JP3554174B2 - Powder-resin complex containing cosmetics - Google Patents
Powder-resin complex containing cosmetics Download PDFInfo
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- JP3554174B2 JP3554174B2 JP02769998A JP2769998A JP3554174B2 JP 3554174 B2 JP3554174 B2 JP 3554174B2 JP 02769998 A JP02769998 A JP 02769998A JP 2769998 A JP2769998 A JP 2769998A JP 3554174 B2 JP3554174 B2 JP 3554174B2
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Landscapes
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Medicinal Preparation (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、色材が分散性或いは沈降性を改善されたことを特徴とする、ペイントや化粧料に好適な着色用の組成物に関する。
【０００２】
【従来の技術】
ベンガラや酸化チタン等に代表される顔料やマイカやセリサイト等の体質粉体等の粉体は、化粧料、ペイント等の分野で広く用いられている。一般にこの様な粉体類の表面は等電点を有しており、水系溶媒に対しては、いわゆる電気二重層を形成して分散するとされている。従って、この様な分散系に於いては、この電気二重層の形成を阻害する電解物質の存在下では、安定な分散系が得られず、粉体凝集が起こることがしばしばであった。特に、被膜剤や増粘剤として用いられるアクリル酸系樹脂やアクリル酸系高分子はこの様な現象を起こしやすいことが既に知られている。即ち、電解性物質、取り分けアクリル酸系樹脂やアクリル酸系高分子と共存しうる粉体分散系が求められているにもかかわらず、得られていないと言っても過言ではなかった。又、この様なメカニズムでの分散では、作成直後安定であっても、経時的に凝集・沈澱を引き起こすこともしばしばであった。更に、親水性高分子をコア・シェル構造でコーティングして分散安定性を向上させる手段も考案され、分散性は著しく向上したが、乳化重合の際に用いる乳化剤がコア部分に入り込んでしまうと言う欠点が残った。即ち、経時的にも安定な粉体分散系は求められているにもかかわらず得られていないと言っても過言ではなかった。従って、この様な色材の分散を必須としている、ペイントや化粧料などの着色用の組成物に於いて、この様な分散性の改良は望まれているにも関わらず未だ充分には達成されていないのが現状と言わざるを得ない。
【０００３】
一方、疎水化処理した粉体と親水性樹脂とアクリル酸、メタクリル酸及びそれらのエステルから選ばれる１種乃至は２種以上の重合体及び／又は共重合体を含有する粉体−樹脂複合体組成物はまだ知られておらず、従ってこのものが分散性に優れることも全く知られていなかった。従って、このものをペイントや化粧料などの着色用の組成物に含有させると、着色剤の分散安定性の良い着色用の組成物が得られることも全く知られていなかった。
【０００４】
【発明が解決しようとする課題】
本発明はこの様な状況下行われたものであり、色材の分散安定性に優れる着色用の組成物を提供することを課題とする。
【０００５】
【課題を解決するための手段】
本発明者等はこの様な状況に鑑みて、着色用の組成物に於ける、色材の分散・安定性の向上を求めて鋭意研究を重ねた結果、ハイドロジェンメチルポリシロキサン焼き付け、ジメチポリシロキサン焼き付け処理、金属石鹸コーティング処理、アシル化アミノ酸塩コーティング処理等の疎水化処理をした粉体と親水性樹脂とアクリル酸、メタクリル酸及びそれらのエステルから選ばれる１種乃至は２種以上の重合体及び／又は共重合体を含有する粉体−樹脂複合体組成物を色材として含有する着色用の組成物にその様な性質を見いだし発明を完成させた。以下、本発明について、発明の実施の形態を中心に詳細に説明する。
【０００６】
【発明の実施の形態】
（１）本発明で使用する粉体−樹脂複合体組成物
本発明の粉体−樹脂複合体組成物は疎水化処理した粉体と親水性樹脂とを含有することを特徴とする。本発明の組成物における疎水化処理粉体の疎水化方法としては、通常知られている疎水化処理であれば特段の限定を受けず、例えば、ハイドロジェンポリシロキサン焼き付け処理、ジメチルポリシロキサン焼き付け処理、金属石鹸コーティング処理、アシル化アミノ酸塩コーティング処理等が挙げられる。本発明の粉体−樹脂複合体組成物は、例えば、次のような手順で製造される。疎水化処理粉体を親水性樹脂でコーティングする。この時、親水性樹脂によるコーティングは、親水性樹脂を固体のまま或いは水溶液の状態でボールミル等で処理しコーティングする方法で行えばよい。この様な方法によれば、親水性樹脂によって疎水化処理粉体が緊密に被覆されるためである。この様にして得られた粉体は、必要に応じて乾燥や粉砕などの処理を行った後、水性担体に分散した後、これにアクリル酸、メタクリル酸及びそれらのエステルから選ばれる１種乃至は２種以上を加え重合させれば得ることができる。
