JP4651883B2 - Skin cosmetics containing spherical porous crosslinked polymer particles - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、ソフトで滑らかな使用感、持続する使用後のさっぱり感、優れた伸展性と透明感を有するクリーム、ゲル、ローション、乳液、軟膏などの皮膚化粧料に関する。
【０００２】
【従来の技術】
従来、皮膚化粧料は油脂、ロウ、炭化水素等の油性基材、溶剤、粉末、顔料、可塑剤等を配合することにより製造されおり、更に伸展性やソフト感を与えるために球状微粒子が配合されている。
また、使用後、皮膚から分泌される皮脂や汗により起こる化粧くずれを防ぎ、さっぱり感を持続させるために球状多孔性樹脂粉体を配合する化粧料が提案されている（特開昭５７−９８２０５号）。
さらに、内部多孔性網状組織を有する微粉末を医薬や化粧料に配合して有効成分を微粒子細孔内に保持させ、局所で少しずつ放出させる、いわゆる徐放性組成物も提案されている（特開平１−１３１１２号）。
【０００３】
【発明が解決しようとする課題】
これら球状多孔性樹脂粉末を使用する技術においては、粒子が硬く、皮膚化粧料の生命である使用時の滑らかさやソフト感に欠ける。また、粒子の細孔径が小さすぎ、皮脂や汗の吸収が遅く且つ吸収量が少ないので、使用後のさっぱり感も充分ではない。さらに細孔径が小さいと孔内に有効成分を吸入させるために減圧下で撹拌するなどの工程を繰り返す必要があり、工程と時間がかかるためコスト面で不利であり、さらに一度吸収させた有効成分が放出されるのに時間がかかりすぎるため、皮膚用製品、例えば塗布薬、ゲル、ローション、乳液、軟膏などの用途には適当でない。
したがって、よりソフトで滑らかな使用感、より持続性のあるさっぱり感を有する皮膚化粧料が望まれていた。
【０００４】
【課題を解決するための手段】
本発明者らは上記事情に鑑み、種々検討の結果、架橋密度が３〜１５重量％、平均粒子径が３〜１５μｍ、全孔容積が０．０１〜０．５０ｃｃ／ｇ、表面積が５〜５０ｍ２／ｇ、平均孔径が０．１〜２．０μｍの球状多孔性架橋ポリマー粒子を３〜３０重量％配合することにより、前述のすべての課題が解決されることをつきとめ、本発明を完成した。すなわち、本発明は、（１）アルキル（メタ）アクリレート（ａ）５０〜９９．９重量部、分子内に２個以上のビニル基を有する多官能性モノマー（ｂ）３〜１５重量部、およびその他の共重合性モノマー（ｃ）０〜４９．９重量部からなるモノマー混合物を多孔質化剤の存在下に共重合するにより得られ、架橋密度５〜１３重量％、平均粒子径３〜１５μｍ、全孔容積０．０１〜０．５０ｃｃ／ｇ、表面積５〜５０ｍ２／ｇおよび平均孔径０．０１〜２．０μｍの球状多孔性架橋ポリマー粒子を３〜３０重量％含有する皮膚化粧料、である。
【０００５】
【発明の実施の形態】
本発明における球状多孔性架橋ポリマー粒子を配合する皮膚化粧料としては、例えばクリーム、ゲル、ローション、乳液、軟膏などの形態が挙げられる。
本発明における球状多孔性架橋ポリマー粒子は、たとえばアルキル（メタ）アクリレート（ａ）５０〜９９．９重量部、分子内に２個以上のビニル基を有する多官能性モノマー（ｂ）３〜１５重量部及びその他の共重合性モノマー（ｃ）０〜４９．９重量部からなるモノマー混合物を多孔質化剤の存在下に共重合することにより得ることができる。
前記のアルキル（メタ）アクリレート（ａ）としては、たとえばメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソノニル（メタ）アクリレート等アルキル基の炭素数が１〜１０の物が挙げられる。
【０００６】
分子内に２個以上のビニル基を有する多官能性モノマー（ｂ）としては、ジビニルベンゼン等の芳香族ジビニルモノマー、エチレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等のアルカンポリオールポリ（メタ）アクリレート、アリル（メタ）アクリレート、ジアリルイタコネート等の異なる反応性のビニル基を有するモノマー、その他に、ウレタンジ（メタ）アクリレート、エポキシ（メタ）アクリレート等が挙げられる。
【０００７】
