JP3543838B2 - Oil-in-water makeup cosmetics - Google Patents

Description

（式中、Ｒは炭素数１〜６の炭化水素またはフェニル基を表し；ｎは１．０〜１．８の値を表す）
で示される平均式の単位からなる有機シリコーン樹脂、芳香族炭化水素樹脂およびポリイソプレン樹脂の中から選ばれる１種または２種以上の油溶性樹脂とを含有してなる水中油型メーキャップ化粧料が提供される。
また本発明によれば、上記内相に疎水性表面をもつ色材をさらに含有してなる上記水中油型メーキャップ化粧料が提供される。
【００１１】
以下、本発明について詳述する。
【００１２】
まず外相（水相）について説明する。本発明においては、外相に水および水溶性高分子としてポリビニルアルコールを必須構成成分として含む。
【００１９】
ポリビニルアルコールは、皮膜形成能が高く、接着性の高い水溶性高分子で、その配合量は、化粧料全重量に対し０．０１〜１０重量％配合されるのが好ましく、通常の洗顔料での落としやすさをより向上させるという点からは０．１〜１０重量％がより好ましく、さらには０．５〜１０重量％が最も好ましい。
【００２０】
なお、この外相にはさらに色材を配合することができる。色材としては、一般の化粧品に用いられる色材であれば何でもよい。ただし、後で説明するように、耐水性という点からは色材は疎水性の表面をもつものを内相（油相）中に配合するのがさらに好ましいが、これに限定されるものではない。
【００２１】
また外相にはさらに、一般に化粧品に用いられるポリマーエマルジョン樹脂を適宜配合してもよい。このポリマーエマルジョン樹脂として、例えばアクリル酸エチル、メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸、塩化ビニリデン等のモノマーと塩酸ビニルとの共重合エマルジョン等が挙げられる。
【００２２】
上記以外にも、目的に応じて本発明の効果を損なわない量的、質的範囲内で、防腐剤、アルコール、多価アルコール、薬剤、界面活性剤、増粘剤、粘土鉱物、香料、酸化防止剤、紫外線吸収剤、保湿剤等を配合してもよい。
【００２３】
本発明においては、外相（水相）の配合量は化粧料全重量に対し３０〜９５重量％であるのが好ましく、使用感（なめらかさ）の点からは４０〜９５重量％がより好ましく、さらには５０〜９０重量％が最も好ましい。
【００２４】
次に内相（油相）について説明する。本発明においては、内相に揮発性油分および油溶性樹脂を必須構成成分として含み、さらに疎水表面をもつ色材を含むことができる。
【００２５】
本発明で用いられる揮発性油分は、油溶性樹脂に対して溶媒となり得るもので、沸点が６０〜２６０℃の範囲にある炭化水素油およびシリコーン油の中から選ばれる１種または２種以上が用いられる。具体的には、例えばアイソパー（登録商標）Ａ、同Ｃ、同Ｄ、同Ｅ、同Ｇ、同Ｈ、同Ｋ、同Ｌ、同Ｍ（以上、いずれもエクソン（株）製）、ソルトロール（登録商標）１００、同１３０、同２２０（以上、いずれもフィリップス（株）製）等が市販品として挙げられ、また下記化３、化４
【００２６】
【化３】

（式中、ｎは０〜３の整数を示す）
【００２７】
【化４】

（式中、ｎは４〜６の整数を示す）
で表される有機シリコーン油等が挙げられる。具体的には、オクタメチルテトラシクロシロキサン（例えば、信越シリコーン（株）製「エキセコールＤ−４」、東レ・ダウコーニング・シリコーン（株）製「ＳＨ２４４」「ＳＨ３４４」）、デカメチルシクロペンタシロキサン（例えば、信越シリコーン（株）製「エキセコールＤ−５」、東レ・ダウコーニング・シリコーン（株）製「ＳＨ２４５」「ＤＣ３４５」）、ドデカメチルシクロヘキサシロキサン（例えば、東レ・ダウコーニング・シリコーン（株）製「ＤＣ２４６」）等が挙げられる。
【００２８】
本発明で用いられる油溶性樹脂としては、下記の化５
【化５】

