JPH07165534A - Iron-containing ultrafine particulate titanium dioxide dispersion - Google Patents
Iron-containing ultrafine particulate titanium dioxide dispersionInfo
- Publication number
- JPH07165534A JPH07165534A JP34143093A JP34143093A JPH07165534A JP H07165534 A JPH07165534 A JP H07165534A JP 34143093 A JP34143093 A JP 34143093A JP 34143093 A JP34143093 A JP 34143093A JP H07165534 A JPH07165534 A JP H07165534A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- titanium dioxide
- dispersion
- containing ultrafine
- 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.)
- Granted
Links
Landscapes
- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本願発明は、鉄含有超微粒子二酸
化チタンを水或いは油に分散させた分散体及びこれを用
いた日焼け止め化粧料、紫外線防止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 a dispersion in which ultrafine titanium dioxide containing iron is dispersed in water or oil, a sunscreen cosmetic using the dispersion, and an ultraviolet protection coating.
【０００２】[0002]
【従来の技術】単一粒子径約０．１μｍ以下の超微粒子
二酸化チタンは、樹脂の膜或いは成形物に配合した場合
に可視光線を透過させるので透明性を示し、一方、紫外
線を遮蔽して紫外線により変色、変質する物質を保護す
るといったように、単一粒子径０．１５〜０．５μｍの
顔料級二酸化チタンとは異なった性質を示すことは良く
知られている。このために自然な肌色を生かし、かつ紫
外線による日焼けを防止するための日焼け止め化粧料と
しての利用が最近特に注目されている。しかしながら、
従来より市販されている超微粒子二酸化チタンは凝集力
が強く、水系、油性系の媒体において一次粒子まで完全
に分散させることが難しいために、例えば、超微粒子二
酸化チタンを配合した日焼け止め化粧料を肌に塗布した
場合、しばしば青みの強い散乱を起こして、青みの色調
を与え、そのために肌を不健康に見せる欠点がある。ま
た、従来の超微粒子二酸化チタンは紫外線Ｂ領域の波長
の光線（波長３２０〜２９０ｎｍ）は十分に遮蔽するも
のの紫外線Ａ領域の波長の光線（波長３８０〜３２０ｎ
ｍ）の遮蔽は不十分であり、近年、Ａ領域の紫外線によ
る皮膚障害が問題となり、このため有機紫外線吸収剤等
を併用しているのが実情である。2. Description of the Related Art Ultrafine particle titanium dioxide having a single particle diameter of about 0.1 μm or less is transparent because it transmits visible light when compounded in a resin film or a molded product, while it shields ultraviolet rays. It is well known that it exhibits properties different from those of pigment-grade titanium dioxide having a single particle diameter of 0.15 to 0.5 μm, such as protection of a substance that is discolored or deteriorated by ultraviolet rays. For this reason, the use as a sunscreen cosmetic for keeping the natural skin color and preventing sunburn due to ultraviolet rays has recently been particularly attracting attention. However,
Conventionally commercially available ultrafine particle titanium dioxide has a strong cohesive force, and it is difficult to completely disperse the primary particles in an aqueous or oily medium.For example, a sunscreen cosmetic compounded with ultrafine particle titanium dioxide is used. When applied to the skin, it often causes a strong bluish scattering and gives a bluish tone, which has the drawback of making the skin appear unhealthy. Further, the conventional ultrafine particle titanium dioxide sufficiently shields a light ray having a wavelength in the ultraviolet B region (wavelength 320 to 290 nm), but a light ray having a wavelength in the ultraviolet A region (wavelength 380 to 320 n).
The shielding of m) is insufficient, and in recent years, skin damage due to ultraviolet rays in the area A has become a problem. Therefore, the actual situation is that an organic ultraviolet absorber or the like is used in combination.
【０００３】上記問題を大幅に改善する超微粒子二酸化
チタンとして、本発明者等は、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３００〜８５０℃で焼成す
ることによって得られる鉄含有超微粒子二酸化チタン及
びチタン塩の酸性水溶液と鉄塩の酸性水溶液をアルカリ
物質の存在下で同時に加水分解させ、しかる後、加水分
解生成物を３００〜８００℃で焼成することによって得
られる鉄含有超微粒子二酸化チタンを提案した（特願平
４−１７０２５６）。As an ultrafine particle titanium dioxide which greatly improves the above problems, the present inventors have used a fine titania sol having a rutile nucleus as a substrate substance, and neutralizing a water-soluble salt of iron in the presence of the fine titania sol. Iron-containing ultrafine particles of titanium dioxide obtained by precipitating and coating hydrous iron oxide on the surface of titania and then calcining at 300 to 850 ° C. and an acidic aqueous solution of iron salt in the presence of an alkaline substance At the same time, an iron-containing ultrafine particle titanium dioxide obtained by simultaneously hydrolyzing the above, and then calcining the hydrolysis product at 300 to 800 ° C. was proposed (Japanese Patent Application No. 4-170256).
