JP3224750B2 - Fine particle titanium dioxide silicone dispersion - Google Patents
Fine particle titanium dioxide silicone dispersionInfo
- Publication number
- JP3224750B2 JP3224750B2 JP28913296A JP28913296A JP3224750B2 JP 3224750 B2 JP3224750 B2 JP 3224750B2 JP 28913296 A JP28913296 A JP 28913296A JP 28913296 A JP28913296 A JP 28913296A JP 3224750 B2 JP3224750 B2 JP 3224750B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- fine particle
- dispersion
- weight
- silicone
- 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
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- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、微粒子二酸化チタ
ンをシリコーン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 fine particle titanium dioxide is dispersed in silicone and a sunscreen cosmetic using the same.
【０００２】[0002]
【従来の技術】単一粒子径約０．１５μｍ以下の微粒子
二酸化チタンは、樹脂などの膜或いは成形物に配合する
と、紫外線を遮蔽して紫外線により変質する物質を保護
する一方、可視光線を透過して透明性を有するといった
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。更に、人体への作用が極めて低く、またそれ自体紫
外線や薬品などによる変質がほとんどないことから、微
粒子二酸化チタンは、安全性、安定性、透明性の高い紫
外線遮蔽剤として、塗料、化粧料、化学繊維に利用され
ている。ところで近年、塗料、化粧品には、耐水性、撥
水性、耐薬品性、耐候性に優れた材料として、シリコー
ンが多く利用されるようになってきた。とくに、化粧料
用には、耐水性などに加えて、肌に塗ったときの伸びの
よさ、さらっとした感触が、極めて優れていることか
ら、非常に注目されている。しかしながら、紫外線遮蔽
性を付与する目的で、シリコーン系の化粧料に二酸化チ
タンを配合しようとすると、二酸化チタン表面が親水性
であるのに対し、シリコーンが高い疎水性を有している
ことから、二酸化チタン粒子がシリコーンになじまずに
凝集してしまい、本来の透明性、紫外線遮蔽性が発揮さ
れないという問題が生じた。2. Description of the Related Art Fine particle titanium dioxide having a single particle diameter of about 0.15 μm or less, when incorporated into a film or a molded product such as a resin, shields ultraviolet rays and protects substances that are altered by ultraviolet rays, while transmitting visible light. It is well known that it exhibits different properties from pigment-grade titanium dioxide having a single particle size of 0.15 to 0.5 μm, such as transparency. Furthermore, since its action on the human body is extremely low, and itself is hardly deteriorated by ultraviolet rays or chemicals, particulate titanium dioxide is safe, stable, highly transparent as an ultraviolet shielding agent, for paints, cosmetics, Used in chemical fibers. In recent years, silicones have come to be widely used in paints and cosmetics as materials having excellent water resistance, water repellency, chemical resistance, and weather resistance. In particular, for cosmetics, in addition to water resistance and the like, it has attracted a great deal of attention because it is extremely excellent in elongation when applied to the skin and in a dry feel. However, when titanium dioxide is blended with silicone-based cosmetics for the purpose of imparting ultraviolet shielding properties, the surface of titanium dioxide is hydrophilic, whereas silicone has high hydrophobicity. The titanium dioxide particles aggregate without being compatible with the silicone, and a problem arises in that the original transparency and ultraviolet shielding properties are not exhibited.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、安全性、安
定性、透明性に優れた紫外線遮蔽剤である微粒子二酸化
チタンについて、シリコーン系の化粧料に配合したとき
に、比較的簡単な分散処理操作で高分散状態に配合し
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 a relatively simple dispersion of fine particle titanium dioxide, which is an ultraviolet ray shielding agent excellent in safety, stability and transparency, when blended in a silicone cosmetic. An object of the present invention is to provide a dispersion which can be blended in a highly dispersed state by a processing operation and can impart an extremely excellent ultraviolet shielding ability.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、微粒子二
酸化チタンについて、シリコーン系の化粧料に配合した
ときに、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、分散剤を用い、シリ
コーンを媒液として、予め良く分散させた形態であれ
ば、前記問題点を解決し得るのに加え、配合した化粧料
の安定性向上、伸びのよさなど使用感の向上など、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。Means for Solving the Problems The present inventors have studied various forms of titanium dioxide fine particles that when used in a silicone-based cosmetic, fully exhibit the inherent ultraviolet shielding ability. As a result, if the dispersant is used and the silicone is used as a solvent and the silicone is used as a medium, the above-mentioned problems can be solved, and the stability of the compounded cosmetics can be improved, and a feeling of use such as good elongation can be obtained. The present inventors have found that the present invention has excellent effects not found in the prior art, such as improvement of the present invention, and completed the present invention.
