるので、過酸化水素/チ
タンのモル比が1よりも過剰に加えることが好ましい。Soluble titanium compounds used as raw materials in the method of the present invention include titanium tetrachloride, titanium sulfate,
Examples thereof include titanium nitrate and alkoxytitanium. Further, the amount of hydrogen peroxide solution added to the aqueous solution of the soluble titanium compound needs to have a hydrogen peroxide / titanium molar ratio of 1 or more, and if the amount is less than that, the peroxo oxidation is not completely completed. Moreover, since some of the added hydrogen peroxide solution decomposes without participating in the reaction, it is preferable to add the hydrogen peroxide / titanium molar ratio in excess of 1.
【0018】可溶性チタン含有溶液に過酸化水素水を加
えるとほとんど瞬時にペルオキソ化が起こり、pHが3
以下では主に陽イオンとして溶解しており、pHが3以
上では主にペルオキソチタン水和物の陰イオンとして存
在している。これはpHが高いほど早く縮合して無定型
のペルオキソチタン水和物の重合体を析出するためであ
ると考えられる。塩基性物質を添加する場合において
も、pHが低いとペルオキソチタン水和物の重合体を析
出する時間が長くなるので、pHが3以上になるまで塩
基性物質を加えることが好ましく、さらに好ましくは中
性域までpHを調整した方が良い。塩基性物質を添加す
ることによって生成したペルオキソチタン水和物の黄色
透明液体から黄色の沈殿物を生成させる場合には、室温
で放置しても良いが、加温することによって析出を促進
することができる。攪拌するとさらに析出が早くなる。When hydrogen peroxide solution is added to the soluble titanium-containing solution, peroxidation occurs almost instantly, and the pH becomes 3 or less.
In the following, it is mainly dissolved as a cation, and when the pH is 3 or more, it mainly exists as an anion of peroxotitanium hydrate. It is considered that this is because the higher the pH, the faster the condensation and the precipitation of the amorphous peroxotitanium hydrate polymer. Even when the basic substance is added, it is preferable to add the basic substance until the pH becomes 3 or more, because the time for precipitating the polymer of peroxotitanium hydrate becomes long when the pH is low. It is better to adjust the pH to the neutral range. When a yellow precipitate is formed from a yellow transparent liquid of peroxotitanium hydrate formed by adding a basic substance, it may be left at room temperature, but it should be heated to promote precipitation. You can Precipitation is further accelerated with stirring.
【0019】析出沈殿物を含む液体中から液体中に含ま
れているアンモニウムイオンや塩素イオン、あるいは原
料に由来する不純物を取り除く工程では、デカンテーシ
ョン、ろ過洗浄、遠心分離などの方法、あるいはイオン
交換反応、逆浸透法を適用してイオン性物質を除去する
方法を用いることができる。In the step of removing ammonium ions and chlorine ions contained in the liquid or impurities derived from the raw material from the liquid containing the precipitate, a method such as decantation, filter washing, centrifugal separation, or ion exchange is performed. A method of removing an ionic substance by applying a reaction or reverse osmosis method can be used.
【0020】不純物の残存量が多い場合は、最終的に得
られるペルオキソチタン水和物の水溶液の安定性や性状
に悪影響を与えるので十分に処理することが望ましい。
とくに、塩素イオン等の陰イオンはペルオキソチタン水
和物の縮合を促すと考えられ、これらの除去が不十分の
場合には完全な透明にならず濁る場合がある。一方、ア
ンモニウムイオン等の陽イオンが残っていても陰イオン
を十分に除くとペルオキソチタン水和物を含む黄色透明
な水溶液を得ることができる。If the residual amount of impurities is large, the stability and properties of the finally obtained aqueous solution of peroxotitanium hydrate will be adversely affected, so it is desirable to treat it sufficiently.
In particular, anions such as chlorine ions are considered to promote condensation of peroxotitanium hydrate, and if these are not removed sufficiently, they may not be completely transparent and may become cloudy. On the other hand, even if cations such as ammonium ions remain, a yellow transparent aqueous solution containing peroxotitanium hydrate can be obtained by sufficiently removing the anions.