【０００４】ところが、本発明者等は、前記鉄含有超微
粒子二酸化チタンは、焼成、乾燥工程を経ており、一部
強く凝集したものが存在し、このものを用いて所望の化
粧料や塗料を調製しようとしても、特に化粧料等の調製
においては、強力な分散エネルギーを適用するすること
は、配合組成物の特性を損なうおそれがあるため嫌忌さ
れており、そのため十分なる紫外線遮蔽能を奏し得るに
は至っていない。また、従来の超微粒子二酸化チタンの
分散体を用いた場合には、特有の青み色調が強調され易
く、特に化粧料分野での使用が嫌忌されている。However, the inventors of the present invention have found that the iron-containing ultrafine titanium dioxide particles have undergone baking and drying steps, and some of them have strongly aggregated. Even when trying to prepare, especially in the preparation of cosmetics and the like, application of strong dispersion energy is disliked because it may impair the properties of the compounded composition, and therefore exhibits sufficient ultraviolet shielding ability. I haven't got it. Further, when a conventional dispersion of ultrafine particles of titanium dioxide is used, a peculiar bluish color tone is easily emphasized, and its use in the field of cosmetics is particularly disliked.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、青みの色調
を与えないという優れた特徴をもつ鉄含有超微粒子二酸
化チタンについて、化粧料、塗料に配合した時に、比較
的簡単な分散処理操作で高分散度に配合し得、非常に優
れた紫外線遮蔽能を付与し得る分散体を提供することに
ある。DISCLOSURE OF THE INVENTION The present invention relates to an iron-containing ultrafine titanium dioxide having an excellent feature that it does not give a bluish color tone, when it is blended in cosmetics and paints by a relatively simple dispersion treatment operation. An object of the present invention is to provide a dispersion which can be blended with a high degree of dispersion and can impart a very excellent ultraviolet ray shielding ability.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、鉄含有超
微粒子二酸化チタンについて、化粧料、塗料に配合した
時に、本来有する紫外線遮蔽能を、完全に発揮するよう
な形態を種々検討した。その結果、配合しようとする系
に適した媒液中に、分散剤を用いて予め良く分散させた
形態であれば、前記問題点がいずれも解決し得るのに加
え、配合した系の安定性向上、化粧料に配合したときの
伸びの良さ等の使用感の向上等、従来技術にない優れた
効果があるとの知見を得、本発明を完成した。本発明の
鉄含有超微粒子二酸化チタン分散体は、配合しようとす
る系に適した媒液、鉄含有超微粒子二酸化チタン、及び
この粒子を分散せしめる分散剤で構成されている。[Means for Solving the Problems] The inventors of the present invention have studied various forms of iron-containing ultrafine titanium dioxide particles in which the ultraviolet ray-shielding ability originally possessed when blended into cosmetics and paints is fully exerted. . As a result, in the case of a form in which a dispersant is well dispersed in a liquid medium suitable for the system to be blended, all the above problems can be solved, and the stability of the blended system is improved. The present invention has been completed based on the finding that there are excellent effects not found in the prior art such as improvement and improvement in feeling of use such as good elongation when blended in cosmetics. The iron-containing ultrafine particle titanium dioxide dispersion of the present invention comprises a liquid medium suitable for the system to be blended, iron-containing ultrafine particle titanium dioxide, and a dispersant for dispersing the particles.
【０００７】水分散体の配合としては、鉄含有超微粒子
二酸化チタン３０〜７０重量部、望ましくは４０〜７０
重量部と、分散剤が、分散剤／鉄含有超微粒子二酸化チ
タンとして０．５〜１０重量％であり、油分散体の配合
としては、鉄含有超微粒子二酸化チタン３０〜７０重量
部、望ましくは４０〜７０重量部と、分散剤が、分散剤
／鉄含有超微粒子二酸化チタンとして１〜３０重量％で
ある。The composition of the aqueous dispersion is 30 to 70 parts by weight of iron-containing ultrafine titanium dioxide, preferably 40 to 70 parts by weight.