【０００７】
（２）本発明で用いる粉体−樹脂複合体組成物の作成に用いる粉体
上記粉体−樹脂複合体組成物で、疎水化処理粉体のベースとして用いることの出来る粉体は、通常化粧料やペイントなどで証されているものであれば、特段の限定無く用いることが出来る。この様な粉体としては、例えば、酸化チタン、ベンガラ、群青、紺青、黄色酸化鉄、酸化亜鉛、酸化クロム、水酸化クロム等の顔料類や、マイカ、セリサイト、タルク等の体質粉体、チタンマイカ等のパール剤等が例示できる。これらの粉体を、例えば、アルミナ処理、シリカ処理、燐酸処理などの疎水化処理以外の表面処理したものも、本発明の効果を損なわない限りに於いて使用することが出来る。粉体は唯一種を用いても良いし、二種以上を用いても良い。
【０００８】
（３）上記粉体の疎水化処理
上記粉体の疎水化処理としては、通常知られている疎水化処理であれば特段の限定を受けず、例えば、ハイドロジェンポリシロキサン焼き付け処理、ジメチルポリシロキサン焼き付け処理、金属石鹸コーティング処理、アシル化アミノ酸塩コーティング処理等が挙げられる。かかる疎水化処理は常法に従って行えば良く、ハイドロジェンメチルポリシロキサンやジメチルポリシロキサン焼き付け処理であれば、ベースとなる粉体に対して０．１〜２０重量部の当該シリコーンを粉体にコーティングし、８０〜２００℃で焼き付け処理すればよい。又、金属石鹸処理であれば、粉体と脂肪酸石鹸を水性担体中に共存させ、塩化アルミニウムや塩化亜鉛等の可溶性金属塩を加え、金属石鹸を粉体上に析出させればよい。このものを取り出し乾燥させれば、金属石鹸コーティング粉体を得ることができる。この方法に準じてアシル化アミノ酸塩コーティング粉体も作成することができる。金属石鹸やアシル化アミノ酸塩はベースになる粉体に対して０．１〜２０重量％用いるのが好ましい。
【０００９】
（４）粉体−樹脂複合体組成物の作成に用いる親水性高分子
上記粉体−樹脂複合体組成物の作成に用いる親水性高分子としては、親水性基を有し水に一様に分散又は可溶化するものであれば特段の限定無く用いることが出来、この様な高分子としては、ビニルアルコール、アクリル酸、メタアクリル酸、アクリル酸アルキル、メタクリル酸アクリル等を構成モノマーに有する、重合体又は共重合体が例示できる。ここで、アルキルとしては、炭素数１〜４の、メチル、エチル、プロピル、イソプロピル、ノルマルブチル、イソブチル、ターシャリーブチルが好ましく、中でもノルマルブチルが特に好ましい。この様な親水性高分子を例示すれば、ポリビニルアルコール、ポリアクリル酸、ポリメタアクリル酸、アクリル酸−ビニルアルコールコポリマー、メタアクリル酸−ビニルアルコールコポリマー、アクリル酸−メタアクリル酸コポリマー及び／又はこれらのエステルが挙げられる。これらはただ一種を用いても、二種以上を組み合わせて用いても良い。更にこれ以外にも、本発明の効果を損なわない範囲で、スチレン、α−メチルスチレン、ブタジエン、アクリロニトリルをコポリマーの成分として含有することが出来る。コポリマーに於いて、ビニルアルコール、アクリル酸、メタアクリル酸の構成割合は５重量％以上が好ましく、より好ましくは１０重量％以上であり、更に好ましくは１５重量％以上である。又、粉体と親水性高分子の好ましい割合は、１：１０〜１０：１であり、より好ましくは１：５〜５：１であり、更に好ましくは２：５〜５：２である。これらを例えば、乾式で溶媒を用いずにボールミル等によって処理したり、水などの溶媒存在下混在させながら溶媒を除去したりすることによってコーティングさせることができる。更に、金属石鹸処理やアシル化アミノ酸塩処理をしたものについては、金属石鹸処理やアシル化アミノ酸塩処理を湿式にて行い、湿潤した状態で水溶性樹脂をコーティングする事もできる。コーティングに際しては、水溶性樹脂はカルボン酸フリーの状態でコーティングし、しかる後必要に応じて中和してイオン化させても良いし、中和してイオン化した状態でコーティングしても良い。
【００１０】
（５）上記粉体−樹脂複合体組成物で用いるアクリル酸系重合体・共重合体
