JP4328103B2 - Cosmetics - Google Patents

Description

【００２７】
（式中、Ｒ¹及びＲ²はそれぞれ独立して、水素原子、炭素数１〜１８のアルキル基又は炭素数６〜１０のアリール基、Ｘ^-は四級アンモニウム塩の対イオンを示し、Ｃｌ^-、Ｂｒ^-等のハロゲンイオン、ＣＨ₃ＳＯ₄ ^-、ＣＨ₃ＣＨ₂ＳＯ₄ ^-等の硫酸エステルイオンが挙げられる。）
又は式（２）：
【００２８】
【化２】

【００２９】
（式中、Ｒ¹、Ｒ²、及びＸ^-は前記と同じ意味を示す。）
で表される基を介して、式（３）：
【００３０】
【化３】

【００３１】
（式中、Ｒ³は水素原子、炭素数１〜２２のアルキル基、炭素数３〜８のシクロアルキル基、炭素数７〜１０のアラルキル基又は炭素数６〜１０のアリール基、ｎは２又は３を示す。）
で表される繰り返し単位からなるポリ（Ｎ−アシルアルキレンイミン）の分子鎖が結合してなり、該ポリ（Ｎ−アシルアルキレンイミン）の分子鎖とオルガノポリシロキサンの分子鎖との質量比が１／５０〜５０／１であり、重量平均分子量が５００〜５００，０００であるシリコーン系高分子化合物が、超臨界二酸化炭素へ分散・溶解しやすい点から、特に好ましい。
【００３２】
例えば、式（１）中のＲ¹及びＲ²がそれぞれ水素原子、Ｘ^-がＣＨ₃ＣＨ₂ＳＯ₄ ^-、式（３）中のＲ³がＣＨ₂ＣＨ₃、ｎが２であるポリ（Ｎ−プロパノイルエチレンイミン）／γ−アミノプロピルメチルシロキサン共重合体（特開平７−１３３３５２号公報記載）が挙げられる。
【００３３】
シリコーン系高分子化合物の重量平均分子量は、超臨界二酸化炭素へ分散・溶解しやすくする点から、好ましくは５００〜５００，０００、より好ましくは１，０００〜３００，０００である。
【００３４】
超臨界二酸化炭素存在下で複合化を行う方法としては、まず、容器内で超臨界二酸化炭素の存在下に、母材と被覆粒子と高分子化合物とを接触させる。高分子化合物の種類によっては、少量の助溶媒を使用することも可能である。助溶媒としては極性溶媒が好ましい。極性溶媒の中では、人体にほとんど無害と考えられているアルコール及び／又は水が好ましい。アルコールとしては、メタノール、エタノール、及び１−プロパノールが好ましく、中でもエタノールがより好ましい。
【００３５】
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できるが、接触後の超臨界二酸化炭素の除去や、減圧を効率的に行う点から、３０８〜３７３Ｋであることが好ましく、より好ましくは３１３〜３５３Ｋである。また、減圧を開始するときの超臨界二酸化炭素の初期圧力は、超臨界二酸化炭素の減圧を効率的に行う点から、好ましくは７．２〜５０ＭＰａ、より好ましくは１０〜４０ＭＰａである。
【００３６】
超臨界二酸化炭素と高分子化合物との混合物は、温度、圧力等の条件によっては、透明となる場合がある。このように透明となる混合物は、粒子の凝集が少なく、形成される高分子化合物の被膜も均一となるので好ましい。
【００３７】
容器内で、超臨界二酸化炭素存在下、高分子化合物と母材と被覆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、高分子化合物で表面を被覆された複合粉体を該容器内で得ることができる。或いは、接触後の混合物を該容器外に二酸化炭素と共に排出して複合粉体を得ることもできる。
【００３８】
容器内で複合粉体を得る方法では、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やすい。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。
【００３９】
容器内の圧力を大気圧まで減圧するのに要する時間は、得られる複合粉体の粒子径や高分子化合物の被覆の膜厚の制御、及び副生粒子の抑制の点から、好ましくは２秒間〜２４０分間、より好ましくは５秒間〜１２０分間である。
【００４０】
容器外で複合粉体を得る方法では、ノズル等を介して混合物を容器外に噴出、排出される方法等が挙げられる。排出条件は、特に限定されないが、ノズルの流入部での温度が臨界温度３０４．２Ｋ以上、圧力が臨界圧力７．３７ＭＰａ以上であることが超臨界流体である点から好ましい。
【００４１】
容器は、二酸化炭素を除去した後、該容器内で複合粉体を得る場合には、バルブ等の排気機構を有していればよく、超臨界二酸化炭素中で、母材と被覆粒子と高分子化合物を溶解又は分散を行うために、容器内に攪拌機構を有するものが好ましい。容器の代表例としては、オートクレーブ、耐圧セル等が挙げられる。
【００４２】
なお、複合粉体中の母材と被覆粒子の合計量は、複合粉体を粒子として取り出すことができると共に、高分子化合物の特性を発現させる点から、２０〜９９．５％、好ましくは７０〜９９．５％である。
【００４３】
また、被覆粒子を被覆する別の方法としては、選択される金属酸化物の前駆物質である金属塩を所定量加水分解し、あるいは同様に所定量の有機金属化合物をアルコール溶媒中で加水分解し、加水分解物を母材あるいは被覆層を形成した複合粉体上に析出させる方法等、従来の公知の方法を用いることもできる。
【００４４】
金属酸化物前駆体を用いる場合、例えば母材を水中に分散させ、これに所定量の硫酸チタニル等の金属塩を添加し、アルカリ雰囲気で加水分解した後、母材表面に金属塩加水分解物を析出させることにより、所定厚の酸化チタン等の金属酸化物被覆層を形成することができる。また、最外層としてシリカを被覆する場合には、シリカより高い屈折率の被覆層が形成された母材の分散液に、所定量のアルカリ金属珪酸塩水溶液又は有機珪素化合物等を添加し、必要に応じて酸又はアルカリを加えて被覆された母材表面にさらに珪酸の重合物（加水分解縮重合物）を付着させる等の方法により、所定厚のシリカ被覆層を形成することができる。なお、シリカの被覆層を形成するには、従来から知られている方法を採用することもできる。
【００４５】
また、被覆粒子の被覆膜厚合計は、本発明に係る化粧料に優れた透明感を出すために、５０ｎｍ以下、更に２０ｎｍ〜５０ｎｍであることが好ましい。被覆粒子の被覆膜厚は、母材の幾何学的表面積あるいは窒素吸着法等で測定される比表面積と母材以外に複合粒子に含まれる物質（例えば、被覆粒子や高分子化合物）の密度より求めることができる。
【００４６】
また、母材上に酸化チタン、酸化アルミニウムの順に被覆する場合は、酸化チタンと酸化アルミニウムの被覆量がＴｉＯ₂／Ａｌ₂Ｏ₃の重量比で０．４２以下であることが、入射光角１０°及び受光角１０°の条件下で測定した表面反射光量から、入射光角−４０°及び受光角６０°の条件下での値を引いた差が大きくならず、ギラツキ感を低減できる点から好ましい。更に、透明性を維持しつつ、使用感が良好で、毛穴等を目立たなくする効果を付与することができる点から、酸化チタンと酸化アルミニウムの合計の被覆量が複合粉体中に１〜５０％、特に５〜４０％であるのが好ましい。また、酸化チタン、酸化アルミニウム、シリカの順に被覆する場合は、酸化チタンと酸化アルミニウムの被覆量がＴｉＯ₂／Ａｌ₂Ｏ₃の重量比で０．６２以下、特に０．４２以下であり、合計の被覆量が１〜５０％、特に５〜４０％であることが好ましい。更に、使用感（きしみ感を低減する）の点から、該粉体に対するＳｉＯ_２の被覆量が０．１〜３０％、特に０．２〜２０％であることが好ましい。
【００４７】
また複合粉体（Ａ）は、撥水性及び／又は撥油性を付与するために、表面をシリコーン、フッ素化合物、レシチン、アミノ酸、ポリエチレン、金属石けん等で処理することが好ましい。さらに、特開平１１−４９６３４号公報記載の表面処理を施して処方中に配合すると、透明性が向上する上に、滑らかでのびがよくしっとり感を有し、しかも皮膚刺激性の少ない化粧料を得ることができ、好ましい。
【００４８】
粉体に対する撥水、撥油化処理剤の処理量は、０．０５〜２０％、特に１〜１０％が、充分な撥水性及び／又は撥油性、良好な使用感及び耐光性が得られ、好ましい。
【００４９】
以上のようにして得られる複合粉体（Ａ）の平均粒子径は、化粧料の粒子として取り扱う点から、０．１〜１０００μｍであることが好ましく、更に０．５〜５００μｍ、特に５〜５０μｍであることが好ましい。
【００５０】
複合粉体（Ａ）は、単独又は２種以上を組み合わせて用いても良い。複合粉体（Ａ）は、本発明の化粧料中に１〜９０％配合されることが好ましく、更に１〜５０％、特に５〜３０％配合されることが使用感（のび、付着性等）、仕上がり（透明感、毛穴隠蔽性等）の点から好ましい。
【００５１】
本発明に用いられるパール光沢を有する粉体（Ｂ）（以下、パール顔料（Ｂ）という）は、マイカを母材としたものが好ましく、表面を酸化チタンで被覆した酸化チタン被覆マイカ、マイカを酸化鉄と酸化チタンで被覆したベンガラ酸化チタン被覆マイカ等の酸化鉄酸化チタン被覆マイカ、マイカと酸化チタン被覆層との間にシリカをはさんだ粉体等が挙げられる。マイカ以外を母材とした粉体としては、シリカフレーク上に酸化チタンを被覆させた粉体、合成マイカに酸化チタンを被覆した粉体、中空状の酸化チタン等が挙げられる。特に好ましいものは、酸化チタンの被覆量が１０〜７５％のパール顔料である。
【００５２】
パール顔料の平均粒子径は、使用感の点から、１〜１００μｍが好ましく、１〜２０μｍが更に好ましい。
【００５３】
パール顔料の市販品としては、フラメンコスーパーパール、フラメンコオレンジ、フラメンコスパークル、フラメンコウルトラスパークル４５００、クロイゾネオレンジ、クロイゾネブルー、クロイゾネヌアンティークブルー、クロイゾネセリーズフランベ、クロイゾネスパークル（ゴールド、カッパー、ブルー、ルージュ）、ティミカゴールデンブロンズ、ティミカヌアンティークカッパー、ティミカゴールドスパークル、ティミカエクストララージスパークル、フラメンコサテンレッド、フラメンコサテンバイオレット、フラメンコサテンブルー、フラメンコスパークル（レッド、ゴールド、グリーン、ブルー、バイオレット）、デュークロムＢＶ等（以上、Engelhard社）、ティミロンスーパー、ティミロンスーパーシルクＭＰ−１００５、ティミロンスーパーシーンＭＰ−１００１、ティミロンスターラスターＭＰ−１１５、コロロナシエナ、コロロナレッドゴールド、コロロナレッドブラウン、コロロナブライトゴールド、コロロナボルドー、コロロナインペリアルレッド、コロロナシエナスパークル、ティミロンゴールドプラスＭＰ−２５、ティミロンスプレンディッド等（以上、メルク社）、プレステージシリーズ（ECKART社）、メタシャイン１０８０ＲＣ−（Ｂ１，Ｇ１，Ｒ１，Ｓ１，Ｙ１）（日本板硝子(株)）、プロミネンスシリーズ等（トピー工業(株)）等が挙げられる。
【００５４】
パール顔料（Ｂ）も、複合粉体（Ａ）と同様に撥水及び／又は撥油化処理して使用することが好ましい。
【００５５】
