JPH09227329A - Perfume base and external perfume - Google Patents
Perfume base and external perfumeInfo
- Publication number
- JPH09227329A JPH09227329A JP2957296A JP2957296A JPH09227329A JP H09227329 A JPH09227329 A JP H09227329A JP 2957296 A JP2957296 A JP 2957296A JP 2957296 A JP2957296 A JP 2957296A JP H09227329 A JPH09227329 A JP H09227329A
- Authority
- JP
- Japan
- Prior art keywords
- cosmetic
- sol
- temperature
- polymer compound
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、香粧品基剤および
外用香粧品に関し、より詳しくは、生体(肌等)に塗布
等により適用する直前の温度では流動性のあるゾル状態
であり、生体に適用した際に体温等により速やかにゲル
状態に変化する香粧品基剤および外用香粧品に関する。
本明細書において、「香粧品」とは、薬事法で規定され
る「化粧品」に加えて、「芳香製品」および「医薬部外
品」をも包含する趣旨で用いる(田村健夫・廣田博「香
粧品科学」第6頁、1990年、フレグランス・ジャー
ナル社)。また、「基剤」(base material)とは、香
粧品を構成する「他の成分」を混和ないし分散させて、
該香粧品の生体への適用を容易とする目的で(該「他の
成分」とtもに)使用される媒体(mediumないしmatri
x)をいう。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic base and a cosmetic for external use, and more specifically, it is in a sol state having fluidity at a temperature immediately before being applied to a living body (skin, etc.) by coating or the like. The present invention relates to a cosmetic base and a cosmetic for external use, which rapidly changes into a gel state due to body temperature and the like when applied to.
In the present specification, “cosmetics” is used to include “aroma products” and “quasi-drugs” in addition to “cosmetics” defined by the Pharmaceutical Affairs Law (Takeo Tamura and Hirota Hirota. Cosmetic Science ", p. 6, 1990, Fragrance Journal). The "base material" is a mixture or dispersion of "other ingredients" that compose a cosmetic product,
The medium (medium or matrix) used for the purpose of facilitating the application of the cosmetics to the living body (as well as the "other components" and t).
x).
【0002】本発明の外用香粧品は、例えば、コスメテ
ィック・パックとして、あるいは除毛剤として、あるい
は脱色剤として好適に使用することが可能である。The external cosmetic composition of the present invention can be suitably used, for example, as a cosmetic pack, a hair remover, or a decolorizing agent.
【0003】[0003]
【従来の技術】従来より、外用香粧品の分野において
は、該香粧品の生体(皮膚等)へ適用する際の容易性
(および安定性、迅速性)、および/又は生体から該外
用香粧品を除去する際の容易性の両立ないしバランスさ
せることが、極めて困難であった。2. Description of the Related Art Conventionally, in the field of cosmetics for external use, the easiness (and stability, quickness) of applying the cosmetics to the living body (skin, etc.) and / or the cosmetic for external use from the living body It has been extremely difficult to balance or balance the ease of removing the.
【0004】例えば、外用香粧品の1態様であるコスメ
ティック・パック(化粧用途のパック)は、無機粉末を
水と混合して肌に塗布、乾燥させて、無機粉末の被膜を
形成させた後、水等で洗い落とす水洗型パックと;被膜
形成用の水溶性高分子(ポリビニルアルコール等)を水
に溶解して肌に塗布、乾燥させて、該水溶性高分子の薄
い被膜を形成させた後、該被膜を剥離する剥離型パック
に大別される。For example, in a cosmetic pack (pack for cosmetic use), which is one aspect of external cosmetics, inorganic powder is mixed with water, applied to the skin, and dried to form a film of the inorganic powder. A water-washable pack that is washed off with water or the like; a water-soluble polymer (polyvinyl alcohol, etc.) for film formation is dissolved in water, applied to the skin, and dried to form a thin film of the water-soluble polymer, It is roughly classified into a peelable pack for peeling the coating film.
【0005】上記したいずれのパックにおいても、主成
分は水であるため、肌上で被膜を形成させるためには水
を蒸発除去する必要があり、したがって該パック塗布か
ら被膜形成までに長時間が必要であった。該パックを夏
期に使用する場合は、発汗あるいは多湿のため被膜形成
までに更なる長時間が必要であった。多忙な現代人にと
って、パックが乾燥するまでに要する時間は貴重である
ため、できるだけ早急に被膜が形成されることがコスメ
ティック・パックの重要な要件となっている。Since the main component of any of the above-mentioned packs is water, it is necessary to evaporate and remove the water in order to form a film on the skin. Therefore, it takes a long time from application of the pack to film formation. Was needed. When the pack was used in the summer, it took a long time to form a film due to sweating or high humidity. Since the time it takes for the pack to dry is valuable for busy modern people, it is an important requirement for cosmetic packs that the coating be applied as quickly as possible.
【0006】従来より、被膜形成までの時間を短縮する
ためにエチルアルコール等の低沸点物質を添加したり、
あるいは無機粉末、水溶性高分子あるいは保湿剤等の増
量剤を添加して、固形分を増やす方法が行われてきた。
しかしながら、エチルアルコール等の多量の低沸点物質
のパックへの添加は、皮膚を過度に刺激する傾向が避け
がたい。また、パックにおける固形分の増加は、該パッ
クの流動性を低減させて、塗布時のパックの延び具合、
およびパック自体の保存安定性を低減させるばかりでな
く、コスメティック・パックの最大の効用であるところ
の、肌に柔軟性と張りを与えるための水分含量を著しく
低減させてしまう結果となる。Conventionally, a low-boiling substance such as ethyl alcohol is added to shorten the time until the formation of a film,
Alternatively, a method has been performed in which a solid content is increased by adding a filler such as an inorganic powder, a water-soluble polymer or a moisturizer.
However, the addition of large amounts of low-boiling substances such as ethyl alcohol to the pack unavoidably tends to over-irritate the skin. Further, an increase in the solid content in the pack reduces the fluidity of the pack, and the extension of the pack during application,
Not only does this reduce the storage stability of the pack itself, but it also results in a significant reduction in the water content, which is the maximum benefit of the cosmetic pack, to impart flexibility and tension to the skin.
【0007】また、特に従来の剥離型パックの場合には
完全に被膜が形成される前に、何らかの理由でパックを
肌から取り除く必要がある場合には、含水する被膜の強
度が弱いため、該パック被膜を物理的に剥離することが
困難であること、また該被膜を部分的に形成した高分子
は水に溶解しにくくなるため、水洗によっても簡単には
除去できないという問題も指摘されていた。Particularly, in the case of the conventional peelable pack, when the pack needs to be removed from the skin for some reason before the film is completely formed, the strength of the film containing water is weak, It has been pointed out that it is difficult to physically peel off the pack film, and the polymer partially forming the film becomes difficult to dissolve in water, so that it cannot be easily removed even by washing with water. .
【0008】一方、外用香粧品の他の態様である除毛剤
においては、従来より、腋の下の毛や、手足の体毛を除
去する目的で、除毛剤(化学的脱毛剤)が一般的に使わ
れてきた。On the other hand, in the depilatory agent which is another aspect of the cosmetic for external use, a depilatory agent (chemical depilatory agent) has been generally used for the purpose of removing hair under the axilla and body hair of limbs. Has been used.
【0009】従来より、上記の化学的除毛剤は、毛髪の
主成分であるケラチン蛋白質のシスチン結合(ジスルフ
ィド結合)を還元して、可溶化する能力を有する主成分
たる還元剤(チオグリコール酸カルシウム等)と、毛髪
を膨潤させるためpHを11以上に調節するためのpH
調整剤(水酸化カルシウム等)とからなる。除毛剤の主
成分である還元剤(チオグリコール酸カルシウム等)
は、空気と接触している除毛剤の表面においては非常に
酸化されやすく除毛効果が消失してしまうため、該脱毛
剤は、通常は、皮膚上に厚く塗布することができるよう
に、ペースト状、あるいはクリーム状の形態を有してい
る。Conventionally, the above chemical depilatory agent is a reducing agent (thioglycolic acid) which is a main component having an ability to solubilize by reducing cystine bond (disulfide bond) of keratin protein which is a main component of hair. Calcium, etc.) and pH to adjust the pH to 11 or higher to swell hair
It consists of a regulator (calcium hydroxide, etc.). Reducing agent (calcium thioglycolate, etc.) which is the main component of hair remover
Is very easily oxidized on the surface of the depilatory that is in contact with air, and the depilatory effect disappears, so that the depilatory is usually applied thickly on the skin. It has a paste-like or cream-like form.
【0010】除毛剤はシェービングと異なり、毛孔の中
から毛を除去するために毛の生長が遅いこと、除毛後の
皮膚が滑らかなことが重要な要素であるが、従来の除毛
剤の形態がペースト状あるいはクリーム状であるため、
細かい毛孔にまで除毛剤が侵入しにくいといった問題が
指摘されている。Unlike the shaving, the depilatory is an important factor that the growth of the hair is slow and the skin after the depilation is smooth in order to remove the hair from the pores. Since the form of is paste or cream,
It has been pointed out that the hair remover is less likely to enter even fine pores.
【0011】また、除毛剤は強い還元作用を有する薬剤
を含有するため皮膚に対しての刺激が強く、除毛後には
できるだけ速やかに、かつ完全に皮膚から除去する必要
がある。しかしながら、従来の除毛剤が粘度の高いペー
スト状あるいはクリーム状であるために、その除去が大
変面倒であることのみならず、除毛剤を完全に除去する
こと、特に毛孔に詰まった除毛剤を除去するためには皮
膚を強くこすったり、洗ったりする必要があった。ま
た、このようなペースト状あるいはクリーム状の除毛剤
の場合、その形態の特性から、誤った場所(例えば、除
毛を欲しない生体表面の箇所)、あるいは生体以外の箇
所(衣類等)に付着した場合においては、その除去は大
変面倒であった。Further, since the depilatory contains a drug having a strong reducing action, it has a strong irritation to the skin, and it is necessary to completely remove it from the skin as quickly as possible after depilation. However, since the conventional depilatory is in the form of paste or cream with high viscosity, it is not only very troublesome to remove it, but it is also necessary to completely remove the depilatory, especially the depilatory clogged in the pores. It was necessary to rub and wash the skin strongly to remove the agent. Further, in the case of such a paste-like or cream-like dehairing agent, due to the characteristics of its form, it may be placed in an incorrect location (for example, a location on the surface of the living body where hair removal is not desired) or a location other than the living body (such as clothing). In the case of adhesion, its removal was very troublesome.
【0012】[0012]
【発明が解決しようとする課題】本発明の目的は、上記
した従来の外用香粧品の欠点を解消した外用香粧品、お
よび「他の成分」とともに該香粧品を与えるべき香粧品
基剤を提供することにある。The object of the present invention is to provide a cosmetic composition for external use which eliminates the above-mentioned drawbacks of conventional cosmetic products for external use, and a cosmetic base which should give the cosmetic product together with "other components". To do.
【0013】本発明の他の目的は、生体(皮膚等)へ適
用する際の容易性(および安定性、迅速性)、および/
又は生体から除去する際の容易性を両立させた外用香粧
品および香粧品基剤を提供することにある。Another object of the present invention is easiness (and stability, rapidity) when applied to a living body (skin, etc.), and / or
Another object of the present invention is to provide a cosmetic for external use and a cosmetic base which have both ease of removal from the living body.
【0014】本発明の更に他の目的は、上記した従来の
コスメティック・パックの被膜形成までに長時間が必要
であるという問題点を、エチルアルコール等の多量の低
沸点物質の添加あるいは固形分の増量という方法を必須
とせずに解消したコスメティック・パックを提供するこ
とにある。Still another object of the present invention is to solve the above-mentioned problem that it takes a long time to form a film of a conventional cosmetic pack, by adding a large amount of a substance having a low boiling point such as ethyl alcohol or a solid content. It is to provide a cosmetic pack that eliminates the need to increase the amount.
【0015】本発明の更に他の目的は、肌に十分な柔軟
性、張り、潤い等を与えるための水分量を充分に含むコ
スメティック・パックを提供することにある。Still another object of the present invention is to provide a cosmetic pack containing a sufficient amount of water for imparting sufficient flexibility, tension and moisturizing to the skin.
【0016】本発明の更に他の目的は、被膜が完全に形
成される前にパックを除去する必要があった場合に、剥
離も水洗除去も困難であるという従来の剥離型パックの
欠点を解消したコスメティック・パックを提供すること
にある。Still another object of the present invention is to eliminate the disadvantage of the conventional peelable pack which is difficult to peel and wash when the pack needs to be removed before the coating is completely formed. The purpose is to provide cosmetic packs.
【0017】本発明の更に他の目的は、従来の除毛剤と
比較して、塗布時に凹凸のある複雑な形状をした肌の表
面にも容易に密着し、毛孔の中まで侵入することができ
る、除毛効果の高い除毛剤を提供することにある。Still another object of the present invention is that, as compared with the conventional hair remover, it can easily adhere even to the surface of skin having a complicated shape with unevenness at the time of application and penetrate into the pores. It is to provide a depilatory having a high depilatory effect.
【0018】本発明の更に他の目的は、従来の除毛剤と
比較して除去が著しく簡便で、かつ毛孔の中からも完全
に除去可能な除毛剤を提供することにある。Still another object of the present invention is to provide a hair remover which is significantly easier to remove than conventional hair removers and which can be completely removed from the pores.
【0019】本発明の更に他の目的は、従来の脱色剤と
比較して、塗布時に凹凸のある複雑な形状をした肌の表
面にも容易に密着し、毛孔の中まで侵入することができ
る、脱色効果の高い脱色剤を提供することにある。Still another object of the present invention is that, as compared with the conventional decolorizing agent, it can easily adhere even to the surface of skin having a complicated shape with unevenness at the time of application and can penetrate into pores. , To provide a decolorizing agent having a high decolorizing effect.
【0020】本発明の更に他の目的は、従来の脱色剤と
比較して除去が著しく簡便で、かつ毛孔の中からも完全
に除去可能な脱色剤を提供することにある。Still another object of the present invention is to provide a decolorizing agent which is remarkably easy to remove as compared with conventional decolorizing agents and which can be completely removed from the pores.
