JP3115760B2 - Iron-containing ultrafine titanium dioxide dispersion - Google Patents
Iron-containing ultrafine titanium dioxide dispersionInfo
- Publication number
- JP3115760B2 JP3115760B2 JP34143093A JP34143093A JP3115760B2 JP 3115760 B2 JP3115760 B2 JP 3115760B2 JP 34143093 A JP34143093 A JP 34143093A JP 34143093 A JP34143093 A JP 34143093A JP 3115760 B2 JP3115760 B2 JP 3115760B2
- Authority
- JP
- Japan
- Prior art keywords
- iron
- titanium dioxide
- ultrafine titanium
- dispersion
- 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.)
- Expired - Lifetime
Links
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- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
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 of iron-containing ultrafine titanium dioxide in water or oil, a sunscreen cosmetic using the same, and an ultraviolet ray preventive paint.
【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 titanium dioxide having a single particle size of about 0.1 μm or less, when incorporated into a resin film or molded product, transmits visible light and thus exhibits transparency. It is well known that it exhibits properties different from those of pigment-grade titanium dioxide having a single particle size of 0.15 to 0.5 μm, such as protection of substances which change color or deteriorate by ultraviolet rays. For this reason, utilization as a sunscreen cosmetic for making use of natural skin color and preventing sunburn due to ultraviolet rays has recently attracted particular attention. However,
Conventionally, commercially available ultrafine 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 containing ultrafine titanium dioxide is used. When applied to the skin, it often has the disadvantage of causing strong scattering of bluish shades, giving bluish tones and, thus, making the skin look unhealthy. Further, the conventional ultrafine titanium dioxide sufficiently shields the light beam having the wavelength in the ultraviolet B region (wavelength 320 to 290 nm), but the light beam having the wavelength in the ultraviolet A region (wavelength 380 to 320 n).
m) is insufficiently shielded, and in recent years, skin damage due to ultraviolet rays in the A region has become a problem. For this reason, it is a fact that organic ultraviolet absorbers and the like are 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 ultrafine titanium dioxide which significantly improves the above problem, the present inventors have used a fine titania sol having a rutile nucleus as a base material, and neutralized a water-soluble salt of iron in the presence of the fine titania sol. Precipitating and coating the surface of titania with hydrated iron hydroxide, and then sintering at 300 to 850 ° C to obtain an iron-containing ultrafine titanium dioxide and an acidic aqueous solution of a titanium salt and an acidic aqueous solution of an iron salt in the presence of an alkaline substance , And thereafter, an iron-containing ultrafine titanium dioxide obtained by 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。[0004] However, the present inventors have reported that the above-mentioned iron-containing ultrafine titanium dioxide has undergone a baking and drying process, and that some of the iron-containing ultrafine titanium dioxide is strongly agglomerated. Even when trying to prepare, especially in the preparation of cosmetics and the like, applying strong dispersing energy is disliked because it may impair the properties of the blended composition, and therefore has sufficient ultraviolet shielding ability I haven't gotten it. In addition, when a conventional dispersion of ultrafine titanium dioxide is used, a specific bluish tone is easily emphasized, and use in the cosmetics field 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。SUMMARY OF THE INVENTION The present invention relates to an ultra-fine iron-containing titanium dioxide having an excellent feature of not giving a bluish color tone, when it is blended into 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 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 present inventors have studied various forms of ultrafine iron-containing titanium dioxide which fully exhibit the inherent ultraviolet shielding ability when blended in cosmetics and paints. . As a result, in a medium suitable for the system to be blended, if the form is well dispersed in advance using a dispersing agent, in addition to solving any of the above problems, the stability of the blended system It has been found that the present invention has excellent effects not found in the prior art, such as improvement and improvement in use feeling such as good elongation when blended in cosmetics, and completed the present invention. The iron-containing ultrafine titanium dioxide dispersion of the present invention comprises a medium suitable for the system to be blended, iron-containing ultrafine 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。[0007] The aqueous dispersion is mixed with 30 to 70 parts by weight of iron-containing ultrafine titanium dioxide, preferably 40 to 70 parts by weight.
Parts by weight and the dispersant are 0.5 to 10% by weight as a dispersant / iron-containing ultrafine titanium dioxide, and 30 to 70 parts by weight, preferably iron-containing ultrafine titanium dioxide, as an oil dispersion. 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。[0008] The iron-containing ultrafine titanium dioxide in the iron-containing ultrafine titanium dioxide dispersion of the present invention has an average single particle diameter of 0.01 to 0.1 µm, and the iron component is contained in the crystal in the form of TiO in terms of Fe. 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。The ultrafine titanium dioxide containing iron is, for example, using a fine titania sol having a rutile nucleus as a base particle, and precipitating and coating an oxide of iron or a hydrated oxide on the surface of the titania, followed by firing, Obtained by grinding. Further, for example, it can also be obtained by hydrolyzing an acidic aqueous solution of a titanium salt and an acidic aqueous solution of an iron salt in the presence of an alkali, and then calcining and pulverizing the obtained hydrolysis product precipitate. This iron-containing ultrafine titanium dioxide has a solid solution of iron component inside the crystal,
Even when blended into cosmetics or paints under strong dispersion conditions, color separation between the iron component and titanium dioxide does not occur, and the ability to block the ultraviolet A region is remarkably improved. Have.