上記粉体−樹脂複合体組成物で用いる、アクリル酸、メタクリル酸及びそれらのエステルから選ばれる１種乃至は２種以上の重合体及び／又は共重合体を構成する、モノマーとしては、通常この様な重合体・共重合体の構成要素として用いられるものであれば、特段の限定を受けず用いることが出来る。この様なモノマーとしては、例えば、アクリル酸、アクリル酸アルキル、メタアクリル酸、メタアクリル酸アルキル等のアクリル酸或いはメタアクリル酸誘導体が好ましく例示でき、これらの中では、２−エチルヘキシルアクリレートやメチルメタアクリレートが好ましく例示できる。これらの重合反応は、必要に応じて水などの溶媒を用い、上記親水性樹脂で処理した疎水化粉体の存在下、例えばアゾビスイソブチロニトリル、過硫酸カリウム、過硫酸アンモニウム等の重合開始剤を用いて反応させればよい。好ましい粉体に対する当該モノマーの割合は、親水性樹脂で処理した疎水化粉体：モノマーの比が、１：１０〜１０：１であり、より好ましくは１：５〜５：１であり、更に好ましくは２：５〜５：２である場合である。更に、疎水化処理が金属石鹸コーティングやアシル化アミノ酸塩コーテイングによる場合は、ベース粉体を水性溶媒に分散させ、水溶性樹脂を中和などでイオン化させた状態でこの水性溶媒に加え、ここに上記アクリル酸系或いはメタクリル酸系のモノマーを滴下し、重合開始剤を加え重合させて本発明の粉体−樹脂複合体としても良い。かくして得られた本発明の必須成分である粉体−樹脂複合体は水性担体に対して優れた分散性を示し、沈降性が著しく改善しているため、本発明の着色組成物である、ファンデーションやネイルカラー等の化粧料原料やペイントなどの原料として極めて有用である。取り分け、使用している樹脂成分と溶媒の種類より、爪に対して優しいネイルカラーを作成する原料として取り分け有用である。
【００１１】
（６）粉体−樹脂複合体組成物の製造例
以下に製造例を示して、本発明について更に詳細に説明するが、本発明の組成物の原料がこれら製造例にのみ限定を受けないことは言うまでもない。
【００１２】
＜参考例１＞
親水性樹脂の作成
攪拌機、還流冷却機、滴下ロート、温度計、窒素導入管を装着した反応器にイソプロピルアルコール５０重量部を秤込み、窒素ガスを吹き込み溶存酸素を除去した。滴下ロートより、イソプロパノール３０重量部、スチレン１５重量部、α−メチルスチレン４７重量部、アクリル酸２８重量部、アクリル酸ブチル１０重量部及びアゾビスイソブチロニトリル０．２重量部を、攪拌下８０℃まで昇温した反応器に滴下した。モノマー滴下終了後２時間８０℃で攪拌し、アゾビスイソブチロニトリル０．２重量部をイソプロパノール１０重量部に溶解させた液を滴下した。３時間８０℃で攪拌を続けた後、アゾビスイソブチロニトリル０．１重量部をイソプロパノール１０重量部で溶解させた液を滴下し、更に５時間８０℃で攪拌を続けた。反応終了後、反応液を室温に戻し、９５％アンモニア水を加えて中和し、水３００重量部を加え、減圧濃縮し固形分３０％の親水性樹脂分散液１を得た。
【００１３】
＜参考例２＞
親水性樹脂の作成
攪拌機、還流冷却機、滴下ロート、温度計、窒素導入管を装着した反応器にイソプロピルアルコール５０重量部を秤込み、窒素ガスを吹き込み溶存酸素を除去した。滴下ロートより、イソプロパノール３０重量部、スチレン１５重量部、α−メチルスチレン４７重量部、アクリル酸ブチル１０重量部、アクリル酸２８重量部及びアゾビスイソブチロニトリル０．２重量部を、攪拌下８０℃まで昇温した反応器に滴下した。モノマー滴下終了後２時間８０℃で攪拌し、アゾビスイソブチロニトリル０．２重量部をイソプロパノール１０重量部に溶解させた液を滴下した。３時間８０℃で攪拌を続けた後、アゾビスイソブチロニトリル０．１重量部をイソプロパノール１０重量部で溶解させた液を滴下し、更に５時間８０℃で攪拌を続けた。反応終了後、反応液を室温に戻し、水３００重量部を加え、減圧乾固し、粉砕し親水性樹脂２を粉体で得た。
【００１４】
＜製造例１＞
３％ステアリン酸アルミニウムコーティングルチル型酸化チタンを６００℃で焼成し、アルミナコーティング酸化チタンと為し、このもの９７重量部に１０％ハイドロジェンメチルポリシロキサン・エタノール溶液３０重量部を加え良く混練りし、溶媒を留去した後、１３０℃で１２時間焼き付け疎水化粉体を得た。この疎水化粉体を１００重量部秤り、スチレン−アクリル酸ブチル−α−メチルスチレン−アクリル酸共重合体（モノマーの構成比１５：１０：４７：２８、親水性樹脂２）１５重量部を加え、遊星ボールミルで２００ｒ．ｐ．ｍ．４時間処理した後、窒素置換し、水３５重量部を加えた後濃アンモニア水で中和した後、ジエチレングリコールモノブチルエーテル２重量部加え、窒素置換し、攪拌しながら２−エチルヘキシルアクリレートを５０重量部滴下し、７５℃に昇温し、過硫酸アンモニウム０．５重量部を水１０重量部に溶かして滴下し、７０〜７５℃で２時間攪拌を続けた。過硫酸アンモニウム０．２重量部を水１０重量部に溶かして加え、２時間攪拌し反応を止めて、粉体−樹脂複合体組成物１を得た。このものは４０℃で１週間放置しても沈降しなかった。対照として、同じ粉体１００重量部を水６５重量部とスチレン−α−メチルスチレン−アクリル酸ブチル−アクリル酸共重合体（モノマーの構成比１５：４７：１０：２８）１５重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００１５】
＜製造例２＞
