JP4684895B2 - Sunscreen cosmetics - Google Patents

Sunscreen cosmetics Download PDF

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Publication number
JP4684895B2
JP4684895B2 JP2006001935A JP2006001935A JP4684895B2 JP 4684895 B2 JP4684895 B2 JP 4684895B2 JP 2006001935 A JP2006001935 A JP 2006001935A JP 2006001935 A JP2006001935 A JP 2006001935A JP 4684895 B2 JP4684895 B2 JP 4684895B2
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viscosity
weight
sunscreen cosmetic
zinc oxide
titanium oxide
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JP2007182402A (en
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真一 洲嵜
國寛 宮本
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Nippon Menard Cosmetic Co Ltd
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Nippon Menard Cosmetic Co Ltd
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Description

本願発明は、経時的な粘度上昇を抑制して粘度安定性が良好であるサンスクリーン化粧料に関する。   The present invention relates to a sunscreen cosmetic that suppresses an increase in viscosity over time and has good viscosity stability.

サンスクリーン化粧料には紫外線に対する防御効果を確保するために、紫外線吸収剤を配合している。紫外線吸収剤にはオキシベンゾン等の有機合成化合物と酸化チタンや酸化亜鉛等の無機化合物が用いられている。さらに最近では安全性の観点から無機化合物のみでSPFやPAの数値を高める商品も出始めている。このような商品の場合には必然的に大量の無機化合物が配合されることになる。   Sunscreen cosmetics are blended with UV absorbers to ensure a protective effect against UV rays. As the ultraviolet absorber, an organic synthetic compound such as oxybenzone and an inorganic compound such as titanium oxide or zinc oxide are used. Furthermore, recently, from the viewpoint of safety, products that increase the SPF and PA values using only inorganic compounds have begun to appear. In the case of such a product, a large amount of an inorganic compound is necessarily blended.

また、トリメチルシロキシケイ酸は化粧塗膜の強化や顔料の分散安定性に用いられているが、サンスクリーン化粧料の粘度上昇抑制効果については全く知られていない。   Further, trimethylsiloxysilicic acid is used for reinforcing a decorative coating film and for dispersion stability of a pigment, but nothing is known about the effect of suppressing the increase in viscosity of sunscreen cosmetics.

そして、ポリグリセリル−3ポリジメチルシロキシエチルジメチコンの粘度上昇抑制効果についても全く知られていない。 Further, the effect of suppressing the increase in viscosity of polyglyceryl-3 polydimethylsiloxyethyl dimethicone is not known at all.

特開平8年−99837号公報JP-A-8-99837 特開平7年−309714号公報JP-A-7-309714

ところが、酸化チタンと酸化亜鉛を併用すると、それぞれ単独に配合して場合に比べ、経時的な粘度上昇が起こり、流動性のある商品の場合容器からベースが出にくくなる等の不都合があった。   However, when titanium oxide and zinc oxide are used in combination, the viscosity increases with time as compared with the case where they are blended singly, and in the case of a product with fluidity, there is a disadvantage that the base is difficult to come out from the container.

このような状況を鑑みて鋭意検討を重ねた結果、酸化チタンと酸化亜鉛を併用する系において経時的にも粘度上昇を抑制する安定なサンスクリーン化粧料を完成させた。
すなわち、本願発明は酸化亜鉛、酸化チタン及びトリメチルシロキシケイ酸を含有する20℃において粘度が10,000mPa・s以下であるサンスクリーン化粧料である。さらにポリグリセリル−3ポリジメチルシロキシエチルジメチコンを併用すると酸化チタンと酸化亜鉛の含有量が大量になっても粘度上昇が抑制できることを見出した。またトリメチルシロキシケイ酸またはトリメチルシロキシケイ酸とポリグリセリル−3ポリジメチルシロキシエチルジメチコンを併用すると、20℃において粘度が10,000mPa・s以下である酸化亜鉛及び酸化チタンを含有するサンスクリーン化粧料の粘度上昇を抑制できることを見出した。
As a result of intensive investigations in view of such circumstances, a stable sunscreen cosmetic that suppresses the increase in viscosity over time in a system using both titanium oxide and zinc oxide was completed.
That is, the present invention is a sunscreen cosmetic having a viscosity of 10,000 mPa · s or less at 20 ° C. containing zinc oxide, titanium oxide and trimethylsiloxysilicate. Furthermore, when polyglyceryl-3 polydimethylsiloxyethyl dimethicone was used in combination, it was found that an increase in viscosity can be suppressed even if the contents of titanium oxide and zinc oxide are increased. Also, when trimethylsiloxysilicic acid or trimethylsiloxysilicic acid and polyglyceryl-3 polydimethylsiloxyethyl dimethicone are used in combination, the viscosity of the sunscreen cosmetic containing zinc oxide and titanium oxide having a viscosity of 10,000 mPa · s or less at 20 ° C. It was found that the increase can be suppressed.

