JP3683850B2 - Cosmetic particles - Google Patents

Description

【０００７】
［式中、Ｘは水素原子、置換基を有していてもよい炭素数１〜４２の炭化水素基、カルボキシ基又はエステル基を示す。Ｙは置換基を有していてもよい炭素数１〜４２の炭化水素基、カルボキシ基、エステル基、又は式−(ＡＯ)_m−Ｒ¹（ここでＲ¹は水素原子、置換基を有していてもよい炭素数１〜２８の炭化水素基、炭素数１〜２２のフルオロアルキル基、炭素数６〜２４のフルオロアリール基、又はケイ素原子数１〜５０のシロキシシリルプロピル基、Ａは炭素数１〜３のアルキレン基、ｍは１〜１００の数を示し、ｍ個のＡは同一でも異なっていてもよい）で表される基を示す。また、ＸとＹは一緒になって環を形成していても良い。］
【０００８】
【発明の実施の形態】
［化粧料用粒子］
本発明の化粧料用粒子の形状は、球状、針状又は繊維状等何れであってもよいが、球状が皮膚上の感触が良好であることから好ましい。
【０００９】
本発明の化粧料用粒子が球状の場合、粒子の平均粒径としては、良好な感触と各種の性能（着色力、隠蔽力）をバランス良く発現させる観点から、０．８ｎｍ〜１ｍｍが好ましく、さらに３ｎｍ〜３００μｍが好ましく、特に５ｎｍ〜５０μｍが好ましい。
【００１０】
この平均粒径は、レーザー回折型粒径分布測定装置（ＬＡ−９１０ 堀場製）により、粒子のアルコール懸濁液を室温（２０℃）において測定した重量平均粒子径である。
【００１１】
本発明の化粧料粒子が針状又は繊維状の場合、その平均長径は、０．８ｎｍ〜１ｍｍが好ましく、３ｎｍ〜３００μｍがさらに好ましく、５ｎｍ〜５０μｍが特に好ましい。平均短径は１ｎｍ〜１００μｍが好ましく、１０ｎｍ〜５０μｍがさらに好ましい。
【００１２】
粒子の種類は、大別して無機物と有機物に分けられる。無機物では、（イ）シリカ、酸化チタン、アルミナ、酸化ジルコニウム、酸化亜鉛、フェライト、コバルト変性酸化鉄、マグネタイト、α−Ｆｅ₂Ｏ₃、γ−Ｆｅ₂Ｏ₃、酸化インジウム−酸化スズ、酸化マグネシウム、酸化カルシウム等の金属酸化物、（ロ）水酸化ナトリウム、水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物、（ハ）炭酸ナトリウム、炭酸水素ナトリウム、炭酸カルシウム、硫酸ナトリウム、硫酸カルシウム（石膏）、硫酸バリウム、塩化ナトリウム、チタン酸カリウム等の金属塩、（ニ）窒化ホウ素、窒化アルミニウム、窒化チタン、窒化ケイ素、シリコンカーバイド等の非酸化物系セラミックス類、（ホ）α−鉄粉、銀粉、銅粉、ケイ素粉等の金属粉、（ヘ）カーボンブラック、グラファイト、カーボンウィスカー等の炭素材、（ト）タルク、マイカ、スメクタイト、モンモリロナイト、セリサイト等の天然鉱物、（チ）ベンガラ、鉛白、黄鉛、紺青、チタン白、チタンイエロー等の無機顔料、（リ）フタロシアニンブルー、染色レーキ等の金属イオン含有有機固体等が挙げられる。
【００１３】
有機物では、（ヌ）炭化水素樹脂、アクリル樹脂、ビニル樹脂、フェノール樹脂、ナイロン樹脂、エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリスチレン樹脂、ウレタン樹脂、シリコン樹脂等の合成樹脂（これらは架橋、非架橋を問わない）、（ル）カルナバロウ、キャンデリラロウ等の天然ワックス、ポリエチレンワックス、エステルワックス、マイクロクリスタリンワックス、パラフィンワックス等のワックスが挙げられる。
【００１４】
これらは２種以上を混合して用いても良い。これらの中で、針状又は繊維状の粒子として、特にガラスファイバー、カーボンファイバー、炭化珪素繊維、アルミナ繊維、β−ウォラストナイト、ゾノライト、チタン酸カリウム繊維、硼酸アルミニウム繊維、テトラポット状酸化亜鉛、塩基性硫酸マグネシウム繊維、窒化ケイ素繊維等の無機繊維材が好ましい。
【００１５】
本発明の化粧料用粒子は、撥水及び撥油性であることが、化粧料中に用いた場合、汗や皮脂による化粧崩れを起こしにくく、好ましい。撥水性は、後述する接触角の測定において、蒸留水に対して１２０°以上であることが好ましく、１２５°以上であることが更に好ましい。撥油性は、後述する接触角の測定において、流動パラフィンに対して９５°以上であることが好ましく、９８°以上であることが更に好ましい。
【００１６】
本発明の化粧料用粒子は、重合単位（Ｉ）を有するポリエーテル（以下、単にポリエーテルという）で表面の少なくとも一部を被覆された粒子であり、化粧料用粒子として実用可能な撥水撥油性能を発現させる観点から、被覆された粒子１００質量部に対して、ポリエーテルが０．０１〜５０質量部表面上に存在することが好ましく、０．１〜１０質量部であることが更に好ましく、０．５〜５質量部であることが特に好ましい。
【００１７】
重合単位（Ｉ）において、Ｘ及び／又はＹが炭化水素基である場合、好ましい例として、炭素数１〜２２のアルキル基もしくはアルケニル基、炭素数６〜１４のアリール基、又は炭素数７〜１８のアリールアルキル基もしくはアルキルアリール基が挙げられる。さらに好ましい例として、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、ｔ−ブチル基、オクチル基、デシル基、ドデシル基、セチル基、ステアリル基、フェニル基、フェネチル基、ブチルフェニル基、ノニルフェニル基等が挙げられる。また、ＸとＹは一緒になって環を形成していても良く、この場合ＸとＹは、―（ＣＨ₂）_s−で表される連結基であることが好ましく、ｓは好ましくは３〜６の整数、更に好ましくは４である。
【００１８】
上記炭化水素基は置換基を有していてもよいが、その置換基として、ヒドロキシ基、炭素数が１〜２２のアルコキシ基、アミノ基、ジメチルアミノ基、ジエチルアミノ基、炭素数１〜１８のアミド基、炭素数１〜１８のアルキルアンモニウム基、アンモニウム基、メチルエステル基、エチルエステル基、フェニルエステル基、炭素数１〜１８のアシル基、シリル基、ＦやＣｌ等のハロゲン原子（以下、「本発明の置換基」という）等が挙げられる。
【００１９】
Ｘ及び／又はＹがカルボキシ基である場合、一般式（Ｉ）中の一部又は全てのカルボキシ基が、リチウム、ナトリウム、カリウム、アンモニウム等のカチオン種の１種又は２種以上と塩を形成していてもよい。これらの中ではナトリウム又はアンモニウム塩が好ましい。
【００２０】
Ｘ及び／又はＹがエステル基である場合、−ＣＯＯＲ²（Ｒ²は炭素数１〜２２の炭化水素基を示す）で表される基が好ましく、更に好ましい例として、メチルエステル、エチルエステル、プロピルエステル、ブチルエステル、オクチルエステル、フェニルエステル、アリルエステル等の基が挙げられる。
【００２１】
重合単位（Ｉ）において、Ｙが式−(ＡＯ)_m−Ｒ¹で表される基である場合、Ａとして、メチレン基、エチレン基又はプロピレン基が例示され、ｍは好ましくは１〜３０、更に好ましくは１〜２０、特に好ましくは１又は５〜１０の数である。またｍ個のＡは同一でも異なっていても良く、ランダム、ブロックのいずれの組み合わせでも良い。Ａとｍの組み合わせとしては、Ａがメチレン基でｍが１である組み合わせが特に好ましい。
【００２２】
また、Ｘ、Ｙは複数の異なる混合物であってもよいが、好ましい組み合わせは、Ｘが水素原子であり、Ｙが一般式−ＣＨ₂Ｏ−(ＡＯ)_m-1−Ｒ¹で表される基で、Ａがエチレン基又はプロピレン基で、ｍが１〜３０の数のものである。
【００２３】
Ｒ¹が炭化水素基である場合、好ましい例として、炭素数１〜２０のアルキル基もしくはアルケニル基、炭素数６〜１４のアリール基、又は炭素数７〜１８のアリールアルキル基もしくはアルキルアリール基が挙げられる。さらに好ましい例として、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、ｔ−ブチル基、オクチル基、デシル基、ドデシル基、セチル基、ステアリル基、フェニル基、ノニルフェニル基等が挙げられる。Ｒ¹がフルオロアルキル基である場合、好ましい例として、１Ｈ，１Ｈ，２Ｈ，２Ｈ−ノナフルオロヘキシル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ −トリデカフルオロオクチル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ −ヘプタデカフルオロデシル基、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンチル基、１Ｈ，１Ｈ，７Ｈ−ドデカフルオロヘプチル基、１Ｈ，１Ｈ，９Ｈ−ヘキサデカフルオロノニル基等が挙げられる。Ｒ¹がフルオロアリール基である場合、好ましい例として、パーフルオロフェニル基が挙げられる。Ｒ¹がシロキシシリルプロピル基である場合、好ましくはケイ素原子数１〜３０、さらに好ましくは１〜２０の直鎖又は分岐鎖のシロキシシリルプロピル基が挙げられる。これらシロキシシリルプロピル基のケイ素原子に結合するアルキル置換基は、同一又は異なっていてもよく、メチル基、ブチル基、ビニル基、フェニル基等が例示できる。Ｒ¹は置換基を有していてもよいが、その置換基として、前記「本発明の置換基」が挙げられる。
【００２４】
本発明に用いられるポリエーテルは、ＷＯ９９／４２５１３に開示されている製法によって、例えば一般式（II）で表されるエポキシ化合物を重合することにより、下記の反応式に従って製造することができる。
【００２５】
【化３】

