JPH08169716A - Granular titanium dioxide and its producion - Google Patents
Granular titanium dioxide and its producionInfo
- Publication number
- JPH08169716A JPH08169716A JP33347894A JP33347894A JPH08169716A JP H08169716 A JPH08169716 A JP H08169716A JP 33347894 A JP33347894 A JP 33347894A JP 33347894 A JP33347894 A JP 33347894A JP H08169716 A JPH08169716 A JP H08169716A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- granular titanium
- titanyl sulfate
- tio
- granular
- 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.)
- Granted
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属化合物およびセラ
ミックスのＴｉ原料として有用な付着性の少ない、優れ
た流動性を有する顆粒状二酸化チタン及びその製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a granular titanium dioxide which is useful as a Ti raw material for metal compounds and ceramics and has a low fluidity and excellent fluidity, and a method for producing the same.
【０００２】[0002]
【従来の技術】市販されている二酸化チタン粉末の大半
は、平均粒径が０．２〜０．５μｍ程度であり、一次粒
子径は大きくても１μｍ程度である。このような二酸化
チタン粉末は、顔料として優れた基本性能を有す反面、
粒子サイズが小さい故に付着力が強く、流動性が低いこ
とから作業上、取り扱い難いことがしばしばあった。工
業的には、二酸化チタン粉末の添加工程が自動制御され
ている場合が多く、流動性を重要な特性として挙げる分
野も少なくない。このような流動性が要求される用途に
対しては従来、サブミクロンオーダーの二酸化チタン粉
末を機械的に造粒させる方法や、二酸化チタン粉末をさ
らに高エネルギーをかけ燒結させて粗大化する方法が試
みられているが、いずれもコスト高となることや不純物
の混入等の問題点があった。１〜２０μｍの二酸化チタ
ン凝集粒子の製造方法として、顔料用のアナターゼ型ま
たはルチル型二酸化チタン一次粒子を硫酸チタニル希薄
水溶液中に懸濁し、該二酸化チタン一次粒子の存在下硫
酸チタニルの加水分解を行う方法（特開昭６１−１７４
２２）が開示されているが機械的造粒以外の方法で、２
０μｍを越える顆粒状二酸化チタンは従来にはなかっ
た。2. Description of the Related Art Most commercially available titanium dioxide powders have an average particle size of about 0.2 to 0.5 μm and a primary particle size of about 1 μm at the maximum. While such titanium dioxide powder has excellent basic performance as a pigment,
Since the particle size is small, the adhesive force is strong and the fluidity is low, so that it was often difficult to handle in work. Industrially, the addition process of titanium dioxide powder is often controlled automatically, and there are many fields in which fluidity is an important characteristic. For applications requiring such fluidity, conventionally, there is a method of mechanically granulating submicron-order titanium dioxide powder or a method of coarsening titanium dioxide powder by further applying high energy. Attempts have been made, but there were problems such as high cost and mixing of impurities. As a method for producing titanium dioxide agglomerated particles having a particle size of 1 to 20 μm, anatase type or rutile type titanium dioxide primary particles for pigments are suspended in a dilute aqueous solution of titanyl sulfate, and titanyl sulfate is hydrolyzed in the presence of the titanium dioxide primary particles. Method (JP-A-61-174
22) is disclosed, but by a method other than mechanical granulation, 2
There has never been a granular titanium dioxide having a particle size exceeding 0 μm.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、機械的顆粒
化工程がないため装置的汚染がなくかつ低コストであ
り、またより優れた流動性のものとするため、顆粒状二
酸化チタンの平均粒径を従来品にはなかった２５μｍ以
上とすることを課題とした。DISCLOSURE OF THE INVENTION The present invention has no mechanical granulation step, is free of equipment contamination, is low in cost, and has an excellent fluidity. The object was to set the particle size to 25 μm or more, which was not found in conventional products.
【０００４】[0004]
【課題を解決するための手段】本発明は、平均粒径とし
て２５〜１００μｍの流動性に優れた顆粒状二酸化チタ
ン粉末を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention is intended to provide a granular titanium dioxide powder having an average particle diameter of 25 to 100 μm and excellent in fluidity.
