JP2004269443A - Cosmetic for skin or for nail - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic for the skin or for the nail, providing good adhesiveness and durability. <P>SOLUTION: The cosmetic for the skin or for the nail contains the following components (A) and (B) and the component (A) is dissolved in the component (B): (A) a polymer composed of 0.1-50 wt.% constituent unit derived from a polysiloxane compound having radically polymerizable unsaturated bonds at both terminals of the molecular chain, and 50-99.9 wt.% constituent unit derived from a radically polymerizable monomer copolymerizable therewith, and having 30,000-1,500,000 weight average molecular weight; and (B) a volatile silicone. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１１】
式中、Ｄ、Ｅは下記式（２）または式（３）で表される不飽和結合含有基を示し、それぞれ同一でも異なっていてもよい。
【００１２】
【化８】

【００１３】
式中Ｒ_１及びＲ_３はそれぞれ同一でも異なっていてもよい、水素原子、炭素原子数１〜１０のアルキル基、アリール基、又は末端がヒドロキシル基、アルコキシ基もしくはアルキルカルボニルオキシ基で置換されたポリオキシアルキレン基を示し、Ｒ_２は水素原子又はメチル基を示し、Ｘはイミノ基又は酸素原子を示し、ｎは４〜５００の整数を示し、ｐは１〜４の整数を示し、ｑは０〜４の整数を示し、ｍは０〜４の整数を示す。
【００１４】
なお、本発明において「溶解している」とは、（Ａ）成分の重合体（以下「重合体（Ａ）と略記することがある）の濃度１０重量％の溶液が、１ｃｍセルを用いた波長５５０ｎｍでの５０℃における透過率が８０％以上の均一透光性液体で、かつ重合体（Ａ）または（Ｂ）成分の揮発性シリコーン（以下「揮発性シリコーン（Ｂ）」と略記することがある）が分離析出していない状態を言う。
【００１５】
また、５０℃未満の温度で不均一だったり、固化していたとしても、５０℃において上記の条件に合致する場合は「溶解している」ものとする。
【００１６】
【発明の実施の形態】
この発明の好ましい態様によれば、化粧料中の重合体（Ａ）の含有量が０．１〜２０重量％であり、揮発性シリコーン（Ｂ）の含有量が０．１〜９９．９重量％である。
重合体（Ａ）と揮発性シリコーン（Ｂ）との比率は重量比で（Ａ）：（Ｂ）＝２：１〜１：１００であるのが好ましい。２：１より重合体（Ａ）が多いと粘度が高すぎて溶液としては使いにくくなりやすく、一方１：１００より重合体（Ａ）が少ないとこれによる柔軟性改良効果が少なくなってしまう。
【００１７】
以下に重合体（Ａ）、及び揮発性シリコーン（Ｂ）のそれぞれの好ましい態様を述べる。
＜重合体（Ａ）＞
重合体は、前記式（１）で示される分子鎖の両末端にラジカル重合性不飽和結合を有するポリシロキサン化合物（以下「化合物（ａ）」と略記することがある）に由来する構成単位０．１〜５０重量％と、これと共重合可能なラジカル重合性単量体（以下「化合物（ｂ）」と略記することがある）に由来する構成単位５０〜９９．９重量％とからなる、重量平均分子量３０，０００〜１，５００，０００の重合体である。より好ましくはポリシロキサン化合物（ａ）に由来する構成単位が０．５〜３０重量％と、これと共重合可能なラジカル重合性単量体（ｂ）に由来する構成単位が７０〜９９．５重量％とからなる重合体である。
【００１８】
化合物（ａ）由来の構成単位が０．１重量％未満であるとポリシロキサン単位に基づく性能が不十分となるだけでなく、揮発性シリコーン（Ｂ）への溶解性が低下してしまう。５０重量％を超えて多いと、ｎが大きい化合物（ａ）を用いたとしても架橋点が多くなってゲル化しやすくなり、所期の目的を達することができない。
【００１９】
化合物（ａ）及び化合物（ｂ）はいずれも上記の構成単位の重量割合の範囲内の重合体を与える限り、一種類のみを用いても、二種類以上を併用してもよい。
化合物（ａ）：ポリシロキサン化合物
化合物（ａ）のポリシロキサン化合物は、下記式（１）で表されるものである。
【００２０】
【化９】

【００２１】
式中Ｒ_１は同一でも異なっていてもよい、水素原子、炭素原子数１〜１０のアルキル基、アリール基、又は末端がヒドロキシル基、アルコキシ基もしくはアルキルカルボニルオキシ基で置換されたポリオキシアルキレン基を示し、Ｄ、Ｅは下記式（２）または式（３）で表される不飽和結合含有基を示し、それぞれ同一でも異なっていてもよい。ｎは４〜５００、より好ましくは５０〜５００の整数である。
【００２２】
【化１０】

【００２３】
式中、Ｒ_２は水素原子又はメチル基を示し、Ｘはイミノ基（−ＮＨ−）又は酸素原子を示し、Ｒ_３は同一でも異なっていてもよい、水素原子、炭素原子数１〜１０のアルキル基、アリール基、又は末端がヒドロキシル基、アルコキシ基もしくはアルキルカルボニルオキシ基で置換されたポリオキシアルキレン基を示し、ｐは１〜４の整数を示し、ｑは０〜４の整数を示し、ｍは０〜４の整数を示す。
【００２４】
上記式（１）及び（３）の置換基Ｒ_１及びＲ_３の炭素原子数１〜１０のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、２−エチルヘキシル基、へプチル基、ｎ−オクチル基等の直鎖又は分岐鎖のアルキル基が挙げられ、アリール基としては、フェニル基、ベンジル基等が挙げられる。アルコキシ基としては、アルキル基部分が上記の炭素原子数１〜１０のアルキル基を有するものが好ましく、アルキルカルボニルオキシ基のアルキル基部分についても同様である。これらのアルキル基としては、炭素原子数１〜４のものがより好ましい。
【００２５】
また、置換されたポリオキシアルキレン基のポリオキシアルキレン部分としては、例えば、下記式（９）で表されるポリオキシアルキレン鎖が挙げられる。
【００２６】
【化１１】
−Ｃ_３Ｈ_６−［Ｏ−Ｃ_２Ｈ_４］ａ−［Ｏ−Ｃ_３Ｈ_６］ｂ− （９）
（式中、ａ及びｂはそれぞれ０〜５の整数であって、かつａとｂの和は１〜１０の整数を示す。好ましいａの値は１〜５、ｂの値は０〜３である。）
置換されたポリオキシアルキレン基としては、上記したポリオキシアルキレン鎖の末端炭素原子がヒドロキシル基や前記のアルコキシ基又はアルキルカルボニルオキシ基と結合したポリオキシアルキレン基が挙げられる。これらの中で、Ｒ_１及びＲ_３としては、水素原子、メチル基、エチル基、プロピル基、ｎ−ブチル基、２−エチルヘキシル基、フェニル基が好ましい。中でもＲ_１としてはメチル基またはフェニル基、特にメチル基が、Ｒ_３としては水素原子が更に好ましい。また、前記式（３）において−（ＣＨ_２）ｑ−基の結合位置は、ＣＨ ＝Ｃ（Ｒ_２）−基の結合位置に対してオルト、メタ若しくはパラ位のどこでもよいが、パラ位が最も好ましい。
【００２７】
化合物（ａ）のポリシロキサン部分の重合度ｎが４未満ではシリコーン化合物による滑らかさの改良効果が不十分となり、一方５００を超えた場合は、他のラジカル重合性単量体との共重合反応性が低下するので好ましくない。ｎが５０〜５００の範囲にあると、滑らかさが特に良好になるのでより好ましい。この化合物（ａ）が、その分子鎖の両末端にラジカル重合性不飽和結合を有することにより、他のラジカル重合性単量体との共重合の際に、重合鎖中に取り入れられる確率が高くなり、従って未反応のまま残留して生成皮膜を軟化させたり、ブリードしたりする可能性を小さくすることができる。
【００２８】
特に、重合度ｎが５０〜５００のように比較的高いものを用いると、二つの重合性不飽和結合を有していても、架橋密度があまり高くなることはなく、従ってゲル化を起こす可能性を減らすことができる。また、これにより適度の架橋構造を有するため、共重合体の分子量を高くすることができ、乾燥後の皮膜の強度も高くなり、耐久性の優れた皮膚用または爪用化粧料を与えることができる。
【００２９】
上記式（１）で表されるポリシロキサン化合物は、市販品として入手できる。例えば、商品名サイラプレーンＦＭ７７２５（式（１）においてＤおよびＥが式（２）の基、Ｒ１がメチル基、Ｒ２がメチル基、Ｘが酸素原子、ｐが３、ｎが１３０）、商品名サイラプレーンＦＭ７７２６（式（１）において、ＤおよびＥが式（２）の基、Ｒ１がメチル基、Ｒ２がメチル基、Ｘが酸素原子、ｐが３、ｎが２７０）、商品名サイラプレーンＦＭ７７２７（式（１）において、ＤおよびＥが式（２）の基、Ｒ１がメチル基、Ｒ２がメチル基、Ｘが酸素原子、ｐが３、ｎが４１０）等がこのポリシロキサン化合物に相当する。（いずれもチッソ（株）製）
また、式（１）のポリシロキサン化合物は、例えば、Ｐｏｌｙｍｅｒ Ｊ． （Ｔｏｋｙｏ） １４（１１），９１３（１９８２） 、Ｍａｃｒｏｍｏｌ． Ｃｈｅｍ． Ｐｈｙｓ． １９５， ２９６５（１９９４）、特公平２−３４１７号公報、特開平２−９２９３３号公報等に記載の方法に従って製造することができる。
化合物（ｂ）：化合物（ａ）と共重合可能なラジカル重合性単量体
本発明の重合体（Ａ）のもう一つの構成単位を与える化合物（ｂ）としては、親水性不飽和単量体（以下「化合物（ｂ１）」と略記することがある）及び／又は疎水性不飽和単量体（以下「化合物（ｂ２）」と略記することがある）を用いることができ、その重合体中の含有割合が、化合物（ｂ１）／化合物（ｂ２）の重量比（ｂ１／ｂ２）が０／１００〜７５／２５の範囲にあるのが好ましく、０／１００〜４０／６０の範囲がより好ましい。
親水性不飽和単量体（化合物（ｂ１））
本発明において、親水性不飽和単量体とは２５℃における水への溶解度が１０（ｇ／１００ｇ水）以上のものを言い、疎水性不飽和単量体とは、親水性不飽和単量体に相当しないものを言う。
【００３０】
親水性不飽和単量体（化合物（ｂ１））として好ましいものは、次の４種類の単量体である。但し、この分類は便宜的なもので、２つ以上の分類に重複して相当する単量体の存在を排除するものではない。
１．ノニオン性基、アニオン性基、カチオン性基、又は両性イオン基を有する単量体。
【００３１】
２．アクリル酸又はその塩、メタクリル酸又はその塩。
３．下記式（４）で表される両性化合物又は両性化によりこれを与える化合物。
【００３２】
【化１２】

