JP3385857B2 - Skin protective agent - Google Patents

Skin protective agent

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Publication number
JP3385857B2
JP3385857B2 JP15481396A JP15481396A JP3385857B2 JP 3385857 B2 JP3385857 B2 JP 3385857B2 JP 15481396 A JP15481396 A JP 15481396A JP 15481396 A JP15481396 A JP 15481396A JP 3385857 B2 JP3385857 B2 JP 3385857B2
Authority
JP
Japan
Prior art keywords
skin
stratum corneum
water
protective agent
clay mineral
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 - Fee Related
Application number
JP15481396A
Other languages
Japanese (ja)
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JPH09315926A (en
Inventor
泰志 小池
成実 太垣
禎 飯原
治夫 角谷
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Lion Corp
Original Assignee
Lion Corp
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Filing date
Publication date
Application filed by Lion Corp filed Critical Lion Corp
Priority to JP15481396A priority Critical patent/JP3385857B2/en
Priority to IDP971746A priority patent/ID16978A/en
Publication of JPH09315926A publication Critical patent/JPH09315926A/en
Application granted granted Critical
Publication of JP3385857B2 publication Critical patent/JP3385857B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】 【0001】 【発明の属する技術分野】本発明は、外部からの皮膚刺
激、特に界面活性剤の経皮吸収性を抑え、角質細胞間脂
質、角質層中の天然保湿因子、角質層中の水分の溶出・
減少を効果的に抑制することができる皮膚保護剤に関す
る。 【0002】 【従来の技術及び発明が解決しようとする課題】皮膚は
外界の環境から身体の内部を守るバリアの役割を担って
いるが、その機能を十分に果たすには角質細胞間脂質や
角質層の天然保湿因子(naturalmoistur
izing factor:NMF)、角質層中の水分
が十分に存在することが大切である。それら成分が不足
すると荒れ肌状態となる。このような荒れ肌を引き起こ
す外的要因は様々であるが、特に皮膚に対する刺激物と
しては界面活性剤がある。界面活性剤は、クリーム、ロ
ーション、身体洗浄剤やシャンプー、リンスは勿論、台
所洗剤、住居用洗剤、衣料用洗剤、柔軟仕上剤などにも
使用され、これらを用いた場合の界面活性剤による皮膚
刺激が従来から問題となっており、このため刺激性の低
い界面活性剤を原料として使用したり、アニオン性、ノ
ニオン性、両性界面活性剤を組み合わせて使用するなど
のことが提案され、また、タンニン酸を配合することも
提案されている。 【0003】しかしながら、これらの提案においても、
界面活性剤の使用による角質細胞間の脂質や角質層中の
天然保湿因子の溶出、角質層中の水分量の減少を十分抑
制することは困難であり、特に荒れ肌の人や頻繁にシャ
ンプーを使う美容師などのヘビーユーザーでは、界面活
性剤による刺激は深刻な問題となっている。 【0004】従って、界面活性剤の使用など、外部の刺
激物によって角質細胞間の脂質、角質層中の天然保湿因
子及び角質層中の水分の溶出、減少を効果的に抑制する
方策が従来より強く要望されていた。 【0005】また、乾燥性皮膚疾患患者、乳幼児、殺菌
消毒剤など皮膚に刺激となる物質にさらされる人などの
敏感肌のトラブルに対する対策として、既に起こって
いるトラブルを沈静化することと同時に、皮膚トラブ
ルの原因となる刺激から皮膚を保護することが重要とさ
れている。皮膚角質層は外界の環境から身体の内部を保
護する役割を担っているが、その機能を十分に果たすに
はコレステロールなどの角質細胞間脂質やウロカニン酸
やピロリドンカルボン酸などの角質層間の水分を保持す
る天然保湿因子(NMF)が十分に存在することが大切
である。それら成分が不足すると荒れ肌状態となる。 【0006】このようなトラブル、特にアレルギー性及
び乾燥性皮膚疾患の治療には抗炎症剤が用いられている
が、抗炎症剤は既に起きてしまった炎症を抑えるのみ
で、予防的な効果は認められず、また副作用の面からも
常用しにくいものである。 【0007】このため従来は、油分や保湿成分を補うこ
とにより、皮膚のトラブルを防止、軽減することが行わ
れていたが、油分や保湿成分によっては十分な皮膚疾患
の治療効果はなく、従って皮膚疾患を効果的に予防、改
善することができる治療剤が要望されていた。 【0008】 【課題を解決するための手段及び発明の実施の形態】本
発明者らは、上記要望に応えるために鋭意検討を行った
結果、粒径1〜1000nm、ゼータ電位の絶対値が3
0mV以上、純度90%以上の水膨潤性粘土鉱物が外部
刺激に対する経皮吸収性を抑制し、更に角質細胞間の脂
質、角質層中の天然保湿因子の溶出を抑制し、角質層中
の水分量の減少を抑制する効果を有し、特に界面活性剤
の使用による皮膚への上記悪影響を防止し得る効果を与
えることを知見した。 【0009】即ち、従来より、粘土鉱物は吸着性、結合
性、懸濁性、膨潤性、皮膜形成性、増粘性等の性質を有
することから、これらの性質を利用して化粧料に配合さ
れてきた。粘土鉱物を化粧料に配合した場合、該化粧料
は、(1)べたつきがなく、なめらかでさわやかな感触
を有する、(2)皮膚表面で伸びが良く、皮膜を形成し
て接着する、(3)増粘する、(4)エマルジョンやサ
スペンジョンの安定性が向上する、(5)ローションや
シャンプーのクレンジング性能が向上する、(6)水や
石鹸による洗い落とし性が改善する等の性質が付与され
ることが知られている。即ち、粘土鉱物を配合すること
により、化粧料の液性が変化すると共に、その使用後の
質感、仕上がり感を向上することができるものである。 【0010】更に、水膨潤性粘土鉱物は、化粧料に上記
のような好ましい使用感を付与すると共に、高分子増粘
剤と同等の増粘効果を示し、安価で、しかも化粧料を容
器から取り出す際の液切れをよくするなどの利点を有し
ている。 【0011】従って、以上のような効果から、水膨潤性
粘土鉱物は従来よりファンデーション、パック剤、クリ
ーム、石鹸やペースト状洗顔剤等の化粧料に用いられて
きた。特に、水膨潤性粘土鉱物は皮膚洗浄剤のような洗
い流してしまうものに配合した場合においても、すすぎ
時にぬるつきがなく、洗い上がりの肌にすべすべした感
触を与えるという効果を有することが知られている。 【0012】しかしながら、上記水膨潤性粘土鉱物が外
部刺激に対する経皮吸収性を抑制し、角質細胞間の脂
質、角質層中の天然保湿因子の溶出を防止し、角質層中
の水分量の減少を抑制する効果を与えるということは従
来知られていないものであるが、本発明者らは、水膨潤
性粘土鉱物が界面活性剤による経皮吸収性を抑制し、角
質細胞間の脂質、角質層中の天然保湿因子の溶出を顕著
に防止し、角質層中の水分量の減少を効果的に抑制する
という効果を与えることを見出し、本発明をなすに至っ
たものである。 【0013】従って、本発明は、粒径が1〜1000n
m、ゼータ電位の絶対値が30mV以上、純度が90%
以上の水膨潤性粘土鉱物を有効成分とする外部刺激に対
する経皮吸収性を抑制し、角質細胞間の脂質、角質層中
の天然保湿因子並びに角質層中の水分の溶出・減少を抑
制する皮膚保護剤を提供する。 【0014】ここで、水膨潤性粘土鉱物としては、天然
又は合成スメクタイト粘土、特に有機変性されていない
非有機変性のスメクタイト粘土が好ましく、モンモリロ
ナイト、バイデライト、ノントロナイト、サポナイト、
ヘクトライト、ソーコナイト、スチーブンサイトなどが
挙げられ、また、膨潤性の雲母なども使用できるが、こ
れらの中ではモンモリロナイト、サポナイトが好まし
い。なお、これらの粘土鉱物は必要により担持物質に担
