JP4205846B2 - Skin cosmetics - Google Patents

Description

【００１４】
で表される。また、粉体層反射光Ｄ_fは、
【００１５】
【数２】

【００１６】
で表される。また、基底層反射光Ｄ_bは、
【００１７】
【数３】

【００１８】
で表される。これらより、表面反射光量Ｙ（Ｓ_B）は、
【００１９】
【数４】

【００２０】
粉体層反射光量Ｙ（Ｄ_f）は、
【００２１】
【数５】

【００２２】
基底層反射光量Ｙ（Ｄ_b）は、
【００２３】
【数６】

【００２４】
で表される。ここで、Ｙ（Ｂsp）、Ｙ（Ｂps）等は、それぞれＢsp、ＢpsのＹ値を示す。
【００２５】
使用する光源としては、昼光光源であるＣ光を用い、受光視野は２°とする。
測定は、入射角を４５°で一定にして、受光角を０°〜９０°まで５°刻みで行い、反射光量差が一番大きい入射角４５°／受光角４５°の条件下と、入射角４５°／受光角０°の条件下での測定値に着目する。
【００２６】
本発明の（Ａ）成分は、これらの条件下でのそれぞれの表面反射光量の差が７〜１５であることが第１の要件である。「表面反射光量の差」が１５より大きくなると、つやが出過ぎて顔がてかって見え、一方、７より小さくなると、つやが少なく顔が暗くくすんだように見えてしまう。
【００２７】
更に、表面反射光量と粉体層反射光量の差がわかりやすい、入射角４５°／受光角０°の条件下での測定値から、表面反射光量と粉体層反射光量の差が−３〜３であることが第２の要件である。「表面反射光量と粉体層反射光量の差」が３より大きくなると、つやが出過ぎて顔がてかって見え、−３より小さくなると、白っぽい顔になってしまう。
【００２８】
本発明で用いる（Ａ）成分の複合無機粉体は、鱗片状基材上に他の金属酸化物を複合させてなり、上記の光学特性を有するように設計される。その鱗片状基材は、平均粒子径が２〜２０μｍで、厚みが０．０５〜１μｍであることが好ましい。このような鱗片状基材としては雲母、セリサイト、タルク、カオリン、スメクタイト属粘土鉱物、合成マイカ、合成セリサイト、板状二酸化チタン、板状シリカ、板状酸化アルミニウム、窒化硼素、硫酸バリウム、板状チタニア・シリカ複合酸化物等が挙げられるが、特にタルクが使用感の点で好ましい。
【００２９】
これら鱗片状基材に複合化される金属酸化物としては二酸化チタン（ＴｉＯ₂）、酸化鉄（Ｆｅ₂Ｏ₃）、酸化セリウム（ＣｅＯ₂）、酸化亜鉛（ＺｎＯ）、シリカ（ＳｉＯ₂）、酸化マグネシウム（ＭｇＯ）、酸化アルミニウム（Ａｌ₂Ｏ₃）、酸化カルシウム（ＣａＯ）、酸化ジルコニウム（ＺｒＯ₂）が挙げられるが、特に二酸化チタン、酸化アルミウニム、シリカが屈折率の点で好ましい。
【００３０】
本発明で用いる（Ａ）成分の複合無機粉体は、前記鱗片状基材に、前記金属酸化物から選択される１〜３種類の屈折率の異なる金属酸化物を、屈折率の高い方から順に被覆することにより調製される。当該金属酸化物は、（Ａ）成分に要求されるカバー力によって選択すればよい。カバー力の高い粉体を得るためには、第１層に屈折率の高い金属酸化物、例えば二酸化チタン等を被覆することが好ましい。他方、カバー力の低い粉体を得るためには、第１層に中程度の屈折率を持つ金属酸化物、例えば、酸化アルミニウム等を被覆することが好ましい。
次いで、必要により第２層以上の層を形成していくが、光の反射を抑制し透明感を出すために、第２層以上は第１層よりも屈折率の小さい金属酸化物であることが望ましい。
【００３１】
金属酸化物の被覆方法は、前記のように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、加水分解物を被覆すべき鱗片状基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、従来の公知の方法が採用できる。
例えば、鱗片状基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、鱗片状基材の表面に金属塩加水分解物を析出させることにより、所定厚の二酸化チタン被覆層を得ることができる。
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を形成した鱗片状基材の分散液に、所定量のアルカリ金属珪酸塩水溶液あるいは有機珪素化合物等を添加し、必要に応じて酸またはアルカリを加えて、上記被覆層を形成した鱗片状基材の表面に珪酸の重合物（加水分解縮重合物）を付着させる等の方法により、所定の厚み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、他の従来法を採用することもできる。
【００３２】
本発明において、金属酸化物の被覆膜厚は、鱗片状基材あるいは金属酸化物を被覆した鱗片状基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、被覆する金属酸化物の密度より求めることができる。また、所定の膜厚となる金属酸化物の量から、添加する所定量の金属塩、有機金属化合物を計算することができる。
【００３３】
本発明において、より透明感を出すためには、各被覆層の金属酸化物の膜厚は、計算値で５０ｎｍ以下であることが好ましい。
【００３４】
鱗片状基材上に二酸化チタン、酸化アルミニウムの順に被覆する場合は、二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、ぎらつき感を低減する点で好ましい。また、これらの金属酸化物の合計の被覆量が（Ａ）成分の１〜５０重量％（以下単に％と記載する）、特には、５〜４０％であるのが好ましい。合計の被覆量が１〜５０％だと、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。
一方、二酸化チタン、酸化アルミニウム、シリカの順に被覆する場合は、二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、特には、０．４２以下であり、合計の被覆量が１〜５０％、特には、５〜４０％であるのが好ましい。また、使用感（きしみ感を低減する）の点から該粉体に対するＳｉＯ₂の被覆量が０．１〜３０％、特には、０．２〜２０％であるのが好ましい。
【００３５】
更に、本発明の（Ａ）成分は、撥水撥油性を持たせ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、金属石けん等の撥水撥油処理剤で処理することが好ましい。また、（Ａ）成分の粉体に特開平１１−４９６３４号公報記載のスフィンゴシン類縁体、ステロール類及び脂肪酸による表面処理を施し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皮膚化粧料を得ることができる。
（Ａ）成分に対する撥水撥油処理剤の処理量は、（Ａ）成分１００重量部に対して０．０５〜２０重量部、特に１〜１０重量部が、十分な撥水撥油性、良好な使用感・耐光性が得られ好ましい。