（式中、Ｒは炭素数１〜６の炭化水素またはフェニル基を表し；ｎは１．０〜１．８の値を表す）
で示される平均式の単位からなる有機シリコーン樹脂、芳香族炭化水素樹脂およびポリイソプレン樹脂の中から選ばれる１種または２種以上が挙げられる。
【００３０】
上記化５（化１、化２と同じ）で示される平均式の単位からなる有機シリコーン樹脂は、ＳｉＯ_２、ＲＳｉＯ_３／２、Ｒ_２ＳｉＯ（Ｒは水素、炭素数１〜６の炭化水素基またはフェニル基を表す）なる構造単位からなる共重合体、あるいはその末端をＲ_３ＳｉＯ_１／２（Ｒは上記と同じ）で封鎖した共重合体であり、具体的にはＫＲ−２８５、同−２７８、同−１１４（以上、いずれも信越化学工業（株）製）等が市販品として例示される。また、ジメチルポリシロキサンの重合度（ｎ）が５，０００〜８，０００のシリコーンゴムも用いることができる。
【００３１】
また、芳香族系炭化水素樹脂として日石ネオポリマーＴ、同１２０、同１４０（いずれも日本石油（株）製）等が、ポリイソプレン樹脂としてエスコレツ１０７１、同１１０３（いずれもエクソン（株）製）等が、それぞれ市販品として例示的に挙げられる。
【００３２】
油溶性樹脂としては、上記樹脂のなかでも特に上記化２で示される平均式単位からなる有機シリコーン樹脂を用いたときに良好な皮膜が得られ、耐水性、耐汗性、耐油性等の点で好ましい。さらにこの有機シリコーン樹脂のなかでも、平均式Ｒ_３ ＳｉＯ_１／２ 単位（Ｒは上記化２で定義したとおり）：ＳｉＯ_２ 単位＝（０．５：１）〜（１．５：１）（モル比）であるようＲ_３ ＳｉＯ_１／２ 単位とＳｉＯ２ 単位とを組み合わせて配合された有機シリコーン樹脂が特に好ましい。
【００３３】
この油溶性樹脂は、固形分として内相（油相）全量中に２〜６０重量％含有されるのが好ましく、使用性（なめらかさ）の点から２〜５０重量％であるのがより好ましく、さらに耐水、耐油性の点から５〜５０重量％が特に好ましい。
【００３４】
請求項２の発明において、内相（油相）には疎水表面をもつ色材がさらに含まれる。すでに述べたように、色材は外相（水相）に含まれていてもよいが、油相に含有させることにより、耐水性、特に耐にじみ性を著しく向上させることができる。この場合、色材を安定に油相中に配合するために色材表面は疎水性である必要がある。
【００３５】
疎水表面をもつ色材の具体的な例としては、カーボンブラック、カーミン、タルク、また赤色２０１号などの有機顔料等の色材、さらにナイロン、ポリエチレン等の樹脂粉末ならびにそれらを着色したもの等が挙げられる。
【００３６】
また、親水性表面をもつ色材であっても、疎水化処理を施した色材であればよい。例えばカオリン、炭酸カルシウム、亜鉛華、二酸化チタン、赤酸化鉄、黄酸化鉄、黒酸化鉄、群青、紺青、低次酸チタン、コバルトバイオレット、酸化クロム、水酸化クロム、チタン酸コバルト、オキシ塩化ビスマス、チタン−マイカ系パール顔料などの無機顔料等を疎水化処理したものも用いることができる。
【００３７】
なお、疎水化処理方法としては、撥水性を付与できる方法であればいかなるものでもよく、その方法は問わないが、例えば気相法、液相法、オートクレーブ法、メカノケミカル法等、通常の表面処理方法を用いることができる。
【００３８】
例えば疎水化処理剤を原料粉末に添加して処理を行う場合、適当な溶媒（ジクロルメタン、クロロホルム、ヘキサン、エタノール、キシレン、揮発性シリコーン等）に希釈して添加してもよく、あるいは直接添加してもよい。粉末と処理剤の混合攪拌には、ボールミル、ホジャーサイトボールミル、振動ボールミル、アトライター、ポットミル、ロッドミル、パンミル、ホモミキサー、ホモディスパー、ヘンシェルミキサー、ナウターミキサー等も使用することができる。この他にも、粉末表面の活性を利用し、気相反応により１００℃以下の低温で環状オルガノシロキサンを粉体表面上で重合させる方法（特公平１−５４３８０号）や、前記方法の後に表面のシリコーンポリマーのＳｉ−Ｈ部分にグリセロール、モノアリルエーテル等のペンダント基を付加させる方法（特公平１−５４３８１号）等を用いることができる。
【００３９】