持されて使用されるが、担持物質は特に限定されない。 【0015】また、水膨潤性粘土鉱物としては、動的光
散乱法により測定した平均粒径が1000nm以下、電
気泳動光散乱法により測定したゼータ電位の絶対値が3
0mV以上、粉末X線回折法により求められた純度が9
0%以上のものを用いる。 【0016】上記粘土鉱物の平均粒径が1000nmを
超えると粘土鉱物単位重量あたりの表面積が小さく皮膚
表面の接触面積が少ないため外的刺激に対する経皮吸収
の抑制、角質細胞の成分溶出抑制効果が劣る。好ましい
平均粒径は500nm以下の範囲である。 【0017】また、ゼータ電位の絶対値は皮膚表面への
(水膨潤性)粘土鉱物吸着量から30mV以上のもので
ある。 【0018】更に、粘土鉱物、特に天然から採取したも
のには、カルサイト、トリジマイト、クリストバライ
ト、石英、各種無機物などの非膨潤性の夾雑物が含まれ
ており、これらの夾雑物が多く含まれていると上記効果
が不十分であり、この点から粘土鉱物の純度は90%以
上であることが必要であり、特に95%以上が好まし
い。 【0019】本発明の上記皮膚角質細胞間及び角質層中
の成分の溶出・減少抑制剤乃至皮膚保護剤は、外部刺
激、特に界面活性剤、とりわけアニオン性界面活性剤を
含有する組成物、例えばクリーム、ローション、身体洗
浄剤、シャンプー、リンス、台所洗剤、住居用洗剤(殺
菌消毒剤)などの使用による界面活性剤の経皮吸収性を
抑制し、角質細胞間の脂質、角質層中の天然保湿因子の
溶出、角質層中の水分量の減少を抑制、防止するために
用いられる。この場合、本発明の保護剤は、界面活性剤
含有組成物中に配合等して用いることができる。なお、
本発明の保護剤を界面活性剤含有組成物などに配合する
場合、その濃度は0.001重量%以上、特に0.1重
量%以上であることがその効果を有効に発揮させる点か
ら好適である。 【0020】 【発明の効果】本発明の保護剤の使用により、外部から
の刺激、特に界面活性剤の使用による経皮への吸収性を
減少させ、角質細胞間の脂質、角質層中の天然保湿因子
並びに角質層中の水分量の減少を顕著に防止することが
できる。 【0021】 【実施例】以下、実施例と比較例を示し、本発明を具体
的に説明するが、本発明は下記の実施例に制限されるも
のではない。 【0022】表1に示す組成のボディーソープに水膨潤
性粘土鉱物(天然モンモリロナイト(Na担持)を使
用)を配合した。なお、この水膨潤性粘土鉱物として
は、平均粒径500nm、ゼータ電位の絶対値が45m
V、純度93%のものを使用した。 【0023】 【表1】 【0024】上記実施例のボディーソープは、比較例の
ものに比べて界面活性剤の経皮への吸収が少なく、また
角質細胞間の脂質、角質層中の天然保湿因子並びに角質
層中の水分の減少を抑制するものであった。
Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to suppressing skin irritation from the outside, in particular, suppressing the percutaneous absorption of a surfactant, and suppressing dermal intercellular lipids and natural moisturizing in the stratum corneum. Factors, elution of water in the stratum corneum
The present invention relates to a skin protective agent capable of effectively suppressing reduction. 2. Description of the Related Art The skin plays a role of a barrier that protects the inside of the body from the environment of the outside world. Natural moisturizing factor of the layer
It is important that there is sufficient water in the stratum corneum (izing factor: NMF). If these components are insufficient, the skin becomes rough. There are various external factors that cause such rough skin, and surfactants are particularly irritants to the skin. Surfactants are used not only in creams, lotions, body cleansers, shampoos, and rinses, but also in kitchen detergents, residential detergents, clothing detergents, softeners, and the like. Stimulation has been a problem in the past, and it has been proposed to use surfactants with low irritation as raw materials, or to use anionic, nonionic, amphoteric surfactants in combination, etc. It has also been proposed to incorporate tannic acid. [0003] However, even in these proposals,
It is difficult to sufficiently suppress the elution of lipids between stratum corneum and natural moisturizing factors in the stratum corneum and the reduction of water content in the stratum corneum by the use of surfactants, especially for people with rough skin and frequent use of shampoos. For heavy users such as hairdressers, irritation by surfactants is a serious problem. [0004] Therefore, there has been a method for effectively suppressing the elution or reduction of lipids between stratum corneum cells, natural moisturizing factors in the stratum corneum and water in the stratum corneum by an external stimulus such as the use of a surfactant. It was strongly requested. In addition, as a countermeasure against troubles on sensitive skin such as dry skin disease patients, infants, persons exposed to substances that irritate the skin such as disinfectants and disinfectants, at the same time as calming down troubles already occurring, It is important to protect the skin from irritation that causes skin troubles. The stratum corneum of the skin plays a role of protecting the inside of the body from the external environment.However, in order to fulfill its function, it is necessary to remove lipids between the stratum corneum such as cholesterol and moisture between the stratum corneum such as urocanic acid and pyrrolidone carboxylic acid. It is important that there be sufficient natural