【００３６】
（Ａ）成分は、本発明の皮膚化粧料中に１〜９０％、特に１０〜８０％、更には２０〜７０％含有するのが使用感（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。
【００３７】
本発明で用いる（Ｂ）成分の粉体は、色差（ΔＥ）が７〜４０のものであって、色差（ΔＥ）は、次法により測定される。まず粉体８mgを黒色人工皮革表面の１０cm×１０cmの部分にとり、スポンジを使用して人工皮革に軽くこするようにして均一に塗布する。これを、例えば変角分光測定計（村上色彩技術研究所製、ＧＣＭＳ−３）を用い、入射光角４５°、受光角−４５°及び−２０°で測色する。このときの２つの干渉色をＣＩＥ１９７６Ｌ^*ａ^*ｂ^*表色系で規定し、入射光角４５°、受光角−４５°のときを（Ｌ_{45, 45} ^*, ａ_{45, 45} ^*, ｂ_{45, 45} ^*）、入射光角４５°、受光角−２０°のときを（Ｌ_{45, 20} ^*, ａ_{45, 20} ^*, ｂ_{45, 20} ^*）とし、これらを用いて次式により色差（ΔＥ）が求められる。
色差（ΔＥ）＝（（Ｌ_{45, 45} ^*−Ｌ_{45, 20} ^*）²＋（ａ_{45, 45} ^*−ａ_{45, 20} ^*）²＋（ｂ_{45, 45} ^*−ｂ_{45, 20} ^*）²）^0.5
なお、このような測定に使用される黒色人工皮革は、同様にして求められる色差（ΔＥ）が７以下のものである。
（Ｂ）成分の色差（ΔＥ）は、肌の色相感覚、透明感等から７〜４０、特に１０〜３５が好ましい。
【００３８】
（Ｂ）成分の平均粒径（測定法：レーザー回折法）は、１２μｍ以下、特に５〜１２μｍのものが、使用感が良好で、かつギラツキ感を低減することができ好ましい。
【００３９】
このような性質を有する（Ｂ）成分は、具体的には金属酸化物粒子で被覆されることにより干渉色を発するものが好ましい。ここで、被覆される母粉体としては、例えば、雲母、板状二酸化チタン、板状酸化鉄、板状アルミナ、板状シリカ、魚鱗箔、オキシ塩化ビスマス等が挙げられ、特に雲母が好ましい。また、母粉体の表面を被覆する金属酸化物としては、例えば二酸化チタン、酸化鉄、酸化ジルコニウム、アルミナ等が挙げられ、これらの１種又は２種以上を組み合わせて使用することができる。特に二酸化チタン、酸化鉄又はこれらの混合物が好ましい。また、二酸化チタンと酸化鉄の混合物を用いて被覆する場合には、二酸化チタンがルチル型であり、スズを含まないのが好ましい。
このような粉体のうち、雲母の表面を二酸化チタン、酸化鉄又はこれらの混合物で被覆したものが好ましい。なお、母粉体を金属酸化物粒子で被覆する方法は、通常の方法に従って行えばよい。
（Ｂ）成分の粉体としては、エンゲルハード社製のフラメンコ サテン（ＦＬＡＭＥＮＣＯ^TM ＳＡＴＩＮ）シリーズの製品を好適に用いることができる。
【００４０】
また、母粉体の表面を被覆する金属酸化物粒子の光学的厚みをコントロールすることにより、様々な色調を作り出すことが可能である。そして、例えば干渉色が青〜紫色系を示す粉体は、肌に透明感を与え、干渉色が緑色系を示す粉体は、くすんだ色にならず、肌の赤みを抑え、干渉色がオレンジ〜赤色系を示す粉体は、肌を健康的に見せ、肌のくすみを隠すことが可能となる。更に、２種以上の粉体を組み合わせて用いることにより、様々な色調を作り出すことも可能である。２種以上の粉体を組み合わせて使用する場合には、混合後の粉体のΔＥが７〜４０であることが好ましい。（Ｂ）成分も、（Ａ）成分と同様に撥水及び／又は撥油化処理して使用することが好ましい。
【００４１】
（Ｂ）成分の含有量は、皮膚化粧料中の０．１％以上、特に２〜８０％であるのが好ましい。更に、化粧水の場合は、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％、粉おしろい、固形おしろい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。
【００４２】
本発明の皮膚化粧料には、上記の必須成分である（Ａ）成分及び（Ｂ）成分以外に、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等を併用してもよい。
これらの粉体は、２種以上を組み合わせて用いることもできる。
【００４３】
本発明の皮膚化粧料は、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、アイブロウ等とすることができる。
【００４４】
【実施例】
（Ａ）成分の製造例：
製造例１
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、二酸化チタン、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の比率）１Ｌに加えて、よく分散させた。これをシリカとして濃度４％の正ケイ酸エチルエタノール溶液２７８ｇを加えて、攪拌しながら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、二酸化チタン、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。
【００４５】
製造例２
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。
【００４６】
製造例３
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、二酸化チタン、酸化アルミニウムで順次被覆されたタルクを得た。
【００４７】
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、二酸化チタン、酸化アルミニウムで順次被覆されたタルクを得た。
【００４８】
実施例１（パウダーファンデーション）
表１及び表２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下記方法に従って実施した結果も表１及び表２に示す。
【００４９】
（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）〜（２２）を８０℃に混合溶解したものを加えて均一混合した。更にこの混合物に成分（２３）を加え混合した後、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。
【００５０】
（評価方法）
パネラー１０名により、顔に試料を塗布したときの使用感（肌へののび、きしみ感のなさ、粉っぽさのなさ、肌上での付着性）と、仕上がり（自然な仕上がり、透明感のある仕上がり、毛穴が目立たない、シミ、ソバカスが目立たない、肌が明るく見える、きめ細かい仕上がり、鏡で見る角度による肌色の違いのなさ、ギラツキ感のなさ）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
【００５１】
【表１】