その他の共重合性モノマー（ｃ）としては、スチレン、ビニルトルエン、α−メチルスチレン等の芳香族ビニル化合物、芳香族ビニリデン、アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物、シアン化ビニリデン、ウレタン（メタ）アクリレート等分子内にビニル基１個を有する共重合性モノマーが挙げられる。また、官能基を持ったモノマー、たとえば、グリシジルメタクリレート等のエポキシ基を持つモノマー、アクリル酸、メタクリル酸、マレイン酸、イタコン酸等のカルボキシル基を持つモノマー、２−ヒドロキシエチル（メタ）アクリレート等の水酸基を持つモノマー、ジエチルアミノエチル（メタ）アクリレート等のアミノ基を持つ共重合性モノマー等も用いることができる。
本発明における球状多孔質架橋ポリマー粒子の合成方法は、乳化重合、懸濁重合、分散重合等の方法が用いられ、好ましくは、懸濁重合を行う。
懸濁重合は、先に述べたモノマー混合物、分散安定剤、界面活性剤、油溶性ラジカル重合開始剤、多孔質化剤等を用いて行われる。油溶性のラジカル重合開始剤及び多孔質化剤は、先に述べたモノマー混合物に予め溶解または、分散させておくことが望ましい。
【０００８】
分散安定剤としては、ゼラチン、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース、ポリエチレングリコール、ポリアクリルアミド、ポリアクリル酸、ポリアクリル酸塩、アルギン酸ナトリウム、ポリビニルアルコールの部分ケン化物等の水溶性高分子、リン酸三カルシウム、酸化チタン、炭酸カルシウム、二酸化珪素等の無機物などが用いられる。また、これらの分散安定剤は、一種類または二種類以上使用できる。
【０００９】
界面活性剤としては、ドデシルベンゼンスルホン酸ナトリウム、ジアルキルスルホコハク酸エステルナトリウム、ラウリル硫酸ナトリウム等のアニオン界面活性剤、ポリエチレングリコールノニルフェニルエーテル等のノニオン界面活性剤等が用いられる。また、これらの界面活性剤は、一種類または二種類以上使用できる。
【００１０】
油溶性ラジカル重合開始剤としては、ベンゾイルパーオキサイド、ο−メトキシベンゾイルパーオキサイド、ο−クロロベンゾイルパーオキサイド、ラウロイルパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−２，４−ジメチルバレロニトリル等のアゾ系化合物等が用いられる。また、これらの油溶性ラジカル重合開始剤は、一種類または二種類以上使用できる。
【００１１】
多孔質化剤はポロゲンとも称され、ポリマー粒子合成の際、粒子を多孔質化する材料をいうが、いくつかのタイプのものが知られている（特開平１−１３１１１２号）。その１つは、たとえばトルエン、イソオクタン、メチルイソブチルケトン等の先に述べたモノマー混合物と混和し、その重合後のポリマーとは混和しない溶剤である。この場合、用いた多孔質化剤は、粒子の乾燥工程によって取り除き、該溶剤が除去された部分が細孔となる。また、別のタイプの多孔質化剤として、炭酸カルシウム、リン酸三カルシウム等の強酸によって溶解する無機物が挙げられる。この場合、用いた多孔質化剤は、重合終了後の粒子を精製する工程で強酸によって溶解させる事によって取り除き、その溶解して取り除かれた部分が細孔となる。更に、別のタイプの多孔質化剤として、先に述べたモノマー混合物に溶解する直鎖状のポリマーが挙げられる。この場合、先に述べたモノマー混合物が重合を進めていく過程において、溶解させておいた直鎖状のポリマーと相分離を起こし、粒子が多孔質化する。用いられる直鎖状のポリマーの種類は特に制限はないが、ポリマーの種類により、細孔の形や大きさが異なってくる。本発明に用いられる球状多孔性架橋ポリマー粒子を得る方法は、上記の方法に限定されないし、一種類または二種類以上を併用してもかまわない。
多孔質化剤の使用量は、モノマー混合物１００重量部に対し通常１０〜２００重量部、好ましくは３０〜１５０重量部程度である。この範囲より少ないと全孔容積、表面積が少なくなり、平均孔径も小さくなる。またこの範囲より多いと、平均孔径が、大きくなりすぎて、細孔形成が困難となる。
【００１２】
本発明に用いられる球状多孔性架橋ポリマー粒子の平均粒子径は通常３〜１５μｍ、好ましくは５〜１２μｍの範囲である。平均粒子径が上記範囲より小さい場合には、伸展性が十分でなく、大きい場合には、皮膚に塗布したときにザラツキ感が出るので好ましくない。
【００１３】
架橋密度は通常３〜１５重量％、好ましくは５〜１３重量％であり、架橋密度が上記範囲よりも小さい場合には粒子の孔質状態が維持できなくなることがあり、大きい場合には化粧料の使用時にソフトな感触が得られない。尚、架橋密度（重量％）は、モノマー（ｂ）の重量をモノマー（ａ）、（ｂ）および（ｃ）の合計重量で除した値に１００を乗じたものである。
【００１４】