【００３３】
式中、Ｒ_２は水素原子又はメチル基を示し、Ｒ_４及びＲ_５はそれぞれ独立して炭素原子数１〜４のアルキル基を示し、Ｘはイミノ（−ＮＨ−）基又は酸素原子を示し、ｒは２〜６の整数を示し、ｓは１〜４の整数を示す。
上記式（４）の単量体は、例えば特開昭５６−９２８０９号公報や特開平８−２８３３５８号公報等に記載されており、例えばこれらの公報に記載されている方法により調製することができる。
【００３４】
４．下記式（５）で表されるアミンオキシド化合物又はオキシド化によりこれを与える化合物。
【００３５】
【化１３】

【００３６】
式中の各記号は上記式（４）と同じ意味を示す。
上記式（５）の単量体は、例えば特開平１０−７２３２３号公報等に記載されていおり、例えば同号公報に記載されているように、アミンオキシド単量体の形で共重合に用いても、また対応する窒素含有前駆体の形で共重合した後に、過酸化物又はオゾン等の酸化剤でオキシド化してもよい。
【００３７】
なお、上記式（４）、（５）において用いることができる炭素原子数１〜４のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等の直鎖又は分岐鎖のアルキル基が挙げられる。
前記の（イ）カチオン性基を有する単量体、（ロ）アニオン性基を有する単量体、（ハ）ノニオン性基を有する単量体、（ニ）両性イオン基を有する単量体としては次のものが例示できる。
（イ）カチオン性基を有する単量体（カチオン性単量体）
（ｉ）アクリル酸又はメタクリル酸（以下これらをまとめて「（メタ）アクリル酸」と記し、アクリレートとメタクリレートとをまとめて「（メタ）アクリレート」と記す）と炭素原子数１〜４のエピハロヒドリン四級化物から誘導される単量体である、（メタ）アクリル酸ヒドロキシプロピルトリメチルアンモニウムクロリドや（メタ）アクリル酸ヒドロキシプロピルトリエチルアンモニウムブロミド等。
【００３８】
（ｉｉ）アクリルアミドもしくはメタクリルアミド（以下まとめて「（メタ）アクリルアミド」と記す）又は（メタ）アクリル酸と炭素原子数１〜４のアルキル基を有するジアルキルアルカノールアミンとから誘導されるアミン誘導体であるジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等、又はジメチルアミノプロピル（メタ）アクリルアミド等。
【００３９】
（ｉｉｉ）上記（ｉｉ）の化合物の、塩酸、乳酸等の酸による中和物、塩化メチル、塩化エチル、臭化メチル、ヨウ化エチル等のハロゲン化アルキルによる変性物、モノクロロ酢酸エチル、モノクロロプロピオン酸メチル等のハロゲン化脂肪酸エステルによる変性物、ジメチル硫酸、ジエチル硫酸等のジアルキル硫酸による変性物。
【００４０】
（ｉｖ） ジアリルジメチルアンモニウムクロリド等のアリル化合物のアミン誘導体。
これらのカチオン性単量体は上記の単量体の形で重合に用いることもできるが、重合を行なった後、いわゆる変性化剤を用いてカチオン性基を与えることができる前駆体を用いてもよい。例えば、ジメチルアミノエチル（メタ）アクリレートを用いて共重合を行ない、次いで上記の塩酸、モノクロロ酢酸エチル、ジメチル硫酸等を用いてカチオン化する方法がこれに相当する。
（ロ）アニオン性基を有する単量体（以下「アニオン性単量体」と略記することがある）
（ｉ）（メタ）アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、クロトン酸等のα、β−不飽和カルボン酸。
【００４１】
（ｉｉ）不飽和多塩基酸無水物（例えば無水コハク酸、無水フタル酸等）とヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート等のヒドロキシル基含有（メタ）アクリレートとの半エステル。
（ｉｉｉ）スチレンスルホン酸、スルホエチル（メタ）アクリレート等のスルホン酸基を有する単量体。
【００４２】
（ｉｖ）アシッドホスホオキシエチル（メタ）アクリレート、３−クロロ−２−アシッドホスホオキシプロピル（メタ）アクリレート等のリン酸基を有する単量体。
これらのアニオン性単量体は、酸のままでも、又は部分中和もしくは完全中和した塩の形でも用いることができ、又は酸の状態で共重合した後に、部分中和もしくは完全中和してもよい。この中和を行なう際に用いることのできる塩基性化合物としては特に制限されないが、例えば、水酸化リチウム、水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物；アンモニア水、モノ−、ジ−もしくはトリエタノールアミン、トリエチルアミン、モルホリン、アミノメチルプロパノール、アミノエチルプロパンジオール等のアミン化合物等が挙げられる。
【００４３】
（ハ）ノニオン性基を有する単量体（以下「ノニオン性単量体」と略記することがある）
ヒドロキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、メトキシポリエチレングリコールモノ（メタ）アクリレート、メトキシポリ（エチレングリコール／プロピレングリコール）モノ（メタ）アクリレート、（メタ）アクリルアミド等の（メタ）アクリル酸又は（メタ）アクリルアミドと炭素原子数２〜４のアルキレンオキサイドとから誘導される単量体及びアクリルアミド、Ｎ−ビニルピロリドン等。
【００４４】
（ニ）両性イオン基を有する単量体（以下「両イオン性単量体」と略記することがある）
前記の（メタ）アクリル酸のアミン誘導体、及び（メタ）アクリルアミド誘導体、例えばジメチルアミノエチル（メタ）アクリレート及びジメチルアミノプロピル（メタ）アクリルアミドのモノクロロ酢酸アミノメチルプロパノール塩、モノクロロ酢酸トリエタノールアミン塩、モノクロロ酢酸カリウム、モノブロモプロピオン酸ナトリウム等のハロゲン化脂肪酸塩による変性物、プロパンサルトンによる変性物等。
【００４５】
上記両イオン性単量体は、前記カチオン性単量体を、例えばハロ酢酸ナトリウム又はカリウム等の変性化剤で処理する等の常法により容易に調製できる。これらの両イオン性単量体は、前記カチオン性単量体と同様に、単量体の形で共重合に用いてもよく、又は、例えば特開昭５６−９２８０９号公報に記載の方法に従い、前駆体の形で共重合した後に、変性化剤を用いて両性化してもよい。なお、両性化により塩が副生する場合は、必要に応じて濾過、イオン交換等により除去することができる。
【００４６】
また、上記単量体の中でも、親水性不飽和単量体（化合物（ｂ１））としては、アニオン性単量体、カチオン性単量体、カチオン性単量体とアニオン性単量体との混合物、両イオン性単量体、両イオン性単量体とカチオン性単量体との混合物、半極性を有する親水性不飽和単量体、又は半極性を有する親水性不飽和単量体とカチオン性単量体との混合物、の少なくとも一種の単量体（混合物）が好ましい。
【００４７】
