JP2022081540A - 油中水型乳化組成物 - Google Patents
油中水型乳化組成物 Download PDFInfo
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- JP2022081540A JP2022081540A JP2022029363A JP2022029363A JP2022081540A JP 2022081540 A JP2022081540 A JP 2022081540A JP 2022029363 A JP2022029363 A JP 2022029363A JP 2022029363 A JP2022029363 A JP 2022029363A JP 2022081540 A JP2022081540 A JP 2022081540A
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- glyceryl ether
- water
- oil
- ether
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Landscapes
- Cosmetics (AREA)
- Colloid Chemistry (AREA)
Abstract
Description
油中水型乳化剤型においては、有機変性粘土鉱物を含有させると乳化安定性が向上することが知られている。
しかしながら、パラベン類は、敏感な使用者においては使用時にピリピリした刺激を感じる場合がある。また、近年、肌に対して優しい使用感の皮膚外用剤が求められる傾向にあるため、パラベン類のみを防腐手段とするだけでは、消費者からの需要に応えきれないという状況にある。
また、パラベン類に代えて、フェノキシエタノールと1,2-アルキレンジオールとを組み合わせることにより、刺激性を抑えつつ防腐力を確保することも提案されている(特許文献1)。
このような状況に鑑みて、本発明は、パラベン類を含有しなくても十分な防腐力を有し、かつ安定性に優れ、低刺激性の油中水型乳化組成物を提供することを課題とする。
[1]モノアルキルグリセリルエーテル、及び有機変性粘土鉱物を含有する、油中水型乳化組成物(以降、「本発明の組成物」とも記す)。
[2]さらに、フェノキシエタノール、及び/又は1,2-アルキレンジオールを含有す
る、[1]に記載の油中水型乳化組成物。
[3]さらに、ポリエーテル変性シリコーン、及び/又はポリグリセリン変性シリコーンを含有する、[1]又は[2]に記載の油中水型乳化組成物。
[4]さらに、微粒子金属酸化物を含有する、[1]~[3]のいずれかに記載の油中水型乳化組成物。
[5]前記モノアルキルグリセリルエーテルが、1-(2-エチルヘキシル)グリセリルエーテルである、[1]~[4]のいずれかに記載の油中水型乳化組成物。
[6]前記モノアルキルグリセリルエーテルの含有量が0.05質量%以上である、[1]~[5]のいずれかに記載の油中水型乳化組成物。
[7]粉体の総含有量が10質量%以上である、[1]~[6]のいずれかに記載の油中水型乳化組成物。
[8]皮膚外用剤である、[1]~[7]のいずれかに記載の油中水型乳化組成物。
モノアルキルグリセリルエーテルにおけるアルキル基は、直鎖又は分岐鎖の、炭素数が3~14のものが好ましく、5~12のものがより好ましい。
モノアルキルグリセリルエーテルとしては例えば、1-ブチルグリセリルエーテル、1-ヘキシルグリセリルエーテル、1-ヘプチルグリセリルエーテル、1-(2-エチルヘキシル)グリセリルエーテル、1-(3,5,5-トリメチルヘキシル)グリセリルエーテル、1-オクチルグリセリルエーテル、1-デシルグリセリルエーテル、1-ドデシルグリセリルエーテル等が挙げられ、これらのうち1-(2-エチルヘキシル)グリセリルエーテル(エチルヘキシルグリセリンとも記す)が特に好ましい。