全孔容積は通常０．０１〜０．５０ｃｃ／ｇ、好ましくは０．０５〜０．４０ｃｃ／ｇ、表面積は通常５〜５０ｍ２／ｇ、好ましくは１０〜４０ｍ２／ｇ、平均孔径は通常０．０１〜２．０μｍ、好ましくは０．１〜１．８μｍの範囲である。平均孔径が０．０１μｍ以下の場合、皮脂や汗の吸収速度が遅く、また細孔内に有効成分を吸入させるためには減圧下で撹拌するなど、工程が増えるためコスト面で不利であり、しかも一度吸収させた有効成分が放出されるのに時間がかかりすぎるため、皮膚化粧品としては適当でない。また、平均孔径が２．０μｍ以上の場合は透明性が悪くなる。化粧料に対する球状多孔性架橋ポリマー粒子の配合量は３〜３０重量％、好ましくは５〜２０重量％の範囲である。配合量が３重量％以下では添加効果がなく、３０重量％以上の場合は使用後粉っぽくなり感触が悪くなる。
球状多孔性架橋ポリマー粒子が、アルキル（メタ）アクリレート（ａ）５０〜９９．９重量部、分子内に２個以上のビニル基を有する多官能性モノマー（ｂ）３〜１５重量部及びその他の共重合性モノマー（ｃ）０〜４９．９重量部からなるモノマー混合物を多孔質化剤の存在下で共重合して得られた物が本発明の目的に適っている。
【００１５】
本発明のポリマー粒子における「球状」とは必ずしも真球状のものでなくてもよく、大きな突起のない粒子状という意味である。
本発明で化粧料で一般に用いられる界面活性剤、油剤、薬剤、保湿剤、香料、紫外線吸収剤、防腐剤、着色剤などは使用性を損なわない範囲で必要に応じて配合することが出来る。
本発明の皮膚化粧料は医薬品などへの応用も可能である。
本発明の皮膚化粧料は既存の化粧品や外用医薬品等と同様に常温下でそれぞれの成分を撹拌、混合して製造することが可能であり、そのために何ら特殊な装置を必要としない。
【００１６】
【実施例】
以下に本発明を参考例、実施例および比較例に基づきさらに具体的に説明するが、本発明はこれらにより限定されるものではない。
【００１７】
参考例１
球状多孔性架橋ポリマー粒子の調製
水５５５ｇにポリビニルアルコール（クラレポバール２０５、（株）クラレ製）５ｇを溶解させた水溶液に、メチルメタクリレート１８４ｇ、トリメチロールプロパントリメタクリレート１６ｇ、ラウロイルパーオキサイド１ｇ、メチルイソブチルケトン１００ｇ、メタクリル酸ブチル樹脂２ｇからなる混合液を加え、これをホモミキサーを用いて撹拌し、モノマー混合液の分散液を調製した。この際ホモミキサーの攪拌翼の回転数をそれぞれ３２００ｒｐｍおよび２１００ｒｐｍとして撹拌し、２種類の粒子径の異なる分散液を調整した。このそれぞれの分散液を撹拌機、環流冷却器、温度計、窒素吹き込み口を備えた４つ口フラスコに移し、窒素気流下で撹拌しながら、６０℃に昇温し、そのまま３時間反応した。得られた懸濁液を室温まで冷却後、濾別水洗し、フィルターケーキを１１０℃で２４時間乾燥させて、球状多孔性架橋ポリマー粒子を得た。得られた架橋ポリマー粒子のうちを平均粒子径の小さい方（回転数３，２００ｒｐｍで得られたもの）をＡ−１とし、大きい方（回転数２１００ｒｐｍで得られたもの）をＡ−２とした。その粒子の性状を〔表１〕に示す。
【００１８】
参考例２
球状多孔性架橋ポリマー粒子の調製
ホモミキサーの攪拌翼の回転数をそれぞれ１０００ｒｐｍおよび１００００ｒｐｍとして撹拌し、その他の条件は参考例１のと同様の方法で得られた球状多孔性有架橋ポリマー粒子をそれぞれＢ−１、Ｂ−２とした。その粒子の性状を〔表１〕に示す。
【００１９】
参考例３
球状非多孔性架橋ポリマー粒子の調製
水５５５ｇにポリビニルアルコール（クラレポバール２０５、（株）クラレ製）５ｇを溶解させた水溶液に、メチルメタクリレート１８４ｇ、トリメチロールプロパントリメタクリレート１６ｇ、ラウロイルパーオキサイド１ｇの混合液を加えた。これをホモミキサーを用いて撹拌し、モノマー混合液の分散液を調製した。この際、ホモミキサーの攪拌の強さを３２００ｒｐｍとし分散液を調整した。このそれぞれの分散液を撹拌機、環流冷却器、温度計、窒素吹き込み口を備えた４つ口フラスコに移し、窒素気流下で撹拌しながら、６０℃に昇温し、そのまま３時間反応した。得られた懸濁液を室温まで冷却後、濾別水洗し、フィルターケーキを１１０℃で２４時間乾燥させて球状非多孔性架橋ポリマー粒子を得た。得られた球状非多孔性架橋ポリマー粒子をＢ−３とした。その粒子の性状を〔表１〕に示す。
【００２０】
参考例４
球状多孔性架橋ポリマー粒子の調製