なお、カチオン性単量体とアニオン性単量体もしくは両イオン性単量体との混合物を用いる場合は、その混合比を９／１〜１／９とするのが好ましい。
これらの中でも、上記式（４）で表される両性化合物又は両性化によりこれを与えることができる化合物、上記式（５）で表されるアミンオキシド化合物又はオキシド化によりこれを与えることができる化合物が特に好ましい。
疎水性不飽和単量体（化合物（ｂ２））
疎水性不飽和単量体（化合物（ｂ２））は、得られる重合体（Ａ）に、揮発性シリコーン（Ｂ）への溶解性を付与したり、得られる皮膜に疎水性（耐湿性）、強度、硬度及び柔軟性等を付与したりするために使用される。
【００４８】
このような疎水性不飽和単量体としては、例えば次のものが挙げられる。
（ホ）メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、アリル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソアミル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、オレイル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート等のアルコール残基の炭素原子数が１〜２４の、飽和又は不飽和の（メタ）アクリル酸エステル。
（ヘ）ブトキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、ダイアセトンアクリルアミド等の疎水性（メタ）アクリル酸系誘導体。
（ト）スチレン、クロロスチレン、ビニルトルエン等の芳香系不飽和単量体及び酢酸ビニル、プロピオン酸ビニル等のビニルエステル類。
【００４９】
これらの中で好ましい化合物は炭素原子数１〜２４のアルキル基を有する、アルキル（メタ）アクリレートであり、炭素原子数４〜２２のアルキル基を有するものがより好ましい。アルキル基は直鎖状でも分岐していても、あるいは環状でもよい。
更に重合体（Ａ）が揮発性シリコーンに溶解するにはラジカル重合性単量体（ｂ）中におけるアルキル基の炭素原子数が１〜２４のアルキルアクリレートの割合が５０重量％以上であるのが好ましく、６０重量％以上が更に好ましい。
【００５０】
爪用化粧料の場合には皮膚用よりも硬い皮膜が必要となるので、より硬い皮膜を与えるラジカル重合性単量体の割合を多くする必要があるが、これらは目的とする化粧料の用途により上記単量体の中から適宜選択することができる。例えば（メタ）アクリレートの各重合体の性状に関しては「新・機能性アクリル系樹脂」（大森英三著、テカル出版）に記載されている。
【００５１】
なお、化合物（ｂ）としてエチレングリコールジ（メタ）アクリレート等の多官能不飽和単量体を用いる場合は、その使用量は全単量体の２重量％以下の量とすることが好ましい。この量が２重量％を超えると得られる重合体の分子量が大きくなり過ぎたり、ゲル化を起こしたりすることがある。このような多官能不飽和単量体の使用量は、化合物（ａ）の二官能性ポリシロキサン化合物の分子量と使用量を考慮して、生成重合体がゲル化しない範囲とすることが好ましい。
重合体の製造方法及び得られる重合体の物性等
本発明の重合体（Ａ）を得るための、化合物（ａ）と化合物（ｂ）との共重合は、通常、ラジカル重合法により、塊状重合、溶液重合、懸濁重合及び乳化重合等により行なうことができる。
【００５２】
これらの内で各単量体を、その溶媒中に溶解し、重合開始剤を添加し窒素気流中で加熱撹拌する方法で実施する溶液重合法が好ましい。ここで用いることができる溶媒としては、水；メタノール、エタノール、イソプロパノール、エチレングリコール、ブチルセロソルブ等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；酢酸エチル、酢酸ブチル等の酢酸エステル類；トルエン、キシレン、イソパラフィン、環状ポリシロキサン、直鎖状ポリシロキサン等が例示できる。これらの溶媒は単独で用いても、又はその二種以上を混合して用いてもよい。
【００５３】
重合体（Ａ）を揮発性シリコーン（Ｂ）に溶解するためには、１）重合後、溶剤を除去した後に揮発性シリコーン（Ｂ）に溶解する方法、２）重合後、揮発性シリコーン（Ｂ）を添加しながら揮発性シリコーン以外の重合溶剤を除去していく方法、３）重合溶剤として揮発性シリコーン（Ｂ）を用いて重合する方法等が挙げられるが、３）の重合溶剤として環状ポリシロキサンや直鎖状ポリシロキサン等の揮発性シリコーンを用いる方法が他の工程を省くことができるので好ましい。
【００５４】
重合開始剤としては、例えば、過酸化ベンゾイル、過酸化ラウロイル等の過酸化物や２，２′−アゾビスイソブチロニトリル、２，２′−アゾビス（２，４−ジメチルバレロニトリル）、２，２′−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）等のアゾ化合物が使用できる。
重合に用いる単量体はその全種類及び全量を重合当初から存在させても良いし、単量体の種類及び（又は）量に関して分割・逐次・連続添加を行なうこともできる。溶媒の使用量は、重合終了後の溶液中の共重合体濃度が５〜６０重量％、好ましくは１０〜５０重量％となるような量を用いるのがよい。
【００５５】
本発明に用いる重合体（Ａ）の重量平均分子量は３０，０００〜１，５００，０００であり、５０，０００〜１，０００，０００がより好ましい。重量平均分子量が３０，０００未満では、得られる皮膜の強度が不十分となり、耐湿性も低下する。一方、分子量が１，５００，０００を超えると、溶液の粘度が高くなって塗布が難しくなったり、乾燥が遅くなったりして、化粧料としての使用上の問題が出る。
【００５６】
この共重合体の分子量は、重合温度、重合開始剤の種類及び量、溶媒使用量、連鎖移動剤等の重合条件を適宜選択することにより任意の分子量を得ることができる。
＜揮発性シリコーン（Ｂ）＞
揮発性シリコーン（Ｂ）としては、下記式（６）で示される直鎖状ポリシロキサンまたは／及び下記式（７）で示される環状ポリシロキサンが好ましい。
【００５７】
【化１４】

【００５８】
式中、Ｒ_６は同一でも異なっていてもよいメチル基、エチル基、フェニル基、ｇは２又は３、ｈは１〜５の整数を示す。
具体例としては、オクタメチルトリシロキサン、デカメチルテトラシロキサン、ヘキサメチルジフェニルトリシロキサン等の直鎖状ポリシロキサン、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、ヘキサエチルシクロトリシロキサン、オクタエチルシクロテトラシロキサン、ヘキサフェニルシクロトリシロキサン、オクタフェニルシクロテトラシロキサン、オクタメチルシクロテトラシロキサン等の環状ポリシロキサンが挙げられる。
【００５９】
これらの中では、下記式（８）で示される環状ジメチルポリシロキサンが好ましい。
【００６０】
【化１５】