【００５２】
【表２】

【００５３】
本発明品はいずれも使用感、仕上がりが優れていた。
【００５４】
実施例２（クリーム状ファンデーション）
（組成）
製造例１の無機複合粉体をシリコーン処理したもの ２０．０％
(TiO₂/A1₂0₃(重量比)0.42、被覆量合計28.4％
SiO₂処理量10％、表面反射光量の差13.7
表面反射光量と粉体層反射光量の差-1.2)
疎水化処理紫系パール剤（エンゲルハード社製、FLAMENCO
SATIN violetをシリコーン処理したもの；ΔＥ＝
２７．５） ５．０
シリコーン処理二酸化チタン ５．０
シリコーン処理赤酸化鉄 ０．５
シリコーン処理黄酸化鉄 １．０
シリコーン処理黒酸化鉄 ０．１
精製水 残量
防腐剤 適量
トリエタノールアミン １．２
ソルビット ２．０
ステアリン酸 ５．５
親油型モノステアリン酸グリセリン ２．５
セトステアリルアルコール １．０
モノラウリルプロピレングリコール ３．０
スクワラン ６．０
オリーブ油 ５．０
香料 微量
【００５５】
実施例３（油性ファンデーション）
（組成）
製造例１の無機複合粉体をフッ素処理したもの ２３．０％
(TiO₂/A1₂0₃(重量比)0.42、被覆量合計28.4％
SiO₂処理量10％、表面反射光量の差13.7
表面反射光量と粉体層反射光量の差-1.2)
疎水化処理紫系パール剤（エンゲルハード社製、FLAMENCO
SATIN orangeをシリコーン処理したもの；ΔＥ＝
３１．７） ５．０
フッ素処理二酸化チタン １０．０
フッ素処理赤酸化鉄 １．０
フッ素処理黄酸化鉄 ３．５
フッ素処理黒酸化鉄 ０．５
タルク 残量
流動パラフィン ３５．０
メチルポリシロキサン １０．０
キャンデリラロウ ８．８
オゾケライト １．０
酸化防止剤 適量
香料 微量
【００５６】
実施例４（固形おしろい）
（組成）
製造例１の無機複合粉体をフッ素処理したもの ５０．０％
(TiO₂/A1₂0₃(重量比)0.42、被覆量合計28.4％
SiO₂処理量10％、表面反射光量の差13.7
表面反射光量と粉体層反射光量の差-1.2)
疎水化処理紫系パール剤（エンゲルハード社製、FLAMENCO
SATIN violetをシリコーン処理したもの、及び
エンゲルハード社製、FLAMENCO SATIN Greenをシリコーン
処理したものの等量混合物；ΔＥ＝２６．０） １０．０
ステアリン酸亜鉛 ３．０
フッ素処理硫酸バリウム ９．０
フッ素処理微粒子二酸化チタン ４．０
フッ素処理マイカ ５．０
フッ素処理タルク 残量
フッ素処理二酸化チタン ０．５
フッ素処理赤酸化鉄 ０．１
フッ素処理黄酸化鉄 ０．１
フッ素処理黒酸化鉄 ０．０１
流動パラフィン ６．０
パラメトキシ桂皮酸２−エチルヘキシル ２．７
ミツロウ ２．０
防腐剤 適量
香料 微量
【００５７】
実施例５（ルースタイプフェイスパウダー）
（組成）
製造例１の無機複合粉体をレシチン処理したもの ５５．０％
(TiO₂/A1₂0₃(重量比)0.42、被覆量合計28.4％
SiO₂処理量10％、表面反射光量の差13.5
表面反射光量と粉体層反射光量の差-2.7)
疎水化処理青系パール剤（エンゲルハード社製、FLAMENCO
SATIN blueをシリコーン処理したもの；ΔＥ＝
２６．５） ８．０
シリコーン処理二酸化チタン ０．５
シリコーン処理赤酸化鉄 ０．１
シリコーン処理黄酸化鉄 ０．１
シリコーン処理タルク 残量
シリコーン処理硫酸バリウム ２０．０
メチルポリシロキサン（６cs） １．０
防腐剤 適量
香料 微量
【００５８】
実施例６（アイシャドー）
（組成）
製造例２の無機複合粉体をフッ素処理したもの ３５．０％
(アルミナ処理22.8％、表面反射光量の差10.9
表面反射光量と粉体層反射光量の差-0.4)
疎水化処理青紫系パール剤（エンゲルハード社製、FLAMENCO
SATIN blueをシリコーン処理したもの、及びエンゲルハード
社製、FLAMENCO SATIN violetをシリコーン処理した
ものの等量混合物；ΔＥ＝２４．３） ２０．０
ステアリン酸亜鉛 ２．０
フッ素処理硫酸バリウム ５．０
フッ素処理微粒子二酸化チタン ４．０
シリコーン処理マイカ 残量
シリコーン処理タルク １０．０
シリコーン処理二酸化チタン １．５
シリコーン処理赤酸化鉄 ０．２
シリコーン処理黄酸化鉄 ０．８
シリコーン処理黒酸化鉄 ０．１
スクワラン ５．０
メチルポリシロキサン（６cs） ３．０
マイクロクリスタリンワックス ０．５
防腐剤 適量
香料 微量
【００５９】
実施例７（頬紅）
（組成）
製造例３の無機複合粉体をフッ素処理したもの ３５．０％
(TiO₂/A1₂0₃(重量比)0.29、被覆量合計27.7％
表面反射光量の差9.8
表面反射光量と粉体層反射光量の差0.5)
疎水化処理赤系パール剤（エンゲルハード社製、FLAMENCO
SATIN radをＮ−ラウロイルリジンで処理したもの、
及びエンゲルハード社製、FLAMENCO SATIN orangeをＮ−ラウ
ロイルリジンで処理したものの等量混合物；ΔＥ＝
２０．０） １５．０
ステアリン酸マグネシウム ２．０
フッ素処理硫酸バリウム ５．０
フッ素処理微粒子二酸化チタン ４．０
フッ素処理マイカ 残量
フッ素処理タルク １０．０
フッ素処理二酸化チタン ２．２
赤色２２６号 ０．５
フッ素処理黄酸化鉄 ０．３
フッ素処理黒酸化鉄 ０．１
流動パラフィン ３．０
メチルポリシロキサン（６cs） ３．０
マイクロクリスタリンワックス ０．９
防腐剤 適量
香料 微量
【００６０】
実施例８（口紅）
（組成）
製造例３の無機複合粉体をシリコーン処理したもの １０．０％
(TiO₂/A1₂0₃(重量比)0.29、被覆量合計27.7％
表面反射光量の差9.8
表面反射光量と粉体層反射光量の差0.5)
疎水化処理赤系パール剤（エンゲルハード社製、FLAMENCO
SATIN orangeをシリコーン処理したもの；ΔＥ＝
２７．５） ３．０
二酸化チタン 残量
赤色２０２号 ２．０
黄色５号アルミニウムレーキ １．０
青色１号アルミニウムレーキ ０．１
ヒマシ油 ３４．９
ジカプリン酸ネオペンチルグリコール ２０．０
ラノリン ５．０
液状ラノリン ５．０
ミツロウ ５．０
オゾケライト ４．０
キャンデリラロウ ７．０
カルナウバロウ １．０
酸化防止剤 適量
防腐剤 適量
香料 微量
【００６１】
実施例９（アイライナー）
（組成）
製造例３の無機複合粉体をフッ素処理したもの ２５．０％
(TiO₂/A1₂0₃(重量比)0.29、被覆量合計27.7％
表面反射光量の差9.8
表面反射光量と粉体層反射光量の差0.5)
疎水化処理青系パール剤（エンゲルハード社製、FLAMENCO
SATIN blueをＮ−ラウロイルリジンで処理した
もの；ΔＥ＝３１．９） １０．０
二酸化チタン １．０
カーボンブラック ２．０
カルナウバロウ ５．０
マイクロクリスタリンワックス １０．０
ミツロウ １．０
白色ワセリン １．０
軽質流動イソパラフィン ４４．５
有機ベントナイト ０．５
防腐剤 適量
【００６２】
実施例１０（Ｏ／Ｗ型クリーム）
（組成）
製造例３の無機複合粉体をフッ素処理したもの ２０．０％
(TiO₂/A1₂0₃(重量比)0.29、被覆量合計27.7％
表面反射光量の差9.8
表面反射光量と粉体層反射光量の差0.5)
青紫系パール剤（エンゲルハード社製、FLAMENCO SATIN blue
をシリコーン処理したもの、及びエンゲルハード社製、
FLAMENCO SATIN violetをシリコーン処理したも
のの等量混合物；ΔＥ＝２４．３） ２．０
ミツロウ ３．０
セタノール ２．０
水添ラノリン ５．０
スクワラン ２０．０
脂肪酸グリセリン ３．５
親油型モノステアリン酸グリセリン ２．０
ポリオキシエチレンソルビタンモノラウリル酸エステル
(20E.O.) ２．０
香料 ０．１
防腐剤 ０．２
酸化防止剤 ０．１
プロピレングリコール １０．０
精製水 残量
【００６３】
実施例２〜１０で得られた皮膚化粧料は、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。
【００６４】
【発明の効果】
本発明の皮膚化粧料は、十分なカバー力がありながらも透明感があり、自然な仕上がりで、毛穴やシミ、ソバカスが目立たず、かつ観測方向による色の変化が少なく、肌の色相感覚を変化させることができる。
【図面の簡単な説明】
【図１】表面反射光、粉体層反射光及び基底層反射光を含む、塗膜からの反射光の説明図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a skin cosmetic.
[0002]
[Prior art]
Scale-like powders such as mica, talc and sericite are blended in makeup cosmetics such as powder foundation. These powders have the characteristics of improving the feeling of use such as spreadability, adhesion and smoothness to the skin, and enhancing the finished feeling such as covering power and moist feeling, but these powders have a refractive index of 1. Since it is 7 or less, there is a drawback that the color change (color dullness) is large when wet with sebum or sweat. For this reason, for example, a pearl pigment (see Japanese Patent Publication No. 43-25644) in which mica is coated with titanium dioxide having a high refractive index is used. In this case, silver white, gold, etc. are caused by light interference by the titanium dioxide thin film on the mica surface. The pearly luster is produced. For this reason, the surface reflection light of the powder becomes large, and when it is blended into a cosmetic, the finish is not preferable.
[0003]
In Japanese Patent Laid-Open No. 58-149959, a powder in which a homogeneous mixed layer of silicon dioxide and aluminum oxide in addition to titanium dioxide is used as a metal oxide layer on mica is used. Interference colors such as blue are generated. Further, the surface reflected light of the powder becomes large, and if blended, an unnatural finish is obtained, which is not preferable.
In JP-A-63-254169, a powder in which the surface of the scaly inorganic powder is coated with titanium dioxide and further coated with aluminum oxide is used, but the weight ratio of titanium dioxide and aluminum oxide is used. Is 30:70 to 70:30, and the ratio of titanium dioxide is large, so that the reflected light becomes high.
[0004]
JP-A-6-56628 and JP-A-8-188723 propose cosmetics having a transparent skin-like makeup finish while covering spots, freckles, and the like. As these substrates, flaky extender pigments such as mica are first coated with titanium dioxide or colored pigment titanium dioxide, and a silica layer or a powder that diffuses and reflects light is coated thereon. When coated with layers, the difference in refractive index between titanium dioxide and silica is large and there is strong light reflection at the interface between the two layers, so that sufficient transparency cannot be obtained.
[0005]