３％ステアリン酸アルミニウムコーティングルチル型酸化チタンを６００℃で焼成し、アルミナコーティング酸化チタンと為し、このもの９７重量部に１０％ジメチルポリシロキサン・エタノール溶液３０重量部を加え良く混練りし、溶媒を留去した後、１３０℃で１２時間焼き付け疎水化粉体を得た。この疎水化粉体を１００重量部秤り、ポリビニルアルコール１５重量部を加え、遊星ボールミルで２００ｒ．ｐ．ｍ．４時間処理した後、窒素置換し、水３５重量部とジエチレングリコールモノブチルエーテル２重量部とを加え、窒素置換し、攪拌しながら２−エチルヘキシルアクリレートを５０重量部滴下し、７５℃に昇温し、過硫酸アンモニウム０．５重量部を水１０重量部に溶かして滴下し、７０〜７５℃で２時間攪拌を続けた。過硫酸アンモニウム０．２重量部を水１０重量部に溶かして加え、２時間攪拌し反応を止めて、粉体−樹脂複合体組成物２を得た。このものは４０℃で１週間放置しても沈降しなかった。対照として、同じ粉体１００重量部を水６５重量部とポリビニルアルコール１５重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００１６】
＜製造例３＞
３％ステアリン酸アルミニウムコーティングルチル型酸化チタンを６００℃で焼成し、アルミナコーティング酸化チタンと為し、これを５０重量部秤り、１．６重量部のステアリン酸ナトリウムを加え、水３０重量部に分散させ、これに塩化アルミニウム０．３重量部を３重量部の水に溶かして加え、固体を濾取した。この固体を湿潤状態のままで、水３０重量部に分散させ、参考例の親水性樹脂分散液１を３０重量部、ジエチレングリコールモノブチルエーテル２重量部加え、窒素置換し、攪拌しながら２−エチルヘキシルアクリレートを５０重量部滴下し、７５℃に昇温し、過硫酸アンモニウム０．５重量部を水１０重量部に溶かして滴下し、７０〜７５℃で２時間攪拌を続けた。過硫酸アンモニウム０．２重量部を水１０重量部に溶かして加え、２時間攪拌し反応を止めて中和し、粉体−樹脂複合体組成物３を得た。このものは４０℃で１週間放置しても沈降しなかった。対照として、同じ粉体５０重量部を同様に金属石鹸処理し、水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００１７】
＜製造例４＞
製造例３の粉体をベンガラに置き換えて同様に処理して、粉体−樹脂複合体組成物４を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００１８】
＜製造例５＞
製造例３の粉体を黄色酸化鉄に置き換えて同様に処理して、粉体−樹脂複合体組成物５を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００１９】
＜製造例６＞
製造例３の粉体を紺青に置き換えて同様に処理して、粉体−樹脂複合体組成物６を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２０】
＜製造例７＞
製造例３の粉体を群青に置き換えて同様に処理して、粉体−樹脂複合体組成物７を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２１】
＜製造例８＞
製造例３の粉体をタルクに置き換えて同様に処理して、粉体−樹脂複合体組成物８を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレートを遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２２】
＜製造例９＞
製造例３の粉体をタルクに置き換えて同様に処理して、粉体−樹脂複合体組成物９を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２３】
＜製造例１０＞
製造例３の粉体をセリサイトに置き換えて同様に処理して、粉体−樹脂複合体組成物１０を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２４】
＜製造例１１＞
製造例３の粉体をチタンマイカに置き換えて同様に処理して、粉体−樹脂複合体組成物１１を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポリ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２５】
＜製造例１２＞
製造例３の粉体を虹彩箔に置き換えて同様に処理して、粉体−樹脂複合体組成物１２を得た。このものは４０℃で１週間良好な分散性を維持した。対照として、同じ粉体５０重量部を水５０重量部と親水性樹脂分散液１を３０重量部とジエチレングリコールモノブチルエーテル２重量部とポエイ−２−エチルヘキシルアクリレート５０重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２６】
＜製造例１３＞
３％ステアリン酸アルミニウムコーティングルチル型酸化チタンを６００℃で焼成し、アルミナコーティング酸化チタンと為し、これを５０重量部秤り１．６重量部のステアリン酸ナトリウムを加え、水３０重量部に分散させ、これに塩化アルミニウム０．３重量部を３重量部の水に溶かして加え、固体を濾取し、８０℃で２４時間乾燥させた。親水性樹脂２の１５重量部を加え、遊星ボールミルで２００ｒ．ｐ．ｍ．４時間処理し、これに水３５重量部を加え濃アンモニア水にて中和し、窒素置換した後、攪拌しながらメチルメタアクリレートを５０重量部滴下し、７５℃に昇温し、過硫酸アンモニウム０．５重量部を水１０重量部に溶かして滴下し、７０〜７５℃で２時間攪拌を続けた。過硫酸アンモニウム０．２重量部を水１０重量部に溶かして加え、２時間攪拌し反応を止めて、粉体−樹脂複合体組成物１３を得た。このものは４０℃で１週間放置しても沈降を見なかった。同じ粉体を製造例１と同様に１５重量部の水性樹脂２で処理し、水３５重量部を加え濃アンモニア水で中和した対照品は４０℃で１週間で完全２層分離していた。