本発明においてパール顔料（Ｂ）は、単独又は２種以上を組み合わせて用いても良い。化粧料中におけるパール顔料（Ｂ）の含有量は、色相感覚を変化させる効果の点から、全粉体の０．１％以上、０．５〜８０％であるのが好ましい。更に、化粧料の剤型が化粧水の場合は全組成中に０．１〜１０％、特に０．５〜５％配合するのが好ましく、乳液及びクリームの場合は、０．１〜１０％、特に０．５〜７％、粉白粉、固形白粉及びフェイスパウダーの場合は０．１〜８０％、特に１〜５０％、パウダーファンデーション及び油性ファンデーションの場合は０．１〜８０％、特に１〜２５％、クリーム状ファンデーション、リキッドファンデーション及びコンシーラーの場合は０．１〜１０％、特に０．５〜７％、口紅及びリップクリームの場合は０．１〜２０％、特に０．５〜１０％、頬紅及びアイシャドーの場合は０．１〜４０％、特に０．５〜２５％、アイライナー及びアイブロウの場合は０．１〜３０％、特に０．５〜２０％配合するのが好ましい。
【００５６】
本発明においては（Ａ）成分と（Ｂ）成分の重量配合比（Ａ：Ｂ）は、色相感覚を変化させる効果の点から、９５：５〜５：９５の範囲が好ましく、９０：１０〜１０：９０の範囲がより好ましく、８０：２０〜２０：８０の範囲が特に好ましい。
【００５７】
本発明の化粧料には、上記の必須成分である（Ａ）及び（Ｂ）成分以外に、通常の化粧料に用いられる成分を本発明の効果を損なわない範囲で配合しても良い。例えばケイ酸、無水ケイ酸、ケイ酸マグネシウム、タルク、セリサイト、マイカ、カオリン等の無機粉体、ポリアミド、ポリエステル、ポリプロピレン、ポリスチレン、ポリウレタン等の有機粉体や有機タール系色素の有機着色料等が挙げられる。これらの粉体は、１種又は２種以上を組み合わせて用いることができる。
【００５８】
また、本発明では、上記粉体成分と共に、通常の化粧料に用いられるポリエチレンワックス、マイクロクリスタリンワックス、セレシンワックス、ワセリン等の炭化水素類；リンゴ酸ジイソステアリル、カプリン酸ネオペンチルグリコール等の合成エステル油；キャンデリラワックス、ホホバ油、オリーブ油等の植物油；シクロメチコン、ジメチコン等のシリコーン油、セタノール、オレイルアルコール等の高級アルコール類；ステアリン酸、オレイン酸等の脂肪酸；グリセリン、１，３−ブタンジオール等の多価アルコール類；非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤等の界面活性剤；エタノール等の低級アルコール類；カーボポール等の増粘剤、防腐剤、メトキシケイヒ酸オクチル等の紫外線吸収剤、抗酸化剤、保湿剤、美白剤、血行促進剤、制汗剤、殺菌剤、皮膚賦活剤等の薬効成分、香料なども併用することができる。
【００５９】
本発明の化粧料は、上記の必須成分である粉体を配合する以外は常法に従って製造することができ、例えば化粧水、乳液、クリーム等の基礎化粧料；パウダーファンデーション、粉おしろい、固形おしろい、フェイスパウダー、油性ファンデーション、クリーム状ファンデーション、リキッドファンデーション、コンシーラー、口紅、リップクリーム、アイシャドー、頬紅、アイライナー、アイブロウ等の形態とすることができる。
【００６０】
【実施例】
（製造例１）
＜溶解工程＞
図１に示す装置を用い、オートクレーブ１０（内容量１００ｍＬ：耐圧硝子工業（株））内に、ポリ（Ｎ−プロパノイルエチレンイミン）／γ−アミノプロピルメチルシロキサン（共重合比４／９６（質量比））共重合体（重量平均分子量１５万、塊状）０．３６ｇ、酸化チタン（平均粒子径０．０５μｍ、表面シリコン処理、テイカ（株））１．８０ｇとタルク（平均粒子径１０μｍ、（株）山口雲母工業所）６．００ｇを充填した。
【００６１】
充填後、ボンベ１よりフィルター２を通して二酸化炭素ガス内のゴミを除去した後、クーラー５から−５℃に制御された冷媒が通液されているコンデンサー３で二酸化炭素を凝縮し、その後ポンプヘッドが冷却された昇圧ポンプ４で昇圧した。昇圧時の圧力は、圧力計６ａにより測定した。なお、安全性を確保するために、圧力計６ａの下流部には、安全弁７ａを配設した。圧力の調整は保圧弁Ｖ−１で行った。
【００６２】
バルブＶ−２を開放して二酸化炭素は予熱器８を通して、所定の温度まで予熱されて送られ、バルブＶ−３を介して安全弁７ｂが付属するオートクレーブ１０に導入した。カートリッジヒーター１２を使用し、温度調節器１３によりオートクレーブ１０内の温度調節を行い、温度計１１及び圧力計６ｂにより、セル内の温度及び圧力をそれぞれ温度３３３Ｋ及び圧力３０ＭＰａに調節し、超臨界二酸化炭素状態とした。この条件下で撹拌機９を回転し、０．５時間溶解・分散を行い、混合物を得た。
【００６３】
＜複合化工程＞
排気バルブＶ−５を徐々に開放し、排気ライン１８（内径２．５ｍｍ）より排気し、１０分間で減圧を行い、複合粉体を得た。この時断熱膨張作用により容器内温度が低下するが、容器内温度は３１３Ｋ以下にならないように減圧を行った。また、排気ラインの凍結を防ぐために、ヒーター２１により加熱した。また、排気ライン１８から若干漏出してくる複合粉体に関しては、バグフィルター１９で捕捉した。得られた複合粉体の表面反射光の差は６、平均粒子径は１５μｍであった。
【００６４】
（製造例２）
製造例１の溶解工程を実施した後、製造例１の複合化工程の代わりに、次の複合化工程を実施した。
【００６５】
＜複合化工程＞
撹拌機９を回転し、０．５時間溶解分散を行った後、バルブＶ−４を開放し、予めヒーター１４で加熱されたラインを通ってノズル１５から粒子回収容器１６内に得られた混合物を噴出させた後、噴出物（粒子）として、凝集のない複合粉体を得た。そのときのノズル入口直前での温度は、温度計２０により確認し、３１３Ｋ以上であった。得られた複合粉体の表面反射光の差は６、平均粒子径は１０μｍであった。
【００６６】
（製造例３）
製造例１で用いたポリ（Ｎ−プロパノイルエチレンイミン）／γ−アミノプロピルメチルシロキサン共重合体の代わりに、ステアリルメタクリレート／２−（パーフルオロオクチル）エチルメタクリレート（共重合比１／９（質量比））共重合体０．３６ｇ（重量平均分子量１８万、粒子径が１〜５ｍｍ程度の粒状物質）を用い、酸化チタン（平均粒子径０．０５μｍ、表面シリコン処理、テイカ（株））の代わりに、酸化チタン（平均粒子径０．２μｍ、表面シリコン処理、石原産業（株））１．８ｇを用いた以外は、製造例１と同様にして、複合粉体を作製した。得られた複合粉体の表面反射光の差は６、平均粒子径は１０μｍであった。
【００６７】
（参考製造例１（旧製造例４））
タルク３４０ｇを純水３１６０ｇに添加して十分に分散し、これに二酸化チタンとして濃度２０％の硫酸チタニル水溶液２００ｇを加え、攪拌しながら加熱し５時間沸騰させた。これを室温まで冷却し、濾過水洗後、１１０℃で乾燥させて、二酸化チタンの水和物が被覆されたタルクを得た。このうち３２０ｇを２６８０ｇの純水中でよく分散させ、これに酸化アルミニウムとして濃度１０％の塩化アルミニウム水溶液８００ｇ及び尿素５００ｇを水１８００ｇに溶かした溶液を加えてよく混合し、９０℃で１０時間加熱した後室温まで冷却した。これを濾過水洗し、１１０℃で乾燥後、６００℃で５時間焼成し、酸化チタン、酸化アルミニウムで順次被覆されたタルクを得た。更にこれを１００ｇ計量しエタノールと水の混合溶剤（７：３の体積比）１Ｌに加えて、よく分散させた。これにシリカとして濃度４％のケイ酸エチルエタノール溶液２７８ｇを加え、撹拌しながら５０℃に加熱し約１０時間保持した。次にこれを冷却後濾過し、エタノール及び純水で十分洗浄した後１１０℃で乾燥し、酸化チタン、酸化アルミニウム、シリカで順次被覆されたタルクを得た。得られた複合粉体の表面反射光の差は１０、平均粒子径は２０μｍであった。
【００６８】
（参考製造例２（旧製造例５））
タルク３６８ｇを純水３１３２ｇに添加して十分に分散し、これに二酸化チタンとして濃度２０％の硫酸チタニル水溶液１５８ｇを加え、攪拌しながら加熱し５時間沸騰させた。これを室温まで冷却し、濾過水洗後、１１０℃で乾燥させて、二酸化チタンの水和物で被覆されたタルクを得た。このうち３１４ｇを２６８６ｇの純水中でよく分散させ、これに酸化アルミニウムとして濃度１０％の塩化アルミニウム水溶液８６０ｇ及び尿素６４０ｇを水２０００ｇに溶かした溶液を加えてよく混合し、９０℃で１０時間加熱した後室温まで冷却した。これを濾過水洗し、１１０℃で乾燥後、６００℃で５時間焼成し、酸化チタン、酸化アルミニウムで順次被覆されたタルクを得た。得られた複合粉体の表面反射光の差は１０、平均粒子径は３０μｍであった。
【００６９】
（参考製造例３（旧製造例６））
セリサイト３０９ｇを純水３６９１ｇに添加して十分に分散し、これに酸化アルミニウムとして濃度１０％の塩化アルミニウム水溶液９１２ｇ及び尿素５８８ｇを水２０００ｇに溶かした溶液を加えてよく混合し、９０℃で１０時間加熱した後室温まで冷却した。これを濾過水洗し、１１０℃で乾燥後、６００℃で５時間焼成し、酸化アルミニウムで被覆されたセリサイトを得た。得られた複合粉体の表面反射光の差は１０、平均粒子径は２０μｍであった。
【００７０】
（比較製造例１）
タルク３６８ｇを純水３１３２ｇに添加して十分に分散し、これに二酸化チタンとして濃度２０％の硫酸チタニル水溶液１５８ｇを加え、攪拌しながら加熱し５時間沸騰させた。これを室温まで冷却し、濾過水洗後、１１０℃で乾燥させて、二酸化チタンの水和物が被覆されたタルクを得た。このうち３７４ｇを３１２６ｇの純水中でよく分散させ、これに酸化アルミニウムとして濃度１０％の塩化アルミニウム水溶液２６４ｇ及び尿素２３６ｇを水８００ｇに溶かした溶液を加えてよく混合し、９０℃で１０時間加熱した後室温まで冷却した。これを濾過水洗し、１１０℃で乾燥後、６００℃で５時間焼成し、酸化チタン、酸化アルミニウムで順次被覆されたタルクを得た。得られた複合粉体の表面反射光の差は１８、平均粒子径は２０μｍであった。
【００７１】
（複合粉体の表面反射光量の測定方法）
１０ｃｍ×５ｃｍのポリウレタン製人工皮革（黒色人工皮革；オカモト（株）ＯＫ−７）を用い、該人工皮革に複合粉体５ｍｇを均一に塗布し、２次元変角分光測色計（村上色彩技術研究所；ＧＣＭＳ−３）で表面反射光量を測定した。Ｃ光による２°視野の受光条件において、入射光角１０°、受光角１０°の条件下及び入射光角−４０°、受光角６０°の条件下で測定した。ここで表面反射光量は、２°視野ＸＹＺ表色系における三刺激値のＹ値を用いた。
【００７２】
（評価方法）
専門パネラー１０名により、顔に試料を塗布したときの使用感（肌への付着性（つき）、肌への延展性（のび）、塗布した感触）と、仕上がり（カバー力、透明感のある仕上がり、ツヤ感のある仕上がり、立体感のある仕上がり、ギラツキのない自然な仕上がり、肌色の補正効果）について官能評価し、以下の基準で判定した。
［判定基準］
◎：８名以上が良好と回答
○：５〜７名が良好と回答
△：２〜４名が良好と回答
×：１名以下が良好と回答
（実施例１〜８、比較例１、２：パウダーファンデーション）
表１に示す組成のパウダーファンデーションを、下記製法に従って製造した。また、これらのファンデーションの使用評価を上記方法に従って実施したのでその結果も表１に示す。
【００７３】
（製法）
成分（１）〜（１７）を混合し粉砕機にて粉砕した。これを高速ブレンダーに移し、成分（１８）〜（２０）を８０℃に混合溶解したものを加えて均一混合した。この混合物に成分（２１）を加えて混合した後再び粉砕してふるいを通した。これを金皿に圧縮成型した。
【００７４】
【表１】