水５５５ｇにポリビニルアルコール（クラレポバール２０５、（株）クラレ製）５ｇを溶解させた水溶液に、メチルメタクリレート１５０ｇ、トリメチロールプロパントリメタクリレート５０ｇ、ラウロイルパーオキサイド１ｇ、メチルイソブチルケトン１００ｇの混合液を加えた。これをホモミキサーを用いて撹拌し、モノマー混合液の分散液を調製した。この際、ホモミキサーの攪拌の強さを３２００ｒｐｍとし分散液を調整した。このそれぞれの分散液を撹拌機、環流冷却器、温度計、窒素吹き込み口を備えた４つ口フラスコに移し、窒素気流下で撹拌しながら、６０℃に昇温し、そのまま３時間反応した。得られた懸濁液を室温まで冷却後、濾別水洗し、フィルターケーキを１１０℃で２４時間乾燥させて、球状多孔性架橋ポリマー粒子を得た。得られた球状多孔性架橋ポリマー粒子をＢ−４とした。その粒子の性状を〔表１〕に示す。
【００２１】
参考例５
球状非多孔性架橋ポリマー粒子の調製
メチルメタクリレート８０ｇ、トリメチロールプロパントリメタクリレート１２０ｇにした以外は参考例４と同様の方法で球状多孔性架橋ポリマー粒子を得た。得られた球状多孔性架橋ポリマー粒子をＢ−５とした。その粒子の性状を〔表１〕に示す。
【００２２】
参考例６
球状多孔性架橋ポリマー粒子の調製
水５５５ｇにポリビニルアルコール（クラレポバール２０５、（株）クラレ製）５ｇを溶解させた水溶液に、メチルメタクリレート１８４ｇ、トリメチロールプロパントリメタクリレート１６ｇ、ラウロイルパーオキサイド１ｇ、メチルイソブチルケトン２５０ｇ、メタクリル酸ブチル樹脂４ｇからなる混合液を加え、これをホモミキサーを用いて撹拌し、モノマー混合液の分散液を調製した。この際ホモミキサーの攪拌翼の回転数を２１００ｒｐｍとして撹拌し、分散液を調整した。この分散液を撹拌機、環流冷却器、温度計、窒素吹き込み口を備えた４つ口フラスコに移し、窒素気流下で撹拌しながら、６０℃に昇温し、そのまま３時間反応した。球状多孔性架橋ポリマー粒子を得た。これをＢ−６とし、その粒子の性状を〔表１〕に示す。
なお、前記各参考例において得られた粒子の各種物性試験は、次の方法によって行った。
平均粒子径（μｍ）：コールターマルチサイザーII（コールター（株）製）により測定し、重量分布の算術径の値を採用した。
表面積（ｍ２／ｇ）： Ｂ．Ｅ．Ｔ．法（窒素多点分析）
全孔体積（ｃｃ／ｇ）：水銀圧入法より求めた。
孔の直径（ｎｍ）：ＳＥＭにより孔の大きさを確認した。
【００２３】
【表１】
実施例１および２、比較例１〜８
日焼け止めローション
製法
〔表２〕における１〜５の油性成分を混合、９０℃に加熱して均一に溶解し、７０℃に保った。ついで〔表２〕の６〜９の水性成分を混合、８０℃に加熱してこれに〔表２〕の１０〜２５を加え均一に分散させた後７０℃に保った。この水性成分に先に調製した油性成分を撹拌下徐々に添加して乳化し、室温に冷却して日焼け止めローションとした。
【００２５】
【表２】
評価方法
使用性の評価
実施例１，２、比較例１〜８の化粧料の使用感すなわち、▲１▼ソフトで滑らかな使用感、▲２▼伸展性、▲３▼使用後のさっぱり感、▲４▼透明感、および▲５▼総合評価（▲１▼〜▲４▼の平均点）を３０名のパネラーにより、〔表３〕のような５点評価を行い、その評価結果を〔表２〕に示した。
【００２７】
【表３】
〔表２〕から明らかなとおり、本発明の実施例１および２の化粧料は、比較例１〜８のいずれの化粧料に比べても、どの使用感も大幅に改善されていることがわかる。
【００２９】
実施例３および４比較例９〜１３
軟膏型ファンデーション
製法
〔表４〕における１〜７の成分を混合、９０℃に加熱し均一に溶解させた。これに前もって混合しておいた８〜２０成分を加え、ロールミルで混合した。
これを９０℃で融解し、２１〜２３成分を加え撹拌しながら脱泡し、６０℃まで冷却して容量に流し込み、固化させた。
【００３０】
【表４】
日焼け止めローションの場合と同様に評価し、その結果を〔表４〕に示した。
【００３１】
〔表４〕から明らかなように、本発明の実施例３および４は、比較例９〜１６のいずれに比べても、どの使用感も大幅に改善されていることがわかった。
【００３２】
【発明の効果】
本発明の皮膚化粧料は、ソフトで滑らかな使用感、伸展性、使用後のさっぱり感などの感触、透明性に優れ、例えばクリーム、ゲル、ローション、軟膏として使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to skin cosmetics such as creams, gels, lotions, emulsions and ointments having a soft and smooth feeling of use, a refreshing feeling after use, and excellent extensibility and transparency.