【００６１】
式中、ｈは１〜５の整数を示す。
中でも、臭気、感触、乾燥性、安定性、化粧品原料としての実績からオクタメチルシクロテトラシロキサン及び／又はデカメチルシクロペンタシロキサンが好ましい。
爪用化粧品等に使用する場合はメタノール、エタノール、イソプロパノール、エチレングリコール、ブチルセロソルブ等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；酢酸エチル、酢酸ブチル等の酢酸エステル類；トルエン、キシレン等の芳香族類、イソパラフィン等の溶剤を揮発性シリコーン（Ｂ）に必要に応じて加えてもよい。但し、これらの溶剤は揮発性シリコーンより一般に沸点が低く、先に揮発するため、こうした溶剤を用いる場合も重合体（Ａ）は揮発性シリコーン（Ｂ）に溶解可能である必要がある。
＜化粧料＞
前述のように、重合体（Ａ）は揮発性シリコーン（Ｂ）に溶解して使用される。本発明の皮膚用化粧料または爪用化粧料は、必須成分である重合体（Ａ）とこれを溶解している揮発性シリコーン（Ｂ）のみをを用いてもよく、あるいは目的に応じて所望の添加剤を適宜加えて、所望の剤型の化粧料として用いることもできる。
【００６２】
ここで用いることができる添加剤としては、例えば通常の化粧料に用いられる成分、例えば、ヒマシ油、カカオ油、ミンク油、アボガド油、ホホバ油、マカデミアンナッツ油、オリーブ油等の脂肪酸グリセリド；ラノリン等のロウ類；ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、ラウリン酸ヘキシル、乳酸セチル等のエステル類；セチルアルコール、オレイルアルコール、ステアリルアルコール、イソステアリルアルコール、ラウリルアルコール、２−オクチルドデカノール等の直鎖及び分岐鎖高級アルコール類；ラウリン酸、ステアリン酸、ミリスチン酸、オレイン酸等の直鎖及び分岐鎖高級脂肪酸類；ポリオキシエチレンラウリルエーテル、ポリオキシプロピレンセチルエーテル、ポリオキシエチレンポリオキシプロピレンステアリルエーテル等の高級アルコールの酸化エチレン及び／又は酸化プロピレン付加物類；オレイン酸ジエタノールアミド、ラウリン酸ジエタノールアミド等のアミド類；ステアリルトリメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライド、ラウリルトリメチルアンモニウムクロライド等のカチオン界面活性剤；ポリオキシエチレンラウリルエーテルサルフェート、ポリオキシエチレンラウリルスルホコハク酸塩等のアニオン界面活性剤；イミダゾリン型、アルキルベタイン型、アミンオキシド型等の両性界面活性剤；コラーゲン加水分解物、ケラチン加水分解物、ポリアミノ酸等の蛋白誘導体、アミノ酸誘導体類；植物抽出物、生薬、ビタミン類、オキシベンゼン等の紫外線吸収剤、エチレンジアミン四酢酸ナトリウム塩等のキレート剤、パラベン等の防腐剤、酸化防止剤、色素、顔料、香料等を、本発明の効果を損なわない範囲で適宜配合してもよい。
【００６３】
また、通常使用されている種々のカチオン性、アニオン性、ノニオン性、両性等の天然高分子又はその変性物、及び合成高分子等を本発明の化粧料の性能を低下させない範囲で併用することができる。
本発明の化粧料の形態としては、特に限定されるものではないが、皮膚用化粧料の場合は、クリーム・乳液等の基礎化粧料や、ファンデーション、白粉、ほほ紅、アイシャドウ、口紅等のメーキャップ化粧料が挙げられ、また、爪用化粧料としてはネールカラー、ネールケア用クリーム、ネールエナメル、ネールエナメル・ベースコート、ネールエナメル・オーバーコートなどが挙げられる。本発明の化粧料は水、エタノール等のアルコール系溶媒、酢酸エチル等のエステル系溶媒、メチルエチルケトン等のケトン系溶媒や流動パラフィン、ワセリン等の炭化水素類などに、溶解又は乳化、分散して製造することができる。
【００６４】
【実施例】
以下、実施例を用いて、本発明を更に具体的に説明するが、本発明は、その要旨を超えない限り以下の実施例によって限定されるものではない。なお、実施例中の部又は％は、特記する場合以外は重量部又は重量％を示す。
＜製造例１＞
還流冷却器、滴下ロート、温度計、窒素ガス導入管及び撹拌装置付きの反応器内にデカメチルシクロペンタシロキサン４００部、末端ラジカル重合性不飽和基含有ポリシロキサン化合物「サイラプレーンＦＭ７７２５」（商品名、チッソ（株）製、式（１）でｎ＝１３０のもの）２０部、２−エチルヘキシルアクリレート２０部、ステアリルアクリレート６０部、２，２′−アゾビスイソブチロニトリル１．５部、を添加して、窒素雰囲気下、８０℃に昇温して８時間反応後、２，２′−アゾビスイソブチロニトリル０．３部を追加して、更に４時間反応を行った結果、僅かに蛍光色を帯びた均一重合体溶液（Ｐ−１、固形分濃度２０％）を得た。
【００６５】
この重合体（Ｐ−１）の重量平均分子量をＧＰＣにより測定したところ６２０，０００であった。またこの溶液は３５℃まで冷却すると全体的に白色固化したが、ポリマーの分離は見られず、５０℃まで加熱すると再び均一な溶液となった。この１０％溶液の５０℃、５５０ｎｍにおける透過率は９１％であった。
またポリシロキサン基含有単量体の反応率は、デカメチルシクロペンタシロキサンを除去した粉末をヘキサンで抽出し、ヘキサンを留去した後の抽出量を測定て算出した結果９８％であった。
＜製造例２＞
実施例１と同様の撹拌装置付きの反応器内にデカメチルシクロペンタシロキサン４００部、片末端ラジカル重合性不飽和基含有ポリシロキサン化合物「サイラプレーンＦＭ０７２５」（商品名、チッソ（株）製、式（１）においてＤが式（２）の基、Ｅがブチル基（不飽和結合なし）、Ｒ_１がメチル基、Ｒ_２がメチル基、Ｘが酸素原子、ｐが３、ｎが１３０のもの）２０部、２−エチルヘキシルアクリレート２０部、ステアリルアクリレート６０部、２，２′−アゾビスイソブチロニトリル１．５部を添加して、窒素雰囲気下、８０℃に昇温して８時間反応後、２，２′−アゾビスイソブチロニトリル０．３部を追加して、更に４時間反応を行った結果、僅かに白濁した透過性均一重合体溶液（Ｐ−２、固形分濃度２０％）を得た。この重合体（Ｐ−２）の重量平均分子量をＧＰＣにより測定したところ１２０，０００であった。
【００６６】
この溶液は２７℃まで冷却すると全体的に白色固化したが、ポリマーの分離は見られず、５０℃まで加熱すると均一な溶液となった。この１０％溶液の５０℃、５５０ｎｍにおける透過率は９４％であった。
またポリシロキサン基含有単量体の反応率は、デカメチルシクロペンタシロキサンを除去した粉末をヘキサンで抽出し、ヘキサン留去後の抽出量を測定した結果８５％であった。
＜使用感評価試験＞
パネラー１０人により、下記の配合の皮膚用化粧料を肌に塗布した時の表面の滑らかさ、光沢及び皮膜の耐久性の実用テストを実施し、５段階評価によりスコアをつけた。スコアの平均値から、表面の滑らかさ，光沢、及び皮膜の耐久性を下記基準に従って評価した。なお、スコアは、その値が大きくなるほど滑らかさ、光沢及び耐久性が良好であることを示す。
【００６７】
平均スコア 評価の表示
４．０以上 ◎
３．０以上４．０未満 ○
２．０以上３．０未満 △
２．０未満 ×
＜実施例１、比較例１＞
製造例１、２で得られた重合体（Ｐ−１、Ｐ−２）を用いて表１に示す組成でハンドクリームを作成した。ハンドクリームの調製方法としては、油性成分と界面活性剤をともに７０℃で加熱溶解し、別途７０℃で加熱溶解した水性成分を混合乳化した後、室温まで冷却する方法を用いた。使用感評価の結果は表２に示す通りである。
【００６８】
【表１】