【０００５】本発明の顆粒状二酸化チタンは、ルチル
型、アナターゼ型ともに樹脂等の充填剤やセラミックス
原料として有用である。またアナターゼ型においては、
表面活性が高く、しかも多孔質体であるので、触媒担体
としても使用出来る。The granular titanium dioxide of the present invention is useful as a filler such as a resin or a raw material for ceramics in both rutile type and anatase type. In the anatase type,
Since it has a high surface activity and is a porous material, it can be used as a catalyst carrier.
【０００６】本発明の顆粒状二酸化チタンは、硫酸チタ
ニル溶液中のＴｉＯ2濃度、硫酸濃度及びＨ2ＳＯ4／Ｔ
ｉＯ2重量比を調整することにより水和硫酸チタニル結
晶を得た後、これを７００〜１２００℃で焼成すること
によって製造することが出来る。顆粒状二酸化チタンと
しての粒子径は、水和硫酸チタニル結晶の大きさ並びに
焼成温度で決定され、すなわちこれらによって平均粒径
を２５〜１００μｍの幅の間に調整することが出来る。
結晶構造は焼成温度によりアナターゼ型またはルチル型
とすることが出来る。The granular titanium dioxide of the present invention is used in the titanyl sulfate solution in the TiO 2 concentration, sulfuric acid concentration and H 2 SO 4 / T.
It can be manufactured by obtaining hydrated titanyl sulfate crystals by adjusting the iO 2 weight ratio and then calcining this at 700 to 1200 ° C. The particle size as granular titanium dioxide is determined by the size of the hydrated titanyl sulfate crystals and the firing temperature, that is, the average particle size can be adjusted within the range of 25 to 100 μm.
The crystal structure can be anatase type or rutile type depending on the firing temperature.
【０００７】このようにして得られる顆粒状二酸化チタ
ンは、非常にサラサラした粉末で、流動性に優れたもの
である。例えば粉末添加の際に、通常の二酸化チタンで
はホッパー部においてブリッジを形成するため流動しな
くなり、バイブレーター等の設置を余儀なくされていた
のに対して、本発明の顆粒状二酸化チタンでは、安息角
が３４゜以下であり、ブリッジの形成など全くない作業
性に優れたものである。The granular titanium dioxide thus obtained is a very smooth powder and has excellent fluidity. For example, when powder is added, ordinary titanium dioxide does not flow because it forms a bridge in the hopper portion, and it was forced to install a vibrator or the like, whereas in the granular titanium dioxide of the present invention, the angle of repose is It has an angle of 34 ° or less and is excellent in workability with no formation of bridges.
【０００８】次に、本発明における製造方法の詳細な説
明を行う。Next, a detailed description will be given of the manufacturing method of the present invention.
【０００９】出発原料である硫酸チタニル溶液は、不純
物量については特定されないが、顆粒状二酸化チタンの
高純度化を図るときは、その要求されるレベルに応じた
純度のものを使用するのが妥当である。しかしながら、
Ｎｂ2Ｏ5などの不純物を多く含む硫酸チタニル溶液を用
いる場合においても、一旦、２水和硫酸チタニル結晶を
生成させ、ろ別分離後、これを硫酸中に再溶解した溶液
を出発原料とすれば、高純度化が可能である。また硫酸
チタニル溶液は、市販の硫酸チタニル試薬を硫酸中に溶
解させてもよく、含水酸化チタンを硫酸に溶解したもの
でも良い。The starting material titanyl sulfate solution is not specified in terms of the amount of impurities, but when purifying granular titanium dioxide to a high degree of purity, it is appropriate to use a solution having a purity corresponding to the required level. Is. However,
Even when a titanyl sulfate solution containing a large amount of impurities such as Nb 2 O 5 is used, once a crystal of titanyl sulfate dihydrate is formed, separated by filtration, and then redissolved in sulfuric acid, the solution is used as a starting material. If so, high purification is possible. The titanyl sulfate solution may be a commercially available titanyl sulfate reagent dissolved in sulfuric acid, or a solution of hydrous titanium oxide in sulfuric acid.