疎水化処理剤としては、特に限定されるものではないが、脂肪酸デキストリン処理粉末、トリメチルシロキシ珪酸処理粉末、フッ素変性トリメチルシロキシ珪酸処理粉末、メチルフェニルシロキシ珪酸処理粉末、フッ素変性メチルフェニルシロキシ珪酸処理粉末、ジメチルポリシロキサン、ジフェニルポリシロキサン、メチルフェニルポリシロキサン等の低粘度〜高粘度油状ポリシリキサン処理粉末、ガム状ポリシロキサン処理粉末、メチルハイドロジェンポリシロキサン処理粉末、フッ素変性メチルハイドロジェンポリシロキサン処理粉末、メチルトリクロルシラン、メチルトリアルコキシシラン、ヘキサメチルジシラン、ジメチルジクロルシラン、ジメチルジアルコキシシラン、トリメチルクロルシラン、トリメチルアルコキシシラン等の有機シリル化合物あるいはそれらのフッ素置換体による処理粉末、エチルトリクロルシラン、エチルトリアルコキシシラン、プロピルトリクロルシラン、プロピルトリアルコキシシラン、ヘキシルトリクロルシラン、ヘキシルトリアルコキシシラン、長鎖アルキルトリクロルシラン、長鎖アルキルトリエトキシシラン等の有機変性シランあるいはそれらのフッ素置換体による処理粉末、アミノ変性ポリシロキサン処理粉末、フッ素変性ポリシロキサン処理粉末、フッ化アルキルリン酸処理粉末等が挙げられる。
【００４０】
これら色材は１種でもよく、あるいは２種以上を混合して用いてもよい。また耐水性の点から、油溶性樹脂に対して容積比３倍以下の割合で配合されるのが好ましい。
【００４１】
なお、油相中には、その他目的に応じて本発明の効果を損なわない量的、質的範囲内で化粧料に一般的に用いられる固型、半固型、液状油分、薬剤、乳化剤、増粘剤、紫外線吸収剤、粘土鉱物、香料、あるいは他の揮発性成分等を配合してもよい。
【００４２】
本発明においては、内相（油相）の配合量は化粧料全重量に対し５〜７０重量％が好ましく、使用感（なめらかさ）の点から５〜６０重量％がより好ましく、さらには１０〜５０重量％が最も好ましい。
【００４３】
【実施例】
次に、実施例によりさらに本発明を詳述する。本発明はこれによって限定されるものではない。なお、配合量（％）は重量％である。
【００４４】
実施例に先立ち、本発明の評価試験方法および評価方法について説明する。
【００４５】
＜評価方法＞
［水との接触角］
平板（スライドガラス板）上に各試料を一定厚（０．８ｍｍ）塗布し、１昼夜乾燥させた後、水滴を落として５分後の水の接触角を測定した。接触角が大きいほど撥水性が高く、耐水性に優れる。
［耐油試験］
５ｍｍ×３ｃｍのアクリル板に各試料を一定厚（０．８ｍｍ）塗布し、これをファンデーションオイル成分（流動パラフィン：イソステアリン酸＝１：１）に浸漬し、２５℃にて放置する。翌日、皮膜成分の状態を評価した。
【００４６】
◎： 皮膜が完全に残っている
○： 皮膜が３／４以上残っている
△： 皮膜が１／２以上残っている
×： 皮膜が１／２未満しか残っていない
また、以下の項目について専門パネル２０名による実使用テストにて試験、評価した。
［耐汗性、耐皮脂性］
各試料を塗布し、晴天時にテニスを２時間実施し、充分に汗をかいた後、肉眼にて判定した。
【００４７】
◎： １８名以上が、にじみなしと回答
○： １４〜１７名が、にじみなしと回答
△： ８〜１３名が、にじみなしと回答
×： ７名以下が、にじみなしと回答
［耐水性］
各試料を塗布し、シャワーを２分当てた後、肉眼にて判定した。
【００４８】
◎： １８名以上が、にじみなしと回答
○： １４〜１７名が、にじみなしと回答
△： ８〜１３名が、にじみなしと回答
×： ７名以下が、にじみなしと回答
［耐油性］
各試料を塗布し、晴天時にテニスを２時間実施し、十分に汗をかいた後、マスカラ、アイライナーの場合は下瞼への２次付着の有無を、ファンデーション、下地化粧料の場合には化粧くずれの状態を、それぞれ肉眼にて判定した。
【００４９】
◎： １８名以上が、２次付着、化粧くずれなしと回答
○： １４〜１７名が、２次付着、化粧くずれなしと回答
△： ８〜１３名が、２次付着、化粧くずれなしと回答
×： ７名以下が、２次付着、化粧くずれなしと回答
［使用性］
各試料を塗布するときの塗布のしやすさ（なめらかさ）などを総合評価した。
【００５０】
○： １５名以上が、良好と回答
△： ８〜１４名が、良好と回答
×： ７名以下が、良好と回答
［落としやすさの試験］
各試料を塗布後、通常の洗顔料を日常用いる程度の用量にて洗顔し、マスカラについてはまつ毛上のマスカラの、ファンデーションについては肌の上のファンデーションの、それぞれの落としやすさを評価した。
【００５１】
○： １５名以上が、落ちていると回答
△： １０〜１４名が、落ちていると回答
×： ９名以下が、落ちていると回答。
【００５２】