【００２７】
＜参考例＞
親水性樹脂の作成
攪拌機、還流冷却機、滴下ロート、温度計、窒素導入管を装着した反応器にイソプロピルアルコール５０重量部を秤込み、窒素ガスを吹き込み溶存酸素を除去した。滴下ロートより、イソプロパノール３０重量部、スチレン１８重量部、α−メチルスチレン５３重量部、アクリル酸２５重量部、アクリル酸ブチル４重量部及びアゾビスイソブチロニトリル０．２重量部を、攪拌下８０℃まで昇温した反応器に滴下した。モノマー滴下終了後２時間８０℃で攪拌し、アゾビスイソブチロニトリル０．２重量部をイソプロパノール１０重量部に溶解させた液を滴下した。３時間８０℃で攪拌を続けた後、アゾビスイソブチロニトリル０．１重量部をイソプロパノール１０重量部で溶解させた液を滴下し、更に５時間８０℃で攪拌を続けた。反応終了後、反応液を室温に戻し、水３００重量部を加え、減圧乾固し、粉砕し親水性樹脂３を粉体で得た。
【００２８】
＜製造例１４＞
酸化チタン（チタン１００Ａ）９７重量部に１０％ハイドロジェンメチルポリシロキサン・エタノール溶液３０重量部を加え良く混練りし、溶媒を留去した後、１３０℃で１２時間焼き付け疎水化粉体を得た。この疎水化粉体を１５重量部秤り、スチレン−アクリル酸ブチル−α−メチルスチレン−アクリル酸共重合体（親水性樹脂３；モノマーの構成比１８：４：５３：２５、水溶性樹脂）５重量部を加え、遊星ボールミルで２００ｒ．ｐ．ｍ．４時間処理した後、窒素置換し、水４０重量部を加えた後濃アンモニア水で中和した後、窒素置換し、攪拌しながらメチルメタクリレート２重量部、２−エチルヘキシルアクリレートを１重量部滴下し、７５℃に昇温し、過硫酸アンモニウム０．５重量部を水１０重量部に溶かして滴下し、７０〜７５℃で２時間攪拌を続けた。過硫酸アンモニウム０．２重量部を水１０重量部に溶かして加え、２時間攪拌し反応を止めて、粉体−樹脂複合体組成物１４を得た。このものは４０℃で１週間放置しても沈降しなかった。対照として、同じ粉体１５重量部を水６５重量部とスチレン−α−メチルスチレン−アクリル酸ブチル−アクリル酸共重合体（モノマーの構成比１５：４７：１０：２８）２８重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００２９】
＜参考例＞
攪拌機、還流冷却機、滴下ロート、温度計、窒素導入管を装着した反応器にイソプロピルアルコール５０重量部を秤込み、窒素ガスを吹き込み溶存酸素を除去した。滴下ロートより、イソプロパノール３０重量部、スチレン１８重量部、α−メチルスチレン５３重量部、アクリル酸２５重量部、アクリル酸ブチル４重量部及びアゾビスイソブチロニトリル０．２重量部を、攪拌下８０℃まで昇温した反応器に滴下した。モノマー滴下終了後２時間８０℃で攪拌し、アゾビスイソブチロニトリル０．２重量部をイソプロパノール１０重量部に溶解させた液を滴下した。３時間８０℃で攪拌を続けた後、アゾビスイソブチロニトリル０．１重量部をイソプロパノール１０重量部で溶解させた液を滴下し、更に５時間８０℃で攪拌を続けた。反応終了後、反応液を室温に戻し、９５％アンモニア水を加えて中和し、水３００重量部を加え、減圧濃縮し固形分３０％の親水性樹脂分散液４を得た。
【００３０】
＜製造例１５＞
二酸化チタン（チタン１００Ａ）１５重量部秤り、０．６重量部のステアリン酸ナトリウムを加え、水３０重量部に分散させ、これに塩化アルミニウム０．１重量部を３重量部の水に溶かして加え、固体を濾取し、遊星ボールミルで２００ｒ．ｐ．ｍ．８時間処理し、これに水を加え遠心分離して水洗し、水３０ｍｌを加えた。これを窒素置換した後、スチレン−アクリル酸ブチル−α−メチルスチレン−アクリル酸共重合体（モノマーの構成比１８：４：５３：２５、水溶性樹脂の固形分３０％；親水性樹脂分散液４）１４重量部を加え、遊星ボールミルで２００ｒ．ｐ．ｍ．１時間処理した。水３０重量部を加えた後、濃アンモニア水で中和した後、窒素置換し、攪拌しながらメチルメタクリレート２重量部、２−エチルヘキシルアクリレートを１重量部滴下し、７５℃に昇温し、過硫酸アンモニウム０．５重量部を水１０重量部に溶かして滴下し、７０〜７５℃で２時間攪拌を続けた。過硫酸アンモニウム０．２重量部を水１０重量部に溶かして加え、２時間攪拌し反応を止めて、粉体−樹脂複合体組成物１５を得た。このものは４０℃で１週間放置しても沈降しなかった。対照として、同じ粉体１５重量部を水６５重量部とスチレン−α−メチルスチレン−アクリル酸ブチル−アクリル酸共重合体（モノマーの構成比１５：４７：１０：２８）１４重量部を遊星ボールミルで処理したものは、４０℃で１週間放置すると、完全に２層分離していた。
