JP2709206B2 - Spherical porous anatase-type titanium dioxide fine particles and method for producing the same - Google Patents
Spherical porous anatase-type titanium dioxide fine particles and method for producing the sameInfo
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- JP2709206B2 JP2709206B2 JP16877791A JP16877791A JP2709206B2 JP 2709206 B2 JP2709206 B2 JP 2709206B2 JP 16877791 A JP16877791 A JP 16877791A JP 16877791 A JP16877791 A JP 16877791A JP 2709206 B2 JP2709206 B2 JP 2709206B2
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- titanium dioxide
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Description
【０００１】[0001]
【技術分野】本発明は、球形多孔質アナターゼ型二酸化
チタン微粒子、特に粉末Ｘ線回折から計算される結晶子
径が３００Å以下のアナターゼ型超微結晶の凝集した球
形粒子から成り、かかる球形粒子の長さ平均径が０．５
〜２．５μｍの範囲で、且つ重量平均径と長さ平均径の
比より求められる多分散指数が１．１以下の狭い粒径分
布を持ち、更にその比表面積が７０ｍ2 ／ｇ以上である
ことを特徴とする球形多孔質アナターゼ型二酸化チタン
微粒子、並びにそれを安価に且つ大量に製造する方法に
関するものである。TECHNICAL FIELD The present invention relates to spherical porous anatase-type titanium dioxide fine particles, particularly, aggregated spherical particles of anatase-type ultrafine crystals having a crystallite diameter of 300 ° or less calculated from powder X-ray diffraction. Length average diameter is 0.5
It has a narrow particle size distribution in which the polydispersity index determined from the ratio of the weight average diameter to the length average diameter is 1.1 or less, and the specific surface area is 70 m 2 / g or more. The present invention relates to a spherical porous anatase-type titanium dioxide fine particle characterized by the above feature, and a method for producing the same inexpensively and in large quantities.
【０００２】[0002]
【背景技術】従来から、二酸化チタン微粒子、例えば微
粉末またはその分散液は、チタン酸バリウム等の各種強
誘電体材料の基本的な原料として用いられているが、特
にアナターゼ型二酸化チタンは、ルチル型に比べて反応
性が高いことから、各種チタン酸塩セラミックスの合成
粉末の出発原料として広く使用されている。例えば、チ
タン酸バリウムの粉末原料は、一般に、アナターゼ型二
酸化チタンと炭酸バリウムとの粉末混合物を１０００℃
以上の温度で固相反応させることによって製造されてい
る。また、二酸化チタンは、屈折率が高く、隠蔽力に優
れるので、白色顔料等としても種々の分野で使用されて
いるが、特にアナターゼ型分散液は、短波長域、紫外線
域での分光反射率が高いことが知られており、このため
日焼け止め化粧品等にも使用されて、特別の価値を持つ
ものである。BACKGROUND ART Conventionally, titanium dioxide fine particles, for example, fine powder or a dispersion thereof have been used as a basic raw material for various ferroelectric materials such as barium titanate. Particularly, anatase type titanium dioxide is rutile. It is widely used as a starting material for synthetic powders of various titanate ceramics because of its higher reactivity than the mold. For example, the powder raw material of barium titanate is generally prepared by mixing a powder mixture of anatase type titanium dioxide and barium carbonate at 1000 ° C.
It is manufactured by performing a solid-phase reaction at the above temperature. Titanium dioxide has a high refractive index and is excellent in hiding power, so it is used in various fields as a white pigment and the like. Particularly, anatase type dispersion liquid has a short wavelength region and a spectral reflectance in an ultraviolet region. Is known to be high, and is therefore used for sunscreen cosmetics and the like, and has special value.
【０００３】ところで、ファインセラミックス、特に焼
結体の原料として用いられる酸化物微粒子は、０．５μ
ｍ程度以下の微粒子では、成形嵩密度が上がり難く、焼
成収縮が大きくなって作業性、生産性が低下する欠点が
あり、また、２．５μｍ程度以上では、焼結による緻密
化が困難となり、一般に粒径範囲は１μｍ前後の球形を
した粒径分布の狭いものが優れていることが知られてい
る。二酸化チタン粉末は、強誘電体セラミックスの原料
粉末、例えばチタン酸バリウム、その他のチタン酸塩の
原料粉末として使用されるが、これらのファインセラミ
ックス用のチタン酸塩の粉末粒子も、やはり１μｍ程度
の球形微粒子が望まれている。しかし、二酸化チタンと
炭酸バリウム等との粉末混合物を高温で固相反応させる
ことによっては、このような１μｍ程度の球形微粒子を
得ることは、従来は全く不可能であり、そのような特徴
を持つ球形二酸化チタン微粒子は、今まで知られていな
かった。Meanwhile, oxide fine particles used as a raw material of fine ceramics, particularly, a sintered body have a particle size of 0.5 μm.
In the case of fine particles of about m or less, there is a disadvantage that the molding bulk density is hardly increased, firing shrinkage is increased, and workability and productivity are reduced. In general, it is known that those having a spherical particle size range of about 1 μm and a narrow particle size distribution are excellent. Titanium dioxide powder is used as a raw material powder for ferroelectric ceramics, for example, barium titanate, and other raw material powders for titanate. These fine ceramic titanate powder particles also have a particle size of about 1 μm. Spherical particles are desired. However, it is conventionally impossible to obtain such spherical fine particles of about 1 μm by performing a solid-phase reaction of a powder mixture of titanium dioxide and barium carbonate at a high temperature. Spherical titanium dioxide fine particles have not been known until now.