製法
（１）ベントナイトとカルボキシメチルセルロースナトリウムを乾燥状態で混ぜ、熱した精製水に加え膨潤させて均一にした（Ａ）。
（２）これにＢを加え６５〜７０℃に加熱した。
（３）ＣにＤを加え、加熱して融解し、放冷して熱ロールミルで練った後、再融解して７０℃に加熱した。
（４）ＡとＢの混合物にＥを加え、ここにさらにＣとＤの混合物を加えて乳化した後、攪拌しながら冷却した。
【００５３】
比較例２（油性乳化型マスカラ）
カルナバロウ ７．０％
ミツロウ ２．０％
マイクロクリスタリンワックス ２０．０％
ラノリン ０．４％
流動ポリイソブチレン ５７．６％
有機変性ベントナイト ３．０％
酸化鉄ブラック １０．０％
防腐剤 適量
製法
流動ポリイソブチレンの一部に有機変性ベントナイトを加え、コロイドミルを通して分散、ゲル化させた。次にワックス類および防腐剤を混合、加熱して溶かし、顔料を加えた後冷却してロールミルで練り、再び加熱して溶かした中に、ベントナイトゲルと残部の流動ポリイソブチレンを加え、攪拌しながら冷却した。
【００５４】

製法
油相： 一部のアイソパーＥを９０℃に加熱し、ポリイソプレン樹脂を溶解し、その後、残りのアイソパーＥおよび他の油相成分を混合し、そのまま攪拌、冷却した。
水相： 一部の水に水膨潤性粘土鉱物を入れ、ホモミキサーで十分に膨潤させた後、残りの水相成分を入れ、攪拌した。
【００５５】
次いで、上記のように調製した水相に、室温で攪拌を行いながら徐々に油相を加えながら乳化させ、さらにホモミキサーまたはディスパーで十分に乳化して調製した。
【００５６】

製法
流動ポリイソブチレンの一部に有機ベントナイトを加え、コロイドミルを通して分散、ゲル化させた。次にワックスおよび防腐剤を混合、加熱して溶かし、顔料を加えた後冷却してロールミルで混練し、再び加熱して溶かした中に、ベントナイトゲルと残部の流動ポリイソブチレンを加え、攪拌しながら冷却して調整した。
【００５７】

製法
基剤成分を混合して７０〜８０℃で加熱、融解した。この溶けた基剤にあらかじめ混合しておいた顔料を加え、この混合物をロールミルで混練した。次いでこれを加熱、溶解し、調色後、脱泡し、香料を加え、型または容器に流し込んで冷却して成形した。
【００５８】

製法
油相： 一部のアイソパーＥを９０℃に加熱し、ポリイソプレン樹脂を溶解し、その後、残りのアイソパーＥおよび他の油相成分を混合し、そのまま攪拌、冷却した。
水相： 一部の水に水膨潤性粘土鉱物を入れ、ホモミキサーで十分に膨潤させた後、残りの水相成分を入れ、攪拌した。
【００５９】
次いで、上記のように調製した水相に、室温で攪拌を行いながら徐々に油相を加えながら乳化させ、さらにホモミキサーまたはディスパーで十分に乳化して調製した。
【００６０】

製法
上記実施例１と同様にして調製した。
【００６１】

製法
上記実施例１と同様にして調製した。
【００６２】

製法
油相： 一部のオクタメチルテトラシクロシロキサンに有機変性粘土鉱物を加え、室温にて十分攪拌し、ゲル化させた。これに残りの油相成分を混合し、そのまま攪拌した。
水相： 一部の水に水膨潤性粘土鉱物を入れ、ホモミキサーで十分に膨潤させた後、残りの水相成分を入れ、攪拌した。
【００６３】
次いで、上記のように調製した水相に室温で攪拌を行いながら徐々に油相を加えながら乳化させ、さらにホモミキサーまたはディスパーで十分に乳化して調製した。
【００６４】

製法
実施例４と同様にして調製した。
【００６５】

製法
上記実施例４と同様にして調製した。
【００６６】
このようにして比較例１〜５で得た比較例品、実施例１〜６で得た実施例品を用いて、上記の評価試験を行った。結果を表１に示す。
【００６７】
【表１】