[0002]
[Prior art]
Conventionally, skin cosmetics are manufactured by blending oily base materials such as fats, waxes and hydrocarbons, solvents, powders, pigments, plasticizers, etc., and spherical fine particles are blended to give extensibility and soft feeling. Has been.
In addition, cosmetics containing spherical porous resin powder have been proposed in order to prevent makeup loss caused by sebum and sweat secreted from the skin after use and to maintain a refreshing feeling (Japanese Patent Laid-Open No. 57-98205). issue).
Furthermore, a so-called sustained-release composition has also been proposed in which a fine powder having an internal porous network structure is blended with a medicine or cosmetic to keep the active ingredient in the fine particle pores and gradually released locally (( JP-A-1-13112).
[0003]
[Problems to be solved by the invention]
In the technology using these spherical porous resin powders, the particles are hard and lack the smoothness and soft feeling during use, which is the life of skin cosmetics. Further, since the pore diameter of the particles is too small, the absorption of sebum and sweat is slow and the amount of absorption is small, the refreshing feeling after use is not sufficient. In addition, if the pore size is small, it is necessary to repeat steps such as stirring under reduced pressure in order to inhale the active ingredient into the pores, which is disadvantageous in terms of cost because it takes time and steps, and the active ingredient once absorbed Takes too long to be released, so it is not suitable for applications such as skin products such as coatings, gels, lotions, emulsions, ointments.
Accordingly, there has been a demand for a skin cosmetic material that has a softer and smoother feeling of use and a refreshing feeling that is more durable.
[0004]
[Means for Solving the Problems]
In view of the above circumstances, as a result of various studies, the present inventors have found that the crosslinking density is 3 to 15% by weight, the average particle size is 3 to 15 μm, the total pore volume is 0.01 to 0.50 cc / g, and the surface area is 5 to 5%. It was found that all the above-mentioned problems were solved by blending 3 to 30% by weight of spherical porous crosslinked polymer particles having an average pore size of 0.1 to 2.0 μm at 50 m 2 / g, and the present invention was completed. did. That is, the present invention comprises (1) 50 to 99.9 parts by weight of alkyl (meth) acrylate (a), 3 to 15 parts by weight of a polyfunctional monomer (b) having two or more vinyl groups in the molecule, and Other copolymerizable monomer (c) obtained by copolymerizing a monomer mixture consisting of 0 to 49.9 parts by weight in the presence of a porosifying agent, having a crosslinking density of 5 to 13 % by weight and an average particle size of 3 to 15 μm Skin cosmetics containing 3 to 30% by weight of spherical porous crosslinked polymer particles having a total pore volume of 0.01 to 0.50 cc / g, a surface area of 5 to 50 m 2 / g and an average pore size of 0.01 to 2.0 μm , It is.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Examples of skin cosmetics that incorporate the spherical porous crosslinked polymer particles in the present invention include forms such as creams, gels, lotions, emulsions, and ointments.
The spherical porous crosslinked polymer particles in the present invention are, for example, alkyl (meth) acrylate (a) 50 to 99.9 parts by weight, and polyfunctional monomer (b) 3 to 15 parts by weight having two or more vinyl groups in the molecule. And other copolymerizable monomers (c) can be obtained by copolymerizing a monomer mixture comprising 0 to 49.9 parts by weight in the presence of a porosifying agent.
Examples of the alkyl (meth) acrylate (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth). Examples of the alkyl group include those having 1 to 10 carbon atoms such as acrylate and isononyl (meth) acrylate.
[0006]
Examples of the polyfunctional monomer (b) having two or more vinyl groups in the molecule include aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di ( Alkane polyols such as (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. having different reactive vinyl groups such as poly (meth) acrylate, allyl (meth) acrylate, diallyl itaconate, etc. In addition to monomers, urethane di (meth) acrylate, epoxy (meth) acrylate, and the like can be given.
[0007]
Other copolymerizable monomers (c) include aromatic vinyl compounds such as styrene, vinyl toluene and α-methylstyrene, vinyl cyanide compounds such as aromatic vinylidene, acrylonitrile and methacrylonitrile, vinylidene cyanide, urethane ( Examples thereof include a copolymerizable monomer having one vinyl group in the molecule such as (meth) acrylate. In addition, a monomer having a functional group, for example, a monomer having an epoxy group such as glycidyl methacrylate, a monomer having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl (meth) acrylate, etc. Monomers having a hydroxyl group, copolymerizable monomers having an amino group such as diethylaminoethyl (meth) acrylate, and the like can also be used.
As the method for synthesizing the spherical porous crosslinked polymer particles in the present invention, methods such as emulsion polymerization, suspension polymerization, and dispersion polymerization are used. Preferably, suspension polymerization is performed.