【００７５】
表１に示された結果から、本発明品である実施例１〜８はいずれも、使用感、及び仕上がり（カバー力、透明感のある仕上がり、ツヤ感のある仕上がり、立体感のある仕上がり、ギラツキのない自然な仕上がり、肌色の補正効果）効果に優れるものであった。一方、（Ａ）成分を含まない比較例１〜３は、特に仕上がり（カバー力、透明感のある仕上がり、ツヤ感のある仕上がり、立体感のある仕上がり、ギラツキのない自然な仕上がり、肌色の補正効果）が実施例に比べて劣るものであった。
【００７６】
（実施例９：クリーム状ファンデーション）
表２に示す組成のクリーム状ファンデーションを、下記製法に従って製造した。得られたクリーム状ファンデーションは、使用感、及び仕上がり（カバー力、透明感のある仕上がり、ツヤ感のある仕上がり、立体感のある仕上がり、ギラツキのない自然な仕上がり、肌色の補正効果）効果に優れるものであった。
【００７７】
(製法)
成分（１）〜（６）を混合粉砕した。別に水相成分（７）〜（１０）を混合した液を調製し、粉砕した顔料を加えて分散した後、７５℃に加熱した。油相成分（１１）〜（１６）を８０℃に加熱溶解したものを、先に調製した水相に撹拌しながら加え、乳化した。これを撹拌しながら冷却し、５０℃で成分（１７）を加え撹拌しながら冷却し、製品を得た。
【００７８】
【表２】

【００７９】
（実施例１０：油性ファンデーション)
表３に示す組成の油性ファンデーションを、下記製法に従って製造した。得られた油性ファンデーションは、使用感、及び仕上がり（カバー力、透明感のある仕上がり、ツヤ感のある仕上がり、立体感のある仕上がり、ギラツキのない自然な仕上がり、肌色の補正効果）効果に優れるものであった。
【００８０】
(製法)
成分（１）〜（７）を混合粉砕した。成分（８）〜（１２）を十分撹拌混合した後加熱融解し、これに粉砕した顔料を加えて分散させ、成分（１３）を添加し、再度撹拌混合した。これを金皿に充填し、冷却し製品を得た。
【００８１】
【表３】

【００８２】
（参考例１（旧実施例１１）：固形白粉）
表４に示す組成の固形白粉を、下記製法に従って製造した。得られた固形白粉は、使用感、及び仕上がり（カバー力、透明感のある仕上がり、ツヤ感のある仕上がり、立体感のある仕上がり、ギラツキのない自然な仕上がり、肌色の補正効果）効果に優れるものであった。
【００８３】
(製法)
成分（１）〜（７）を混合粉砕した。これを、高速ブレンダーに移し、更に成分（８）〜（１１）を８０℃で加熱溶解したものを加えて均一に混合した。この混合物に成分（１２）を加えて混合した後再び粉砕しふるいを通した。これを金皿に圧縮成型し、製品を得た。
【００８４】
【表４】

【００８５】
（参考例２（旧実施例１２）：ルースタイプフェイスパウダー）
表５に示す組成のルースタイプフェイスパウダーを、下記製法に従って製造した。得られたルースタイプフェースパウダーは、使用感、及び仕上がり（カバー力、透明感のある仕上がり、ツヤ感のある仕上がり、立体感のある仕上がり、ギラツキのない自然な仕上がり、肌色の補正効果）効果に優れるものであった。
【００８６】
(製法)
成分（１）〜（７）を混合粉砕後、高速ブレンダーに移し、撹拌しつつ成分（８）〜（１０）を添加し、均一に混合した。得られた混合物を再びふるいを通して、製品を得た。
【００８７】
【表５】