以下、本願発明の構成について詳述する。
本願発明においてサンスクリーン化粧料は乳化系でも、オイル系でもどちらでも良い。乳化系の場合にはO/W型でもW/O型でもどちらでも良い。好ましくはW/O型である。さらに紫外線吸収剤としてはメトキシケイ皮酸エステルやオキシベンゾン等の有機合成
化合物を含有しても、酸化亜鉛、酸化チタン等の無機化合物のみでも良い。
本願発明において粘度上昇抑制剤とは、20℃において粘度が10,000mPa・s以下である酸化亜鉛及び酸化チタンを含有するサンスクリーン化粧料に配合することにより経時的な粘度上昇を抑制できる成分をいう。
Hereinafter, the configuration of the present invention will be described in detail.
In the present invention, the sunscreen cosmetic may be emulsified or oily. In the case of an emulsifying system, either O / W type or W / O type may be used. The W / O type is preferable. Further, the ultraviolet absorber may contain an organic synthetic compound such as methoxycinnamic acid ester or oxybenzone, or only an inorganic compound such as zinc oxide or titanium oxide.
In the present invention, the viscosity increase inhibitor is a component capable of suppressing the increase in viscosity over time by blending in a sunscreen cosmetic containing zinc oxide and titanium oxide having a viscosity of 10,000 mPa · s or less at 20 ° C. Say.

本願発明の酸化チタンはシリコン等で表面処理をしても、何も処理していないものでもどちらでも良い。表面処理の方法は例えば以下の方法がある。低粘度〜高粘度油状ポリシロキサン処理、メチルハイドロジェンポリシロキサン処理、フッ素変性メチルハイドロジェンポリシロキサン処理等である。
またその配合量は特に限定されないが好ましくは1.0〜20重量%である。1.0%
以下ではSPF効果が充分でない場合があり、また20%以上では流動性が出ない場合が
あるので好ましくない場合がある。
本願発明の酸化亜鉛はシリコン等で表面処理をしても、何も処理していないものでもどちらでも良い。表面処理の方法は例えば以下の方法がある。低粘度〜高粘度油状ポリシロキサン処理、メチルハイドロジェンポリシロキサン処理、フッ素変性メチルハイドロジェンポリシロキサン処理等である。またその配合量は特に限定されないが好ましくは、1.0〜20重量%である。1.0%以下ではPA効果が充分でない場合があり、また20%以上では流動性が出ない場合があるので好ましくない。
本願発明のトリメチルシロキシケイ酸の配合量は特に限定されないが好ましくは0.1〜5.0重量%である。0.1%以下では処方系によっては効果が十分でない場合もあり、また5.0%以上では効果は発揮されるが使用性が良くない場合がある。トリメチルシロキシケイ酸はネイルエナメル等の皮膜剤として普通に使用されている。例えば信越化学工業株式会社製のシリコーン KF−7312Jがある。
The titanium oxide of the present invention may be surface treated with silicon or the like, or may be untreated. Examples of the surface treatment method include the following methods. Low viscosity to high viscosity oily polysiloxane treatment, methyl hydrogen polysiloxane treatment, fluorine-modified methyl hydrogen polysiloxane treatment, and the like.
The blending amount is not particularly limited, but is preferably 1.0 to 20% by weight. 1.0%
In the following, the SPF effect may not be sufficient, and if it is 20% or more, fluidity may not be obtained, which may be undesirable.
The zinc oxide of the present invention may be surface treated with silicon or the like, or may be untreated. Examples of the surface treatment method include the following methods. Low viscosity to high viscosity oily polysiloxane treatment, methyl hydrogen polysiloxane treatment, fluorine-modified methyl hydrogen polysiloxane treatment, and the like. Moreover, the compounding quantity is although it does not specifically limit, Preferably, it is 1.0 to 20 weight%. If it is 1.0% or less, the PA effect may not be sufficient, and if it is 20% or more, fluidity may not be obtained.
Although the compounding quantity of the trimethylsiloxy silicic acid of this invention is not specifically limited, Preferably it is 0.1 to 5.0 weight%. If it is 0.1% or less, the effect may not be sufficient depending on the prescription system, and if it is 5.0% or more, the effect is exhibited but the usability may not be good. Trimethylsiloxysilicic acid is commonly used as a coating agent for nail enamel and the like. For example, there is silicone KF-7312J manufactured by Shin-Etsu Chemical Co., Ltd.