Furthermore, conventional makeup cosmetics are applied to change the texture of the skin, so a powder with a strong diffuse reflection is blended to obtain a matte finish, or a powder with a strong specular reflection such as mica is blended. I get a glossy finish. In addition, in order to cover dull skin due to poor blood circulation and aging, etc., pigments with high hiding power such as titanium dioxide and iron oxide are added, or red color such as Bengala, lake pigments and organic pigments is added to the skin hue Changing senses is done. On the other hand, it is possible to change the skin sensation of the skin by using a green pigment, which is a complementary color of red, to conceal red face and red acne scars, or using a blue or purple pigment to give a clear feeling. Has been done. However, when a pigment with high hiding power is used, there is a problem that the natural feeling is lost. In addition, when the principle of complementary colors is used, there is a problem that although the hue can be covered, the saturation is lowered and the skin color is dull. These problems occur because the method is a hue control based on subtractive color mixture, and is caused by the fact that if the colors are overlapped, the saturation is lowered and the color approaches gray. As described above, in the conventional makeup cosmetics, it has been difficult to change the hue sensation of the skin color while providing a transparent feeling.
[0006]
[Problems to be solved by the invention]
An object of the present invention is a skin cosmetic that has sufficient covering power but is transparent, pores, stains and freckles are not noticeable, and there is no color change depending on the observation direction, and the skin hue can be changed. Is to provide.
[0007]
[Means for Solving the Problems]
The present inventor has realized so far by surface interference color when a specific composite inorganic powder (A) having specific surface reflected light characteristics and a powder (B) having a specific color difference (ΔE) are used in combination. A skin cosmetic that can change the skin's hue sensation with a natural finish, pores, stains, and freckles that are difficult to do, yet has deep transparency and a natural finish. I found out that
[0008]
The present invention relates to a sample in which (A) 10 mg of a mixture of composite inorganic powder, talc and squalane (weight ratio 47: 47: 6) is uniformly applied to a 10 cm × 5 cm portion of the surface of black artificial leather. Using a variable angle spectrocolorimeter equipped with an S-polarizing plate or a P-polarizing plate on the light receiving side, respectively, the incident light is measured when the surface reflected light amount and the powder layer reflected light amount under the 2 ° field light receiving condition with C light are measured. The difference in the amount of reflected light on each surface measured under conditions of an angle of 45 ° and a light receiving angle of 45 ° and an incident light angle of 45 ° and a light receiving angle of 0 ° is 7 to 15, and the incident light angle of 45 ° and Composite inorganic powder having a difference between the amount of reflected light on the surface and the amount of reflected light on the powder layer measured at a light receiving angle of 0 °, and (B) 8 mg of powder on a 10 cm × 10 cm portion of the black artificial leather surface For a uniformly coated sample, an incident light angle of 45 ° and a light receiving angle of -4 When colorimetry at ° and ^{-20 °, CIE1976L * a * b} * 2 one interference colors defined by the color system ^{_{(L 45, 45 *, a}} 45, 45 *, b 45, 45 *) and (L _{45, 20} ^* , a _{45, 20} ^* , b _{45, 20} ^* ), the following formula:
Color difference (ΔE) = ((L _{45, 45} ^* -L _{45, 20} ^* ) ² + (a _{45, 45} ^* -a _{45, 20} ^* ) ² + (b _{45, 45} ^* -b _{45, 20} ^* ) ^{2 0.5}
It provides a skin cosmetic containing a powder having a color difference (ΔE) of 7 to 40 determined by the above.
[0009]
In the past, so-called pearl powders have been blended into foundations, etc., giving the pearl unique luster while producing a glaring sensation, resulting in a poor finish, or depending on the observation angle. And the color tone due to interference may change. This is because, in the conventional pearl powder, the interference color is directional with respect to the incident angle of light, is strongly expressed in the vicinity of regular reflection, and is hardly observable in other directions. On the other hand, the powder of the component (B) used in the present invention has little change in color tone depending on the observation angle, and can observe interference colors in a wide range.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, in order to evaluate the optical properties of the composite inorganic powder of component (A), a sample obtained by applying a mixture of the composite inorganic powder, talc and squalane on artificial leather will be described in detail below. Measure the amount of reflected light.
[0011]
That is, a 10 cm × 5 cm polyurethane artificial leather (black artificial leather: OK-7 made by Okamoto, white artificial leather: OK-mat made by Okamoto), and a mixture (weight) of composite inorganic powder, talc and squalane for each artificial leather 10 mg of the ratio 47: 47: 6) is applied, and measurement is performed using a two-dimensional variable angle spectrocolorimeter GCMS-3 manufactured by Murakami Color Research Laboratory under a light receiving condition of 2 ° visual field with C light. Here, talc has an average particle size (measured by laser diffraction method) of 15 to 20 μm, for example, FK-300S (average particle size 17.8 μm, manufactured by Yamaguchi Mica Industry Co., Ltd.), and squalane is a cosmetic grade. For example, Nikkor Squalane (manufactured by Nikko Chemicals Co., Ltd.) is used. As shown in FIG. 1, the reflected light from the coating film includes surface reflected light, powder layer reflected light, and base layer reflected light. Depending on the polarization mode in incident light and light reception, the reflected light component Are different. In measuring, the incident light side and the light receiving side are respectively combined with S polarizing plates or P polarizing plates, and from the measured values obtained with black artificial leather and the measured values obtained with white artificial leather, the surface reflected light amount, The body layer reflected light amount and the base layer reflected light amount can be calculated respectively.
[0012]
Using black artificial leather, the value measured with the S polarizing plate on the incident light side and the S polarizing plate on the light receiving side was measured, and the value measured with the S polarizing plate on the incident light side and the P polarizing plate on the light receiving side was measured. Is Bsp, the value measured with the P polarizing plate on the incident light side and the S polarizing plate on the light receiving side is Bps, and the value measured with the P polarizing plate on the incident light side and the P polarizing plate on the light receiving side is Bpp. . Similarly, when white artificial leather is used, Wss, Wsp, Wps and Wpp are used. Each measurement value includes tristimulus values X, Y, and Z in the XYZ color system, and can be measured as individual numerical values.
From each measured value, the surface reflected light S _B is
[0013]
[Expression 1]