【００８８】
（実施例１３：アイシャドー）
表６に示す組成のアイシャドーを、下記製法に従って製造した。得られたアイシャドーは、使用感、及び仕上がり（透明感、ツヤ感、立体感、ギラツキのない自然な仕上がり）効果に優れるものであった
（製法)
成分（１）〜（１１）を混合粉砕した。これを高速ブレンダーに移し、更に成分（１２）〜（１５）を８０℃で混合溶解したものを加えて均一に混合した。この混合物に成分（１６）を加え混合した後、再び粉砕しふるいを通した。これを金皿に圧縮成型し、製品を得た。
【００８９】
【表６】

【００９０】
（実施例１４：頬紅）
表７に示す組成の頬紅を、下記製法に従って製造した。得られた頬紅は、使用感、及び仕上がり（透明感、ツヤ感、立体感、ギラツキのなさと自然さ）効果に優れるものであった。
【００９１】
(製法)
成分(１) 〜（１１）を混合粉砕した。これを高速ブレンダーに移し、更に成分(１２) 〜（１５）を８０℃で混合溶解したものを加えて均一に混合した。この混合物に成分（１６）を加え混合した後再び粉砕しふるいを通した。これを金皿に圧縮成型し、製品を得た。
【００９２】
【表７】

【００９３】
（実施例１５：口紅）
表８に示す組成の口紅を、下記製法に従って製造した。得られた口紅は、使用感、及び仕上がり（カバー力、透明感、ツヤ感、立体感、ギラツキのない自然さ）効果に優れるものであった
(製法)
成分（７）〜（１４）を加熱融解し均一に混合した。これに（１）〜（６）を加え、ロールミルで練り均一に分散させた後、再融解して（１５）〜（１７）を加え、脱泡してから型に流し込み急冷して固めた。固まったものを型から取り出し、容器に装填した。次にスティックの外観を整えてから、炎の中を通し、表面を均一にし、製品を得た。
【００９４】
【表８】

【００９５】
（実施例１６：アイライナー）
表９に示す組成のアイライナーを、下記製法に従って製造した。得られたアイライナーは、使用感に優れるものであった。
【００９６】
(製法)
成分（９）の一部に（１０）を加え、コロイドミルを通して分散、ゲル化させた。一方、（５）〜（８）及び（１１）を混合し、加熱して溶解し、（１）〜（４）を加えた後冷却してロールミルで練り、再び加熱して溶かした中に、ベントナイトゲルと残部の（９）を加え、撹拌しながら冷却し、製品を得た。
【００９７】
【表９】

【００９８】
（実施例１７：Ｏ／Ｗ型クリーム）
表１０に示す組成のＯ／Ｗ型クリームを、下記製法に従って製造した。得られたクリームは、使用感、及び仕上がり（透明感、ツヤ感、立体感、ギラツキのない自然さ、肌色の補正効果）効果に優れるものであった。
【００９９】
(製法)
成分（１）、（８）、（１１）、（１３）及び（１４）を撹拌混合し、８０℃に保った。他の成分を混合し、加熱溶解して８０℃とした。この油相部に前述の水相部を加えて予備乳化し、ホモミキサーで均一に乳化した後,３０℃まで冷却し、製品を得た。
【０１００】
【表１０】

【０１０１】
実施例１〜１７で得られた化粧料は、いずれも透明感があり、毛穴やシミ、ソバカスが目立たたず、肌が明るく滑らかに見え、きめ細かく自然な仕上がりで、しかも観測方向による色の変化がなく、肌の色相感覚を変化させることができた。
【０１０２】
【発明の効果】
本発明に係る化粧料においては、特定の表面反射光特性を有する薄片状複合粉体（Ａ）とパール光沢を有する顔料（Ｂ）を併用するため、薄片状粉体としては特異的な粉体（Ａ）の表面反射光特性（抑えられた表面光沢）により、顔料（Ｂ）が生じる表面干渉色等の顔料の色を薄めることなく発色・着色性を発揮させることが可能になる。従って、本発明の化粧料は、より肌の色相感覚を変化させることができるが不自然なギラツキ感がなく、且つ、透明感がありながら充分なカバー力を有し、毛穴やシミ・ソバカスを目立たなくすることが可能な化粧料である。
【図面の簡単な説明】
【図１】本発明に係る複合粉体（Ａ）の製造装置の１構成例を模式的に示す図である。
【符号の説明】
１…ボンベ
２…フィルター
３…コンデンサー
４…昇圧ポンプ
５…クーラー
６（６ａ、６ｂ）…圧力計
７（７ａ、７ｂ）…安全弁
８…予熱器
９…撹拌機
１０…オートクレーブ
１１…温度計
１２…カートリッジヒーター
１３…温度調節器
１４…ヒーター
１５…ノズル
１６…粒子回収容器
１７…複合粉体
１８…排気ライン
１９…バグフィルター
２０…温度計
２１…ヒーター
Ｖ−１…保圧弁
Ｖ−２…バルブ
Ｖ−３…バルブ
Ｖ−４…バルブ
Ｖ−５…排気バルブ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cosmetic containing a flaky composite powder having specific optical properties and a pearlescent pigment.
[0002]
[Prior art]
In recent years, makeup cosmetics have been used to change the skin color sensation using pearl pigments that produce pearl effects such as mica titanium with mica coated with titanium oxide, natural fish scale foil, and bismuth oxychloride. However, when such a pearl pigment is blended in cosmetics, it is not enough to change the hue sensation as a whole because the color saturation is low enough to feel a slight color change in the regular reflection direction. Further, when the blending amount of the pearl pigment is increased in order to increase the change in the hue sensation, there is a problem that an unnatural feeling of glare appears.
[0003]
Therefore, for example, a metal oxide plate-like powder having a hollow structure (Patent Document 1) or a high-chroma powder coated with metal oxide in the order of titanium oxide, silicon oxide, and titanium oxide using synthetic mica as a base material ( Techniques for increasing the saturation of the pearl pigment itself, such as using Patent Document 2), have been studied. However, since these composite pigments have higher saturation of the individual pigments compared to conventional pearl pigments, they are generally used in makeup cosmetics, especially when formulated in cosmetics. Mixing with powders with very large surface gloss such as mica and talc blended, the effects of canceling the color development and changing the hue sensation could not be sufficiently exhibited.
[Patent Document 1]
JP 2001-172118 A
[Patent Document 2]
JP 2001-288038 A
[0004]
[Problems to be solved by the invention]
The object of the present invention is to improve the coloring efficiency of pigments such as interference colors, so that the skin hue sensation can be changed without an unnatural glare, and has sufficient covering power while being transparent, The object is to provide cosmetics that make pores, spots and freckles inconspicuous.
[0005]
[Means for Solving the Problems]
The inventors have used a specific powder (A) as a flaky powder by using a flaky composite powder (A) having a specific surface reflection light characteristic and a pigment (B) having a pearly luster. The surface reflected light characteristics (suppressed surface gloss) of the pigment (B) have improved color development and colorability without diminishing the surface interference color of the pigment (B), and have found that the above problems can be solved.
[0006]
  That is, the present invention relates to (A) a metal oxide having an average particle diameter of 2 to 20 μm and a metal oxide having an average particle diameter of 1/5 or less of the average particle diameter of the base material. Select one of the materials and cover the surface of the base material.TheFurthermore, it contains a flaky composite powder coated with at least one polymer compound selected from the group consisting of a fluorine polymer compound and a silicone polymer compound, and (B) a pigment having a pearly luster. It provides cosmetics.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The “flaky shape” of the flaky composite powder (A) used in the present invention has an aspect ratio (ratio of major axis to thickness of the powder) of 5 to 100, particularly 10 to 70, This is preferable from the viewpoint that the friction between powders is reduced and the usability is improved.
[0008]
In the present invention, the surface reflected light amount of the flaky composite powder (A) (hereinafter referred to as composite powder (A)) is measured by the following method.
Using a 10cm x 5cm polyurethane artificial leather (black artificial leather: OK-7 made by Okamoto), 5 mg of composite powder is uniformly applied to the artificial leather, and a two-dimensional variable angle spectrophotometer (Murakami Color Research Laboratory). GCMS-3) measures the amount of surface reflected light. Measurement is performed under the conditions of an incident light angle of 10 ° and a light reception angle of 10 ° and an incident light angle of −40 ° and a light reception angle of 60 ° under the light reception conditions of 2 ° visual field by C light. Here, the Y value of the tristimulus value in the 2 ° visual field XYZ color system is used as the surface reflected light amount. The surface reflected light is light that is reflected when incident light is applied to a sample applied to artificial leather. The incident light angle is an angle formed by the normal line of the reflecting surface and the incident light beam, and the light receiving angle is an angle formed by the normal line of the reflecting surface and the reflected light beam.
[0009]
In the composite powder (A) used in the present invention, the difference in the amount of surface reflection measured under the above conditions is 12 or less, more preferably 10 or less, and particularly preferably 9 or less.
[0010]
The composite powder (A) of the present invention contains other particles (hereinafter referred to as coated particles) so as to cover the surface of the powder as a base material. The state of the coating is a form in which the surface of the base material is present in layers or scattered, or a part of the coating particles is embedded in the base material. By covering the surface of the base material in this way, the reflection of the composite powder can be controlled.
[0011]
The base material preferably has an average particle size of 2 to 20 μm. Moreover, it is preferable that the thickness of a base material is 0.05-1 micrometer. Examples of such a base material include talc, mica, sericite, kaolin, smectite clay mineral, synthetic mica, synthetic sericite, plate-like titanium oxide, plate-like silica, plate-like aluminum oxide, boron nitride, barium sulfate, plate In particular, talc is preferable from the viewpoint of usability.
[0012]
The content of the base material in the composite powder (A) is preferably 50 to 95% by weight (hereinafter simply referred to as “%”), and more preferably 60 to 80%.
[0013]
The coated particles present on the surface of the base material preferably have an average particle size of 1/5 or less, more preferably 1/10 or less of the average particle size of the base material. In addition, an average particle diameter points out the average particle diameter measured with the electron microscope. As the covering particles, it is preferable to use a metal oxide. TiO as a metal oxide₂, Fe₂O_Three, CeO₂, ZnO, SiO₂, MgO, Al₂O_Three, CaO, ZrO₂It is preferable that Of these, especially TiO₂, Al₂O_Three, SiO₂Is preferable in terms of refractive index.
[0014]
The content of the coated particles in the composite powder (A) is preferably 5 to 50%, and more preferably 10 to 30%.
The composite powder (A) is obtained by, for example, selecting 1 to 3 types having different refractive indexes from the metal oxide as the coated particles and coating the surface of the base material in order from the higher refractive index of the coated particles. Can be formed. The said metal oxide is selected by the cover force required when compound powder (A) is mix | blended with cosmetics. For example, when increasing the covering power of the composite powder (A), it is preferable to coat the first layer with a metal oxide having a high refractive index, such as titanium oxide. On the other hand, when it is desired to set the covering force to be low, it is preferable to coat the first layer with a metal oxide having a medium refractive index, such as aluminum oxide. Next, the second and subsequent layers are covered. In order to suppress the reflection of light and provide a transparent feeling, it is desirable that the metal oxide has a refractive index smaller than that of the first layer.
[0015]
In the present invention, as a method of coating the base material with the coated particles, a method of combining particles in general, such as a method of coating in a supercritical state or a method of coating by hydrolysis, can be used.
[0016]
As a coating method in the case where the coated particles are metal oxides, a method in which a specific polymer compound is brought into contact with the base material and the metal oxide as the coated particles in the presence of supercritical carbon dioxide to form a composite is preferable.
[0017]
Here, supercritical carbon dioxide refers to carbon dioxide at a critical temperature (304.2K) or higher and a critical pressure (7.37 MPa) or higher, and the density changes suddenly by a slight pressure change near the critical point. Has properties. 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.
[0018]
When complexing is performed in the presence of supercritical carbon dioxide, the composite powder (A) usually has a structure covered with a polymer compound. More specifically, a composite form in which coated particles are present on the base material in a state where both the base material and the coated particles are coated with the polymer compound. Alternatively, coated particles may be present on the surface of the base material, and the whole may be coated with a polymer compound.
[0019]
The polymer compound used in the composite powder (A) of the present invention preferably has a property that it has a small intermolecular force and is easily dissolved or dispersed in supercritical carbon dioxide. As a specific material, at least one polymer compound selected from fluorine-based polymer compounds and silicone-based polymer compounds can be used.
[0020]
The fluorine-based polymer compound may be a polymer compound having a fluorine atom. The fluorine atom content in the fluorine-based polymer compound is preferably 9 to 80%, more preferably 20 to 70%, and still more preferably 40 to 65%, from the viewpoint of facilitating dispersion and dissolution in supercritical carbon dioxide. It is.
[0021]
Among the fluorine-based polymer compounds, a (meth) acrylic acid ester polymer having a fluoroalkyl group or a perfluoro group, and a (meth) acrylic acid ester-long chain alkyl (meth) having a fluoroalkyl group or a perfluoro group An acrylate copolymer is particularly preferable because it can be easily dispersed and dissolved in supercritical carbon dioxide. In addition, a (meth) acrylate homopolymer having a perfluoroalkyl group having 4 or more carbon atoms, a polyfluoroalkyl group or a perfluoropolyether group, and (meth) having this compound and an alkyl group having 8 to 22 carbon atoms. The copolymer with the acrylate is most preferable because it can be easily dispersed and dissolved in supercritical carbon dioxide.
[0022]
The weight average molecular weight of the fluorine-based polymer compound is preferably from 3,000 to 500,000, more preferably from 5,000 to 500 because it is easily dispersed and dissolved in supercritical carbon dioxide and is solid at 25 ° C. 300,000.
[0023]
The silicone polymer compound is not particularly limited as long as it is dissolved or dispersed in supercritical carbon dioxide alone or in a mixture of supercritical carbon dioxide and a cosolvent.
[0024]
Among the silicone polymer compounds, dimethylpolysiloxane, cyclic dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, cyclic methylhydrogenpolysiloxane, dimethylsiloxane methyl (polyoxypropylene) siloxane copolymer, Polyether-modified silicone, methylstyryl-modified silicone, alkyl-modified silicone, fluorine-modified silicone, higher fatty acid ester-modified silicone, higher alkoxy-modified silicone, silicone-modified acrylic resin, etc. are easy to disperse and dissolve in supercritical carbon dioxide and adsorb to particles. It is preferable from the point of being easy.
[0025]
More preferably, at the terminal / or side chain of the molecular chain of the organopolysiloxane, the formula (1):
[0026]
[Chemical 1]