【０００５】本発明の微粒子二酸化チタン分散体は、媒
液としてのシリコーン、微粒子二酸化チタン、およびこ
の粒子を安定的に分散せしめる分散剤で構成されてい
る。The fine particle titanium dioxide dispersion of the present invention comprises silicone as a medium, fine particle titanium dioxide, and a dispersant for stably dispersing the particles.
【０００６】分散体の配合としては、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／微粒子二酸化チタンとして１〜４０
重量％である。[0006] The composition of the dispersion is 30 to 70 parts by weight, preferably 40 to 70 parts by weight of fine titanium dioxide.
The dispersant is 1 to 40 as a dispersant / particulate titanium dioxide.
% By weight.
【０００７】本発明の微粒子二酸化チタン分散体におけ
る微粒子二酸化チタンの形状は、長さが０．０５〜０．
６μｍ、軸比が3以上の棒状であって、平均単一粒子径
が０．００５〜０．１５μｍである。棒状粒子の体積を
求めてその体積と等価の真球状を想定し、その径を平均
単一粒子径とした。The shape of the fine particle titanium dioxide in the fine particle titanium dioxide dispersion of the present invention has a length of 0.05 to 0.1.
It has a rod shape of 6 μm and an axial ratio of 3 or more, and has an average single particle diameter of 0.005 to 0.15 μm. The volume of the rod-shaped particles was determined, a spherical shape equivalent to the volume was assumed, and the diameter was defined as the average single particle diameter.
【０００８】本発明において使用する微粒子二酸化チタ
ンは、種々の方法によって製造し得るが、例えば四塩化
チタン水溶液をアルカリで中和加水分解し、得られた含
水二酸化チタンを焼成するか、あるいは含水二酸化チタ
ンを水酸化ナトリウムで加熱処理し、得られた反応生成
物を酸で加熱熟成して得ることができる。このものは、
さらに必要に応じて焼成して粒子径や粒子形状の調整、
更に耐候性の向上をはかってもよい。また、硫酸チタン
水溶液や四塩化チタン水溶液を加熱加水分解して得られ
た含水二酸化チタンを酸で解こう処理したものや、この
ものをさらに焼成したものであってもよい。さらに微粒
子二酸化チタンは、分散剤との親和性や耐光性の向上を
はかるべく、例えばアルミニウム、珪素、ジルコニウ
ム、チタン、亜鉛およびスズの少なくとも１種の酸化物
または含水酸化物で被覆されている方が好ましい。The fine particle titanium dioxide used in the present invention can be produced by various methods. For example, an aqueous titanium tetrachloride solution is neutralized and hydrolyzed with an alkali, and the obtained hydrous titanium dioxide is calcined or hydrous titanium dioxide is produced. Titanium can be heat-treated with sodium hydroxide, and the resulting reaction product can be obtained by heat aging with an acid. This one is
Further calcination if necessary, adjustment of particle size and particle shape,
Further, the weather resistance may be improved. Further, a hydrous titanium dioxide solution obtained by heating and hydrolyzing a titanium sulfate aqueous solution or a titanium tetrachloride aqueous solution may be pulverized with an acid, or may be further baked. Furthermore, the fine particle titanium dioxide is coated with at least one oxide or hydrated oxide of, for example, aluminum, silicon, zirconium, titanium, zinc and tin in order to improve the affinity with the dispersant and the light resistance. Is preferred.
【０００９】本発明において使用する媒液としてのシリ
コーンとしては、デカメチルシクロペンタシロキサンで
ある。 The silicone used as a solvent in the present invention is decamethylcyclopentasiloxane.
is there.