moisturizing factor (NMF) to retain. If these components are insufficient, the skin becomes rough. [0006] Anti-inflammatory agents have been used to treat such troubles, especially allergic and dry skin diseases. However, anti-inflammatory agents only suppress inflammation that has already occurred, and have a preventive effect. It is not recognized, and it is difficult to use regularly from the viewpoint of side effects. For this reason, conventionally, skin troubles have been prevented or reduced by supplementing oils and moisturizing components. However, oils and moisturizing components have no sufficient therapeutic effect on skin diseases. There is a need for a therapeutic agent that can effectively prevent and improve skin diseases. Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to respond to the above demand, and as a result, the particle diameter is 1 to 1000 nm and the absolute value of the zeta potential is 3
A water-swellable clay mineral having a purity of 0 mV or more and a purity of 90% or more suppresses percutaneous absorption to external stimuli, further suppresses the elution of lipids between keratinocytes and natural moisturizing factors in the horny layer, and reduces the moisture in the horny layer. It has been found that it has an effect of suppressing a decrease in the amount, and particularly has an effect of preventing the above-mentioned adverse effects on the skin due to use of a surfactant. That is, conventionally, clay minerals have properties such as adsorptiveness, binding, suspending, swelling, film-forming properties, and viscosity increasing. Have been. When a clay mineral is blended in a cosmetic, the cosmetic is (1) non-sticky, has a smooth and refreshing feel, (2) stretches well on the skin surface, forms a film and adheres, (3) And (4) improving the stability of emulsions and suspensions, (5) improving the cleansing performance of lotions and shampoos, and (6) improving the washability with water and soap. It is known. That is, by blending the clay mineral, the liquid properties of the cosmetic can be changed, and the texture and finish after use can be improved. [0010] Furthermore, the water-swellable clay mineral imparts the above-mentioned preferable feeling of use to the cosmetic, exhibits a thickening effect equivalent to that of the polymer thickener, is inexpensive, and allows the cosmetic to be removed from the container. It has advantages such as better drainage when taking out. Therefore, water swellable clay minerals have hitherto been used in cosmetics such as foundations, packs, creams, soaps and paste-like facial cleansing agents due to the above effects. In particular, water-swellable clay minerals are known to have the effect of giving a smooth feel to washed skin even when mixed with a thing that is washed away, such as a skin cleanser, without slimy when rinsing. ing. However, the water-swellable clay mineral suppresses percutaneous absorption to external stimuli, prevents elution of lipids between keratinocytes and natural moisturizing factors in the stratum corneum, and reduces water content in the stratum corneum. Although it has not been known that it has an effect of suppressing liposomes, the present inventors have found that water-swellable clay minerals suppress percutaneous absorption by a surfactant, and lipids between keratinocytes, keratin It has been found that the elution of the natural moisturizing factor in the stratum corneum is remarkably prevented, and the effect of effectively suppressing the decrease in the amount of water in the stratum corneum is achieved, and the present invention has been accomplished. Therefore, according to the present invention, the particle size is 1 to 1000 n.
m, absolute value of zeta potential is 30 mV or more, purity is 90%
