JP2852482B2 - Iron-containing titanium dioxide and method for producing the same - Google Patents
Iron-containing titanium dioxide and method for producing the sameInfo
- Publication number
- JP2852482B2 JP2852482B2 JP23104193A JP23104193A JP2852482B2 JP 2852482 B2 JP2852482 B2 JP 2852482B2 JP 23104193 A JP23104193 A JP 23104193A JP 23104193 A JP23104193 A JP 23104193A JP 2852482 B2 JP2852482 B2 JP 2852482B2
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- JP
- Japan
- Prior art keywords
- titanium dioxide
- iron
- containing titanium
- oxide
- weight
- 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]
【産業上の利用分野】本願発明は、鉄を含有する二酸化
チタン、その製造方法およびこれを用いた化粧料、塗料
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to iron-containing titanium dioxide, a method for producing the same, and cosmetics and paints using the same.
【０００２】[0002]
【従来の技術】よく知られているように、化粧料や塗料
などの分野において、白色顔料例えば大きな隠蔽力を有
しかつ安全性の高い二酸化チタン顔料と、種々の顔料例
えば酸化鉄顔料とを混合使用して黄色で肌色系の所望の
色味を付与することが通常行なわれている。しかしなが
ら、この場合着色剤それぞれのもつ結晶型、比重、媒体
親和性などの相違により、その適用系で色分かれ、色ム
ラ等の現象を惹起し易く、また塗布適用系で肌色が白く
浮き上がったようないわゆる白浮き現象を生じ易く、し
かもこの傾向は経時とともにこの傾向が一層強くなるな
ど、その解決が強く希求されている。2. Description of the Related Art As is well known, in the fields of cosmetics and paints, white pigments such as titanium dioxide pigments having large hiding power and high safety, and various pigments such as iron oxide pigments are used. It is common practice to use a mixture to impart a desired flesh color tone with a yellow color. However, in this case, due to differences in the crystal type, specific gravity, medium affinity, etc. of each colorant, it is easy to cause phenomena such as color separation and color unevenness in the application system, and it seems that the skin color has risen white in the application system. The so-called white floating phenomenon is likely to occur, and this tendency becomes stronger over time, and the solution is strongly desired.
【０００３】しかして、前記色分かれ、白浮きを防止す
るため、二酸化チタンと酸化鉄とを単一顔料化しようと
する方法がいくつか提案されている。例えば、平均粒
径０．０１〜１μｍの二酸化チタン粒子に含水酸化鉄等
の処理を施し、乾燥ないし焼成する（特公平４−５００
１号）、酸化チタンと水酸化鉄あるいは酸化鉄を混合
し、焼成する（特開昭５６−１２２３０６号）等が挙げ
られ、これらはいずれも二酸化チタン粒子に対して、そ
の粒子表面上に鉄の水酸化物または酸化物を被覆処理
し、乾燥または焼成することによって、二酸化チタン粒
子上に酸化鉄の被覆層を形成させる方法である。しかし
ながら、これらの従来方法によっても、前記問題点はあ
る程度改善されるものの、未だ色分かれや白浮き現象を
十分満足に抑制し得るには至っておらず、その解決が急
がれている。[0003] In order to prevent the color separation and the whitening, several methods have been proposed for converting titanium dioxide and iron oxide into a single pigment. For example, titanium dioxide particles having an average particle diameter of 0.01 to 1 μm are treated with iron oxide hydroxide or the like and dried or fired (Japanese Patent Publication No. 4-500).
No. 1), mixing titanium oxide with iron hydroxide or iron oxide and calcining the mixture (Japanese Patent Application Laid-Open No. 56-122306). Is coated with a hydroxide or oxide, and dried or fired to form a coating layer of iron oxide on the titanium dioxide particles. However, even with these conventional methods, although the above problems are improved to some extent, color separation and white floating phenomenon have not yet been satisfactorily suppressed, and the solutions are urgently needed.