【０００４】二酸化チタン微粒子の製造においては、従
来から、硫酸チタニル（オキシ硫酸チタン）溶液や四塩
化チタン溶液等を、種々の方法を用いて加熱処理し、加
水分解をすることが、広く行なわれている。しかし、一
般に、比較的希薄な溶液が用いられており、Ｔｉ濃度が
１mol/l 程度以上の高濃度の溶液を用いた例は極めて少
なく、特に反応終了時の酸の濃度が３Ｎ以上の強酸性溶
液となる条件を用いた例はない。例えば、特開昭６３−
８２１０号公報には、硫酸チタニル水溶液にアンモニア
を添加した白濁液を、解放容器を用いて、沸点付近の温
度で２時間程度処理することにより、１０μｍ以上の、
はるかに粗大な球形粒子を製造しようとする方法が明ら
かにされている。しかしながら、かかる方法では、アン
モニアを硫酸チタニル水溶液に添加し、溶液のｐＨを上
昇させるので、極めて短時間の析出反応とはなるが、反
応終了時の溶液の酸の濃度を高く保つことが出来ず、本
発明のような１μｍ程度の極めて均一な粒径の球形粒子
を形成させることは不可能である。[0004] In the production of titanium dioxide fine particles, conventionally, a titanyl sulfate (titanium oxysulfate) solution, a titanium tetrachloride solution, and the like have been widely subjected to heat treatment by various methods to be hydrolyzed. ing. However, in general, relatively dilute solutions are used, and very few examples use high-concentration solutions having a Ti concentration of about 1 mol / l or more. Particularly, a strongly acidic solution having an acid concentration of 3 N or more at the end of the reaction is used. There is no example using the conditions that result in a solution. For example, JP-A-63-
No. 8210 discloses that a white turbid liquid obtained by adding ammonia to an aqueous solution of titanyl sulfate is treated for about 2 hours at a temperature near the boiling point using an open container, whereby
Methods have been described which attempt to produce much coarser spherical particles. However, in such a method, since ammonia is added to the aqueous solution of titanyl sulfate and the pH of the solution is raised, the precipitation reaction becomes extremely short, but the acid concentration of the solution at the end of the reaction cannot be kept high. It is impossible to form spherical particles having a very uniform particle size of about 1 μm as in the present invention.
【０００５】また、球形で、単分散性の高い、狭い粒度
分布を有する二酸化チタン微粒子の製造については、従
来から、アルコキシド法と水溶液熟成法の二つの方法が
知られている。アルコキシド法については、例えばS.Ko
mernen,et al. ［J.Amer.Ceram.Soc. ］65,C-199(1982)
や特開昭６２−９１４１８号公報等において、種々報
告されているが、それらは、一般に、チタンのアルコキ
シドの０．２mol/l以下を含む希薄なアルコール溶液
に、水を加えて加水分解させるものであって、生成物は
サブミクロンの球形ではあるが、全て非晶質となり、し
かも希薄溶液で、処理量に対して生成量が少なく、また
原料のアルコキシドが高価なため、結果として非常に高
価なものとなり、用途は極めて特殊なものに限定されて
いるのである。[0005] For the production of titanium dioxide fine particles having a spherical shape, a high monodispersibility and a narrow particle size distribution, two methods, an alkoxide method and an aqueous solution aging method, are conventionally known. For the alkoxide method, for example, S. Ko
mernen, et al. [J. Amer. Ceram. Soc.] 65, C-199 (1982)
And various reports in JP-A-62-91418, etc., which are generally produced by adding water to a dilute alcohol solution containing 0.2 mol / l or less of titanium alkoxide and hydrolyzing the solution. Although the product is a submicron spherical shape, it is all amorphous, and it is a dilute solution. Therefore, the use is limited to a very special one.
【０００６】一方、前記水溶液熟成法にあっても、それ
は E.Matijevic,et al.［ J.Electrochem.Soc. ］120,8
93 (1973) に明記されているように、極めて希薄な水溶
液を長時間熟成することにより、球形微粒子を製造する
ものであるが、この方法で得られた微粒子は、アナター
ゼ型ではなく、ルチル型の二酸化チタンであり、また大
容量、長時間の処理でも、極めて僅かしか製造すること
が出来ないため、工業的に有利な生産を行なうことが出
来ない等の問題があった。[0006] On the other hand, even in the above-mentioned aqueous solution aging method, it is disclosed in E. Matjejevic, et al. [J. Electrochem. Soc.] 120,8.
As specified in 93 (1973), spherical fine particles are produced by aging a very dilute aqueous solution for a long time.The fine particles obtained by this method are not anatase type but rutile type. However, there is a problem that industrially advantageous production cannot be performed because very little titanium dioxide can be produced even with a large-capacity, long-time treatment.
【０００７】[0007]
【解決課題】ここにおいて、本発明は、かかる事情を背
景にしてなされたものであって、その解決課題とすると
ころは、均一、球形で、粒子径が１μｍ前後の、高品位
の二酸化チタン微粒子を、安価に且つ大量に製造する方
法を提供することにあり、また特に、炭酸バリウム等と
の反応性が高く、固相反応によって、１μｍ前後の任意
の大きさのチタン酸塩の球形微粒子を与えることの出来
る、極めて特徴的な二酸化チタン微粒子、即ち結晶子径
が３００Å以下のアナターゼ型超微結晶の凝集した球形
粒子から成り、球形粒子の長さ平均径が０．５〜２．５
μｍの範囲で、且つ重量平均粒子径と長さ平均粒子径の
比より求められる多分散指数が１．１以下の狭い粒径分
布を持ち、その比表面積が７０ｍ2 ／ｇ以上である、球
形多孔質アナターゼ型二酸化チタン微粒子を提供するこ
とにある。The present invention has been made in view of such circumstances, and it is an object of the present invention to provide high-quality titanium dioxide fine particles having a uniform, spherical shape and a particle diameter of about 1 μm. Inexpensively and in large quantities, and is particularly highly reactive with barium carbonate or the like, and is capable of forming spherical particles of titanate having an arbitrary size of about 1 μm by a solid-phase reaction. It can be provided with very distinctive titanium dioxide fine particles, that is, agglomerated spherical particles of anatase type ultrafine crystals having a crystallite diameter of 300 ° or less, wherein the average length of the spherical particles is 0.5 to 2.5.
a spherical particle having a narrow particle size distribution in a range of μm, a polydispersity index obtained from a ratio of a weight average particle diameter to a length average particle diameter of 1.1 or less, and a specific surface area of 70 m 2 / g or more. An object of the present invention is to provide porous anatase type titanium dioxide fine particles.
【０００８】[0008]
【解決手段】本発明者らは、かかる課題を解決すべく、
多数の実験研究を繰り返し、その結果、従来試みられた
ことのない組成領域、即ち加水分解反応終了時の酸の濃
度が３．０Ｎ〜８．０Ｎの強酸性領域となるように予め
出発状態で調整した、濃厚な硫酸チタニル若しくは硫酸
チタンの酸性水溶液を、一定条件下で充分に長時間加熱
熟成処理を続けた時にのみ、析出した超微粒子が全て球
形に凝集し、均一で多孔質のアナターゼ型二酸化チタン
微粒子が生成することを見い出し、本発明を完成するに
至ったのである。[MEANS FOR SOLVING PROBLEMS] The present inventors have set out to solve this problem.
A number of experimental studies were repeated, and as a result, the starting conditions were previously determined so that the composition range had never been attempted before, that is, the acid concentration at the end of the hydrolysis reaction was 3.0 N to 8.0 N. Only when the concentrated, concentrated aqueous solution of titanyl sulfate or titanium sulfate is heated and aged for a long period of time under certain conditions, the precipitated ultrafine particles are all aggregated in a spherical form, and are uniform and porous anatase type. They found that titanium dioxide fine particles were generated, and completed the present invention.