【００３１】
（７）本発明の着色用の組成物
本発明の着色用の組成物は、上記粉体−樹脂複合組成物を含有することを特徴とする。組成物の種類としては、着色用であれば特段の限定は受けず、例えば、ペイント、ファンデーションやマニキュア等の化粧料等が例示できる。更に、二酸化チタンや酸化亜鉛のような色材は、紫外線吸収剤としても使用されるので、内容物や皮膚を紫外線から防護する目的で、着色以外の目的で化粧料や医薬品に含有させることも本発明の技術的範囲に属するものであり、この様な組成物も本発明の組成物に属する。これらの内特に好ましいものは化粧料である。これは、本発明の組成物に於いて色材の分散性が優れると共に、安全性に優れるためである。これは色材が樹脂によってコートされている為である。本発明の着色用の組成物では、必須成分である粉体−樹脂複合組成物以外に通常化粧料やペイントで使用される任意成分を含有することができる。この様な任意成分としては、例えば、ワセリンやマイクロクリスタリンワックス等のような炭化水素類、ホホバ油やゲイロウ等のエステル類、牛脂、オリーブ油等のトリグリセライド類、セタノール、オレイルアルコール等の高級アルコール類、ステアリン酸、オレイン酸等の脂肪酸、グリセリンや１，３−ブタンジオール等の多価アルコール類、非イオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、エタノール、カーボポール等の増粘剤、防腐剤、紫外線吸収剤、抗酸化剤、色素、粉体類等が好ましく例示できる。本発明の着色用の組成物に於ける、粉体−樹脂複合組成物の好ましい含有量は、乾燥重量で、０．０１〜５０重量％であり、より好ましくは、０．０５〜３０重量％であり、更に好ましくは０．１〜２０重量％である。本発明の着色用の組成物は、常法に従って製造することができる。
【００３２】
【実施例】
以下に実施例を挙げて、本発明について更に詳細に説明を加えるが、本発明がこれら実施例にのみ限定を受けないことは言うまでもない。
【００３３】
＜実施例１〜１５＞
以下に示す処方に従って、ネイルカラーを作成した。即ち、処方成分をボールミルで良く混合し、ネイルカラーを得た。これらは何れも４０℃、１カ月の保存条件で異常を認めなかった。これより本発明の組成物は安定性に優れることがわかる。
粉体−樹脂複合組成物＊ ５０ 重量部
クエン酸トリエチル １ 重量部
１，３−ブタンジオール ３ 重量部
エタノール ２０ 重量部
水 ２６ 重量部
＊粉体−樹脂複合組成物の詳細は表１に示す。
【００３４】
【表１】
＜実施例１６＞
上記実施例１〜１５のマニュキアをハートレー系モルモット１群５匹（雄性２５０〜３５０ｇ、）の背部に２４時間貼付し、皮膚反応を観察した。皮膚反応はドレーズの基準に従って判定した。即ち、＋＋：浮腫を伴う反応、＋：明らかな紅斑を伴う反応、±：疑わしい紅斑を伴う反応、−：無反応の基準である。結果は、いずれの動物も無反応（−）であり、本発明の着色用の組成物が優れた安全性を有していることが証明された。
【００３６】
＜実施例１７＞
下記処方に従って、ファンデーションを作成した。即ち、処方成分をボールミルに仕込み、十分に混合し、ファンデーションを得た。このものは４０℃、１カ月でも安定であった。
粉体−樹脂複合体３ １２ 重量部
粉体−樹脂複合体４ １ 重量部
粉体−樹脂複合体５ ５ 重量部
粉体−樹脂複合体７ ０．１重量部
粉体−樹脂複合体８ ７ 重量部
１，３−ブタンジオール ５ 重量部
エタノール １０ 重量部
水 ５９．９重量部
【００３７】
＜実施例１８＞
下記処方に従って、医薬組成物を作成した。即ち、処方成分をボールミルに仕込み、十分に混合し、抗炎症皮膚外用剤を得た。このものは、光毒性の発現が抑制されていた。
粉体−樹脂複合体１ ５ 重量部
インドメタシン １ 重量部
エタノール ５０ 重量部
水 ４４ 重量部
【００３８】
＜実施例１９＞
下記処方に従って、医薬組成物を作成した。即ち、処方成分をボールミルに仕込み、十分に混合し、抗真菌外用剤を得た。このものは、光毒性の発現が抑制されていた。
粉体−樹脂複合体１ ５ 重量部
ブテナフィン １ 重量部
エタノール ５０ 重量部
水 ４４ 重量部
【００３９】
＜実施例２０〜３４＞
下記処方に従って、ペイントを作成した。即ち、処方成分をボールミルでよく混合し、ペイントを得た。これらは優れた分散性を有していると同時に、再分散性も有していた。
アクリル酸エステルエマルジョン ５０ 重量部
粉体−樹脂複合組成物＊＊ ５０ 重量部
＊＊粉体−樹脂複合組成物の詳細は表２に示す。
【００４０】
【表２】
【発明の効果】
本発明によれば、色材の分散安定性に優れる着色用の組成物を提供出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coloring composition suitable for paints and cosmetics, characterized in that the colorant has improved dispersibility or sedimentation.