【０００４】[0004]
【発明が解決しようとする課題】本願発明は、白色顔料
と有色顔料との色分かれ防止が大きく改善され、白浮き
現象を与えない化粧料または塗料などに最適の鉄含有二
酸化チタンを得ることである。The object of the present invention is to obtain an iron-containing titanium dioxide which is greatly improved in preventing color separation between a white pigment and a colored pigment and which does not give rise to a whitening phenomenon. is there.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、かねてよ
り色分かれを防止しかつ白浮き現象を実質的に抑制し得
る黄〜肌色系色味の二酸化チタン顔料を得るべく種々検
討を行った。その結果、基体物質としてルチル核を有す
る微小チタニアゾルを用い、このものの存在下に鉄の水
溶性塩を中和して該チタニアの表面に含水酸化鉄を沈
殿、被覆させ、しかる後７００〜１１００℃で焼成する
ことにより、平均単一粒子径が０．１２〜０．３５μｍ
であり、その結晶内部に鉄成分を固溶した二酸化チタン
とすることによって、前記問題点がいずれも解決し得る
ことの知見を得、本発明は完成したものである。Means for Solving the Problems The present inventors have conducted various studies to obtain a titanium dioxide pigment having a yellowish-skinish tint which can prevent color separation and substantially suppress the whitening phenomenon. Was. As a result, a fine titania sol having a rutile nucleus is used as a base material, and a water-soluble salt of iron is neutralized in the presence of the sol to precipitate and coat the surface of the titania with hydrous iron oxide. By firing, the average single particle diameter is 0.12 to 0.35 μm
The inventors have found that titanium dioxide in which an iron component is dissolved as a solid solution in the crystal can solve any of the above problems, and the present invention has been completed.
【０００６】こうして得られた本願発明の鉄含有二酸化
チタンは、大きな隠蔽力や安全性の高い二酸化チタン顔
料の特性を維持し、かつ色分かれが防止でき、これを配
合した化粧料等を肌に塗布しても白浮き現象が極めて少
ないものであって、通常の化粧料或いはシミ、ソバカス
などを被覆する化粧料をはじめ、その他種々の用途適用
において極めて有用な黄〜肌色系色味の二酸化チタン顔
料である。即ち、本願発明は平均単一粒子径が０．１２
〜０．３５μｍの二酸化チタンであり、その結晶内部に
鉄成分をＦｅとしてＴｉＯ２に対し、１〜１５重量％含
有していることを特徴とする鉄含有二酸化チタンであ
る。[0006] The iron-containing titanium dioxide of the present invention thus obtained has a high hiding power and high safety.
Maintaining the charge characteristics, and color separation can be prevented, whitening phenomenon by applying to the skin a cosmetic or the like blended with this there is extremely little usual cosmetic or stains, freckles
It is a titanium dioxide pigment having a yellow to flesh-tone tint which is extremely useful in various other applications, including cosmetics for coating cosmetics. That is, the present invention has an average single particle diameter of 0.12.
It is titanium dioxide of about 0.35 μm, and contains 1 to 15% by weight, based on TiO 2 , of an iron component as Fe in the crystal thereof.
【０００７】本願発明における鉄含有二酸化チタンの結
晶系としては、ルチル、アナタース、ブルッカイトのい
ずれのものでもよいが、ルチルの場合は着色力、隠蔽
力、紫外線吸収能、光活性の点で一層好ましい。また本
願発明においては、微小チタニアゾルを基体粒子として
用い、その表面に含水酸化鉄を被覆した後焼成するため
に、被覆物である酸化鉄または含水酸化鉄が焼成により
二酸化チタンの結晶内部に固溶し、強い分散条件で化
粧料または塗料に配合しても、鉄成分と二酸化チタンの
色分かれが生じることなく、化粧料、塗料に配合した
際白浮き現象が発生しない等、従来技術に見られない顕
著に優れた効果を発現する。The crystal system of the iron-containing titanium dioxide in the present invention may be any of rutile, anatase and brookite, but rutile is more preferable in view of coloring power, hiding power, ultraviolet absorbing ability and photoactivity. . In addition, in the present invention, since the fine titania sol is used as the base particles, and the surface is coated with hydrated iron oxide and then fired, the coated iron oxide or hydrated iron oxide is solid-dissolved inside the titanium dioxide crystal by firing. However, even when blended in cosmetics or paints under strong dispersion conditions, the iron component and titanium dioxide do not undergo color separation, and the whitening phenomenon does not occur when blended in cosmetics or paints. Not express remarkably excellent effects.
【０００８】本願発明の鉄含有二酸化チタンの平均粒子
径は、電子顕微鏡写真による平均単一粒子径として０．
１２〜０．３５μｍ望ましくは０．２〜０．３μｍのも
のである。二酸化チタン中に固溶する鉄成分の量は、Ｆ
ｅ換算で、二酸化チタンに対して１〜１５重量％、好ま
しくは２〜１０重量％である。該鉄成分の量が前記範囲
より多きに過ぎると、結晶内部に固溶しない鉄成分が多
くなり、その鉄分による着色が強くなりすぎたり、二酸
化チタンの耐熱性、耐薬品性等が損なわれる等の問題が
生じる。また、前記範囲より少なきに過ぎると、充分な
着色、白浮き防止能力等が得られ難くなる。[0008] The average particle diameter of the iron-containing titanium dioxide of the present invention is 0.1 as an average single particle diameter in an electron micrograph.