【００１０】本発明において使用する分散剤は、シリコ
ーン系の化合物であるトリメチルシロキシケイ酸であ
る。シリコーン系分散剤は、酸化チタンの重量基準で１
〜４０％、好ましくは、５〜３０％配合することによっ
て、分散性、粘度、安定性等の点で良好なシリコーン分
散体が得られる。概ね、二酸チタンの比表面積が大きい
ほど、また、表面被覆剤の量が多いほど、分散剤の最適
配合は多くなる。また、超微粒子二酸化チタンの製法、
表面被覆剤の種類によっても分散剤の最適配合量は異な
ってくる。 [0010] dispersing agent for use in the present invention, Oh in Ru compound der silicone trimethylsiloxysilicate
You. The amount of the silicone-based dispersant is 1 based on the weight of titanium oxide.
A good silicone dispersion in terms of dispersibility, viscosity, stability, and the like can be obtained by blending at from 40 to 40%, preferably from 5 to 30%. In general, the larger the specific surface area of titanium dioxide and the larger the amount of the surface coating agent, the more the optimum blending of the dispersant. Also, the production method of ultrafine titanium dioxide,
The optimum amount of the dispersant varies depending on the type of the surface coating agent .
【００１１】次に、本発明の微粒子二酸化チタンシリコ
ーン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
混合したのち、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、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
整する上で重要であるが、例えば縦型、横型のサンドミ
ルで直径０．５ｍｍのジルコニアビーズを用いて粉砕す
るのが望ましい。Next, a method for producing the fine particle titanium dioxide silicone dispersion of the present invention will be described. The dispersion of the present invention is a specific dispersant, a medium solution and fine particle titanium dioxide, after premixed using a blade-type stirrer, a disper, a homomixer, and the like, using a pulverizer such as a sand mill, a pebble mill, and a disk mill. And fine particles of titanium dioxide are dispersed. The type of crusher, selection of crushing media, and setting of the optimum crushing conditions are important in adjusting the advanced dispersion.For example, a vertical type, a horizontal type sand mill using zirconia beads having a diameter of 0.5 mm is used. It is desirable to pulverize.
【００１２】このようにして得られた微粒子二酸化チタ
ンシリコーン分散体は、微粒子二酸化チタンを非常に良
く分散した状態で含有するため、化粧料に配合すると、
微粒子二酸化チタンが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、配合した化粧料の安定性向
上、伸びのよさなどの使用感の向上の効果を発現する。[0012] The fine particle titanium dioxide silicone dispersion thus obtained contains the fine particle titanium dioxide in a very dispersed state.
In addition to fully exhibiting the excellent ultraviolet shielding ability inherent in the fine particle titanium dioxide, it also has the effect of improving the stability of the compounded cosmetic and improving the usability such as good elongation.
【００１３】微粒子二酸化チタンシリコーン分散体は、
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
れたのち、所望の化粧料に配合されるため、微粒子二酸
化チタンが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、化粧料に粉末を配合するような
方法で微粒子二酸化チタンを配合しても、微粒子二酸化
チタンが本来有する紫外線遮蔽能が十分発揮されないば
かりか、経時的に微粒子二酸化チタンがシリコーン成分
から分離して沈降するなどの問題が生ずることが多い。
本発明の微粒子二酸化チタンシリコーン分散体を日焼け
止め化粧料として利用する場合には、例えばシリコーン
を主とする油性成分、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 fine particle titanium dioxide silicone dispersion comprises:
After being prepared under conditions very suitable for dispersing the particulate titanium dioxide, it is blended with the desired cosmetics, so that the inherent ultraviolet shielding capability of the particulate titanium dioxide is sufficiently exhibited. On the other hand, in general, even if the fine particle titanium dioxide is blended in such a way that the powder is blended into the cosmetic, not only the inherent ultraviolet shielding ability of the fine particle titanium dioxide is not sufficiently exerted, but also the fine particle titanium dioxide becomes silicone over time. Problems such as sedimentation from components often occur.
When the fine particle titanium dioxide silicone dispersion of the present invention is used as a sunscreen cosmetic, for example, an oily component mainly containing silicone, a humectant, a surfactant, a pigment, a fragrance, a preservative, water, alcohols, Combined with a thickener, lotion, cream, paste, stick,
It can be used in various forms such as emulsion.
【００１４】[0014]
【発明の実施の形態】本発明を下記実施例により例示し
ながら更に詳しく説明する。実施例は本発明の特定の態
様であり、限定的なものではない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples. The examples are specific embodiments of the present invention and are not limiting.