【００２６】
（式中、Ｘ及びＹは前記と同じ意味を示す。）
ここで用いられる重合触媒としては、サマリウムアルコキシド、サマリウムトリス（テトラメチルヘプタンジオネート）等の希土類金属とアルキルアルミニウム化合物の組み合わせで得られる希土類金属系触媒等が挙げられる。
【００２７】
本発明に用いられるポリエーテルは、重合単位（Ｉ）の単一重合体であってもよいが、上記一般式（II）で表されるエポキシ化合物と共重合可能な他のモノマーを共重合させた共重合体でもよい。その場合、ポリエーテル主鎖におけるそれらの配列様式は、ブロック、交互、ランダムの何れであってもよい。
【００２８】
共重合可能な、他のモノマーの具体例としては、エチレンオキシド等のエポキシ化合物、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル等の（メタ）アクリル酸エステル化合物、スチレン、酢酸ビニル、ブチルビニルケトン等のビニル化合物、ラクタム類、カーボネート類、その他、イソプレン、ブタジエン、フルオロアルキルグリシジルエーテル等が挙げられる。
【００２９】
ポリエーテルが共重合体である場合、共重合体中、重合単位（Ｉ）のモル分率は、０．１以上１．０未満が好ましく、０．３以上１．０未満がさらに好ましい。
【００３０】
本発明に用いられるポリエーテルの数平均分子量は、２，０００〜１０，０００，０００が好ましく、５，０００〜５，０００，０００が特に好ましい。数平均分子量は、後述の測定法によって求めることができる。
【００３１】
本発明の化粧料用粒子は、ポリエーテルによる高い撥水撥油性を有し、超臨界二酸化炭素存在下で、ポリエーテルと粒子を接触させて得られるため、粒子同士の凝集がほとんど無い。凝集がないことは、粒径分布測定から確認できる。また、凝集がほとんどないことにより、ポリエーテルで表面を被覆された粒子は、サラサラした良好な感触を呈する。
【００３２】
［化粧料用粒子の製造法］
本発明において、超臨界二酸化炭素とは、臨界温度（３０４．２Ｋ）以上でかつ臨界圧力（７．３７ＭＰａ）以上の圧力である二酸化炭素をいい、臨界点付近では、僅かな圧力変化によって密度が急変するという性質を有する。従って、臨界圧力及び臨界温度を僅かに超えた超臨界二酸化炭素の圧力を増加させると、気相の密度が急増するため、臨界圧力を超えた領域で溶質の溶解度が急激に増加する。
【００３３】
本発明の化粧料用粒子は、容器内で、超臨界二酸化炭素存在下、ポリエーテルと粒子を接触させて得られる。
【００３４】
超臨界二酸化炭素は、二酸化炭素が超臨界状態を発現する温度、圧力であれば任意の組み合わせで用いることが出来るが、その中でも温度は、３０８Ｋ（３５℃）〜３７３Ｋ（１００℃）が好ましく、３０８Ｋ（３５℃）〜３３３Ｋ（６０℃）が更に好ましい。圧力は、７．４〜５０ＭＰａが好ましく、８〜３０ＭＰａが更に好ましく、９〜２０ＭＰａが特に好ましい。この範囲では、超臨界二酸化炭素中へのポリエーテルの溶解性が高い。
【００３５】
ポリエーテルと粒子を接触させる時間は、特に制限は無いが、ポリエーテルで粒子の表面を被覆させるためには１〜６０分が好ましい。ポリエーテルと粒子の割合は、粒子１００質量部に対してポリエーテルを０．０１〜５０質量部、さらに好ましくは０．０５〜１０質量部存在させることが好ましい。また、ポリエーテルと粒子の接触は、両者を攪拌させて接触させることが好ましい。
【００３６】
容器内で、超臨界二酸化炭素存在下、ポリエーテルと粒子を接触させた後、容器に備えられている排気バルブ等を開放し、該容器を減圧させることにより、ポリエーテルで表面を被覆された化粧料用粒子を得ることが出来る。該容器を減圧させるとは、超臨界状態の二酸化炭素の圧力を低下させることである。
【００３７】
しかし、臨界圧力以上から、超臨界状態の二酸化炭素の圧力を低下させる際、二酸化炭素の断熱膨張により、該容器内の温度が低下して二酸化炭素の臨界温度以下になると、液化二酸化炭素が生じ、粉体の凝集が発生し易い。従って、該容器を減圧させる際、該容器内の温度を二酸化炭素の臨界温度以上に保持しながら、該容器内の二酸化炭素を減圧し、超臨界状態の二酸化炭素を、気体の二酸化炭素とすることが好ましい。そのため、該容器内の二酸化炭素を臨界圧力以上から大気圧まで、減圧を緩やかに行い、等温膨張で圧力を低下させるように行うことが好ましい。具体的には好ましい臨界圧力以上の圧力（好ましくは７．４〜５０ＭＰａ、更に好ましくは８〜３０ＭＰａ、特に好ましくは９〜２０ＭＰａ）から大気圧（約０．１ＭＰａ）に減圧させるのに、３〜１２０分間程度、さらに好ましくは５〜６０分間程度をかけて徐々に減圧するのがよい。平均の減圧速度は、０．０６〜１６．６３ＭＰａ／ｍｉｎが好ましく、０．１２〜９．９８ＭＰａ／ｍｉｎが更に好ましい。
【００３８】
または、液化二酸化炭素の発生をできる限り抑制するために急激に減圧させる方法も好ましい。その際、該容器内の超臨界状態の二酸化炭素は、液化二酸化炭素をほとんど生ずることなく、気体の二酸化炭素となるため、粉体の凝集を引き起こすことがほとんどない。具体的な方法としては、該容器内の超臨界状態の二酸化炭素を排出し、瞬間的に大気圧まで減圧することが挙げられ、該容器内の二酸化炭素を臨界圧力以上から大気圧まで、具体的には好ましい臨界圧力以上の圧力（好ましくは７．４〜５０ＭＰａ、更に好ましくは８〜３０ＭＰａ、特に好ましくは９〜２０ＭＰａ）から大気圧（約０．１ＭＰａ）まで、好ましくは３秒以下、更に好ましくは２秒以下で減圧する。この急激な二酸化炭素の排出の際、化粧料用粒子も排出されるが、この時二酸化炭素の排出口部分に捕集用の装置（粒子が、通り抜けられないような大きさの目開きを有する布袋または紙袋、もしくは充分大きな容量を有する箱状のものならば何でもよい）を設置しておけば、化粧料用粉体の取り出しも同時に行えるため便利である。
【００３９】
［化粧料］
本発明の粒子を含有した本発明の化粧料は、例えばファンデーション、コンシーラー、ほほ紅、アイシャドウ、口紅等のメイクアップ化粧料として好ましく用いられる。本発明の化粧料中の本発明の粒子の含有量は、０．０１〜１０質量％が好ましく、０．１〜５質量％が更に好ましい。
【００４０】
本発明の化粧料は、本発明の粒子以外に、染料、顔料等の着色剤、可塑剤、保湿剤、冷感剤、温感剤、エモリエント成分及び粘度調整剤等を含有することが出来る。
【００４１】
染料・顔料としては、「医薬品などに使用することができるタール色素を定める省令」（昭和４１年８月３１日厚生省令第３０号）に記載のタール系顔料・染料が挙げられる。その他、酸化亜鉛、二酸化チタン、ベンガラ、チタン酸鉄、γ−酸化鉄、黄酸化鉄、黄土、黒酸化鉄、カーボンブラック、低次酸化チタン、マンゴバイオレット、コバルトバイオレット、酸化クロム、水酸化クロム、チタン酸コバルト、群青、紺青、魚鱗箔、酸化チタン被覆マイカ、酸化チタン被覆タルク等の無機顔料なども配合することが出来る。
【００４２】
可塑剤としては、セロソルブ類、カルビトール類、フタル酸エステル等、保湿剤としては、グリセリン、エチレングリコール、アロエエキス等の公知のものが使用できる。冷感剤としては、ｌ−メントール等の公知のもの、温感剤としては、トウガラシエキス、バニリルブチルエーテル等の公知のものが用いられる。
【００４３】
他にエモリエント成分として、スクワラン、流動パラフィン等の炭化水素油；ミリスチン酸イソステアリル、ノナン酸イソトリデシル、ジカプリン酸ネオペンチルグリコール、ヘキサオキシステアリン酸ジペンタエリトット、トリイソステアリン酸トリメチロールプロパン、イソステアリン酸イソステアリル、リンゴ酸ジイソステアリル、メタクリル酸ステアリル、Ｎ−ラウロイル−Ｌ−グルタミン酸ジ（コレステリル、オクチルドデシル）、パラメトキシ桂皮酸オクチル等のエステル油；ひまし油、ホホバ油、マカデミアンナッツ油、月見草油、オリーブ油、ハッカ油、液状ラノリン等の動植物油；ジメチルポリシロキサン、メチルフェニルポリシロキサン等のシリコーン油；パーフルオロポリエーテル、フッ素変性シリコーン等のフッ素化油剤；アルコール、ポリオール、ジグリセライド、トリグリセライド等が挙げられる。エモリエント成分は単独あるいは２種以上の組み合わせで使用することが出来る。
【００４４】
粘度調整用の増粘剤としては、スメクタイト、ラポナイト等の無機系増粘剤、アクリル酸ナトリウム共重合ゲル、アクリル系エマルジョン、多糖系増粘剤等の高分子増粘剤などが挙げられる。粘度調整剤は単独あるいは２種以上の組み合わせで使用することが出来る。
【００４５】
その他、油剤、固形・半固形油、水溶性及び油溶性ポリマー、界面活性剤、エタノール、制汗剤、紫外線吸収剤、紫外線散乱剤、酸化防止剤、防腐殺菌剤、ｐＨ調整剤、ビタミン類、血行促進剤、美白剤、皮膚賦活剤、薬効剤、動植物からの抽出物、防腐剤、制汗剤、殺菌剤、香料、水等を適宜配合できる。
本発明の化粧料は、常法により、製造することが出来る。
【００４６】
【実施例】
ポリエーテルの数平均分子量は、昭和電工（株）製ゲルパーミエーションクロマトグラフィーシステム ＳＹＳＴＥＭ１１（溶離液：ヘキサフルオロイソプロパノール、１．０ｍｌ／ｍｉｎ、カラム：昭和電工（株）製ＨＦＩＰ−８０Ｍ×２、カラム温度：４０℃、検出器：ＲＩ）を用いて測定した、ポリスチレン換算の値である。
【００４７】
合成例１
パーフルオロオクチルエチルグリシジルエーテル４ｇ｛一般式（II）において、Ｘ：水素原子、Ｙ：−ＣＨ₂−ＯＲ²、ここでＲ²＝パーフルオロオクチルエチル基｝を、サマリウムアルコキシド−メチルアルモキサン触媒１モル％（モノマー全量に対するモル％、以下同様）を用いて重合した（１３０℃、１２時間）。反応液から再沈精製により、下記式で表される重合単位を有する白色固体のポリエーテル▲１▼を得た。数平均分子量は１２万であった。
【００４８】
【化４】