【００６９】
【表２】

【００７０】
＜結果の評価＞
表２に示す通り、本発明の組成物に基づくハンドクリームは、パネラーによる使用感評価で、全ての項目において良好な結果が得られた。特に皮膜の耐久性において良好な結果が得られていることが判る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a film-forming cosmetic. More specifically, the present invention relates to skin or nail cosmetics having low rigidity, high flexibility, and excellent feeling in use. More specifically, the present invention relates to a cosmetic for skin or nails comprising a polymer composed of a structural unit derived from a polymerizable polysiloxane compound having a specific structure and a radical polymerizable monomer, and a volatile silicone.
[0002]
[Prior art]
A polymer obtained by copolymerizing a polysiloxane compound having a radical polymerizable unsaturated bond with a specific other copolymerizable monomer has a film-forming property and has a slip, feel, gloss, etc. characteristic of silicone. Many applications have been filed for cosmetic applications as polymers. (See Patent Documents 1 to 3)
These nail polish polymers make use of the excellent characteristics of polysiloxane, and include acetate solvents such as ethyl acetate and butyl acetate, alcoholic solvents such as isopropyl alcohol, aromatic solvents such as toluene, Alternatively, they are used by dissolving them in a mixed organic solvent, and have good drying properties and can give nails excellent gloss and smooth feel.
[0003]
On the other hand, volatile silicones give a good feel, and cyclic dimethylsiloxane in particular has little irritation or stickiness to the skin and gives an invigorating feel, and at the same time, the compound itself is stable, so that it is widely used in cosmetics. Several applications have also been filed regarding cosmetics in which these volatile or low-viscosity silicones are combined with a polymer obtained by copolymerizing a monomer having a polysiloxane group. (See Patent Documents 4 to 7)
Further, Patent Document 8 discloses a cosmetic in which a polymer obtained by copolymerizing a polysiloxane compound having a radical polymerizable unsaturated bond is combined with a low-viscosity or volatile silicone and an alcohol.
[0004]
However, all of these polymers are copolymers of a polysiloxane compound having a radical polymerizable unsaturated bond at one end (a so-called silicon macromonomer) and another monomer, and although the smoothness is improved, However, the reactivity of the silicon macromonomer was not sufficient, and particularly when a high molecular weight silicon macromonomer was used, unreacted macromonomer was likely to remain. Further, according to the study of the present inventors, it is difficult to produce a high-molecular-weight silicone macromonomer having a radically polymerizable unsaturated group at one end with extremely high purity, and this is also an unreacted macromonomer component ( In fact, it also includes a component having no radically polymerizable unsaturated group). When these so-called unreacted macromonomers and the like remain, they act as a plasticizer for the dried film, lowering the film strength, or causing bleed-out and lowering the adhesion to the substrate, causing peeling, When laminated and used, there was a problem that adhesion between the coating films was insufficient and durability was insufficient. Therefore, the performance of a polymer obtained by copolymerizing such a monomer having a polysiloxane group could not be fully utilized.
[0005]
In order to reduce these so-called unreacted macromonomer components, the present inventors used a polymer obtained by copolymerizing a polysiloxane-based monomer having a radically polymerizable unsaturated group at both terminals as a nail polymer. It has been proposed (Patent Document 9).
[0006]
[Patent Document 1]
JP-A-5-213719 (cosmetics for nails)
[Patent Document 2]
JP-A-8-143427 (same)
[Patent Document 3]
JP-A-9-183711 (same)
[Patent Document 4]
JP-A-2-250812 (eye makeup cosmetics)
[Patent Document 5]
Japanese Patent No. 2700816 (gel cosmetic)
[Patent Document 6]
Japanese Patent No. 2767633 (the same)
[Patent Document 7]
Japanese Patent No. 2835617 (solid cosmetics)
[Patent Document 8]
JP-A-4-295409 (skin protection agent)
[Patent Document 9]
JP 2001-131248 A (cosmetics for nails)
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a cosmetic for skin or nails which has good surface smoothness and luster when used as a cosmetic for skin or nails, and has excellent durability of a film. Furthermore, another object of the present invention is to provide a cosmetic method using these skin or nail cosmetics.
[0008]
[Means for Solving the Problems]
The present inventors have conducted various studies in order to achieve the above object, and as a result, obtained by dissolving a polymer using a specific amount of a specific polysiloxane compound having a radical polymerizable unsaturated bond at both terminals in a volatile silicone. The present inventors have found that satisfactory performance can be obtained when the product is used as a cosmetic for skin or nails, and arrived at the present invention.
[0009]
That is, according to the present invention, there is provided a skin or nail cosmetic comprising the following components (A) and (B), and wherein the component (A) is dissolved in the component (B). Provided.
(A) 0.1 to 50% by weight of a structural unit derived from a polysiloxane compound (a) having a radical polymerizable unsaturated bond at both ends of a molecular chain represented by the formula (1), and copolymerizable with the structural unit. A polymer having a weight average molecular weight of 30,000 to 1,500,000, comprising 50 to 99.9% by weight of a structural unit derived from a radical polymerizable monomer (b).
(B) Volatile silicone
[0010]
Embedded image

[0011]
In the formula, D and E each represent an unsaturated bond-containing group represented by the following formula (2) or (3), and may be the same or different.
[0012]
Embedded image

[0013]
Where R₁And R₃May be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a hydroxyl group, a polyoxyalkylene group substituted with an alkoxy group or an alkylcarbonyloxy group, R₂Represents a hydrogen atom or a methyl group, X represents an imino group or an oxygen atom, n represents an integer of 4-500, p represents an integer of 1-4, q represents an integer of 0-4, m Represents an integer of 0 to 4.
[0014]
In the present invention, “dissolved” means that a solution of a polymer of the component (A) (hereinafter, may be abbreviated as “polymer (A)”) at a concentration of 10% by weight uses a 1 cm cell. A volatile silicone of the polymer (A) or (B) component, which is a uniform translucent liquid having a transmittance of 80% or more at 50 ° C. at a wavelength of 550 nm (hereinafter abbreviated as “volatile silicone (B)”) ) Is a state in which no separated precipitation occurs.
[0015]
In addition, even if it is non-uniform or solidified at a temperature lower than 50 ° C., it is regarded as “dissolved” if the above conditions are satisfied at 50 ° C.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
According to a preferred embodiment of the present invention, the content of the polymer (A) in the cosmetic is 0.1 to 20% by weight, and the content of the volatile silicone (B) is 0.1 to 99.9% by weight. %.
The ratio between the polymer (A) and the volatile silicone (B) is preferably (A) :( B) = 2: 1 to 1: 100 by weight. When the amount of the polymer (A) is more than 2: 1, the viscosity is too high and it becomes difficult to use the solution, and when the amount of the polymer (A) is less than 1: 100, the effect of improving flexibility is reduced.
[0017]
Preferred embodiments of the polymer (A) and the volatile silicone (B) are described below.
<Polymer (A)>
The polymer has a structural unit 0 derived from a polysiloxane compound having a radically polymerizable unsaturated bond at both ends of the molecular chain represented by the formula (1) (hereinafter sometimes abbreviated as “compound (a)”). 0.1 to 50% by weight, and 50 to 99.9% by weight of a structural unit derived from a radical polymerizable monomer copolymerizable therewith (hereinafter may be abbreviated as “compound (b)”). And a polymer having a weight average molecular weight of 30,000 to 1,500,000. More preferably, the constituent unit derived from the polysiloxane compound (a) is 0.5 to 30% by weight, and the constituent unit derived from the radical polymerizable monomer (b) copolymerizable therewith is 70 to 99.5. % By weight.
[0018]
When the content of the structural unit derived from the compound (a) is less than 0.1% by weight, not only the performance based on the polysiloxane unit becomes insufficient, but also the solubility in the volatile silicone (B) decreases. If the content is more than 50% by weight, even if the compound (a) having a large n is used, the number of cross-linking points is increased and gelation is easily caused, and the intended purpose cannot be achieved.
[0019]
Each of the compound (a) and the compound (b) may be used alone or in combination of two or more as long as a polymer within the above range of the weight ratio of the constituent units is provided.
Compound (a): polysiloxane compound
The polysiloxane compound of the compound (a) is represented by the following formula (1).
[0020]
Embedded image

[0021]
Where R₁Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a polyoxyalkylene group whose terminal is substituted with a hydroxyl group, an alkoxy group or an alkylcarbonyloxy group, which may be the same or different; And E represent an unsaturated bond-containing group represented by the following formula (2) or (3), and may be the same or different. n is an integer of 4 to 500, more preferably 50 to 500.
[0022]
Embedded image