粘土鉱物としては、スクメタイト系のヘクトライト、ベントナイトやモントリロナイト、カオリナイト、イライト、マリーン粘土鉱物(海泥)、デザートローズ粘土鉱物、パスカライトなどが挙げられる。有機化合物としては、4級アミノ基を有する化合物が挙げられる。具体的には、ステアリルトリメチルアンモニウムクロリド、ジメチルジステアリルアンモニウムクロリド等が挙げられる。
本発明においては、有機変性粘土鉱物として、ジメチルジステアリルアンモニウムクロリド変性ヘクトライト(ジステアリルジモニウムヘクトライト)を用いることが好ましい。
本発明において、有機変性粘土鉱物の含有量は、組成物全体に対して0.5~4質量%が好ましく、より好ましくは1.5~3質量%である。少なすぎると組成物の安定性が不十分になる場合があり、多すぎるとかえって安定性を損なう場合があり、また組成物の処
方設計の自由度が制限される場合がある。
本発明において、フェノキシエタノールの含有量は、組成物全体に対して0.2~2質量%が好ましく、より好ましくは0.3~1質量%である。また、本発明において、1,2-アルキレンジオールの総含有量は、組成物全体に対して1~5質量%が好ましく、より好ましくは2~4質量%である。
ポリエーテル変性シリコーン類としては、例えば、ポリエチレングリコール-10ジメチコン、ポリエチレングリコール-12ジメチコン等が挙げられ、ポリグリセリン変性シリコーン類としては、例えば、ポリグリセリル-3ジシロキサンジメチコン、ポリグリセリル-3ポリジメチルシロキシエチルジメチコン、(ポリグリセリル-3/ラウリルポリジメチルシロキシエチルジメチコン)クロスポリマー等が挙げられ、これらを1種又は2種以上含有させることにより、組成物の安定性をより高めることができる。
本発明において、ポリエーテル変性シリコーン又はポリグリセリン変性シリコーンの総含有量は、組成物全体に対して0.5~15質量%が好ましく、より好ましくは1~10質量%、さらに好ましくは2~7質量%である。
微粒子とは、通常、電子顕微鏡観察により測定される一次粒子径が、約10~80nmの範囲にあるものをいう。
微粒子金属酸化物としては、微粒子二酸化チタン、微粒子酸化亜鉛、微粒子酸化ジルコニウム、微粒子酸化セリウム等が好適挙げられ、紫外線散乱効果に優れることから微粒子二酸化チタン、微粒子酸化亜鉛が特に好ましい。
また、これらの表面は、シリカ、アルミナ等の無機化合物、または脂肪酸金属石鹸、シリコーン、パーフルオロアルキル基等の有機化合物により被覆されていてもよい。
本発明において、各微粒子金属酸化物の含有量は総量で、組成物全体に対して1~20質量%が好ましく、より好ましくは2~15質量%である。
粉体としては、例えば、無機粉末(例えば、タルク、カオリン、雲母、絹雲母(セリサイト)、白雲母、金雲母、合成雲母、紅雲母、黒雲母、パーミキュライト、炭酸マグネシウム、炭酸カルシウム、ケイ酸アルミニウム、ケイ酸バリウム、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ酸ストロンチウム、タングステン酸金属塩、マグネシウム、シリカ、アルミナ、ゼオライト、硫酸バリウム、焼成硫酸カルシウム(焼セッコウ)、リン酸カルシウム、フッ素アパタイト、ヒドロキシアパタイト、セラミックパウダー、金属石鹸(例えば、ミリスチン酸亜鉛、パルミチン酸カルシウム、ステアリン酸アルミニウム)、窒化ホウ素等);有機粉末(例えば、ポリアミド樹脂粉末(ナイロン粉末)、ポリエチレン粉末、ポリ(メタ)クリル酸メチル粉末、ポリスチレン粉末、スチレンとアクリル酸の共重合体樹脂粉末、シリコーン樹脂粉末、ベンゾグアナミン樹脂粉末、ポリ四フッ化エチレン粉末、セルロース粉末等);無機白色顔料(例えば、二酸化チタン、酸化亜鉛等);無機赤色系顔料(例えば、酸化鉄(ベンガラ)、チタン酸鉄等);無機褐色系顔料(例えば、γ-酸化鉄等);無機黄色系顔料(例えば、黄酸化鉄、黄土等);無機黒色系顔料(例えば、黒酸化鉄、低次酸化