【００４９】
実施例１
酸化チタン（チタン工業社製酸化チタンＫＲＯＮＯＳ ＫＡ１５）５０ｇとポリエーテル▲１▼２．５ｇを撹拌装置の付いた耐圧容器に入れ、二酸化炭素を容器に導入して４０℃、１０ＭＰａで１０分間撹拌を継続しながら保持した。その後３０分間をかけて徐々に大気圧まで降圧した後に内容物を取り出し、表面処理酸化チタン▲１▼を得た。
【００５０】
実施例２
酸化チタン（実施例１と同品）５０ｇとポリエーテル▲１▼２．５ｇを撹拌装置の付いた耐圧容器に入れ、二酸化炭素を容器に導入して４０℃、１０ＭＰａで１０分間撹拌を継続しながら保持した。その後排出バルブを全開し、１秒間で一気に大気圧まで降圧した。この時排出バルブの出口に付けた布袋で捕集された内容物を回収し、表面処理酸化チタン▲２▼を得た。
【００５１】
実施例３
酸化チタンの代わりに酸化鉄（チタン工業社製合成酸化鉄ＴＡＲＯＸ ＢＬ１００）５０ｇを用いた以外は実施例１と同様の操作で、表面処理酸化鉄▲１▼を得た。
【００５２】
実施例４
酸化チタンの代わりに酸化鉄（実施例３と同品）５０ｇを用いた以外は実施例２と同様の操作で、表面処理酸化鉄▲２▼を得た。
【００５３】
実施例５
酸化チタンの代わりに酸化鉄（チタン工業社製合成酸化鉄ＴＡＲＯＸ ＬＬ−ＸＬＯ）５０ｇを用いた以外は実施例１と同様の操作で、表面処理酸化鉄▲３▼を得た。
【００５４】
実施例６
酸化チタンの代わりに酸化鉄（実施例５と同品）５０ｇを用いた以外は実施例２と同様の操作で、表面処理酸化鉄▲４▼を得た。
【００５５】
実施例７
酸化チタンの代わりに酸化鉄（チタン工業社製合成酸化鉄ＴＡＲＯＸ Ｒ１１０）５０ｇを用いた以外は実施例１と同様の操作で、表面処理酸化鉄▲５▼を得た。
【００５６】
実施例８
酸化チタンの代わりに酸化鉄（実施例７と同品）５０ｇを用いた以外は実施例２と同様の操作で、表面処理酸化鉄▲６▼を得た。
【００５７】
実施例９
酸化チタンの代わりにマイカ（（株）山口雲母工業所製 雲母粉 Ｙ２３００）５０ｇを用いた以外は実施例１と同様の操作で、表面処理マイカ▲１▼を得た。
【００５８】
実施例１０
酸化チタンの代わりにマイカ（実施例９と同品）５０ｇを用いた以外は実施例２と同様の操作で、表面処理マイカ▲２▼を得た
比較例１
酸化チタン（実施例１と同品）５０ｇ、アサヒガード（旭硝子社製フッ素系撥水撥油剤、３０％水溶液）８ｇを小型ミキサーで充分混合した後に乾燥した。その後解砕機で解砕し、ふるいで分級して１００ミクロン以上の粗大粒子を取り除くことでフッ素系撥水撥油剤によって表面処理された酸化チタン▲３▼を得た。
【００５９】
比較例２
酸化チタンの代わりに酸化鉄（実施例３と同品）を用いた以外は比較例１と同様の操作でフッ素系撥水撥油剤によって表面処理された酸化鉄▲７▼を得た。
【００６０】
比較例３
酸化チタンの代わりに酸化鉄（実施例５と同品）を用いた以外は比較例１と同様の操作でフッ素系撥水撥油剤によって表面処理された酸化鉄▲８▼を得た。
【００６１】
比較例４
酸化チタンの代わりに酸化鉄（実施例７と同品）を用いた以外は比較例１と同様の操作でフッ素系撥水撥油剤によって表面処理された酸化鉄▲９▼を得た。
【００６２】
比較例５
酸化チタンの代わりにマイカ（実施例９と同品）を用いた以外は比較例１と同様の操作でフッ素系撥水撥油剤によって表面処理されたマイカ▲３▼を得た。
【００６３】
試験例１
実施例１〜１０及び比較例１〜５で得られた、表面処理された酸化チタン、酸化鉄、マイカを圧縮成型し、得られた板状体表面の接触角を、協和界面科学（株）製ＣＡ−Ａ型を用いて室温（２０℃）で測定し、撥水撥油性を評価した。結果を表１に示す。
【００６４】
【表１】