0.5 parts by weight of the dispersant / iron-containing ultrafine particle titanium dioxide as a dispersant, and 30 to 70 parts by weight of the iron-containing ultrafine particle titanium dioxide, preferably, the oil dispersion is blended. 40 to 70 parts by weight, and the dispersant is 1 to 30% by weight as the dispersant / iron-containing ultrafine titanium dioxide.
【０００８】本発明の鉄含有超微粒子二酸化チタン分散
体における鉄含有超微粒子二酸化チタンは、平均単一粒
子径が０．０１〜０．１μｍであり、その結晶内部に鉄
成分をＦｅ換算でＴｉＯ2 に対して１〜３０重量％含有
する。The iron-containing ultrafine-particle titanium dioxide in the iron-containing ultrafine-particle titanium dioxide dispersion of the present invention has an average single particle diameter of 0.01 to 0.1 μm, and the iron component inside the crystal is TiO in terms of Fe. It is contained in an amount of 1 to 30% by weight based on 2 .
【０００９】この鉄含有超微粒子二酸化チタンは、例え
ば、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、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、被覆させ、次に焼成し、粉砕することによ
って得られる。また、例えば、チタン塩の酸性水溶液と
鉄塩の酸性水溶液とをアルカリの存在下で加水分解さ
せ、次に得られた加水分解生成物沈澱を焼成し、粉砕す
ることによっても得られる。この鉄含有超微粒子二酸化
チタンは、結晶内部に鉄成分が固溶しているために、
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、紫外線
Ａ領域の遮蔽能力が著しく向上し、青みの色調を示し
にくい等の優れた性能を備えている。This iron-containing ultrafine titanium dioxide is obtained, for example, by using a fine titania sol having a rutile nucleus as a base particle, and precipitating and coating an iron oxide or a hydrous oxide on the surface of this titania, followed by firing, Obtained by crushing. It can also be obtained, for example, by hydrolyzing an acidic aqueous solution of titanium salt and an acidic aqueous solution of iron salt in the presence of alkali, and then calcining and pulverizing the obtained hydrolysis product precipitate. This iron-containing ultrafine particle titanium dioxide has an iron component as a solid solution inside the crystal,
Even when blended in cosmetics or paints under strong dispersion conditions, the iron component and titanium dioxide do not separate into different colors, the shielding ability in the ultraviolet A region is significantly improved, and excellent performance such as difficulty in showing a bluish color tone is achieved. I have it.
【００１０】本発明のチタンの鉄含有超微粒子二酸化チ
タンにおける媒液は、配合しようとする化粧料、塗料に
合わせて選択すればよい。この媒液は、水、植物油、動
物油、鉱油、シリコーン油類のいずれに属するものであ
ってもよいが、粘度が１０００ｃｐを越えるものは、分
散体製造の際の粉砕工程がある程度の流動性を必要とす
ることから好ましくない。The liquid medium for the iron-containing ultrafine titanium dioxide particles of titanium according to the present invention may be selected according to the cosmetic and paint to be blended. This medium may belong to any of water, vegetable oils, animal oils, mineral oils, and silicone oils. However, if the viscosity exceeds 1000 cp, the pulverization step in the production of the dispersion will give a certain degree of fluidity. It is not preferable because it is necessary.
【００１１】本発明の鉄含有超微粒子二酸化チタンにお
ける分散剤は、媒液に可溶で、配合しようとする化粧
料、塗料に適合するものであるのが望ましい。媒液が水
であれば、縮合リン酸化合物、ポリカルボン酸化合物、
アミノ酸化合物、ポリオキシエチレンアルキルエーテ
ル、アミノアルコール等が分散剤として用いられる。媒
液が油であれば、ポリオキシエチレンアルキルエーテ
ル、ソルビタン脂肪酸エステル、ポリオキシエチレンア
ルキルリン酸エステル、脂肪酸アルカノールアミド、ポ
リエーテル変成シリコーン油、シリコーン樹脂等が分散
剤として用いられる。これらの分散剤は、１種のものに
限定する必要はなく、２種以上のものを組み合わせて使
用してもよい。また、必要に応じて防腐剤、例えばアル
キルパラベン類などを、さらには必要に応じ消泡剤、例
えばシリコン化合物や界面活性剤などを添加することが
できる。The dispersant in the iron-containing ultrafine titanium dioxide of the present invention is preferably soluble in a liquid medium and compatible with the cosmetic or paint to be blended. If the liquid medium is water, a condensed phosphoric acid compound, a polycarboxylic acid compound,
Amino acid compounds, polyoxyethylene alkyl ethers, amino alcohols and the like are used as dispersants. If the liquid medium is an oil, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene alkyl phosphate ester, fatty acid alkanolamide, polyether modified silicone oil, silicone resin and the like are used as the dispersant. These dispersants are not limited to one type, and two or more types may be used in combination. If necessary, a preservative such as an alkylparaben can be added, and if necessary, an antifoaming agent such as a silicon compound or a surfactant can be added.