【0021】 次いで、析出沈殿物を含む分散液、ある
いは泥状物を加熱処理する。加熱温度は、70℃以上で
あることが好ましく、70℃よりも低温では、アナター
ゼの結晶性チタン酸化物粒子の生成が充分ではない。ま
た、加熱温度は80℃ないし200℃とすることがより
好ましい。200℃以上では、ごく短時間にアナターゼ
の析出が起こるために、処理時間の調整が困難となる。
また、加熱時間は、5分間ないし20時間とすることが
好ましい。オートクレーブ中において加熱することによ
って、短時間で結晶性チタン酸化物粒子を製造すること
が可能となる。オートクレーブ処理では、100℃ない
し200℃で行うことが好ましい。Next, the dispersion containing the precipitate or the mud is heat-treated. The heating temperature is preferably 70 ° C. or higher, and if the temperature is lower than 70 ° C., the production of crystalline titanium oxide particles of anatase is not sufficient. The heating temperature is more preferably 80 ° C to 200 ° C. At 200 ° C. or higher, the precipitation of anatase occurs in a very short time, making it difficult to adjust the treatment time.
The heating time is preferably 5 minutes to 20 hours. By heating in an autoclave, it becomes possible to produce crystalline titanium oxide particles in a short time. The autoclave treatment is preferably performed at 100 ° C to 200 ° C.
【0022】また、沈殿物の処理においては、沈殿物が
乾燥すると脱水固化をして、結晶性チタン酸化物粒子分
散液体の製造工程に悪影響を及ぼすので乾燥させないよ
うにすることが必要である。本発明の方法では、沈殿物
を加熱すると、結晶性粒子の生成と共に、粒子の分散液
体が生成する。In the treatment of the precipitate, it is necessary to prevent dehydration and solidification of the precipitate when it is dried and adversely affect the production process of the crystalline titanium oxide particle-dispersed liquid. In the method of the present invention, when the precipitate is heated, a dispersion liquid of particles is formed together with the formation of crystalline particles.
【0023】また、本発明の結晶性酸化チタン粒子分散
液体は塗布するのみで結晶性のチタニア膜が形成できる
ため、加熱処理をできない材料の塗布剤として有用であ
る。また、保護被膜や光触媒、合成樹脂フィルムの気体
の透過阻止材等種々の用途に利用可能であり、しかも比
較的密度が高く密着性の良いものを比較的低温で得るこ
とができる。Further, the crystalline titanium oxide particle-dispersed liquid of the present invention can form a crystalline titania film only by coating, so that it is useful as a coating agent for materials that cannot be heat-treated. Further, it can be used for various applications such as a protective film, a photocatalyst, and a gas permeation blocking material for a synthetic resin film, and a material having a relatively high density and good adhesion can be obtained at a relatively low temperature.
【0024】本発明の結晶性チタン酸化物粒子を分散し
た液体は各種の固体微粒子と混合して、超音波やボール
ミル等で分散させることができ、それを塗布して乾燥焼
成などで得られる酸化チタン膜の中に、他の物質を担持
あるいは分散した複合体を作成することも可能である。
また、塗布する基体としては、セラミックス、陶磁器、
金属、プラスチックス、繊維、建材等、用途に応じた加
熱処理に耐え得る素材であればあらゆるものに塗布可能
であり、多孔体の内部や粉体の表面処理を行なうことも
可能であり、本発明で作製されるチタン酸化物塗布剤は
各種材料製品の保護被膜、光触媒膜、紫外線カット被
膜、着色塗布膜、誘電体膜、膜型センサー、酸化チタン
ゾルの製造などの分野に利用され得る。The liquid in which the crystalline titanium oxide particles of the present invention are dispersed can be mixed with various kinds of solid fine particles and dispersed by ultrasonic waves, a ball mill, etc. Oxidation obtained by applying it and drying and firing. It is also possible to create a composite in which another substance is supported or dispersed in the titanium film.
In addition, as the substrate to be applied, ceramics, ceramics,
It can be applied to any material, such as metal, plastics, fibers, and building materials, as long as it can withstand heat treatment according to the application, and it can also be surface-treated inside the porous body or powder. The titanium oxide coating agent produced by the present invention can be used in fields such as production of protective coatings for various material products, photocatalyst coatings, ultraviolet cut coatings, colored coating coatings, dielectric coatings, membrane sensors, titanium oxide sols.