[0023]
Where R₂Represents a hydrogen atom or a methyl group; X represents an imino group (—NH—) or an oxygen atom;₃Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a polyoxyalkylene group whose terminal is substituted with a hydroxyl group, an alkoxy group or an alkylcarbonyloxy group, which may be the same or different; Represents an integer of 1 to 4, q represents an integer of 0 to 4, and m represents an integer of 0 to 4.
[0024]
Substituent R of the above formulas (1) and (3)₁And R₃Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, heptyl, and n-octyl. A chain or branched alkyl group is mentioned, and as the aryl group, a phenyl group, a benzyl group and the like are mentioned. The alkoxy group preferably has an alkyl group having the above-mentioned alkyl group having 1 to 10 carbon atoms, and the same applies to the alkyl group of the alkylcarbonyloxy group. As these alkyl groups, those having 1 to 4 carbon atoms are more preferable.
[0025]
Examples of the polyoxyalkylene moiety of the substituted polyoxyalkylene group include a polyoxyalkylene chain represented by the following formula (9).
[0026]
Embedded image
-C₃H₆-[OC₂H₄] A- [OC₃H₆] B- (9)
(Wherein a and b are each an integer of 0 to 5, and the sum of a and b represents an integer of 1 to 10. The preferred value of a is 1 to 5, and the value of b is 0 to 3. is there.)
Examples of the substituted polyoxyalkylene group include the above-described polyoxyalkylene groups in which the terminal carbon atom of the polyoxyalkylene chain is bonded to a hydroxyl group or the aforementioned alkoxy group or alkylcarbonyloxy group. In these, R₁And R₃Preferred are a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a 2-ethylhexyl group, and a phenyl group. Above all R₁Is preferably a methyl group or a phenyl group, particularly a methyl group,₃Is more preferably a hydrogen atom. In the above formula (3),-(CH₂) The bond position of the q-group is CH 2 = C (R₂)-The group may be in the ortho, meta or para position relative to the point of attachment, but the para position is most preferred.
[0027]
If the degree of polymerization n of the polysiloxane portion of the compound (a) is less than 4, the effect of improving the smoothness by the silicone compound becomes insufficient, while if it exceeds 500, the copolymerization reaction with other radically polymerizable monomers occurs. It is not preferable because the property is lowered. It is more preferable that n is in the range of 50 to 500, since smoothness becomes particularly good. Since this compound (a) has a radical polymerizable unsaturated bond at both ends of its molecular chain, it has a high probability of being incorporated into the polymer chain at the time of copolymerization with another radical polymerizable monomer. Therefore, it is possible to reduce the possibility that the resulting film remains unreacted and softens or bleeds.
[0028]
In particular, when a polymer having a relatively high degree of polymerization n of 50 to 500 is used, the crosslink density does not become too high even if it has two polymerizable unsaturated bonds, and therefore gelation may occur. Sex can be reduced. In addition, since it has an appropriate crosslinked structure, the molecular weight of the copolymer can be increased, the strength of the film after drying can be increased, and a highly durable skin or nail cosmetic can be provided. it can.
[0029]
The polysiloxane compound represented by the above formula (1) can be obtained as a commercial product. For example, trade name Cylaprene FM7725 (in the formula (1), D and E are groups of the formula (2), R1 is a methyl group, R2 is a methyl group, X is an oxygen atom, p is 3, and n is 130). Thyraplane FM7727 (In the formula (1), D and E are groups of the formula (2), R1 is a methyl group, R2 is a methyl group, X is an oxygen atom, p is 3, and n is 270). (In the formula (1), D and E are groups of the formula (2), R1 is a methyl group, R2 is a methyl group, X is an oxygen atom, p is 3, n is 410) and the like correspond to the polysiloxane compound. . (All manufactured by Chisso Corporation)
Further, the polysiloxane compound of the formula (1) is described, for example, in Polymer J .; (Tokyo) 14 (11), 913 (1982), Macromol. Chem. Phys. 195, 2965 (1994), JP-B-2-3417, JP-A-2-92933, and the like.
Compound (b): radical polymerizable monomer copolymerizable with compound (a)
The compound (b) that provides another structural unit of the polymer (A) of the present invention includes a hydrophilic unsaturated monomer (hereinafter may be abbreviated as “compound (b1)”) and / or a hydrophobic compound. Unsaturated monomers (hereinafter sometimes abbreviated as “compound (b2)”) can be used, and the content ratio in the polymer is determined by the weight ratio of compound (b1) / compound (b2) (b1 / b2) is preferably in the range of 0/100 to 75/25, and more preferably in the range of 0/100 to 40/60.
Hydrophilic unsaturated monomer (compound (b1))
In the present invention, the hydrophilic unsaturated monomer means a compound having a solubility in water at 25 ° C. of 10 (g / 100 g water) or more, and the hydrophobic unsaturated monomer is a hydrophilic unsaturated monomer. What does not correspond to the body.
[0030]
Preferred as the hydrophilic unsaturated monomer (compound (b1)) are the following four types of monomers. However, this classification is for the sake of convenience and does not exclude the presence of monomers corresponding to two or more classifications.
1. A monomer having a nonionic group, an anionic group, a cationic group, or a zwitterionic group.
[0031]
2. Acrylic acid or a salt thereof, methacrylic acid or a salt thereof.
3. An amphoteric compound represented by the following formula (4) or a compound which gives this by amphoteric formation.
[0032]
Embedded image

[0033]
Where R₂Represents a hydrogen atom or a methyl group;₄And R₅Each independently represents an alkyl group having 1 to 4 carbon atoms, X represents an imino (—NH—) group or an oxygen atom, r represents an integer of 2 to 6, and s represents an integer of 1 to 4. Show.
The monomer of the above formula (4) is described in, for example, JP-A-56-92809 and JP-A-8-283358, and can be prepared, for example, by the methods described in these publications. it can.
[0034]
4. An amine oxide compound represented by the following formula (5) or a compound which gives the compound by oxidation.
[0035]
Embedded image

[0036]
Each symbol in the formula has the same meaning as in the above formula (4).
The monomer of the above formula (5) is described in, for example, JP-A-10-72323, and is used for copolymerization in the form of an amine oxide monomer as described in, for example, JP-A-10-72323. Alternatively, after copolymerization in the form of the corresponding nitrogen-containing precursor, it may be oxidized with an oxidizing agent such as peroxide or ozone.
[0037]
Examples of the alkyl group having 1 to 4 carbon atoms that can be used in the above formulas (4) and (5) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec. And straight-chain or branched-chain alkyl groups such as -butyl group and tert-butyl group.
(A) a monomer having a cationic group, (b) a monomer having an anionic group, (c) a monomer having a nonionic group, and (d) a monomer having an amphoteric group. The following can be exemplified.
(B) Monomer having a cationic group (cationic monomer)
(I) acrylic acid or methacrylic acid (hereinafter collectively referred to as “(meth) acrylic acid”, and acrylate and methacrylate collectively as “(meth) acrylate”) and epihalohydrin-4 having 1 to 4 carbon atoms Hydroxypropyltrimethylammonium (meth) acrylate, hydroxypropyltriethylammonium (meth) acrylate, and the like, which are monomers derived from graded products.
[0038]
(Ii) An amine derivative derived from acrylamide or methacrylamide (hereinafter collectively referred to as “(meth) acrylamide”) or (meth) acrylic acid and a dialkylalkanolamine having an alkyl group having 1 to 4 carbon atoms. Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, or dimethylaminopropyl (meth) acrylamide;
[0039]
(Iii) The above compound (ii) is neutralized with an acid such as hydrochloric acid or lactic acid, modified with an alkyl halide such as methyl chloride, ethyl chloride, methyl bromide or ethyl iodide, ethyl monochloroacetate, monochloropropion Modified products by halogenated fatty acid esters such as methyl acid, and modified products by dialkyl sulfate such as dimethyl sulfate and diethyl sulfate.
[0040]
(Iv) An amine derivative of an allyl compound such as diallyldimethylammonium chloride.
These cationic monomers can be used for polymerization in the form of the above monomers, but after polymerization, using a precursor capable of providing a cationic group using a so-called modifying agent Is also good. For example, a method in which copolymerization is performed using dimethylaminoethyl (meth) acrylate and then cationization is performed using the above-described hydrochloric acid, ethyl monochloroacetate, dimethyl sulfate, or the like.
(B) a monomer having an anionic group (hereinafter sometimes abbreviated as “anionic monomer”)