本願発明のポリグリセリル−3ポリジメチルシロキシエチルジメチコンの配合量は特に限定されないが好ましくは0.1〜5.0重量%である。0.1%以下では処方系によっては効果が十分でない場合もあり、また5.0%以上では効果は発揮されるが使用性が良くない場合がある。例えば信越化学工業株式会社製のシリコーン KF−6104がある。   Although the compounding quantity of the polyglyceryl-3 polydimethylsiloxyethyl dimethicone of this invention is not specifically limited, Preferably it is 0.1 to 5.0 weight%. If it is 0.1% or less, the effect may not be sufficient depending on the prescription system, and if it is 5.0% or more, the effect is exhibited but the usability may not be good. An example is silicone KF-6104 manufactured by Shin-Etsu Chemical Co., Ltd.

本願発明のサンスクリーン化粧料は20℃において粘度が10,000mPa・S以下である。10,000mPa・s以上であると、容器から出しにくく、肌への塗布に対しても不都合が出るからである。尚、本願発明の粘度は東京計器(株)社製BL型のB型粘度計で測定し、測定開始後30秒後の値を示す。   The sunscreen cosmetic of the present invention has a viscosity of 10,000 mPa · S or less at 20 ° C. It is because it is hard to take out from a container as it is 10,000 mPa * s or more, and it will become inconvenient also with respect to application | coating to skin. The viscosity of the present invention is measured with a BL type B type viscometer manufactured by Tokyo Keiki Co., Ltd., and indicates a value 30 seconds after the start of measurement.

本願発明のサンスクリーン化粧料は上記必須成分の他に、油性成分、シリコーン、保湿剤、増粘剤、界面活性剤、薬効成分、防腐剤、顔料、粉体、pH調整剤、紫外線吸収剤、抗酸化剤、香料等を適宜配合することができる。   In addition to the above essential components, the sunscreen cosmetic of the present invention is an oil component, silicone, humectant, thickener, surfactant, medicinal component, preservative, pigment, powder, pH adjuster, ultraviolet absorber, An antioxidant, a fragrance | flavor, etc. can be mix | blended suitably.

本願発明は実験1〜3及び実施例で証明されたとおり、酸化チタンと酸化亜鉛を併用した20℃において粘度が10,000Pa・s以下である系において、トリメチルシロキシケイ酸を含有すると粘度上昇が抑制できるサンスクリーン化粧料である。 As demonstrated in Experiments 1 to 3 and the Examples of the present invention, in a system having a viscosity of 10,000 Pa · s or less at 20 ° C. in which titanium oxide and zinc oxide are used in combination, when trimethylsiloxysilicic acid is contained, the viscosity increases. It is a sunscreen cosmetic that can be suppressed.

以下に実施例により本願発明を詳細に説明するが、本願発明はこれらに限定されるものではない。尚、表中の数値は含有量(wt%)を表す。また粘度の単位はmPa・sである。経時的な粘度上昇の抑制効果は50℃で顕著に現れるので、本実験は50℃、1ヶ月後の結果で判断した。   EXAMPLES The present invention will be described in detail below by examples, but the present invention is not limited to these examples. In addition, the numerical value in a table | surface represents content (wt%). The unit of viscosity is mPa · s. Since the effect of suppressing the increase in viscosity over time appears remarkably at 50 ° C., this experiment was judged based on the result after 1 month at 50 ° C.