【００６５】
試験例２
実施例１と比較例１で得られた表面処理された酸化チタン▲１▼、▲３▼の粒径分布を、ＨＯＲＩＢＡ ＬＡ−９２０を用いてエタノール中、２０℃で測定した（相対屈折率は２．０）。実施例１の表面処理された酸化チタン▲１▼の結果を図１に、比較例１の表面処理された酸化チタン▲３▼の結果を図２に示す。また、これらの結果から得られた実施例１及び比較例１の表面処理された酸化チタンの算術平均粒径及び算術標準偏差を表２に示す。
【００６６】
【表２】

【００６７】
試験例３
表３に示す処方により液状ファンデーション及びパウダーファンデーションを調製し、専門パネラー１０人による使用感評価を実施し、次の基準で５段階評価した。結果を表３に示す。
【００６８】
＜評価基準＞
５：９〜１０人が良いと判断した。
４：７〜８人が良いと判断した。
３：５〜６人が良いと判断した。
２：３〜４人が良いと判断した。
１：１〜２人が良いと判断した。
【００６９】
【表３】

【００７０】
【発明の効果】
本発明の化粧料用粒子は、撥水性、撥油性、分散性に優れ、化粧料に用いた時に、良好な使用感を示す。
【図面の簡単な説明】
【図１】 実施例１で得られた表面処理された酸化チタン▲１▼の粒径分布測定結果を示す図である。
【図２】 比較例１で得られた表面処理された酸化チタン▲３▼の粒径分布測定結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to particles useful for cosmetics, a method for producing the same, and cosmetics containing the same.
[0002]
[Prior art and problems to be solved by the invention]
The disappearance of cosmetic ingredients, facial shine, aging, dullness, shading, and other makeup collapses due to the effects of human secretions such as sweat, tears, and sebum are significant. In order to improve this, cosmetics are required to have high water and oil repellency. Usually, the powder used as a raw material for cosmetics is low in water and oil repellency as it is, and therefore surface treatment is usually performed with a coating agent having water and oil repellency.
[0003]
A specific method of surface treatment is to dissolve or disperse the coating agent in a solvent or water, immerse the core microparticles in the liquid phase, and then apply heat treatment to coat the surface of the microparticles with the coating agent. The method (liquid phase coating method) has been used exclusively. However, in this method, since the coating agent tightly binds the fine particles, the formation of aggregated particles is inevitable, and the touch is deteriorated. For this reason, when actually used as a cosmetic, it is necessary to make fine particles by crushing, which causes a significant increase in cost.
[0004]
An object of the present invention is to provide cosmetic particles having high dispersibility, high water and oil repellency, and a good feel, a method for producing the same, and a cosmetic containing the same.
[0005]
[Means for Solving the Problems]
In the present invention, the surface is coated with a polyether obtained by bringing particles into contact with a polyether having a polymerization unit represented by general formula (I) (hereinafter referred to as polymerization unit (I)) in the presence of supercritical carbon dioxide. Provided cosmetic particles, a process for producing the same, and a cosmetic containing the same.
[0006]
[Chemical formula 2]