【０００９】本発明者らの研究の結果によれば、生成物
が均一球形の凝集微粒子となるためには、反応終了時に
おける硫酸の濃度が３．０Ｎ〜８．０Ｎの強酸性領域と
なるように、予め出発状態で調整することが必須の条件
であり、このように調整した硫酸チタニル若しくは硫酸
チタンの比較的濃厚な酸性水溶液を、密閉容器中におい
て、９５℃〜２００℃の温度で、沸騰させることなく熱
処理を加え、加水分解反応による酸化チタン水和物を析
出させるだけでなく、その後も更に加熱処理を続け、析
出物が全て球形凝集化するまで、充分に長時間、加熱熟
成処理を続ける必要のあることが分かった。そして、こ
のような組成範囲と極めて長時間の加熱処理によって生
成する沈降物は、従来全く製造されたことのない、前述
のような特性を有する、極めて特異な球形多孔質アナタ
ーゼ型二酸化チタン微粒子となることを見い出したので
ある。According to the results of the study by the present inventors, in order for the product to be uniform spherical aggregated fine particles, the concentration of sulfuric acid at the end of the reaction is in a strongly acidic region of 3.0 N to 8.0 N. As described above, it is an essential condition to adjust in a starting state in advance, and a relatively concentrated acidic aqueous solution of titanyl sulfate or titanium sulfate adjusted in this manner is placed in a closed container at a temperature of 95 ° C to 200 ° C. Heat treatment is applied without boiling, not only to precipitate titanium oxide hydrate by hydrolysis reaction, but also to further heat treatment after that, heat aging treatment for a long enough time until all precipitates are spherically aggregated I knew I needed to continue. And the sediment generated by such a composition range and extremely long-time heat treatment is a very unique spherical porous anatase type titanium dioxide fine particles having the characteristics described above, which has never been produced before. I found it to be.
【００１０】本発明による球形多孔質アナターゼ型二酸
化チタン微粒子は、見掛けの結晶子径が３００Å以下の
アナターゼ型超微粒子の凝集した球形粒子から成り、球
形粒子の長さ平均径が０．５〜２．５μｍの範囲で、且
つ重量平均径と長さ平均径の比より求められる多分散指
数が１．１以下の狭い粒径分布を持ち、その比表面積が
７０ｍ2 ／ｇ以上であることを特徴とし、その粒子径
は、任意に選択、調整することが可能である。なお、こ
こで言う結晶子径とは、粉末Ｘ線回折像のピークの半価
幅より、下記数１［但し、式中、λは特性Ｘ線の波長
（Å）、β1 は試料の半価幅（ラジアン）、β2 は補正
材料の半価幅（ラジアン）、θは回折角を表わす］にて
算出されるものである。また、多分散指数とは、重量平
均径と長さ平均径の比であって、走査型電子顕微鏡写真
中、２００個の粒子より求めた粒径分布より、下記数２
［但し、式中、Ｎは全粒子数、ｒi は粒径（μｍ）、ｎ
i はｒi の粒径を持つ粒子数を表わす］にて算出される
ものである。The spherical porous anatase-type titanium dioxide fine particles according to the present invention are composed of aggregated spherical particles of anatase-type ultrafine particles having an apparent crystallite diameter of 300 ° or less, and have an average length of 0.5 to 2 spherical particles. It has a narrow particle size distribution in the range of 0.5 μm and a polydispersity index obtained from the ratio of the weight average diameter to the length average diameter of 1.1 or less, and has a specific surface area of 70 m 2 / g or more. The particle diameter can be arbitrarily selected and adjusted. Here, the crystallite diameter to say, from the half width of the peak of the powder X-ray diffraction pattern, the number 1 [where below, wherein, lambda is the wavelength of the characteristic X-ray (Å), beta 1 is a half of the sample value width (radian), beta 2 is the half-width of the additional material (radian), theta is intended to be calculated in representing the diffraction angle. The polydispersity index is the ratio of the weight average diameter to the length average diameter, and is calculated from the particle size distribution obtained from 200 particles in a scanning electron micrograph according to the following equation.
[Wherein, N is the total number of particles, r i is the particle size (μm), n
i are those calculated by representing the number of particles having a particle size of r i].
【００１１】[0011]
【数１】 (Equation 1)
【００１２】[0012]
【数２】 (Equation 2)
【００１３】このような超微結晶、均一球形凝集及び多
孔質大比表面積の条件を備えた二酸化チタンの微粒子
は、従来全く認識されていなかったもので、チタニアを
含む各種のセラミックスの原料粉末として優れるのみな
らず、むしろ酸化チタンを含む各種のファインセラミッ
クスの原料粉末合成用の出発原料として特別の価値を持
つものである。即ち、例えばチタン酸バリウム等のペロ
ブスカイト型チタン酸塩の合成用の原料として使用する
と、混合する金属化合物との固相反応において、二酸化
チタン球状粒子がアナターゼ型超微結晶の凝集微粒子で
あり、しかも多孔質であるため、反応物質は容易に二酸
化チタンの粒子内部まで到達し、固相反応が均一に速や
かに進行するだけでなく、驚くべきことに、反応生成物
は元の二酸化チタン微粒子の球形状を保有し、結果とし
て、平均粒子径が１μｍ前後で且つ単分散性の高い、狭
い粒径分布を持つ各種チタン酸塩の球形微粒子の合成も
可能とするのである。このように、粉末混合物の固相反
応によって、１μｍ前後で且つ単分散性の高い、狭い粒
径分布を持つ各種チタン酸塩の球形微粒子を与えること
の出来る二酸化チタン微粒子は、従来全く知られていな
いものである。The fine particles of titanium dioxide provided with such conditions of ultra-fine crystals, uniform spherical aggregation and porous large specific surface area have never been recognized before and are used as raw material powders for various ceramics including titania. Not only is it excellent, but rather has special value as a starting material for synthesizing raw material powders for various fine ceramics containing titanium oxide. That is, for example, when used as a raw material for synthesizing perovskite titanate such as barium titanate, in a solid phase reaction with a mixed metal compound, titanium dioxide spherical particles are aggregated fine particles of anatase type ultrafine crystals, and Being porous, the reactants easily reach the interior of the titanium dioxide particles, and not only do the solid-state reaction proceed uniformly and quickly, but also, surprisingly, the reaction product is a sphere of the original titanium dioxide particles. As a result, it is possible to synthesize spherical fine particles of various titanates having an average particle diameter of about 1 μm, a high monodispersity, and a narrow particle size distribution. As described above, titanium dioxide fine particles capable of giving spherical fine particles of various titanates having a narrow particle size distribution of about 1 μm and having a high monodispersity by a solid phase reaction of a powder mixture have not been known at all. Not something.