【００１２】本発明の鉄含有超微粒子二酸化チタン分散
剤における鉄含有超微粒子二酸化チタンは、分散剤との
親和性、耐候性等を向上させる目的で、アルミニウム、
チタン、ジルコニウム、ケイ素、亜鉛、スズ等の酸化物
または水酸化物で表面を被覆してもよい。さらに、化粧
料や塗料分野で使用される種々の有機系処理剤、例えば
カルボン酸類、ポリオール類、アミン類、シロキサン化
合物、シランカップリング剤などの有機物の少なくとも
１種で被覆されてもよい。その場合、化粧料、塗料への
分散性や塗膜の耐久性を一層向上させることができる。The iron-containing ultrafine particle titanium dioxide in the iron-containing ultrafine particle titanium dioxide dispersant of the present invention is made of aluminum, for the purpose of improving affinity with the dispersant, weather resistance and the like.
The surface may be coated with an oxide or hydroxide of titanium, zirconium, silicon, zinc, tin or the like. Further, it may be coated with various organic treatment agents used in the field of cosmetics and coating materials, for example, at least one organic material such as carboxylic acids, polyols, amines, siloxane compounds, and silane coupling agents. In that case, the dispersibility in the cosmetics and paints and the durability of the coating film can be further improved.
【００１３】次に、本発明の分散体の製造方法について
述べる。本発明の分散体は、特定の分散剤、媒液及び鉄
含有超微粒子二酸化チタンを羽根型攪拌機、ディスパ
ー、ホモミキサー等を用いて予備混合した後、サンドミ
ル、ペブルミル、ディスクミル等の粉砕機を用いて、鉄
含有超微粒子二酸化チタンを分散せしめることにより得
られる。なお、粉砕機の種類、粉砕メディアの選定、最
適粉砕条件の設定は、高度な分散体を調製する上で重要
であるが、例えば竪型、横型のサンドミルで直径０．５
ｍｍのジルコニアビーズを用いて行うのが望ましい。Next, a method for producing the dispersion of the present invention will be described. The dispersion of the present invention is a specific dispersant, a medium liquid, and iron-containing ultrafine titanium dioxide particles, which are premixed using a blade stirrer, a disper, a homomixer, and then a pulverizer such as a sand mill, a pebble mill, and a disc mill. It is obtained by dispersing ultrafine titanium dioxide containing iron. The type of crusher, selection of crushing media, and setting of optimum crushing conditions are important for preparing advanced dispersions. For example, a vertical or horizontal sand mill has a diameter of 0.5.
It is desirable to use mm zirconia beads.
【００１４】予備混合を均一に且つ短時間で行うこと
は、最終的に得られる分散体の品質及び生産性の面から
重要であり、そのためには分散剤の性質に合った混合方
法を選ぶ必要がある。分散剤が媒液に易溶であれば、予
め媒液に分散剤を溶解し、次に鉄含有超微粒子二酸化チ
タンを投入、混合するのが好ましい。分散剤が難溶性の
粉末であれば、分散剤と鉄含有超微粒子二酸化チタン粉
末を予め乾式混合し、これに媒液に投入、混合するのが
好ましい。It is important to carry out the pre-mixing uniformly and in a short time from the viewpoint of quality and productivity of the finally obtained dispersion, and for that purpose, it is necessary to select a mixing method suitable for the properties of the dispersant. There is. If the dispersant is readily soluble in the liquid medium, it is preferable to dissolve the dispersant in the liquid medium in advance and then add and mix the iron-containing ultrafine titanium dioxide. If the dispersant is a sparingly soluble powder, it is preferable to dry-mix the dispersant and the iron-containing ultrafine titanium dioxide powder in advance, and then add and mix them in the medium.
【００１５】また、媒液が水である場合、鉄含有超微粒
子二酸化チタンは、その工程途中の仕上げ乾燥前のケー
キを使用してもよい。この場合、乾燥による強い凝集を
避けることができ、分散体製造時の粉砕工程を簡略化で
きる。When the liquid medium is water, the iron-containing ultrafine particle titanium dioxide may be a cake before finish drying during the process. In this case, strong agglomeration due to drying can be avoided, and the crushing process at the time of manufacturing the dispersion can be simplified.