チタン等);無機紫色系顔料(例えば、マンゴバイオレット、コバルトバイオレット等);無機緑色系顔料(例えば、酸化クロム、水酸化クロム、チタン酸コバルト等);無機青色系顔料(例えば、群青、紺青等);パール顔料(例えば、酸化チタンコーテッドマイカ、酸化チタンコーテッドオキシ塩化ビスマス、酸化チタンコーテッドタルク、着色酸化チタンコーテッドマイカ、オキシ塩化ビスマス、魚鱗箔等);金属粉末顔料(例えば、アルミニウムパウダー、カッパーパウダー等);ジルコニウム、バリウム又はアルミニウムレーキ等の有機顔料(例えば、赤色201号、赤色202号、赤色204号、赤色205号、赤色220号、赤色226号、赤色228号、赤色405号、橙色203号、橙色204号、黄色205号、黄色401号、及び青色404号などの有機顔料、赤色3号、赤色104号、赤色106号、赤色227号、赤色230号、赤色401号、赤色505号、橙色205号、黄色4号、黄色5号、黄色202号、黄色203号、緑色3号及び青色1号等);天然色素(例えば、クロロフィル、β-カロチン等)等が挙げられる。
マグネシウム、ポリアクリル酸メチルやポリメタクリル酸メチル等のアクリル樹脂、ナイロン、ポリエチレン、シリコーン等の球状粉体、またはこれらに表面処理を施したものが挙げられる。
なお、粉体の含有量の上限は、組成物全体に対して、40質量%以下が好ましく、35質量%以下がより好ましい。
前記オリゴマーエステルとしては、例えば、特開2007-137847号公報記載の方法により調製したものを使用できるが、市販品も存在するので、かかる市販品を入手して使用することもできる。このような市販品としては、具体的には、(エイコサン二酸/テトラデカン二酸)ポリグリセリル-10である「Neosolue-AquaS」(日本精化株式会社製)が好適に例示される。
なお、「実質的に含有しない」とは、組成物全体に対して好ましくは0.1質量%以下、より好ましくは0.01質量%以下、さらに好ましくは0.001質量%以下であることをいう。
なお、本発明において水相成分は、水及び水溶性の成分をいい、水溶性の成分とは、通常は25~65℃の水に混合して溶解する成分をいう。また、後述する油剤等が、通常は油相に含まれる。
本発明の組成物において内相比は特に限定されないが、安定性の観点から水相:油相=1:9~5:5が好ましい。
シリコーン油としては、ジメチルポリシロキサン(ジメチコン、好ましくは粘度10~10000csのもの)、シクロペンタシロキサン、デカメチルシクロペンタシロキサン、カプリリルメチコン、(ジメチコン/ビニルジメチコン)クロスポリマー、(ジメチコン/フェニルビニルジメチコン)クロスポリマー等が挙げられ、これらのうちジメチコンが好ましい。
本発明の組成物においてはジメチコンを油剤として、組成物全量に対して1~10質量%含有することが好ましく、3~7質量%含有することがより好ましい。
炭化水素油としては、イソドデカン、イソヘキサデカン、スクワラン、ワセリン、水添ポリ(C6-12オレフィン)、水添ポリイソブテン等が挙げられる。
アニオン界面活性剤としては、例えば、脂肪酸セッケン(例えば、ラウリン酸ナトリウム、パルミチン酸ナトリウム等);高級アルキル硫酸エステル塩(例えば、ラウリル硫酸ナトリウム、ラウリル硫酸カリウム等);アルキルエーテル硫酸エステル塩(例えば、POEラウリル硫酸トリエタノールアミン、POEラウリル硫酸ナトリウム等);N-アシルサルコシン酸(例えば、ラウロイルサルコシンナトリウム等);高級脂肪酸アミドスルホン酸塩(例えば、N-ミリストイル-N-メチルタウリンナトリウム、ヤシ油脂肪酸メチルタウリッドナトリウム、ラウリルメチルタウリッドナトリウム等);リン酸エステル塩(POEオレイルエーテルリン酸ナトリウム、POEステアリルエーテルリン酸等);スルホコハク酸塩(例えば、ジ-2-エチルヘキシルスルホコハク酸ナトリウム、モノラウロイルモノエタノールアミドポリオキシエチレンスルホコハク酸ナトリウム、ラウリルポリプロピレングリコールスルホコハク酸ナトリウム等);アルキルベンゼンスルホン酸塩(例えば、リニアドデシルベンゼンスルホン酸ナトリウム、リニアドデシルベンゼンスルホン酸トリエタノールアミン、リニアドデシルベンゼンスルホン酸等);高級脂肪酸エステル硫酸エステル塩(例えば、硬化ヤシ油脂肪酸グリセリン硫酸ナトリウム等);N-