【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 medium in the iron-containing ultrafine titanium dioxide of the present invention may be selected according to the cosmetics and paints to be blended. This medium may belong to any of water, vegetable oil, animal oil, mineral oil and silicone oil, but those having a viscosity of more than 1000 cp have a certain degree of fluidity in the pulverization step in the production of the dispersion. 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 desirably soluble in a medium and compatible with cosmetics and paints to be blended. If the 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. When the medium is oil, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene alkyl phosphate, fatty acid alkanolamide, polyether modified silicone oil, silicone resin and the like are used as dispersants. These dispersants need not be limited to one kind, and two or more kinds may be used in combination. Further, a preservative, for example, alkyl parabens, and the like, and an antifoaming agent, for example, a silicon compound and a surfactant can be added as needed.
【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。[0012] The iron-containing ultrafine titanium dioxide in the iron-containing ultrafine titanium dioxide dispersant of the present invention contains aluminum, ultrafine titanium dioxide for improving the affinity with the dispersant, the 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 treating agents used in the field of cosmetics and paints, for example, at least one kind of organic substances such as carboxylic acids, polyols, amines, siloxane compounds and silane coupling agents. In that case, the dispersibility in 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 solution and iron-containing ultrafine titanium dioxide are premixed using a blade-type stirrer, a disper, a homomixer, etc. It is obtained by dispersing iron-containing ultrafine titanium dioxide. The type of crusher, selection of crushing media, and setting of optimum crushing conditions are important in preparing an advanced dispersion. For example, a vertical or horizontal sand mill with a diameter of 0.5 mm is used.
It is preferable to use zirconia beads of mm.
【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 perform the pre-mixing uniformly and in a short time in view of the 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 easily soluble in the medium, it is preferable to dissolve the dispersant in the medium in advance, and then add and mix the iron-containing ultrafine titanium dioxide particles. If the dispersing agent is a hardly soluble powder, it is preferable to dry-mix the dispersing agent and the iron-containing ultrafine titanium dioxide powder in advance, and then put the mixture into a medium and mix.
【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。In the case where the medium is water, the iron-containing ultrafine titanium dioxide may be a cake before finishing and drying in the middle of the process. In this case, strong agglomeration due to drying can be avoided, and the pulverizing step 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 titanium dioxide dispersion thus obtained contains the iron-containing ultrafine titanium dioxide in a very well dispersed state. In addition to sufficiently exhibiting the ultraviolet shielding ability, it exhibits the effect of improving the stability of the compounded system and, in the case of cosmetics, improving the usability such as good elongation.
【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。The iron-containing ultrafine titanium dioxide dispersion is prepared under conditions very suitable for dispersing the iron-containing ultrafine titanium dioxide, and then blended into a desired system. Be demonstrated. In contrast,
Even if iron-containing ultrafine titanium dioxide is mixed in such a way that powder is mixed into cosmetics and paints, the inherent ultraviolet shielding ability is often not sufficiently exhibited. When utilizing the iron-containing ultrafine titanium dioxide dispersion of the present invention as a sunscreen cosmetic, for example, an oily component, a humectant, 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 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, acryl-styrene It is mixed with a copolymer, a cellulose resin, a phenol resin, an amino resin, and the like, 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。Although the iron-containing ultrafine titanium dioxide dispersion of the present invention is useful for various sunscreen cosmetics and UV protection paints as described above, wood paints for UV protection have recently attracted attention and are becoming popular. It is also suitable.
【0020】[0020]
【実施例】 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 solution of titanium tetrachloride at a concentration of 200 g / l as TiO 2 at room temperature, an aqueous solution of sodium hydroxide was added to adjust the pH to 7.0, and the colloidal amorphous Hydrous titanium oxide was precipitated and subsequently 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, 7% 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. 600 ° C of the obtained washed cake
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。The slurry is heated to 70 ° C., and while stirring well, a 2.0% by weight aqueous solution of aluminum sulfate as Al 2 O 3 with respect to TiO 2 is added thereto over 30 minutes. Add sodium hydroxide solution,
The pH was adjusted to 7.0, and the hydrated alumina was precipitated and coated.