[0014]
It is represented by The powder layer reflected light D _f is
[0015]
[Expression 2]

[0016]
It is represented by The base layer reflected light _Db is
[0017]
[Equation 3]

[0018]
It is represented by From these, the surface reflected light amount Y (S _B ) is
[0019]
[Expression 4]

[0020]
The powder layer reflected light amount Y (D _f ) is
[0021]
[Equation 5]

[0022]
The base layer reflected light amount Y (D _b ) is
[0023]
[Formula 6]

[0024]
It is represented by Here, Y (Bsp), Y (Bps), etc. indicate the Y values of Bsp and Bps, respectively.
[0025]
As a light source to be used, C light which is a daylight source is used, and a light receiving field is set to 2 °.
Measurement is performed with the incident angle constant at 45 °, the light receiving angle in increments of 5 ° from 0 ° to 90 °, and the incident angle is 45 ° / light receiving angle is 45 ° with the largest difference in the amount of reflected light. Attention is paid to the measured value under the condition of angle 45 ° / light receiving angle 0 °.
[0026]
The first requirement for the component (A) of the present invention is that the difference in the amount of reflected light on each surface under these conditions is 7 to 15. If the “difference in the amount of reflected light from the surface” is greater than 15, the face appears too glossy, while if it is less than 7, the face appears to be dark and dull with less gloss.
[0027]
Furthermore, the difference between the surface reflected light amount and the powder layer reflected light amount is -3 to 3 based on the measured value under the condition of 45 ° incident angle / 0 ° light receiving angle, in which the difference between the surface reflected light amount and the powder layer reflected light amount is easily understood. That is the second requirement. If the “difference between the reflected light amount on the surface and the reflected light amount on the powder layer” is greater than 3, the face appears too glossy, and if it is smaller than −3, the face becomes whitish.
[0028]
The composite inorganic powder of the component (A) used in the present invention is designed so as to have other optical oxides on a scaly substrate and to have the above optical characteristics. The scaly substrate preferably has an average particle diameter of 2 to 20 μm and a thickness of 0.05 to 1 μm. Such scale-like substrates include mica, sericite, talc, kaolin, smectite clay minerals, synthetic mica, synthetic sericite, plate-like titanium dioxide, plate-like silica, plate-like aluminum oxide, boron nitride, barium sulfate, Examples thereof include plate-like titania / silica composite oxide, and talc is particularly preferable from the viewpoint of usability.
[0029]
As metal oxides to be compounded with these scaly substrates, titanium dioxide (TiO ₂ ), iron oxide (Fe ₂ O ₃ ), cerium oxide (CeO ₂ ), zinc oxide (ZnO), silica (SiO ₂ ), Examples include magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), calcium oxide (CaO), and zirconium oxide (ZrO ₂ ). In particular, titanium dioxide, aluminum oxide, and silica are preferable in terms of refractive index.
[0030]
In the composite inorganic powder of component (A) used in the present invention, 1 to 3 types of metal oxides having different refractive indexes selected from the metal oxides are added to the scale-like substrate from the higher refractive index. It is prepared by coating sequentially. What is necessary is just to select the said metal oxide by the cover force requested | required of (A) component. In order to obtain a powder having a high covering power, it is preferable to coat the first layer with a metal oxide having a high refractive index, such as titanium dioxide. On the other hand, in order to obtain a powder with low covering power, it is preferable to coat the first layer with a metal oxide having a medium refractive index, such as aluminum oxide.
Next, if necessary, the second layer or more is formed, but the second layer or more is a metal oxide having a refractive index smaller than that of the first layer in order to suppress the reflection of light and to give a transparent feeling. Is desirable.
[0031]
The metal oxide coating method includes hydrolyzing a predetermined amount of a metal salt which is a precursor of the metal oxide selected as described above, or similarly hydrolyzing a predetermined amount of an organometallic compound in an alcohol solvent. Conventionally known methods such as a method of depositing on a scale-like substrate to be coated with a hydrolyzate or a composite powder on which a coating layer is formed can be employed.
For example, dispersing a scaly base material in water, adding a predetermined amount of a metal salt such as titanyl sulfate, hydrolyzing in an alkaline atmosphere, and depositing a metal salt hydrolyzate on the surface of the scaly base material Thus, a titanium dioxide coating layer having a predetermined thickness can be obtained.
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 a dispersion of a scaly substrate having a coating layer having a higher refractive index than silica, A silica coating layer having a predetermined thickness is added by a method such as adding an acid or alkali to the surface of the scaly substrate on which the coating layer is formed, if necessary, and attaching a silicic acid polymer (hydrolyzed condensation polymer). Can be formed. In order to form a silica coating layer, other conventional methods may be employed.
[0032]
In the present invention, the coating thickness of the metal oxide covers the geometric surface area of the flaky substrate or the flaky substrate coated with the metal oxide, or the specific surface area measured by a nitrogen adsorption method or the like. It can obtain | require from the density of a metal oxide. Further, a predetermined amount of metal salt or organometallic compound to be added can be calculated from the amount of metal oxide having a predetermined film thickness.
[0033]
In the present invention, in order to obtain a more transparent feeling, the thickness of the metal oxide of each coating layer is preferably 50 nm or less as a calculated value.
[0034]
When coating on a scaly substrate in the order of titanium dioxide and aluminum oxide, the amount of coating of titanium dioxide and aluminum oxide is 0.42 or less in terms of the weight ratio of TiO ₂ / Al ₂ O ₃ . It is preferable at the point which reduces. The total coating amount of these metal oxides is preferably 1 to 50% by weight (hereinafter simply referred to as “%”) of the component (A), particularly 5 to 40%. When the total coating amount is 1 to 50%, it is possible to impart an effect of making the feeling of use good and making pores inconspicuous while maintaining transparency.
On the other hand, when coating is performed in the order of titanium dioxide, aluminum oxide, and silica, the coating amount of titanium dioxide and aluminum oxide is 0.62 or less in weight ratio of TiO ₂ / Al ₂ O ₃ , especially 0.42 or less. The total coating amount is preferably 1 to 50%, particularly 5 to 40%. From the viewpoint of feeling of use (reducing squeaky feeling), the coating amount of SiO _{2 on} the powder is preferably 0.1 to 30%, particularly preferably 0.2 to 20%.
[0035]
Furthermore, the component (A) of the present invention is preferably treated with a water / oil repellent treatment agent such as silicone, fluorine compound, lecithin, amino acid, polyethylene, metal soap, etc. in order to impart water / oil repellency. Moreover, when the powder of component (A) is subjected to surface treatment with sphingosine analogs, sterols and fatty acids described in JP-A No. 11-49634, and blended in the formulation, the transparency is improved, and smooth spreading It is possible to obtain a skin cosmetic that has a moist feeling and little skin irritation.