【００１０】本発明において重要なことは、これらの硫
酸チタニル溶液中にさらに硫酸を添加して、ＴｉＯ2濃
度が３０〜１４０ｇ／リットル、硫酸濃度が８００〜１
１５０ｇ／リットル、ならびにＨ2ＳＯ4／ＴｉＯ2重量
比が８〜３０となる様に調整することである。このいず
れの条件をも満足しないと粒状の水和硫酸チタニル結晶
は得られず、例えば硫酸濃度で言えば、硫酸濃度が８０
０ｇ／リットルより低いと針状の硫酸チタニル結晶の生
成が認められ、硫酸濃度が１１５０ｇ／リットルを越え
ると無水硫酸チタニル結晶となり粒状物は得難い。What is important in the present invention is that sulfuric acid is further added to these titanyl sulfate solutions so that the TiO 2 concentration is 30 to 140 g / liter and the sulfuric acid concentration is 800 to 1
150 g / liter, and the H 2 SO 4 / TiO 2 weight ratio should be adjusted to 8 to 30. If neither of these conditions is satisfied, granular hydrated titanyl sulfate crystals cannot be obtained. For example, in terms of sulfuric acid concentration, the sulfuric acid concentration is 80%.
When it is lower than 0 g / liter, needle-like titanyl sulfate crystals are observed to be formed, and when the sulfuric acid concentration exceeds 1150 g / liter, anhydrous titanyl sulfate crystals are formed, and it is difficult to obtain particulate matter.
【００１１】次に所定濃度に調整した硫酸チタニル溶液
を撹拌しながら沸点まで加熱し、沸点到達後３〜２０時
間撹拌保持する。晶析は必ずしも沸点で行う必要はない
が、晶析時間及び収率を考慮すると沸点ないし沸点より
２０℃低い範囲で行うのが好ましい。晶析終了後は、溶
液を冷却させ、自然沈降により晶析物を沈めた後、上澄
み液を除去する。この上澄み液は高濃度硫酸であり、濃
度調整用硫酸として再利用出来る。晶析物すなわち水和
硫酸チタニル結晶は濾別後アルコール等で洗浄し、１０
０〜１１０℃で乾燥させる。Next, the titanyl sulfate solution adjusted to a predetermined concentration is heated to the boiling point while stirring, and is stirred and held for 3 to 20 hours after reaching the boiling point. The crystallization does not necessarily have to be carried out at the boiling point, but it is preferably carried out at the boiling point or in a range lower than the boiling point by 20 ° C. in consideration of the crystallization time and the yield. After completion of the crystallization, the solution is cooled and the crystallized product is submerged by natural precipitation, and then the supernatant liquid is removed. This supernatant is high-concentration sulfuric acid and can be reused as sulfuric acid for concentration adjustment. The crystallized product, that is, the hydrated titanyl sulfate crystal was separated by filtration, washed with alcohol, etc.
Dry at 0-110 ° C.
【００１２】水和硫酸チタニル結晶の粒径は、出発原料
である硫酸チタニル中のＴｉＯ2濃度もしくはＨ2ＳＯ4
／ＴｉＯ2重量比に依存する。すなわちＴｉＯ2濃度が低
く、Ｈ2ＳＯ4／ＴｉＯ2重量比が大きくなると核の発生
数が少なくなるので粒径が大きくなるが、逆にＴｉＯ2
濃度が低くすぎると核に吸着していくＴｉの供給がたた
れるため大きく成長しない。The particle size of the hydrated titanyl sulfate crystals is determined by the concentration of TiO 2 or H 2 SO 4 in the starting material titanyl sulfate.
/ TiO 2 weight ratio. That TiO 2 concentration is low, H 2 SO 4 / Because TiO 2 weight ratio is the number of occurrences of the nucleus decreases increases but the particle size is large, TiO 2 conversely
If the concentration is too low, the supply of Ti adsorbed to the nuclei will drop and the growth will not be large.
【００１３】より大きな粒径の顆粒状二酸化チタンを得
るには、あらかじめ生成させた水和硫酸チタニル結晶も
しくは顆粒状二酸化チタンを所定濃度に調整した硫酸チ
タニル溶液中に母体として添加する方法がよい。焼成温
度にもよるが、母体を添加しない場合は得られる顆粒状
二酸化チタンの平均粒径が２５〜５０μｍであるのに対
して、母体を添加する方法によれば５０〜１００μｍの
顆粒状二酸化チタンが得られる。また母体添加により得
られた顆粒状二酸化チタンは、顆粒状粒子の形状がより
真球体に近くなり、粒度分布が狭いものとなる。In order to obtain granular titanium dioxide having a larger particle size, it is preferable to add a preformed hydrated titanyl sulfate crystal or granular titanium dioxide to a titanyl sulfate solution adjusted to a predetermined concentration as a matrix. Although it depends on the firing temperature, the average particle size of the granular titanium dioxide obtained when the matrix is not added is 25 to 50 μm, while the granular titanium dioxide according to the method of adding the matrix is 50 to 100 μm. Is obtained. Further, in the granular titanium dioxide obtained by adding the matrix, the shape of granular particles becomes closer to a true sphere, and the particle size distribution becomes narrow.