【００１６】このようにして得られた鉄含有超微粒子二
酸化チタン分散体は、鉄含有超微粒子二酸化チタンを非
常によく分散した状態で含有するため、化粧料、塗料に
配合すると、本来有する優れた紫外線遮蔽能を十分に発
揮するのに加え、配合した系の安定性向上、化粧品の場
合には、その伸びの良さ等の使用感の向上の効果を発現
する。The iron-containing ultrafine particle titanium dioxide dispersion thus obtained contains the iron-containing ultrafine particle titanium dioxide in a very well-dispersed state. In addition to sufficiently exerting the ultraviolet ray shielding ability, it exhibits the effects of improving the stability of the compounded system and improving the feeling of use such as good elongation in the case of cosmetics.
【００１７】鉄含有超微粒子二酸化チタン分散体は、鉄
含有超微粒子二酸化チタンの分散に非常に適した条件で
作製された後、所望の系に配合されるため、本来有する
紫外線遮蔽能が十分に発揮される。これに対し、通常、
化粧品や塗料に粉末を配合するような方法で鉄含有超微
粒子二酸化チタンを配合しても本来有する紫外線遮蔽能
が十分に発揮されないことが多い。本発明の鉄含有超微
粒子二酸化チタン分散体を日焼け止め化粧料として利用
する場合には、例えば油性成分、保湿剤、界面活性剤、
顔料、香料、防腐剤、水、アルコール類、増粘剤等と配
合し、ローション状、クリーム状、ペースト状、スティ
ック状、乳液状など、各種の形態で用いることができ
る。Since the iron-containing ultrafine particle titanium dioxide dispersion is prepared under conditions very suitable for dispersion of the iron-containing ultrafine particle titanium dioxide, and then blended into a desired system, the ultraviolet ray-shielding ability originally possessed is sufficient. To be demonstrated. On the other hand, usually
Even if iron-containing ultrafine particle titanium dioxide is blended by a method of blending powder into cosmetics or paint, the ultraviolet ray-shielding ability originally possessed is often not sufficiently exhibited. When the iron-containing ultrafine particle titanium dioxide dispersion of the present invention is used as a sunscreen cosmetic, for example, an oily component, a moisturizer, a surfactant,
It can be mixed with pigments, fragrances, preservatives, water, alcohols, thickeners and the like and used in various forms such as lotions, creams, pastes, sticks and emulsions.
【００１８】紫外線防止用塗料として利用する場合に
は、例えばポリビニルアルコール樹脂、塩ビ−酢ビ樹
脂、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、アル
キッド樹脂、ポリエステル樹脂、エチレン酢酸ビニル共
重合体、アクリル−スチレン共重合体、繊維素樹脂、フ
ェノール樹脂、アミノ樹脂などに配合され、水又は溶媒
中で分散される。When it is used as a coating for preventing ultraviolet rays, for example, polyvinyl alcohol resin, vinyl chloride-vinyl acetate resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, polyester resin, ethylene vinyl acetate copolymer, acrylic-styrene. It is mixed with a copolymer, a fibrin resin, a phenol resin, an amino resin, etc., and dispersed in water or a solvent.
【００１９】本願発明の鉄含有超微粒子二酸化チタン分
散体は、前記した如く種々の日焼け止め化粧料や紫外線
防止用塗料に有用なものであるが、最近注目され普及し
つつある紫外線防止用木材塗料にも好適なものである。The iron-containing ultrafine particle titanium dioxide dispersion of the present invention is useful for various sunscreen cosmetics and UV-preventive coatings as described above, but it has recently been attracting attention and is becoming widespread. It is also suitable for
【００２０】[0020]
実施例１ 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７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６００℃
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、超微粒子二酸化チタンのスラリーとした。Example 1 While maintaining an aqueous titanium tetrachloride solution having a concentration of 200 g / l as TiO 2 , an aqueous sodium hydroxide solution was added to adjust the pH to 7.0 to obtain colloidal amorphous titanium hydroxide. Precipitation and subsequent aging gave rutile type titania sol. After washing this sol well,
2 was a hydrous titanium oxide aqueous slurry having a concentration of 200 g / l. The slurry was heated to 70 ° C. and stirred well, and the content of Fe was 7 wt% with respect to TiO 2.