It is 12 to 0.35 μm, preferably 0.2 to 0.3 μm. The amount of iron component dissolved in titanium dioxide is F
In terms of e, it is 1 to 15% by weight, preferably 2 to 10% by weight based on titanium dioxide. If the amount of the iron component is more than the above range, the amount of the iron component that does not form a solid solution inside the crystal increases, and the coloring due to the iron content becomes too strong, and the heat resistance and chemical resistance of titanium dioxide are impaired. Problem arises. On the other hand, if the amount is less than the above range, it is difficult to obtain sufficient coloring, white floating prevention ability, and the like.
【０００９】本願発明の鉄含有二酸化チタンは、前記鉄
成分とともに、必要に応じアルミニウム、亜鉛、ナトリ
ウム、カリウム、マグネシウム、リン等の金属元素の少
なくとも一種をその結晶内に少量含有しても良い。この
ことにより、得られる鉄含有二酸化チタンの粒子径を制
御したり、耐久性を向上させたりすることができる。更
に、本発明の鉄含有二酸化チタンは、その表面がアルミ
ニウム、ケイ素、チタン、ジルコニウム、スズ、アンチ
モン等の金属の酸化物または水酸化物の少なくとも一種
の無機化合物を表面処理することができる。また、化粧
品分野や塗料分野で使用される種々の有機系処理剤、例
えばカルボン酸、ポリオール、アミン、シロキサン、シ
ランカップリング剤等の有機物の少なくとも一種で被覆
されても良く、その場合、化粧料、塗料への分散性及び
塗膜の耐久性を一層向上させることができる。The iron-containing titanium dioxide of the present invention may contain a small amount of at least one of metal elements such as aluminum, zinc, sodium, potassium, magnesium, and phosphorus in the crystal together with the iron component, if necessary. Thereby, the particle size of the obtained iron-containing titanium dioxide can be controlled and the durability can be improved. Further, the surface of the iron-containing titanium dioxide of the present invention can be surface-treated with at least one inorganic compound of a metal oxide or hydroxide such as aluminum, silicon, titanium, zirconium, tin, and antimony. Further, it may be coated with various organic treating agents used in the field of cosmetics and paints, for example, at least one kind of organic substance such as carboxylic acid, polyol, amine, siloxane, and silane coupling agent. In addition, the dispersibility in the paint and the durability of the coating film can be further improved.
【００１０】次に本願発明の鉄含有二酸化チタンの製造
方法について説明する。本願発明においては、好ましく
は基体粒子として、ルチル核を有する微小チタニアゾル
を用い、まずこのチタニアの表面に鉄の酸化物または含
水酸化物を沈殿させる。ここで用いるルチル核を有する
微小チタニアゾルとは、Ｘ線回折法による測定でルチル
型結晶のピークを示す微小水和酸化チタンのゾルであ
り、その平均結晶子径は普通５０〜１２０Åのものであ
る。このものは例えば、硫酸法二酸化チタン顔料の製造
において、二酸化チタンのルチル化促進及び粒径の調節
を目的に硫酸チタン溶液の加水分解の際に種晶として用
いられるものであり、結晶構造、表面活性の面から一般
の水酸化チタン例えば非晶質のメタチタン酸、オルトチ
タン酸などとは異なるものである。Next, a method for producing the iron-containing titanium dioxide of the present invention will be described. In the present invention, a fine titania sol having a rutile nucleus is preferably used as the base particles, and first, an oxide of iron or a hydrated oxide is precipitated on the surface of the titania. The fine titania sol having a rutile nucleus used herein is a sol of finely hydrated titanium oxide showing a peak of a rutile crystal as measured by an X-ray diffraction method, and its average crystallite diameter is usually 50 to 120 °. . For example, in the production of a sulfuric acid method titanium dioxide pigment, it is used as a seed crystal during hydrolysis of a titanium sulfate solution for the purpose of promoting rutile conversion of titanium dioxide and adjusting the particle size, and has a crystal structure and a surface. It is different from general titanium hydroxide such as amorphous metatitanic acid and orthotitanic acid in terms of activity.