【0025】[0025]
【実施例】以下に、実施例を示し本発明を説明する。
実施例1
四塩化チタン60%水溶液5mlを蒸留水で500ml
に希釈した溶液に、過酸化水素水30%溶液を20ml
加えて攪拌して褐色の透明液体を作製し、この溶液にア
ンモニア水(1:9)を滴下してpHを7とし、黄色透
明の溶液を作製した。得られた溶液を25℃で一昼夜放
置し、黄色の析出沈殿物を生成させた。これを、ろ過洗
浄後、蒸留水で約150mlとし、陽イオン交換樹脂及
び陰イオン交換樹脂をそれぞれ25gずつ投入して30
分間放置し、陽イオン性物質、陰イオン性物質を除去し
た。陽イオン交換樹脂としては、オルガノ製アンバーラ
イトIR120B(Na+置換型)を2N塩酸で1時間
処理した後に洗浄して、H+ 置換型としたものを用い、
陰イオン交換樹脂としては、オルガノ製アンバーライト
IRA410(Cl - 置換型)を1N水酸化ナトリウム
で1時間処理した後に洗浄して、OH- 置換型としたも
のを用いた。EXAMPLES The present invention will be described below with reference to examples.
Example 1
Titanium tetrachloride 60% aqueous solution 5 ml with distilled water 500 ml
20ml of 30% hydrogen peroxide solution to the diluted solution
Add and stir to make a brown transparent liquid, and add to this solution.
Water (1: 9) was added dropwise to adjust the pH to 7 and the yellow transparent
A bright solution was made. Release the resulting solution at 25 ° C overnight
Then, a yellow precipitate was formed. This is filtered and washed
After purification, make up to about 150 ml with distilled water and use cation exchange resin and
And anion exchange resin 25g each
Leave for a minute to remove cationic substances and anionic substances.
It was As a cation exchange resin, amber made by Organo
Ito IR120B (Na+Substitution type) with 2N hydrochloric acid for 1 hour
After processing, wash and+ Use the substitution type,
As anion exchange resin, Amberlite made by Organo
IRA410 (Cl - Substitution type) 1N sodium hydroxide
Treated for 1 hour, then washed and OH- The replacement type
Was used.
【0026】得られた黄色沈殿物を含む液体を150m
lとし、ガラス容器に密閉して100℃において5時間
加熱したところ、淡黄色半透明の液が生成した。生成し
た液体を乾燥して得られた粉末をX線回折装置(理学電
機製 RAD−B)によって、銅ターゲットを用い、加
速電圧30kV、電流15mAの測定条件で測定し、そ
の結果を図1に示す。図1には、結晶性のアナターゼを
示すピークが確認され、淡黄色半透明の液の乾燥物には
結晶性のアナターゼが存在していることが確認できた。
回折ピークの半値幅から求めた結晶子径は8nmであっ
た。また、生成した液体をスライドガラス上に塗布し
て、60℃で乾燥、加熱処理することによって酸化チタ
ン膜が得られた。The liquid containing the obtained yellow precipitate is set to 150 m.
When it was made 1 and sealed in a glass container and heated at 100 ° C. for 5 hours, a pale yellow translucent liquid was produced. The powder obtained by drying the generated liquid was measured by an X-ray diffractometer (RAD-B manufactured by Rigaku Denki) using a copper target under the measurement conditions of an acceleration voltage of 30 kV and a current of 15 mA, and the result is shown in FIG. Show. In FIG. 1, a peak showing crystalline anatase was confirmed, and it was confirmed that crystalline anatase was present in the dried product of the pale yellow translucent liquid.
The crystallite diameter determined from the half width of the diffraction peak was 8 nm. In addition, a titanium oxide film was obtained by applying the produced liquid on a slide glass, drying it at 60 ° C., and heating it.
【0027】実施例2
四塩化チタン60%水溶液5mlを蒸留水で500ml
に希釈した溶液に、過酸化水素水30%溶液を20ml
加えて攪拌して褐色の透明液体を作製し、この溶液にア
ンモニア水(1:9)を滴下してpHを7とし、黄色透
明の溶液を作製した。得られた溶液を25℃で一昼夜放
置し、黄色の析出沈殿物を生成させた。これを、ろ過洗
浄後、蒸留水で約150mlとし、ガラス容器に密閉し
て100℃において5時間加熱した点を除き、実施例1
と同様に処理したところ、実施例1と同様のアナターゼ
の結晶性チタン酸化物を含有する分散体が得られた。Example 2 5 ml of 60% titanium tetrachloride aqueous solution was diluted with distilled water to 500 ml.