Solution of ferrous sulfate (Fe concentration: 50 g / l) is added over 30 minutes, and then sodium hydroxide solution is added over 40 minutes to adjust the pH to 9 to hydrate the surface of the hydrous titanium oxide particles. Iron oxide was precipitated and coated. Then, it was aged for 60 minutes, filtered and washed. The obtained washed cake is 600 ° C.
It was calcined for 3 hours, dispersed in water, and wet-ground with a sand mill to obtain a slurry of ultrafine titanium dioxide.
【００２１】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。This slurry was heated to 70 ° C., and while stirring well, a 2.0% by weight aluminum sulfate aqueous solution as Al 2 O 3 with respect to TiO 2 was added thereto over 30 minutes, and subsequently, Add sodium hydroxide solution,
The pH was adjusted to 7.0 to precipitate and coat hydrous alumina.
【００２２】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０．０４μｍの鉄含有超微
粒子二酸化チタンを得た。After that, it is aged for 60 minutes, filtered, washed,
After drying, it was pulverized with a fluid energy mill to obtain ultrafine titanium dioxide containing iron having an average single particle diameter of 0.04 μm by an electron micrograph.
【００２３】この鉄含有超微粒子二酸化チタン５０重量
部とヘキサメタリン酸ナトリウム１重量部を乳鉢で混合
した後、精製水４９重量部に投入し、ディスパーで混合
した。次に、これをジルコンビーズを粉砕メディアとし
て用い、サンドミルで粉砕したところ、粘度９５ｃＰ、
ｐＨ８．２の水分散体（Ａ）を得た。50 parts by weight of this iron-containing ultrafine titanium dioxide and 1 part by weight of sodium hexametaphosphate were mixed in a mortar, then added to 49 parts by weight of purified water and mixed by a disper. Next, this was crushed by a sand mill using zircon beads as a crushing medium, and the viscosity was 95 cP.
An aqueous dispersion (A) having a pH of 8.2 was obtained.
【００２４】比較例１ 実施例１の鉄含有超微粒子二酸化チタンを粉末（Ｂ）と
して用いた。Comparative Example 1 The iron-containing ultrafine particle titanium dioxide of Example 1 was used as the powder (B).
【００２５】実施例２ 実施例１の水分散体作成前の乾燥、粉砕粉末４５重量部
を分散剤（トリメチルシロキシケイ酸）１５重量部と分
散媒（オクタメチルシクロテトラシロキサン）４０重量
部との混合液中にディスパーを用いて混合した。次に、
これをジルコンビーズを粉砕メディアとして用い、サン
ドミルで粉砕したところ、粘度１００ｃＰのシリコンオ
イル分散体（Ｃ）を得た。Example 2 45 parts by weight of dried and ground powder before preparation of the aqueous dispersion of Example 1 was mixed with 15 parts by weight of a dispersant (trimethylsiloxysilicic acid) and 40 parts by weight of a dispersion medium (octamethylcyclotetrasiloxane). The mixture was mixed using a disper. next,
This was crushed with a sand mill using zircon beads as a crushing medium to obtain a silicone oil dispersion (C) having a viscosity of 100 cP.
【００２６】[0026]
試験例１ 鉄含有超微粒子二酸化チタン水分散体（Ａ）及び粉末
（Ｂ）をそれぞれ下記の処方で合計量が１００重量部に
なるように配合して日焼け止めクリーム（Ｏ／Ｗエマル
ジョン）（ａ）及び（ｂ）を得た。 （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水分散体（Ａ） ６．０重量部 又は超微粒子二酸化チタン粉末（Ｂ） 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 残部 （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）を添加し日焼け止めクリームを調製し
た。Test Example 1 Iron-containing ultrafine particle titanium dioxide aqueous dispersion (A) and powder (B) were blended in the following formulations so that the total amount was 100 parts by weight, and a sunscreen cream (O / W emulsion) (a ) And (b) were obtained. (1) Stearic acid 2.5 parts by weight (2) White beeswax 3.5 parts by weight (3) Cetanol 3.5 parts by weight (4) Squalane 17.0 parts by weight (5) Glycerin monostearate 3.0 parts by weight (6) 6.0 parts by weight of ultrafine titanium dioxide aqueous dispersion (A) or 3.0 parts by weight of ultrafine titanium dioxide powder (B) (7) 0.1 parts by weight of methylparaben (8) 12.0 parts by weight of glycerin (9) Triethanolamine 1.0 parts by weight (10) Purified water balance (11) Perfume 0.3 parts by weight Components (1) to (6) heated and mixed at 80 ° C. to obtain components (7) to ( 10) is added to the mixture which is heated and mixed at 80 ° C., well mixed with a homomixer, and stirred vigorously. 45 ° C
(11) was added in the vicinity to prepare a sunscreen cream.