【００１１】このような微小チタニアゾルは例えば、
ＴｉＯ2 として１５０〜２２０ｇ／ｌの四塩化チタン水
溶液を沸点で２〜１０時間加熱して加水分解する、Ｔ
ｉＯ2 として１５０〜２２０ｇ／ｌの硫酸チタン水溶液
或いは四塩化チタン水溶液を５〜３０℃に保持しながら
水酸化ナトリウムなどのアルカリ溶液で中和してコロイ
ド状の非晶質水酸化チタンを析出させ、このコロイド状
水酸化チタンを６０〜８０℃で１〜１０時間熟成する、
メタチタン酸或いはオルトチタン酸などの非晶質含水
酸化チタンを水酸化ナトリウム水溶液に入れ、８０℃〜
沸点で１〜１０時間加熱処理した後濾過、洗浄し、その
後塩酸溶液中で８０℃〜沸点で１〜１０時間加熱処理す
る等の方法で得られる。Such a fine titania sol is, for example,
Hydrolyzed titanium tetrachloride aqueous solution 150~220g / l as TiO 2 is heated at the boiling point 2 to 10 hours, T
While maintaining a 150 to 220 g / l aqueous solution of titanium sulfate or an aqueous solution of titanium tetrachloride as iO 2 at 5 to 30 ° C., neutralize with an alkaline solution such as sodium hydroxide to precipitate colloidal amorphous titanium hydroxide. Aging this colloidal titanium hydroxide at 60-80 ° C. for 1-10 hours,
Amorphous titanium oxide such as metatitanic acid or orthotitanic acid is placed in an aqueous sodium hydroxide solution at 80 ° C.
After heating at a boiling point for 1 to 10 hours, filtration and washing are carried out, and then heat treatment is performed in a hydrochloric acid solution at 80 ° C. to a boiling point for 1 to 10 hours.
【００１２】本願発明の方法において、該チタニアの表
面に鉄の酸化物、含水酸化物を沈殿させるには、例えば
前記微小チタニアゾルを４０〜９０℃望ましくは６０〜
８０℃に加熱しながら、この中にＦｅ換算で、二酸化チ
タンに対して１〜１５重量％、好ましくは２〜１０重量
％となるように水溶性鉄塩を添加し、次に苛性ソーダ、
アンモニア水等のアルカリ性水溶液を添加して中和する
ことにより、行うことができる。使用するチタニアゾル
は必要に応じてチタニア（ＴｉＯ2 ）濃度を５０〜３０
０ｇ／ｌに調整するのがよい。添加する水溶性塩として
は塩化第一鉄、硫酸第一鉄、硝酸第一鉄、塩化第二鉄、
硫酸第二鉄、硝酸第二鉄等を挙げることができる。な
お、中和反応は系のｐＨを８〜１０に調整しながら行う
のがよい。In the method of the present invention, in order to precipitate an oxide of iron and a hydrated oxide on the surface of the titania, for example, the fine titania sol is heated at 40 to 90 ° C., preferably 60 to 90 ° C.
While heating to 80 ° C., a water-soluble iron salt is added thereto in an amount of 1 to 15% by weight, preferably 2 to 10% by weight, based on titanium dioxide, in terms of Fe.
It can be carried out by adding an alkaline aqueous solution such as aqueous ammonia to neutralize the solution. The titania sol used may have a titania (TiO 2 ) concentration of 50 to 30 if necessary.
It is good to adjust to 0 g / l. Ferrous chloride, ferrous sulfate, ferrous nitrate, ferric chloride,
Ferric sulfate, ferric nitrate and the like can be mentioned. The neutralization reaction is preferably performed while adjusting the pH of the system to 8 to 10.
【００１３】次に前記の工程で得られた生成物を分別、
洗浄した後、乾燥し、または乾燥せずに７００〜１１０
０℃の温度で焼成し、粉砕することにより、０．１２〜
０．３５μｍの鉄含有二酸化チタンとする。粉砕はサン
ドミル、ペブルミル、デイスクミル等による湿式粉砕、
流体エネルギーミル、ハンマーミル、エッジランナーミ
ル等による乾式粉砕等により行うことができる。Next, the product obtained in the above step is fractionated,
After washing, dry or without drying 700-110
By firing at a temperature of 0 ° C. and pulverizing,
0.35 μm iron-containing titanium dioxide. Grinding is wet grinding with a sand mill, pebble mill, disk mill, etc.
It can be performed by dry pulverization using a fluid energy mill, a hammer mill, an edge runner mill, or the like.