Suspension polymerization is performed using the monomer mixture, dispersion stabilizer, surfactant, oil-soluble radical polymerization initiator, porosifying agent, and the like described above. The oil-soluble radical polymerization initiator and the porosifying agent are desirably dissolved or dispersed in advance in the monomer mixture described above.
[0008]
Dispersion stabilizers include water-soluble polymers such as gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyacrylate, sodium alginate, and partially saponified products of polyvinyl alcohol. Inorganic substances such as tricalcium phosphate, titanium oxide, calcium carbonate, and silicon dioxide are used. These dispersion stabilizers can be used alone or in combination of two or more.
[0009]
As the surfactant, anionic surfactants such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate and sodium lauryl sulfate, and nonionic surfactants such as polyethylene glycol nonylphenyl ether are used. These surfactants can be used alone or in combination of two or more.
[0010]
Examples of the oil-soluble radical polymerization initiator include organic peroxides such as benzoyl peroxide, ο-methoxybenzoyl peroxide, ο-chlorobenzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and 2,2′-azobisiso An azo compound such as butyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile is used. These oil-soluble radical polymerization initiators can be used alone or in combination of two or more.
[0011]
The porosifying agent is also called a porogen, and refers to a material that makes particles porous when synthesizing polymer particles, but several types are known (Japanese Patent Laid-Open No. 1-113112). One of them is a solvent that is miscible with the above-mentioned monomer mixture such as toluene, isooctane, methyl isobutyl ketone, etc., and immiscible with the polymer after the polymerization. In this case, the used porosifying agent is removed by a drying step of the particles, and the portions where the solvent is removed become pores. Another type of porosifying agent is an inorganic material that dissolves with a strong acid such as calcium carbonate or tricalcium phosphate. In this case, the porosifying agent used is removed by dissolving with a strong acid in the step of purifying the particles after completion of the polymerization, and the portion removed by dissolution becomes pores. Yet another type of porosifying agent is a linear polymer that dissolves in the monomer mixture described above. In this case, in the process of proceeding the polymerization of the monomer mixture described above, phase separation occurs with the dissolved linear polymer, and the particles become porous. The type of linear polymer used is not particularly limited, but the shape and size of the pores vary depending on the type of polymer. The method for obtaining the spherical porous crosslinked polymer particles used in the present invention is not limited to the above method, and one kind or two or more kinds may be used in combination.
The amount of the porous agent used is usually about 10 to 200 parts by weight, preferably about 30 to 150 parts by weight, based on 100 parts by weight of the monomer mixture. When the amount is less than this range, the total pore volume and surface area are reduced, and the average pore size is also reduced. On the other hand, if the amount is larger than this range, the average pore diameter becomes too large, making it difficult to form pores.
[0012]
The average particle diameter of the spherical porous crosslinked polymer particles used in the present invention is usually 3 to 15 μm, preferably 5 to 12 μm. When the average particle diameter is smaller than the above range, the extensibility is not sufficient, and when the average particle diameter is large, it is not preferable because it feels rough when applied to the skin.
[0013]
The crosslinking density is usually 3 to 15% by weight, preferably 5 to 13% by weight. When the crosslinking density is lower than the above range, the porous state of the particles may not be maintained. Soft feel is not obtained when using The crosslinking density (% by weight) is obtained by multiplying the value obtained by dividing the weight of the monomer (b) by the total weight of the monomers (a), (b) and (c) by 100.
[0014]
Total pore volume is usually 0.01~0.50cc / g, preferably 0.05~0.40cc / g, the surface area is usually 5 to 50 m 2 / g, preferably 10 to 40 m 2 / g, average pore size is generally The range is 0.01 to 2.0 μm, preferably 0.1 to 1.8 μm. When the average pore size is 0.01 μm or less, the absorption rate of sebum and sweat is slow, and in order to inhale the active ingredient into the pores, stirring is performed under reduced pressure, which is disadvantageous in terms of cost because the number of processes increases. Moreover, since it takes too much time for the active ingredient once absorbed to be released, it is not suitable as a skin cosmetic. Further, when the average pore diameter is 2.0 μm or more, the transparency is deteriorated. The blending amount of the spherical porous crosslinked polymer particles with respect to the cosmetic is 3 to 30% by weight, preferably 5 to 20% by weight. If the blending amount is 3% by weight or less, there is no effect of addition, and if it is 30% by weight or more, it becomes powdery after use and the feel becomes worse.
Spherical porous cross-linked polymer particles are alkyl (meth) acrylate (a) 50-99.9 parts by weight, polyfunctional monomer (b) 3-15 parts by weight having two or more vinyl groups in the molecule, and other A product obtained by copolymerizing a monomer mixture comprising 0 to 49.9 parts by weight of the copolymerizable monomer (c) in the presence of a porosifying agent is suitable for the purpose of the present invention.
[0015]
The “spherical shape” in the polymer particles of the present invention does not necessarily have to be a true spherical shape, and means a particle shape without large protrusions.
In the present invention, surfactants, oils, drugs, humectants, fragrances, ultraviolet absorbers, preservatives, colorants and the like that are generally used in cosmetics can be blended as needed without impairing usability.