表１の結果から明らかなように、本発明に係る実施例品は、通常の洗顔料で落としやすいにもかかわらず、耐水性、耐汗性、耐皮脂性、耐油性、使用性（なめらかさ）のいずれにおいても優れ、化粧もちに優れる。
【００６８】
【発明の効果】以上詳述したように、本発明によれば、外相に水とポリビニルアルコールとを含有し、内相に揮発性油分（揮発性炭化水素油、揮発性シリコーン油）と油溶性樹脂（有機シリコーン樹脂、芳香族炭化水素樹脂、ポリイソプレン樹脂）とを含有するようにしたので、通常の洗顔料で落としやすいにもかかわらず、耐水性、耐汗性、耐皮脂性、耐油性、使用性（なめらかさ）のいずれにおいても優れ、化粧もちに優れた水中油型メーキャップ化粧料を提供することができるという効果を奏する。[0001]
[Industrial applications]
The present invention relates to an oil-in-water make-up cosmetic, and more particularly, is excellent in water resistance, sweat resistance, sebum resistance, oil resistance, and usability (smoothness) despite being easy to remove with a normal face wash. The present invention relates to an oil-in-water makeup cosmetic such as mascara, eyeliner, eyeshadow, and foundation, which has excellent makeup.
[0002]
[Prior art]
Conventionally used makeup cosmetics such as mascara, eyeliner, eyeshadow and foundation can be broadly classified into emulsifying type, emulsifying film type and oily type.
[0003]
The emulsified type is obtained by emulsifying a solid, semi-solid, oil-in-water base mainly composed of a liquid oil-water system. This has the advantage of excellent usability such as uniformity and spreading of the film, drying property, stability, etc.On the other hand, it is easy to fall off with water, sweat, tears, etc., especially in eyeliner, mascara, etc. There is a problem that it is easy to stain around the eyes.
[0004]
In order to solve this problem in mascara and the like, an emulsified film type of a solid, semi-solid, liquid oil-water-polymer emulsion system as disclosed in JP-A-50-125043, etc. It is. However, this type can also delay the permeation of water by adding a polymer emulsion.However, although the water resistance of the polymer emulsion itself is not considered, there is an advantage that it can be easily dropped with water. Conversely, water resistance is not always perfect.
[0005]
The oily type is a solid type, semi-solid type, mainly containing a liquid oil component to a volatile branched hydrocarbon system. It has good water resistance and drying properties, but its composition is such that solid paraffin, wax, lanolin derivatives, etc. are dissolved in volatile branched hydrocarbons and various pigment powders are dispersed therein, so oil resistance is high. There is a disadvantage that it is inferior. Therefore, especially in the case of mascara, etc., even after application and drying, the eyelids dissolve in oil contained in sebum and other cosmetics such as foundation due to blinking, and the pigment is chipped from the coating film and adheres to the lower eyelid (secondary) Adhering) and easily stain the area around the eyes. In addition, it is necessary to use a special oily remover for removing makeup, and there is also a disadvantage that it takes a considerable amount of time to clean.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and the object thereof is to provide a water-resistant, sweat-resistant, sebum-resistant, oil-resistant, and easy-to-use (even though easy to remove with a normal face wash). An object of the present invention is to provide an oil-in-water makeup cosmetic such as mascara, eyeliner, eyeshadow, and foundation, which is excellent in cosmetic durability.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive research to solve the problems of the above conventional example,
(1) The external phase that directly touches the eyelashes and skin, etc. is made into an aqueous phase, and by adding a water-soluble polymer to it, it is excellent in usability, safety, stability, etc., and is resistant to rain and tears Nevertheless, it is easy to remove from normal face wash, and it can prevent bleeding by oil. (2) A volatile oil component and an oil-soluble resin are blended in the internal phase (oil phase). This has led to the finding that the water resistance, particularly the bleeding resistance can be significantly improved, and the like, and the present invention has been completed based on these findings.
[0008]
That is, according to the present invention, containing water and polyvinyl alcohol in the external phase, boiling point internal phase one or more selected from among hydrocarbon oils and silicone oils in the range of sixty to two hundred and sixty ° C. Volatile components and the following chemical formula 1
Embedded image

(Wherein, R represents a hydrocarbon having 1 to 6 carbon atoms or a phenyl group; n represents a value of 1.0 to 1.8)
An oil-in-water makeup cosmetic comprising one or more oil-soluble resins selected from organic silicone resins, aromatic hydrocarbon resins and polyisoprene resins comprising units of the average formula represented by Provided.
According to the present invention, there is provided the oil-in-water makeup cosmetic further comprising a coloring material having a hydrophobic surface in the internal phase.
[0011]
Hereinafter, the present invention will be described in detail.
[0012]
First, the external phase (aqueous phase) will be described. In the present invention, the outer phase contains water and polyvinyl alcohol as a water-soluble polymer as essential components.
[0019]
Polyvinyl alcohol is a water-soluble polymer having high film-forming ability and high adhesiveness , and is preferably incorporated in an amount of 0.01 to 10% by weight based on the total weight of the cosmetic. From the viewpoint of further improving the ease of dropping, 0.1 to 10% by weight is more preferable, and 0.5 to 10% by weight is most preferable.
[0020]
It should be noted that a coloring material can be further added to this external phase. The coloring material may be any coloring material used in general cosmetics. However, as described later, from the viewpoint of water resistance, it is more preferable to mix a colorant having a hydrophobic surface in the internal phase (oil phase), but the present invention is not limited to this. .
[0021]
Further, a polymer emulsion resin generally used for cosmetics may be appropriately added to the outer phase. Examples of the polymer emulsion resin include a copolymer emulsion of a monomer such as ethyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid, and vinylidene chloride with vinyl chloride.
[0022]
In addition to the above, depending on the purpose, within the quantitative and qualitative ranges that do not impair the effects of the present invention, preservatives, alcohols, polyhydric alcohols, drugs, surfactants, thickeners, clay minerals, fragrances, oxidation You may mix an inhibitor, an ultraviolet absorber, a humectant, etc.
[0023]
In the present invention, the amount of the external phase (aqueous phase) is preferably 30 to 95% by weight based on the total weight of the cosmetic, and more preferably 40 to 95% by weight from the viewpoint of feeling of use (smoothness). Most preferably, the content is 50 to 90% by weight.
[0024]
Next, the internal phase (oil phase) will be described. In the present invention, the internal phase contains a volatile oil component and an oil-soluble resin as essential components, and may further contain a coloring material having a hydrophobic surface.
[0025]
Volatile oil component used in the present invention, which can be a solvent for the oil-soluble resin, one or more boiling point is selected from hydrocarbon oils and silicone oils in the range of sixty to two hundred and sixty ° C. Is used. Specifically, for example, Isopar (registered trademark) A, C, D, E, G, H, K, L, M (all of which are manufactured by Exxon), Saltrol (Registered trademark) 100, 130 and 220 (all manufactured by Philips Co., Ltd.) and the like.
[0026]
Embedded image