(I) α, β-unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid.
[0041]
(Ii) A half ester of an unsaturated polybasic acid anhydride (for example, succinic anhydride, phthalic anhydride or the like) and a hydroxyl group-containing (meth) acrylate such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate.
(Iii) Monomers having a sulfonic acid group such as styrene sulfonic acid and sulfoethyl (meth) acrylate.
[0042]
(Iv) Monomers having a phosphate group such as acid phosphooxyethyl (meth) acrylate and 3-chloro-2-acid phosphooxypropyl (meth) acrylate.
These anionic monomers can be used as an acid or in the form of a partially or completely neutralized salt, or after partially or completely neutralized after copolymerization in an acid state. You may. The basic compound that can be used in the neutralization is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; aqueous ammonia, mono-, di- Alternatively, amine compounds such as triethanolamine, triethylamine, morpholine, aminomethylpropanol, aminoethylpropanediol and the like can be mentioned.
[0043]
(C) a monomer having a nonionic group (hereinafter may be abbreviated as "nonionic monomer")
(Meth) acrylic acid such as hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, (meth) acrylamide or Monomers derived from (meth) acrylamide and alkylene oxides having 2 to 4 carbon atoms, acrylamide, N-vinylpyrrolidone and the like.
[0044]
(D) Monomer having a zwitterionic group (hereinafter sometimes abbreviated as "zwitterionic monomer")
Amino acid derivatives of (meth) acrylic acid and (meth) acrylamide derivatives, for example, dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide monochloroacetic acid aminomethylpropanol salt, monochloroacetic acid triethanolamine salt, monochloroacetic acid Modified products with halogenated fatty acid salts such as potassium acetate and sodium monobromopropionate, modified products with propane sultone, etc.
[0045]
The zwitterionic monomer can be easily prepared by a conventional method such as treating the cationic monomer with a modifying agent such as sodium or potassium haloacetate. These zwitterionic monomers may be used for copolymerization in the form of a monomer in the same manner as the cationic monomer, or according to the method described in, for example, JP-A-56-92809. After copolymerization in the form of a precursor, amphoteric may be carried out using a modifying agent. In addition, when a salt is by-produced due to amphoteric conversion, it can be removed by filtration, ion exchange, or the like, if necessary.
[0046]
Among the above monomers, the hydrophilic unsaturated monomer (compound (b1)) includes an anionic monomer, a cationic monomer, and a cationic monomer and an anionic monomer. A mixture, a zwitterionic monomer, a mixture of a zwitterionic monomer and a cationic monomer, a semi-polar hydrophilic unsaturated monomer, or a semi-polar hydrophilic unsaturated monomer; At least one monomer (mixture) of a mixture with a cationic monomer is preferred.
[0047]
When a mixture of a cationic monomer and an anionic monomer or a zwitterionic monomer is used, the mixing ratio is preferably from 9/1 to 1/9.
Among them, the amphoteric compound represented by the above formula (4) or a compound capable of providing the same by amphoteric, the amine oxide compound represented by the above formula (5) or the compound capable of providing the same by oxidization Is particularly preferred.
Hydrophobic unsaturated monomer (compound (b2))
The hydrophobic unsaturated monomer (compound (b2)) imparts solubility to the volatile silicone (B) to the obtained polymer (A), and imparts hydrophobicity (moisture resistance) to the resulting film. It is used for imparting strength, hardness, flexibility and the like.
[0048]
Examples of such a hydrophobic unsaturated monomer include the following.
(E) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, allyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) A) alcohol residues such as acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate A saturated or unsaturated (meth) acrylate having 1 to 24 carbon atoms in the group.
(F) Hydrophobic such as butoxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, diacetone acrylamide, etc. (Meth) acrylic acid derivatives.
(G) Aromatic unsaturated monomers such as styrene, chlorostyrene and vinyltoluene, and vinyl esters such as vinyl acetate and vinyl propionate.
[0049]
Among these, preferred compounds are alkyl (meth) acrylates having an alkyl group having 1 to 24 carbon atoms, and more preferably those having an alkyl group having 4 to 22 carbon atoms. The alkyl group may be linear, branched, or cyclic.
Further, in order for the polymer (A) to dissolve in the volatile silicone, the ratio of the alkyl acrylate having 1 to 24 carbon atoms of the alkyl group in the radical polymerizable monomer (b) must be 50% by weight or more. Preferably, it is more preferably at least 60% by weight.
[0050]
In the case of nail cosmetics, a film that is harder than that for the skin is required, so it is necessary to increase the proportion of radical polymerizable monomers that give a harder film, but these are the intended uses of cosmetics. Can be appropriately selected from the above monomers. For example, the properties of each polymer of (meth) acrylate are described in "New and Functional Acrylic Resin" (Eizo Omori, Tekka Shuppan).
[0051]
When a polyfunctional unsaturated monomer such as ethylene glycol di (meth) acrylate is used as the compound (b), the amount used is preferably 2% by weight or less of all monomers. When this amount exceeds 2% by weight, the molecular weight of the obtained polymer may be too large or gelation may occur. The amount of such a polyfunctional unsaturated monomer to be used is preferably in a range that does not cause gelation of the resulting polymer in consideration of the molecular weight and the amount of the bifunctional polysiloxane compound of the compound (a).
Method for producing polymer and physical properties of obtained polymer
The copolymerization of the compound (a) with the compound (b) for obtaining the polymer (A) of the present invention is usually carried out by a radical polymerization method by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like. be able to.
[0052]
Among these, a solution polymerization method is preferred in which each monomer is dissolved in the solvent, a polymerization initiator is added, and the mixture is heated and stirred in a nitrogen stream. Examples of the solvent that can be used here include water; alcohols such as methanol, ethanol, isopropanol, ethylene glycol and butyl cellosolve; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; acetate esters such as ethyl acetate and butyl acetate; Examples thereof include toluene, xylene, isoparaffin, cyclic polysiloxane, and linear polysiloxane. These solvents may be used alone or in combination of two or more.
[0053]
In order to dissolve the polymer (A) in the volatile silicone (B), 1) a method of dissolving the polymer in the volatile silicone (B) after removing the solvent after the polymerization, and 2) a method of dissolving the polymer in the volatile silicone (B). 3) a method of removing the polymerization solvent other than the volatile silicone while adding 3), a method of polymerizing using the volatile silicone (B) as the polymerization solvent, and the like. A method using volatile silicone such as siloxane or linear polysiloxane is preferable because other steps can be omitted.
[0054]
Examples of the polymerization initiator include peroxides such as benzoyl peroxide and lauroyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), And azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).
The monomers used in the polymerization may be present in their entirety and in their entirety from the beginning of the polymerization, or may be divided, sequentially or continuously added with respect to the type and / or amount of the monomer. The amount of the solvent used should be such that the copolymer concentration in the solution after the polymerization is 5 to 60% by weight, preferably 10 to 50% by weight.
[0055]
The weight average molecular weight of the polymer (A) used in the present invention is from 30,000 to 1,500,000, more preferably from 50,000 to 1,000,000. If the weight average molecular weight is less than 30,000, the strength of the obtained film becomes insufficient, and the moisture resistance also decreases. On the other hand, when the molecular weight exceeds 1,500,000, the viscosity of the solution becomes high and application becomes difficult, and drying becomes slow, which causes a problem in use as a cosmetic.
[0056]
The molecular weight of the copolymer can be arbitrarily determined by appropriately selecting polymerization conditions such as polymerization temperature, type and amount of polymerization initiator, amount of solvent used, and chain transfer agent.
<Volatile silicone (B)>
As the volatile silicone (B), a linear polysiloxane represented by the following formula (6) and / or a cyclic polysiloxane represented by the following formula (7) are preferable.
[0057]
Embedded image