Skin that suppresses percutaneous absorption to external stimuli containing the above water-swellable clay mineral as an active ingredient and suppresses the dissolution and reduction of lipids between keratinocytes, natural moisturizing factors in the stratum corneum and water in the stratum corneum Provide protective agent. Here, as the water-swellable clay mineral, natural or synthetic smectite clay, particularly non-organic modified smectite clay which is not organically modified, is preferably used.
Examples include hectorite, sauconite, and stevensite, and swelling mica can also be used. Of these, montmorillonite and saponite are preferred. In addition, these clay minerals are used by being supported on a supporting substance as necessary, but the supporting substance is not particularly limited. The water-swellable clay mineral has an average particle diameter of 1000 nm or less as measured by a dynamic light scattering method and an absolute value of zeta potential of 3 or less as measured by an electrophoretic light scattering method.
0 mV or more, purity determined by powder X-ray diffraction method is 9
Use the one with 0% or more. When the average particle diameter of the clay mineral exceeds 1000 nm, the surface area per unit weight of the clay mineral is small and the contact area of the skin surface is small, so that the effect of suppressing percutaneous absorption to external stimuli and the effect of suppressing the elution of keratinocyte components are reduced. Inferior. The preferred average particle size is in the range of 500 nm or less. The absolute value of the zeta potential is 30 mV or more based on the amount of (water-swellable) clay mineral adsorbed on the skin surface. Furthermore, clay minerals, especially those collected from nature, contain non-swelling impurities such as calcite, tridymite, cristobalite, quartz and various inorganic substances, and these impurities are abundant. In this case, the above effect is insufficient. From this point, the purity of the clay mineral needs to be 90% or more, and particularly preferably 95% or more. The above-mentioned agent for inhibiting elution / decrease of components between skin keratinocytes and in the stratum corneum or the skin protective agent of the present invention is a composition containing an external stimulus, particularly a surfactant, particularly a surfactant containing an anionic surfactant, for example, Suppresses the percutaneous absorption of surfactants by using creams, lotions, body cleansers, shampoos, rinses, kitchen detergents, household detergents (bactericide), lipids between keratinocytes, natural in the horny layer It is used to suppress or prevent the elution of moisturizing factors and the decrease in the amount of water in the stratum corneum. In this case, the protective agent of the present invention can be used by being incorporated into a surfactant-containing composition. In addition,
When the protective agent of the present invention is incorporated into a surfactant-containing composition or the like, the concentration is preferably 0.001% by weight or more, particularly preferably 0.1% by weight or more, from the viewpoint of exhibiting its effect effectively. is there. EFFECT OF THE INVENTION The use of the protective agent of the present invention reduces the external stimulus, in particular, the absorption into the skin via the use of a surfactant, and reduces lipids between keratinocytes, It is possible to remarkably prevent the moisture retention factor and the water content in the stratum corneum from decreasing. EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. A water-swellable clay mineral (using natural montmorillonite (supporting Na)) was added to a body soap having the composition shown in Table 1. The water-swellable clay mineral has an average particle size of 500 nm and an absolute value of zeta potential of 45 m.
V, those having a purity of 93% were used. [Table 1] The body soap of the above example has less surfactant percutaneous absorption than that of the comparative example, and also contains lipids between keratinocytes, natural moisturizing factors in the stratum corneum and water in the stratum corneum. Was suppressed.