【0021】[0021]
【課題を解決するための手段】本発明者らは鋭意研究の
結果、従来の外用香粧品に含有されていた成分とは全く
異なる特性を有する高分子化合物;すなわち、その水溶
液が特定のゾル-ゲル転移温度を有し、且つゾル-ゲル転
移温度より高い温度で実質的に水不溶性を示し、該ゾル
-ゲル転移温度よりも低い温度で可逆的に水可溶性を示
す高分子化合物を、ゲル形成成分(ゲル化成分)として
用いて、香粧品基剤ないし香粧品を構成することが、上
記の問題点解決に極めて効果的であることを見出した。Means for Solving the Problems As a result of intensive studies by the present inventors, a polymer compound having characteristics completely different from the components contained in conventional cosmetics for external use; that is, its aqueous solution has a specific sol- A sol having a gel transition temperature and being substantially water-insoluble at a temperature higher than the sol-gel transition temperature,
-Use of a polymer compound reversibly soluble in water at a temperature lower than the gel transition temperature as a gel-forming component (gelling component) to form a cosmetic base or a cosmetic product has the above-mentioned problems. It was found to be extremely effective in solving the problem.
【0022】本発明の香粧品基剤は上記知見に基づくも
のであり、より詳しくは水と、ゲル形成成分とを少なく
とも含む香粧品基剤であって;該ゲル形成成分が、その
水溶液が0℃より高く37℃より低いゾル-ゲル転移温
度を有する高分子化合物からなり;且つ、基剤全体とし
て前記ゾル-ゲル転移温度より高い温度で実質的に水不
溶性を示し、該ゾル-ゲル転移温度より低い温度で可逆
的に水可溶性を示すことを特徴とするものである。The cosmetic base of the present invention is based on the above findings, and more specifically, it is a cosmetic base containing at least water and a gel-forming component; A polymer compound having a sol-gel transition temperature higher than 37 ° C. and lower than 37 ° C .; and, as a whole base material, is substantially water-insoluble at a temperature higher than the sol-gel transition temperature, It is characterized by being reversibly water-soluble at a lower temperature.
【0023】本発明によれば、更に、水と、ゲル形成成
分とを少なくとも含む香粧品であって;該ゲル形成成分
が、その水溶液が0℃より高く37℃より低いゾル-ゲ
ル転移温度を有する高分子化合物からなり;且つ、香粧
品全体として前記ゾル-ゲル転移温度より高い温度で実
質的に水不溶性を示し、該ゾル-ゲル転移温度より低い
温度で可逆的に水可溶性を示すことを特徴とする外用香
粧品が提供される。According to the present invention, there is further provided a cosmetic product containing at least water and a gel-forming component; the gel-forming component having an aqueous solution whose sol-gel transition temperature is higher than 0 ° C and lower than 37 ° C. A high molecular weight compound having; and that the cosmetic as a whole exhibits substantially water insolubility at a temperature higher than the sol-gel transition temperature and reversibly exhibits water solubility at a temperature lower than the sol-gel transition temperature. A featured cosmetic for external use is provided.
【0024】本発明の外用香粧品(ないし基剤)は、ゲ
ル形成成分として、その水溶液が0℃より高く37℃よ
り低いゾル−ゲル転移温度を有する高分子化合物を含
み;且つ香粧品として前記ゾル−ゲル転移温度より高い
温度で実質的に水不溶性を示し、ゾル−ゲル転移温度よ
り低い温度で可逆的に水可溶性を示すため、該香粧品を
生体(皮膚等)へ適用する直前には、(例えば、香粧品
の温度を前記ゾル−ゲル転移温度より低温とすることに
より)流動性の高いゾル状態(液体状態;水可溶性の状
態)として、生体に容易に塗布等により適用することが
できる。生体への適用後には、体温等による香粧品自体
の温度上昇により、該香粧品は速やかにゲル化する(実
質的に水に不溶性の状態となる)ため、生体上で迅速に
安定な被膜を形成することができる。The external cosmetic preparation (or base) of the present invention contains, as a gel-forming component, a polymer compound whose aqueous solution has a sol-gel transition temperature higher than 0 ° C. and lower than 37 ° C .; Immediately before applying the cosmetic to the living body (skin etc.), it is substantially water-insoluble at a temperature higher than the sol-gel transition temperature and reversibly water-soluble at a temperature lower than the sol-gel transition temperature. , (For example, by setting the temperature of cosmetics to be lower than the sol-gel transition temperature) in a highly fluid sol state (liquid state; water-soluble state), which can be easily applied to a living body by application or the like. it can. After application to a living body, the temperature of the cosmetic itself rises due to body temperature, etc., so that the cosmetic immediately gels (becomes substantially insoluble in water), so a stable film is quickly formed on the living body. Can be formed.
【0025】他方、生体から該外用香粧品を除去する際
には、例えば、香粧品の温度を低温としてゾル状態に戻
すことにより、極めて容易、且つ、より完全な生体から
の除去が可能となる。すなわち、従来の外用香粧品では
極めて困難であったところの、生体への適用の容易性
(および安定性、迅速性)と、生体から該外用香粧品を
除去する際の容易性との両立が可能となる。On the other hand, when removing the external cosmetic composition from the living body, for example, by returning the cosmetic composition to a sol state by lowering the temperature of the cosmetic composition, it becomes possible to remove the cosmetic composition from the living body extremely easily and completely. . In other words, both the ease of application to the living body (and stability and rapidity) and the ease of removing the external use cosmetic from the living body, which were extremely difficult with conventional external use cosmetics, are compatible. It will be possible.
【0026】上述した本発明の外用香粧品を「コスメテ
ィック・パック」の態様とした場合には、該パックは上
記ゾル−ゲル転移温度より低い温度(例えば室温)では
ゾル(液体)状態であるため、肌の表面等の複雑な凹凸
のある生体表面に簡便に塗布することができるのみなら
ず、皺等の凹凸の中にまで該パックを進入させることが
できる。一方、本発明のコスメティック・パックは該ゾ
ル−ゲル転移温度より高い温度、即ち肌の表面の温度で
は、速やかにゲル状態に変化するため、肌上への滞留性
が著しく向上する。When the above-mentioned cosmetic for external use of the present invention is used as a "cosmetic pack", the pack is in a sol (liquid) state at a temperature lower than the sol-gel transition temperature (for example, room temperature). Not only can it be simply applied to the surface of a living body having complicated irregularities such as the surface of the skin, but the pack can be made to enter even irregularities such as wrinkles. On the other hand, the cosmetic pack of the present invention rapidly changes into a gel state at a temperature higher than the sol-gel transition temperature, that is, the temperature of the surface of the skin, so that the retention property on the skin is remarkably improved.
【0027】従来のコスメティック・パックは、既に述
べたように、肌に塗布した後に水を蒸散させることによ
って被膜を形成するために、被膜が形成されるまでに長
時間かかるという問題があったが、本発明のコスメティ
ック・パックは肌に塗布すると速やかにゲル化し、被膜
が形成されるため、被膜形成までの時間が著しく短縮さ
れるという特徴を有する。また従来の剥離型パックの場
合には被膜形成の途中、即ち生乾きの状態では被膜の強
度が弱いため、該被膜を物理的に剥離することが困難で
あったが、本発明のコスメティック・パックは肌に塗布
すると直ちにゲル状の被膜が形成されるため、塗布後に
は速やかに(何時でも)物理的に剥離することが可能で
あるという特徴を有している。As described above, the conventional cosmetic pack has a problem that it takes a long time to form a film because it forms a film by evaporating water after being applied to the skin. The cosmetic pack of the present invention is characterized in that when applied to the skin, it rapidly gels and forms a film, so that the time until the film formation is significantly shortened. Further, in the case of the conventional peelable pack, it is difficult to physically peel the coating during the formation of the coating, that is, in the state of being dry, the coating is weak, but the cosmetic pack of the present invention is Since the gel-like film is formed immediately when applied to the skin, it has a feature that it can be physically peeled off quickly (at any time) after application.
【0028】また本発明のコスメティック・パックはゾ
ル−ゲル転移温度を有し、該ゾル−ゲル転移温度より低
い温度ではゾル状態に変化するため、例えば冷たい水で
洗浄することによって該コスメティック・パックを簡単
に除去することができる。また、本発明のコスメティッ
ク・パックは肌上で多量の水を含有するハイドロゲルを
形成するため、肌に対して柔軟性、張り、潤いを充分に
付与することができる。また本発明のコスメティック・
パックは肌に塗布すると直ちにゲル状態に変化し、徐々
に水分が蒸散し最後には従来のコスメティック・パック
と同様、本発明の成分である高分子化合物の薄い被膜が
形成されるため、物理的に剥離が可能である。Further, the cosmetic pack of the present invention has a sol-gel transition temperature and changes to a sol state at a temperature lower than the sol-gel transition temperature. Therefore, the cosmetic pack is washed with cold water, for example. It can be easily removed. Further, since the cosmetic pack of the present invention forms a hydrogel containing a large amount of water on the skin, it can sufficiently impart flexibility, tension and moisturization to the skin. The cosmetics of the present invention
When the pack is applied to the skin, it immediately changes into a gel state, gradually evaporates water, and finally forms a thin film of the polymer compound, which is a component of the present invention, like the conventional cosmetic pack. It can be peeled off.
【0029】更には、本発明のコスメティック・パック
の場合も従来から使用されてきた皮膚保護剤、抗酸化
剤、保存安定化剤、洗浄剤等を添加することができ、肌
に塗布されて直ちにゲル化するために、上記した各成分
をゲル中に均一に分散することができるという特徴を有
している。Further, in the case of the cosmetic pack of the present invention, it is possible to add conventionally used skin protectants, antioxidants, storage stabilizers, detergents, etc., and immediately after application to the skin. For gelation, each of the above components can be uniformly dispersed in the gel.
【0030】他方、本発明の外用香粧品を「除毛剤」の
態様とした場合には、該除毛剤は、該ゾルーゲル転移温
度より低い温度、例えば室温ではゾル(液体)状態であ
り、従来のクリーム状あるいはペースト状の従来の除毛
剤よりも粘度が著しく低いため、塗布時に凹凸のある複
雑な形状をした肌の表面に密着し、毛孔の中まで容易に
侵入させることができる。本発明の除毛剤は該ゾルーゲ
ル転移温度より高い温度、即ち肌の表面の温度で速やか
にゲル状態に変化し、肌上で密着した状態での滞留性が
著しく向上すると同時に、(従来のクリーム状あるいは
ペースト状の除毛剤の表面と異なり)ゲル表面のベタつ
きが少なく、衣類などへの付着も著しく低減させること
ができる。On the other hand, when the cosmetic for external use of the present invention is used as a "hair removal agent", the hair removal agent is in a sol (liquid) state at a temperature lower than the sol-gel transition temperature, for example, room temperature, Since the viscosity is significantly lower than that of the conventional cream- or paste-type conventional depilatory agent, it adheres to the surface of the skin having a complicated shape having irregularities at the time of application and can easily penetrate into the pores. The hair remover of the present invention rapidly changes into a gel state at a temperature higher than the sol-gel transition temperature, that is, the temperature of the surface of the skin, and at the same time, the retention property in the state of being adhered on the skin is remarkably improved. (Unlike the surface of a depilatory agent in the form of paste or paste), the surface of the gel is less sticky, and adhesion to clothes and the like can be significantly reduced.
【0031】本発明の除毛剤を皮膚に塗布し除毛を実行
した後には、本発明の除毛剤の塗布膜はゲル化している
ため、該ゲル化塗膜は、容易に物理的に肌から剥離する
ことができ(特に毛孔からの除去も容易に行うことがで
き)、従来のクリーム状あるいはペースト状の除毛剤の
ように肌を強く拭き取ったり、水洗いするというような
煩雑な手間を省くことができる。After the hair remover of the present invention has been applied to the skin and the hair has been removed, the applied film of the hair remover of the present invention has gelled, so that the gelled coating film can be easily and physically formed. It can be peeled off from the skin (especially it can be easily removed from the pores), and it is a troublesome task such as strongly wiping the skin or washing with water like a conventional cream or paste dehairing agent. Can be omitted.
【0032】他方、本発明の外用香粧品を「脱色剤」の
態様とした場合には、該脱色剤は、該ゾルーゲル転移温
度より低い温度、例えば室温ではゾル(液体)状態であ
り、従来のクリーム状あるいはペースト状の従来の脱色
剤よりも粘度が著しく低いため、塗布時に凹凸のある複
雑な形状をした肌の表面に密着し、毛孔の中まで容易に
侵入させることができる。本発明の脱色剤は該ゾルーゲ
ル転移温度より高い温度、即ち肌の表面の温度で速やか
にゲル状態に変化し、肌上で密着した状態での滞留性が
著しく向上すると同時に、(従来のクリーム状あるいは
ペースト状の脱色剤の表面と異なり)ゲル表面のベタつ
きが少なく、衣類などへの付着も著しく低減させること
ができる。On the other hand, when the cosmetic for external use of the present invention is used as a "decoloring agent", the decolorizing agent is in a sol (liquid) state at a temperature lower than the sol-gel transition temperature, for example, at room temperature, Since the viscosity is significantly lower than that of a conventional decolorizing agent in the form of cream or paste, it adheres to the surface of skin having a complicated shape having irregularities during application and can easily penetrate into pores. The decolorizing agent of the present invention rapidly changes into a gel state at a temperature higher than the sol-gel transition temperature, that is, the temperature of the surface of the skin, remarkably improves the retention property in the state of being adhered on the skin, and Alternatively, unlike the surface of a paste-like decolorizing agent), the surface of the gel is less sticky, and the adhesion to clothes can be significantly reduced.
【0033】本発明の脱色剤を皮膚に塗布し脱色を実行
した後には、本発明の脱色剤の塗布膜はゲル化している
ため、該ゲル化塗膜は、容易に物理的に肌から剥離する
ことができ(特に毛孔からの除去も容易に行うことがで
き)、従来のクリーム状あるいはペースト状の脱色剤の
ように肌を強く拭き取ったり、水洗いするというような
煩雑な手間を省くことができる。After the decoloring agent of the present invention is applied to the skin to carry out decolorization, the coating film of the decolorizing agent of the present invention is gelated, so that the gelled coating film is easily physically peeled from the skin. It can be removed (especially easily removed from pores), and you can save the troublesome work of wiping off the skin strongly and washing with water like a conventional cream or paste decolorizer. it can.
【0034】[0034]
【発明の実施の形態】以下、本発明を詳細に説明する。
以下の記述において、量比を表す「%」および「部」
は、特に断らない限り重量基準(すなわち、重量%およ
び重量部)とする。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the following description, "%" and "part" that represent the quantitative ratio
Is on a weight basis (ie, wt% and parts by weight) unless otherwise noted.