(Where n represents an integer of 0 to 3)
[0027]
Embedded image

(Where n represents an integer of 4 to 6)
And the like. Specifically, octamethyltetracyclosiloxane (for example, “EXECOL D-4” manufactured by Shin-Etsu Silicone Co., Ltd., “SH244” and “SH344” manufactured by Dow Corning Toray Silicone Co., Ltd.), decamethylcyclopentasiloxane ( For example, "EXECOL D-5" manufactured by Shin-Etsu Silicone Co., Ltd., "SH245" and "DC345" manufactured by Dow Corning Toray Silicone Co., Ltd.), dodecamethylcyclohexasiloxane (for example, Dow Corning Toray Silicone Co., Ltd.) “DC246”).
[0028]
As the oil-soluble resin used in the present invention, the following formula 5
Embedded image

(Wherein, R represents a hydrocarbon having 1 to 6 carbon atoms or a phenyl group; n represents a value of 1.0 to 1.8)
And one or more selected from organic silicone resins, aromatic hydrocarbon resins, and polyisoprene resins comprising units of the average formula represented by the following formula:
[0030]
Organic silicone resins composed of units of the average formula represented by the above formulas (the same as formulas 1 and 2) include SiO ₂ , RSiO _3/2 , and R ₂ SiO (R is hydrogen, a hydrocarbon having 1 to 6 carbon atoms). Or a phenyl group), or a copolymer whose terminal is blocked with R ₃ SiO _1/2 (R is the same as described above), specifically KR-285, Examples thereof are -278 and -114 (both manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Further, a silicone rubber having a polymerization degree (n) of dimethylpolysiloxane of 5,000 to 8,000 can also be used.
[0031]
Further, Nisseki Neopolymer T, 120 and 140 (all manufactured by Nippon Oil Co., Ltd.) and the like are used as aromatic hydrocarbon resins , and Escholes 1071 and 1103 (all are manufactured by Exxon Corporation) are used as polyisoprene resins . ) And the like are each exemplified as commercially available products.
[0032]
As the oil-soluble resin, a good film is obtained particularly when an organic silicone resin having the average formula unit represented by the above formula 2 is used among the above-mentioned resins, and water resistance, sweat resistance, oil resistance and the like are obtained. Is preferred. Further, among these organic silicone resins, the average formula R ₃ SiO _1/2 unit (R is as defined in the above formula 2): SiO ₂ unit = (0.5: 1) to (1.5: 1) ( (Molar ratio), an organosilicone resin combined with a combination of R ₃ SiO _1/2 units and SiO ₂ units is particularly preferable.
[0033]
This oil-soluble resin is preferably contained as a solid content in the entire internal phase (oil phase) in an amount of 2 to 60% by weight, and more preferably 2 to 50% by weight from the viewpoint of usability (smoothness). From the viewpoints of water resistance and oil resistance, 5 to 50% by weight is particularly preferable.
[0034]
In the invention of claim 2, the inner phase (oil phase) further includes a coloring material having a hydrophobic surface. As described above, the coloring material may be contained in the external phase (aqueous phase), but when it is contained in the oil phase, the water resistance, particularly the bleeding resistance, can be remarkably improved. In this case, the surface of the coloring material needs to be hydrophobic in order to stably blend the coloring material into the oil phase.
[0035]
Specific examples of coloring materials having a hydrophobic surface include carbon black, carmine, talc, coloring materials such as organic pigments such as Red No. 201, and resin powders such as nylon and polyethylene and those obtained by coloring them. No.
[0036]
Further, even a coloring material having a hydrophilic surface may be a coloring material subjected to a hydrophobic treatment. For example, kaolin, calcium carbonate, zinc white, titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, navy blue, lower hypotitanium, cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, bismuth oxychloride And those obtained by subjecting an inorganic pigment such as a titanium-mica pearl pigment to a hydrophobic treatment.
[0037]
The hydrophobic treatment method may be any method as long as it can impart water repellency, and the method is not limited. For example, a gas phase method, a liquid phase method, an autoclave method, a mechanochemical method, or the like may be used. Processing methods can be used.
[0038]
For example, when the treatment is carried out by adding a hydrophobizing agent to the raw material powder, it may be diluted with an appropriate solvent (dichloromethane, chloroform, hexane, ethanol, xylene, volatile silicone, etc.) and added, or may be added directly. You may. For mixing and stirring the powder and the treating agent, a ball mill, a Hogersight ball mill, a vibrating ball mill, an attritor, a pot mill, a rod mill, a pan mill, a homomixer, a homodisper, a Henschel mixer, a Nauter mixer and the like can also be used. In addition to this, a method of polymerizing a cyclic organosiloxane on a powder surface at a low temperature of 100 ° C. or less by a gas phase reaction utilizing the activity of the powder surface (Japanese Patent Publication No. 1-54380), A method of adding a pendant group such as glycerol or monoallyl ether to the Si-H portion of the silicone polymer (Japanese Patent Publication No. 1-54381) can be used.