[0007]
[Wherein, X represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 42 carbon atoms, a carboxy group or an ester group. Y is an optionally substituted hydrocarbon group having 1 to 42 carbon atoms, a carboxy group, an ester group, or a formula — (AO) _m —R ¹ (where R ¹ has a hydrogen atom or a substituent). An optionally substituted hydrocarbon group having 1 to 28 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, a fluoroaryl group having 6 to 24 carbon atoms, or a siloxysilylpropyl group having 1 to 50 silicon atoms, A is An alkylene group having 1 to 3 carbon atoms, m represents a number of 1 to 100, and m A's may be the same or different. X and Y may form a ring together. ]
[0008]
DETAILED DESCRIPTION OF THE INVENTION
[Cosmetic particles]
The shape of the cosmetic particles of the present invention may be spherical, acicular or fibrous, but spherical is preferred because of the good feel on the skin.
[0009]
When the cosmetic particles of the present invention are spherical, the average particle size of the particles is preferably 0.8 nm to 1 mm from the viewpoint of expressing a good feel and various performances (coloring power, hiding power) in a balanced manner, Furthermore, 3 nm-300 micrometers are preferable, and 5 nm-50 micrometers are especially preferable.
[0010]
This average particle diameter is a weight average particle diameter obtained by measuring an alcohol suspension of particles at room temperature (20 ° C.) with a laser diffraction type particle size distribution measuring apparatus (LA-910, manufactured by Horiba).
[0011]
When the cosmetic particles of the present invention are acicular or fibrous, the average major axis is preferably 0.8 nm to 1 mm, more preferably 3 nm to 300 μm, and particularly preferably 5 nm to 50 μm. The average minor axis is preferably 1 nm to 100 μm, and more preferably 10 nm to 50 μm.
[0012]
The types of particles are roughly classified into inorganic substances and organic substances. Among inorganic substances, (i) silica, titanium oxide, alumina, zirconium oxide, zinc oxide, ferrite, cobalt-modified iron oxide, magnetite, α-Fe ₂ O ₃ , γ-Fe ₂ O ₃ , indium oxide-tin oxide, magnesium oxide , Metal oxides such as calcium oxide, (b) metal hydroxides such as sodium hydroxide, magnesium hydroxide, aluminum hydroxide, (c) sodium carbonate, sodium bicarbonate, calcium carbonate, sodium sulfate, calcium sulfate (gypsum) ), Metal salts such as barium sulfate, sodium chloride, potassium titanate, (d) non-oxide ceramics such as boron nitride, aluminum nitride, titanium nitride, silicon nitride, silicon carbide, (e) α-iron powder, Metal powder such as silver powder, copper powder, silicon powder, (f) carbon black, graphite, carbon powder Carbon materials such as scars, natural minerals such as (g) talc, mica, smectite, montmorillonite, sericite, (chi) bengara, lead white, yellow lead, bitumen, titanium white, titanium yellow and other inorganic pigments, And metal ion-containing organic solids such as phthalocyanine blue and dye lake.
[0013]
For organic substances, (nu) hydrocarbon resins, acrylic resins, vinyl resins, phenol resins, nylon resins, epoxy resins, polyester resins, polyamide resins, polystyrene resins, urethane resins, silicone resins, and other synthetic resins (these are crosslinked and non-crosslinked) And (le) natural waxes such as carnauba wax and candelilla wax, and waxes such as polyethylene wax, ester wax, microcrystalline wax and paraffin wax.
[0014]
You may use these in mixture of 2 or more types. Among these, as needle-like or fibrous particles, glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, β-wollastonite, zonolite, potassium titanate fiber, aluminum borate fiber, tetrapotted zinc oxide Inorganic fiber materials such as basic magnesium sulfate fiber and silicon nitride fiber are preferable.
[0015]
The cosmetic particles of the present invention are preferably water- and oil-repellent when used in cosmetics because they do not easily cause makeup collapse due to sweat or sebum. The water repellency is preferably 120 ° or more, more preferably 125 ° or more with respect to distilled water in the measurement of the contact angle described later. The oil repellency is preferably 95 ° or more and more preferably 98 ° or more with respect to liquid paraffin in the measurement of the contact angle described later.
[0016]
The cosmetic particles of the present invention are particles having at least a part of the surface coated with a polyether having a polymerization unit (I) (hereinafter simply referred to as polyether), and are water repellent that can be used as cosmetic particles. From the viewpoint of developing oil repellency, it is preferable that the polyether is present on the surface of 0.01 to 50 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the coated particles. More preferred is 0.5-5 parts by mass.
[0017]
In the polymerization unit (I), when X and / or Y is a hydrocarbon group, preferred examples include an alkyl group or alkenyl group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 to 7 carbon atoms. 18 arylalkyl groups or alkylaryl groups. Further preferred examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, octyl group, decyl group, dodecyl group, cetyl group, stearyl group, phenyl group, phenethyl group, A butylphenyl group, a nonylphenyl group, etc. are mentioned. X and Y may be combined to form a ring. In this case, X and Y are preferably a linking group represented by — (CH ₂ ) _s —, and s is preferably 3 An integer of ˜6, more preferably 4.
[0018]
The hydrocarbon group may have a substituent, and as the substituent, a hydroxy group, an alkoxy group having 1 to 22 carbon atoms, an amino group, a dimethylamino group, a diethylamino group, or a carbon atom having 1 to 18 carbon atoms. Amide group, C1-C18 alkyl ammonium group, ammonium group, methyl ester group, ethyl ester group, phenyl ester group, C1-C18 acyl group, silyl group, halogen atoms such as F and Cl (hereinafter, "Substituents of the present invention") and the like.
[0019]
When X and / or Y is a carboxy group, a part or all of the carboxy groups in the general formula (I) form a salt with one or more of cation species such as lithium, sodium, potassium, and ammonium. You may do it. Of these, sodium or ammonium salts are preferred.
[0020]
When X and / or Y is an ester group, a group represented by —COOR ² (R ² represents a hydrocarbon group having 1 to 22 carbon atoms) is preferable, and methyl ester, ethyl ester, Examples include propyl ester, butyl ester, octyl ester, phenyl ester, allyl ester and the like.
[0021]
In the polymer unit (I), when Y is a group represented by the formula-(AO) _m -R ¹ , examples of A include a methylene group, an ethylene group or a propylene group, and m is preferably 1 to 30, More preferably, it is 1-20, Most preferably, it is 1 or the number of 5-10. The m A's may be the same or different, and any combination of random and block may be used. As a combination of A and m, a combination in which A is a methylene group and m is 1 is particularly preferable.
[0022]
X and Y may be a plurality of different mixtures, but a preferred combination is that X is a hydrogen atom and Y is represented by the general formula —CH ₂ O— (AO) _m−1 —R ^1. Wherein A is an ethylene or propylene group and m is a number from 1 to 30.
[0023]
When R ¹ is a hydrocarbon group, preferred examples include an alkyl group or alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group or alkylaryl group having 7 to 18 carbon atoms. Can be mentioned. Further preferred examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, octyl group, decyl group, dodecyl group, cetyl group, stearyl group, phenyl group, nonylphenyl group. Etc. When R ¹ is a fluoroalkyl group, preferred examples include 1H, 1H, 2H, 2H-nonafluorohexyl group, 1H, 1H, 2H, 2H-tridecafluorooctyl group, 1H, 1H, 2H, 2H-hepta. Examples include a decafluorodecyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 7H-dodecafluoroheptyl group, 1H, 1H, 9H-hexadecafluorononyl group and the like. When R ¹ is a fluoroaryl group, a preferred example is a perfluorophenyl group. When R ¹ is a siloxysilylpropyl group, a linear or branched siloxysilylpropyl group having 1 to 30 silicon atoms, more preferably 1 to 20 is preferable. These alkyl substituents bonded to the silicon atom of the siloxysilylpropyl group may be the same or different, and examples thereof include a methyl group, a butyl group, a vinyl group, and a phenyl group. R ¹ may have a substituent, and examples of the substituent include the “substituent of the present invention”.
[0024]
The polyether used in the present invention can be produced according to the following reaction formula by polymerizing an epoxy compound represented by the general formula (II), for example, by the production method disclosed in WO99 / 42513.
[0025]
[Chemical 3]