下記表1〜表3の結果からわかるように、本願発明のサンスクリーン化粧料は経時的な粘度上昇が抑制されており良好な結果となっている。   As can be seen from the results in the following Tables 1 to 3, the sunscreen cosmetic of the present invention has good results with suppressed increase in viscosity over time.

実験1 トリメチルシロキシケイ酸の粘度抑制効果
本実験のサンスクリーン乳液の調製方法:成分(1)〜成分(9)を混合して溶解し、次に成分(10)〜成分(13)を混合して溶解する。両者を混合してW/O乳化型サンスクリーン乳液を調製した。
Experiment 1 Viscosity inhibiting effect of trimethylsiloxysilicic acid Preparation method of sunscreen emulsion of this experiment: Components (1) to (9) are mixed and dissolved, and then components (10) to (13) are mixed. Dissolve. Both were mixed to prepare a W / O emulsion type sunscreen emulsion.

粘度の測定は試料を20℃の恒温器に1日放置した後にB型粘度計(東京計器(株)BL型社製)で行った。比較例1の1ヶ月後の測定はローターNo.4、30rpm、それ以外はローターNo.2、30rpmで測定した。   The viscosity was measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd. BL type) after leaving the sample in a thermostat at 20 ° C. for 1 day. The measurement of one month after Comparative Example 1 was performed using the rotor No. 4, 30 rpm, otherwise rotor No. 2. Measured at 30 rpm.

尚各処方は実施例1を基本とし、変化させた数値のみ記載した。 Each formulation is based on Example 1, and only the changed values are shown.

Figure 0004684895
Figure 0004684895

実験2 トリメチルシロキシケイ酸とポリグリセリル−3ポリジメチルシロキシエチルジメチコンを併用した場合の粘度上昇抑制効果 Experiment 2 Inhibition of viscosity increase when trimethylsiloxysilicic acid and polyglyceryl-3polydimethylsiloxyethyl dimethicone are used in combination

本実験のサンスクリーン乳液の調製方法:成分(1)〜成分(10)を混合して溶解し、次に成分(11)〜成分(14)を混合して溶解する。両者を混合してW/O乳化型サンスクリーン乳液を調製した。 Preparation method of sunscreen emulsion of this experiment: Components (1) to (10) are mixed and dissolved, and then components (11) to (14) are mixed and dissolved. Both were mixed to prepare a W / O emulsion type sunscreen emulsion.

粘度の測定は試料を20℃の恒温器に1日放置した後にB型粘度計で行った。比較例2の1ヶ月後の測定はローターNo.4、12rpm、それ以外はローターNo.2、12rpmで測定した。   The viscosity was measured with a B-type viscometer after the sample was left in a thermostat at 20 ° C. for 1 day. The measurement after 1 month of Comparative Example 2 was conducted using the rotor No. 4, 12 rpm, otherwise rotor No. The measurement was performed at 2, 12 rpm.

尚各処方は実施例6を基本とし、変化させた数値のみ記載した。 Each formulation is based on Example 6, and only the changed values are shown.

Figure 0004684895
Figure 0004684895

実験3 トリメチルシロキシケイ酸を他のレジン等に変更した場合の粘度上昇抑制効果
実施例3の処方、製造方法で、本発明のトリメチルシロキシケイ酸を他の一般的に用いられる皮膜剤に置き換えて試料を調製した。 粘度の測定は試料を20℃の恒温器に1日放置した後にB型粘度計で行った。比較例3,4の1ヶ月後の測定はローターNo.4、12rpm、それ以外はローターNo.2、30rpmで測定した。
Experiment 3 Viscosity increase inhibiting effect when trimethylsiloxysilicic acid is changed to other resin etc. In the formulation and production method of Example 3, the trimethylsiloxysilicic acid of the present invention is replaced with other commonly used coating agents. Samples were prepared. The viscosity was measured with a B-type viscometer after the sample was left in a thermostat at 20 ° C. for 1 day. The measurement after one month of Comparative Examples 3 and 4 is rotor No. 4, 12 rpm, otherwise rotor No. 2. Measured at 30 rpm.