[0027]
(Wherein R¹And R²Are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 10 carbon atoms, X^-Represents a counter ion of a quaternary ammonium salt, Cl^-, Br^-Halogen ions such as CH_ThreeSO_Four ^-, CH_ThreeCH₂SO_Four ^-And sulfate ester ions. )
Or formula (2):
[0028]
[Chemical formula 2]

[0029]
(Wherein R¹, R²And X^-Indicates the same meaning as described above. )
Through the group represented by formula (3):
[0030]
[Chemical 3]

[0031]
(Wherein R^ThreeRepresents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n represents 2 or 3. )
The molecular chain of poly (N-acylalkyleneimine) consisting of repeating units represented by the formula is bonded, and the mass ratio of the molecular chain of poly (N-acylalkylenimine) to the molecular chain of organopolysiloxane is 1. A silicone polymer compound having a / 50 to 50/1 weight average molecular weight of 500 to 500,000 is particularly preferred from the viewpoint of being easily dispersed and dissolved in supercritical carbon dioxide.
[0032]
For example, R in formula (1)¹And R²Are respectively hydrogen atoms and X^-Is CH_ThreeCH₂SO_Four ^-, R in formula (3)^ThreeIs CH₂CH_ThreeAnd poly (N-propanoylethyleneimine) / γ-aminopropylmethylsiloxane copolymer in which n is 2 (described in JP-A-7-133352).
[0033]
The weight average molecular weight of the silicone-based polymer compound is preferably 500 to 500,000, more preferably 1,000 to 300,000, from the viewpoint of facilitating dispersion and dissolution in supercritical carbon dioxide.
[0034]
As a method of performing the composite in the presence of supercritical carbon dioxide, first, the base material, the coated particles, and the polymer compound are brought into contact in the presence of supercritical carbon dioxide in a container. Depending on the type of polymer compound, a small amount of a cosolvent can be used. The cosolvent is preferably a polar solvent. Among polar solvents, alcohol and / or water which are considered to be almost harmless to the human body are preferable. As the alcohol, methanol, ethanol, and 1-propanol are preferable, and ethanol is more preferable.
[0035]
Supercritical carbon dioxide can be used in any combination as long as the temperature and pressure at which carbon dioxide develops a supercritical state. However, from the viewpoint of efficiently removing supercritical carbon dioxide after contact and reducing the pressure efficiently. 308 to 373K, more preferably 313 to 353K. In addition, the initial pressure of supercritical carbon dioxide when starting depressurization is preferably 7.2 to 50 MPa, more preferably 10 to 40 MPa, from the viewpoint of efficiently depressurizing supercritical carbon dioxide.
[0036]
A mixture of supercritical carbon dioxide and a polymer compound may become transparent depending on conditions such as temperature and pressure. Such a transparent mixture is preferable because there is little aggregation of particles and a coating film of the polymer compound formed becomes uniform.
[0037]
In the container, the polymer compound, the base material, and the coated particles are brought into contact with each other in the presence of supercritical carbon dioxide, and then the exhaust valve provided in the container is opened, and the container is decompressed, whereby the polymer compound is decompressed. A composite powder whose surface is coated with can be obtained in the container. Alternatively, the mixture after contact can be discharged out of the container together with carbon dioxide to obtain a composite powder.
[0038]
In the method of obtaining a composite powder in a container, when the pressure of carbon dioxide in a supercritical state is decreased from a critical pressure or higher, the temperature in the container is decreased due to adiabatic expansion of carbon dioxide, and the critical temperature of carbon dioxide is reduced. When it becomes below, liquefied carbon dioxide will arise and it will be easy to generate | occur | produce aggregation of a powder. 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.
[0039]
The time required to reduce the pressure in the container to atmospheric pressure is preferably 2 seconds from the viewpoint of controlling the particle diameter of the obtained composite powder, the film thickness of the coating of the polymer compound, and suppressing by-product particles. ˜240 minutes, more preferably 5 seconds to 120 minutes.
[0040]
Examples of the method for obtaining the composite powder outside the container include a method in which the mixture is ejected outside the container via a nozzle or the like. The discharge conditions are not particularly limited, but the temperature at the inflow portion of the nozzle is preferably 304.2 K or higher, and the pressure is preferably 7.37 MPa or higher from the viewpoint of the supercritical fluid.
[0041]
In order to obtain a composite powder in the container after removing the carbon dioxide, the container may have an exhaust mechanism such as a valve. In order to dissolve or disperse the molecular compound, those having a stirring mechanism in the container are preferable. Typical examples of the container include an autoclave and a pressure cell.
[0042]
The total amount of the base material and the coated particles in the composite powder is 20 to 99.5%, preferably 70 from the viewpoint that the composite powder can be taken out as particles and the characteristics of the polymer compound are expressed. ~ 99.5%.
[0043]
Another method for coating the coated particles is to hydrolyze a predetermined amount of a metal salt which is a precursor of a selected metal oxide, or similarly to hydrolyze a predetermined amount of an organometallic compound in an alcohol solvent. A conventionally known method such as a method of depositing a hydrolyzate on a composite powder on which a base material or a coating layer is formed can also be used.
[0044]
When using a metal oxide precursor, for example, a base material is dispersed in water, a predetermined amount of a metal salt such as titanyl sulfate is added thereto, and after hydrolysis in an alkaline atmosphere, a metal salt hydrolyzate on the surface of the base material By depositing, a metal oxide coating layer such as titanium oxide having a predetermined thickness can be formed. In addition, when silica is coated as the outermost layer, a predetermined amount of an alkali metal silicate aqueous solution or an organic silicon compound is added to the dispersion of the base material on which the coating layer having a higher refractive index than silica is formed. Accordingly, a silica coating layer having a predetermined thickness can be formed by a method such as attaching a silicic acid polymer (hydrolytic condensation polymer) to the surface of the base material coated with acid or alkali according to the above. In order to form the silica coating layer, a conventionally known method may be employed.
[0045]
In addition, the total coating film thickness of the coated particles is preferably 50 nm or less, and more preferably 20 nm to 50 nm, in order to give an excellent transparency to the cosmetic according to the present invention. The coating film thickness of the coated particle is determined by the geometric surface area of the base material or the specific surface area measured by the nitrogen adsorption method, etc., and the density of the substance (for example, the coated particle or polymer compound) contained in the composite particle in addition to the base material. It can be obtained more.
[0046]
When the base material is coated with titanium oxide and aluminum oxide in this order, the coating amount of titanium oxide and aluminum oxide is TiO.₂/ Al₂O_ThreeThe weight ratio is 0.42 or less, based on the amount of surface reflected light measured under conditions of an incident light angle of 10 ° and a light receiving angle of 10 °, under the conditions of an incident light angle of −40 ° and a light receiving angle of 60 °. This is preferable because the difference obtained by subtracting the value does not increase and the glare can be reduced. Furthermore, the total coating amount of titanium oxide and aluminum oxide is 1 to 50 in the composite powder from the viewpoint that the feeling of use is good and the effect of making pores and the like inconspicuous while maintaining transparency. %, In particular 5 to 40%. When coating with titanium oxide, aluminum oxide, and silica in this order, the coating amount of titanium oxide and aluminum oxide is TiO.₂/ Al₂O_ThreeIt is preferable that the total coating amount is 1 to 50%, particularly 5 to 40%. Furthermore, from the point of use feeling (reducing the squeaky feeling), SiO for the powder.₂Is preferably 0.1 to 30%, particularly preferably 0.2 to 20%.
[0047]
The composite powder (A) is preferably treated on the surface with silicone, fluorine compound, lecithin, amino acid, polyethylene, metal soap or the like in order to impart water repellency and / or oil repellency. Furthermore, when the surface treatment described in JP-A-11-49634 is applied and blended in the formulation, a transparency is improved, and it is smooth, has a good feeling of moistness, and has little skin irritation. It can be obtained and is preferable.
[0048]
The treatment amount of the water and oil repellency treatment agent for the powder is 0.05 to 20%, particularly 1 to 10%, and sufficient water repellency and / or oil repellency, good feeling of use and light resistance are obtained. ,preferable.
[0049]
The average particle size of the composite powder (A) obtained as described above is preferably 0.1 to 1000 μm, more preferably 0.5 to 500 μm, particularly 5 to 50 μm from the viewpoint of handling as cosmetic particles. It is preferable that
[0050]
The composite powder (A) may be used alone or in combination of two or more. The composite powder (A) is preferably blended in the cosmetic composition of the present invention in an amount of 1 to 90%, more preferably 1 to 50%, and particularly preferably 5 to 30% (feeling of spread, adhesion, etc.) ) And finish (transparency, pore concealment, etc.).
[0051]
The pearly luster powder (B) (hereinafter referred to as pearl pigment (B)) used in the present invention is preferably made of mica as a base material, and titanium oxide-coated mica whose surface is coated with titanium oxide, mica Examples thereof include iron oxide-titanium oxide-coated mica such as bengara titanium oxide-coated mica coated with iron oxide and titanium oxide, and powder having silica sandwiched between mica and titanium oxide-coated layer. Examples of powders other than mica as a base material include powders obtained by coating silica flakes with titanium oxide, powders obtained by coating synthetic mica with titanium oxide, and hollow titanium oxides. Particularly preferred is a pearl pigment having a titanium oxide coating amount of 10 to 75%.
[0052]
The average particle diameter of the pearl pigment is preferably from 1 to 100 μm, more preferably from 1 to 20 μm, from the viewpoint of usability.
[0053]
Commercially available pearl pigments include Flamenco Super Pearl, Flamenco Orange, Flamenco Sparkle, Flamenco Ultra Sparkle 4500, Croizone Orange, Croizone Blue, Croizonenu Antique Blue, Croizone Cerise Flambe, Croizone Sparkle (Gold, Copper, Blue, Rouge), Timika Golden Bronze, Timikanu Antique Copper, Timika Gold Sparkle, Timica Extra Large Sparkle, Flamenco Satin Red, Flamenco Satin Violet, Flamenco Satin Blue, Flamenco Sparkle (Red, Gold, Green, Blue, Violet) ), Duchrome BV, etc. (above, Engelhard), Timilon Super, Timilon Super Silk MP-1005 Timilon Super Scene MP-1001, Timilon Star Raster MP-115, Colorona Siena, Colorona Red Gold, Colorona Red Brown, Colorona Bright Gold, Colorona Bordeaux, Colorona Imperial Red, Colorona Ciena Sparkle, Timilon Gold Plus MP-25, Timilon Splendid (Merck), Prestige Series (ECKART), Metashine 1080RC- (B1, G1, R1, S1, Y1) (Nippon Sheet Glass Co., Ltd.), Prominence Series, etc. (Topy) Kogyo Co., Ltd.).
[0054]
The pearl pigment (B) is also preferably used after being subjected to water repellency and / or oil repellency treatment in the same manner as the composite powder (A).
[0055]
In the present invention, the pearl pigment (B) may be used alone or in combination of two or more. The content of the pearl pigment (B) in the cosmetic is preferably 0.1% or more and 0.5 to 80% of the total powder from the viewpoint of the effect of changing the hue sensation. Further, when the cosmetic dosage form is lotion, it is preferably 0.1 to 10%, particularly 0.5 to 5% in the total composition, and in the case of emulsions and creams, 0.1 to 10%. In particular, 0.5 to 7%, in the case of powdered white powder, solid white powder and face powder, 0.1 to 80%, particularly 1 to 50%, in the case of powder foundation and oily foundation, 0.1 to 80%, especially 1 ~ 25%, 0.1 to 10% for creamy foundations, liquid foundations and concealers, especially 0.5 to 7%, 0.1 to 20% for lipsticks and lip balms, especially 0.5 to 10% %, 0.1 to 40% for blusher and eye shadow, especially 0.5 to 25%, 0.1 to 30%, especially 0.5 to 20% for eyeliner and eyebrow. .