[0026]
(In the formula, X and Y have the same meaning as described above.)
Examples of the polymerization catalyst used here include rare earth metal catalysts obtained by combining a rare earth metal such as samarium alkoxide and samarium tris (tetramethylheptanedionate) with an alkylaluminum compound.
[0027]
The polyether used in the present invention may be a single polymer of the polymerized unit (I), but is copolymerized with another monomer copolymerizable with the epoxy compound represented by the general formula (II). A copolymer may be used. In that case, the arrangement pattern in the polyether main chain may be block, alternating, or random.
[0028]
Specific examples of other monomers that can be copolymerized include epoxy compounds such as ethylene oxide, (meth) acrylate compounds such as methyl (meth) acrylate and butyl (meth) acrylate, styrene, vinyl acetate, and butyl vinyl. Examples include vinyl compounds such as ketones, lactams, carbonates, others, isoprene, butadiene, and fluoroalkyl glycidyl ethers.
[0029]
When the polyether is a copolymer, the molar fraction of the polymer units (I) in the copolymer is preferably from 0.1 to less than 1.0, and more preferably from 0.3 to less than 1.0.
[0030]
The number average molecular weight of the polyether used in the present invention is preferably from 2,000 to 10,000,000, particularly preferably from 5,000 to 5,000,000. The number average molecular weight can be determined by the measurement method described later.
[0031]
The cosmetic particles of the present invention have high water and oil repellency due to the polyether and are obtained by bringing the polyether and particles into contact with each other in the presence of supercritical carbon dioxide, so that there is almost no aggregation between the particles. The absence of aggregation can be confirmed from the particle size distribution measurement. Moreover, since there is almost no aggregation, the particles whose surface is coated with polyether exhibit a smooth and smooth feel.
[0032]
[Method for producing cosmetic particles]
In the present invention, supercritical carbon dioxide refers to carbon dioxide having a pressure not lower than the critical temperature (304.2 K) and not lower than the critical pressure (7.37 MPa). It has the property of changing suddenly. Therefore, when the pressure of supercritical carbon dioxide slightly exceeding the critical pressure and critical temperature is increased, the density of the gas phase increases rapidly, so that the solubility of the solute rapidly increases in the region exceeding the critical pressure.
[0033]
The cosmetic particles of the present invention can be obtained by bringing a polyether and particles into contact in a container in the presence of supercritical carbon dioxide.
[0034]
Supercritical carbon dioxide can be used in any combination as long as the temperature and pressure at which carbon dioxide develops a supercritical state. Among them, the temperature is preferably 308 K (35 ° C.) to 373 K (100 ° C.), 308 K (35 ° C.) to 333 K (60 ° C.) is more preferable. The pressure is preferably 7.4 to 50 MPa, more preferably 8 to 30 MPa, and particularly preferably 9 to 20 MPa. In this range, the solubility of the polyether in supercritical carbon dioxide is high.
[0035]
The time for contacting the polyether with the particles is not particularly limited, but is preferably 1 to 60 minutes in order to coat the surface of the particles with the polyether. The ratio of the polyether to the particles is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 10 parts by mass of the polyether with respect to 100 parts by mass of the particles. The contact between the polyether and the particles is preferably carried out by stirring both.
[0036]
After contacting the particles with the polyether in the presence of supercritical carbon dioxide in the container, the exhaust valve provided in the container was opened, and the surface was coated with the polyether by reducing the pressure of the container. Cosmetic particles can be obtained. To depressurize the container is to reduce the pressure of carbon dioxide in a supercritical state.
[0037]
However, when the pressure of carbon dioxide in the supercritical state is lowered from above the critical pressure, liquefied carbon dioxide is produced when the temperature in the container is lowered below the critical temperature of carbon dioxide due to adiabatic expansion of carbon dioxide. Aggregation of powder is likely to occur. Therefore, when depressurizing the container, the carbon dioxide in the container is depressurized while maintaining the temperature in the container at or above the critical temperature of carbon dioxide, and the supercritical carbon dioxide is converted to gaseous carbon dioxide. It is preferable. Therefore, it is preferable that the carbon dioxide in the container is gradually reduced in pressure from above the critical pressure to atmospheric pressure so as to reduce the pressure by isothermal expansion. Specifically, in order to depressurize the pressure above the critical pressure (preferably 7.4 to 50 MPa, more preferably 8 to 30 MPa, particularly preferably 9 to 20 MPa) to atmospheric pressure (about 0.1 MPa), 3 to The pressure should be gradually reduced over about 120 minutes, more preferably about 5 to 60 minutes. The average pressure reduction speed is preferably 0.06 to 16.63 MPa / min, and more preferably 0.12 to 9.98 MPa / min.
[0038]
Alternatively, a method of rapidly reducing the pressure in order to suppress the generation of liquefied carbon dioxide as much as possible is also preferable. At that time, the carbon dioxide in the supercritical state in the container hardly forms liquefied carbon dioxide and becomes gaseous carbon dioxide, and therefore hardly causes aggregation of the powder. As a specific method, it is possible to discharge supercritical carbon dioxide in the container and instantaneously reduce the pressure to atmospheric pressure. The carbon dioxide in the container is increased from the critical pressure to atmospheric pressure. In particular, the pressure is preferably equal to or higher than the critical pressure (preferably 7.4 to 50 MPa, more preferably 8 to 30 MPa, particularly preferably 9 to 20 MPa) to atmospheric pressure (about 0.1 MPa), preferably 3 seconds or less. The pressure is preferably reduced in 2 seconds or less. During the sudden discharge of carbon dioxide, cosmetic particles are also discharged. At this time, the carbon dioxide discharge port has a collecting device (with an opening large enough to prevent particles from passing through). If a cloth bag, a paper bag, or a box having a sufficiently large capacity is used, it is convenient because the powder for cosmetics can be taken out at the same time.
[0039]
[Cosmetics]
The cosmetics of the present invention containing the particles of the present invention are preferably used as makeup cosmetics such as foundations, concealers, cheeks, eye shadows, and lipsticks. 0.01-10 mass% is preferable and, as for content of the particle | grains of this invention in the cosmetics of this invention, 0.1-5 mass% is still more preferable.
[0040]
The cosmetic of the present invention can contain, in addition to the particles of the present invention, colorants such as dyes and pigments, plasticizers, humectants, cooling sensates, warming sensates, emollient components, viscosity modifiers, and the like.
[0041]
Examples of the dye / pigment include tar-based pigments / dyes described in "Ministerial Ordinance for Determining Tar Colors that can be Used in Pharmaceuticals" (August 31, 1968, Ministry of Health and Welfare Ordinance No. 30). Others, zinc oxide, titanium dioxide, bengara, iron titanate, γ-iron oxide, yellow iron oxide, ocher, black iron oxide, carbon black, low-order titanium oxide, mango violet, cobalt violet, chromium oxide, chromium hydroxide, Inorganic pigments such as cobalt titanate, ultramarine, bitumen, fish scale foil, titanium oxide-coated mica, and titanium oxide-coated talc can also be blended.
[0042]
As the plasticizer, cellosolves, carbitols, phthalates and the like can be used, and as the humectant, known ones such as glycerin, ethylene glycol and aloe extract can be used. As a cooling sensation agent, well-known things, such as l-menthol, and as a warming sensation agent, well-known things, such as a pepper extract and vanillyl butyl ether, are used.
[0043]
Other emollient components include hydrocarbon oils such as squalane and liquid paraffin; isostearyl myristate, isotridecyl nonanoate, neopentyl glycol dicaprate, dipentaerythritol hexaoxystearate, trimethylolpropane triisostearate, isoisostearate isoisostearate Ester oils such as stearyl, diisostearyl malate, stearyl methacrylate, N-lauroyl-L-glutamate di (cholesteryl, octyldodecyl), octyl paramethoxycinnamate; castor oil, jojoba oil, macadamia nut oil, evening primrose oil, olive oil Animal and vegetable oils such as peppermint oil and liquid lanolin; silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane; fluorine such as perfluoropolyether and fluorine-modified silicone Oil, alcohols, polyols, diglycerides, triglycerides, and the like. Emollient components can be used alone or in combination of two or more.
[0044]
Examples of the thickener for viscosity adjustment include inorganic thickeners such as smectite and laponite, polymer thickeners such as sodium acrylate copolymer gel, acrylic emulsion, and polysaccharide thickener. A viscosity modifier can be used individually or in combination of 2 or more types.
[0045]
Others, oil agent, solid / semi-solid oil, water-soluble and oil-soluble polymer, surfactant, ethanol, antiperspirant, UV absorber, UV scattering agent, antioxidant, antiseptic disinfectant, pH adjuster, vitamins, A blood circulation promoter, a whitening agent, a skin activator, a medicinal agent, an extract from animals and plants, an antiseptic, an antiperspirant, a disinfectant, a fragrance, water, and the like can be appropriately blended.
The cosmetic of the present invention can be produced by a conventional method.
[0046]
【Example】
The number average molecular weight of the polyether was measured by Showa Denko KK Gel Permeation Chromatography System SYSTEM 11 (eluent: hexafluoroisopropanol, 1.0 ml / min, column: Showa Denko HFIP-80M × 2, column It is the value of polystyrene conversion measured using temperature: 40 ° C., detector: RI).
[0047]
Synthesis example 1
4 g of perfluorooctylethyl glycidyl ether {in general formula (II), X: hydrogen atom, Y: —CH ₂ —OR ² , where R ² = perfluorooctylethyl group} is converted to samarium alkoxide-methylalumoxane catalyst 1 Polymerization was carried out using mol% (mol% based on the total amount of monomers, hereinafter the same) (130 ° C., 12 hours). A white solid polyether (1) having a polymer unit represented by the following formula was obtained by reprecipitation purification from the reaction solution. The number average molecular weight was 120,000.
[0048]
[Formula 4]