Figure 0004684895
Figure 0004684895

実施例11〜実施例13はいずれも経時的な粘度上昇が抑制された良好なサンスクリー
ン化粧料であった。
Examples 11 to 13 were all good sunscreen cosmetics in which the increase in viscosity over time was suppressed.

実施例11 W/O型サンスクリーン乳液
配合成分 配合量(重量%)
(1) オクタメチルシクロテトラシロキサン 50.0
(2) 流動パラフィン 3.0
(3) ポリオキシエチレン・メチルポリシロキサン共重合体 0.02
(4) トリメチルシロキシケイ酸(KF−7312J) 0.2
(5) ステアリン酸アルミニウム処理酸化チタン 10.6
(6) メチルハシドロジェンポリシロキサン処理酸化亜鉛 10.0
(7) 有機変性ベントナイト(ベントン38) 0.3
(8) メチルパラベン 0.2
(9) 未変性95エタノール 5.0
(10)硫酸マグネシウム 0.3
(11)精製水 残余
Example 11 W / O type sunscreen emulsion Blending component Blending amount (% by weight)
(1) Octamethylcyclotetrasiloxane 50.0
(2) Liquid paraffin 3.0
(3) Polyoxyethylene / methylpolysiloxane copolymer 0.02
(4) Trimethylsiloxysilicic acid (KF-7312J) 0.2
(5) Titanium oxide treated with aluminum stearate 10.6
(6) Zinc oxide treated with methylhadridogen polysiloxane 10.0
(7) Organically modified bentonite (Benton 38) 0.3
(8) Methylparaben 0.2
(9) Native 95 ethanol 5.0
(10) Magnesium sulfate 0.3
(11) Purified water residue

〔製法〕(1)〜(7)を混合する。次に(8)〜(11)を添加、乳化する。   [Production Method] (1) to (7) are mixed. Next, (8) to (11) are added and emulsified.

実施例12 W/O型サンスクリーン乳液
配合成分 配合量(重量%)
(1) デカメチルシクロテトラシロキサン 40.0
(2) 軽質イソパラフィン 5.0
(3) ジグリセリンジイソステアレート 2.0
(4) グリセリルモノステアレート 1.0
(5) スクワラン 5.0
(6) トリメチルシロキシケイ酸(KF−7312J) 0.2
(7) ポリグリセリル−3ポリジメチルシロキシエチルジメチコン 0.5
(8) メチルポリシロキサン処理酸化チタン 5.0
(9) メチルポリシロキサン処理酸化亜鉛 5.0
(10)1,3−ブチレングリコール 5.0
(11)メチルパラベン 0.1
(12)硫酸マグネシウム 0.5
(13)精製水 残余
Example 12 W / O type sunscreen emulsion Blending component Blending amount (% by weight)
(1) Decamethylcyclotetrasiloxane 40.0
(2) Light isoparaffin 5.0
(3) Diglycerin diisostearate 2.0
(4) Glyceryl monostearate 1.0
(5) Squalane 5.0
(6) Trimethylsiloxysilicic acid (KF-7312J) 0.2
(7) Polyglyceryl-3 polydimethylsiloxyethyl dimethicone 0.5
(8) Methylpolysiloxane-treated titanium oxide 5.0
(9) Zinc oxide treated with methylpolysiloxane 5.0
(10) 1,3-butylene glycol 5.0
(11) Methylparaben 0.1
(12) Magnesium sulfate 0.5
(13) Purified water residue

〔製法〕(1)〜(9)を混合する。次に(10)〜(13)を添加、乳化する。   [Production method] (1) to (9) are mixed. Next, (10) to (13) are added and emulsified.