【００１４】このようにして得られた粒状の晶析物を、
７００〜１２００℃の温度で焼成することにより、アナ
ターゼ型またはルチル型の結晶構造を有したものとな
る。残存するＳＯ3量、焼成方法もしくは焼成時間にも
よるが、概ね８００〜９００℃がアナターゼ型からルチ
ル型への転移温度である。アナターゼ型顆粒状二酸化チ
タンの比表面積はその形状から推定される値よりかなり
大きく、すなわち多孔質体であるので触媒的な使用も可
能となる。また粒子強度を必要とする場合は、ルチル型
顆粒状二酸化チタンがよい。The granular crystallization product thus obtained is
By firing at a temperature of 700 to 1200 ° C., a product having an anatase type or rutile type crystal structure is obtained. The transition temperature from anatase type to rutile type is approximately 800 to 900 ° C., although it depends on the amount of remaining SO 3 , the firing method or the firing time. The specific surface area of the anatase-type granular titanium dioxide is considerably larger than the value estimated from its shape, that is, it is a porous material, and therefore it can be used catalytically. When the particle strength is required, rutile type granular titanium dioxide is preferable.
【００１５】[0015]
【実施例】以下に実施例を挙げて本発明をさらに詳細に
説明する。以下の実施例は単に例示のために記すもので
あり、発明の範囲がこれらによって制限されるものでは
ない。 ［実施例１］ ＴｉＯ2濃度７０ｇ／リットル、硫酸濃
度９１０ｇ／リットル、Ｈ2ＳＯ4／ＴｉＯ2重量比とし
て１３に調整した硫酸チタニル溶液２リットルをガラス
製セパラブルフラスコに入れ、新東科学製３−１モータ
ーを用いて撹拌しながら沸点まで加温した。沸点到達後
８時間撹拌保持し、粒状の水和硫酸チタニル結晶を得
た。自然沈降により上澄み液を除去し濾別した後エタノ
ールにて洗浄し、これを１００℃で乾燥した。乾燥物を
１０００℃の電気炉において３時間の焼成を行い、顆粒
状二酸化チタン粉末（試料１）を得た。 ［実施例２］ 実施例１において、乾燥物を７００℃の
電気炉において３時間焼成すること以外は同様にして行
い、顆粒状二酸化チタン粉末（試料２）を得た。 ［実施例３］ 実施例１において、硫酸チタニル溶液を
ＴｉＯ2濃度５０ｇ／リットル、硫酸濃度９１０ｇ／リ
ットル、Ｈ2ＳＯ4／ＴｉＯ2重量比として１８に調整
し、乾燥物を１０００℃の電気炉において６時間の焼成
すること以外は同様にして行い、顆粒状二酸化チタン粉
末（試料３）を得た。 ［実施例４］ ＴｉＯ2濃度７０ｇ/リットル、硫酸濃度
９１０ｇ/リットル、Ｈ2ＳＯ4／ＴｉＯ2重量比を１３に
調整した硫酸チタニル溶液２リットルと実施例１により
得られた粒状の水和硫酸チタニル結晶７０ｇを、ガラス
製セパラブルフラスコに入れた。新東科学製３−１モー
ターを用いて撹拌しながら１３５℃まで加温し、１３５
℃で４時間撹拌保持した。溶液を十分冷却した後、自然
沈降により上澄み液を除去した。これを濾別し、エタノ
ールにて洗浄した後、１００℃で乾燥した。乾燥物を８
００℃の電気炉において３時間の焼成を行い、顆粒状二
酸化チタン粉末（試料４）を得た。The present invention will be described in more detail with reference to the following examples. The following examples are provided for illustration only and the scope of the invention is not limited thereby. [Example 1] A TiO 2 concentration of 70 g / liter, a sulfuric acid concentration of 910 g / liter, and 2 liters of a titanyl sulfate solution adjusted to a H 2 SO 4 / TiO 2 weight ratio of 13 were placed in a glass separable flask and manufactured by Shinto Kagaku. The mixture was heated to the boiling point with stirring using a 3-1 motor. After reaching the boiling point, the mixture was kept stirring for 8 hours to obtain granular hydrated titanyl sulfate crystals. The supernatant was removed by spontaneous sedimentation, filtered off, washed with ethanol, and dried at 100 ° C. The dried product was baked in an electric furnace at 1000 ° C. for 3 hours to obtain granular titanium dioxide powder (Sample 1). [Example 2] Granular titanium dioxide powder (Sample 2) was obtained in