【0035】(ゾル−ゲル転移温度)本発明に用いられ
る「ゾル−ゲル転移温度を有する高分子化合物」の「ゾ
ル−ゲル転移温度」の定義および測定は、文献(H. Yos
hioka ら、Journal of Macromolecular Science, A31
(1), 113 (1994))に記載された定義および方法に基づ
く。即ち、観測周波数1Hzにおける試料の動的弾性率
を低温側から高温側へ徐々に温度を変化(1℃/1分)
させて測定し、該試料の貯蔵弾性率(G´、弾性項)が
損失弾性率(G″、粘性項)を上回る点の温度をゾル−
ゲル転移温度とする。一般に、G″>G´の状態がゾル
であり、G″<G´の状態がゲルであると定義される。
このゾル−ゲル転移温度の測定に際しては、下記の測定
条件が好適に使用可能である。(Sol-Gel Transition Temperature) The definition and measurement of the “sol-gel transition temperature” of the “polymer compound having a sol-gel transition temperature” used in the present invention are described in the literature (H. Yos.
hioka et al., Journal of Macromolecular Science, A31
(1), 113 (1994)). That is, the dynamic elastic modulus of the sample at the observation frequency of 1 Hz gradually changes from the low temperature side to the high temperature side (1 ° C / 1 minute)
The temperature at which the storage elastic modulus (G ′, elastic term) of the sample exceeds the loss elastic modulus (G ″, viscous term) is measured by the sol-
It is the gel transition temperature. Generally, the state of G ″> G ′ is defined as sol, and the state of G ″ <G ′ is defined as gel.
When measuring the sol-gel transition temperature, the following measurement conditions can be preferably used.
【0036】<動的・損失弾性率の測定条件> 測定機器(商品名):ストレス制御式レオメーターCS
L700、Carri-Med社製 試料溶液(ないし分散液)の濃度(ただし「ゾル−ゲル
転移温度を有する高分子化合物」の濃度として):10
(重量)% 試料溶液の量:約0.8 g 測定用セルの形状・寸法:アクリル製平行円盤(直径
4.0cm)、ギャップ600μm。<Dynamic / Loss Elastic Modulus Measuring Conditions> Measuring instrument (trade name): stress control rheometer CS
L700, manufactured by Carri-Med, Inc. Sample solution (or dispersion) concentration (provided as "polymer compound having sol-gel transition temperature" concentration): 10
(Weight)% Amount of sample solution: about 0.8 g Shape / dimension of measuring cell: acrylic parallel disk (diameter 4.0 cm), gap 600 μm.
【0037】適用ストレス:線形領域内。Applied stress: Within the linear region.
【0038】上記の「ゾル−ゲル転移温度を有する高分
子化合物」は、その水溶液または水分散液が上記ゾル−
ゲル転移温度より高い温度では流動性の乏しいゲル状
(ハイドロゲル)となり、一方、該温度より低い温度で
はゾル(ないし液状)となる特性を有する。The above-mentioned "polymer compound having a sol-gel transition temperature" is an aqueous solution or dispersion of the sol-gel.
At a temperature higher than the gel transition temperature, it becomes a gel (hydrogel) having poor fluidity, while at a temperature lower than the temperature, it becomes a sol (or liquid).
【0039】本発明に用いられる高分子は、0℃より高
く、37℃より低いゾル−ゲル転移温度を有する。生体
表面(肌等)の温度(約37℃)において効率的なゲル
化を可能とする点からは、該ゾル−ゲル転移温度は、1
5℃以上35℃以下(更には20℃以上30℃以下)で
あることが好ましい。The polymers used in the present invention have a sol-gel transition temperature above 0 ° C and below 37 ° C. The sol-gel transition temperature is 1 in terms of enabling efficient gelation at the temperature (about 37 ° C.) of the surface of the living body (skin, etc.).
It is preferably 5 ° C. or higher and 35 ° C. or lower (further, 20 ° C. or higher and 30 ° C. or lower).
【0040】このように好適なゾル−ゲル転移温度を有
する高分子化合物は、外用香粧品のゲル形成成分として
使用可能な(前述した一般的特性を有する)種々の高分
子化合物の中から、上記したスクリーニング方法(ゾル
−ゲル転移温度測定法)に従って容易に選択することが
できる。The polymer compound having a suitable sol-gel transition temperature as described above is selected from among the various polymer compounds (having the above-mentioned general characteristics) that can be used as a gel-forming component for external cosmetics. It can be easily selected according to the screening method (sol-gel transition temperature measurement method).
【0041】(ゾル−ゲル転移温度を有する高分子化合
物)本発明の外用香粧品に使用可能な高分子化合物は、
0℃より高く、37℃より低いゾル−ゲル転移温度を有
するものであれば特に制限されないが、速やかな水不溶
性への変化が容易な点からは、該高分子化合物は、その
水溶液が0℃より高く37℃より低いLCSTを有する
温度感応性高分子部分(ブロック)と、親水性高分子部
分とが結合されてなる高分子化合物であることが好まし
く、該「LCSTを有する温度感応性高分子部分」が一
分子中に複数存在する高分子化合物であることが更に好
ましい。(Polymer Compound Having Sol-Gel Transition Temperature) The polymer compound usable in the external cosmetics of the present invention is
The polymer compound is not particularly limited as long as it has a sol-gel transition temperature higher than 0 ° C. and lower than 37 ° C. However, from the viewpoint of easy rapid change to water insolubility, the polymer compound has an aqueous solution of 0 ° C. A polymer compound in which a temperature-sensitive polymer portion (block) having an LCST higher than 37 ° C. and lower than 37 ° C. and a hydrophilic polymer portion are bonded is preferable, and the “temperature-sensitive polymer having LCST” is preferable. It is further preferable that the “part” is a polymer compound having a plurality of molecules in one molecule.
【0042】本発明に用いられる「その水溶液がLCS
Tを有する温度感応性高分子」部分とは、水に対する溶
解度温度係数が負を示す高分子化合物であり、低温にて
生成する高分子化合物と水分子との水素結合に依存する
水和物(オキソニウムヒドロキシド)が高温で分解し、
脱水和により高分子化合物同士が凝集し沈澱する特徴を
有する。As used in the present invention, "the aqueous solution is LCS
The “temperature-sensitive polymer having T” is a polymer compound having a negative temperature coefficient of solubility in water, and a hydrate (which depends on the hydrogen bond between the polymer compound formed at low temperature and a water molecule ( Oxonium hydroxide) decomposes at high temperature,
It is characterized in that polymer compounds aggregate and precipitate by dehydration.
【0043】本発明において、LCST(Lower Critic
al Solution Temperature)とは、高分子化合物の水和
と脱水和の転移温度をいう(例えば、ヘスキンズ(M. He
skins)らの J. Macromol. Sci.-Chem., A2 (8), 1441
(1968)参照)。該温度感応性高分子部分はLCSTより
低い温度では親水性で水に可溶性であるが、LCSTよ
り高い温度では疎水性となって水中で不溶性であって沈
澱し、この変化は可逆的である。本発明においては、前
述した高分子化合物が生体表面の温度および「これより
低い温度」に速やかに対応した可溶性−不溶性の可逆的
変化を与える点からは、上記温度感応性高分子部分のL
CSTは0℃より高く37℃未満(更には15〜37
℃)であることが好ましい。In the present invention, LCST (Lower Critic)
al Solution Temperature) refers to the transition temperature of hydration and dehydration of a polymer compound (for example, Heskins (M. He
skins) et al. J. Macromol. Sci.-Chem., A2 (8), 1441
(1968)). The temperature-sensitive polymer portion is hydrophilic at a temperature lower than LCST and soluble in water, but becomes hydrophobic at a temperature higher than LCST, becomes insoluble in water and precipitates, and this change is reversible. In the present invention, from the viewpoint that the above-mentioned polymer compound gives a reversible change of soluble-insoluble rapidly responding to the temperature of the living body surface and "the temperature lower than this", L of the above temperature-sensitive polymer portion is used.
CST is higher than 0 ° C and lower than 37 ° C (further, 15-37
C).
【0044】上記LCSTを有する限り、本発明におい
ては上記温度感応性高分子として特に制限なく使用する
ことが可能である。本発明に好適に使用可能な高分子化
合物としては、例えば、ポリN−置換アクリルアミド誘
導体、ポリN−置換メタアクリルアミド誘導体、これら
の共重合体;ポリプロピレンオキサイド、プロピレンオ
キサイドと他のアルキレンオキサイドとの共重合体;ポ
リビニルメチルエーテル、ポリビニルアルコール部分酢
化物、ポリアルキレンオキサイド等が挙げられる。As long as it has the above-mentioned LCST, it can be used as the above temperature-sensitive polymer in the present invention without any particular limitation. Examples of the polymer compound that can be preferably used in the present invention include poly N-substituted acrylamide derivatives, poly N-substituted methacrylamide derivatives, copolymers thereof; polypropylene oxide, and copolymers of propylene oxide and other alkylene oxides. Polymers: polyvinyl methyl ether, polyvinyl alcohol partial acetic acid, polyalkylene oxide and the like.
【0045】本発明において好適な温度感応性高分子化
合物を、以下にLCSTが低い順に列挙する。The temperature-sensitive polymer compounds suitable for the present invention are listed below in the order of increasing LCST.
【0046】ポリ−N−アクリロイルピペリジン;ポリ
−N−n−プロピルメタアクリルアミド;ポリ−N−イ
ソプロピルアクリルアミド;ポリ−N,N−ジエチルア
クリルアミド;ポリ−N−イソプロピルメタアクリルア
ミド;ポリ−N−シクロプロピルアクリルアミド;ポリ
−N−アクリロイルピロリジン;ポリ−N、N−エチル
メチルアクリルアミド;ポリ−N−シクロプロピルメタ
アクリルアミド;ポリ−N−エチルアクリルアミド;上
記の高分子は単独重合体(ホモポリマー)であってもよ
く、また上記重合体を構成する単量体と、他の単量体と
の共重合体であってもよい。このような共重合体を構成
する他の単量体としては、親水性単量体、疎水性単量体
のいずれを用いることもできる。Poly-N-acryloylpiperidine; poly-N-n-propylmethacrylamide; poly-N-isopropylacrylamide; poly-N, N-diethylacrylamide; poly-N-isopropylmethacrylamide; poly-N-cyclopropyl Acrylamide; poly-N-acryloylpyrrolidine; poly-N, N-ethylmethylacrylamide; poly-N-cyclopropylmethacrylamide; poly-N-ethylacrylamide; the above-mentioned polymer is a homopolymer It may be a copolymer of a monomer constituting the above polymer and another monomer. As the other monomer constituting such a copolymer, any of a hydrophilic monomer and a hydrophobic monomer can be used.
【0047】上記親水性単量体としては、N−ビニルピ
ロリドン、ビニルピリジン、アクリルアミド、メタアク
リルアミド、N−メチルアクリルアミド、ヒドリキシエ
チルメタアクリレート、ヒドロキシエチルアクリレー
ト、ヒドロキシメチルメタアクリレート、ヒドロキシメ
チルアクリレート、酸性基を有するアクリル酸、メタア
クリル酸及びそれらの塩、ビニルスルホン酸、スチレン
スルホン酸等、並びに塩基性基を有するN,N−ジメチ
ルアミノエチルメタクリレート、N,N−ジエチルアミ
ノエチルメタクリレート、N,N−ジメチルアミノプロ
ピルアクリルアミド及びそれらの塩等が挙げられるが、
これらに限定されるものではない。Examples of the hydrophilic monomer include N-vinylpyrrolidone, vinylpyridine, acrylamide, methacrylamide, N-methylacrylamide, hydridoxyethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl methacrylate, hydroxymethyl acrylate, and acid. Group-containing acrylic acid, methacrylic acid and salts thereof, vinyl sulfonic acid, styrene sulfonic acid, etc., and basic group-containing N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N- Examples include dimethylaminopropyl acrylamide and salts thereof,
It is not limited to these.
【0048】一方、上記疎水性単量体としては、エチル
アクリレート、メチルメタクリレート、ブチルメタクリ
レート、グリシジルメタクリレート等のアクリレート誘
導体およびメタクリレート誘導体、N−n−ブチルメタ
アクリルアミド等のN−置換アルキルメタアクリルアミ
ド誘導体、塩化ビニル、アクリロニトリル、スチレン、
酢酸ビニル等が挙げられるが、これに限定されるもので
はない。On the other hand, as the hydrophobic monomer, acrylate derivatives and methacrylate derivatives such as ethyl acrylate, methyl methacrylate, butyl methacrylate and glycidyl methacrylate, N-substituted alkyl methacrylamide derivatives such as Nn-butyl methacrylamide, Vinyl chloride, acrylonitrile, styrene,
Examples thereof include, but are not limited to, vinyl acetate and the like.
【0049】一般的には、上記高分子化合物に親水性単
量体を共重合することにより、LCSTを上昇させるこ
とが可能となり、一方疎水性単量体を共重合することに
より、LCSTを下降させることが可能となる。従っ
て、これらの共重合成分(親水性単量体および/又は疎
水性単量体)を選択することによっても、所望のLCS
Tを有する高分子化合物を得ることができる。Generally, it is possible to increase the LCST by copolymerizing a hydrophilic monomer with the above-described polymer compound, while decreasing the LCST by copolymerizing a hydrophobic monomer. It becomes possible. Therefore, the desired LCS can also be obtained by selecting these copolymerization components (hydrophilic monomer and / or hydrophobic monomer).
A polymer compound having T can be obtained.
【0050】一方、本発明において温度感応性高分子化
合物と結合させる親水性高分子化合物としては、例え
ば、メチルセルロース、デキストラン、ポリエチレンオ
キサイド、ポリビニルアルコール、ポリN−ビニルピロ
リドン、ポリビニルピリジン、ポリアクリルアミド、ポ
リメタアクリルアミド、ポリN−メチルアクリルアミ
ド、ポリヒドロキシメチルアクリレート、ポリアクリル
酸、ポリメタクリル酸、ポリビニルスルホン酸、ポリス
チレンスルホン酸およびそれらの塩、ポリN,N−ジメ
チルアミノエチルメタクリレート、ポリN,N−ジエチ
ルアミノエチルメタクリレート、ポリN,N−ジメチル
アミノプロピルアクリルアミドおよびそれらの塩等が挙
げられる。On the other hand, in the present invention, examples of the hydrophilic polymer compound to be combined with the temperature-sensitive polymer compound include methyl cellulose, dextran, polyethylene oxide, polyvinyl alcohol, poly N-vinylpyrrolidone, polyvinyl pyridine, polyacrylamide and poly. Methacrylamide, poly N-methyl acrylamide, poly hydroxymethyl acrylate, polyacrylic acid, polymethacrylic acid, polyvinyl sulfonic acid, polystyrene sulfonic acid and salts thereof, poly N, N-dimethylaminoethyl methacrylate, poly N, N-diethylamino Examples thereof include ethyl methacrylate, poly N, N-dimethylaminopropyl acrylamide and salts thereof.