フロントページの続き (72)発明者 角谷 治夫 東京都墨田区本所1丁目3番7号 ライ オン株式会社内 (56)参考文献 特開 昭64−47711(JP,A) 特開 昭64−40565(JP,A) 特開 昭63−51310(JP,A) 特開 平2−267113(JP,A) 特開 平4−334312(JP,A) 特開 昭63−66111(JP,A) 特開 平4−187628(JP,A) 特開 平7−258055(JP,A) 特開 昭63−139105(JP,A) 特開 昭62−48614(JP,A) 特開 平3−20227(JP,A) 特開 平8−175928(JP,A) 特開 平9−316485(JP,A) 特開 平8−151597(JP,A) (58)調査した分野(Int.Cl.7,DB名) A61K 7/00 - 7/50 Continuation of the front page (72) Inventor Haruo Kadoya 1-3-7 Honjo, Sumida-ku, Tokyo Inside Rion Co., Ltd. (56) References JP-A-64-47711 (JP, A) JP-A-64-40565 JP-A-63-51310 (JP, A) JP-A-2-267113 (JP, A) JP-A-4-334312 (JP, A) JP-A-63-66111 (JP, A) JP-A-4-187628 (JP, A) JP-A-7-258055 (JP, A) JP-A-63-139105 (JP, A) JP-A-62-48614 (JP, A) JP-A-3-20227 ( JP, A) JP-A-8-179528 (JP, A) JP-A-9-316485 (JP, A) JP-A-8-151597 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) A61K 7/00-7/50