【００１４】本願発明の方法においては、基体粒子とし
てチタニアゾルを用いるので、比較的低い温度で焼成し
ても鉄成分の二酸化チタン結晶中への固溶が容易に進行
し、かつ安定した鉄含有二酸化チタンを容易に得ること
ができる。本願発明方法においては、前記方法で得られ
た鉄含有二酸化チタン粒子の表面にアルミニウム、ケイ
素、チタニウム、ジルコニウム、スズ、アンチモンなど
の金属の含水酸化物を沈殿させ、被覆させてもよい。こ
の方法は例えば、焼成、粉砕して得られた鉄含有二酸化
チタンを水に分散させてスラリーとし、必要に応じて湿
式粉砕、分級処理した後、この中にアルミニウム、ケイ
素、チタニウム、ジルコニウム、スズ及びアンチモンの
各水溶性塩の群から選ばれた少なくとも一種を二酸化チ
タンに対して酸化物換算総量で１〜１５重量％添加後、
該水溶性塩がスラリー中でアルカリ性を示す場合は硫
酸、塩酸等の酸性溶液で、該水溶性塩がスラリー中で酸
性を示す場合は苛性ソーダ、アンモニア水等のアルカリ
性溶液で中和して該二酸化チタン粒子の表面に沈殿、被
覆させ、このものを分別後、乾燥、粉砕することにより
行うことができる。この被覆処理により鉄含有二酸化チ
タンの分散媒体における、分散性、耐久性などを向上さ
せることができる。In the method of the present invention, since titania sol is used as the base particles, the solid solution of the iron component in the titanium dioxide crystal easily progresses even when calcined at a relatively low temperature. Titanium can be easily obtained. In the method of the present invention, hydrated oxides of metals such as aluminum, silicon, titanium, zirconium, tin and antimony may be precipitated and coated on the surface of the iron-containing titanium dioxide particles obtained by the above method. In this method, for example, the iron-containing titanium dioxide obtained by calcining and pulverizing is dispersed in water to form a slurry, and if necessary, wet pulverizing and classifying, and then aluminum, silicon, titanium, zirconium, tin And after adding at least one selected from the group of water-soluble salts of antimony to titanium dioxide in a total oxide equivalent of 1 to 15% by weight,
When the water-soluble salt shows alkalinity in the slurry, the solution is neutralized with an acidic solution such as sulfuric acid or hydrochloric acid. It can be carried out by precipitating and coating the surface of the titanium particles, separating and drying and pulverizing the particles. By this coating treatment, the dispersibility, durability and the like of the iron-containing titanium dioxide dispersion medium can be improved.
【００１５】本願発明の鉄含有二酸化チタンは、前記し
た如く種々の化粧料や塗料に有用なものである。The iron-containing titanium dioxide of the present invention is useful for various cosmetics and paints as described above.
【００１６】[0016]
実施例 ＴｉＯ2 として２００ｇ／ｌの濃度の四塩化チタン水溶
液を室温に保持しながら、水酸化ナトリウム水溶液を添
加し、ｐＨを７．０に調整してコロイド状の非晶質含水
酸化チタンを析出させ、引き続き熟成してルチル型のチ
タニアゾルを得た。このゾルをよく洗浄した後、ＴｉＯ
2 として２００ｇ／ｌの濃度の含水酸化チタン水性スラ
リーとした。このスラリーを７０℃に加熱し、よく攪拌
しながら、この中にＴｉＯ2 に対しＦｅとして５重量％
の硫酸第一鉄水溶液（Ｆｅ濃度５０ｇ／ｌ）を３０分を
要して添加した後、水酸化ナトリウム溶液を４０分間を
要して添加してｐＨ９に調整して含水酸化チタン粒子表
面に含水酸化鉄を沈殿、被覆させた。その後６０分間熟
成し、濾過、洗浄した。得られた洗浄ケーキを８５０℃
で３時間焼成し、水中に分散させ、サンドミルで湿式粉
砕して、鉄含有二酸化チタンのスラリーとした。このス
ラリーを７０℃に加熱し、よく攪拌しながら、この中に
ＴｉＯ2 に対してＡｌ2 Ｏ3 として２．０重量％の硫酸
アルミニウム水溶液を３０分間を要して添加し、引き続
き水酸化ナトリウム溶液を添加し、ｐＨを７．０に調整
して含水アルミナを沈殿、被覆させた。その後、６０分
間熟成し、濾過、洗浄し、乾燥した後、流体エネルギー
ミルで粉砕して電子顕微鏡写真法による平均単一粒子径
０．２５μｍの本発明の鉄含有二酸化チタン（試料Ａ）
を得た。EXAMPLE While maintaining a 200 g / l aqueous solution of titanium tetrachloride as TiO 2 at room temperature, an aqueous solution of sodium hydroxide was added to adjust the pH to 7.0 to precipitate colloidal amorphous hydrous titanium oxide. The mixture was then aged to obtain a rutile-type titania sol. After thoroughly washing this sol, TiO
2 was used as a hydrous titanium oxide aqueous slurry having a concentration of 200 g / l. This slurry was heated to 70 ° C., and with good stirring, 5% by weight of Fe relative to TiO 2 was contained therein.