【0051】本発明に用いられる「ゾル−ゲル転移温度
を有する高分子化合物」における、その水溶液がLCS
Tを有する高分子部分(A)と親水性高分子部分(B)
とを結合してなる共重合体の結合様式は特に制限されな
いが、例えば、AとBのブロック共重合体、あるいは主
鎖Aに側鎖Bが結合したグラフト共重合体、または主鎖
Bに側鎖Aが結合したグラフト共重合体等の様式が好適
に使用可能である。The aqueous solution of the "polymer compound having a sol-gel transition temperature" used in the present invention is LCS.
Polymer part having T (A) and hydrophilic polymer part (B)
The bonding mode of the copolymer obtained by bonding and is not particularly limited, but for example, a block copolymer of A and B, a graft copolymer in which a side chain B is bonded to the main chain A, or a main chain B A mode such as a graft copolymer in which the side chain A is bonded can be preferably used.
【0052】LCSTを有する高分子部分と、親水性高
分子部分とのブロック共重合体は、例えば予め両者に反
応活性な官能基(水酸基、カルボキシル基、アミノ基、
イソシアネート基等)を複数導入し、両者を化学反応に
より結合させることによって得ることが可能である。The block copolymer of the polymer part having LCST and the hydrophilic polymer part has, for example, a functional group (hydroxyl group, carboxyl group, amino group, or
Can be obtained by introducing a plurality of isocyanate groups or the like and bonding them by a chemical reaction.
【0053】また、一般にグラフト共重合体の合成法と
しては、1)重合体の連鎖移動反応を利用する方法、
2)幹重合体に遊離基に分裂し得る官能基を導入し、該
官能基から重合を開始する方法、3)幹重合体からイオ
ン重合を開始せしめる方法等が知られている。本発明に
使用すべきグラフト共重合体をこれらの方法によって得
ることもできるが、側鎖の重合度を制御するという観点
からは、LCSTを有する高分子部分中に1個の重合性
官能基を導入し、親水性高分子部分を与える単量体と共
重合させる;あるいは、親水性高分子部分中に1個の重
合性官能基を導入し、LCSTを有する高分子部分を与
える単量体と共重合させることで得ることが有利であ
る。Generally, as a method for synthesizing a graft copolymer, 1) a method utilizing a chain transfer reaction of a polymer,
There are known 2) a method in which a functional group capable of being split into free radicals is introduced into the trunk polymer, and polymerization is started from the functional group. 3) A method in which ionic polymerization is started from the trunk polymer. The graft copolymer to be used in the present invention can be obtained by these methods, but from the viewpoint of controlling the degree of polymerization of side chains, one polymerizable functional group is added to the polymer portion having LCST. Introduced and copolymerized with a monomer that gives a hydrophilic polymer moiety; or with a monomer that introduces one polymerizable functional group into the hydrophilic polymer moiety and gives a polymer moiety having an LCST. It is advantageous to obtain it by copolymerization.
【0054】本発明の外用香粧品に用いられる「ゾル−
ゲル転移温度を有する高分子化合物」の分子量は特に制
限されないが、分散系(エマルション、ディスパージョ
ン等)に用いた場合の分散の安定性の点からは、分子量
が大きい程有利である。より具体的には、本発明におい
ては、上記「ゾル−ゲル転移温度を有する高分子化合
物」としては、その分子量が10万以上のものを少なく
とも含むものが好ましく用いられる。ここに「分子量1
0万以上の高分子化合物」とは、該ゾル−ゲル転移温度
より低い温度においてその水溶液(濃度:約1%)を分
画分子量10万の限外濾過膜(アミコン社製、商品名:
H1P100−43)を用いて限外濾過した際に、実質
的に濾過されないものをいう。ここに、「実質的に濾過
されない」とは、原液の容量を1/3まで限外濾過濃縮
した時、濾液中に検出される該高分子化合物の濃度が原
液(濃縮前)中の該高分子化合物の濃度の1/10以下
であることをいう。この「実質的に濾過されない」こと
は、例えば、原液と濾液中の高分子化合物の濃度比をU
V測定等により確認することが可能である。The "sol-" used in the cosmetics for external use of the present invention
The molecular weight of the "polymer compound having a gel transition temperature" is not particularly limited, but from the viewpoint of dispersion stability when used in a dispersion system (emulsion, dispersion, etc.), a larger molecular weight is more advantageous. More specifically, in the present invention, as the “polymer compound having a sol-gel transition temperature”, those containing at least those having a molecular weight of 100,000 or more are preferably used. "Molecular weight 1
"A polymer having a molecular weight of more than 0,000" means an aqueous solution (concentration: about 1%) having a molecular weight cut off of 100,000 at a temperature lower than the sol-gel transition temperature (manufactured by Amicon, trade name:
H1P100-43) means a substance which is not substantially filtered when subjected to ultrafiltration. Here, "substantially not filtered" means that when the volume of the stock solution is concentrated by ultrafiltration to 1/3, the concentration of the polymer compound detected in the filtrate is the high level in the stock solution (before concentration). It is 1/10 or less of the concentration of the molecular compound. This “not substantially filtered” means that, for example, the concentration ratio of the polymer compound in the stock solution and the filtrate is U
It can be confirmed by V measurement or the like.
【0055】上記した限外濾過に際しては、下記の実験
条件が好適に使用可能である。In the above ultrafiltration, the following experimental conditions can be suitably used.
【0056】<限外濾過の確認測定条件> 高分子水溶液の原液量:約3000ml 限外濾過膜:アミコン社製、商品名:H1P100−4
3(ホローファイバー型)。<Confirmation measurement conditions of ultrafiltration> Stock amount of polymer aqueous solution: about 3000 ml Ultrafiltration membrane: manufactured by Amicon, trade name: H1P100-4
3 (hollow fiber type).
【0057】温度:「ゾル−ゲル転移温度を有する高分
子化合物」水溶液のゾル-ゲル転移温度以下。 限外濾過加圧:1kg/cm2 循環流速:5l/min 本発明に用いる「ゾル−ゲル転移温度を有する高分子化
合物」の水溶液は、低温(ゾル−ゲル転移より低い温
度)では流動性のある水溶液状態を呈し、高温(ゾル−
ゲル転移より高い温度)では、流動性を失ってハイドロ
ゲル状態を呈する、熱可逆性ゾル−ゲル転移を示す。本
発明者の知見によれば、このような熱可逆性ゾル−ゲル
転移のメカニズムは、以下のように推定される。Temperature: Below the sol-gel transition temperature of the "polymer compound having a sol-gel transition temperature" aqueous solution. Ultrafiltration Pressurization: 1 kg / cm 2 Circulation flow rate: 5 l / min The aqueous solution of the “polymer compound having a sol-gel transition temperature” used in the present invention is fluid at low temperature (temperature lower than sol-gel transition). It is in the form of an aqueous solution and has a high temperature (sol-
At a temperature higher than the gel transition), it exhibits a thermoreversible sol-gel transition in which it loses fluidity and assumes a hydrogel state. According to the findings of the present inventors, the mechanism of such a thermoreversible sol-gel transition is presumed as follows.
【0058】すなわち、分子内に存在する温度感応性高
分子部分のLCSTより低い温度では、該温度感応性高
分子部分、親水性高分子部分ともに水溶性であるため、
該「ゾル−ゲル転移温度を有する高分子化合物」は完全
に水に溶解可能となる。しかしながら、この水溶液の温
度を該LCSTより高い温度に昇温すると、該温度感応
性高分子部分が非水溶性(疎水性)となり、疎水相互作
用によって、別個の分子間で会合する。That is, at a temperature lower than the LCST of the temperature-sensitive polymer portion present in the molecule, both the temperature-sensitive polymer portion and the hydrophilic polymer portion are water-soluble.
The “polymer compound having a sol-gel transition temperature” can be completely dissolved in water. However, when the temperature of this aqueous solution is raised to a temperature higher than the LCST, the temperature-sensitive polymer portion becomes water-insoluble (hydrophobic), and the hydrophobic interaction causes association between different molecules.
【0059】他方、親水性高分子部分は該LCSTより
高い温度においても水溶性を保つため、このような親水
性高分子部分の存在が、上記「LCSTを有する高分子
部分」間の凝集が巨視的な相分離に至ることを防止し
て、安定なハイドロゲル形成に寄与する。On the other hand, since the hydrophilic polymer portion remains water-soluble even at a temperature higher than the LCST, the presence of such a hydrophilic polymer portion indicates that the aggregation between the “polymer portion having LCST” is macroscopic. Phase separation and contribute to stable hydrogel formation.
【0060】このようにして生成したハイドロゲルの温
度を、再び、分子内に存在する温度感応性高分子部分の
LCSTより低い温度に冷却すると、該温度感応性高分
子部分が水溶性となって疎水性会合による架橋点が解放
され、ハイドロゲル構造が消失する。このため、本発明
に用いる「ゾル−ゲル転移温度を有する高分子化合物」
再び、完全に水に溶解可能となる。このように、このゾ
ル−ゲル転移は、分子内に存在する温度感応性高分子部
分のLCSTにおける可逆的な親水性−疎水性の変化に
基づくものであるため、温度変化に対応して完全な可逆
性を有する。When the temperature of the hydrogel thus formed is cooled again to a temperature lower than the LCST of the temperature-sensitive polymer portion present in the molecule, the temperature-sensitive polymer portion becomes water-soluble. Crosslinking points due to hydrophobic association are released, and the hydrogel structure disappears. Therefore, the “polymer compound having a sol-gel transition temperature” used in the present invention
Once again, it is completely soluble in water. As described above, this sol-gel transition is based on the reversible hydrophilic-hydrophobic change in the LCST of the temperature-sensitive polymer part existing in the molecule, and therefore, the sol-gel transition is completely dependent on the temperature change. Has reversibility.
【0061】LCSTを有する温度感応性高分子部分と
親水性高分子部分との組成、両高分子部分の疎水性度、
親水性度、及び/又はそれらの分子量を調整することに
よって上記高分子化合物のゾル−ゲル転移温度、即ち、
本発明の外用香粧品のゾル−ゲル転移温度が0℃より高
く、37℃より低くなるように制御することができる。
また、該高分子化合物水溶液に添加される「他の成分」
(例えば、尿素、グアニジン、チオグリコール酸塩、p
H調製剤など)を含んでいても、該ゾル−ゲル転移温度
を0℃より高く、37℃より低くなるように制御するこ
とができる。The composition of a temperature-sensitive polymer portion having an LCST and a hydrophilic polymer portion, the degree of hydrophobicity of both polymer portions,
By adjusting the hydrophilicity and / or the molecular weight thereof, the sol-gel transition temperature of the polymer compound, that is,
The sol-gel transition temperature of the cosmetic composition for external use of the present invention can be controlled so as to be higher than 0 ° C and lower than 37 ° C.
In addition, "other components" added to the aqueous solution of the polymer compound
(Eg urea, guanidine, thioglycolate, p
It is possible to control the sol-gel transition temperature to be higher than 0 ° C. and lower than 37 ° C. even when a H adjusting agent is included.
【0062】本発明の外用香粧品を構成する高分子化合
物水溶液中の、上記高分子化合物濃度は、実質的にゾル
−ゲル転移が生じる濃度範囲内であれば特に制限されな
い。外用香粧品としての含水率、ないし浸透圧作用等に
基づく生体への刺激抑制の点からは、外用濃度は、通常
0.5%〜50%(更には2%〜20%)の範囲である
ことが好ましい。The concentration of the above-mentioned polymer compound in the polymer compound aqueous solution constituting the cosmetic for external use of the present invention is not particularly limited as long as it is within the concentration range in which the sol-gel transition occurs substantially. From the viewpoint of water content as a cosmetic for external use or suppression of irritation to a living body based on osmotic action, the external concentration is usually in the range of 0.5% to 50% (further, 2% to 20%). It is preferable.
【0063】(粘度)生体に塗布等により適用する際の
容易性(延び等)の点からは、本発明の外用香粧品の粘
度は、「ゾル−ゲル転移温度を有する高分子化合物」水
溶液のゾル-ゲル転移温度以下(たとえば20℃)で、
1000センチポイズ以下、更には500センチポイズ
以下(特に200センチポイズ以下)であることが好ま
しい。本発明において、外用香粧品の粘度は、例えば、
以下の測定条件で測定することが可能である。(Viscosity) From the viewpoint of easiness (extension, etc.) when applied to a living body by coating or the like, the viscosity of the cosmetic for external use of the present invention is the same as that of the "polymer compound having a sol-gel transition temperature" aqueous solution. Below the sol-gel transition temperature (eg 20 ° C),
It is preferably 1000 centipoise or less, more preferably 500 centipoise or less (particularly 200 centipoise or less). In the present invention, the viscosity of external cosmetics is, for example,
It is possible to measure under the following measurement conditions.
【0064】<粘度測定条件> 測定機器:東京計器(株)社製、商品名:B型粘度計 ローター:「No.3 ローター」を使用 ずり速度:38s-1 (分散媒)本発明において、上述した「ゾル−ゲル転移
温度を有する高分子」とともにハイドロゲルを構成する
分散媒は、水ないし水性(aqueous)の液状媒体である
ことが好ましい。<Viscosity measuring conditions> Measuring instrument: manufactured by Tokyo Keiki Co., Ltd., trade name: B type viscometer rotor: "No. 3 rotor" is used Shear rate: 38 s -1 (dispersion medium) In the present invention, The dispersion medium that constitutes the hydrogel together with the “polymer having a sol-gel transition temperature” described above is preferably water or an aqueous liquid medium.
【0065】ここに「水性の分散媒」は、溶液、分散液
(ディスパージョン、エマルション等)のいずれの形態
であってもよい。生体表面に対する刺激性の点からは、
水性媒体を水とともに構成する「他の液状媒体」(下記
アルコール等)は、10%以下(更には5%以下)であ
ることが好ましい。このような態様における「他の液状
媒体」としては、例えば、エタノール等の1価アルコー
ル、エチレングリコール等の2価アルコール、グリセリ
ン等の3価アルコールを始めとする1価ないし多価アル
コールが好適に使用可能である。The "aqueous dispersion medium" may be in the form of a solution or a dispersion (dispersion, emulsion, etc.). From the point of stimulating the surface of the living body,
The "other liquid medium" (the following alcohol etc.) that constitutes the aqueous medium together with water is preferably 10% or less (more preferably 5% or less). As the "other liquid medium" in such an embodiment, for example, monohydric or polyhydric alcohols such as monohydric alcohols such as ethanol, dihydric alcohols such as ethylene glycol, and trihydric alcohols such as glycerin are preferable. It can be used.