[0056]
In the present invention, the weight blending ratio (A: B) of the component (A) and the component (B) is preferably in the range of 95: 5 to 5:95 from the viewpoint of the effect of changing the hue sensation. The range of 10:90 is more preferable, and the range of 80:20 to 20:80 is particularly preferable.
[0057]
In addition to the above-described essential components (A) and (B), the cosmetics of the present invention may be blended with components used in ordinary cosmetics within a range that does not impair the effects of the present invention. For example, inorganic powders such as silicic acid, anhydrous silicic acid, magnesium silicate, talc, sericite, mica, kaolin, organic powders such as polyamide, polyester, polypropylene, polystyrene, polyurethane, and organic colorants such as organic tar dyes Is mentioned. These powders can be used alone or in combination of two or more.
[0058]
Further, in the present invention, together with the above powder components, hydrocarbons such as polyethylene wax, microcrystalline wax, ceresin wax, petrolatum and the like used in normal cosmetics; synthesis of diisostearyl malate, neopentyl glycol caprate, etc. Ester oils; vegetable oils such as candelilla wax, jojoba oil, olive oil; silicone oils such as cyclomethicone and dimethicone; higher alcohols such as cetanol and oleyl alcohol; fatty acids such as stearic acid and oleic acid; glycerin and 1,3-butane Polyhydric alcohols such as diols; Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and other surfactants; ethanol and other lower alcohols; Carbopol and other thickeners Purple, such as preservatives, preservatives, octyl methoxycinnamate Linear absorption agents, antioxidants, moisturizers, skin lightening agents, blood circulation promoters, antiperspirants, fungicides, medicinal ingredients such as skin activators, perfumes, etc. can be used in combination.
[0059]
The cosmetic of the present invention can be produced according to a conventional method except that the powder as the essential component described above is blended. For example, basic cosmetics such as skin lotion, emulsion, cream, etc .; powder foundation, powder powder, solid powder , Face powder, oily foundation, creamy foundation, liquid foundation, concealer, lipstick, lip balm, eye shadow, blusher, eyeliner, eyebrow and the like.
[0060]
【Example】
(Production Example 1)
<Dissolution process>
1, poly (N-propanoylethyleneimine) / γ-aminopropylmethylsiloxane (copolymerization ratio 4/96 (mass) is placed in an autoclave 10 (content volume 100 mL: pressure-resistant glass industry). Ratio)) copolymer (weight average molecular weight 150,000, lump) 0.36 g, titanium oxide (average particle size 0.05 μm, surface siliconized, Teika Co., Ltd.) 1.80 g and talc (average particle size 10 μm, ( Yamaguchi Mica Industry Co., Ltd.) was charged with 6.00 g.
[0061]
After filling, after removing dust in the carbon dioxide gas through the filter 2 from the cylinder 1, the carbon dioxide is condensed by the condenser 3 through which the refrigerant controlled to −5 ° C. is passed from the cooler 5, and then the pump head is The pressure was increased by the cooled pressure increasing pump 4. The pressure at the time of pressurization was measured with the pressure gauge 6a. In addition, in order to ensure safety, the safety valve 7a was arrange | positioned in the downstream part of the pressure gauge 6a. The pressure was adjusted with the pressure holding valve V-1.
[0062]
The valve V-2 was opened and carbon dioxide was preheated to a predetermined temperature through the preheater 8 and sent to the autoclave 10 to which the safety valve 7b was attached via the valve V-3. Using the cartridge heater 12, the temperature in the autoclave 10 is adjusted by the temperature controller 13, and the temperature and pressure in the cell are adjusted to a temperature of 333 K and a pressure of 30 MPa by the thermometer 11 and the pressure gauge 6 b, respectively. The carbon state was assumed. Under this condition, the stirrer 9 was rotated and dissolved and dispersed for 0.5 hours to obtain a mixture.
[0063]
<Composite process>
The exhaust valve V-5 was gradually opened, exhausted from the exhaust line 18 (inner diameter 2.5 mm), and the pressure was reduced for 10 minutes to obtain a composite powder. At this time, the temperature in the container was lowered by the adiabatic expansion action, but the pressure was reduced so that the temperature in the container did not become 313K or less. In addition, the heater 21 was heated to prevent the exhaust line from freezing. Further, the composite powder slightly leaking from the exhaust line 18 was captured by the bag filter 19. The resulting composite powder had a difference in surface reflected light of 6 and an average particle size of 15 μm.
[0064]
(Production Example 2)
After performing the dissolution process of Production Example 1, instead of the compounding process of Production Example 1, the following compounding process was performed.
[0065]
<Composite process>
The mixture obtained by rotating the stirrer 9 and carrying out dissolution and dispersion for 0.5 hour, then opening the valve V-4 and passing through a line previously heated by the heater 14 from the nozzle 15 into the particle collection container 16. Was ejected, and composite powder without aggregation was obtained as ejected matter (particles). The temperature immediately before the nozzle inlet at that time was confirmed by the thermometer 20 and was 313K or more. The resulting composite powder had a difference in surface reflected light of 6 and an average particle size of 10 μm.
[0066]
(Production Example 3)
Instead of the poly (N-propanoylethyleneimine) / γ-aminopropylmethylsiloxane copolymer used in Production Example 1, stearyl methacrylate / 2- (perfluorooctyl) ethyl methacrylate (copolymerization ratio 1/9 (mass) Ratio)) 0.36 g of copolymer (weight average molecular weight 180,000, granular material having a particle size of about 1 to 5 mm) and titanium oxide (average particle size 0.05 μm, surface siliconized, Teika Co., Ltd.) Instead, a composite powder was produced in the same manner as in Production Example 1 except that 1.8 g of titanium oxide (average particle size 0.2 μm, surface silicon treatment, Ishihara Sangyo Co., Ltd.) was used. The resulting composite powder had a difference in surface reflected light of 6 and an average particle size of 10 μm.
[0067]
  (Reference production example 1 (old production example 4))
  340 g of talc was added to 3160 g of pure water and sufficiently dispersed. To this was added 200 g of a 20% strength titanyl sulfate aqueous solution as titanium dioxide, heated with stirring and boiled for 5 hours. This was cooled to room temperature, washed with filtered water, and dried at 110 ° C. to obtain talc coated with a hydrate of titanium dioxide. Of these, 320 g was well dispersed in 2680 g of pure water, and 800 g of 10% strength aluminum chloride aqueous solution and 500 g of urea dissolved in 1800 g of water as aluminum oxide were added and mixed well, followed by heating at 90 ° C. for 10 hours. And then cooled to room temperature. This was washed with filtered water, dried at 110 ° C., and then calcined at 600 ° C. for 5 hours to obtain talc coated with titanium oxide and aluminum oxide sequentially. Furthermore, 100 g of this was weighed and added to 1 L of a mixed solvent of ethanol and water (volume ratio of 7: 3) and well dispersed. To this was added 278 g of a 4% concentration ethyl silicate ethanol solution as silica, heated to 50 ° C. with stirring and held for about 10 hours. Next, this was cooled, filtered, thoroughly washed with ethanol and pure water, and then dried at 110 ° C. to obtain talc coated sequentially with titanium oxide, aluminum oxide, and silica. The resulting composite powder had a difference in surface reflected light of 10 and an average particle size of 20 μm.
[0068]
  (Reference production example 2 (old production example 5))
  368 g of talc was added to 3132 g of pure water and sufficiently dispersed. To this, 158 g of a 20% titanyl sulfate aqueous solution as titanium dioxide was added, heated with stirring and boiled for 5 hours. This was cooled to room temperature, washed with filtered water and dried at 110 ° C. to obtain talc coated with a hydrate of titanium dioxide. Of these, 314 g was well dispersed in 2686 g of pure water, and a solution prepared by dissolving 860 g of 10% aluminum chloride aqueous solution and 640 g of urea in 2000 g of water as aluminum oxide was added and mixed well, and heated at 90 ° C. for 10 hours. And then cooled to room temperature. This was washed with filtered water, dried at 110 ° C., and then calcined at 600 ° C. for 5 hours to obtain talc coated with titanium oxide and aluminum oxide sequentially. The resulting composite powder had a difference in surface reflected light of 10 and an average particle size of 30 μm.
[0069]
  (Reference production example 3 (old production example 6))
  309 g of sericite was added to 3691 g of pure water and sufficiently dispersed, and a solution prepared by dissolving 912 g of a 10% aluminum chloride aqueous solution and 588 g of urea in 2000 g of water as aluminum oxide was added and mixed well. After heating for hours, it was cooled to room temperature. This was washed with filtered water, dried at 110 ° C., and then calcined at 600 ° C. for 5 hours to obtain sericite coated with aluminum oxide. The resulting composite powder had a difference in surface reflected light of 10 and an average particle size of 20 μm.
[0070]
(Comparative Production Example 1)
368 g of talc was added to 3132 g of pure water and sufficiently dispersed. To this, 158 g of a 20% titanyl sulfate aqueous solution as titanium dioxide was added, heated with stirring and boiled for 5 hours. This was cooled to room temperature, washed with filtered water, and dried at 110 ° C. to obtain talc coated with a hydrate of titanium dioxide. Of these, 374 g was well dispersed in 3126 g of pure water, and a solution prepared by dissolving 264 g of 10% aluminum chloride aqueous solution and 236 g of urea in 800 g of water as aluminum oxide was added and mixed well, and heated at 90 ° C. for 10 hours. And then cooled to room temperature. This was washed with filtered water, dried at 110 ° C., and then calcined at 600 ° C. for 5 hours to obtain talc coated with titanium oxide and aluminum oxide sequentially. The resulting composite powder had a difference in surface reflected light of 18 and an average particle size of 20 μm.
[0071]
(Measurement method of surface reflected light quantity of composite powder)
Using a 10 cm x 5 cm polyurethane artificial leather (black artificial leather; Okamoto Co., Ltd. OK-7), 5 mg of composite powder was uniformly applied to the artificial leather, and a two-dimensional variable angle spectrophotometer (Murakami Color Technology). The amount of surface reflected light was measured by a laboratory: GCMS-3). Measurement was performed under the conditions of an incident light angle of 10 ° and a light reception angle of 10 °, and an incident light angle of −40 ° and a light reception angle of 60 ° under the light reception conditions of 2 ° field of view with C light. Here, the Y value of the tristimulus value in the 2 ° visual field XYZ color system was used as the surface reflected light amount.
[0072]
(Evaluation methods)
10 expert panelists feel that the sample is applied to the face (adhesion to the skin (attachment), spreadability to the skin (extended), applied feel), and finish (covering power, transparency) The finish, glossy finish, three-dimensional finish, natural finish without glare, skin color correction effect) were sensory evaluated and judged according to the following criteria.
[Criteria]
◎: 8 or more responded good
○: 5-7 responded that they were good
Δ: 2 to 4 people answered good
×: 1 or less responded good
(Examples 1-8, Comparative Examples 1 and 2: Powder Foundation)
A powder foundation having the composition shown in Table 1 was produced according to the following production method. Moreover, since the use evaluation of these foundations was implemented according to the said method, the result is also shown in Table 1.
[0073]
(Manufacturing method)
Components (1) to (17) were mixed and pulverized with a pulverizer. This was transferred to a high-speed blender, and components (18) to (20) mixed and dissolved at 80 ° C. were added and mixed uniformly. The component (21) was added to the mixture and mixed, then ground again and passed through a sieve. This was compression molded into a metal pan.
[0074]
[Table 1]