アシルグルタミン酸塩(例えば、N-ラウロイルグルタミン酸モノナトリウム、N-ステアロイルグルタミン酸ジナトリウム、N-ミリストイル-L-グルタミン酸モノナトリウム等);硫酸化油(例えば、ロート油等);POEアルキルエーテルカルボン酸;POEアルキルアリルエーテルカルボン酸塩;α-オレフィンスルホン酸塩;高級脂肪酸エステルスルホン酸塩;二級アルコール硫酸エステル塩;高級脂肪酸アルキロールアミド硫酸エステル塩;ラウロイルモノエタノールアミドコハク酸ナトリウム;N-パルミトイルアスパラギン酸ジトリエタノールアミン;カゼインナトリウム等が挙げられる。
,5-メチレンピペリジニウム);アルキル四級アンモニウム塩;アルキルジメチルベンジルアンモニウム塩;アルキルイソキノリニウム塩;ジアルキルモリホニウム塩;POEアルキルアミン;アルキルアミン塩;ポリアミン脂肪酸誘導体;アミルアルコール脂肪酸誘導体;塩化ベンザルコニウム;塩化ベンゼトニウム等が挙げられる。
ルグルタミン酸塩、アシルβ-アラニンナトリウム、グルタチオン、ピロリドンカルボン酸等が挙げられる。
ノールアミン、モルホリン、トリイソプロパノールアミン、2-アミノ-2-メチル-1,3-プロパンジオール、2-アミノ-2-メチル-1-プロパノール等が挙げられる。
酸化防止助剤としては、例えば、リン酸、クエン酸、アスコルビン酸、マレイン酸、マロン酸、コハク酸、フマル酸、ケファリン、ヘキサメタフォスフェイト、フィチン酸、エチレンジアミン四酢酸等が挙げられる。
、トウモロコシ、バレイショ、コムギ)、グリチルリチン酸);微生物系高分子(例えば、キサンタンガム、デキストラン、サクシノグルカン、ブルラン等);動物系高分子(例えば、コラーゲン、カゼイン、アルブミン、ゼラチン等)等の天然の水溶性高分子、
デンプン系高分子(例えば、カルボキシメチルデンプン、メチルヒドロキシプロピルデンプン等);セルロース系高分子(メチルセルロース、エチルセルロース、メチルヒドロキシプロピルセルロース、ヒドロキシエチルセルロース、セルロース硫酸ナトリウム、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、カルボキシメチルセルロースナトリウム、結晶セルロース、セルロース末等);アルギン酸系高分子(例えば、アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等)等の半合成の水溶性高分子、
ビニル系高分子(例えば、ポリビニルアルコール、ポリビニルメチルエーテル、ポリビニルピロリドン、カルボキシビニルポリマー等);ポリオキシエチレン系高分子(例えば、ポリエチレングリコール20,000、40,000、60,000等);アクリル系高分子(例えば、ポリアクリル酸ナトリウム、ポリエチルアクリレート、ポリアクリルアミド等);ポリエチレンイミン;カチオンポリマー等の合成の水溶性高分子が挙げられる。
表1に示す処方に従って、微粒子金属酸化物を含有しない油中水型乳化組成物(実施例1~7及び比較例1~3)を調製した。すなわち、まず成分A、成分B、及び成分Cをそれぞれ80℃に加熱溶解して混合した。次いで成分Aに成分Bを添加し、撹拌混合したところにさらに成分Cを徐々に添加し、撹拌混合して、室温まで冷却し、油中水型乳化組成物を得た。
また、表2に示す処方に従って、微粒子金属酸化物を含有する油中水型乳化組成物(実施例8~13及び比較例4~5)も同様に調製した。
調製した各組成物の「安定性」、「防腐力」及び「刺激性」について、それぞれ以下の基準で評価を行った。結果を表1及び表2にそれぞれ示す。