【００２７】試験例２ 鉄含有超微粒子二酸化チタンのシリコンオイル分散体
（Ｃ）及び粉末（Ｂ）をそれぞれ下記の処方で合計量が
１００重量部になるように配合して日焼け止めクリーム
（Ｗ／Ｏエマルジョン）（ｃ）及び（ｄ）を得た。 （１）オクタメチルシクロテトラシロキサン 残部 （２）ジメチルポリシロキサン １５．７重量部 （３）ポリオキシエチレン変性ジメチル ０．５重量部 ポリシロキサン （４）超微粒子二酸化チタン分散体（Ｃ） ６．７重量部 又は超微粒子二酸化チタン粉末（Ｂ） ３．０重量部 （５）ナイロンパウダー（粒子径５μｍ） １２．５重量部 （６）エタノール １０．０重量部 （７）グリセリン ２．５重量部 （８）精製水 ２７．５重量部 成分（１）〜（５）を混合してディスパーで分散したも
のに、予め混合した成分（６）〜（８）の混合物を攪拌
しながら徐々に添加して日焼け止めクリームを調製し
た。Test Example 2 Silicone oil dispersion (C) and powder (B) of ultrafine titanium dioxide containing iron were blended in the following formulations so that the total amount would be 100 parts by weight, and a sunscreen cream (W / O emulsion) (c) and (d) were obtained. (1) Octamethylcyclotetrasiloxane balance (2) Dimethylpolysiloxane 15.7 parts by weight (3) Polyoxyethylene-modified dimethyl 0.5 part by weight Polysiloxane (4) Ultrafine particle titanium dioxide dispersion (C) 6.7 Part by weight or ultrafine titanium dioxide powder (B) 3.0 parts by weight (5) Nylon powder (particle size 5 μm) 12.5 parts by weight (6) Ethanol 10.0 parts by weight (7) Glycerin 2.5 parts by weight ( 8) Purified water 27.5 parts by weight The components (1) to (5) are mixed and dispersed with a disper, and the mixture of the components (6) to (8) mixed in advance is gradually added while stirring. A sunscreen cream was prepared.
【００２８】評価方法１ 上記各クリームを石英ガラス上に２５μｍの膜厚となる
ように塗布し、分光光度計にて７５０〜３００ｎｍの透
過率を測定した。Evaluation Method 1 Each of the above creams was applied onto a quartz glass so as to have a film thickness of 25 μm, and the transmittance of 750 to 300 nm was measured with a spectrophotometer.
【００２９】評価方法２ 上記各クリームを２０〜５２歳の女性１０名に通常に使
用してもい、肌の上での伸びの良さの使用感を相互に評
価してもらった。以上の評価結果を表１に示した。Evaluation Method 2 Each of the above-mentioned creams was used by 10 women aged 20 to 52 years, and the feeling of extension on the skin was evaluated mutually. The above evaluation results are shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明で得られる鉄含有超微粒子二酸化
チタン分散体は、化粧料、塗料などに配合すると鉄含
有超微粒子二酸化チタンの有する紫外線遮蔽能が十分に
発揮されるものであり、また化粧料に配合した場合に
青みが抑えられた健康な肌色感や使用感、安定性等に一
層優れた効果を付与することができる。INDUSTRIAL APPLICABILITY The iron-containing ultrafine particle titanium dioxide dispersion obtained in the present invention is capable of sufficiently exerting the ultraviolet ray shielding ability of the iron-containing ultrafine particle titanium dioxide when blended in cosmetics, paints and the like. When blended in a cosmetic composition, it is possible to impart more excellent effects such as a healthy flesh tones with suppressed bluishness, a feeling of use, and stability.
Claims (5)
化チタン粒子及び分散剤を含む水分散体で、該鉄含有二
酸化チタンが、平均単一粒子径０．０１〜０．１μｍを
もち、その結晶内部に鉄成分をＦｅ換算でＴｉＯ2 に対
して１〜３０重量％含有する鉄含有超微粒子二酸化チタ
ン分散体。1. An aqueous dispersion comprising water as a dispersion medium, iron-containing ultrafine titanium dioxide particles and a dispersant, wherein the iron-containing titanium dioxide has an average single particle diameter of 0.01 to 0.1 μm. An iron-containing ultrafine particle titanium dioxide dispersion containing an iron component in the crystal in an amount of 1 to 30% by weight based on TiO 2 in terms of Fe.