【００１５】[0015]
【実施例】参考例１ 四塩化チタン水溶液（ＴｉＯ２ ２００ｇ／ｌ）を室温
に保持しながら、水酸化ナトリウム水溶液で中和してコ
ロイド状の非晶質水酸化チタンを析出させ、その後熟成
してルチル型の微小チタニアゾルを得た。このゾルを濾
過、洗浄したのち６００℃で３時間焼成し、流体エネル
ギーミルで粉砕して平均粒子径２０ｎｍの超微粒子二酸
化チタン粉末を得た。この超微粒子二酸化チタン粉末を
水中に分散させてサンドミルで湿式粉砕して超微粒子二
酸化チタンスラリー（ＴｉＯ２２００ｇ／ｌ）とした。
このスラリーを７０℃に加熱した後よく攪拌しながらア
ルミン酸ナトリウムをＡｌ２ Ｏ３ としてＴｉＯ２ 重
量基準で５％添加し、引き続き熟成してアルミニウムの
水和酸化物を該二酸化チタン粒子上に沈殿、被覆させ
た。その固形分を濾過、洗浄し、洗浄ケーキを乾燥した
のちハンマータイプミルで粉砕して超微粒子二酸化チタ
ン粉末（平均単一粒子径 ０．０２μｍ）を得た。 Reference Example 1 While maintaining an aqueous solution of titanium tetrachloride (TiO 2 200 g / l) at room temperature, neutralization was carried out with an aqueous solution of sodium hydroxide to precipitate colloidal amorphous titanium hydroxide, which was then aged. Thus, a rutile-type fine titania sol was obtained. This sol was filtered, washed, calcined at 600 ° C. for 3 hours, and pulverized with a fluid energy mill to obtain ultrafine titanium dioxide powder having an average particle diameter of 20 nm. This ultrafine titanium dioxide powder was dispersed in water and wet-pulverized with a sand mill to obtain an ultrafine titanium dioxide slurry (TiO 2 200 g / l).
After heating this slurry to 70 ° C., 5% by weight of sodium aluminate as Al 2 O 3 was added as TiO 2 while stirring well, followed by aging to precipitate aluminum hydrated oxide on the titanium dioxide particles. , Coated. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain ultrafine titanium dioxide powder (average single particle diameter 0.02 μm).
【００１６】この微粒子二酸化チタン粉末４０重量部を
分散剤（トリメチルシロキシケイ酸）１２重量部と分散
媒（オクタメチルシクロテトラシロキサン）４８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メディアとして用い、サンドミル
で粉砕したところ、粘度１５０ｃＰのシリコーンオイル
分散体（Ａ）を得た。Forty parts by weight of the fine titanium dioxide powder were mixed with a dispersant (trimethylsiloxysilicic acid) (12 parts by weight) and a dispersion medium (octamethylcyclotetrasiloxane) (48 parts by weight) using a disper. Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (A) having a viscosity of 150 cP.
【００１７】実施例１ 四塩化チタン水溶液の加水分解により得られた含水酸化
チタンをＴｉＯ２ 換算１００ｇ／ｌの濃度の水性懸濁
液とした。この水性懸濁液２ｌに４８％水酸化ナトリウ
ム水溶液１４００ｇを攪拌しながら添加し、９５℃で１
２０分加熱後、ろ過し、十分に洗浄を行った。洗浄ケー
キを水でレパルプし、ＴｉＯ２ 換算１００ｇ／ｌの濃
度の水性懸濁液とし、この水性懸濁液１．５ｌを還流器
付きフラスコに入れ、３５％塩酸４００ｇを攪拌しなが
ら添加したのち、９５℃で１２０分間加熱熟成し、ルチ
ル型結晶の長軸０．２０μｍ、軸比５．０（平均単一粒
子径で表すと、０．０７８μｍ）の棒状微粒子酸化チタ
ンの水性懸濁液を得た。[0017] was an aqueous suspension with a concentration of the hydrous titanium oxide obtained by hydrolysis of Example 1 of titanium tetrachloride aqueous solution in terms of TiO 2 100 g / l. To 2 liters of this aqueous suspension, 1400 g of a 48% aqueous sodium hydroxide solution was added with stirring, and the mixture was added at 95 ° C for 1 hour.
After heating for 20 minutes, the mixture was filtered and sufficiently washed. The washed cake is repulped with water to form an aqueous suspension having a concentration of 100 g / l in terms of TiO 2. 1.5 l of this aqueous suspension is placed in a flask equipped with a reflux condenser, and 400 g of 35% hydrochloric acid is added with stirring. At 95 ° C. for 120 minutes to give an aqueous suspension of rod-shaped fine particle titanium oxide having a major axis of rutile type crystal of 0.20 μm and an axial ratio of 5.0 (expressed as an average single particle diameter of 0.078 μm). Obtained.