【0066】(香粧品基剤)本発明の香粧品基剤は、水
と、ゲル形成成分とを少なくとも含み;該ゲル形成成分
が、その水溶液が0℃より高く37℃より低いゾル-ゲ
ル転移温度を有する高分子化合物からなり;且つ、基剤
全体として前記ゾル-ゲル転移温度より高い温度で実質
的に水不溶性を示し、該ゾル-ゲル転移温度より低い温
度で可逆的に水可溶性を示す。(Cosmetic base) The cosmetic base of the present invention contains at least water and a gel-forming component; the gel-forming component is a sol-gel transition in which the aqueous solution thereof is higher than 0 ° C and lower than 37 ° C. It is composed of a polymer compound having a temperature; and, as the whole base material, is substantially water-insoluble at a temperature higher than the sol-gel transition temperature and reversibly water-soluble at a temperature lower than the sol-gel transition temperature. .
【0067】上記香粧品基剤とともに香粧品を構成する
「他の成分」は、上記の温度変化に基づくゾル−ゲル転
移を実質的に阻害しない限り、従来より公知の香粧品成
分から選択された1以上の成分を特に制限なく使用する
ことができる。この場合においても、本発明の基剤の使
用に基づき、生体への適用の容易性(および安定性、迅
速性)と、生体から除去する際の容易性とをバランス良
く両立させた香粧品を得ることが可能となる。このよう
な態様で使用可能な上記した「他の成分」の例として
は、例えば、基礎化粧品、メークアップ化粧品、頭髪用
化粧品、芳香性化粧品、歯科用香粧品(歯磨き等)、特
殊化粧品(制汗・脱臭剤、日焼け止め・サンタン製品、
にきび用製品)等を構成する成分が挙げられる。これら
の種々の成分については、例えば、上記した文献(田村
健夫・廣田博「香粧品科学」1990年、フレグランス
・ジャーナル社)の目次第3〜10頁を参照することが
可能である。The "other ingredients" constituting the cosmetics together with the cosmetic base are selected from the conventionally known cosmetic ingredients as long as they do not substantially inhibit the sol-gel transition due to the temperature change. One or more components can be used without particular limitation. Even in this case, based on the use of the base of the present invention, there is provided a cosmetic product in which the easiness of application to the living body (and stability and quickness) and the ease of removal from the living body are well balanced. It becomes possible to obtain. Examples of the above-mentioned "other ingredients" that can be used in such an embodiment include, for example, basic cosmetics, makeup cosmetics, cosmetics for hair, aromatic cosmetics, dental cosmetics (toothpaste etc.), special cosmetics (system Sweat / deodorant, sunscreen / Santan products,
The components that make up acne products) and the like. For these various components, it is possible to refer to, for example, pages 3 to 10 of the above-mentioned document (Takeo Tamura / Hiroshi Hirota "Cosmetics Science", 1990, Fragrance Journal).
【0068】(コスメティック・パック)本発明の外用
香粧品を「コスメティック・パック」の態様とする場
合、該コスメティック・パックは、水と;その水溶液が
0℃より高く37℃より低いゾル−ゲル転移温度を有す
る高分子化合物からなるゲル形成成分とを少なくとも含
む。(Cosmetic pack) When the cosmetic for external use of the present invention is in the form of "cosmetic pack", the cosmetic pack comprises water; and the aqueous solution thereof has a sol-gel transition of higher than 0 ° C and lower than 37 ° C. At least a gel-forming component made of a polymer compound having a temperature.
【0069】コスメティック・パック全体として、上記
した好適な粘度を有する限り、コスメティック・パック
を構成する固形分の量比は特に制限されないが、通常5
0%以下(コスメティック・パック構成成分全体の合計
重量を基準として)、更には30%以下であることが好
ましい。The amount ratio of solids constituting the cosmetic pack is not particularly limited as long as it has the above-mentioned preferable viscosity as a whole, but usually 5
It is preferably 0% or less (based on the total weight of all the components of the cosmetic pack), and more preferably 30% or less.
【0070】(水溶性高分子)上記したコスメティック
・パックの被膜の剥離性等を改良する目的で、該パック
のゾル−ゲル転移特性が実質的に損なわれない範囲内
で、従来からコスメティック・パックに使用されている
水溶性高分子化合物(ポリビニルアルコール等)を、
「他の成分」として添加することができる。前述したパ
ック全体としての「好適な粘度」を有する限り、該水溶
性高分子の量比は特に制限されないが、パックを構成す
る水100(重量)部に対して、通常20部以下、更に
は10部以下であることが好ましい。(Water-Soluble Polymer) For the purpose of improving the releasability of the coating film of the above-mentioned cosmetic pack, the conventional cosmetic pack is used as long as the sol-gel transition property of the pack is not substantially impaired. The water-soluble polymer compound (polyvinyl alcohol, etc.) used in
It can be added as "another component". The amount ratio of the water-soluble polymer is not particularly limited as long as it has the “suitable viscosity” as the whole pack described above, but is usually 20 parts or less, and more preferably 20 parts or less with respect to 100 parts by weight of water constituting the pack. It is preferably 10 parts or less.
【0071】(除毛剤)本発明の外用香粧品を「除毛
剤」の態様とする場合、該除毛剤は、水と;その水溶液
が0℃より高く37℃以下であるゾルーゲル転移温度を
有する高分子化合物とを少なくとも含む。このような成
分の除毛剤を用いた場合には、例えば、物理的剥離によ
る除毛が可能である。除毛を緩和な条件下で効率的に行
う点からは、該除毛剤は更にチオグリコール酸塩を含む
ことが好ましい。該チオグリコール酸塩の使用量は特に
制限されないが、除毛剤を構成する水100部に対し
て、通常1部以上、更には1〜10部程度(特に3〜7
部程度)であることが好ましい。(Hair Removal Agent) When the cosmetic for external use of the present invention is used as a “hair removal agent”, the hair removal agent is water; and the sol-gel transition temperature at which the aqueous solution is higher than 0 ° C. and lower than 37 ° C. And a polymer compound having When a hair remover having such a component is used, for example, it is possible to remove hair by physical peeling. From the viewpoint of efficiently removing hair under mild conditions, it is preferable that the hair removing agent further contains thioglycolate. The amount of the thioglycollate used is not particularly limited, but is usually 1 part or more, further 1 to 10 parts (particularly 3 to 7 parts) with respect to 100 parts of water constituting the depilatory.
It is preferably about 1 part.
【0072】上記除毛剤は、必要に応じて、他の成分を
含有していてもよい。このような「他の成分」として
は、実質的に該ゾル−ゲル転移が損なわれない範囲内
で、従来の除毛剤の添加剤として公知のものを用いるこ
とが可能である。前述した除毛剤全体としての「好適な
粘度」を有する限り、該「他の成分」の量比は特に制限
されないが、除毛剤を構成する水100部に対して、通
常15部以下、更には10部以下であることが好まし
い。The above hair remover may contain other components, if necessary. As such “other components”, it is possible to use those known as conventional additives for dehairing agents within the range where the sol-gel transition is not substantially impaired. The amount ratio of the "other components" is not particularly limited as long as it has the "suitable viscosity" as the above-mentioned hair remover, but is usually 15 parts or less relative to 100 parts of water constituting the hair remover, Further, it is preferably 10 parts or less.
【0073】このような目的で用いる「他の成分」とし
ては、例えば、従来の除毛剤用の添加剤として公知のp
H調節剤(水酸化カルシウム、カセイアルカリ等);あ
るいは助剤(尿素および/またはグアニジン等)を含有
していてもよい。Examples of the "other components" used for such a purpose include p known as an additive for conventional hair removers.
An H regulator (calcium hydroxide, caustic alkali, etc.); or an auxiliary agent (urea and / or guanidine, etc.) may be contained.
【0074】(添加剤)上述したように本発明の香粧品
は、特定のゾル−ゲル転移温度を有する高分子化合物
と、水を少なくとも含むが、必要に応じて他の「添加
剤」を含有していてもよい。このような「添加剤」とし
ては、実質的に該ゾル−ゲル転移が損なわれない範囲内
で、従来の外用香粧品用の添加剤として公知のものを用
いることが可能である。前述した香粧品全体としての
「好適な粘度」を有する限り、該「添加剤」の量比は特
に制限されないが、香粧品を構成する水100部に対し
て、通常20部以下、更には10部以下であることが好
ましい。(Additive) As described above, the cosmetic of the present invention contains at least a polymer compound having a specific sol-gel transition temperature and water, but may further contain other "additives". You may have. As such an "additive", it is possible to use a conventionally known additive for cosmetics for external use, within a range in which the sol-gel transition is not substantially impaired. The amount ratio of the "additive" is not particularly limited as long as it has the "suitable viscosity" as the above-mentioned cosmetics as a whole. It is preferably not more than part.
【0075】このような目的で用いる「添加剤」として
は、例えば、従来の香粧品の添加剤として公知の皮膚保
護剤、抗酸化剤、保存安定化剤、洗浄剤、香料等が挙げ
られる。Examples of the "additive" used for such a purpose include a skin protective agent, an antioxidant, a storage stabilizer, a detergent, and a fragrance which are known as conventional additives for cosmetics.
【0076】以下に実施例を示し、本発明を更に具体的
に説明するが、本発明の範囲は特許請求の範囲により限
定されるものであり、本実施例によって限定されるもの
ではない。The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is limited by the claims and is not limited by the examples.
【0077】[0077]
【実施例】実施例1 (ゾル−ゲル転移温度を有する高分子の合成)N−イソ
プロピルアクリルアミド(イーストマンコダック社製)
10.2gと、N−アクリロキシスクシンイミド(国産
化学(株)製)1.71gとを反応容器内のクロロホル
ム400mlに溶解し、該反応容器内を窒素で置換した
後、N,N´−アゾビスイソブチロニトリル0.135
gを加えて、60℃で、6時間重合させた。反応終了
後、反応生成物を減圧下で濃縮し、次いで、ジエチルエ
ーテル中に沈澱させた。得られた沈殿を濾過により分離
した後、約40℃で約24時間真空乾燥して、8.8g
のポリ(N−イソプロピルアクリルアミド−co−N−
アクリロキシスクシンイミド)を得た。EXAMPLES Example 1 (Synthesis of polymer having sol-gel transition temperature) N-isopropylacrylamide (manufactured by Eastman Kodak Company)
After dissolving 10.2 g and 1.71 g of N-acryloxysuccinimide (manufactured by Kokusan Kagaku Co., Ltd.) in 400 ml of chloroform in the reaction vessel and replacing the inside of the reaction vessel with nitrogen, N, N'-azo was obtained. Bisisobutyronitrile 0.135
g was added and the mixture was polymerized at 60 ° C. for 6 hours. After the reaction was complete, the reaction product was concentrated under reduced pressure and then precipitated in diethyl ether. The obtained precipitate was separated by filtration and then vacuum dried at about 40 ° C. for about 24 hours to obtain 8.8 g.
Poly (N-isopropylacrylamide-co-N-
Acryloxysuccinimide) was obtained.
【0078】上記により得たポリ(N−イソプロピルア
クリルアミド−co−N−アクリロキシスクシンイミ
ド)1.0gと、両末端アミノ化ポリエチレンオキシド
(分子量6,000、川研ファインケミカル(株)製)
0.5gとを、クロロホルム100mlに溶解し、室温
で終夜(約10時間)反応させた。次いで、イソプロピ
ルアミン0.1gを加え、25℃で終夜(約10時間)
放置した。1.0 g of the poly (N-isopropylacrylamide-co-N-acryloxysuccinimide) obtained above and aminated polyethylene oxide having both ends aminated (molecular weight 6,000, manufactured by Kawaken Fine Chemicals Co., Ltd.)
0.5 g was dissolved in 100 ml of chloroform and reacted at room temperature overnight (about 10 hours). Next, 0.1 g of isopropylamine is added, and the mixture is placed at 25 ° C. overnight (about 10 hours).
I left it.
【0079】得られた反応生成物を減圧下で濃縮した
後、ジエチルエーテル中に沈澱させた。得られた沈殿を
濾過により分離、乾燥した後、蒸留水1000mlに希
釈し、分画分子量10万のホローファイバー型限外濾過
膜(アミコン社製H1P100−43)を用いて10℃
で300mlまで濃縮した。該濃縮液に蒸留水700m
lを加えて希釈し、上記希釈操作を再度行った。上記の
希釈、限外濾過濃縮操作をさらに5回繰り返し、分子量
10万以下のものを除去した。この限外濾過により濾過
されなかったもの(限外濾過膜内に残留したもの)を回
収して凍結乾燥して、約40℃で約10時間真空乾燥し
て、1.3gの「高分子化合物 I」(ゾル−ゲル転移
温度を有する高分子化合物)を得た。The reaction product obtained was concentrated under reduced pressure and then precipitated in diethyl ether. The obtained precipitate is separated by filtration, dried and then diluted with 1000 ml of distilled water, and 10 ° C. using a hollow fiber type ultrafiltration membrane (H1P100-43 manufactured by Amicon) having a cut-off molecular weight of 100,000.
Was concentrated to 300 ml. 700 m of distilled water in the concentrate
1 was added to dilute, and the above dilution operation was repeated. The above-mentioned dilution and ultrafiltration concentration operations were repeated 5 times to remove those having a molecular weight of 100,000 or less. What was not filtered by this ultrafiltration (remaining in the ultrafiltration membrane) was collected, freeze-dried, and vacuum dried at about 40 ° C. for about 10 hours to obtain 1.3 g of “polymer compound”. I ”(a polymer compound having a sol-gel transition temperature) was obtained.
【0080】このようにして得た「高分子化合物 I」
1gを、9gの蒸留水に室温で溶解した。この水溶液の
ゾル−ゲル転移温度を、上記した貯蔵弾性率(G´、弾
性項)が損失弾性率(G″、粘性項)を上回る点の温度
として測定したところ、該ゾル−ゲル転移温度は35℃
であった。“Polymer compound I” thus obtained
1 g was dissolved in 9 g of distilled water at room temperature. The sol-gel transition temperature of this aqueous solution was measured as the temperature at which the above-mentioned storage elastic modulus (G ', elastic term) exceeds the loss elastic modulus (G ", viscous term). 35 ° C
Met.