[0058]
Where R₆Represents a methyl group, an ethyl group, or a phenyl group which may be the same or different, g represents 2 or 3, and h represents an integer of 1 to 5.
Specific examples include linear polysiloxanes such as octamethyltrisiloxane, decamethyltetrasiloxane, and hexamethyldiphenyltrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaethylcyclotrisiloxane, and octaethylcyclotetrasiloxane. Examples thereof include cyclic polysiloxanes such as siloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, and octamethylcyclotetrasiloxane.
[0059]
Among these, a cyclic dimethylpolysiloxane represented by the following formula (8) is preferable.
[0060]
Embedded image

[0061]
In the formula, h represents an integer of 1 to 5.
Among them, octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane are preferable from the viewpoint of odor, feel, drying property, stability, and performance as a cosmetic raw material.
When used in nail cosmetics, alcohols such as methanol, ethanol, isopropanol, ethylene glycol and butyl cellosolve; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; acetates such as ethyl acetate and butyl acetate; toluene and xylene Or a solvent such as isoparaffin may be added to the volatile silicone (B) as needed. However, since these solvents generally have a lower boiling point than volatile silicones and volatilize first, even when such a solvent is used, the polymer (A) needs to be soluble in the volatile silicone (B).
<Cosmetics>
As described above, the polymer (A) is used by dissolving it in the volatile silicone (B). The skin cosmetic or nail cosmetic of the present invention may use only the essential component of the polymer (A) and the volatile silicone (B) in which the polymer (A) is dissolved. Can be used as a cosmetic of a desired dosage form by appropriately adding the above additives.
[0062]
Examples of the additives that can be used here include components used in ordinary cosmetics, for example, fatty acid glycerides such as castor oil, cacao oil, mink oil, avocado oil, jojoba oil, macadamian nut oil, olive oil; lanolin Esters such as isopropyl myristate, octyldodecyl myristate, hexyl laurate, and cetyl lactate; linear chains such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, lauryl alcohol, and 2-octyldodecanol And straight-chain and higher-chain fatty acids such as lauric acid, stearic acid, myristic acid, and oleic acid; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether, and polyoxyethylene polyoxypropyl. Ethylene oxide and / or propylene oxide adducts of higher alcohols such as unstearyl ether; amides such as oleic acid diethanolamide and lauric acid diethanolamide; stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryltrimethylammonium chloride and the like Cationic surfactants; anionic surfactants such as polyoxyethylene lauryl ether sulfate and polyoxyethylene lauryl sulfosuccinate; amphoteric surfactants such as imidazoline type, alkyl betaine type and amine oxide type; collagen hydrolyzate, keratin hydrolysis Decomposed products, protein derivatives such as polyamino acids, amino acid derivatives; plant extracts, crude drugs, vitamins, ultraviolet absorbers such as oxybenzene, ethylene diamine Chelating agents such as sodium salt, preservatives such as paraben, antioxidants, dyes, pigments, perfumes and the like may be suitably compounded within a range not to impair the effects of the present invention.
[0063]
In addition, various commonly used cationic, anionic, nonionic, amphoteric or other natural polymers or modified products thereof, and synthetic polymers and the like may be used in combination as long as the performance of the cosmetic of the present invention is not reduced. Can be.
The form of the cosmetic of the present invention is not particularly limited, but in the case of skin cosmetics, basic cosmetics such as creams and emulsions, foundations, white powder, blush, eyeshadow, lipsticks and the like Makeup cosmetics are included, and nail cosmetics include nail color, nail care cream, nail enamel, nail enamel base coat, nail enamel overcoat, and the like. The cosmetic of the present invention is produced by dissolving or emulsifying or dispersing in water, an alcohol solvent such as ethanol, an ester solvent such as ethyl acetate, a ketone solvent such as methyl ethyl ketone, or a liquid paraffin, or a hydrocarbon such as petrolatum. can do.
[0064]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. In the examples, parts or% indicate parts by weight or% by weight, unless otherwise specified.
<Production Example 1>
In a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas inlet tube and a stirrer, 400 parts of decamethylcyclopentasiloxane, a polysiloxane compound containing a terminal radically polymerizable unsaturated group “Silaprene FM7725” (trade name) 20 parts, 2-ethylhexyl acrylate 20 parts, stearyl acrylate 60 parts, 2,2'-azobisisobutyronitrile 1.5 parts, manufactured by Chisso Corp. The mixture was heated to 80 ° C. in a nitrogen atmosphere and reacted for 8 hours. Then, 0.3 part of 2,2′-azobisisobutyronitrile was added and the reaction was further performed for 4 hours. To obtain a homogeneous polymer solution (P-1, solid content concentration 20%) having a fluorescent color.
[0065]
The weight average molecular weight of this polymer (P-1) measured by GPC was 620,000. When the solution was cooled to 35 ° C., the solution solidified as a whole, but no separation of the polymer was observed. When the solution was heated to 50 ° C., the solution became a uniform solution again. The transmittance of this 10% solution at 50 ° C. and 550 nm was 91%.
The conversion of the polysiloxane group-containing monomer was 98% as a result of extracting the powder from which decamethylcyclopentasiloxane had been removed with hexane and measuring the amount of extraction after distilling off hexane.
<Production Example 2>
400 parts of decamethylcyclopentasiloxane and a polysiloxane compound containing one end radically polymerizable unsaturated group “Silaprene FM0725” (trade name, manufactured by Chisso Corporation) in a reactor equipped with a stirrer in the same manner as in Example 1; In (1), D is a group of the formula (2), E is a butyl group (no unsaturated bond), R₁Is a methyl group, R₂Is a methyl group, X is an oxygen atom, p is 3, n is 130) 20 parts, 2-ethylhexyl acrylate 20 parts, stearyl acrylate 60 parts, 2,2'-azobisisobutyronitrile 1.5 parts The mixture was heated to 80 ° C. in a nitrogen atmosphere and reacted for 8 hours. Then, 0.3 part of 2,2′-azobisisobutyronitrile was added and the reaction was further performed for 4 hours. To obtain a cloudy transparent homogeneous polymer solution (P-2, solid content concentration 20%). The weight average molecular weight of this polymer (P-2) measured by GPC was 120,000.
[0066]
When this solution was cooled to 27 ° C., it solidified as a whole in white, but no separation of the polymer was observed, and when heated to 50 ° C., a uniform solution was obtained. The transmittance of this 10% solution at 50 ° C. and 550 nm was 94%.
The conversion of the polysiloxane group-containing monomer was 85% as a result of extracting the powder from which decamethylcyclopentasiloxane had been removed with hexane and measuring the extraction amount after distilling off hexane.
<Usability evaluation test>
Ten panelists carried out practical tests on the smoothness of the surface, the gloss, and the durability of the film when the cosmetic for skin having the following composition was applied to the skin, and a score was given on a five-point scale. From the average value of the scores, the surface smoothness, gloss, and durability of the film were evaluated according to the following criteria. The score indicates that the greater the value, the better the smoothness, gloss and durability.
[0067]
Average score Show rating
4.0 or more ◎
3.0 or more and less than 4.0 ○
2.0 or more and less than 3.0 △
Less than 2.0 ×
<Example 1, Comparative Example 1>
Using the polymers (P-1 and P-2) obtained in Production Examples 1 and 2, hand creams were prepared with the compositions shown in Table 1. As a method for preparing the hand cream, a method was used in which both the oily component and the surfactant were dissolved by heating at 70 ° C., the aqueous component separately heated and dissolved at 70 ° C. was mixed and emulsified, and then cooled to room temperature. The results of the usability evaluation are as shown in Table 2.
[0068]
[Table 1]

[0069]
[Table 2]

[0070]
<Evaluation of results>
As shown in Table 2, in the hand cream based on the composition of the present invention, favorable results were obtained in all items in the evaluation of feeling of use by panelists. In particular, it can be seen that good results were obtained in the durability of the film.

Claims (14)

A cosmetic for skin or nails comprising the following components (A) and (B), and wherein the component (A) is dissolved in the component (B).
(A) 0.1 to 50% by weight of a structural unit derived from a polysiloxane compound (a) having a radical polymerizable unsaturated bond at both ends of a molecular chain represented by the formula (1), and copolymerizable with the structural unit. Polymer (B) volatile silicone having a weight average molecular weight of 30,000 to 1,500,000, comprising 50 to 99.9% by weight of a structural unit derived from a radical polymerizable monomer (b)

In the formula, D and E each represent an unsaturated bond-containing group represented by the following formula (2) or (3), and may be the same or different.

In the formula, R ₁ and R ₃ may be the same or different and each has a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a terminal substituted with a hydroxyl group, an alkoxy group or an alkylcarbonyloxy group. Represents a polyoxyalkylene group, R ₂ represents a hydrogen atom or a methyl group, X represents an imino group or an oxygen atom, n represents an integer of 4 to 500, p represents an integer of 1 to 4, q represents M represents an integer of 0 to 4; m represents an integer of 0 to 4; The skin or nail cosmetic according to claim 1, wherein the content of the component (A) is 0.1 to 20% by weight. The skin or nail cosmetic according to claim 1 or 2, wherein the content of the component (B) is 0.1 to 99.9% by weight. The skin or nail cosmetic according to any one of claims 1 to 3, wherein in the polysiloxane compound (a) of the formula (1), n is an integer of 50 to 500. The content of the structural unit derived from the polysiloxane compound (a) represented by the formula (1) in the polymer of the component (A) is 0.5 to 30% by weight, and the radical polymerizable monomer (b 5. The cosmetic for skin or nails according to any one of claims 1 to 4, wherein the content of the structural unit derived from the above) is 70 to 99.5% by weight. The structural unit derived from the radical polymerizable monomer (b) is a structural unit derived from the hydrophilic unsaturated monomer (b1) or a structural unit derived from the hydrophobic unsaturated monomer (b2). And the content thereof is in the range of hydrophilic unsaturated monomer (b1) / hydrophobic unsaturated monomer (b2) = 0/100 to 75/25 by weight ratio. The cosmetic for skin or nails according to any one of claims 1 to 5. The cosmetic for skin or nails according to claim 6, wherein the hydrophobic unsaturated monomer (b2) is at least one kind of alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms. The skin or nail cosmetic according to claim 6 or 7, wherein the proportion of the alkyl acrylate having an alkyl group having 1 to 24 carbon atoms in the radical polymerizable monomer (b) is 50% by weight or more. The hydrophilic unsaturated monomer (b1) is a hydrophilic unsaturated monomer having an anionic group, a hydrophilic unsaturated monomer having a cationic group, a hydrophilic unsaturated monomer having a cationic group And a mixture of a hydrophilic unsaturated monomer having an anionic group, a hydrophilic unsaturated monomer having a zwitterionic group, a hydrophilic unsaturated monomer having a zwitterionic group and a hydrophilic group having a cationic group A mixture of an unsaturated monomer, a hydrophilic unsaturated monomer having a semipolar property, or a mixture of a hydrophilic unsaturated monomer having a semipolar property and a hydrophilic unsaturated monomer having a cationic group, The skin or nail cosmetic according to any one of claims 6 to 8, which is at least one of the following. The cosmetic for skin or nails according to claim 9, wherein the hydrophilic unsaturated monomer (b1) is an amphoteric compound represented by the following formula (4) or a compound that gives the amphoteric compound by amphoteric treatment.

In the formula, R ₂ represents a hydrogen atom or a methyl group; R ₄ and R ₅ each independently represent an alkyl group having 1 to 4 carbon atoms; X represents an imino group or an oxygen atom; 6 represents an integer, and s represents an integer of 1 to 4. The cosmetic for skin or nails according to claim 9, wherein the hydrophilic unsaturated monomer (b1) is an amine oxide compound represented by the following formula (5) or a compound that gives the amine oxide compound by oxidation.

In the formula, R ₂ represents a hydrogen atom or a methyl group; R ₄ and R ₅ each independently represent an alkyl group having 1 to 4 carbon atoms; X represents an imino group or an oxygen atom; Indicates an integer of 6. The volatile silicone of the component (B) is a linear polysiloxane represented by the following formula (6) and / or a cyclic polysiloxane represented by the following formula (7). Skin or nail cosmetics as described

In the formula, R ₆ represents a methyl group, an ethyl group, a phenyl group which may be the same or different, g represents 2 or 3, and h represents an integer of 1 to 5. The cosmetic for skin or nails according to any one of claims 1 to 12, wherein the volatile silicone as the component (B) is a cyclic dimethylpolysiloxane represented by the following formula (8).

In the formula, h represents an integer of 1 to 5. A cosmetic method, comprising applying the cosmetic according to any one of claims 1 to 13 to skin or nails.