The processing amount of the water / oil repellent treatment agent with respect to the component (A) is 0.05 to 20 parts by weight, particularly 1 to 10 parts by weight with respect to 100 parts by weight of the component (A). A good feeling of use and light resistance are obtained, which is preferable.
[0036]
Component (A) is contained in the skin cosmetic of the present invention in an amount of 1 to 90%, particularly 10 to 80%, and more preferably 20 to 70%. From the viewpoint of pore concealing properties and the like.
[0037]
The powder of component (B) used in the present invention has a color difference (ΔE) of 7 to 40, and the color difference (ΔE) is measured by the following method. First, 8 mg of the powder is taken on a 10 cm × 10 cm portion of the surface of the black artificial leather, and uniformly applied by lightly rubbing the artificial leather using a sponge. This is measured using, for example, a variable angle spectrometer (GCMS-3, manufactured by Murakami Color Research Laboratory) at an incident light angle of 45 °, a light receiving angle of −45 °, and −20 °. The two interference colors at this time are defined by the CIE 1976 L ^* a ^* b ^* color system, and when the incident light angle is 45 ° and the light receiving angle is −45 ° (L _{45, 45} ^* , a _{45, 45} ^* , b _{45). , 45} ^* ), when the incident light angle is 45 ° and the light receiving angle is −20 °, (L _{45, 20} ^* , a _{45, 20} ^* , b _{45, 20} ^* ) are used, and the color difference (ΔE ) Is required.
Color difference (ΔE) = ((L _{45, 45} ^* -L _{45, 20} ^* ) ² + (a _{45, 45} ^* -a _{45, 20} ^* ) ² + (b _{45, 45} ^* -b _{45, 20} ^* ) ^{2 0.5}
In addition, the black artificial leather used for such a measurement has a color difference (ΔE) obtained in the same manner of 7 or less.
The color difference (ΔE) of the component (B) is preferably 7 to 40, more preferably 10 to 35 from the viewpoint of skin hue, transparency, and the like.
[0038]
The average particle size (measurement method: laser diffraction method) of the component (B) is preferably 12 μm or less, and particularly preferably 5 to 12 μm, because the feeling in use is good and the glare is reduced.
[0039]
Specifically, the component (B) having such properties preferably emits an interference color when coated with metal oxide particles. Here, examples of the mother powder to be coated include mica, plate-like titanium dioxide, plate-like iron oxide, plate-like alumina, plate-like silica, fish scale foil, and bismuth oxychloride, and mica is particularly preferable. Examples of the metal oxide that covers the surface of the mother powder include titanium dioxide, iron oxide, zirconium oxide, and alumina. These can be used alone or in combination. Particularly preferred is titanium dioxide, iron oxide or a mixture thereof. Moreover, when coat | covering using the mixture of titanium dioxide and iron oxide, it is preferable that titanium dioxide is a rutile type and does not contain tin.
Among such powders, those in which the surface of mica is coated with titanium dioxide, iron oxide, or a mixture thereof are preferable. In addition, what is necessary is just to perform the method of coat | covering mother powder with a metal oxide particle according to a normal method.
The powder of the component (B) can be used Engelhard Corporation Flamenco Satin products (FLAMENCO ^TM SATIN) Series favorably.
[0040]
In addition, various color tones can be created by controlling the optical thickness of the metal oxide particles covering the surface of the mother powder. For example, a powder whose interference color is blue to purple gives a transparent feeling to the skin, and a powder whose interference color is green does not become dull, suppresses redness of the skin, The powder showing orange to red can make the skin look healthy and hide the dullness of the skin. Furthermore, it is also possible to produce various color tones by using a combination of two or more powders. When two or more kinds of powders are used in combination, it is preferable that ΔE of the powder after mixing is 7 to 40. The component (B) is also preferably used after being subjected to water and / or oil repellency treatment in the same manner as the component (A).
[0041]
The content of the component (B) is preferably 0.1% or more, particularly 2 to 80% in the skin cosmetic. Furthermore, in the case of lotion, it is preferable to mix 0.1 to 10%, particularly 0.5 to 5%, and in the case of emulsions and creams, 0.1 to 10%, particularly 0.5 to 7%, 0.1 to 80%, especially 1 to 50% in the case of powder, solid and face powder, 0.1 to 80%, especially 1 to 25% in the case of powder foundation and oily foundation, creamy foundation, liquid 0.1-10% for foundations and concealers, especially 0.5-7%, 0.1-20% for lipsticks and lip balms, especially 0.5-10%, for blushers and eye shadows 0.1 to 40%, particularly 0.5 to 25%, and in the case of eyeliner and eyebrow, 0.1 to 30%, particularly 0.5 to 20%, is preferable.
[0042]
In the skin cosmetic of the present invention, in addition to the essential components (A) and (B), inorganic materials such as silicic acid, silicic anhydride, magnesium silicate, talc, sericite, mica, kaolin, etc. You may use together organic powders, such as powder, polyamide, polyester, a polypropylene, a polystyrene, a polyurethane, or an organic tar type pigment | dye.
These powders can be used in combination of two or more.
[0043]
The skin cosmetic of the present invention can be produced in accordance with a conventional method except that the powder as the essential component described above is blended. For example, basic cosmetics such as skin lotion, milky lotion, cream, etc .; powder foundation, powder powder, solid Interesting, face powder, oily foundation, creamy foundation, liquid foundation, concealer, lipstick, lip balm, eye shadow, blusher, eyeliner, eyebrow, etc.
[0044]
【Example】
Example of production of component (A):
Production Example 1
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 calcined at 600 ° C. for 5 hours to obtain talc coated with titanium dioxide and aluminum oxide in this order. Further, 100 g of this was weighed and added to 1 L of a mixed solvent of ethanol and water (ratio of 7: 3) and well dispersed. 278 g of a 4% concentration ethyl silicate ethanol solution was added as silica and heated to 50 ° C. with stirring for about 10 hours. Next, this was cooled, filtered, sufficiently washed with ethanol and pure water, and then dried at 110 ° C. to obtain talc coated sequentially with titanium dioxide, aluminum oxide, and silica.
[0045]
Production Example 2
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.
[0046]
Production Example 3
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 calcined at 600 ° C. for 5 hours to obtain talc coated with titanium dioxide and aluminum oxide in this order.
[0047]
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 calcined at 600 ° C. for 5 hours to obtain talc coated with titanium dioxide and aluminum oxide in this order.
[0048]
Example 1 (powder foundation)
Powder foundations having the compositions shown in Table 1 and Table 2 were produced according to the following production method. In addition, Tables 1 and 2 also show the results of evaluating the use of these foundations according to the following method.
[0049]
(Production Method) Components (1) to (17) were mixed and pulverized with a pulverizer. This was transferred to a high-speed blender, and components (18) to (22) mixed and dissolved at 80 ° C. were added and mixed uniformly. Further, the component (23) was added to the mixture and mixed, and then pulverized again and passed through a sieve. This was compression molded into a metal pan.
[0050]
(Evaluation methods)
10 panelists gave us a feeling of use when the sample was applied to the face (no skin spread, no squeaky feeling, no powderiness, no adhesion on the skin) and finish (natural finish, transparency) Sensory evaluation on the following criteria: No. did.
Judgment criteria ◎: 8 or more responded good ○: 5-7 answered good △: 2-4 answered good ×: 1 or less answered good
[Table 1]