また、いずれの実施例の組成物も、特に不快なにおいは生じなかった。
40℃で1ヶ月保管した後の乳化状態について観察した。
◎:均一な乳化状態
○:ほぼ均一な乳化状態
△:やや不均一な乳化状態
×:油相と水相が分離している
調製した各乳化組成物について、日本薬局方の「保存効力試験法」に準じ、微生物試験を行い、防腐力を評価した。具体的には、各乳化組成物を調製後、30gずつに分け、大腸菌、緑膿菌、黄色ブドウ球菌、酵母(カンジダ)、又はカビ(クロコウジカビ)の菌液を接種し、塗沫法により菌数の経日変化を追跡した。試験は4週間実施し、得られた結果を以下の4段階に分類し、その総合評価を微生物試験の結果とした。
(評価基準)
◎:確実に減少した
○:減少したが、減少速度がやや遅かった
△:減少したが、減少速度が明らかに遅かった ×:増減なし
スティンギングテストにより組成物の塗布時の刺激性を評価した。化粧料において、一過性の刺激を感じやすいパネラー10名を用い、刺激感を感じた場合に教えてほしいと伝え、目の下の頬に各サンプルを少量塗ってもらい、刺激の有無を確認した。評価基準としては、
2点:刺激を感じない
1点:少し刺激を感じる
0点:刺激を感じる
と設定し、各サンプルについて算出した10名の被験者の平均点に基づき、以下の4段階評価を行った。
◎:1.5点以上
○:1.5~1点
△:1~0.5点。
×:0.5点以下
Claims (8)
- モノアルキルグリセリルエーテル、有機変性粘土鉱物、及び微粒子金属酸化物を含有する油中水型乳化組成物であって、
前記モノアルキルグリセリルエーテルは、1-(2-エチルヘキシル)グリセリルエーテル、1-ヘキシルグリセリルエーテル、1-ヘプチルグリセリルエーテル、1-(3,5,5-トリメチルヘキシル)グリセリルエーテル、1-オクチルグリセリルエーテル、1-デシルグリセリルエーテル、1-ドデシルグリセリルエーテルからなる群から選択され、
前記モノアルキルグリセリルエーテルの含有量が、組成物全体に対して0.05質量%以上であり、
粉体の総含有量が組成物全体に対して10質量%以上であり、
パラベン類を実質的に含有しない、油中水型乳化組成物。 - モノアルキルグリセリルエーテル、有機変性粘土鉱物、及び微粒子金属酸化物を含有する油中水型乳化組成物であって、
前記モノアルキルグリセリルエーテルは、1-(2-エチルヘキシル)グリセリルエーテル、1-ヘキシルグリセリルエーテル、1-ヘプチルグリセリルエーテル、1-(3,5,5-トリメチルヘキシル)グリセリルエーテル、1-オクチルグリセリルエーテル、1-デシルグリセリルエーテル、1-ドデシルグリセリルエーテルからなる群から選択され、
前記有機変性粘土鉱物の含有量が組成物全体に対して0.5~4質量%であり、
粉体の総含有量が組成物全体に対して10質量%以上であり、
パラベン類を実質的に含有しない、油中水型乳化組成物。 - さらに、フェノキシエタノール、及び/又は1,2-アルキレンジオールを含有する、請求項1又は2に記載の油中水型乳化組成物。
- さらに、ポリエーテル変性シリコーン、及び/又はポリグリセリン変性シリコーンを含有する、請求項1~3のいずれか一項に記載の油中水型乳化組成物。
- 前記モノアルキルグリセリルエーテルの含有量が組成物全体に対して0.05質量%以上である、請求項2~4のいずれか一項に記載の油中水型乳化組成物。
- 炭素数14~22の直鎖又は分岐鎖の2価カルボン酸の少なくとも1種と、平均重合度8~15のポリグリセリンとのオリゴマーエステルを含有する、請求項2~5のいずれか一項に記載の油中水型乳化組成物。
- 粉体の総含有量が組成物全体に対して40質量%以下である、請求項1~6のいずれか一項に記載の油中水型乳化組成物。
- 皮膚外用剤である、請求項1~7のいずれか一項に記載の油中水型乳化組成物。
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