【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, aging for 60 minutes, filtration and washing,
After drying, the powder was pulverized with a fluid energy mill to obtain ultrafine iron-containing titanium dioxide having an average single particle diameter of 0.04 μm by 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。After 50 parts by weight of the iron-containing ultrafine titanium dioxide and 1 part by weight of sodium hexametaphosphate were mixed in a mortar, the mixture was added to 49 parts by weight of purified water and mixed with a disper. Next, when this was pulverized with a sand mill using zircon beads as a pulverizing medium, 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 titanium dioxide of Example 1 was used as a 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 the dried and ground powder before the 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 pulverized with a sand mill using zircon beads as a pulverizing medium to obtain a silicon 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 A sunscreen cream (O / W emulsion) (a) was prepared by blending the iron-containing ultrafine titanium dioxide aqueous dispersion (A) and the powder (B) in the following formulation so that the total amount would be 100 parts by weight. ) And (b) were obtained. (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 aqueous dispersion (A) 6.0 parts by weight or ultrafine titanium dioxide powder (B) 3.0 parts by weight (7) Methylparaben 0.1 parts by weight (8) Glycerin 12.0 parts by weight (9) 1.0 part by weight of triethanolamine (10) Remaining purified water (11) 0.3 part by weight of fragrance Components (1) to (6) obtained by heating and mixing at 80 ° C. are mixed with components (7) to ( 10) is added to the mixture obtained by heating at 80 ° C., mixed well with a homomixer, and stirred vigorously. 45 ° C
In the vicinity, (11) was added 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 A sunscreen cream (W / W) was prepared by blending a silicon oil dispersion (C) and a powder (B) of iron-containing ultrafine titanium dioxide in the following formulation so that the total amount would be 100 parts by weight. O emulsion) (c) and (d) were obtained. (1) Octamethylcyclotetrasiloxane balance (2) Dimethylpolysiloxane 15.7 parts by weight (3) Polyoxyethylene-modified dimethyl 0.5 parts by weight polysiloxane (4) Ultrafine titanium dioxide dispersion (C) 6.7 Parts by weight or ultrafine titanium dioxide powder (B) 3.0 parts by weight (5) Nylon powder (particle diameter 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 To components obtained by mixing components (1) to (5) and dispersing them with a disper, gradually add a mixture of components (6) to (8) mixed in advance 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 on quartz glass so as to have a thickness of 25 μm, and the transmittance at 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 creams was commonly used by 10 women aged 20 to 52 years, and the use feeling of good stretch on the skin was mutually evaluated. Table 1 shows the above evaluation results.
【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。The iron-containing ultrafine titanium dioxide dispersion obtained by the present invention, when blended in cosmetics, paints, etc., can sufficiently exhibit the ultraviolet shielding ability of the iron-containing ultrafine titanium dioxide. When blended in cosmetics, it is possible to impart more excellent effects such as a healthy skin tone with reduced blueness, a feeling of use, and stability.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭48−67196(JP,A) 特開 昭64−7941(JP,A) 特開 昭64−3020(JP,A) (58)調査した分野(Int.Cl.7,DB名) A61K 7/02 A61K 7/42 C01G 23/053 C09C 1/36 C09D 5/33 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-48-67196 (JP, A) JP-A 64-7941 (JP, A) JP-A 64-3020 (JP, A) (58) Field (Int.Cl. 7 , DB name) A61K 7/02 A61K 7/42 C01G 23/053 C09C 1/36 C09D 5/33
Claims (7)
二酸化チタンを30〜70重量部及び分散剤を0.15
〜7重量部含む水分散体であって、該鉄含有二酸化チタ
ンが、ルチル核を有する微小チタニアゾルのチタニアの
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、粉砕して得られ、かつ平均単一粒子径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%含有することを
特徴とする鉄含有超微粒子二酸化チタン分散体。[Claim 1 wherein] in water as a dispersion medium, 30 to 70 parts by weight of iron-containing ultrafine titanium dioxide and dispersing agents 0.15
7-A aqueous dispersion containing parts, iron-containing titanium dioxide, the titania fine titania sol comprising rutile nuclei
Precipitate and coat iron oxide or hydrated oxide on the surface ,
It is then calcined and pulverized and has an average single particle size of 0.1.
And the iron component is Fe
In that it contains 1 to 30 wt% with respect to TiO2 in terms of
An iron-containing ultrafine titanium dioxide dispersion.
二酸化チタンを30〜70重量部及び分散剤を0.3〜
21重量部含む油分散体であって、該鉄含有二酸化チタ
ンが、ルチル核を有する微小チタニアゾルのチタニアの
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、粉砕して得られ、かつ平均単一粒子径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%含有することを
特徴とする鉄含有超微粒子二酸化チタン分散体。Wherein in oil as a dispersion medium, 0.3 to 30 to 70 parts by weight and a dispersant iron containing ultrafine titanium dioxide
21 be an oil dispersion comprising parts, iron-containing titanium dioxide, the titania fine titania sol comprising rutile nuclei
Precipitate and coat iron oxide or hydrated oxide on the surface ,
It is then calcined and pulverized and has an average single particle size of 0.1.