20ml of 30% hydrogen peroxide solution to the diluted solution
In addition, the mixture was stirred to prepare a brown transparent liquid, and aqueous ammonia (1: 9) was added dropwise to this solution to adjust the pH to 7 to prepare a yellow transparent solution. The obtained solution was left at 25 ° C. for a whole day and night to produce a yellow precipitate. This was filtered, washed, and made up to about 150 ml with distilled water, sealed in a glass container, and heated at 100 ° C. for 5 hours, except that Example 1 was used.
When treated in the same manner as in Example 1, the same dispersion containing crystalline titanium oxide of anatase as in Example 1 was obtained.
【0028】比較例1
四塩化チタン60%水溶液5mlを蒸留水で500ml
に希釈した溶液に、過酸化水素水30%溶液を20ml
加えて撹拌して褐色の透明液体を作製し、この溶液にア
ンモニア水(1:9)を滴下してpHを7とし、黄色透
明の溶液を作製し、60℃で2時間加熱し、得られた黄
色の沈殿物を十分にろ過洗浄した。この黄色の沈殿物を
含む液体を150mlとし、ガラス容器に密閉して75
℃で12時間加熱し、黄色半透明の液体を得た。この液
体を乾燥して得た粉末をX線回折で測定した結果を図2
に示す。図2には、結晶性のアナターゼを示すピークは
存在しているものの、実施例を示す図1に比べてピーク
が小さく実施例に比べて結晶性のアナターゼは不充分な
ものであった。Comparative Example 1 Titanium tetrachloride 60% aqueous solution 5 ml was distilled water 500 ml
20ml of 30% hydrogen peroxide solution to the diluted solution
The solution was stirred to prepare a brown transparent liquid, ammonia water (1: 9) was added dropwise to this solution to adjust the pH to 7, and a yellow transparent solution was prepared, which was heated at 60 ° C. for 2 hours to obtain The yellow precipitate was thoroughly filtered and washed. Make up the liquid containing this yellow precipitate to 150 ml and seal it in a glass container.
The mixture was heated at ℃ for 12 hours to obtain a yellow translucent liquid. The result of measuring the powder obtained by drying this liquid by X-ray diffraction is shown in FIG.
Shown in. Although a peak showing crystalline anatase was present in FIG. 2, the peak was smaller than that in FIG. 1 showing the example and the amount of crystalline anatase was insufficient as compared with the example.
【0029】比較例2
四塩化チタン60%水溶液5mlを蒸留水で500ml
に希釈した溶液に、過酸化水素水30%溶液を20ml
加えて撹拌して褐色の透明液体を作製し、この溶液にア
ンモニア水(1:9)を滴下してpHを7とし、黄色透
明の溶液を作製し、60℃で2時間加熱し、得られた黄
色の沈殿物を十分にろ過洗浄した。この黄色の沈殿物を
含む液体を150mlとし、ガラス容器に密閉して60
℃で12時間加熱した点を除き、比較例1と同様に処理
したところ黄色不透明の液体を得た。この液体を乾燥し
て得られた粉末をX線回折で測定した結果を図3に示
す。図3には、結晶性の物質が存在することを示す明確
なピークは認められず、この液体中には結晶性のアナタ
ーゼが存在していないことが確認された。Comparative Example 2 5 ml of 60% titanium tetrachloride aqueous solution was diluted with distilled water to 500 ml.
20ml of 30% hydrogen peroxide solution to the diluted solution
The solution was stirred to prepare a brown transparent liquid, ammonia water (1: 9) was added dropwise to this solution to adjust the pH to 7, and a yellow transparent solution was prepared, which was heated at 60 ° C. for 2 hours to obtain The yellow precipitate was thoroughly filtered and washed. The liquid containing this yellow precipitate is made up to 150 ml and sealed in a glass container.
A yellow opaque liquid was obtained by treating in the same manner as in Comparative Example 1 except that heating was performed at 12 ° C. for 12 hours. The result of measuring the powder obtained by drying this liquid by X-ray diffraction is shown in FIG. In FIG. 3, no clear peak indicating the presence of a crystalline substance was observed, and it was confirmed that crystalline anatase was not present in this liquid.