Ferrous sulfate aqueous solution (Fe concentration 50 g / l) was added over a period of 30 minutes, and a sodium hydroxide solution was added over a period of 40 minutes to adjust the pH to 9 and water was added to the surface of the hydrous titanium oxide particles. The iron oxide was precipitated and coated. After aging for 60 minutes, the mixture was filtered and washed. 850 ° C
For 3 hours, dispersed in water, and wet-pulverized with a sand mill to obtain a slurry of iron-containing titanium dioxide. This slurry was heated to 70 ° C., and while stirring well, an aqueous solution of aluminum sulfate of 2.0% by weight as Al 2 O 3 with respect to TiO 2 was added thereto over 30 minutes. The solution was added, the pH was adjusted to 7.0, and the hydrated alumina was precipitated and coated. Thereafter, it is aged for 60 minutes, filtered, washed, dried, and then pulverized by a fluid energy mill to obtain an iron-containing titanium dioxide of the present invention having an average single particle diameter of 0.25 μm by electron micrograph (sample A).
I got
【００１７】比較例１ 市販の酸化チタン（平均単一粒子径０．２５μｍ、ルチ
ル型）と市販の黄色酸化鉄（粒子径約０．２μｍ）をＴ
ｉＯ2 ：Ｆｅとして１００：５の重量比となるように混
合して混合粉末（試料Ｂ）を得た。Comparative Example 1 Commercially available titanium oxide (average single particle diameter 0.25 μm, rutile type) and commercially available yellow iron oxide (particle diameter about 0.2 μm) were mixed with T
Mixing was performed so that the weight ratio of iO 2 : Fe was 100: 5 to obtain a mixed powder (sample B).
【００１８】比較例２ 市販の酸化チタン（平均単一粒子径０．２５μｍ、ルチ
ル型）を、ＴｉＯ2 として３００ｇ／ｌのスラリーと
し、このスラリーを７０℃に加熱し、よく攪拌しながら
この中にＴｉＯ2 に対してＦｅとして５重量％の硫酸第
一鉄水溶液（Ｆｅ濃度５０ｇ／ｌ）を３０分を要して添
加した後、水酸化ナトリウム溶液を４０分を要して添加
してｐＨ７に調整して酸化チタン粒子表面に含水酸化鉄
を沈澱、被覆させた。その後、６０分間熟成し、濾過、
洗浄した。得られた洗浄ケーキを８５０℃で３時間焼成
した後、流体エネルギーミルで粉砕して鉄含有二酸化チ
タン（試料Ｃ）を得た。Comparative Example 2 Commercially available titanium oxide (average single particle size: 0.25 μm, rutile type) was made into a slurry of 300 g / l as TiO 2 , and this slurry was heated to 70 ° C. after 5 weight% of an aqueous ferrous sulfate solution as Fe with respect to TiO 2 and (Fe concentration 50 g / l) was added over a period of 30 minutes, it was added over a period of 40 minutes sodium hydroxide solution to pH7 Then, the surface of the titanium oxide particles was precipitated with iron oxide hydroxide and coated. After aging for 60 minutes, filtration,
Washed. The obtained washed cake was calcined at 850 ° C. for 3 hours and then pulverized with a fluid energy mill to obtain iron-containing titanium dioxide (sample C).
【００１９】比較例３ 比較例１の混合粉末（試料Ｂ）を８５０℃で３時間焼成
した後、流体エネルギーミルで粉砕して鉄含有二酸化チ
タン（試料Ｄ）を得た。Comparative Example 3 The mixed powder of Comparative Example 1 (Sample B) was calcined at 850 ° C. for 3 hours and then pulverized with a fluid energy mill to obtain iron-containing titanium dioxide (Sample D).
【００２０】比較例４ 比較例１において、市販の酸化チタンとして、平均単一
粒子径０．１５μｍの市販のアナタース型酸化チタンを
用いた以外は同様にして混合粉末（試料Ｅ）を得た。Comparative Example 4 A mixed powder (sample E) was obtained in the same manner as in Comparative Example 1, except that a commercially available anatase-type titanium oxide having an average single particle diameter of 0.15 μm was used as the commercially available titanium oxide.
【００２１】[0021]
試験例１ 前記（Ａ）〜（Ｅ）の各試料１０ｇ、流動パラフィン３
００ｇをホモミキサーを用い、２０分の分散時間で十分
に分散させた後、５００ＣＣの試験管に入れて静置さ
せ、５時間経過後の色分かれの状況を目視判定した。Test Example 1 10 g of each sample of (A) to (E) above, liquid paraffin 3
After sufficiently dispersing 00 g using a homomixer for a dispersion time of 20 minutes, the mixture was placed in a test tube of 500 CC and allowed to stand, and the state of color separation after 5 hours was visually judged.