[0039]
Examples of the hydrophobizing agent include, but are not particularly limited to, fatty acid dextrin-treated powder, trimethylsiloxysilicate-treated powder, fluorine-modified trimethylsiloxysilicate-treated powder, methylphenylsiloxysilicate-treated powder, and fluorine-modified methylphenylsiloxysilicate-treated powder Dimethylpolysiloxane, diphenylpolysiloxane, low-viscosity oily polysiloxane treatment powder such as methylphenylpolysiloxane, gum-like polysiloxane treatment powder, methylhydrogenpolysiloxane treatment powder, fluorine-modified methylhydrogenpolysiloxane treatment powder, Methyltrichlorosilane, methyltrialkoxysilane, hexamethyldisilane, dimethyldichlorosilane, dimethyldialkoxysilane, trimethylchlorosilane, trimethylalkoxysilane, etc. Powder treated with an organic silyl compound or a fluorine-substituted product thereof, ethyltrichlorosilane, ethyltrialkoxysilane, propyltrichlorosilane, propyltrialkoxysilane, hexyltrichlorosilane, hexyltrialkoxysilane, long-chain alkyltrichlorosilane, long-chain alkyltrichlorosilane Powders treated with an organically modified silane such as ethoxysilane or a fluorine-substituted product thereof, powders treated with an amino-modified polysiloxane, powders treated with a fluorine-modified polysiloxane, and powders treated with a fluoroalkylphosphoric acid are exemplified.
[0040]
These coloring materials may be used alone or in combination of two or more. Also, from the viewpoint of water resistance, it is preferable to mix the oil-soluble resin at a volume ratio of 3 times or less.
[0041]
In the oil phase, depending on the other purpose, the solid, semi-solid, liquid oil, liquid oil, drug, emulsifier, which are generally used in cosmetics within a quantitative and qualitative range that do not impair the effects of the present invention, Thickeners, ultraviolet absorbers, clay minerals, perfumes, or other volatile components may be added.
[0042]
In the present invention, the amount of the internal phase (oil phase) is preferably from 5 to 70% by weight, more preferably from 5 to 60% by weight, and more preferably from 10 to 60% by weight, based on the total weight of the cosmetic. ~ 50% by weight is most preferred.
[0043]
【Example】
Next, the present invention will be described in more detail with reference to examples. The present invention is not limited by this. The amount (%) is% by weight.
[0044]
Prior to the examples, an evaluation test method and an evaluation method of the present invention will be described.
[0045]
<Evaluation method>
[Contact angle with water]
Each sample was applied on a flat plate (slide glass plate) at a constant thickness (0.8 mm), dried for one day and night, dropped, dropped, and the contact angle of water was measured 5 minutes later. The larger the contact angle, the higher the water repellency and the better the water resistance.
[Oil resistance test]
Each sample is applied to a 5 mm × 3 cm acrylic plate at a constant thickness (0.8 mm), immersed in a foundation oil component (liquid paraffin: isostearic acid = 1: 1), and left at 25 ° C. The next day, the state of the film components was evaluated.
[0046]
◎: The film remains completely ○: The film remains ／ or more △: The film remains 以上 or more ×: The film remains less than １ ／ and specializes in the following items Tests and evaluations were conducted in actual use tests by 20 panelists.
[Sweat resistance, sebum resistance]
Each sample was applied, tennis was performed for 2 hours in fine weather, and after sufficient sweating, it was visually judged.
[0047]
◎: 18 or more respondents with no bleeding ○: 14 to 17 respondents with no bleeding △: 8 to 13 respondents with no bleeding ×: 7 or less responded with no bleeding [waterproof]
After applying each sample and applying a shower for 2 minutes, it was judged visually.
[0048]
◎: 18 or more people answered that no bleeding ○: 14 to 17 people answered that they did not bleed △: 8 to 13 people answered that they did not bleed ×: 7 or less answered that they did not bleed [oil resistance]
After applying each sample and playing tennis for 2 hours in fine weather, after sweating enough, in the case of mascara and eyeliner, check for the presence or absence of secondary adhesion to the lower eyelid, in the case of foundation, base makeup The state of makeup loss was visually determined.
[0049]
◎: 18 or more answered that secondary adhesion and no makeup loss ○: 14 to 17 responded that secondary adhesion and no makeup loss △: 8 to 13 responded that secondary adhesion and no makeup loss ×: Less than 7 people answered that secondary adhesion and makeup loss did not occur [Usability]
The ease of application (smoothness) when applying each sample was comprehensively evaluated.
[0050]
：: 15 or more answered that it was good △: 8 to 14 answered that it was good X: 7 or less answered that it was good [Test for ease of dropping]
After the application of each sample, the face was washed with an ordinary facial cleanser at a dose of daily use, and the ease of removal of the mascara on the eyelashes for mascara and the foundation on the skin for foundation was evaluated.
[0051]
：: 15 or more respondents have fallen △: 10 to 14 respondents have fallen ×: 9 or less respondents have fallen
[0052]