化チタン粒子及び分散剤を含む油分散体で、該鉄含有二
酸化チタンが、平均単一粒子径０．０１〜０．１μｍを
もち、その結晶内部に鉄成分をＦｅ換算でＴｉＯ2 に対
して１〜３０重量％含有する鉄含有超微粒子二酸化チタ
ン分散体。2. An oil dispersion comprising oil as a dispersion medium, iron-containing ultrafine titanium dioxide particles and a dispersant, wherein the iron-containing titanium dioxide has an average single particle diameter of 0.01 to 0.1 μm, An iron-containing ultrafine particle titanium dioxide dispersion containing an iron component in the crystal in an amount of 1 to 30% by weight based on TiO 2 in terms of Fe.
請求項２に記載の鉄含有超微粒子二酸化チタン分散体。3. The iron-containing ultrafine particle titanium dioxide dispersion according to claim 2, wherein the oil as the dispersion medium is a silicone oil.
化チタン分散体を含有する日焼け止め化粧料。4. A sunscreen cosmetic containing the iron-containing ultrafine particle titanium dioxide dispersion according to claim 1.
化チタン分散体を含有する紫外線防止塗料。5. An anti-UV coating material containing the iron-containing ultrafine particle titanium dioxide dispersion according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34143093A JP3115760B2 (en) | 1993-12-10 | 1993-12-10 | Iron-containing ultrafine titanium dioxide dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34143093A JP3115760B2 (en) | 1993-12-10 | 1993-12-10 | Iron-containing ultrafine titanium dioxide dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07165534A true JPH07165534A (en) | 1995-06-27 |
| JP3115760B2 JP3115760B2 (en) | 2000-12-11 |
Family
ID=18346020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34143093A Expired - Lifetime JP3115760B2 (en) | 1993-12-10 | 1993-12-10 | Iron-containing ultrafine titanium dioxide dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3115760B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1121224A (en) * | 1997-07-04 | 1999-01-26 | Nippon Shikizai Kogyo Kenkyusho:Kk | Cosmetic material |
| WO2003083008A1 (en) * | 2002-03-29 | 2003-10-09 | Isi Corporation | Ultraviolet shielding powder, dispersion having the powder, ultraviolet shielding film and ultraviolet shielding container |
| DE10057509B4 (en) * | 2000-11-21 | 2006-04-06 | Chemische Werke Brockhues Ag | Transparent pigments |
| JP2006131715A (en) * | 2004-11-04 | 2006-05-25 | Ishihara Sangyo Kaisha Ltd | Titanium dioxide pigment |
| JP2008255072A (en) * | 2007-04-09 | 2008-10-23 | Kao Corp | Resin particle |
| CN109438990A (en) * | 2018-11-16 | 2019-03-08 | 山东道安新材料有限公司 | A kind of compound silicone oil emulsion and preparation method thereof |
| JP2020529392A (en) * | 2017-07-31 | 2020-10-08 | リ, ホ ソンLEE, Ho Seog | Compositions for the prevention or treatment of scars |
-
1993
- 1993-12-10 JP JP34143093A patent/JP3115760B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1121224A (en) * | 1997-07-04 | 1999-01-26 | Nippon Shikizai Kogyo Kenkyusho:Kk | Cosmetic material |
| DE10057509B4 (en) * | 2000-11-21 | 2006-04-06 | Chemische Werke Brockhues Ag | Transparent pigments |
| WO2003083008A1 (en) * | 2002-03-29 | 2003-10-09 | Isi Corporation | Ultraviolet shielding powder, dispersion having the powder, ultraviolet shielding film and ultraviolet shielding container |
| JP2006131715A (en) * | 2004-11-04 | 2006-05-25 | Ishihara Sangyo Kaisha Ltd | Titanium dioxide pigment |
| JP4668583B2 (en) * | 2004-11-04 | 2011-04-13 | 石原産業株式会社 | Titanium dioxide pigment |
| JP2008255072A (en) * | 2007-04-09 | 2008-10-23 | Kao Corp | Resin particle |
| JP2020529392A (en) * | 2017-07-31 | 2020-10-08 | リ, ホ ソンLEE, Ho Seog | Compositions for the prevention or treatment of scars |
| US11497702B2 (en) | 2017-07-31 | 2022-11-15 | Ho Seog LEE | Composition for preventing or treating scars |
| CN109438990A (en) * | 2018-11-16 | 2019-03-08 | 山东道安新材料有限公司 | A kind of compound silicone oil emulsion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3115760B2 (en) | 2000-12-11 |
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