[0049]
Example 1
50 g of titanium oxide (titanium oxide KRONOS KA15 manufactured by Titanium Industry Co., Ltd.) and 2.5 g of polyether (1) are put into a pressure vessel equipped with a stirrer, carbon dioxide is introduced into the vessel, and the mixture is stirred at 40 ° C. and 10 MPa for 10 minutes. Hold while continuing. Thereafter, the pressure was gradually reduced to atmospheric pressure over 30 minutes, and then the contents were taken out to obtain surface-treated titanium oxide (1).
[0050]
Example 2
50 g of titanium oxide (same product as in Example 1) and 2.5 g of polyether (1) are put into a pressure vessel equipped with a stirrer, carbon dioxide is introduced into the vessel, and stirring is continued at 40 ° C. and 10 MPa for 10 minutes. Hold while. Thereafter, the discharge valve was fully opened, and the pressure was reduced to atmospheric pressure in one second. At this time, the contents collected by the cloth bag attached to the outlet of the discharge valve were collected to obtain surface-treated titanium oxide (2).
[0051]
Example 3
Surface-treated iron oxide (1) was obtained in the same manner as in Example 1 except that 50 g of iron oxide (synthetic iron oxide TAROX BL100 manufactured by Titanium Industry Co., Ltd.) was used instead of titanium oxide.
[0052]
Example 4
Surface-treated iron oxide (2) was obtained in the same manner as in Example 2, except that 50 g of iron oxide (same as in Example 3) was used instead of titanium oxide.
[0053]
Example 5
Surface-treated iron oxide (3) was obtained in the same manner as in Example 1 except that 50 g of iron oxide (synthetic iron oxide TAROX LL-XLO manufactured by Titanium Industry Co., Ltd.) was used instead of titanium oxide.
[0054]
Example 6
Surface-treated iron oxide (4) was obtained in the same manner as in Example 2, except that 50 g of iron oxide (same as in Example 5) was used instead of titanium oxide.
[0055]
Example 7
Surface-treated iron oxide (5) was obtained in the same manner as in Example 1 except that 50 g of iron oxide (synthetic iron oxide TAROX R110 manufactured by Titanium Industry Co., Ltd.) was used instead of titanium oxide.
[0056]
Example 8
Surface-treated iron oxide (6) was obtained in the same manner as in Example 2, except that 50 g of iron oxide (same product as Example 7) was used instead of titanium oxide.
[0057]
Example 9
Surface-treated mica (1) was obtained in the same manner as in Example 1 except that 50 g of mica (Mica powder Y2300 manufactured by Yamaguchi Mica Industry Co., Ltd.) was used instead of titanium oxide.
[0058]
Example 10
Comparative Example 1 in which surface-treated mica (2) was obtained in the same manner as in Example 2 except that 50 g of mica (same product as Example 9) was used instead of titanium oxide.
50 g of titanium oxide (same product as in Example 1) and 8 g of Asahi Guard (fluorinated water and oil repellent, 30% aqueous solution manufactured by Asahi Glass Co., Ltd.) were sufficiently mixed with a small mixer and then dried. Thereafter, the mixture was crushed by a crusher, classified by sieving, and coarse particles of 100 microns or more were removed to obtain titanium oxide (3) surface-treated with a fluorine-based water and oil repellent.
[0059]
Comparative Example 2
Iron oxide (7) surface-treated with a fluorinated water and oil repellent was obtained in the same manner as in Comparative Example 1 except that iron oxide (same product as Example 3) was used instead of titanium oxide.
[0060]
Comparative Example 3
Iron oxide (8) surface-treated with a fluorine-based water and oil repellent was obtained in the same manner as in Comparative Example 1 except that iron oxide (same product as Example 5) was used instead of titanium oxide.
[0061]
Comparative Example 4
Iron oxide (9) surface-treated with a fluorine-based water and oil repellent was obtained in the same manner as in Comparative Example 1 except that iron oxide (same product as Example 7) was used instead of titanium oxide.
[0062]
Comparative Example 5
Mica (3) surface-treated with a fluorine-based water / oil repellent was obtained in the same manner as in Comparative Example 1 except that mica (same product as Example 9) was used instead of titanium oxide.
[0063]
Test example 1
The surface-treated titanium oxide, iron oxide, and mica obtained in Examples 1 to 10 and Comparative Examples 1 to 5 were compression molded, and the contact angle of the obtained plate-like body surface was determined as Kyowa Interface Science Co., Ltd. It measured at room temperature (20 degreeC) using manufactured CA-A type | mold, and evaluated water and oil repellency. The results are shown in Table 1.
[0064]
[Table 1]