[0075]
From the results shown in Table 1, all of Examples 1 to 8 which are the products of the present invention have a feeling of use and a finish (covering power, a finish with a transparent feeling, a finish with a glossy feeling, a finish with a three-dimensional feeling, The natural finish without glare and the effect of correcting the skin color were excellent. On the other hand, Comparative Examples 1 to 3 that do not contain the component (A) are particularly finished (covering power, transparent finish, glossy finish, three-dimensional finish, natural finish without glare, skin color correction) The effect) was inferior to that of the example.
[0076]
(Example 9: Creamy foundation)
A creamy foundation having the composition shown in Table 2 was produced according to the following production method. The resulting creamy foundation is excellent in use feeling and finish (covering power, clear finish, glossy finish, three-dimensional finish, natural finish without glare, skin color correction effect) It was a thing.
[0077]
(Manufacturing method)
Components (1) to (6) were mixed and ground. Separately, a liquid in which the aqueous phase components (7) to (10) were mixed was prepared, and the pulverized pigment was added and dispersed, followed by heating to 75 ° C. What heated and melt | dissolved oil phase component (11)-(16) at 80 degreeC was added to the aqueous phase prepared previously, stirring, and emulsified. This was cooled with stirring, and the component (17) was added at 50 ° C. and cooled with stirring to obtain a product.
[0078]
[Table 2]