【0081】実施例2 N−イソプロピルアクリルアミド 9.61gと、N−
アクリロキシスクシンイミド1.71gと、n−ブチル
メタクリレート0.71gとを、反応容器中でクロロホ
ルム400mlに溶解し、該反応容器中を窒素で置換し
た後、N,N´−アゾビスイソブチロニトリル0.13
5gを加えて、60℃で、6時間重合させた。得られた
反応生成物を減圧下で濃縮した後、ジエチルエーテルに
沈澱させた。得られた沈殿を濾過により分離した後、約
40℃で約24時間真空乾燥して、7.8gのポリ(N
−イソプロピルアクリルアミド−co−N−アクリロキ
シスクシンイミド−co−n−ブチルメタクリレート)
を得た。Example 2 9.61 g of N-isopropylacrylamide and N-
1.71 g of acryloxysuccinimide and 0.71 g of n-butyl methacrylate were dissolved in 400 ml of chloroform in a reaction vessel, and the inside of the reaction vessel was replaced with nitrogen, followed by N, N'-azobisisobutyronitrile. 0.13
5 g was added and polymerized at 60 ° C. for 6 hours. The obtained reaction product was concentrated under reduced pressure, and then precipitated in diethyl ether. The resulting precipitate was separated by filtration and then dried in vacuo at about 40 ° C. for about 24 hours to obtain 7.8 g of poly (N
-Isopropylacrylamide-co-N-acryloxysuccinimide-co-n-butyl methacrylate)
I got
【0082】上記により得たポリ(N−イソプロピルア
クリルアミド−co−N−アクリロキシスクシンイミド
−co−n−ブチルメタクリレート)1.0gと、両末
端アミノ化ポリエチレンオキシド(分子量6,000、
川研ファインケミカル(株)製)0.5gとを、クロロ
ホルム100mlに溶解し、室温で終夜(約10時間)
反応させた後、イソプロピルアミン0.1gを加え、約
25℃で終夜(約10時間)放置した。得られた反応生
成物を減圧下で濃縮した後、ジエチルエーテル中に沈澱
させた。得られた沈殿を濾過により分離、約40℃で約
24時間真空乾燥した後、蒸留水1000mlに希釈
し、分画分子量10万のホローファイバー型限外濾過膜
(アミコン社製H1P100−43)を用いて10℃で
300mlまで濃縮した。該濃縮液に蒸留水700ml
を加えて希釈し、上記希釈操作を再度行った。上記の希
釈、限外濾過濃縮操作をさらに5回繰り返し、分子量1
0万以下のものを除去した。この限外濾過により濾過さ
れなかったもの(限外濾過膜内に残留したもの)を回収
して凍結乾燥して、1.3gの「高分子化合物 II」
(ゾル−ゲル転移温度を有する高分子化合物)を得た。1.0 g of poly (N-isopropylacrylamide-co-N-acryloxysuccinimide-co-n-butylmethacrylate) obtained above and aminated polyethylene oxide having both ends at a molecular weight of 6,000,
0.5 g of Kawaken Fine Chemical Co., Ltd.) was dissolved in 100 ml of chloroform and left overnight at room temperature (about 10 hours).
After the reaction, 0.1 g of isopropylamine was added, and the mixture was left at about 25 ° C. overnight (about 10 hours). The reaction product obtained was concentrated under reduced pressure and then precipitated in diethyl ether. The obtained precipitate is separated by filtration, vacuum dried at about 40 ° C. for about 24 hours, and then diluted with 1000 ml of distilled water to obtain a hollow fiber type ultrafiltration membrane (H1P100-43 manufactured by Amicon) having a molecular weight cut off of 100,000. It was concentrated to 300 ml at 10 ° C. 700 ml of distilled water in the concentrate
Was added for dilution, and the above-mentioned dilution operation was repeated. The above-mentioned dilution and ultrafiltration concentration operation are repeated 5 times to obtain a molecular weight of 1
Those less than 0,000 were removed. What was not filtered by this ultrafiltration (remaining in the ultrafiltration membrane) was collected and lyophilized to give 1.3 g of "polymer compound II".
(A polymer compound having a sol-gel transition temperature) was obtained.
【0083】上記により得た「高分子化合物II」1g
を、9gの蒸留水に氷冷下で溶解した。この水溶液のゾ
ル−ゲル転移温度を実施例1と同様の方法で測定したと
ころ、該ゾル−ゲル転移温度は21℃であった。1 g of "polymer compound II" obtained above
Was dissolved in 9 g of distilled water under ice cooling. When the sol-gel transition temperature of this aqueous solution was measured by the same method as in Example 1, the sol-gel transition temperature was 21 ° C.
【0084】実施例3 両末端アミノ化ポリエチレンオサイド(分子量6,00
0、川研ファインケミカル(株)製)3gをクロロホル
ム100mlに溶解した後、ジイソシアン酸トリレン
(コロネートT65、日本ポリウレタン工業(株)製)
0.1gと、末端に1級アミノ基を有するトリアミノポ
リプロピレンオキサイド(平均分子量約3000、米国
ジェファーソンケミカル社製:ジェファーミンT−30
00)1gとを加え、室温で5分反応させた。次いで、
イソプロピルアミン1gを加え、室温終夜(約10時
間)反応させた。溶媒を減圧下で留去して、「高分子化
合物」III(ゾル−ゲル転移温度を有する高分子化合
物)を得た。Example 3 Polyethylene oxide with aminated polyethylene at both ends (molecular weight: 6,000)
0, Kawaken Fine Chemical Co., Ltd. (3 g) was dissolved in 100 ml of chloroform, and then tolylene diisocyanate (Coronate T65, manufactured by Nippon Polyurethane Industry Co., Ltd.)
0.1 g of triaminopolypropylene oxide having a primary amino group at a terminal (average molecular weight: about 3,000, manufactured by Jefferson Chemical Company, USA: Jeffamine T-30)
00), and reacted at room temperature for 5 minutes. Then
Isopropylamine (1 g) was added, and the mixture was reacted overnight at room temperature (about 10 hours). The solvent was distilled off under reduced pressure to obtain "polymer compound" III (polymer compound having a sol-gel transition temperature).
【0085】上記により得た「高分子化合物III」1g
を、9gの蒸留水に氷冷下で溶解した。この水溶液のゾ
ル−ゲル転移温度を実施例1と同様の方法で測定したと
ころ、該ゾル−ゲル転移温度は15℃であった。1 g of "polymer compound III" obtained above
Was dissolved in 9 g of distilled water under ice cooling. When the sol-gel transition temperature of this aqueous solution was measured in the same manner as in Example 1, the sol-gel transition temperature was 15 ° C.
【0086】実施例4 両末端アミノ化ポリエチレンオキサイド(分子量6,0
00、川研ファインケミカル(株)製)30gをクロロ
ホルム1000mlに溶解した後、ジイソシアン酸トリ
レン(コロネートT65、日本ポリウレタン工業(株)
製)1gと、末端に1級アミノ基を有するトリアミノポ
リプロピレンオキサイド(平均分子量約5000、米国
ジェファーソンケミカル社製:ジェファーミンT−50
00)17gとを加え、室温で5分反応させた。次い
で、イソプロピルアミン10gを加え、室温で終夜(約
10時間)反応させた。溶媒を減圧下で留去して、「高
分子化合物IV」(ゾル−ゲル転移温度を有する高分子化
合物)を得た。Example 4 Polyethylene oxide with aminated ends (molecular weight 6,0
00, manufactured by Kawaken Fine Chemicals Co., Ltd., 30 g was dissolved in 1000 ml of chloroform, and then tolylene diisocyanate (Coronate T65, Nippon Polyurethane Industry Co., Ltd.)
1) and triaminopolypropylene oxide having a primary amino group at the terminal (average molecular weight: about 5,000, manufactured by Jefferson Chemical Co., USA: Jeffamine T-50)
00) 17 g and reacted at room temperature for 5 minutes. Next, 10 g of isopropylamine was added and reacted at room temperature overnight (about 10 hours). The solvent was distilled off under reduced pressure to obtain "polymer compound IV" (polymer compound having sol-gel transition temperature).
【0087】上記により得た「高分子化合物IV」1g
を、9gの蒸留水に氷冷下で溶解した。この水溶液のゾ
ル−ゲル転移温度を実施例1と同様の方法で測定したと
ころ、該ゾル−ゲル転移温度は9℃であった。1 g of "polymer compound IV" obtained above
Was dissolved in 9 g of distilled water under ice cooling. The sol-gel transition temperature of this aqueous solution was measured in the same manner as in Example 1, and the sol-gel transition temperature was 9 ° C.
【0088】実施例5 片末端に1級アミノ基を有するポリプロピレンオキサイ
ド(平均分子量約2000、米国ジェファーソンケミカ
ル社製:ジェファーミンM−2005)20gを四塩化
炭素50mlに溶解した後、アクリル酸クロライド(国
産化学(株)製)0.91gと、トリエチルアミン1.
38mlとを加えて、室温で終夜(約10時間)反応さ
せた。反応により生成した固形分を濾過で分離した後、
濾液から溶媒を減圧下で留去して、片末端に重合性官能
基を導入したポリプロピレンオキサイドモノアクリルア
ミド体を得た。Example 5 Polypropylene oxide having a primary amino group at one end (average molecular weight of about 2000, Jefferson Chemical Co., USA: Jeffamine M-2005) (20 g) was dissolved in carbon tetrachloride (50 ml), and then acrylic acid chloride ( Domestic Chemicals Co., Ltd. 0.91 g and triethylamine 1.
38 ml was added, and the mixture was reacted overnight at room temperature (about 10 hours). After separating the solid generated by the reaction by filtration,
The solvent was distilled off from the filtrate under reduced pressure to obtain a polypropylene oxide monoacrylamide compound having a polymerizable functional group introduced at one end.
【0089】上記により得たポリプロピレンオキサイド
モノアクリルアミド体10gと、アクリルアミド20g
とを反応容器内で蒸留水970mlに氷冷下で溶解し、
該反応容器内を窒素で置換した後、過硫酸アンモニウム
0.3gとテトラメチルエチレンジアミン200μlと
を加え、氷冷・窒素雰囲気下で終夜(約10時間)反応
させた。10 g of the polypropylene oxide monoacrylamide body obtained above and 20 g of acrylamide
And are dissolved in 970 ml of distilled water in a reaction vessel under ice cooling,
After purging the inside of the reaction vessel with nitrogen, 0.3 g of ammonium persulfate and 200 μl of tetramethylethylenediamine were added, and the reaction was carried out overnight (about 10 hours) in an ice-cooled nitrogen atmosphere.
【0090】得られた反応液を蒸留水で3lに希釈し、
分画分子量10万のホローファイバー型限外濾過膜(ア
ミコン社製H1P100−43)を用いて10℃で1l
まで濃縮した。該濃縮液に蒸留水2lを加えて希釈し、
上記希釈操作を再度行った。上記の希釈、限外濾過濃縮
操作をさらに5回繰り返し、分子量10万以下のものを
除去した。この限外濾過により濾過されなかったもの
(限外濾過膜内に残留したもの)を回収して凍結乾燥し
て、ポリアクリルアミド主鎖にポリプロピレンオキサイ
ド側鎖を結合してなる、分子量10万以上の「高分子化
合物V」(ゾル−ゲル転移温度を有する高分子化合物)
27gを得た。The reaction solution obtained was diluted to 3 liters with distilled water,
1 l at 10 ° C. using a hollow fiber type ultrafiltration membrane (H1P100-43 manufactured by Amicon) having a molecular weight cutoff of 100,000.
Concentrated. Dilute the concentrated solution with 2 l of distilled water,
The above dilution operation was performed again. The above-mentioned dilution and ultrafiltration concentration operations were repeated 5 times to remove those having a molecular weight of 100,000 or less. Those which have not been filtered by this ultrafiltration (those remaining in the ultrafiltration membrane) are collected and freeze-dried to form a polyacrylamide main chain with a side chain of polypropylene oxide having a molecular weight of 100,000 or more. "Polymer compound V" (polymer compound having sol-gel transition temperature)
27 g were obtained.
【0091】上記により得た「高分子化合物V」1g
を、9gの蒸留水に氷冷下で溶解した。この水溶液のゾ
ル−ゲル転移温度を実施例1と同様の方法で測定したと
ころ、該ゾル−ゲル転移温度は20℃であった。1 g of "polymer compound V" obtained as described above
Was dissolved in 9 g of distilled water under ice cooling. When the sol-gel transition temperature of this aqueous solution was measured in the same manner as in Example 1, the sol-gel transition temperature was 20 ° C.
【0092】実施例6 N−イソプロピルアクリルアミド37gと、n−ブチル
メタクリレート3gと、ポリエチレンオキサイドモノア
クリレート(分子量4,000、日本油脂(株)製:P
ME−4000)28gとを、ベンゼン340mlに溶
解した後、2,2´−アゾビスイソブチロニトリル0.
8gを加え、60℃で6時間反応させた。得られた反応
生成物にクロロホルム600mlを加えて溶解し、該溶
液をエーテル20L(リットル)に滴下して沈澱させ
た。得られた沈殿を濾過により回収し、該沈澱を約40
℃で24時間真空乾燥した後、蒸留水6Lに再び溶解
し、分画分子量10万のホローファイバー型限外濾過膜
(アミコン社製H1P100−43)を用いて10℃で
2lまで濃縮した。該濃縮液に蒸留水4lを加えて希釈
し、上記希釈操作を再度行った。上記の希釈、限外濾過
濃縮操作をさらに5回繰り返し、分子量10万以下のも
のを除去した。この限外濾過により濾過されなかったも
の(限外濾過膜内に残留したもの)を回収して凍結乾燥
し、分子量10万以上の「高分子化合物VI」(ゾル−ゲ
ル転移温度を有する高分子化合物)60gを得た。 Example 6 37 g of N-isopropylacrylamide, 3 g of n-butyl methacrylate, and polyethylene oxide monoacrylate (molecular weight 4,000, manufactured by NOF Corporation: P
ME-4000) (28 g) was dissolved in 340 ml of benzene, and then 2,2'-azobisisobutyronitrile (0.2 g) was added.
8 g was added and reacted at 60 ° C. for 6 hours. Chloroform (600 ml) was added to the obtained reaction product to dissolve it, and the solution was added dropwise to 20 L (liter) of ether to cause precipitation. The resulting precipitate was collected by filtration and the precipitate
After vacuum-drying at 24 ° C. for 24 hours, it was redissolved in 6 L of distilled water, and concentrated to 2 liters at 10 ° C. using a hollow fiber type ultrafiltration membrane (H1P100-43 manufactured by Amicon) having a cut-off molecular weight of 100,000. 4 l of distilled water was added to the concentrated solution to dilute it, and the above dilution operation was repeated. The above-mentioned dilution and ultrafiltration concentration operations were repeated 5 times to remove those having a molecular weight of 100,000 or less. What was not filtered by this ultrafiltration (remaining in the ultrafiltration membrane) was recovered and freeze-dried to obtain a "polymer compound VI" (polymer having a sol-gel transition temperature) having a molecular weight of 100,000 or more. Compound (60 g) was obtained.