[0065]
Test example 2
The particle size distribution of the surface-treated titanium oxides {circle around (1)} and {circle around (3)} obtained in Example 1 and Comparative Example 1 was measured at 20 ° C. in ethanol using HORIBA LA-920 (relative refractive index is 2.0). The result of the surface-treated titanium oxide (1) in Example 1 is shown in FIG. 1, and the result of the surface-treated titanium oxide (3) in Comparative Example 1 is shown in FIG. Table 2 shows the arithmetic average particle diameter and arithmetic standard deviation of the surface-treated titanium oxide of Example 1 and Comparative Example 1 obtained from these results.
[0066]
[Table 2]

[0067]
Test example 3
A liquid foundation and a powder foundation were prepared according to the formulation shown in Table 3, and the feeling of use was evaluated by 10 professional panelists. The results are shown in Table 3.
[0068]
<Evaluation criteria>
5: 9-10 people judged good.
4: 7-8 people judged good.
3: 5-6 people judged good.
2: 3-4 people judged good.
1: 1 to 2 people judged good.
[0069]
[Table 3]

[0070]
【The invention's effect】
The cosmetic particles of the present invention are excellent in water repellency, oil repellency and dispersibility, and show a good feeling when used in cosmetics.
[Brief description of the drawings]
1 is a graph showing the particle size distribution measurement result of surface-treated titanium oxide {circle around (1)} obtained in Example 1. FIG.
2 is a graph showing the particle size distribution measurement result of the surface-treated titanium oxide (3) obtained in Comparative Example 1. FIG.

Claims (4)

In a container, in the presence of supercritical carbon dioxide , a homopolymer of an epoxy compound represented by general formula ( II ) (hereinafter referred to as epoxy compound ( II )), or an epoxy compound ( II ) and other than epoxy compound ( II ) A copolymer of at least one copolymerizable monomer selected from epoxy compounds of (meth) acrylic acid ester compounds, vinyl compounds, lactams, carbonates, isoprene, butadiene and fluoroalkyl glycidyl ethers, After contacting particles with a polyether having a polymerization unit represented by the general formula (I) (hereinafter referred to as polymerization unit (I)) having a number average molecular weight of 2,000 to 10,000,000 , the container While maintaining the internal temperature at or above the critical temperature of carbon dioxide, the carbon dioxide in the vessel is reduced from the critical pressure to atmospheric pressure. Alternatively, a cosmetic particle whose surface is coated with a polyether, which is obtained by reducing the pressure of carbon dioxide in the container from a critical pressure to an atmospheric pressure in 3 seconds or less .

[Wherein, X represents a hydrogen atom, a hydrocarbon group having 1 to 42 carbon atoms, a carboxy group or an ester group. Y is a hydrocarbon group having 1 to 42 carbon atoms , a carboxy group, an ester group, or a formula — (AO) _m —R ¹ (wherein R ¹ is a hydrogen atom, a hydroxy group as a substituent , and having 1 to 22 carbon atoms) Alkoxy group, amino group, dimethylamino group, diethylamino group, amide group having 1 to 18 carbon atoms, alkylammonium group having 1 to 18 carbon atoms, ammonium group, methyl ester group, ethyl ester group, phenyl ester group, carbon number 1 A hydrocarbon group having 1 to 28 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, and a fluoroaryl having 6 to 24 carbon atoms, which may have a group selected from -18 acyl groups, silyl groups and halogen atoms Group, or a siloxysilylpropyl group having 1 to 50 silicon atoms, A is an alkylene group having 1 to 3 carbon atoms, m is a number from 1 to 100, and m A's are the same or different. Or a group represented by: X and Y may form a ring together. ]   A cosmetic comprising the cosmetic particles according to claim 1. In a vessel, the supercritical carbon dioxide presence, a homopolymer of an epoxy compound according to claim 1, wherein (II), or an epoxy compound (II), an epoxy compound (II) other than the epoxy compounds, (meth) acrylic acid ester A copolymer with at least one copolymerizable monomer selected from a compound, a vinyl compound, lactams, carbonates, isoprene, butadiene and fluoroalkyl glycidyl ether, having a number average molecular weight of 2,000 to 10, After bringing the particles into contact with the polyether having the polymerized unit (I) according to claim 1, which is 000,000, the temperature in the container is maintained at a temperature equal to or higher than the critical temperature of carbon dioxide. A process for producing cosmetic particles whose surface is covered with polyether, wherein carbon dioxide is reduced from a critical pressure to atmospheric pressure. The epoxy compound according to claim 1, in the presence of supercritical carbon dioxide in a container. II ) Homopolymer or epoxy compound ( II ) And epoxy compounds ( II ) Other than epoxy compounds, (meth) acrylic acid ester compounds, vinyl compounds, lactams, carbonates, isoprene, butadiene and fluoroalkyl glycidyl ethers. Then, after contacting the particles having the number average molecular weight of 2,000 to 10,000,000 with the polyether having the polymerization unit (I) according to claim 1, the carbon dioxide in the container is brought to a critical pressure or higher. A process for producing particles for cosmetics whose surface is covered with polyether, wherein the pressure is reduced from 3 to atmospheric pressure in 3 seconds or less.

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