[0079]
(Example 10: Oily foundation)
An oily foundation having the composition shown in Table 3 was produced according to the following production method. The resulting oily foundation has excellent usability and finish (covering power, transparent finish, glossy finish, three-dimensional finish, natural finish without glare, skin color correction effect) Met.
[0080]
(Manufacturing method)
Components (1) to (7) were mixed and ground. Components (8) to (12) were sufficiently stirred and mixed and then heated and melted. The pulverized pigment was added and dispersed therein, and component (13) was added and again stirred and mixed. This was filled in a metal pan and cooled to obtain a product.
[0081]
[Table 3]

[0082]
  (Reference example 1 (old example 11): solid white powder)
  Solid white powder having the composition shown in Table 4 was produced according to the following production method. The obtained solid white powder has excellent usability and finish (covering power, transparent finish, glossy finish, three-dimensional finish, natural finish without glare, skin color correction effect) Met.
[0083]
(Manufacturing method)
Components (1) to (7) were mixed and ground. This was transferred to a high-speed blender, and components (8) to (11) were dissolved by heating at 80 ° C. and mixed uniformly. Component (12) was added to the mixture and mixed, and then ground again and passed through a sieve. This was compression molded into a metal pan to obtain a product.
[0084]
[Table 4]

[0085]
  (Reference example 2 (old example 12): loose type face powder)
  Loose type face powder having the composition shown in Table 5 was produced according to the following production method. The resulting loose type face powder has a feeling of use and finish (covering power, clear finish, glossy finish, solid finish, natural finish without glare, skin color correction effect) It was excellent.
[0086]
(Manufacturing method)
Components (1) to (7) were mixed and ground, then transferred to a high-speed blender, and components (8) to (10) were added while stirring and mixed uniformly. The resulting mixture was sieved again to obtain a product.
[0087]
[Table 5]

[0088]
(Example 13: Eye shadow)
Eye shadows having the compositions shown in Table 6 were produced according to the following production method. The obtained eye shadow was excellent in feeling of use and finish (transparent, glossy, three-dimensional, natural finish free of glare).
(Manufacturing method)
Components (1) to (11) were mixed and ground. This was transferred to a high-speed blender, and components (12) to (15) mixed and dissolved at 80 ° C. were added and mixed uniformly. Component (16) was added to the mixture and mixed, and then ground again and passed through a sieve. This was compression molded into a metal pan to obtain a product.
[0089]
[Table 6]

[0090]
(Example 14: Blusher)
Blusher having the composition shown in Table 7 was produced according to the following production method. The resulting blusher was excellent in use feeling and finish (transparency, luster, three-dimensionality, lack of glare and naturalness).
[0091]
(Manufacturing method)
Components (1) to (11) were mixed and ground. This was transferred to a high-speed blender, and components (12) to (15) mixed and dissolved at 80 ° C. were added and mixed uniformly. The component (16) was added to the mixture and mixed, then ground again and passed through a sieve. This was compression molded into a metal pan to obtain a product.
[0092]
[Table 7]

[0093]
(Example 15: Lipstick)
Lipsticks having the compositions shown in Table 8 were produced according to the following production method. The obtained lipstick was excellent in use feeling and finish (covering power, transparency, gloss, three-dimensional effect, naturalness without glare) effect.
(Manufacturing method)
Components (7) to (14) were heated and melted and mixed uniformly. (1) to (6) were added to this, kneaded with a roll mill and dispersed uniformly, and then remelted to add (15) to (17), defoamed, poured into a mold, rapidly cooled and hardened. The hardened material was removed from the mold and loaded into a container. Next, after adjusting the appearance of the stick, it was passed through a flame and the surface was made uniform to obtain a product.
[0094]
[Table 8]

[0095]
(Example 16: Eyeliner)
An eyeliner having the composition shown in Table 9 was produced according to the following production method. The obtained eyeliner was excellent in usability.
[0096]
(Manufacturing method)
(10) was added to a part of the component (9) and dispersed and gelled through a colloid mill. On the other hand, (5) to (8) and (11) are mixed, heated to dissolve, added (1) to (4), cooled and kneaded with a roll mill, and heated again to dissolve. Bentonite gel and the remainder (9) were added and cooled with stirring to obtain a product.
[0097]
[Table 9]

[0098]
(Example 17: O / W type cream)
O / W type creams having the compositions shown in Table 10 were produced according to the following production method. The obtained cream was excellent in use feeling and finish (transparency, gloss, three-dimensional effect, naturalness without glare, skin color correction effect).
[0099]
(Manufacturing method)
Components (1), (8), (11), (13) and (14) were stirred and mixed and kept at 80 ° C. Other components were mixed and dissolved by heating to 80 ° C. The aforementioned aqueous phase was added to the oil phase and pre-emulsified, and the mixture was uniformly emulsified with a homomixer and then cooled to 30 ° C. to obtain a product.
[0100]
[Table 10]

[0101]
The cosmetics obtained in Examples 1 to 17 are all transparent, pores, spots and freckles are not noticeable, the skin looks bright and smooth, has a fine and natural finish, and changes in color depending on the observation direction. It was possible to change the skin hue sensation.
[0102]
【The invention's effect】
In the cosmetic according to the present invention, since the flaky composite powder (A) having a specific surface reflection light characteristic and the pigment (B) having pearly luster are used in combination, a specific powder is used as the flaky powder. Due to the surface reflected light characteristic (suppressed surface gloss) of (A), it is possible to exhibit color development / coloring properties without diminishing the color of the pigment such as the surface interference color produced by the pigment (B). Therefore, the cosmetic of the present invention can change the skin hue sensation more, but does not have an unnatural glare and has a sufficient covering power while having a transparent feeling, and prevents pores, spots and freckles. It is a cosmetic that can be made inconspicuous.
[Brief description of the drawings]
FIG. 1 is a diagram schematically showing one configuration example of an apparatus for producing a composite powder (A) according to the present invention.
[Explanation of symbols]
1 ... cylinder
2 ... Filter
3 ... Condenser
4 ... Booster pump
5 ... Cooler
6 (6a, 6b) ... pressure gauge
7 (7a, 7b) ... Safety valve
8 ... Preheater
9 ... Agitator
10 ... autoclave
11 ... Thermometer
12 ... Cartridge heater
13 ... Temperature controller
14 ... Heater
15 ... Nozzle
16 ... Particle collection container
17 ... Composite powder
18 ... Exhaust line
19 ... Bug filter
20 ... Thermometer
21 ... Heater
V-1 ... Holding valve
V-2 ... Valve
V-3 ... Valve
V-4 ... Valve
V-5 ... Exhaust valve

Claims (5)

(A) To a base material having an average particle diameter of 2 to 20 μm, a metal oxide having an average particle diameter of 1/5 or less of the average particle diameter of the base material is selected from the metal oxides. Ri Na coated on the base material surface is selected, further, a fluorine-based polymer compound, and at least one flake-like composite powder is coated with a polymer compound selected from the group consisting of silicone polymer compound And (B) a cosmetic comprising a pigment having a pearly luster. The flaky composite powder (A) is applied to the surface of black artificial leather at a rate of 5 mg / 50 cm ² , and the incident light angle is 10 ° under the light receiving condition of 2 ° field of view with the C light of the variable angle spectrocolorimeter. 2. The cosmetic according to claim 1, wherein a difference obtained by subtracting the surface reflection light amount measured at an incident light angle of −40 ° and a light reception angle of 60 ° from the surface reflection light amount measured at a light reception angle of 10 ° is 6 or less. .   The fluoropolymer compound is a (meth) acrylic acid ester polymer having a fluoroalkyl group or a perfluoro group, and a (meth) acrylic acid ester-long chain alkyl (meth) acrylate having a fluoroalkyl group or a perfluoro group. The cosmetic according to claim 1 or 2, wherein the cosmetic is at least one polymer compound selected from copolymers.   The silicone polymer is a dimethylpolysiloxane, cyclic dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, cyclic methylhydrogenpolysiloxane, dimethylsiloxane-methyl (polyoxypropylene) siloxane copolymer, poly It is at least one polymer compound selected from ether-modified silicone, methylstyryl-modified silicone, alkyl-modified silicone, fluorine-modified silicone, higher fatty acid ester-modified silicone, higher alkoxy-modified silicone, and silicone-modified acrylic resin. The cosmetic according to any one of claims 1 to 3.   The cosmetic according to any one of claims 1 to 4, wherein the powder (B) having pearly luster has a mica surface coated with metal oxide particles.

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