the same manner as in Example 1, except that the dried product was baked in an electric furnace at 700 ° C for 3 hours. Example 3 In Example 1, the titanyl sulfate solution was adjusted to a TiO 2 concentration of 50 g / liter, a sulfuric acid concentration of 910 g / liter, and a H 2 SO 4 / TiO 2 weight ratio of 18, and the dried product was heated to an electric furnace of 1000 ° C. In the same manner as above, except that firing was performed for 6 hours, a granular titanium dioxide powder (Sample 3) was obtained. Example 4 2 liters of a titanyl sulfate solution adjusted to a TiO 2 concentration of 70 g / liter, a sulfuric acid concentration of 910 g / liter, and a H 2 SO 4 / TiO 2 weight ratio of 13 and the granular hydrated sulfuric acid obtained in Example 1 70 g of titanyl crystals were placed in a glass separable flask. While stirring with a Shinto Kagaku 3-1 motor, heat up to 135 ° C, then 135
The mixture was kept stirring at 4 ° C for 4 hours. After the solution was sufficiently cooled, the supernatant was removed by spontaneous sedimentation. This was separated by filtration, washed with ethanol, and then dried at 100 ° C. 8 dried products
Firing was performed for 3 hours in an electric furnace at 00 ° C to obtain granular titanium dioxide powder (Sample 4).
【００１６】以上、実施例１〜４で得られた試料の測定
結果を表１に示す。また実施例で述べる測定値は、下記
の要領で測定した値である。The measurement results of the samples obtained in Examples 1 to 4 are shown in Table 1. Further, the measured values described in the examples are the values measured in the following manner.
【００１７】（１）平均粒径の測定 試料を０．０５％ヘキサメタリン酸ソーダ中に分散させ
た後、セイシン企業（株）製レーザー回折式粒度分析計
ＰＲＯ−７０００Ｓにて粒度分布を測定した。(1) Measurement of average particle size After the sample was dispersed in 0.05% sodium hexametaphosphate, the particle size distribution was measured with a laser diffraction particle size analyzer PRO-7000S manufactured by Seishin Enterprise Co., Ltd.
【００１８】（２）比表面積の測定 （株）島津製作所製の流動式比表面積自動測定装置フロ
ーソーブ２３００型により、試料の比表面積を測定し
た。(2) Measurement of Specific Surface Area The specific surface area of the sample was measured by a flow type automatic surface area measuring apparatus Flowsorb 2300 manufactured by Shimadzu Corporation.
【００１９】（３）安息角 ホソカワミクロン（株）製のパウダーテスターＰＴ−Ｅ
を用いて安息角を測定した。(3) Angle of repose Powder tester PT-E manufactured by Hosokawa Micron Co., Ltd.
Was used to measure the angle of repose.
【００２０】[0020]
【表１】 [Table 1]
【図１】実施例１で得られた顆粒状二酸化チタンの粒子
構造を表す２００倍の走査型電子顕微鏡写真である。FIG. 1 is a scanning electron micrograph (magnification: 200) showing the particle structure of the granular titanium dioxide obtained in Example 1.
【図２】実施例４で得られた顆粒状二酸化チタンの粒子
構造を表す２００倍の走査型電子顕微鏡写真である。FIG. 2 is a scanning electron micrograph (magnification: 200) showing the particle structure of the granular titanium dioxide obtained in Example 4.