【００１８】この懸濁液を７０℃に加熱した後よく攪拌
しながらアルミン酸ナトリウムをＡｌ2 Ｏ3 としてＴｉ
Ｏ2 重量基準で５％添加し、引き続き熟成してアルミニ
ウムの水和酸化物を該二酸化チタン粒子上に沈殿、被覆
させた。その固形分を濾過、洗浄し、洗浄ケーキを乾燥
したのちハンマータイプミルで粉砕して棒状微粒子二酸
化チタン粉末を得た。After heating this suspension to 70 ° C., while stirring well, sodium aluminate was converted to Al 2 O 3
5% by weight of O 2 was added, followed by aging to precipitate and coat the hydrated aluminum oxide on the titanium dioxide particles. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain bar-shaped fine titanium dioxide powder.
【００１９】この棒状微粒子二酸化チタン粉末４０重量
部を分散剤（トリメチルシロキシケイ酸）１２重量部と
分散媒（デカメチルシクロペンタシロキサン）４８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のシリコーンオイ
ル分散体（Ｂ）を得た。Forty parts by weight of the rod-shaped fine particle titanium dioxide powder were mixed with a dispersion of 12 parts by weight of a dispersant (trimethylsiloxysilicic acid) and 48 parts by weight of a dispersion medium (decamethylcyclopentasiloxane) using a disper. next,
This was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (B) having a viscosity of 100 cP.
【００２０】参考例２ 四塩化チタン水溶液の加水分解により得られた含水酸化
チタンをＴｉＯ２ 換算１００ｇ／ｌの濃度の水性懸濁
液とした。この水性懸濁液２ｌに４８％水酸化ナトリウ
ム水溶液１４００ｇを攪拌しながら添加し、９５℃で１
２０分加熱後、ろ過し、十分に洗浄を行った。洗浄ケー
キを水でレパルプし、ＴｉＯ２ 換算１００ｇ／ｌの濃
度の水性懸濁液とし、この水性懸濁液１．５ｌを還流器
付きフラスコに入れ、３５％塩酸５７０ｇを攪拌しなが
ら瞬時に添加したのち、９５℃で１２０分間加熱熟成
し、ルチル型結晶の長軸０．３０μｍ、短軸０．０５５
μｍ（平均単一粒子径で表すと、０．１１μｍ）の樹枝
状微粒子酸化チタンの水性懸濁液を得た。[0020] and Reference Example 2 four hydrous titanium oxide obtained by hydrolysis of titanium chloride aqueous solution having a concentration of TiO 2 in terms 100 g / l aqueous suspension. To 2 liters of this aqueous suspension, 1400 g of a 48% aqueous sodium hydroxide solution was added with stirring, and the mixture was added at 95 ° C for 1 hour.
After heating for 20 minutes, the mixture was filtered and sufficiently washed. The washed cake is repulped with water to form an aqueous suspension having a concentration of 100 g / l in terms of TiO 2. 1.5 l of this aqueous suspension is placed in a flask equipped with a reflux condenser, and 570 g of 35% hydrochloric acid is added instantaneously with stirring. After that, it was aged by heating at 95 ° C. for 120 minutes, and the major axis of the rutile crystal was 0.30 μm and the minor axis was 0.055 μm.
An aqueous suspension of dendritic titanium oxide particles having a diameter of 0.1 μm (expressed as an average single particle diameter) was obtained.
【００２１】この懸濁液を７０℃に加熱した後よく攪拌
しながらアルミン酸ナトリウムをＡｌ2 Ｏ3 としてＴｉ
Ｏ2 重量基準で５％添加し、引き続き熟成してアルミニ
ウムの水和酸化物を該二酸化チタン粒子上に沈殿、被覆
させた。その固形分を濾過、洗浄し、洗浄ケーキを乾燥
したのちハンマータイプミルで粉砕して樹枝状微粒子二
酸化チタン粉末を得た。This suspension was heated to 70 ° C., and the sodium aluminate was converted to Al 2 O 3 while stirring well.