【００２２】試験例２ 前記（Ａ）〜（Ｅ）の各試料をそれぞれ下記の処方でク
リームとした。 （１）ステアリン酸 ２．５重量部 （２）サラシミツロウ ３．５重量部 （３）セタノール ３．５重量部 （４）スクワラン １７．０重量部 （５）モノステアリン酸グリセリン ３．０重量部 （６）超微粒子二酸化チタン ３．０重量部 （７）メチルパラベン ０．１重量部 （８）グリセリン １２．０重量部 （９）トリエタノールアミン １．０重量部 （１０）精製水 ５４．１重量部 （１１）香料 ０．３重量部 成分（１）〜（６）を８０℃で加熱混合したものを、成
分（７）〜（１０）を８０℃で加熱混合したものに加
え、ホモミキサーでよく混合し、強く攪拌する。４５℃
付近で（１１）を添加してクリームを調整した。Test Example 2 Each of the samples (A) to (E) was used as a cream according to the following formulation. (1) 2.5 parts by weight of stearic acid (2) 3.5 parts by weight of beeswax (3) 3.5 parts by weight of cetanol (4) 17.0 parts by weight of squalane (5) 3.0 parts by weight of glycerin monostearate (6) Ultrafine titanium dioxide 3.0 parts by weight (7) Methyl paraben 0.1 parts by weight (8) Glycerin 12.0 parts by weight (9) Triethanolamine 1.0 parts by weight (10) Purified water 54.1 parts by weight Part (11) Perfume 0.3 parts by weight A mixture obtained by heating and mixing components (1) to (6) at 80 ° C. is added to a mixture obtained by heating and mixing components (7) to (10) at 80 ° C. Mix well and stir vigorously. 45 ° C
A cream was prepared by adding (11) in the vicinity.
【００２３】評価方法１ 上記各クリームを２０〜５２歳の女性５名に通常に使用
してもらった後、暗室にてフラッシュを使い写真撮影を
行なった。写真を見て白浮きに関して相互に目視評価し
てもらった。以上の評価結果を表１に示した。なお、色
分かれの評価において、○は色分かれが認められない、
△は若干認められる、×は完全に認められることを示
す。また、白浮き感は５段階評価であり、数値が大きい
程白浮き感が顕著なことを示している。Evaluation Method 1 After each of the above creams was commonly used by five women aged 20 to 52, photographs were taken using a flash in a dark room. The photographer asked each other to visually evaluate the whitening. Table 1 shows the above evaluation results. In the evaluation of color separation, ○ indicates no color separation,
Δ indicates that it is slightly recognized, and X indicates that it is completely recognized. The whitening feeling was evaluated on a five-point scale, and the larger the value, the more noticeable the whitening feeling.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】本発明で得られる鉄含有二酸化チタン
は、二酸化チタンの結晶内部に鉄成分が固溶しているた
め、強い分散条件で化粧料または塗料に配合しても、
鉄成分と二酸化チタンの色分かれがない、化粧料に適
用した場合、肌に塗布しても、白浮き感がない等、顕著
に優れた効果を発現する。The iron-containing titanium dioxide obtained by the present invention has a solid solution of an iron component in the crystal of titanium dioxide.
When applied to cosmetics, there is no color separation between the iron component and titanium dioxide, and when applied to the skin, a remarkably excellent effect such as no whitening is exhibited.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｃ 1/36 Ｃ０９Ｃ 1/36 (56)参考文献 特開 平２−204326（ＪＰ，Ａ) 特開 平５−279235（ＪＰ，Ａ) 特開 平５−330825（ＪＰ，Ａ) 特開 平６−10353（ＪＰ，Ａ) 特開 平６−345438（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 23/00 - 23/047 A61K 7/02 - 7/42 C01G 49/00────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification symbol FI C09C 1/36 C09C 1/36 (56) References JP-A-2-204326 (JP, A) JP-A 5-279235 (JP) JP-A-5-330825 (JP, A) JP-A-6-10353 (JP, A) JP-A-6-345438 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB Name) C01G 23/00-23/047 A61K 7/02-7/42 C01G 49/00
Claims (8)
ｍの二酸化チタン顔料であり、その結晶内部に鉄成分を
Ｆｅ換算で、該二酸化チタンに対して１〜１５重量％の
割合で含有する鉄含有二酸化チタン。An average single particle size of 0.12 to 0.35 μm
m-titanium dioxide pigment, wherein the iron component is contained in the crystal in an amount of 1 to 15% by weight with respect to the titanium dioxide in terms of Fe in terms of Fe.