And the iron component is Fe
In that it contains 1 to 30 wt% with respect to TiO2 in terms of
An iron-containing ultrafine titanium dioxide dispersion.
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 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 comprising the iron-containing ultrafine titanium dioxide dispersion of claim 1 or 2.
化チタン分散体を含有する紫外線防止塗料。5. An anti-ultraviolet coating comprising the iron-containing ultrafine titanium dioxide dispersion of claim 1 or 2.
7重量部及びルチル核を有する微小チタニアゾルのチタTitan of fine titania sol having 7 parts by weight and rutile nucleus
ニアの表面に鉄の酸化物または含水酸化物を沈殿Precipitation of iron oxide or hydrated oxide on the near surface 、, 被覆Coating
させ、次に焼成し、粉砕して得られる平均単一粒子径And then calcined and crushed to obtain the average single particle size
0.01〜0.1μmをもち、その結晶内部に鉄成分をIt has a thickness of 0.01 to 0.1 μm, and contains an iron component inside the crystal.
Fe換算でTiO2に対して1〜30重量%含有する鉄Iron containing 1 to 30% by weight of TiO2 in terms of Fe
含有超微粒子二酸化チタン30〜70重量部を予備混合30-70 parts by weight of ultrafine titanium dioxide
した後、粉砕機を用いて鉄含有超微粒子二酸化チタンをAfter that, the iron-containing ultrafine titanium dioxide is
分散せしめることを特徴とする請求項1に記載の鉄含有The iron-containing composition according to claim 1, wherein the composition is dispersed.
超微粒子二酸化チタン分散体の製造方法。Method for producing ultrafine titanium dioxide dispersion.
1重量部及びルチル核を1 part by weight and rutile nucleus 有する微小チタニアゾルのチタOf titania sol with fine titania
ニアの表面に鉄の酸化物または含水酸化物を沈殿Precipitation of iron oxide or hydrated oxide on the near surface 、, 被覆Coating
させ、次に焼成し、粉砕して得られる平均単一粒子径And then calcined and crushed to obtain the average single particle size
0.01〜0.1μmをもち、その結晶内部に鉄成分をIt has a thickness of 0.01 to 0.1 μm, and contains an iron component inside the crystal.
Fe換算でTiO2に対して1〜30重量%含有する鉄Iron containing 1 to 30% by weight of TiO2 in terms of Fe
含有超微粒子二酸化チタン30〜70重量部を予備混合30-70 parts by weight of ultrafine titanium dioxide
した後、粉砕機を用いて鉄含有超微粒子二酸化チタンをAfter that, the iron-containing ultrafine titanium dioxide is
分散せしめることを特徴とする請求項2に記載の鉄含有3. The iron-containing composition according to claim 2, wherein the composition is dispersed.
超微粒子二酸化チタン分散体の製造方法。Method for producing ultrafine titanium dioxide dispersion.
Priority Applications (1)
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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 JPH07165534A (en) | 1995-06-27 |
JP3115760B2 true JP3115760B2 (en) | 2000-12-11 |
Family
ID=18346020
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JP34143093A Expired - Lifetime JP3115760B2 (en) | 1993-12-10 | 1993-12-10 | Iron-containing ultrafine titanium dioxide dispersion |
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JP (1) | JP3115760B2 (en) |
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JP3792843B2 (en) * | 1997-07-04 | 2006-07-05 | 株式会社日本色材工業研究所 | Cosmetics |
DE10057509B4 (en) * | 2000-11-21 | 2006-04-06 | Chemische Werke Brockhues Ag | Transparent pigments |
JPWO2003083008A1 (en) * | 2002-03-29 | 2005-08-04 | 有限会社アイエスアイ | Ultraviolet shielding powder, dispersion containing the powder, ultraviolet shielding film, and ultraviolet shielding container |
JP4668583B2 (en) * | 2004-11-04 | 2011-04-13 | 石原産業株式会社 | Titanium dioxide pigment |
JP5009028B2 (en) * | 2007-04-09 | 2012-08-22 | 花王株式会社 | Resin particles |
KR20190013101A (en) | 2017-07-31 | 2019-02-11 | 이호석 | Composition for preventing or treating scar |
CN109438990B (en) * | 2018-11-16 | 2021-02-02 | 山东道安新材料有限公司 | Composite silicone oil emulsion and preparation method thereof |
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- 1993-12-10 JP JP34143093A patent/JP3115760B2/en not_active Expired - Lifetime
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