[0052]
[Table 2]

[0053]
All of the products of the present invention were excellent in feeling of use and finish.
[0054]
Example 2 (Cream Foundation)
(composition)
Silicone-treated inorganic composite powder of Production Example 1 20.0%
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.42, total coverage 28.4%
SiO ₂ treatment amount 10%, surface reflected light difference 13.7
(Difference between surface reflected light amount and powder layer reflected light amount -1.2)
Hydrophobic-purified purple pearl agent (manufactured by Engelhard, FLAMENCO
SATIN violet treated with silicone; ΔE =
27.5) 5.0
Silicone-treated titanium dioxide 5.0
Silicone-treated red iron oxide 0.5
Silicone-treated yellow iron oxide 1.0
Silicone-treated black iron oxide 0.1
Purified water Residual amount of preservative Appropriate amount Triethanolamine 1.2
Sorbit 2.0
Stearic acid 5.5
Lipophilic glyceryl monostearate 2.5
Cetostearyl alcohol 1.0
Monolauryl propylene glycol 3.0
Squalane 6.0
Olive oil 5.0
Perfume Trace [0055]
Example 3 (oil-based foundation)
(composition)
Fluorine-treated inorganic composite powder of Production Example 1 23.0%
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.42, total coverage 28.4%
SiO ₂ treatment amount 10%, surface reflected light difference 13.7
(Difference between surface reflected light amount and powder layer reflected light amount -1.2)
Hydrophobic-purified purple pearl agent (manufactured by Engelhard, FLAMENCO
SATIN orange treated with silicone; ΔE =
31.7) 5.0
Fluorine-treated titanium dioxide 10.0
Fluorine-treated red iron oxide 1.0
Fluorine-treated yellow iron oxide 3.5
Fluorine-treated black iron oxide 0.5
Talc remaining liquid paraffin 35.0
Methyl polysiloxane 10.0
Candelilla Row 8.8
Ozokerite 1.0
Antioxidant Appropriate amount perfume Trace amount [0056]
Example 4 (Solid white)
(composition)
Fluorine-treated inorganic composite powder of Production Example 1 50.0%
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.42, total coverage 28.4%
SiO ₂ treatment amount 10%, surface reflected light difference 13.7
(Difference between surface reflected light amount and powder layer reflected light amount -1.2)
Hydrophobic-purified purple pearl agent (manufactured by Engelhard, FLAMENCO
SATIN violet silicone-treated and Engelhard's FLAMENCO SATIN Green silicone-equivalent mixture; ΔE = 26.0) 10.0
Zinc stearate 3.0
Fluorine-treated barium sulfate 9.0
Fluorine-treated fine particle titanium dioxide 4.0
Fluorine-treated mica 5.0
Fluorine-treated talc Remaining fluorine-treated titanium dioxide 0.5
Fluorine-treated red iron oxide 0.1
Fluorine-treated yellow iron oxide 0.1
Fluorine-treated black iron oxide 0.01
Liquid paraffin 6.0
2-Ethylhexyl paramethoxycinnamate 2.7
Beeswax 2.0
Preservative Suitable amount perfume Trace amount [0057]
Example 5 (loose type face powder)
(composition)
55.0% of the lecithin-treated inorganic composite powder of Production Example 1
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.42, total coverage 28.4%
SiO ₂ treatment amount 10%, surface reflected light difference 13.5
(Difference between surface reflected light amount and powder layer reflected light amount -2.7)
Hydrophobic blue pearlescent agent (manufactured by Engelhard, FLAMENCO
SATIN blue treated with silicone; ΔE =
26.5) 8.0
Silicone-treated titanium dioxide 0.5
Silicone-treated red iron oxide 0.1
Silicone-treated yellow iron oxide 0.1
Silicone-treated talc Remaining silicone-treated barium sulfate 20.0
Methyl polysiloxane (6cs) 1.0
Preservative, proper amount of fragrance, trace amount [0058]
Example 6 (Eye Shadow)
(composition)
Fluorine-treated inorganic composite powder of Production Example 2 35.0%
(Alumina treatment 22.8%, surface reflected light difference 10.9
(Difference between surface reflected light amount and powder layer reflected light amount -0.4)
Hydrophobic blue-purple pearl agent (manufactured by Engelhard, FLAMENCO
SATIN blue silicone-treated, and Engelhard's FLAMENCO SATIN violet silicone-treated equivalent mixture: ΔE = 24.3) 20.0
Zinc stearate 2.0
Fluorine-treated barium sulfate 5.0
Fluorine-treated fine particle titanium dioxide 4.0
Silicone-treated mica Remaining silicone-treated talc 10.0
Silicone-treated titanium dioxide 1.5
Silicone-treated red iron oxide 0.2
Silicone-treated yellow iron oxide 0.8
Silicone-treated black iron oxide 0.1
Squalane 5.0
Methyl polysiloxane (6cs) 3.0
Microcrystalline wax 0.5
Preservative, proper amount of fragrance, trace amount [0059]
Example 7 (blusher)
(composition)
Fluorine-treated inorganic composite powder of Production Example 3 35.0%
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.29, total coating amount 27.7%
Difference in surface reflected light 9.8
(Difference between surface reflected light amount and powder layer reflected light amount 0.5)
Hydrophobic treated red pearl agent (manufactured by Engelhard, FLAMENCO
SATIN rad treated with N-lauroyllysine,
And Engelhard, FLAMENCO SATIN orange treated with N-lauroyl lysine;
20.0) 15.0
Magnesium stearate 2.0
Fluorine-treated barium sulfate 5.0
Fluorine-treated fine particle titanium dioxide 4.0
Fluorine treatment mica Remaining fluorine treatment talc 10.0
Fluorine-treated titanium dioxide 2.2
Red 226 0.5
Fluorine-treated yellow iron oxide 0.3
Fluorine-treated black iron oxide 0.1
Liquid paraffin 3.0
Methyl polysiloxane (6cs) 3.0
Microcrystalline wax 0.9
Preservative, proper amount of fragrance, trace amount [0060]
Example 8 (lipstick)
(composition)
Silicone-treated inorganic composite powder of Production Example 3 10.0%
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.29, total coating amount 27.7%
Difference in surface reflected light 9.8
(Difference between surface reflected light amount and powder layer reflected light amount 0.5)
Hydrophobic treated red pearl agent (manufactured by Engelhard, FLAMENCO
SATIN orange treated with silicone; ΔE =
27.5) 3.0
Titanium dioxide remaining red 202 No. 2.0
Yellow No. 5 aluminum lake 1.0
Blue No. 1 aluminum lake 0.1
Castor oil 34.9
Neopentyl glycol dicaprate 20.0
Lanolin 5.0
Liquid lanolin 5.0
Beeswax 5.0
Ozokerite 4.0
Candelilla Row 7.0
Carnauba 1.0
Antioxidant Appropriate amount Preservative Appropriate amount perfume Small amount [0061]
Example 9 (eyeliner)
(composition)
Fluorine-treated inorganic composite powder of Production Example 3 25.0%
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.29, total coating amount 27.7%
Difference in surface reflected light 9.8
(Difference between surface reflected light amount and powder layer reflected light amount 0.5)
Hydrophobic blue pearlescent agent (manufactured by Engelhard, FLAMENCO
SATIN blue treated with N-lauroyllysine; ΔE = 31.9) 10.0
Titanium dioxide 1.0
Carbon black 2.0
Carnauba Arrow 5.0
Microcrystalline wax 10.0
Beeswax 1.0
White petrolatum 1.0
Light liquid isoparaffin 44.5
Organic bentonite 0.5
Preservative appropriate amount [0062]
Example 10 (O / W type cream)
(composition)
Fluorine-treated inorganic composite powder of Production Example 3 20.0%
(TiO ₂ / A1 ₂ 0 ₃ (weight ratio) 0.29, total coating amount 27.7%
Difference in surface reflected light 9.8
(Difference between surface reflected light amount and powder layer reflected light amount 0.5)
Blue-purple pearl agent (FLAMENCO SATIN blue, manufactured by Engelhard)
Made with silicone, and manufactured by Engelhard,
Equal volume mixture of FLAMENCO SATIN violet treated with silicone; ΔE = 24.3) 2.0
Beeswax 3.0
Cetanol 2.0
Hydrogenated lanolin 5.0
Squalane 20.0
Fatty acid glycerin 3.5
Lipophilic glyceryl monostearate 2.0
Polyoxyethylene sorbitan monolaurate
(20E.O.) 2.0
Fragrance 0.1
Preservative 0.2
Antioxidant 0.1
Propylene glycol 10.0
Purified water remaining amount [0063]
The skin cosmetics obtained in Examples 2 to 10 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.
[0064]
【The invention's effect】
The skin cosmetic of the present invention has a clear feeling while having sufficient covering power, has a natural finish, does not notice pores, spots and freckles, has little color change depending on the observation direction, and has a skin hue sensation. Can be changed.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of reflected light from a coating film including surface reflected light, powder layer reflected light, and base layer reflected light.