【図３】実施例３と実施例４で得られた顆粒状二酸化チ
タンの粒度分布図である。FIG. 3 is a particle size distribution chart of the granular titanium dioxides obtained in Example 3 and Example 4.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原田 孝 山口県宇部市大字小串1978番地の25 チタ ン工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Harada 25 Titanium Industry Co., Ltd., 1978, Kogushi, Ube City, Yamaguchi Prefecture
Claims (4)
つ、比表面積が１〜５０ｍ2／ｇである顆粒状二酸化チ
タン。1. Granular titanium dioxide having an average particle size of 25 to 100 μm and a specific surface area of 1 to 50 m 2 / g.
型であり、ＴｉＯ2純度が９９％以上であることを特徴
とする請求項１記載の顆粒状二酸化チタン。2. The granular titanium dioxide according to claim 1, which has a rutile type or anatase type crystal structure and a TiO 2 purity of 99% or more.
ル、硫酸濃度が８００〜１１５０ｇ／リットル、Ｈ2Ｓ
Ｏ4／ＴｉＯ2重量比を８〜３０に調整した硫酸チタニル
溶液を加熱晶析することにより水和硫酸チタニル結晶を
得、これを７００〜１２００℃の温度で焼成することを
特徴とする請求項１記載の顆粒状二酸化チタンの製造方
法。3. A TiO 2 concentration of 30 to 140 g / liter, a sulfuric acid concentration of 800 to 1150 g / liter, and H 2 S.
A hydrated titanyl sulfate crystal is obtained by heating and crystallization of a titanyl sulfate solution having an O 4 / TiO 2 weight ratio adjusted to 8 to 30, and the crystal is calcined at a temperature of 700 to 1200 ° C. 1. The method for producing granular titanium dioxide according to 1.
ル、硫酸濃度が８００〜１１５０ｇ／リットル、Ｈ2Ｓ
Ｏ4／ＴｉＯ2重量比を８〜３０に調整した硫酸チタニル
溶液中に水和硫酸チタニル結晶もしくは顆粒状二酸化チ
タンを母体として添加し加熱晶析することにより得た晶
析物を、７００〜１２００℃の温度で焼成することを特
徴とする請求項１記載の顆粒状二酸化チタンの製造方
法。4. A TiO 2 concentration of 30 to 140 g / liter, a sulfuric acid concentration of 800 to 1150 g / liter, and H 2 S.
A crystallized product obtained by adding hydrated titanyl sulfate crystals or granular titanium dioxide as a matrix to a titanyl sulfate solution adjusted to have an O 4 / TiO 2 weight ratio of 8 to 30 and heating and crystallizing the mixture was 700 to 1200. The method for producing granular titanium dioxide according to claim 1, wherein the firing is performed at a temperature of ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33347894A JP3653112B2 (en) | 1994-12-15 | 1994-12-15 | Granular titanium dioxide and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33347894A JP3653112B2 (en) | 1994-12-15 | 1994-12-15 | Granular titanium dioxide and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JPH08169716A true JPH08169716A (en) | 1996-07-02 |
| JP3653112B2 JP3653112B2 (en) | 2005-05-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33347894A Expired - Fee Related JP3653112B2 (en) | 1994-12-15 | 1994-12-15 | Granular titanium dioxide and method for producing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006312572A (en) * | 2005-05-09 | 2006-11-16 | Nippon Chem Ind Co Ltd | Granular titanium oxide, its manufacturing method and optical glass |
| JP2013028563A (en) * | 2011-07-29 | 2013-02-07 | Ishihara Sangyo Kaisha Ltd | Titanium dioxide pigment for cosmetic and method for producing the same |
| JP2013542160A (en) * | 2010-09-22 | 2013-11-21 | サハトレーベン・ヒェミー・ゲーエムベーハー | Porous spherical titanium dioxide |
-
1994
- 1994-12-15 JP JP33347894A patent/JP3653112B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006312572A (en) * | 2005-05-09 | 2006-11-16 | Nippon Chem Ind Co Ltd | Granular titanium oxide, its manufacturing method and optical glass |
| JP2013542160A (en) * | 2010-09-22 | 2013-11-21 | サハトレーベン・ヒェミー・ゲーエムベーハー | Porous spherical titanium dioxide |
| JP2013028563A (en) * | 2011-07-29 | 2013-02-07 | Ishihara Sangyo Kaisha Ltd | Titanium dioxide pigment for cosmetic and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3653112B2 (en) | 2005-05-25 |
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