[0002]
[Prior art]
2. Description of the Related Art Powders such as pigments represented by red iron oxide and titanium oxide, and extender powders such as mica and sericite are widely used in the fields of cosmetics and paints. Generally, the surface of such powders has an isoelectric point, and it is said that a so-called electric double layer is formed and dispersed in an aqueous solvent. Therefore, in such a dispersion, in the presence of an electrolytic substance that inhibits the formation of the electric double layer, a stable dispersion cannot be obtained, and powder aggregation often occurs. In particular, it is already known that acrylic resins and acrylic polymers used as coating agents and thickeners are liable to cause such a phenomenon. That is, it is not an exaggeration to say that a powder dispersion system that can coexist with an electrolytic substance, particularly an acrylic acid resin or an acrylic acid polymer, is not obtained. In addition, the dispersion by such a mechanism often causes agglomeration and precipitation over time, even if the dispersion is stable immediately after the preparation. In addition, a means has been devised to improve the dispersion stability by coating a hydrophilic polymer with a core-shell structure, and the dispersibility has been significantly improved, but it is said that the emulsifier used in emulsion polymerization enters the core part. The disadvantages remain. That is, it was not an exaggeration to say that a powder dispersion system that was stable over time was not obtained despite the demand. Accordingly, in a coloring composition such as a paint or a cosmetic, in which such a dispersion of a coloring material is essential, such improvement in dispersibility is still sufficiently achieved even though it is desired. I have to say that it is not done.
[0003]
On the other hand, a powder-resin composite containing a hydrophobized powder, a hydrophilic resin, and one or more polymers and / or copolymers selected from acrylic acid, methacrylic acid and esters thereof. The composition was not yet known, and it was not known at all that it had excellent dispersibility. Therefore, it has not been known at all that if this is contained in a coloring composition such as paint or cosmetics, a coloring composition having good dispersion stability of the coloring agent can be obtained.
[0004]
[Problems to be solved by the invention]
The present invention has been made under such circumstances, and it is an object of the present invention to provide a coloring composition having excellent dispersion stability of a coloring material.
[0005]
[Means for Solving the Problems]
In view of such circumstances, the present inventors have conducted intensive studies in an attempt to improve the dispersion and stability of the coloring material in the coloring composition. As a result, hydrogen methylpolysiloxane baking, dimethipoly Hydrophobic treatment powder such as siloxane baking treatment, metal soap coating treatment, acylated amino acid salt coating treatment, hydrophilic resin, and one or two or more kinds of acrylic acid, methacrylic acid and esters thereof. The inventors have found such properties in a coloring composition containing a powder-resin composite composition containing a coalesced and / or copolymer as a coloring material, and completed the invention. Hereinafter, the present invention will be described in detail focusing on embodiments of the invention.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
(1) Powder-resin composite composition used in the present invention
The powder-resin composite composition of the present invention is characterized by containing a powder subjected to a hydrophobic treatment and a hydrophilic resin. The method of hydrophobizing the powder of the hydrophobizing treatment in the composition of the present invention is not particularly limited as long as it is a generally known hydrophobizing treatment. For example, hydrogen polysiloxane baking treatment, dimethyl polysiloxane baking treatment And a metal soap coating treatment, an acylated amino acid salt coating treatment and the like. The powder-resin composite composition of the present invention is produced, for example, by the following procedure. The hydrophobized powder is coated with a hydrophilic resin. At this time, the coating with the hydrophilic resin may be performed by a method of coating the hydrophilic resin in a solid state or in an aqueous solution state with a ball mill or the like. This is because, according to such a method, the hydrophobized powder is tightly covered with the hydrophilic resin. The powder thus obtained is subjected to treatment such as drying and pulverization as necessary, then dispersed in an aqueous carrier, and then added to one or more selected from acrylic acid, methacrylic acid and esters thereof. Can be obtained by polymerizing two or more kinds.