5% by weight of O 2 was added, followed by aging to precipitate and coat the hydrated aluminum oxide on the titanium dioxide particles. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain dendritic particulate titanium dioxide powder.
【００２２】この樹枝状微粒子二酸化チタン粉末４０重
量部を分散剤（トリメチルシロキシケイ酸）１２重量部
と分散媒（デカメチルシクロペンタシロキサン）４８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メディアとして用い、サン
ドミルで粉砕したところ、粘度１３０ｃＰのシリコーン
オイル分散体（Ｃ）を得た。Forty parts by weight of the dendritic fine particle titanium dioxide powder was mixed with a dispersant (trimethylsiloxysilicic acid) (12 parts by weight) and a dispersion medium (decamethylcyclopentasiloxane) (48 parts by weight) using a disper. . Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (C) having a viscosity of 130 cP.
【００２３】参考例３ 参考 例１の微粒子二酸化チタン粉末４０重量部を分散剤
（トリメチルシロキシケイ酸６重量部とジメチルポリシ
ロキサン・メチル（ポリオキシエチレン）シロキサン共
重合体６重量部）計１２重量部と分散媒（オクタメチル
シクロテトラシロキサン）４８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
ズをメディアとして用い、サンドミルで粉砕したとこ
ろ、粘度９０ｃＰのシリコーンオイル分散体（Ｄ）を得
た。 REFERENCE EXAMPLE 3 A total of 12 parts by weight of a dispersant (6 parts by weight of trimethylsiloxysilicic acid and 6 parts by weight of dimethylpolysiloxane-methyl (polyoxyethylene) siloxane copolymer) was added to 40 parts by weight of the fine titanium dioxide powder of Reference Example 1. Parts and a dispersion medium (octamethylcyclotetrasiloxane) of 48 parts by weight were mixed using a disper. Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (D) having a viscosity of 90 cP.
【００２４】比較例１参考 例１の微粒子二酸化チタンを粉末（Ｅ）として用い
た。Comparative Example 1 The fine particle titanium dioxide of Reference Example 1 was used as a powder (E).
【００２５】比較例２ 実施例１の棒状微粒子二酸化チタンを粉末（Ｆ）として
用いた。Comparative Example 2 The rod-shaped fine particle titanium dioxide of Example 1 was used as a powder (F).
【００２６】比較例３参考 例２の樹枝状微粒子二酸化チタンを粉末（Ｇ）とし
て用いた。Comparative Example 3 The dendritic fine particle titanium dioxide of Reference Example 2 was used as a powder (G).
【００２７】試験例１ 微粒子二酸化チタンのシリコーン分散体（Ａ）〜（Ｄ）
及び粉末（Ｅ）〜（Ｇ）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）（ａ）（ｂ）（ｃ）（ｄ）
（ｅ）（ｆ）（ｇ）を得た。 （１）オクタメチルシクトテトラシロキサン 残部 （２）ジメチルポリシロキサン １５．７重量部 （３）ジメチルポリシロキサン・ メチル（ポリオキシエチレン）シロキサン共重合体 ０．５重量部 （４）微粒子二酸化チタンシリコーン分散体（Ａ）〜（Ｄ） ７．５重量部 又は微粒子二酸化チタン粉末（Ｅ）〜（Ｇ） 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整し
た。Test Example 1 Silicone Dispersions of Fine Particle Titanium Dioxide (A) to (D)
And sunscreen cream (W / O emulsion) (a) (b) (c) (d) by blending powders (E) to (G) with the following formulations so that the total amount is 100 parts by weight.
(E) (f) (g) was obtained. (1) Octamethyl sictotetrasiloxane residue (2) Dimethylpolysiloxane 15.7 parts by weight (3) Dimethylpolysiloxane / methyl (polyoxyethylene) siloxane copolymer 0.5 parts by weight (4) Fine particle titanium dioxide silicone 7.5 parts by weight of dispersions (A) to (D) or 3.0 parts by weight of fine titanium dioxide powders (E) to (G) (5) Nylon powder (particle size: 5 μm) 12.5 parts by weight (6) Ethanol 10.0 parts by weight (7) 2.5 parts by weight of glycerin (8) 27.5 parts by weight of purified water Component (6) mixed in advance with components (1) to (5) mixed and dispersed with a disper The mixture of (8) was gradually added with stirring to prepare a sunscreen cream.