The skin cosmetics of the present invention can be applied to pharmaceuticals and the like.
The skin cosmetic of the present invention can be produced by stirring and mixing each component at room temperature in the same manner as existing cosmetics and external medicines, and therefore no special equipment is required.
[0016]
【Example】
Hereinafter, the present invention will be described more specifically based on reference examples, examples and comparative examples, but the present invention is not limited thereto.
[0017]
Reference example 1
Preparation of spherical porous crosslinked polymer particles In an aqueous solution in which 5 g of polyvinyl alcohol (Kuraray Poval 205, Kuraray Co., Ltd.) was dissolved in 555 g of water, 184 g of methyl methacrylate, 16 g of trimethylolpropane trimethacrylate, 1 g of lauroyl peroxide, methyl isobutyl A liquid mixture consisting of 100 g of ketone and 2 g of butyl methacrylate resin was added and stirred using a homomixer to prepare a dispersion of the monomer liquid mixture. At this time, the stirring blades of the homomixer were stirred at 3200 rpm and 2100 rpm, respectively, to prepare two types of dispersions having different particle diameters. Each of these dispersions was transferred to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing port. The temperature was raised to 60 ° C. while stirring under a nitrogen stream, and the reaction was continued for 3 hours. The obtained suspension was cooled to room temperature, then filtered and washed with water, and the filter cake was dried at 110 ° C. for 24 hours to obtain spherical porous crosslinked polymer particles. Of the obtained crosslinked polymer particles, the smaller average particle diameter (obtained at a rotational speed of 3,200 rpm) is designated as A-1, and the larger average particle diameter (obtained at a rotational speed of 2100 rpm) is designated as A-2. did. The properties of the particles are shown in [Table 1].
[0018]
Reference example 2
Preparation of Spherical Porous Crosslinked Polymer Particles Stirring speeds of the homomixer stirring blades were 1000 rpm and 10,000 rpm, respectively, and the other conditions were the same for spherical porous crosslinked polymer particles obtained in the same manner as in Reference Example 1. It was set as B-1 and B-2. The properties of the particles are shown in [Table 1].
[0019]
Reference example 3
Spherical shaped non-porous cross-linked polyvinyl alcohol preparation water 555g of the polymer particles (Kuraray Poval 205, Ltd. Kuraray) in an aqueous solution obtained by dissolving 5g, methyl methacrylate 184 g, trimethylol propane trimethacrylate 16g, lauroyl peroxide 1g The mixture was added. This was stirred using a homomixer to prepare a dispersion of the monomer mixture. At this time, the intensity of stirring of the homomixer was set to 3200 rpm to prepare a dispersion. Each of these dispersions was transferred to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing port. The temperature was raised to 60 ° C. while stirring under a nitrogen stream, and the reaction was continued for 3 hours. The obtained suspension was cooled to room temperature, filtered and washed with water, and the filter cake was dried at 110 ° C. for 24 hours to obtain spherical nonporous crosslinked polymer particles. The resulting spherical non-porous crosslinked polymer particle was designated as B-3. The properties of the particles are shown in [Table 1].
[0020]
Reference example 4
Preparation of spherical porous crosslinked polymer particles In an aqueous solution in which 5 g of polyvinyl alcohol (Kuraray Poval 205, Kuraray Co., Ltd.) was dissolved in 555 g of water, 150 g of methyl methacrylate, 50 g of trimethylolpropane trimethacrylate, 1 g of lauroyl peroxide, methyl isobutyl A mixture of 100 g of ketone was added. This was stirred using a homomixer to prepare a dispersion of the monomer mixture. At this time, the intensity of stirring of the homomixer was set to 3200 rpm to prepare a dispersion. Each of these dispersions was transferred to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing port. The temperature was raised to 60 ° C. while stirring under a nitrogen stream, and the reaction was continued for 3 hours. The obtained suspension was cooled to room temperature, then filtered and washed with water, and the filter cake was dried at 110 ° C. for 24 hours to obtain spherical porous crosslinked polymer particles. The resulting spherical porous crosslinked polymer particle was designated as B-4. The properties of the particles are shown in [Table 1].
[0021]
Reference Example 5
Preparation of Spherical Nonporous Crosslinked Polymer Particles Spherical porous crosslinked polymer particles were obtained in the same manner as in Reference Example 4 except that 80 g of methyl methacrylate and 120 g of trimethylolpropane trimethacrylate were used. The resulting spherical porous crosslinked polymer particle was designated as B-5. The properties of the particles are shown in [Table 1].
[0022]
Reference Example 6
Preparation of spherical porous crosslinked polymer particles In an aqueous solution in which 5 g of polyvinyl alcohol (Kuraray Poval 205, Kuraray Co., Ltd.) was dissolved in 555 g of water, 184 g of methyl methacrylate, 16 g of trimethylolpropane trimethacrylate, 1 g of lauroyl peroxide, methyl isobutyl A liquid mixture consisting of 250 g of ketone and 4 g of butyl methacrylate resin was added and stirred using a homomixer to prepare a dispersion of the monomer liquid mixture. At this time, the number of revolutions of the stirring blade of the homomixer was stirred at 2100 rpm to prepare a dispersion. The dispersion was transferred to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing port, heated to 60 ° C. while stirring under a nitrogen stream, and reacted for 3 hours. Spherical porous crosslinked polymer particles were obtained. This is designated as B-6, and the properties of the particles are shown in Table 1.
In addition, the various physical property tests of the particles obtained in the respective reference examples were performed by the following methods.
Average particle diameter (μm): Measured by Coulter Multisizer II (manufactured by Coulter Co., Ltd.), and the value of the arithmetic diameter of the weight distribution was adopted.
Surface area (m 2 / g): B. E. T.A. Method (nitrogen multipoint analysis)
Total pore volume (cc / g): determined by mercury porosimetry.
Hole diameter (nm): The size of the hole was confirmed by SEM.
[0023]
[Table 1]
Examples 1 and 2, Comparative Examples 1-8
The oily components 1 to 5 in the sunscreen lotion manufacturing method [Table 2] were mixed, heated to 90 ° C., uniformly dissolved, and kept at 70 ° C. Next, 6 to 9 aqueous components in [Table 2] were mixed, heated to 80 ° C., 10 to 25 in [Table 2] were added and dispersed uniformly, and the mixture was kept at 70 ° C. The oily component prepared previously was gradually added to this aqueous component with stirring to emulsify, and cooled to room temperature to obtain a sunscreen lotion.
[0025]
[Table 2]
Evaluation Method Usability Evaluation Usability of cosmetics of Examples 1 and 2 and Comparative Examples 1 to 8, ie, (1) soft and smooth use feeling, (2) extensibility, and (3) refreshing feeling after use, (4) Transparency and (5) Comprehensive evaluation (average score of (1) to (4)) were evaluated by 30 panelists as shown in [Table 3]. 2].
[0027]
[Table 3]
As is apparent from [Table 2], it can be seen that the cosmetics of Examples 1 and 2 of the present invention are greatly improved in the feeling of use compared to any of the cosmetics of Comparative Examples 1-8. .
[0029]
Examples 3 and 4 Comparative Examples 9-13
Components 1 to 7 in the ointment type foundation production method [Table 4] were mixed and heated to 90 ° C. to be uniformly dissolved. To this, 8 to 20 components previously mixed were added and mixed with a roll mill.
This was melted at 90 ° C., 21 to 23 components were added, deaerated while stirring, cooled to 60 ° C., poured into a volume, and solidified.
[0030]
[Table 4]
[0031]
As is apparent from [Table 4], it was found that Examples 3 and 4 of the present invention were greatly improved in usability compared to any of Comparative Examples 9-16.
[0032]
【The invention's effect】
The skin cosmetic composition of the present invention is excellent in soft and smooth feeling of use, extensibility, fresh feeling after use, and transparency, and can be used, for example, as a cream, gel, lotion or ointment.
Claims (1)
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| JP4597469B2 (en) * | 2002-05-30 | 2010-12-15 | 花王株式会社 | Porous particles and process for producing the same |
| FR2874321B1 (en) * | 2004-08-17 | 2010-11-26 | Oreal | TOPICAL COMPOSITION COMPRISING POROUS CHARGED PARTICLES AND A SEBUM ABSORBING COMPOUND |
| US20080102050A1 (en) * | 2006-10-26 | 2008-05-01 | Mingxla Li | Water-based skin care composition with polyalkylsilsesquioxane powder emulsion and method for making the same |
| US20120034281A1 (en) * | 2009-04-03 | 2012-02-09 | Shiseido Company, Ltd. | Solid Powder Cosmetic And Method For Producing The Same |
| JP5865399B2 (en) | 2012-01-31 | 2016-02-17 | 積水化成品工業株式会社 | Porous resin particles, production method thereof, dispersion and use thereof |
| US9200154B2 (en) | 2012-03-27 | 2015-12-01 | Sekisui Plastics Co., Ltd. | Porous resin particles, method of manufacturing the same, and use of the same |
| KR101634938B1 (en) | 2012-09-26 | 2016-06-30 | 세키스이가세이힝코교가부시키가이샤 | Porous resin particles, method of manufacturing porous resin particles, and use of porous resin particles |
| EP2783678B1 (en) | 2013-03-28 | 2016-01-20 | Sekisui Plastics Co., Ltd. | Porous resin particles, method of manufacturing the same, and use of the same |
| CN103202774B (en) * | 2013-04-11 | 2015-06-10 | 丽鑫生技化妆品（上海）有限公司 | Container structure for loading cosmetics and manufacture method thereof |
| JPWO2022131128A1 (en) | 2020-12-17 | 2022-06-23 |
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| JPS5798205A (en) * | 1980-12-09 | 1982-06-18 | Pola Chem Ind Inc | Cosmetic giving durable make-up |
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