【0093】上記により得た「高分子化合物VI」1g
を、9gの蒸留水に氷冷下で溶解した。この水溶液のゾ
ル−ゲル転移温度を実施例1と同様の方法で測定したと
ころ、該ゾル−ゲル転移温度は25℃であった。1 g of "polymer compound VI" obtained above
Was dissolved in 9 g of distilled water under ice cooling. When the sol-gel transition temperature of this aqueous solution was measured in the same manner as in Example 1, the sol-gel transition temperature was 25 ° C.
【0094】実施例7 (コスメティック・パックの調製)実施例2で合成した
約21℃のゾル−ゲル転移温度を有する「高分子化合物
II」3gを27gの冷水に溶解して、濃度10wt%の
水溶液を調製した。該高分子化合物水溶液は18℃で粘
性のある液体状態で、肌の上に塗布すると体温によって
1分以内でゲル化することが認められた。 Example 7 (Preparation of cosmetic pack) "Polymer compound having a sol-gel transition temperature of about 21 ° C synthesized in Example 2"
3 g of “II” was dissolved in 27 g of cold water to prepare an aqueous solution having a concentration of 10 wt%. It was observed that the aqueous solution of the polymer compound was in a viscous liquid state at 18 ° C. and when applied on the skin, gelled within 1 minute depending on the body temperature.
【0095】また、このようにゲル化した該高分子化合
物の塗膜は、従来のコスメティック・パックと異なり、
乾燥させた状態でなくても、肌から容易に剥離する事が
可能であった。塗布から約10分後に塗膜を肌から剥離
したところ、肌の清涼感が得られた。The coating film of the polymer compound thus gelled is different from the conventional cosmetic pack,
It could be easily peeled off from the skin even if it was not dried. When the coating film was peeled off from the skin about 10 minutes after the application, a refreshing feeling of the skin was obtained.
【0096】一方、上記のゲル化塗膜は、従来のコスメ
ティック・パックと同様に、充分乾燥して被膜を形成さ
せた後においても、剥離が容易であった。On the other hand, like the conventional cosmetic pack, the above gelled coating film was easily peeled off even after being sufficiently dried to form a coating film.
【0097】実施例8 (コスメティック・パックの調製)ポリビニルアルコー
ル(平均分子量:約40,000、ケン化度:約80モ
ル%)2.2gを40gの水に加温(約90℃)・攪拌
下に溶解して、濃度が約5wt%のポリビニルアルコー
ル水溶液を調製した。次いで、該ポリビニルアルコール
水溶液中に、実施例2で合成した約21℃のゾル−ゲル
転移温度を有する「高分子化合物II」3gを冷却・攪拌
下に溶解して、ポリビニルアルコール(5wt%)と
「高分子化合物II」(7wt%)との混合溶液を作製し
た。Example 8 (Preparation of cosmetic pack) 2.2 g of polyvinyl alcohol (average molecular weight: about 40,000, saponification degree: about 80 mol%) was heated (about 90 ° C.) in 40 g of water and stirred. It melt | dissolved below and prepared the polyvinyl alcohol aqueous solution whose density | concentration is about 5 wt%. Next, 3 g of “polymer compound II” having a sol-gel transition temperature of about 21 ° C. synthesized in Example 2 was dissolved in the polyvinyl alcohol aqueous solution under cooling and stirring to obtain polyvinyl alcohol (5 wt%). A mixed solution with "polymer compound II" (7 wt%) was prepared.
【0098】このようにして得られた混合溶液は、18
℃で粘性のある液状で、肌に容易に且つ均一に塗布する
ことが可能で、一旦、肌上に塗布されると体温で直ちに
ゲル化することが認められた。The mixed solution thus obtained was 18
It was found that it is a viscous liquid at ℃, can be easily and uniformly applied to the skin, and once applied on the skin, it immediately gels at body temperature.
【0099】該ゲル化被膜は、従来のコスメティック・
パックと異なり、乾燥させた状態でなくても、肌から容
易に剥離することが可能であった。塗布から約20分後
に塗膜を肌から剥離したところ、肌の清涼感が得られ
た。The gelled film is a conventional cosmetic
Unlike the pack, it could be easily peeled from the skin without being dried. When the coating film was peeled from the skin about 20 minutes after the application, a refreshing feeling of the skin was obtained.
【0100】一方、上記のゲル化塗膜は、従来のコスメ
ティック・パックと同様に、充分乾燥させて薄い被膜を
形成させた後においても、剥離することが容易であっ
た。On the other hand, like the conventional cosmetic pack, the above gelled coating film was easily peeled off even after being sufficiently dried to form a thin coating film.
【0101】実施例9 (除毛剤の調製)チオグリコール酸カルシウム5gと、
水酸化カルシウム7gとを混合して、全量が100ml
となるように蒸留水を加え、撹拌下に溶解した。このよ
うにして得られた水溶液100ml中に、実施例2で合
成した約21℃のゾル−ゲル転移温度を有する「高分子
化合物II」約7.5gを加えて冷却下に溶解し、濃度が
約7wt%の「高分子化合物II」の水溶液を作製し除毛
剤とした。 Example 9 (Preparation of depilatory) 5 g of calcium thioglycolate,
Mix with 7g of calcium hydroxide to make 100ml
Distilled water was added so as to be dissolved in the solution with stirring. To 100 ml of the aqueous solution thus obtained, about 7.5 g of “polymer compound II” having a sol-gel transition temperature of about 21 ° C. synthesized in Example 2 was added and dissolved under cooling to a concentration of An aqueous solution of about 7 wt% of "polymer compound II" was prepared and used as a depilatory.
【0102】上記により得られた除毛剤は、約18℃で
は流動性のある液体状態で、皮膚上に塗布すると直ちに
ゲル化した。該除毛剤約5mlを皮膚(脚部、大きさ=
約5cm×5cm)上に10分間、放置して除毛を行っ
た。肉眼観察においては、上記除毛剤配置部分は良好に
除毛されていた。The dehairing agent obtained as described above was in a fluid liquid state at about 18 ° C. and immediately gelled when applied on the skin. Approximately 5 ml of the depilatory is applied to the skin (legs, size =
The hair was removed by leaving it on the surface (about 5 cm × 5 cm) for 10 minutes. In the naked eye observation, the hair removal agent-disposed portion was satisfactorily dehaired.
【0103】上記の除毛後、該ゲル状の除毛剤は容易に
皮膚から物理的に剥離することができた。該剥離後の皮
膚上には肉眼で何等の残存物は認められず、皮膚の拭き
取り、あるいは洗浄の必要は全く認められなかった。After the above hair removal, the gel-like hair remover could be easily physically removed from the skin. No residue was visually observed on the skin after the peeling, and there was no need to wipe or wash the skin.
【0104】実施例10 (脱色剤の調製)過酸化水素水(濃度約3%)80ml
と、強アンモニア水(比重約0.90%)20mlとを
混合して、全量が100mlとなるように蒸留水を加
え、撹拌下に混合した。このようにして得られた水溶液
100ml中に、実施例2で合成した約21℃のゾル−
ゲル転移温度を有する「高分子化合物II」約7.5gを
加えて冷却下に溶解し、濃度が約7wt%の「高分子化
合物II」の水溶液を作製して脱色剤とした。 Example 10 (Preparation of decolorizing agent) 80 ml of hydrogen peroxide solution (concentration about 3%)
And 20 ml of strong ammonia water (specific gravity: about 0.90%) were mixed, distilled water was added so that the total amount became 100 ml, and the mixture was mixed with stirring. The sol of about 21 ° C. synthesized in Example 2 was added to 100 ml of the thus obtained aqueous solution.
About 7.5 g of "polymer compound II" having a gel transition temperature was added and dissolved under cooling to prepare an aqueous solution of "polymer compound II" having a concentration of about 7 wt% to prepare a decolorizing agent.
【0105】上記により得られた脱色剤は、約18℃で
は流動性のある液体状態で、皮膚上に塗布すると直ちに
ゲル化した。該脱色剤約5mlを皮膚(脚部、大きさ=
約5cm×5cm)上に10分間、放置して脱色を行っ
た。肉眼観察においては、上記脱色剤配置部分は良好に
脱色されていた。The decolorizing agent obtained above was in a fluid liquid state at about 18 ° C. and immediately gelled when applied on the skin. About 5 ml of the decolorizing agent is applied to the skin (leg, size =
Decolorization was carried out by leaving it on a sheet (about 5 cm × 5 cm) for 10 minutes. In the naked eye observation, the decolorizing agent-disposed portion was well decolorized.
【0106】上記の脱色後、該ゲル状の脱色剤は容易に
皮膚から物理的に剥離することができた。該剥離後の皮
膚上には肉眼で何等の残存物は認められず、皮膚の拭き
取り、あるいは洗浄の必要は全く認められなかった。After the above decolorization, the gel decolorizing agent could be easily physically peeled from the skin. No residue was visually observed on the skin after the peeling, and there was no need to wipe or wash the skin.
【0107】[0107]
【発明の効果】上述したように本発明によれば、水と、
ゲル形成成分とを少なくとも含む香粧品基剤であって;
該ゲル形成成分が、その水溶液が0℃より高く37℃よ
り低いゾル-ゲル転移温度を有する高分子化合物からな
り;且つ、基剤全体として前記ゾル-ゲル転移温度より
高い温度で実質的に水不溶性を示し、該ゾル-ゲル転移
温度より低い温度で可逆的に水可溶性を示す香粧品基剤
が提供される。As described above, according to the present invention, water and
A cosmetic base comprising at least a gel-forming component,
The gel-forming component consists of a polymer compound whose aqueous solution has a sol-gel transition temperature higher than 0 ° C. and lower than 37 ° C .; and, as a whole base, substantially water at a temperature higher than the sol-gel transition temperature. Provided is a cosmetic base which is insoluble and reversibly water-soluble at a temperature lower than the sol-gel transition temperature.
【0108】本発明によれば、更に、水と、ゲル形成成
分とを少なくとも含む香粧品であって;該ゲル形成成分
が、その水溶液が0℃より高く37℃より低いゾル-ゲ
ル転移温度を有する高分子化合物からなり;且つ、香粧
品全体として前記ゾル-ゲル転移温度より高い温度で実
質的に水不溶性を示し、該ゾル-ゲル転移温度より低い
温度で可逆的に水可溶性を示す外用香粧品が提供され
る。According to the present invention, there is further provided a cosmetic product which contains at least water and a gel-forming component; the gel-forming component having an aqueous solution whose sol-gel transition temperature is higher than 0 ° C and lower than 37 ° C. A fragrance for external use, which is composed of a polymer compound having: and is substantially water-insoluble at a temperature higher than the sol-gel transition temperature as a whole, and reversibly water-soluble at a temperature lower than the sol-gel transition temperature as a whole. Cosmetics are provided.
【0109】本発明の外用香粧品は、上述したような特
殊なゾル−ゲル転移挙動を示すため、該香粧品を生体
(皮膚等)への適用する直前には、(例えば、香粧品の
温度を前記ゾル−ゲル転移温度より低温とすることによ
り)流動性の高いゾル(液体)状態として、生体に容易
に塗布等により適用することができる。生体への適用後
には、体温等による香粧品自体の温度上昇により、該香
粧品は速やかにゲル化するため、生体上で迅速に安定な
被膜を形成することができる。Since the external cosmetic composition of the present invention exhibits the special sol-gel transition behavior as described above, immediately before the cosmetic composition is applied to a living body (skin or the like) (for example, the temperature of the cosmetic composition is changed). Can be easily applied to a living body by coating or the like in a sol (liquid) state having high fluidity (by setting the temperature lower than the sol-gel transition temperature). After application to a living body, the temperature of the cosmetic itself rises due to body temperature and the like, so that the cosmetic quickly gels, so that a stable film can be rapidly formed on the living body.
【0110】他方、生体から該外用香粧品を除去する際
には、例えば、香粧品の温度を低温としてゾル状態に戻
すことにより、極めて容易、且つより完全な生体からの
除去が可能となる。すなわち、従来の外用香粧品では極
めて困難であったところの、生体への適用の容易性(お
よび安定性、迅速性)と、生体から該外用香粧品を除去
する際の容易性との両立が可能となる。On the other hand, when the cosmetic for external use is removed from the living body, for example, by returning the cosmetic to a sol state by lowering the temperature of the cosmetic, the removal from the living body becomes extremely easy and more complete. In other words, both the ease of application to the living body (and stability and rapidity) and the ease of removing the external use cosmetic from the living body, which were extremely difficult with conventional external use cosmetics, are compatible. It will be possible.
【0111】上述した本発明の外用香粧品を「コスメテ
ィック・パック」の態様とした場合、該コスメティック
・パックは肌への塗布時は流動性があり、複雑な凹凸の
ある肌の表面上に簡便に塗布することができると同時に
皺の中まで侵入させることができる。また一旦、肌の表
面に塗布されると本発明のコスメティック・パックは直
ちにゲル状態に変化して肌上への滞留性が著しく向上す
る。また本発明のコスメティック・パックの剥離は従来
のコスメティック・パックの場合のように水分が蒸発
し、乾燥被膜が形成されるまで長時間待つ必要はなく塗
布した後、直ちにゲル化した被膜が形成されるために、
何時でも物理的に剥離が可能である。更に冷水を用いて
該ゲル化膜をゾル状態に変化させ洗浄除去することも可
能である。より高いのように本発明のコスメティック・
パックは体温によるゲル化現象を利用したもため、従来
のコスメティック・パックのように肌に過剰な刺激を与
える低沸点物質を添加する必要がないばかりか、肌に柔
軟性、張り、潤いを与える水分の含量を従来のコスメテ
ィック・パックと比較して著しく高めることが可能であ
る。When the above-mentioned cosmetic for external use of the present invention is in the form of "cosmetic pack", the cosmetic pack has fluidity when applied to the skin and can be easily applied on the surface of the skin having complicated irregularities. Can be applied to the wrinkles and at the same time penetrate into the wrinkles. Further, once applied to the surface of the skin, the cosmetic pack of the present invention immediately changes into a gel state and remarkably improves the retention property on the skin. Further, peeling off of the cosmetic pack of the present invention does not require waiting for a long time until the water evaporates and a dry film is formed as in the case of the conventional cosmetic pack, and after application, a gelled film is immediately formed. In order to
Physical peeling is possible at any time. Furthermore, it is possible to change the gelled film into a sol state by using cold water and wash and remove it. Cosmetics of the invention like higher
Since the pack utilizes the gelation phenomenon due to body temperature, it is not necessary to add a low boiling point substance that causes excessive irritation to the skin like conventional cosmetic packs, but it also gives the skin flexibility, tension and moisture. It is possible to significantly increase the water content compared to conventional cosmetic packs.