【００１４】また、日焼け止め化粧品としても、見掛け
の結晶子径が３００Å以下の短波長域、紫外線域での分
光反射率の高いアナターゼ型二酸化チタン超微結晶が、
相対密度が５０％程度の、多孔質の、０．５〜２．５μ
ｍ程度の微小球であるため、アナターゼ型二酸化チタン
超微結晶の特徴を保有したまま、その混合量を多くして
も化粧品は流動性を保ち、結果として、被覆力の極めて
優れたアナターゼ型二酸化チタン超微結晶の分散性、均
一性の極めて高い高級化粧品を与えることが出来るので
ある。Also, as sunscreen cosmetics, anatase-type titanium dioxide ultrafine crystals having a high spectral reflectance in the short wavelength region and ultraviolet region having an apparent crystallite diameter of 300 ° or less,
Porous, 0.5-2.5μ with relative density of about 50%
Since the microspheres are about m in size, the cosmetics retain the fluidity even if the amount of the mixture is increased, while retaining the characteristics of anatase-type titanium dioxide ultra-fine crystals. As a result, the anatase-type titanium dioxide having extremely excellent covering power is obtained. It is possible to provide a high-grade cosmetic product having extremely high dispersibility and uniformity of titanium microcrystals.
【００１５】[0015]
【具体的構成】本発明にて得られる二酸化チタン球形粒
子は、結晶子径が３００Å以下のアナターゼ型超微結晶
の凝集して成るものであり、その粒子径は、熱処理温度
が高いほど、幾らか小さく、また硫酸チタニルの濃度に
依存するが、特に反応終了時での溶液中の酸の濃度に最
も大きく影響を受ける。即ち、反応終了時における溶液
中、酸の濃度が高いほど、凝集粒子径は大きくなる。し
かしながら、酸濃度が８Ｎ以上になると、凝集粒子径が
粗大となり過ぎ、且つ球形化が不完全となる。また、酸
濃度が３．０Ｎ以下では、凝集粒子径が小さくなり過
ぎ、且つその球形化が不充分となり、また凝集粒子同士
の２次凝集も起こり始める。従って、本発明において
は、反応終了時における酸の濃度が３．０Ｎ〜８．０Ｎ
の範囲となるように、予め硫酸等を添加し、目的の凝集
粒子径に応じて出発溶液の組成が適宜選定されるのであ
る。DETAILED DESCRIPTION OF THE INVENTION The titanium dioxide spherical particles obtained by the present invention are formed by agglomeration of anatase type ultrafine crystals having a crystallite diameter of 300 ° or less. Although it depends on the concentration of titanyl sulfate, it is most affected by the concentration of acid in the solution at the end of the reaction. That is, the higher the concentration of the acid in the solution at the end of the reaction, the larger the aggregated particle diameter. However, when the acid concentration is 8N or more, the aggregated particle diameter becomes too coarse and the spheroidization becomes incomplete. If the acid concentration is 3.0 N or less, the diameter of the aggregated particles becomes too small, the spheroidization becomes insufficient, and secondary aggregation of the aggregated particles starts to occur. Therefore, in the present invention, the concentration of the acid at the end of the reaction is 3.0N to 8.0N.
, Sulfuric acid or the like is added in advance so as to fall within the range, and the composition of the starting solution is appropriately selected according to the target aggregated particle diameter.
【００１６】なお、本発明者らの研究の結果から、反応
終了時の酸の濃度が高いほど、凝集粒子径が増大するこ
とが分かったが、硫酸に代えて塩酸を使用しても、凝集
粒子径増大効果は認められるものの、粒子の球形化が著
しく不完全となる他、安定なルチル型二酸化チタンが生
成し始め、比表面積の高いアナターゼ型のみの二酸化チ
タン凝集微粒子を得ることは出来なくなることが分かっ
た。従って、本発明における酸の濃度は、主として硫酸
から与えられるものでなければならないのである。From the results of the study by the present inventors, it was found that the higher the concentration of the acid at the end of the reaction, the larger the agglomerated particle diameter was. Although the effect of increasing the particle diameter is recognized, the spherical spheroidization of the particles becomes extremely incomplete, and stable rutile-type titanium dioxide starts to be generated, and it becomes impossible to obtain titanium dioxide aggregated fine particles of only anatase type having a high specific surface area. I understood that. Therefore, the concentration of the acid in the present invention must be given mainly from sulfuric acid.
【００１７】また、Ｔｉ濃度は、もし充分な硫酸が加え
られるなら、１．０mol/l 以下の溶液でも球形凝集微粒
子を与えるが、その場合には、析出物の量が少なく、同
一の処理から得られるアナターゼ型二酸化チタン凝集粒
子の数が少なくなり、経済的に、実用的でないものとな
る。また一方、Ｔｉ濃度は高いほど、生成粒子が大量に
得られて経済的であるが、Ｔｉ濃度が３．０mol/l 以上
では、球形凝集化が不充分となり、塊状粒子が混在する
ようになるところから、Ｔｉ濃度としては、通常、１．
０mol/l 〜３．０mol/l の範囲において選択されること
となる。If the concentration of Ti is sufficient, if a sufficient amount of sulfuric acid is added, even a solution of 1.0 mol / l or less gives spherical aggregated fine particles. The number of anatase-type titanium dioxide aggregated particles obtained is reduced, which makes it economically impractical. On the other hand, the higher the Ti concentration is, the more economically it is possible to obtain a large amount of produced particles, but if the Ti concentration is 3.0 mol / l or more, spherical agglomeration becomes insufficient, and massive particles are mixed. However, the Ti concentration is usually 1.
It will be selected in the range of 0 mol / l to 3.0 mol / l.
【００１８】そして、このような硫酸酸性水溶液が、所
定の密閉容器内に収容されて、９５℃〜２００℃の温度
において、沸騰することなく加熱処理されるが、この加
熱処理時の温度は、９５℃より低いと、孤立分散した微
粒子が得られず、また２００℃より高い温度では、水熱
処理設備の費用が過大となって実際的でないだけでな
く、結晶子径が増大し、反応活性その他の特性を劣化さ
せることから、本発明にあっては、９５℃〜２００℃の
温度範囲において適宜設定される。[0018] Such a sulfuric acid aqueous solution is accommodated in a predetermined closed container and is heated without boiling at a temperature of 95 ° C to 200 ° C. If the temperature is lower than 95 ° C., isolated and dispersed fine particles cannot be obtained, and if the temperature is higher than 200 ° C., the cost of the hydrothermal treatment equipment becomes excessive, which is not only practical but also increases the crystallite diameter, and increases the reaction activity and other factors. Therefore, in the present invention, the temperature is appropriately set in a temperature range of 95 ° C. to 200 ° C.