Claims (1)

(57)【特許請求の範囲】 【請求項1】 粒径が1〜1000nm、ゼータ電位の
絶対値が30mV以上、純度が90%以上の水膨潤性粘
土鉱物を有効成分とする皮膚保護剤。
(57) [Claim 1] A skin protective agent comprising a water-swellable clay mineral having a particle size of 1 to 1000 nm, an absolute value of zeta potential of 30 mV or more and a purity of 90% or more as an active ingredient.
JP15481396A 1996-05-27 1996-05-27 Skin protective agent Expired - Fee Related JP3385857B2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP15481396A JP3385857B2 (en) 1996-05-27 1996-05-27 Skin protective agent
IDP971746A ID16978A (en) 1996-05-27 1997-05-26 SKIN PROTECTIVE SUBSTANCE

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP15481396A JP3385857B2 (en) 1996-05-27 1996-05-27 Skin protective agent

Publications (2)

Publication Number Publication Date
JPH09315926A JPH09315926A (en) 1997-12-09
JP3385857B2 true JP3385857B2 (en) 2003-03-10

Family

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Country Status (2)

Country Link
JP (1) JP3385857B2 (en)
ID (1) ID16978A (en)

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JP4684377B2 (en) * 1998-06-26 2011-05-18 ライオン株式会社 Pollen allergy prevention agent
JP4841075B2 (en) * 2000-09-22 2011-12-21 旭化成ケミカルズ株式会社 Whitening cosmetics
JP4822580B2 (en) * 2000-10-17 2011-11-24 ライオン株式会社 Mite allergen treatment agent and mite allergen inactivation method
TWI306764B (en) * 2002-03-28 2009-03-01 Shiseido Co Ltd Insoluble powder, reviving powder for skin barrier function, powder for preventing and ameliorating coarse skin, troubles, and preparation containing the same for external use
JP2004217621A (en) * 2002-12-27 2004-08-05 Shiseido Co Ltd Oily skin lotion
US9308397B2 (en) 2004-04-30 2016-04-12 The Procter & Gamble Company Long-wearing cosmetic compositions
JP2013023438A (en) * 2011-07-15 2013-02-04 Mikimoto Pharmaceut Co Ltd Cornification promoter, filaggrin production promoter, loricrin production promoter, padi-1 production promoter, and histidase production promoter
JP6177595B2 (en) * 2012-06-29 2017-08-09 ライオン株式会社 Skin cosmetics

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JPS6248614A (en) * 1985-08-28 1987-03-03 Shiseido Co Ltd Solid cosmetic
JPS6351310A (en) * 1986-08-20 1988-03-04 Shiseido Co Ltd Cosmetic compounded with spherical clay mineral
JPS6366111A (en) * 1986-09-05 1988-03-24 Shiseido Co Ltd Cosmetic blended with spherical organic complex clay mineral
JPH07527B2 (en) * 1986-12-01 1995-01-11 鐘紡株式会社 Cosmetics for wrinkle straightening
JP2519465B2 (en) * 1987-08-05 1996-07-31 株式会社資生堂 Composite powder and manufacturing method thereof
JP2514373B2 (en) * 1987-08-19 1996-07-10 株式会社資生堂 Cosmetics
JPH02267113A (en) * 1989-04-06 1990-10-31 Shiseido Co Ltd Organic complex clay mineral
JPH0320227A (en) * 1989-06-19 1991-01-29 Shiseido Co Ltd External drug for skin
JP3005039B2 (en) * 1990-11-20 2000-01-31 株式会社資生堂 Non-aqueous detergent composition and method for producing the same
JPH04334312A (en) * 1991-05-10 1992-11-20 Kao Corp Hair cosmetic
JP3417649B2 (en) * 1994-03-18 2003-06-16 株式会社資生堂 Sunscreen cosmetics
JPH08151597A (en) * 1994-11-29 1996-06-11 Lion Corp Liquid detergent composition
JPH08175928A (en) * 1994-12-22 1996-07-09 Lion Corp Cosmetic
JP3539074B2 (en) * 1996-05-24 2004-06-14 ライオン株式会社 Liquid cleaning composition for skin and hair

Also Published As

Publication number Publication date
JPH09315926A (en) 1997-12-09
ID16978A (en) 1997-11-27

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