【００２８】評価方法１ 上記各クリームを石英ガラス板上に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 a quartz glass plate 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
用してもらい、肌の上での伸びのよさの使用感を相互に
評価してもらった。以上の試験・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 feeling of good stretch on the skin was mutually evaluated. Table 1 shows the above test and evaluation results.
【００３０】[0030]
【表１】試料を配合した日焼け止めクリ−ムの透過率
（％） （注）使用感は１０段階で評価。数値が大きい程、伸び
が良いことを示す。Table 1 Permeability (%) of sunscreen cream containing the sample (Note) Usability was evaluated on a 10-point scale. The larger the value, the better the elongation.
【００３１】[0031]
【発明の効果】本発明の微粒子二酸化チタンシリコーン
分散体は、安全性、安定性、透明性に優れた紫外線遮蔽
剤である微粒子二酸化チタンを非常に良く分散した状態
で含有するため、化粧料に配合すると、微粒子二酸化チ
タンが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、配合した化粧料の安定性向上、伸びのよさな
どの使用感の向上の効果を発現する化粧料を提供する。The fine particle titanium dioxide silicone dispersion of the present invention contains finely divided titanium dioxide, which is an ultraviolet ray shielding agent excellent in safety, stability and transparency, in a very well-dispersed state. When blended, it provides a cosmetic that expresses the effects of improving the feeling of use, such as improving the stability of the blended cosmetics and improving elongation, in addition to fully exhibiting the excellent ultraviolet shielding ability inherent in fine particle titanium dioxide I do.
フロントページの続き (56)参考文献 特開 平３−115211（ＪＰ，Ａ) 特開 平６−239728（ＪＰ，Ａ) 特開 平７−165532（ＪＰ，Ａ) 特開 平９−202722（ＪＰ，Ａ) 特開 平９−110639（ＪＰ，Ａ) 特開 平９−110112（ＪＰ，Ａ) 特開 平９−12439（ＪＰ，Ａ) 特開 平８−295620（ＪＰ，Ａ) 特開 平８−127514（ＪＰ，Ａ) 特開 平８−104613（ＪＰ，Ａ) 特開 平７−309714（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) A61K 7/00 - 7/50 B01J 13/00 - 13/22 Continuation of the front page (56) References JP-A-3-115211 (JP, A) JP-A-6-239728 (JP, A) JP-A-7-165532 (JP, A) JP-A-9-202722 (JP, A) JP-A-9-110639 (JP, A) JP-A-9-110112 (JP, A) JP-A-9-12439 (JP, A) JP-A 8-295620 (JP, A) 8-127514 (JP, A) JP-A-8-104613 (JP, A) JP-A-7-309714 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) A61K 7/00 -7/50 B01J 13/00-13/22
Claims (2)
シロキサン、微粒子二酸化チタン粒子及び分散剤として
のトリメチルシロキシケイ酸を含むシリコーン分散体
で、該微粒子二酸化チタンが長さが０．０５〜０．６μ
ｍ、軸比が3以上の棒状であり、平均単一粒子径０．０
０５〜０．１５μｍをもつ二酸化チタン分散体。1. Decamethylcyclopenta as a dispersion medium
Siloxane, a fine titanium dioxide particles and dispersing agent
A silicone dispersion containing trimethylsiloxysilicic acid , wherein the fine particle titanium dioxide has a length of 0.05 to 0.6 μm.
m, a rod shape having an axial ratio of 3 or more, and an average single particle diameter of 0.0
A titanium dioxide dispersion having a particle size of 0.5 to 0.15 μm.