チタニウム、ジルコニウム、スズ及びアンチモンの群か
ら選ばれる少なくとも一種の元素の含水酸化物または酸
化物の被覆を有し、その被覆量が鉄含有二酸化チタン粒
子に対して、各元素の酸化物換算総量で１〜１５重量％
である請求項１の鉄含有二酸化チタン。2. The particle surface has aluminum, silicon,
Titanium, zirconium, tin and having a coating of a hydrated oxide or oxide of at least one element selected from the group of tin and antimony, the coating amount with respect to the iron-containing titanium dioxide particles, the total oxide equivalent of each element 1 to 15% by weight
The iron-containing titanium dioxide according to claim 1, which is:
ものである請求項１または２の鉄含有二酸化チタン。3. The iron-containing titanium dioxide according to claim 1, wherein the iron-containing titanium dioxide is a rutile crystal.
塩を中和して該チタニアの表面に含水酸化鉄をＦｅ換算
で、二酸化チタンに対して１〜１５重量％になるように
沈殿させる第一工程、第一工程の生成物を分別し、７０
０〜１１００℃の温度で焼成する第二工程からなる鉄含
有二酸化チタンの製造方法。4. A water-soluble salt of iron is neutralized in the presence of a fine titania sol, and iron oxide hydroxide is precipitated on the surface of the titania so as to be 1 to 15% by weight of titanium dioxide with respect to titanium dioxide. First step, separating the product of the first step, 70
A method for producing iron-containing titanium dioxide, comprising a second step of firing at a temperature of 0 to 1100 ° C.
請求項４の鉄含有二酸化チタンの製造方法。5. The method for producing iron-containing titanium dioxide according to claim 4, wherein the fine titania sol has a rutile nucleus.
有二酸化チタンをスラリーとし、アルミニウム、ケイ
素、チタニウム、ジルコニウム、スズ及びアンチモンの
各水溶性塩の群から選ばれた少なくとも一種を酸化物換
算総量で、鉄含有二酸化チタンに対して１〜１５重量％
添加後、中和し、該元素の含水酸化物を鉄含有二酸化チ
タン粒子表面に被覆させることよりなる鉄含有二酸化チ
タンの製造方法。6. A slurry of the iron-containing titanium dioxide obtained by the method of claim 4 or 5, wherein at least one selected from the group of water-soluble salts of aluminum, silicon, titanium, zirconium, tin and antimony is oxidized. 1-15% by weight based on iron-containing titanium dioxide
A method for producing iron-containing titanium dioxide, comprising neutralizing after addition, and coating the surface of the iron-containing titanium dioxide particles with a hydrated oxide of the element.
タンを含有する化粧料。7. A cosmetic comprising the iron-containing titanium dioxide of claim 1, 2 or 3.
タンを含有する塗料。8. A paint containing the iron-containing titanium dioxide according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23104193A JP2852482B2 (en) | 1993-08-24 | 1993-08-24 | Iron-containing titanium dioxide and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23104193A JP2852482B2 (en) | 1993-08-24 | 1993-08-24 | Iron-containing titanium dioxide and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0769636A JPH0769636A (en) | 1995-03-14 |
| JP2852482B2 true JP2852482B2 (en) | 1999-02-03 |
Family
ID=16917357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23104193A Expired - Lifetime JP2852482B2 (en) | 1993-08-24 | 1993-08-24 | Iron-containing titanium dioxide and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2852482B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003083008A1 (en) * | 2002-03-29 | 2003-10-09 | Isi Corporation | Ultraviolet shielding powder, dispersion having the powder, ultraviolet shielding film and ultraviolet shielding container |
| JP2007291090A (en) * | 2006-03-31 | 2007-11-08 | Kose Corp | Powdery cosmetic |
| EP2140854A1 (en) * | 2008-07-01 | 2010-01-06 | The Procter & Gamble | Cosmetic Composition |
| EP2140855A1 (en) * | 2008-07-01 | 2010-01-06 | The Procter and Gamble Company | Cosmetic Composition |
| ATE493964T1 (en) * | 2008-07-01 | 2011-01-15 | Procter & Gamble | METHOD FOR REDUCING THE APPEARANCE OF SICKLY OR PALE SKIN |
| WO2012012497A2 (en) | 2010-07-23 | 2012-01-26 | The Procter & Gamble Company | Cosmetic composition |
| JP2012197255A (en) | 2011-03-23 | 2012-10-18 | Ihi Corp | Ultraviolet absorbent, and cosmetic using the same |
| BR112014000203A2 (en) * | 2011-07-07 | 2017-02-07 | Shepherd Color Co | low overhead inorganic titanate pigments for use in infrared reflective colors |
-
1993
- 1993-08-24 JP JP23104193A patent/JP2852482B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0769636A (en) | 1995-03-14 |
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