【0030】[0030]
【発明の効果】本発明に係る製造方法によって、ペルオ
キソチタン水和物の縮合の抑制を容易に行うことがで
き、ペルオキソチタン水和物の沈殿物から直接的に粒径
が小さなアナターゼを分散した結晶性チタン酸化物粒子
を分散液を得ることができ、塗布剤として用いた場合に
は、緻密な酸化チタン膜を形成することができる。EFFECTS OF THE INVENTION By the production method according to the present invention, the condensation of peroxotitanium hydrate can be easily suppressed, and anatase having a small particle size is directly dispersed from the precipitate of peroxotitanium hydrate. A dispersion of crystalline titanium oxide particles can be obtained, and when used as a coating agent, a dense titanium oxide film can be formed.
【図1】図1は、本発明の一実施例で得られた淡黄色半
透明液の乾燥物のX線回折結果を説明する図である。FIG. 1 is a diagram illustrating an X-ray diffraction result of a dried product of a pale yellow translucent liquid obtained in one example of the present invention.
【図2】図2は、本発明の比較例で得られた淡黄色半透
明液の乾燥物のX線回折結果を説明する図である。FIG. 2 is a diagram illustrating an X-ray diffraction result of a dried product of a pale yellow translucent liquid obtained in a comparative example of the present invention.
【図3】図3は、本発明の他の比較例で得られた淡黄色
不透明液の乾燥物のX線回折結果を説明する図である。FIG. 3 is a diagram illustrating an X-ray diffraction result of a dried product of a pale yellow opaque liquid obtained in another comparative example of the present invention.
Claims (3)
方法において、チタン含有原料水溶液に過酸化水素水を
加えてペルオキソチタン錯体を形成させた後に、塩基性
物質を添加して得られた溶液を放置してペルオキソチタ
ン水和物の重合体の沈殿物を形成した後に、少なくとも
チタン含有原料水溶液に由来する水以外の溶解成分を除
去した後に、水分を分離しない状態で70℃以上の温度
において加熱することを特徴とする結晶性チタン酸化物
粒子分散液体の製造方法。1. A method for producing a crystalline titanium oxide particle-dispersed liquid, comprising: adding a hydrogen peroxide solution to a titanium-containing raw material aqueous solution to form a peroxotitanium complex, and then adding a basic substance to the solution. Is allowed to stand to form a polymer precipitate of peroxotitanium hydrate, and then at least the dissolved components other than water derived from the titanium-containing raw material aqueous solution are removed. A method for producing a crystalline titanium oxide particle-dispersed liquid, which comprises heating.
来する水以外の溶解成分も除去することを特徴とする請
求項1記載の結晶性チタン酸化物粒子分散液体の製造方
法。2. The method for producing a crystalline titanium oxide particle-dispersed liquid according to claim 1, wherein dissolved components other than water derived from the basic substance added for forming a hydrate are also removed.
交換反応によって行うことを特徴とする請求項1または
2に記載の結晶性チタン酸化物粒子分散液体の製造方
法。3. The method for producing a crystalline titanium oxide particle-dispersed liquid according to claim 1 or 2, wherein the dissolved components are removed by washing with water or an ion exchange reaction.
Priority Applications (7)
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JP05086899A JP3490012B2 (en) | 1999-02-26 | 1999-02-26 | Method for producing crystalline titanium oxide particle dispersion liquid |
TW089102931A TW460416B (en) | 1999-02-26 | 2000-02-21 | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
KR10-2000-0008733A KR100394695B1 (en) | 1999-02-26 | 2000-02-23 | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
CA002299187A CA2299187C (en) | 1999-02-26 | 2000-02-23 | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
US09/512,656 US6602918B1 (en) | 1999-02-26 | 2000-02-24 | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
DE60041997T DE60041997D1 (en) | 1999-02-26 | 2000-02-25 | A process for producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
EP00103431A EP1031538B1 (en) | 1999-02-26 | 2000-02-25 | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
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US7175825B2 (en) | 2003-12-04 | 2007-02-13 | Sundecor Co., Ltd. | Method of producing titania solution |
WO2006123425A1 (en) * | 2005-05-20 | 2006-11-23 | Axtis Company | Process for producing solution for forming titanium oxide film |
JP4829771B2 (en) * | 2006-12-22 | 2011-12-07 | 石原産業株式会社 | Spherical peroxotitanium hydrate and method for producing spherical titanium oxide |
JP4841421B2 (en) * | 2006-12-25 | 2011-12-21 | 石原産業株式会社 | Spherical peroxotitanium hydrate and method for producing spherical titanium oxide |
JP5000684B2 (en) * | 2009-05-20 | 2012-08-15 | 信越化学工業株式会社 | Method for producing titanium oxide fine particle dispersion |
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