実施例13 W/O型サンスクリーン乳液
配合成分 配合量(重量%)
(1) フッ素処理酸化チタン 15.0
(2) フッ素処理酸化亜鉛 15.0
(3) イソノナン酸イソトリデシル 25.0
(4) トリメチルシロキシケイ酸(KF−7312J) 5.0
(5) ポリグリセリル−3ポリジメチルシロキシエチルジメチコン 3.0
(6) ジメチコン(1CS) 5.0
(7) PEG−9ジメチコン 2.0
(8) (ジメチコン/ビニルジメチコン/メチコン)クロスポリマー 1.0
(9) トリイソステアリン酸PEG−20水添ヒマシ油 0.7
(10)ジステアリルジモニウムヘクトライト 0.2
(11)硫酸マグネシウム 0.3
(12)未変95エタノール 6.0
(13)メチルパラベン 0.3
(14)精製水 残余
Example 13 W / O type sunscreen emulsion Ingredient Ingredient Amount (% by weight)
(1) Fluorine-treated titanium oxide 15.0
(2) Fluorine-treated zinc oxide 15.0
(3) Isotridecyl isononanoate 25.0
(4) Trimethylsiloxysilicic acid (KF-7312J) 5.0
(5) Polyglyceryl-3 polydimethylsiloxyethyl dimethicone 3.0
(6) Dimethicone (1CS) 5.0
(7) PEG-9 Dimethicone 2.0
(8) (Dimethicone / vinyl dimethicone / methicone) cross polymer 1.0
(9) PEG-20 hydrogenated castor oil triisostearate 0.7
(10) Distearyldimonium hectorite 0.2
(11) Magnesium sulfate 0.3
(12) Unmodified 95 ethanol 6.0
(13) Methylparaben 0.3
(14) Purified water residue

〔製法〕(1)〜(10)を混合する。次に(11)〜(14)を加えて攪拌、乳化する。
[Production method] (1) to (10) are mixed. Next, (11) to (14) are added and stirred and emulsified.

Claims (4)

酸化亜鉛、酸化チタントリメチルシロキシケイ酸及びポリグリセリル−3ポリジメチルシロキシエチルジメチコンを含有する20℃において粘度が10,000mPa・s以下であるサンスクリーン化粧料。ただし、次の成分A)〜成分D)の全てを含むことを特徴とする油中水型化粧料を除く。
A)1種又は2種以上の圧縮強度5.0MPa以下の有機樹脂粉末
B)1種又は2種以上のHLB2〜12の非シリコーン系非イオン界面活性剤
C)1種又は2種以上のポリエーテル変性シリコーン油
D)1種又は2種以上のポリグリセリン変性シリコーン油
A sunscreen cosmetic containing zinc oxide, titanium oxide , trimethylsiloxysilicic acid and polyglyceryl-3 polydimethylsiloxyethyl dimethicone and having a viscosity of 10,000 mPa · s or less at 20 ° C. However, water-in-oil cosmetics characterized by including all of the following components A) to D) are excluded.
A) One or more organic resin powders having a compressive strength of 5.0 MPa or less
B) One or more HLB 2-12 non-silicone nonionic surfactants
C) One or more polyether-modified silicone oils
D) One or more polyglycerol-modified silicone oils
ポリグリセリル−3ポリジメチルシロキシエチルジメチコンの含有量が0.1〜5.0重量%である請求項に記載のサンスクリーン化粧料。 The sunscreen cosmetic according to claim 1 , wherein the content of polyglyceryl-3 polydimethylsiloxyethyl dimethicone is 0.1 to 5.0% by weight. 酸化チタンの含有量が1.0〜20重量%、酸化亜鉛の含有量が1.0〜20重量%である請求項1又は2に記載のサンスクリーン化粧料。 The sunscreen cosmetic according to claim 1 or 2 , wherein the content of titanium oxide is 1.0 to 20% by weight and the content of zinc oxide is 1.0 to 20% by weight. トリメチルシロキシケイ酸の含有量が0.1〜5.0重量%である請求項1〜3のいずれか一項に記載のサンスクリーン化粧料。
The sunscreen cosmetic according to any one of claims 1 to 3 , wherein the content of trimethylsiloxysilicic acid is 0.1 to 5.0% by weight.
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JP5184031B2 (en) * 2007-10-01 2013-04-17 ポーラ化成工業株式会社 Emulsifier-type powder-containing external skin preparation
JP5653401B2 (en) * 2012-10-16 2015-01-14 ポーラ化成工業株式会社 Method for producing powder-containing external preparation for skin containing emulsifier
EP3292857A4 (en) * 2015-05-07 2019-01-02 Shin-Etsu Chemical Co., Ltd. Cosmetic composition
JP6650718B2 (en) * 2015-09-30 2020-02-19 花王株式会社 Water-in-oil emulsion cosmetics

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