Claims (2)

Next (A) component and (B) component:
(A) (a1) A composite inorganic powder having a scaly substrate coated with titanium dioxide and aluminum oxide in this order, and having a weight ratio (TiO ₂ / Al ₂ O ₃ ) of 0.42 or less, or
(a2) A scaly substrate is coated with titanium dioxide, aluminum oxide, and silica in that order, and the weight ratio of titanium dioxide to aluminum oxide (TiO ₂ / Al ₂ O ₃ ) is 0.62 or less, and SiO ₂ is a composite inorganic powder having a coating amount of 0.1 to 30% by weight,
For a sample in which 10 mg of a mixture of composite inorganic powder and talc and squalane (weight ratio 47: 47: 6) is uniformly applied to a 10 cm × 5 cm portion of the surface of black artificial leather, S polarizing plates are respectively provided on the incident light side and the light receiving side. Alternatively, using a variable angle spectrocolorimeter equipped with a P-polarizing plate, when the surface reflected light amount and the powder layer reflected light amount under the light receiving condition of 2 ° field of view with C light are measured, the incident light angle is 45 ° and the light receiving angle is 45. The difference in the amount of reflected light on each surface measured under the condition of ° and the incident light angle of 45 ° and the light receiving angle of 0 ° is 7 to 15, and the difference is measured at the incident light angle of 45 ° and the light receiving angle of 0 °. The difference between the reflected light amount on the surface and the reflected light amount on the powder layer is −3 to 3 ,
A composite inorganic powder in which the total coating amount of the metal oxide is 1 to 50% by weight of the component (A) ;
(B) A sample having an average particle diameter of 5 to 12 μm, in which the surface of mica is coated with a mixture of titanium oxide and iron oxide, and 8 mg of the powder is uniformly applied to a 10 cm × 10 cm portion of the black artificial leather surface When the color is measured at an incident light angle of 45 °, a light receiving angle of −45 ° and −20 °, two interference colors defined by the CIE 1976 L ^* a ^* b ^* color system (L _45,45 ^* , a _{45, 45} ^* , b _45,45 ^* ) and (L _45,20 ^* , a _45,20 ^* , b _45,20 ^* ), the following formula:
Color difference (ΔE) = [(L _45,45 ^* −L _45,20 ^* ) ² + (a _45,45 ^* −a _45,20 ^* ) ² + (b _45,45 ^* −b _45,20 ^* ) ² ] ^0.5
A skin cosmetic containing a powder having a color difference (ΔE) of 7 to 40 determined by the above.   The skin cosmetic according to claim 1, wherein the scaly substrate of component (A) is talc.

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