Production method (1) Bentonite and sodium carboxymethylcellulose were mixed in a dry state, added to heated purified water, and allowed to swell to be uniform (A).
(2) B was added thereto and heated to 65 to 70 ° C.
(3) D was added to C, melted by heating, allowed to cool, kneaded with a hot roll mill, then melted again and heated to 70 ° C.
(4) E was added to the mixture of A and B, and the mixture of C and D was further added thereto for emulsification, and then cooled while stirring.
[0053]
Comparative Example 2 (oil-based emulsified mascara)
Carnauba wax 7.0%
Beeswax 2.0%
Microcrystalline wax 20.0%
Lanolin 0.4%
Liquid polyisobutylene 57.6%
Organically modified bentonite 3.0%
Iron oxide black 10.0%
Preservative appropriate amount
Production method An organically modified bentonite was added to a part of the liquid polyisobutylene, and dispersed and gelled through a colloid mill. Next, the waxes and preservatives are mixed and heated to dissolve, the pigment is added, then the mixture is cooled and kneaded with a roll mill, and again heated and melted, while the bentonite gel and the remaining liquid polyisobutylene are added, and the mixture is stirred. Cool.
[0054]

Production method Oil phase: A portion of Isopar E was heated to 90 ° C. to dissolve the polyisoprene resin, and then the remaining Isopar E and other oil phase components were mixed, stirred and cooled as they were.
Aqueous phase: A water-swellable clay mineral was added to a part of water, and after sufficiently swelling with a homomixer, the remaining aqueous phase components were added and stirred.
[0055]
Next, the aqueous phase prepared as described above was emulsified while gradually adding an oil phase while stirring at room temperature, and then sufficiently emulsified with a homomixer or a disper to prepare.
[0056]

Production method Organic bentonite was added to a part of the liquid polyisobutylene, and dispersed and gelled through a colloid mill. Next, the wax and the preservative are mixed and heated to dissolve, the pigment is added, then the mixture is cooled and kneaded with a roll mill, and then heated and melted again, while the bentonite gel and the remaining liquid polyisobutylene are added and stirred. Cooled and adjusted.
[0057]

Production method The base components were mixed and heated and melted at 70-80 ° C. The premixed pigment was added to the dissolved base, and the mixture was kneaded with a roll mill. Then, this was heated and dissolved, and after toning, defoamed, added with a fragrance, poured into a mold or a container, cooled and molded.
[0058]

Production method Oil phase: A portion of Isopar E was heated to 90 ° C. to dissolve the polyisoprene resin, and then the remaining Isopar E and other oil phase components were mixed, stirred and cooled as they were.
Aqueous phase: A water-swellable clay mineral was added to a part of water, and after sufficiently swelling with a homomixer, the remaining aqueous phase components were added and stirred.
[0059]
Next, the aqueous phase prepared as described above was emulsified while gradually adding an oil phase while stirring at room temperature, and further emulsified sufficiently using a homomixer or a disper.
[0060]

Production method Prepared in the same manner as in Example 1 above.
[0061]

Production method Prepared in the same manner as in Example 1 above.
[0062]

Production method Oil phase: An organically modified clay mineral was added to a part of octamethyltetracyclosiloxane, and the mixture was sufficiently stirred at room temperature to gel. The remaining oil phase components were mixed with the mixture and stirred as it was.
Aqueous phase: A water-swellable clay mineral was added to a part of water, and after sufficiently swelling with a homomixer, the remaining aqueous phase components were added and stirred.
[0063]
Subsequently, the aqueous phase prepared as described above was emulsified while gradually adding an oil phase while stirring at room temperature, and then sufficiently emulsified with a homomixer or a disper to prepare.
[0064]

Production method Prepared in the same manner as in Example 4.
[0065]

Production method Prepared in the same manner as in Example 4 above.
[0066]
The evaluation test described above was performed using the comparative product obtained in Comparative Examples 1 to 5 and the product obtained in Examples 1 to 6 in this way. Table 1 shows the results.
[0067]
[Table 1]

As is evident from the results in Table 1, the products of Examples according to the present invention are water-resistant, sweat-resistant, sebum-resistant, oil-resistant, and easy to use (smoothness) despite being easy to remove with normal face wash. ) Is excellent in any of the above, and is excellent in make-up.
[0068]
As described in detail above, according to the present invention, the outer phase contains water and polyvinyl alcohol, and the inner phase contains volatile oil (volatile hydrocarbon oil, volatile silicone oil) and oil-soluble oil. It contains resin (organic silicone resin, aromatic hydrocarbon resin, polyisoprene resin) , so it is easy to remove with normal face wash, but water resistance, sweat resistance, sebum resistance, oil resistance In addition, the present invention has an effect of being able to provide an oil-in-water make-up cosmetic which is excellent in all of usability (smoothness) and is excellent in makeup.

Claims (2)

Containing water and polyvinyl alcohol in the external phase, and one or more volatile components boiling point is selected from hydrocarbon oils and silicone oils in the range of sixty to two hundred and sixty ° C. in the internal phase, the following Chemical 1

(Wherein, R represents a hydrocarbon having 1 to 6 carbon atoms or a phenyl group; n represents a value of 1.0 to 1.8)
An oil-in-water makeup cosmetic comprising one or more oil-soluble resins selected from among organic silicone resins, aromatic hydrocarbon resins and polyisoprene resins comprising units of the average formula represented by the formula: . The oil-in-water makeup cosmetic according to claim 1, further comprising a coloring material having a hydrophobic surface in the internal phase.