【0112】上述した本発明の外用香粧品を「除毛剤」
ないし「脱色剤」の態様とした場合、該除毛剤/脱色剤
は、皮膚への塗布時には流動性が有り、凹凸のある複雑
な形状をした皮膚に密着し、毛孔の中まで侵入すること
ができるため除毛/脱色効果が極めて高い。また一旦、
皮膚に塗布されると本発明の除毛剤/脱色剤は直ちにゲ
ル状態に変化するために、表面のベタつきが著しく減じ
衣類等に誤って付着することが極めて効果的に防止でき
る。また、除毛/脱色後は、本発明の除毛剤/脱色剤は
ゲル化しているため、容易に物理的に皮膚から剥離する
ことができる。特に毛孔からの除去も容易で、従来の除
毛剤/脱色剤のように、肌の拭き取りあるいは洗浄など
の面倒な手間が省ける。The above-mentioned external cosmetic composition of the present invention is used as a "hair remover".
In the case of the form of "depigmenting agent", the depilatory agent / depigmenting agent has fluidity when applied to the skin, adheres to the skin having a complicated shape with irregularities, and penetrates into the pores. As a result, hair removal / bleaching effects are extremely high. Also once
When applied to the skin, the depilatory / bleaching agent of the present invention immediately changes into a gel state, so that the stickiness of the surface is remarkably reduced and accidental adhesion to clothing or the like can be very effectively prevented. In addition, after the hair removal / bleaching, the hair remover / bleaching agent of the present invention is gelated, and thus can be easily physically peeled from the skin. In particular, it can be easily removed from the pores, and the troublesome work of wiping or washing the skin like conventional hair removers / decolorants can be saved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C08L 29/04 LGX C08L 29/04 LGX ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08L 29/04 LGX C08L 29/04 LGX
Claims (14)
香粧品基剤であって;該ゲル形成成分が、その水溶液が
0℃より高く37℃より低いゾル-ゲル転移温度を有す
る高分子化合物からなり;且つ、基剤全体として前記ゾ
ル-ゲル転移温度より高い温度で実質的に水不溶性を示
し、該ゾル-ゲル転移温度より低い温度で可逆的に水可
溶性を示すことを特徴とする香粧品基剤。1. A cosmetic base comprising at least water and a gel-forming component; the gel-forming component being a polymer compound whose aqueous solution has a sol-gel transition temperature higher than 0 ° C. and lower than 37 ° C. And a scent that is substantially water-insoluble at a temperature higher than the sol-gel transition temperature and reversibly water-soluble at a temperature lower than the sol-gel transition temperature as a whole. Cosmetic base.
香粧品であって;該ゲル形成成分が、その水溶液が0℃
より高く37℃より低いゾル-ゲル転移温度を有する高
分子化合物からなり;且つ、香粧品全体として前記ゾル
-ゲル転移温度より高い温度で実質的に水不溶性を示
し、該ゾル-ゲル転移温度より低い温度で可逆的に水可
溶性を示すことを特徴とする外用香粧品。2. A cosmetic product comprising at least water and a gel-forming component; the gel-forming component having an aqueous solution thereof at 0 ° C.
A polymer compound having a sol-gel transition temperature higher than 37 ° C. and lower than 37 ° C .;
-A cosmetic for external use, which is substantially water-insoluble at a temperature higher than the gel transition temperature and reversibly water-soluble at a temperature lower than the sol-gel transition temperature.
記載の外用香粧品。3. A cosmetic pack as claimed in claim 2.
Topical cosmetics described.
より高く37℃より低いLCST(Lower Critical Sol
ution Temperature;下限臨界共溶温度)を有する温度
感応性高分子化合物と、親水性高分子化合物が結合され
てなる高分子化合物である請求項2に記載の外用香粧
品。4. The aqueous solution of the polymer compound is 0 ° C.
LCST (Lower Critical Sol)
3. The cosmetic preparation for external use according to claim 2, which is a polymer compound in which a temperature-sensitive polymer compound having a ution temperature (lower critical solution temperature) and a hydrophilic polymer compound are bonded.
求項2に記載の外用香粧品。5. The cosmetic preparation for external use according to claim 2, which further contains a water-soluble polymer compound.
アルコールである請求項5に記載の外用香粧品。6. The cosmetic preparation for external use according to claim 5, wherein the water-soluble polymer compound is polyvinyl alcohol.
化剤、および洗浄剤から選ばれた1種以上の成分を含有
する請求項2に記載の外用香粧品。7. The cosmetic preparation for external use according to claim 2, further comprising one or more components selected from a skin protecting agent, an antioxidant, a storage stabilizer, and a detergent.
品。8. The cosmetic for external use according to claim 2, which is a depilatory.
8に記載の外用香粧品。9. The cosmetic for external use according to claim 8, which further comprises a thioglycollate.
ウムまたはカセイアルカリを含有する請求項8に記載の
外用香粧品。10. The cosmetic preparation for external use according to claim 8, which further contains calcium hydroxide or caustic alkali as a pH adjusting agent.
グアニジンを含有する請求項8に記載の外用香粧品。11. The cosmetic preparation for external use according to claim 8, which further contains urea and / or guanidine as an auxiliary agent.
の外用香粧品。12. The cosmetic for external use according to claim 2, further comprising a fragrance.
粧品。13. The cosmetic preparation for external use according to claim 2, which is a decolorizing agent.
合物を含む請求項13に記載の外用香粧品。14. The cosmetic preparation for external use according to claim 13, further comprising a mixture of hydrogen peroxide and ammonia.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP02957296A JP3585309B2 (en) | 1996-02-16 | 1996-02-16 | Cosmetic base and external cosmetics |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP02957296A JP3585309B2 (en) | 1996-02-16 | 1996-02-16 | Cosmetic base and external cosmetics |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09227329A true JPH09227329A (en) | 1997-09-02 |
JP3585309B2 JP3585309B2 (en) | 2004-11-04 |
Family
ID=12279838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP02957296A Expired - Fee Related JP3585309B2 (en) | 1996-02-16 | 1996-02-16 | Cosmetic base and external cosmetics |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3585309B2 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001070022A1 (en) * | 2000-03-21 | 2001-09-27 | Yuichi Mori | Coating materials for biological tissues, coated biological tissues and method of coating biological tissues |
WO2002016496A1 (en) * | 2000-08-23 | 2002-02-28 | National Institute Of Advanced Industrial Science And Technology | Temperature-responsive polymer/polymer complex |
US7115255B2 (en) | 2000-07-21 | 2006-10-03 | L'oreal | Polymer comprising water-soluble units and LCST units, and aqueous composition comprising same |
JP2007217348A (en) * | 2006-02-17 | 2007-08-30 | Shiseido Co Ltd | Thickener and cosmetic and cleaner containing the same |
JP2007269712A (en) * | 2006-03-31 | 2007-10-18 | Kanebo Cosmetics Inc | Release type pack cosmetic |
JP2007269713A (en) * | 2006-03-31 | 2007-10-18 | Kanebo Cosmetics Inc | Cosmetic for makeup or antisunburn |
JP2008001628A (en) * | 2006-06-22 | 2008-01-10 | Ichimaru Pharcos Co Ltd | Hair cosmetic |
JP2008239590A (en) * | 2007-03-29 | 2008-10-09 | Kose Corp | Cosmetic |
JP2008247852A (en) * | 2007-03-30 | 2008-10-16 | Kose Corp | Impregnated pack cosmetic |
JP2008247867A (en) * | 2007-03-30 | 2008-10-16 | Kose Corp | Cleansing agent for makeup cosmetics |
JP2008247769A (en) * | 2007-03-29 | 2008-10-16 | Kose Corp | Cosmetic for correction of unevenness |
US7456275B2 (en) | 2002-04-18 | 2008-11-25 | Chugai Seiyaku Kabushiki Kaisya | Hyaluronic acid modification product |
JP2009235022A (en) * | 2008-03-28 | 2009-10-15 | Kose Corp | Massage cosmetic |
JP2009235025A (en) * | 2008-03-28 | 2009-10-15 | Kose Corp | Mist cosmetic |
JP2009542758A (en) * | 2006-07-13 | 2009-12-03 | ロレアル | Cosmetic or dermatological composition in the form of an oil-in-water or water-in-oil-in-water emulsion comprising a heat gelled polymer, a water miscible volatile organic solvent and an organic UV screening agent |
US7655702B2 (en) | 2001-01-15 | 2010-02-02 | L'oreal | Foaming emulsions and foaming compositions containing a polymer comprising water-soluble units and units with an LCST, especially for cosmetic uses |
WO2016204258A1 (en) * | 2015-06-19 | 2016-12-22 | 日産化学工業株式会社 | Polymer for gel formation and dermatological adhesive material |
-
1996
- 1996-02-16 JP JP02957296A patent/JP3585309B2/en not_active Expired - Fee Related
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001070022A1 (en) * | 2000-03-21 | 2001-09-27 | Yuichi Mori | Coating materials for biological tissues, coated biological tissues and method of coating biological tissues |
US7115255B2 (en) | 2000-07-21 | 2006-10-03 | L'oreal | Polymer comprising water-soluble units and LCST units, and aqueous composition comprising same |
US7722859B2 (en) | 2000-07-21 | 2010-05-25 | L'oreal | Polymer comprising water-soluble units and LCST units, and aqueous composition comprising it |
US7883692B2 (en) | 2000-07-21 | 2011-02-08 | L'oreal | Polymer comprising water soluble units and LCST units, and aqueous composition comprising same |
JP2008179822A (en) * | 2000-07-21 | 2008-08-07 | L'oreal Sa | Polymer having water-soluble unit and lcst unit, and aqueous composition containing the polymer |
WO2002016496A1 (en) * | 2000-08-23 | 2002-02-28 | National Institute Of Advanced Industrial Science And Technology | Temperature-responsive polymer/polymer complex |
US6863437B2 (en) | 2000-08-23 | 2005-03-08 | National Institute Of Advanced Industrial Science And Technology | Temperature-responsive polymer/polymer complex |
JP4904511B2 (en) * | 2000-08-23 | 2012-03-28 | 独立行政法人産業技術総合研究所 | Temperature-responsive interpolymer complex |
US7655702B2 (en) | 2001-01-15 | 2010-02-02 | L'oreal | Foaming emulsions and foaming compositions containing a polymer comprising water-soluble units and units with an LCST, especially for cosmetic uses |
US7456275B2 (en) | 2002-04-18 | 2008-11-25 | Chugai Seiyaku Kabushiki Kaisya | Hyaluronic acid modification product |
JP2007217348A (en) * | 2006-02-17 | 2007-08-30 | Shiseido Co Ltd | Thickener and cosmetic and cleaner containing the same |
JP2007269713A (en) * | 2006-03-31 | 2007-10-18 | Kanebo Cosmetics Inc | Cosmetic for makeup or antisunburn |
JP2007269712A (en) * | 2006-03-31 | 2007-10-18 | Kanebo Cosmetics Inc | Release type pack cosmetic |
JP2008001628A (en) * | 2006-06-22 | 2008-01-10 | Ichimaru Pharcos Co Ltd | Hair cosmetic |
JP2009542758A (en) * | 2006-07-13 | 2009-12-03 | ロレアル | Cosmetic or dermatological composition in the form of an oil-in-water or water-in-oil-in-water emulsion comprising a heat gelled polymer, a water miscible volatile organic solvent and an organic UV screening agent |
JP2008239590A (en) * | 2007-03-29 | 2008-10-09 | Kose Corp | Cosmetic |
JP2008247769A (en) * | 2007-03-29 | 2008-10-16 | Kose Corp | Cosmetic for correction of unevenness |
JP2008247852A (en) * | 2007-03-30 | 2008-10-16 | Kose Corp | Impregnated pack cosmetic |
JP2008247867A (en) * | 2007-03-30 | 2008-10-16 | Kose Corp | Cleansing agent for makeup cosmetics |
JP2009235025A (en) * | 2008-03-28 | 2009-10-15 | Kose Corp | Mist cosmetic |
JP2009235022A (en) * | 2008-03-28 | 2009-10-15 | Kose Corp | Massage cosmetic |
WO2016204258A1 (en) * | 2015-06-19 | 2016-12-22 | 日産化学工業株式会社 | Polymer for gel formation and dermatological adhesive material |
Also Published As
Publication number | Publication date |
---|---|
JP3585309B2 (en) | 2004-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH09227329A (en) | Perfume base and external perfume | |
US4920158A (en) | Hydrogel-forming wound dressing or skin coating material | |
US5013769A (en) | Method of making a hydrogel-forming wound dressing or skin coating material | |
US6613315B1 (en) | Cosmetic composition comprising at least one nonionic amphiphilic associative polyurethane and at least one nonionic polymer with fatty chains | |
US5879684A (en) | Skin tightening formulation and method for treating skin | |
JPH054913A (en) | Thickener for product for local application | |
TWI471142B (en) | Hairdressing cosmetic | |
JP3708531B2 (en) | Thickener and cosmetics containing the same | |
EP1055406A2 (en) | Oil-in-water emulsion composition and use of said composition in cosmetics | |
JPH08506824A (en) | Thickener mixture based on guar gum or non-ionic cellulose and cross-linked polymer, and cosmetic or dermatological hair or skin care composition containing this mixture | |
EP1747240A1 (en) | Conditioning/styling tetrapolymers | |
JP3488494B2 (en) | Cosmetics containing cationic thickener | |
JP2001288365A (en) | Water-in-oil emulsion type composition and its use for cosmetic | |
EP1245636B1 (en) | Composition for hydrogel, hydrogel, and use thereof | |
JP4808829B2 (en) | Use of W / O emulsions containing water-swellable cross-linked polymers as thickeners, such emulsions and cosmetic or pharmaceutical formulations | |
JP3934117B2 (en) | Cleansing composition | |
JP3649299B2 (en) | Water-soluble thickener and cosmetics containing the same | |
JP2651918B2 (en) | Gel hair styling composition | |
JP3492383B2 (en) | Cosmetic composition based on associative polyurethane and anionic polymer with fatty chains | |
EP0973490B1 (en) | Depilatory compositions, their preparation and use | |
JP2000034212A (en) | Gelatinous hairdressing material | |
JP2021504358A (en) | A mascara composition containing a polymer having a cyclic amide, a cyclic amine, and acrylamide. | |
JP4424677B2 (en) | Thickener | |
JP6230805B2 (en) | Hair cosmetics | |
JP5071613B2 (en) | Adhesive composition for poorly water-soluble active ingredient and method for attaching poorly water-soluble active ingredient |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040311 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040406 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040607 |
|
TRDD | Decision of grant or rejection written | ||
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20040607 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040706 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040803 |
|
R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080813 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080813 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090813 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100813 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100813 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110813 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120813 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130813 Year of fee payment: 9 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |