JP2022103271A - アクリル系ポリマー含有ピッカリングエマルション - Google Patents
アクリル系ポリマー含有ピッカリングエマルション Download PDFInfo
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- JP2022103271A JP2022103271A JP2022077109A JP2022077109A JP2022103271A JP 2022103271 A JP2022103271 A JP 2022103271A JP 2022077109 A JP2022077109 A JP 2022077109A JP 2022077109 A JP2022077109 A JP 2022077109A JP 2022103271 A JP2022103271 A JP 2022103271A
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- oil
- pickering emulsion
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- acrylate
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- 239000000843 powder Substances 0.000 claims abstract description 47
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
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Abstract
Description
本発明の解決しようとする課題は、ピッカリングエマルションの乳化安定性を向上させる技術を提供することにある。特に油相成分として極性油剤を含有する形態にも応用可能なピッカリングエマルションの乳化安定性向上技術を提供することを課題とする。
本発明の乳化組成物は乳化安定性に優れる。
従来、油相成分として極性油を含む場合、安定なピッカリングエマルションを調製することが困難であった。本発明の適用により、油相成分として極性油を含む形態のピッカリングエマルションの安定性を向上させることができる。
従来、このような高極性油を含む形態のピッカリングエマルションは安定性に劣るものであった。本発明によれば、このような高極製油を含む形態であっても安定したピッカリングエマルションを提供することができる。
従来技術では、油剤に占める極性油の割合が60質量%以上のピッカリングエマルションは、安定的に調製することが困難であった。本発明によれば、このような極性油を高含有で含む形態であっても、乳化安定性に優れたピッカリングエマルションを提供することができる。
本発明によれば、紫外線吸収剤を含む形態のピッカリングエマルションの乳化安定性を向上させることができる。
本発明によれば、このような紫外線吸収剤高含有のピッカリングエマルションを提供することができる。
このような形態のピッカリングエマルションは乳化安定性に優れる。
界面活性剤フリーの形態としても、本発明のピッカリングエマルションは優れた乳化安定性を示す。
本発明のピッカリングエマルションは、アクリル系ポリマーを必須の構成要素として含む。アクリル系ポリマーには、(メタ)アクリル酸並びにそのアミド及びエステルから選択される(メタ)アクリル系モノマーを構成モノマーとする、ポリマー又はコポリマーが含まれる。
本発明においては、ランダム共重合体、交互共重合体又はブロック共重合体であるアクリル系コポリマーを用いることが好ましい。
(メタ)アクリル酸アルキルエステルにおけるアルキル基の炭素数は特に限定されず、好ましくは1~20、より好ましくは1~10、さらに好ましくは1~4を例示することができる。
置換基としては、糖残基、アミノ酸残基、ホスホリルコリンなどの生体構成物質に由来する置換基であってもよい。
このような構成モノマーとしては、クロトン酸等の不飽和モノカルボン酸;スチレン等の芳香族ビニル化合物;イタコン酸、マレイン酸、フマル酸、無水マレイン酸、シトラコン酸等の不飽和ジカルボン酸;マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、イタコン酸モノアルキルエステル等の不飽和ジカルボン酸のモノアルキルエステル;スルホン酸基含有単量体としては、例えばビニルスルホン酸、(メタ)アリルスルホン酸等のアルケンスルホン酸;α-メチルスチレンスルホン酸等の芳香族ビニル基含有スルホン酸;(メタ)アリルアミン等の1~3級アミノ基含有不飽和化合物;N,N-ジメチルアミノスチレン等のアミノ基含有芳香族ビニル系化合物;ジビニルベンゼン、ジイソプロフェニルベンゼン、トリビニルベンゼン等のエチレン性不飽和二重結合を2個以上有する化合物;エチレン性不飽和二重結合を2個以上有するウレタンオリゴマー;エチレン性不飽和二重結合を2個以上有するシリコーン化合物;酢酸ビニル、塩化ビニル、ビニルピロリドン等が例示される。
具体的には、INCI名(International Cosmetic Ingredient Dictionary and Handbook,第14版,第1巻,CTFA,2012年,p.60~61)で「ACRYLATES COPOLYMER(アクリレーツコポリマー)」と表記される化合物が挙げられる。
重合は、アゾビスブチロニトリル等の重合開始剤の存在下、常法に従って行えばよい。
本発明のピッカリングエマルションにおいては、粉体が乳化界面に吸着している。この粉体としては、通常、ピッカリングエマルションに用いられる乳化能力を有する粉体であれば特段の制限なく用いることができる。
ここでいう金属酸化物には、ケイ素などの半金属の酸化物も含まれる。
金属酸化物粉体としては、シリカ、二酸化チタン、酸化亜鉛、酸化鉄、酸化ジルコニウム及び酸化セリウムなどを例示することができる。
乾式シリカ粉末としては、例えばAerosilシリーズ(日本アエロジル株式会社)、CAB-O-SILシリーズ(キャボットコーポレーション)、HDKシリーズ(旭化成ワッカーシリコーン株式会社)、湿式シリカ粉末としては、例えばNipsilシリーズ(東ソー・シリカ株式会社)、HI-SILシリーズ(PPG)等の市販品の市販品を用いることができる。
特に好ましくは、有機ケイ素化合物又はシリコーンを疎水化処理剤として金属酸化物粉体を処理する。
なお、平均二次粒子径は外用組成物の調製の際に加える応力によって調整することができる。
また、粉体の含有量の上限は、特に限定されないが、好ましくは10質以下、より好ましくは5質量%以下、さらに好ましくは3質量%以下、さらに好ましくは2質量%以下を目安とすることができる。
極性油剤としては、ツバキ油、トウモロコシ油、ミンク油、オリーブ油、アボカド油、サザンカ油、ヒマシ油、ホホバ油、ヒマワリ油、ナタネ油、ゴマ油、大豆油等の植物油;2-エチルヘキサン酸セチル、ミリスチン酸イソプロピル、オクタン酸セチル、パルミチン酸オクチル、ステアリン酸イソセチル、イソステアリン酸イソプロピル、イソパルミチン酸オクチル、セバシン酸イソプロピル等のモノエステル油;セバシン酸ジエチル、セバシン酸ジイソプロピル、セバシン酸ジ-2-エチルヘキシル、フタル酸ジイソプロピル等のジエステル油;トリ2-エチルへキサン酸グリセリル、トリ(カプリル・カプリン酸)グリセリン等のトリエステル油などを特に好ましく例示することができる。
これは、前記UVA吸収剤は、油剤への溶解性が低く、特に低温において析出等の問題が存するためである。本発明によれば、UVA吸収剤を安定に含有せしめることができる。
また、水中油型の形態とする場合には、全体に占める油剤の割合は、好ましくは50質量%以下、より好ましくは40質量%以下とすることができる。
本発明のピッカリングエマルションは、油中水型としてもよいし、水中油型としてもよい。好ましくは水中油型とする。
アクリル系ポリマーと粉体の質量比を前記範囲とすることによってピッカリングエマルションの乳化安定性を向上させることができる。
ポリオールとしては、ポリエチレングリコール、グリセリン、1,3-ブチレングリコール、エリスリトール、ソルビトール、キシリトール、マルチトール、プロピレングリコール、ジプロピレングリコール、ジグリセリン、イソプレングリコール、1,2-ペンタンジオール、2,4-ヘキシレングリコール、1,2-ヘキサンジオール、1,2-オクタンジオール等が挙げられ、中でも、グリセリン、1,3-ブチレングリコール、ソルビトールが好ましく挙げられる。これらの含有量は、ピッカリングエマルション全体の好ましくは0.5~20質量%、より好ましくは3~10質量%である。また、これらの含有量は、水相の好ましくは3~15質量%、さらに好ましくは5~10質量%である。
また、増粘剤を含有することも好ましい。増粘剤としては、キサンタンガム、ジェランガム、グアガム、クインスシード、カラギーナン、ガラクタン、アラビアガム、ペクチン、マンナン、デンプン、カードラン、メチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルヒドロキシプロピルセルロース、コンドロイチン硫酸、デルマタン硫酸、グリコーゲン、ヘパラン硫酸、ヒアルロン酸、ヒアルロン酸ナトリウム、トラガントガム、ケラタン硫酸、コンドロイチン、ムコイチン硫酸、ヒドロキシエチルグアガム、カルボキシメチルグアガム、デキストラン、ケラト硫酸、ローカストビーンガム,サクシノグルカン、カロニン酸、キチン、キトサン、カルボキシメチルキチン、寒天、ポリビニルアルコール、ポリビニルピロリドン、カルボキシビニルポリマー、ポリアクリル酸ナトリウム、ポリエチレングリコール、アクリル酸ナトリウムグラフトデンプン、ステアロキシヒドロキシプロピルメチルセルロース、ベントナイト等が挙げられ、よりこのましくはキサンタンガム、グアガム等の水溶性多糖類、寒天、アクリル酸ナトリウムグラフトデンプン、ステアロキシヒドロキシプロピルメチルセルロース。さらに好ましくは、キサンタンガム、グアガム等の水溶性多糖類、寒天が好ましく挙げられる。これらの含有量は、ピッカリングエマルション全体の好ましくは0.05~5質量%、より好ましくは0.1~1質量%である。また、これらの含有量は、水相の好ましくは0.1~3質量%、さらに好ましくは0.3~1質量%である。
また、水の含有量は、水相に対し好ましくは70~90質量%、より好ましくは75~85質量%である。
なお、平均乳化粒子径は、光学顕微鏡で20℃下観察し、無作為に選出した乳化粒子10個の最大径の個数平均を算出することにより求めることができる。
また、相対値としては調製直後の平均乳化粒子径の値に対して、40℃で2週間以上、好ましくは1か月静置したときの平均乳化粒子径の値が、好ましくは2倍以下、より好ましくは1.2倍以下であることが好ましい。
中でも、化粧料に用いることが好ましく、化粧下地、ファンデーション等とすることが好ましい。
なお、試験例1で使用したシリル化シリカは、シリカ微粒子(AEROSIL社製、平均一次粒子径12nm(測定方法は前述のとおり))とモノ、ジ、及びトリメチルシリル疎水化処理剤を混合することにより得られたものを使用した。
実施例及び比較例のピッカリングエマルションを40℃で1か月放置した。放置前後の平均乳化粒子径を計測し、経時による平均乳化粒子径の増加率を計算し、以下の基準に従い乳化安定性を評価した。結果を表1に示す。
○・・・100%~120%
△・・・120%~200%
×・・・200%~
実施例及び比較例のピッカリングエマルションを光学顕微鏡で観察し、上述の方法により平均乳化粒子径を測定した。結果を表1に示す。また、実施例1と比較例1のピッカリングエマルションの顕微鏡像を図1に示す。
実施例及び比較例のピッカリングエマルションを、サージカルテープ(Transporeスリーエムヘルスケア株式会社製)に、2mg/cm2の載り量で6.4cm×6.4cmの広さで塗布し、Labsphere社製UV-2000S SPFアナライザーを用いて10回測定して得られた平均防御スペクトルからSPF値を求めた。SPF50以上であったものを◎、SPF30以上50未満であったものを〇、SPF15以上30未満であったものを△、SPF15未満のものを×、として評価結果を表1に示す。
この効果は、アクリル系ポリマーによって乳化界面に吸着する粉体の分散性が向上したことに起因するものと考えられる。
従来技術では安定したピッカリングエマルションを得ることができる油相の種類や組成が限定されていた(要すれば比較例1)。しかし、表1に示した結果は、本発明の適用によりその自由度を大幅に向上させることができることを示している。
従来技術では紫外線吸収剤を多量に含むピッカリングエマルションの調製は困難であった(要すれば比較例1)。しかし、表1に示した結果は、アクリル系ポリマーの添加によって、紫外線吸収剤を多量に含むピッカリングエマルションの乳化安定性を顕著に向上させることができることを示している。
Claims (9)
- 粉体が乳化界面に吸着しており、アクリル系ポリマーを含み、
前記アクリル系ポリマーが、(メタ)アクリル酸アルキルから誘導される構成単位を含むコポリマーであり、
前記アクリル系ポリマーの含有量が0.1質量%以上であることを特徴とする、ピッカリングエマルション。 - 前記アクリル系ポリマーが、アクリレーツコポリマーであることを特徴とする、請求項1に記載のピッカリングエマルション。
- 油相成分として極性油を含むことを特徴とする、請求項1又は2の何れか一項に記載のピッカリングエマルション。
- 前記極性油としてIOB値0.1以上の高極性油を含むことを特徴とする、請求項3に記載のピッカリングエマルション。
- ピッカリングエマルションに含まれる油剤に占める極性油の割合が、60質量%以上であることを特徴とする、請求項3又は4に記載のピッカリングエマルション。
- 前記極性油として紫外線吸収剤を含むことを特徴とする、請求項3~5の何れか一項に記載のピッカリングエマルション。
- ピッカリングエマルションに含まれる油剤に占める紫外線吸収剤の割合が、30質量%以上であることを特徴とする、請求項6に記載のピッカリングエマルション。
- 平均乳化粒子径が15μm以下であることを特徴とする、請求項1~7の何れか一項に記載のピッカリングエマルション。
- 前記粉体以外の界面活性剤の含有量が0.1質量%以下であることを特徴とする、請求項1~8の何れか一項に記載のピッカリングエマルション。
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