【００１９】また、本発明において、加熱熟成の処理時
間は重要且つ不可欠の要素で、発明の目的を達成するだ
けでなく、析出物がアナターゼ型二酸化チタンに結晶化
すると共に、均一球形に凝集することによって、静置す
れば容易に自然沈降を起こすようになるまで充分に長時
間、加熱熟成処理を続けることが必要である。この異常
に長い時間の処理によって、初めて目的とする孤立した
均一な球形多孔質アナターゼ型二酸化チタンの凝集微粒
子を得ることが可能となることを、本発明者が初めて発
見したものである。この処理時間は、温度が高いほど短
縮することが出来るが、例えば１００℃の温度では、１
μｍ程度の球形微粒子を得るために、一般に、１０日間
程の加熱熟成処理が必要となる。因みに、その処理時間
が充分でない場合には、球形が不完全となるか、或いは
球形化しない凝集粒子となるのである。In the present invention, the heat aging treatment time is an important and indispensable factor, and not only achieves the object of the invention, but also precipitates crystallize into anatase-type titanium dioxide and coagulate into a uniform sphere. In this case, it is necessary to continue the heat aging treatment for a sufficiently long time until the natural sedimentation easily occurs when left still. The present inventors have found for the first time that it is possible to obtain, for the first time, the desired isolated uniform spherical porous anatase-type titanium dioxide aggregated fine particles by this treatment for an extremely long time. This processing time can be shortened as the temperature is higher.
In order to obtain spherical fine particles of about μm, heat aging treatment is generally required for about 10 days. By the way, if the treatment time is not sufficient, the spheres will be incomplete or will be aggregated particles that do not become spheroidal.
【００２０】[0020]
【実施例】以下に、本発明の幾つかの実施例を示し、本
発明を更に具体的に明らかにすることとするが、本発明
が、そのような実施例の記載によって、何等の制約を受
けるものでないことは言うまでもないところである。EXAMPLES Hereinafter, some examples of the present invention will be described to clarify the present invention more specifically. However, the present invention imposes some restrictions by the description of such examples. Needless to say, it is not what we receive.
【００２１】実施例１ 硫酸チタニル粉末（ＴｉＯＳＯ4 ・２Ｈ2 Ｏ、他に遊離
のＨ2 ＳＯ4 及びＨ2 Ｏを含む）を蒸留水に溶解し、溶
液中のＴｉ濃度及びＳＯ4 2-イオン濃度を化学分析によ
り定量し、追加硫酸量及び蒸留水の量を調整して、表１
に示すような、Ｔｉ濃度１．０mol/l 〜３．０mol/l 、
並びに各反応終了時における硫酸の濃度２．８Ｎ〜８．
４Ｎの範囲の、各種の透明な溶液を調製した。次いで、
それらの溶液をそれぞれテフロン製容器中に一定量分取
し、密閉した後、１１０℃（一部は９８℃）の恒温槽内
に静置し、１日、３日、５日、１０日、及び１５日間の
加熱処理を行なった。この熱処理により析出した反応生
成物は、先ず遠心分離器にかけ、回転数１５００rpm の
場合の沈降物（沈澱粒子部とする）と残液部分とに分
け、残液部分中に残る沈降しなかった微粒子部分は塩酸
を添加することにより、別に凝集沈降させた（浮遊粒子
部とする）。Example 1 A titanyl sulfate powder (TiOSO 4 .2H 2 O, including free H 2 SO 4 and H 2 O) was dissolved in distilled water, and the Ti concentration and SO 4 2− ion in the solution were dissolved. The concentration was determined by chemical analysis, and the amount of additional sulfuric acid and the amount of distilled water were adjusted.
As shown in the following, the Ti concentration is 1.0 mol / l to 3.0 mol / l,
In addition, the concentration of sulfuric acid at the end of each reaction is 2.8N-8.
Various clear solutions in the range of 4N were prepared. Then
A predetermined amount of each of these solutions was taken in a Teflon container, and after sealing, the container was allowed to stand still in a thermostat at 110 ° C. (partly at 98 ° C.), for 1, 3, 5, 10 days. And a heat treatment for 15 days. The reaction product precipitated by this heat treatment is first subjected to a centrifugal separator, and separated into a sediment at 1500 rpm (precipitated particle portion) and a residual liquid portion. The portion was separately coagulated and settled by adding hydrochloric acid (to be a suspended particle portion).
【００２２】各処理時間後に得られた沈澱粒子部及び浮
遊粒子部の量は、全て１０００℃で２時間仮焼し、二酸
化チタンとして秤量して求めた。この結果は、図１に示
す通りである。ここで、沈澱粒子部は、本発明に係る球
形多孔質アナターゼ型二酸化チタン微粒子の前段状態に
相当し、やや不完全な球形の凝集粒子から成る部分であ
るが、浮遊粒子部は、遠心分離器によって沈降しない超
微粒子部分で、仮焼前６０℃乾燥物のＸ線観察によれ
ば、アナターゼ型二酸化チタンであり、仮焼後はルチル
型二酸化チタンとなる。従って各処理時間後の沈澱粒子
部と浮遊粒子部の合計が、加水分解反応率に相当する。
図から求めた各試料の加水分解反応の終了時間及び球形
凝集化完了時間を、球形凝集化完了後の凝集粒子径と共
に表１に示した。なお、ここで言う変動係数とは、標準
偏差を平均径で除したものであって、数値が小さいほ
ど、粒径が均一であることを示している。The amounts of precipitated particles and suspended particles obtained after each treatment time were all calcined at 1000 ° C. for 2 hours and weighed as titanium dioxide. The result is as shown in FIG. Here, the precipitated particle portion corresponds to the former stage of the spherical porous anatase-type titanium dioxide fine particles according to the present invention, and is a portion composed of slightly imperfect spherical aggregated particles. According to X-ray observation of the dried product at 60 ° C. before calcining, the ultrafine particle portion that does not settle out is anatase type titanium dioxide, and becomes rutile type titanium dioxide after calcining. Therefore, the sum of the precipitated particle portion and the suspended particle portion after each treatment time corresponds to the hydrolysis reaction rate.
The end time of the hydrolysis reaction and the completion time of the spherical aggregation of each sample determined from the figure are shown in Table 1 together with the diameter of the aggregated particles after the completion of the spherical aggregation. Here, the variation coefficient is a value obtained by dividing the standard deviation by the average diameter, and the smaller the numerical value, the more uniform the particle diameter.
【００２３】[0023]
【表１】 [Table 1]
【００２４】図１及び表１から明らかなように、１１０
℃の熱処理では、加水分解反応は濃度によって数時間か
ら３日間で略終了するが、球形凝集粒子化が完了するに
は更に長時間が必要であり、Ｔｉ濃度よりも反応終了時
における硫酸の濃度の影響が大きいことが分かる。この
硫酸濃度が４．２Ｎ（試料Ｄ）、５．６Ｎ（試料Ｅ）、
及び７．０Ｎ（試料Ｇ）の溶液では、それぞれ約３日
間、約１０日間の熱処理熟成が必要となる。そして、加
水分解反応が終了しただけでは、その生成物は、超微粒
子と球形化不完全な凝集粒子の混合物であり、これ自体
均一な微粒子でないでけでなく、これから超微粒子だけ
を除去することも困難で、これを乾燥すれば、球形粒子
は２次凝集を起こし易く、均一な、孤立した球形の凝集
粒子を得ることは、通常困難である。As is clear from FIG. 1 and Table 1, 110
In the heat treatment at ° C., the hydrolysis reaction is almost completed within several hours to 3 days depending on the concentration. However, it takes a longer time to complete the formation of spherical aggregated particles, and the sulfuric acid concentration at the end of the reaction is lower than the Ti concentration. It can be seen that the influence of is large. This sulfuric acid concentration is 4.2N (sample D), 5.6N (sample E),
And 7.0N (sample G) solutions require heat treatment aging for about 3 days and about 10 days, respectively. When the hydrolysis reaction is completed, the product is a mixture of ultrafine particles and incompletely spheroidized agglomerated particles. When this is dried, the spherical particles are liable to undergo secondary agglomeration, and it is usually difficult to obtain uniform, isolated spherical agglomerated particles.
【００２５】充分長時間の熟成により、球形凝集粒子化
が完了した段階では、析出粒子は全て球形化して沈降
し、透明な上澄み液が形成される。この最終沈降物は、
走査型電子顕微鏡（ＳＥＭ）観察によれば、試料Ａは、
粒径がやや小さく、球形化が幾らか不完全であり、試料
Ｈは、１５日間に亘る加熱処理によってもまだ球形化が
完了せず、生成物は不完全凝集球及び未凝集の析出物
で、乾燥後は塊状物となるが、本発明の範囲に入る他の
試料では、全て大きさの均一な球形の微粒子が、極めて
よく孤立、分散していることが認められた。例として、
試料Ｅの走査型電子顕微鏡（ＳＥＭ）写真を図２、試料
Ｇの走査型電子顕微鏡（ＳＥＭ）写真を図３にそれぞれ
示す。何れもきれいな球形粒子となっていることが認め
られる。At the stage when spherical coagulation and particle formation are completed by aging for a sufficiently long time, all of the precipitated particles are formed into spherical particles and settle, forming a clear supernatant liquid. This final sediment is
According to scanning electron microscope (SEM) observation, sample A
The particle size was rather small, spheronization was somewhat incomplete, and sample H was not yet spheroidized by heat treatment for 15 days, and the product was incompletely agglomerated spheres and unagglomerated precipitates. After drying, it forms a lump, but in the other samples falling within the scope of the present invention, it was recognized that spherical fine particles having a uniform size in all cases were isolated and dispersed very well. As an example,
FIG. 2 shows a scanning electron microscope (SEM) photograph of Sample E, and FIG. 3 shows a scanning electron microscope (SEM) photograph of Sample G. It can be seen that all of the particles are fine spherical particles.
【００２６】生成物の平均粒子径は、同一処理温度でＴ
ｉ濃度の同じ試料（試料ＡとＢ，及び試料ＥとＦ）を比
較すると、反応終了時の酸の濃度によって大きく変化
し、酸の濃度が高い程大きくなり、また、この酸の濃度
がほぼ同じ場合（試料ＢとＤ，及び試料ＦとＧ）では、
Ｔｉの濃度が変わっても平均粒子径には大きな差が生じ
ないことが分かる。これらのＳＥＭ写真から求めた各球
形粒子の粒径分布を求め、重量平均径と長さ平均径の比
より求められる多分散指数を計算したところ、表に示す
ように、全て１．１以下であった。また、これらの球形
の微粒子は、Ｘ線回折の測定から、表に示すように、全
て結晶子径３００Å以下のアナターゼ型の超微結晶から
成るものであり、また、何れも２００℃乾燥粉末の比表
面積が７０ｍ2 ／ｇ以上であることが分かった。The average particle size of the product is T at the same processing temperature.
Comparing the samples having the same i concentration (samples A and B and samples E and F), the concentration greatly changes depending on the concentration of the acid at the end of the reaction, and increases as the concentration of the acid increases. In the same case (samples B and D and samples F and G),
It can be seen that even if the concentration of Ti changes, no large difference occurs in the average particle diameter. The particle size distribution of each spherical particle determined from these SEM photographs was determined, and the polydispersity index determined from the ratio of the weight average diameter to the length average diameter was calculated. there were. As shown in the table, these spherical fine particles are all composed of ultrafine crystals of anatase type having a crystallite diameter of 300 ° or less, as shown in the table. It was found that the specific surface area was 70 m 2 / g or more.
【００２７】以上のうち、代表的な試料Ｅについて、４
００℃及び７００℃にそれぞれ２時間、空気中で仮焼し
た粉末に対し、比表面積を測定したところ、それぞれ９
１ｍ2 ／ｇ及び２８ｍ2 ／ｇであり、４００℃までは極
めて高い比表面積を保っていた。更に、試料Ｅの６０℃
乾燥物（アナターゼ型）、９００℃、２時間の仮焼粉末
（アナターゼ型）及び１０００℃、２時間の仮焼粉末
（ルチル型）、並びに炭酸バリウムとの等モル混合物
を、９００℃２４時間仮焼して生成したチタン酸バリウ
ムの粉末について、ＳＥＭ観察をしたところ、仮焼後も
全ての試料粉末粒子は球形であり、何れも粒径がよく揃
っており、粒径分布の狭い極めて均一な状態を保ってい
た。これらの粉末粒子に対し、ＳＥＭ写真から計測した
粒径分布を図４に示した。Of the above, for the representative sample E, 4
The specific surface area of the powder calcined in air at 00 ° C. and 700 ° C. for 2 hours was 9
They were 1 m 2 / g and 28 m 2 / g, and maintained an extremely high specific surface area up to 400 ° C. Further, the temperature of the sample E was 60 ° C.
A dried product (anatase type), a calcined powder (anatase type) at 900 ° C. for 2 hours, a calcined powder (rutile type) at 1000 ° C. for 2 hours, and an equimolar mixture with barium carbonate were temporarily mixed at 900 ° C. for 24 hours. When barium titanate powder produced by sintering was subjected to SEM observation, all the sample powder particles were spherical even after calcination, all of which had a uniform particle size, and a very uniform particle size distribution was narrow. I was keeping my condition. FIG. 4 shows the particle size distribution of these powder particles measured from an SEM photograph.
【００２８】本発明の球形多孔質アナターゼ型二酸化チ
タン微粒子単独では、これを仮焼することよって、個々
の球形凝集粒子は、球形を保ちながら収縮して、粒子径
を減少させる。この粒子径の減少から、試料Ｅの球形粒
子の相対密度は約５０％程度と計算される。本発明の球
形粒子が、アナターゼ型超微結晶から成ることの他に、
この相対密度が低く、比表面積の高いことが、他の金属
化合物との反応性を高め、しかもチタン酸塩等の反応生
成物の形状が球状に保たれることの原因と考えられる。
図４から分かるように、固相反応の結果生成するチタン
酸バリウムの粒子径並びに粒径分布は、原料二酸化チタ
ンである試料Ｅの粒子径並びに粒径分布にほぼ類似した
ものとなる。このようなことは、従来の二酸化チタン微
粒子を原料として用いた場合には、全く得ることの出来
ない結果である。The spherical porous anatase-type titanium dioxide fine particles of the present invention alone are calcined, so that the individual spherical aggregated particles shrink while maintaining the spherical shape to reduce the particle diameter. From the decrease in the particle diameter, the relative density of the spherical particles of the sample E is calculated to be about 50%. In addition to the spherical particles of the present invention being composed of anatase-type microcrystals,
It is considered that the low relative density and high specific surface area increase the reactivity with other metal compounds and keep the shape of the reaction product such as titanate in a spherical shape.
As can be seen from FIG. 4, the particle size and particle size distribution of barium titanate produced as a result of the solid phase reaction are substantially similar to the particle size and particle size distribution of sample E which is the raw material titanium dioxide. Such a result cannot be obtained at all when conventional titanium dioxide fine particles are used as a raw material.
【００２９】実施例２ 実施例１と同様にして、硫酸チタニル粉末を蒸留水に溶
解し、溶液中のＴｉ濃度及びＳＯ4 2-イオン濃度を、追
加硫酸量及び蒸留水の量を調整して、Ｔｉ濃度並びに反
応終了時における硫酸の濃度を種々変えた透明な溶液を
調整した。次いで、これらの各溶液を、それぞれステン
レス製の耐圧容器内に収容されたテフロン容器（容量：
２５cm3 ）の中に入れ、密封した後、１５０℃及び２０
０℃の恒温槽内にて２日間、それぞれ加熱保持した。こ
の結果、全ての試料に白色の析出物が認められ、析出物
は全て沈降し、透明な上澄み液が認められた。その後、
これらの試料に水を添加し、撹拌した後数回に亘って、
遠心分離器による析出物の分離、洗浄を実施し、乾燥し
た。得られた乾燥物の粒子形状は、ＳＥＭにより観察し
た結果、全て球形の凝集粒子であり、その長さ平均径
は、表２に示すようであった。Example 2 In the same manner as in Example 1, titanyl sulfate powder was dissolved in distilled water, and the Ti concentration and SO 4 2- ion concentration in the solution were adjusted by adjusting the amount of additional sulfuric acid and the amount of distilled water. , Ti concentration and the concentration of sulfuric acid at the end of the reaction were variously changed to prepare transparent solutions. Next, each of these solutions was placed in a Teflon container (capacity:
25cm 3 ), sealed and then placed at 150 ° C and 20 ° C.
Each was heated and held in a thermostat at 0 ° C. for 2 days. As a result, a white precipitate was observed in all the samples, all the precipitates settled, and a clear supernatant liquid was observed. afterwards,
After adding water to these samples and stirring, several times,
The precipitate was separated by a centrifugal separator, washed, and dried. As a result of observation by SEM, the particle shape of the obtained dried product was all spherical aggregated particles, and the average length of the particles was as shown in Table 2.
【００３０】表から、１５０℃の処理温度でも、加水分
解反応完了時の酸の濃度が高いほど、一般に平均粒子径
は大きくなり、また加水分解反応完了時の酸の濃度が同
じ場合（試料ＪとＭ，及び試料ＫとＱ）では、Ｔｉ濃度
が変わっても大きな差がないことは、表１の１１０℃の
場合と同様である。また、表１及び表２において、ほぼ
同じ酸の濃度で、熱処理温度を変えた場合（試料Ｃと
Ｄ，及び試料Ｅ，ＮとＯ）を比較すると、処理温度が高
くなると、結晶子径は増大し、平均粒子径は幾らか小さ
くなることが認められる。As can be seen from the table, even at a processing temperature of 150 ° C., the higher the acid concentration at the time of completion of the hydrolysis reaction, the larger the average particle diameter generally becomes. And M, and samples K and Q), there is no significant difference even when the Ti concentration changes, as in the case of 110 ° C. in Table 1. Also, in Tables 1 and 2, when the heat treatment temperature is changed (samples C and D, and samples E, N and O) at substantially the same acid concentration, the crystallite diameter becomes larger as the treatment temperature increases. It is observed that the average particle size increases somewhat.
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【発明の効果】以上の説明から明らかなように、本発明
に従えば、見掛けの結晶子径が３００Å以下のアナター
ゼ型超微結晶の凝集球形粒子から成り、粒子の長さ平均
径が０．５〜２．５μｍの範囲であり、且つ重量平均径
と長さ平均径の比が１．１以下の狭い粒径分布を持ち、
しかも比表面積が７０ｍ2 ／ｇ以上であることを特徴と
する球形多孔質アナターゼ型二酸化チタン微粒子、例え
ば微粉末若しくは微粒子分散液を、簡単な工程で、しか
も原料が安価であるところから、大量に且つ安価に生産
することが可能となり、実用的で、経済的効果が極めて
高いものとなるのであるが、更に本発明によって得られ
る球形多孔質アナターゼ型二酸化チタン微粒子、例えば
微粉末若しくは微粒子分散液は、粒子の均一性、易混合
性、易分散性、易反応性、紫外線高反射性等が良好であ
るところから、誘電体材料、セラミックス原料、顔料、
紫外線遮蔽コーティング剤、化粧品用剤等の、各種の用
途に好適に用いられて、それらの高性能化を達成するも
のである。中でも、ファインセラミック原料の出発原料
としては、既に述べたように、特に強誘電体セラミック
スのペロブスカイト型チタン酸塩の出発原料として、極
めて特徴的な高い価値を持つものである。As is apparent from the above description, according to the present invention, an anatase type ultrafine crystal aggregated spherical particle having an apparent crystallite diameter of 300 ° or less is formed, and the average length of the particle is 0.1 mm. Having a narrow particle size distribution of 5 to 2.5 μm, and a ratio of weight average diameter to length average diameter of 1.1 or less;
In addition, spherical porous anatase-type titanium dioxide fine particles having a specific surface area of 70 m 2 / g or more, such as fine powder or fine particle dispersion, can be produced in a large amount in a simple process and because the raw material is inexpensive. And it is possible to produce at low cost, practical and economical effect is extremely high, furthermore, the spherical porous anatase type titanium dioxide fine particles obtained by the present invention, for example, fine powder or fine particle dispersion is , From the fact that the uniformity of the particles, the ease of mixing, the ease of dispersing, the ease of reacting, the high reflectivity of ultraviolet rays, etc. are good, the dielectric materials, ceramic raw materials, pigments,
It is suitably used for various uses such as an ultraviolet shielding coating agent and a cosmetic agent, and achieves high performance thereof. Among them, as described above, the starting material of the fine ceramic material has a very characteristic high value, particularly as the starting material of the perovskite titanate of ferroelectric ceramics.
【図１】加熱処理時間と加水分解生成物の生成率並びに
球形凝集化の進行の程度の測定結果である。FIG. 1 shows the results of measurement of the heat treatment time, the production rate of hydrolysis products, and the degree of progress of spherical agglomeration.
【図２】代表的な試料Ｅの電子顕微鏡（ＳＥＭ）写真で
ある。FIG. 2 is an electron microscope (SEM) photograph of a representative sample E.
【図３】代表的な試料Ｇの電子顕微鏡（ＳＥＭ）写真で
ある。FIG. 3 is an electron microscope (SEM) photograph of a representative sample G.
【図４】試料Ｅ及びその仮焼生成物、並びに炭酸バリウ
ムとの反応生成物の粒子径分布図である。FIG. 4 is a particle size distribution diagram of a sample E, a calcined product thereof, and a reaction product with barium carbonate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 加藤 悦朗 愛知県愛知郡長久手町大字熊張字早稲田 956 (56)参考文献 特開 昭63−8219（ＪＰ，Ａ) 特開 昭63−134517（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Etsuro Kato 956, Waseda, Kumabari, Nagakute-cho, Aichi-gun, Aichi (56) References JP-A-63-8219 (JP, A) JP-A-63-134517 (JP, A)
Claims (2)
算される結晶子径が３００Å以下のアナターゼ型超微結
晶の凝集した球形粒子から成り、該球形粒子の長さ平均
径が０．５〜２．５μｍの範囲で、且つ重量平均径と長
さ平均径の比より求められる多分散指数が１．１以下の
狭い粒径分布を持ち、その比表面積が７０ｍ2 ／ｇ以上
であることを特徴とする球形多孔質アナターゼ型二酸化
チタン微粒子。An anatase type ultrafine crystal having a crystallite diameter of 300 ° or less, which is calculated from the half width of a peak of a powder X-ray diffraction image, is composed of aggregated spherical particles, and the average length of the spherical particles is 0%. It has a narrow particle size distribution in the range of 0.5 to 2.5 μm and a polydispersity index determined from the ratio of the weight average diameter to the length average diameter of 1.1 or less, and has a specific surface area of 70 m 2 / g or more. Spherical porous anatase type titanium dioxide fine particles.
しめ、二酸化チタンを析出させる方法において、反応終
了時における酸の濃度が３．０Ｎ〜８．０Ｎの強酸性領
域となるように、主として硫酸からなる酸にて予め出発
状態で調整した、濃厚な硫酸チタニル若しくは硫酸チタ
ンの酸性水溶液を用い、加熱処理による反応生成物の殆
どが球形凝集化を完了するまで、９５℃〜２００℃の温
度で加熱熟成処理を続けることを特徴とする球形多孔質
アナターゼ型二酸化チタン微粒子の製造方法。2. A method for heating and hydrolyzing a titanyl sulfate solution to precipitate titanium dioxide, wherein sulfuric acid is mainly used so that the acid concentration at the end of the reaction is in a strongly acidic region of 3.0N to 8.0N. Using a concentrated acidic aqueous solution of titanyl sulfate or titanium sulfate prepared in advance in the starting state with an acid consisting of, at a temperature of 95 ° C. to 200 ° C. until most of the reaction products by the heat treatment complete spherical agglomeration. A method for producing spherical porous anatase-type titanium dioxide fine particles, characterized by continuing heat aging treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16877791A JP2709206B2 (en) | 1991-06-13 | 1991-06-13 | Spherical porous anatase-type titanium dioxide fine particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16877791A JP2709206B2 (en) | 1991-06-13 | 1991-06-13 | Spherical porous anatase-type titanium dioxide fine particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04367512A JPH04367512A (en) | 1992-12-18 |
| JP2709206B2 true JP2709206B2 (en) | 1998-02-04 |
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ID=15874274
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|---|---|---|---|
| JP16877791A Expired - Fee Related JP2709206B2 (en) | 1991-06-13 | 1991-06-13 | Spherical porous anatase-type titanium dioxide fine particles and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5700451A (en) * | 1995-05-24 | 1997-12-23 | The Procter & Gamble Company | Sunscreen composition |
| JP4153066B2 (en) * | 1997-12-01 | 2008-09-17 | 石原産業株式会社 | Method for producing strongly cohesive titanium oxide |
| JP3959213B2 (en) * | 1999-06-30 | 2007-08-15 | 住友化学株式会社 | Titanium oxide, photocatalyst body using the same, and photocatalyst body coating agent |
| JP2008230964A (en) * | 2008-04-03 | 2008-10-02 | Ishihara Sangyo Kaisha Ltd | Strong cohesive titanium oxide |
| JP5743417B2 (en) * | 2010-03-31 | 2015-07-01 | 大阪瓦斯株式会社 | Titanium oxide nanoparticles aggregate |
-
1991
- 1991-06-13 JP JP16877791A patent/JP2709206B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04367512A (en) | 1992-12-18 |
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