る日焼け止め化粧料。2. A sunscreen containing titanium dioxide dispersion according to claim 1 cosmetics.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28913296A JP3224750B2 (en) | 1995-11-28 | 1996-10-11 | Fine particle titanium dioxide silicone dispersion |
| PCT/JP1997/002760 WO1998016193A1 (en) | 1996-10-11 | 1997-08-07 | Dispersion of particulate titanium dioxide in silicone |
| AU37840/97A AU3784097A (en) | 1996-10-11 | 1997-08-07 | Dispersion of particulate titanium dioxide in silicone |
| TW86111438A TW409127B (en) | 1996-10-11 | 1997-08-09 | Dispersing element of titanium dioxide and poly-silicone oxide fine particle |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-333927 | 1995-11-28 | ||
| JP33392795 | 1995-11-28 | ||
| JP28913296A JP3224750B2 (en) | 1995-11-28 | 1996-10-11 | Fine particle titanium dioxide silicone dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09208438A JPH09208438A (en) | 1997-08-12 |
| JP3224750B2 true JP3224750B2 (en) | 2001-11-05 |
Family
ID=26557468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28913296A Expired - Lifetime JP3224750B2 (en) | 1995-11-28 | 1996-10-11 | Fine particle titanium dioxide silicone dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3224750B2 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3609262B2 (en) * | 1998-08-07 | 2005-01-12 | 石原産業株式会社 | Titanium oxide sol and method for producing the same |
| TWI285113B (en) | 1999-11-25 | 2007-08-11 | Shiseido Co Ltd | Manufacturing method of cosmetics |
| JP2002338245A (en) * | 2001-05-16 | 2002-11-27 | Tayca Corp | Dispersion with high concentration of particulate titanium oxide |
| WO2003014022A1 (en) | 2001-08-03 | 2003-02-20 | Nippon Soda Co., Ltd. | Dispersed ingredient having metal-oxygen |
| US7422642B2 (en) | 2002-03-12 | 2008-09-09 | Nippon Soda Co., Ltd. | Method for preparing chemical adsorption film and solution for preparing chemical adsorption film used in the method |
| KR100746067B1 (en) | 2002-11-13 | 2007-08-03 | 닛뽕소다 가부시키가이샤 | Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film |
| KR100835865B1 (en) * | 2002-12-31 | 2008-06-09 | (주)아모레퍼시픽 | Microfine emulsion containing titanium dioxide and zinc oxide and composition of external application to the skin containing thereof |
| EP1621258B1 (en) | 2003-04-15 | 2011-07-27 | Nippon Soda Co., Ltd. | Method for producing organic thin film |
| GB0328693D0 (en) * | 2003-12-11 | 2004-01-14 | Ici Plc | Metal oxide dispersions |
| JP4385052B2 (en) | 2004-07-22 | 2009-12-16 | 日本曹達株式会社 | Organic thin film formation method |
| CN101087679B (en) | 2004-12-28 | 2011-09-21 | 日本曹达株式会社 | Molding die or master pattern for electroforming each having release layer |
| CN101330898A (en) | 2005-12-14 | 2008-12-24 | 株式会社资生堂 | Dispersion of fine titanium oxide particles and cosmetic preparation containing the same |
| KR101249078B1 (en) * | 2006-01-20 | 2013-03-29 | 삼성전기주식회사 | Siloxane Dispersant and Nanoparticle Paste Composition Comprising the Same |
| US7820584B2 (en) | 2006-03-14 | 2010-10-26 | Nihon Nohyaku Co., Ltd. | Visible light-responsive photocatalyst, method for producing same, photocatalyst coating agent using same, and photocatalyst dispersion |
| KR101161189B1 (en) | 2006-07-31 | 2012-07-02 | 닛뽕소다 가부시키가이샤 | Method for producing organic thin film by using film physical property improving process |
| EP2161080A4 (en) | 2006-11-13 | 2011-03-09 | Nippon Soda Co | Method for forming organic thin film |
| US8329290B2 (en) | 2008-12-22 | 2012-12-11 | Nitto Denko Corporation | Silicone resin composition |
| JP2010150467A (en) * | 2008-12-26 | 2010-07-08 | Fujifilm Corp | Ink composition and inkjet recording method |
| JP5697858B2 (en) * | 2009-08-03 | 2015-04-08 | 日本メナード化粧品株式会社 | Solid oily cosmetic |
| JP5793198B2 (en) | 2011-10-18 | 2015-10-14 | 日本曹達株式会社 | Surface-coated inorganic powder |
| CN104395327B (en) | 2012-07-05 | 2017-06-23 | 日本曹达株式会社 | Organo-silicon compound, film-forming composition and organic film using it |
| JP6054709B2 (en) * | 2012-11-06 | 2016-12-27 | 花王株式会社 | Sunscreen cosmetics |
| WO2017058713A1 (en) * | 2015-09-28 | 2017-04-06 | Rohm And Haas Company | Skin care formulations containing copolymers, inorganic metal oxide particles, and silicones |
-
1996
- 1996-10-11 JP JP28913296A patent/JP3224750B2/en not_active Expired - Lifetime
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|---|---|
| JPH09208438A (en) | 1997-08-12 |
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