[0007]
(2) Powder used for preparing powder-resin composite composition used in the present invention
In the powder-resin composite composition, the powder that can be used as the base of the hydrophobized powder can be used without any particular limitation as long as it is generally proved in cosmetics and paints. I can do it. Examples of such powders include pigments such as titanium oxide, red iron oxide, ultramarine blue, navy blue, yellow iron oxide, zinc oxide, chromium oxide, and chromium hydroxide, and constitutional powders such as mica, sericite, and talc. Examples include pearlescent agents such as titanium mica. Powders obtained by subjecting these powders to surface treatment other than hydrophobic treatment such as alumina treatment, silica treatment, and phosphoric acid treatment can be used as long as the effects of the present invention are not impaired. Only one kind of powder may be used, or two or more kinds may be used.
[0008]
(3) Hydrophobizing treatment of the powder
The hydrophobic treatment of the powder is not particularly limited as long as it is a commonly known hydrophobic treatment. For example, hydrogen polysiloxane baking treatment, dimethyl polysiloxane baking treatment, metal soap coating treatment, acylation treatment Amino acid salt coating treatment and the like. Such a hydrophobizing treatment may be carried out according to a conventional method. In the case of hydrogen methylpolysiloxane or dimethylpolysiloxane baking treatment, the powder is coated with 0.1 to 20 parts by weight of the silicone based on the base powder. Then, a baking process may be performed at 80 to 200 ° C. In the case of metal soap treatment, the powder and the fatty acid soap may coexist in an aqueous carrier, and a soluble metal salt such as aluminum chloride or zinc chloride may be added to precipitate the metal soap on the powder. If this product is taken out and dried, a metal soap-coated powder can be obtained. An acylated amino acid salt-coated powder can also be prepared according to this method. The metal soap and the acylated amino acid salt are preferably used in an amount of 0.1 to 20% by weight based on the base powder.
[0009]
(4) Hydrophilic polymer used for preparing powder-resin composite composition
The hydrophilic polymer used for preparing the powder-resin composite composition can be used without any particular limitation as long as it has a hydrophilic group and is uniformly dispersed or solubilized in water. Examples of such a polymer include a polymer or copolymer having vinyl alcohol, acrylic acid, methacrylic acid, alkyl acrylate, acrylic methacrylate, or the like as a constituent monomer. Here, as the alkyl, methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl and tertiary butyl having 1 to 4 carbon atoms are preferable, and normal butyl is particularly preferable. Examples of such a hydrophilic polymer include polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, acrylic acid-vinyl alcohol copolymer, methacrylic acid-vinyl alcohol copolymer, acrylic acid-methacrylic acid copolymer and / or Esters. These may be used alone or in combination of two or more. In addition, styrene, α-methylstyrene, butadiene, and acrylonitrile can be contained as components of the copolymer, as long as the effects of the present invention are not impaired. In the copolymer, the constituent ratio of vinyl alcohol, acrylic acid, and methacrylic acid is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more. Further, a preferable ratio of the powder and the hydrophilic polymer is 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and further preferably 2: 5 to 5: 2. These can be coated by, for example, dry treatment using a ball mill or the like without using a solvent, or removing the solvent while mixing the solvent in the presence of a solvent such as water. Furthermore, when the metal soap treatment or the acylated amino acid salt treatment is performed, the metal soap treatment or the acylated amino acid salt treatment can be performed by a wet method, and the water-soluble resin can be coated in a wet state. At the time of coating, the water-soluble resin may be coated in a carboxylic acid-free state, and thereafter, may be neutralized and ionized as necessary, or may be coated in a neutralized and ionized state.
[0010]
(5) Acrylic acid-based polymer / copolymer used in the powder-resin composite composition
As the monomer constituting one or two or more polymers and / or copolymers selected from acrylic acid, methacrylic acid and esters thereof, which is used in the powder-resin composite composition, As long as it is used as a component of such a polymer / copolymer, it can be used without any particular limitation. Preferred examples of such a monomer include acrylic acid or methacrylic acid derivatives such as acrylic acid, alkyl acrylate, methacrylic acid and alkyl methacrylate. Among these, 2-ethylhexyl acrylate and methyl methacrylate are preferred. Acrylate is a preferred example. These polymerization reactions, if necessary, using a solvent such as water, in the presence of a hydrophobized powder treated with the above hydrophilic resin, for example, start the polymerization of azobisisobutyronitrile, potassium persulfate, ammonium persulfate, etc. What is necessary is just to make it react using an agent. A preferable ratio of the monomer to the powder is such that the ratio of the hydrophobized powder treated with the hydrophilic resin to the monomer is 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and The ratio is preferably 2: 5 to 5: 2. Furthermore, when the hydrophobic treatment is performed by metal soap coating or acylated amino acid salt coating, the base powder is dispersed in an aqueous solvent, and the water-soluble resin is ionized by neutralization or the like and added to the aqueous solvent. The above-mentioned acrylic or methacrylic acid-based monomer may be added dropwise, a polymerization initiator may be added thereto, and the mixture may be polymerized to obtain the powder-resin composite of the present invention. The powder-resin complex thus obtained, which is an essential component of the present invention, exhibits excellent dispersibility in an aqueous carrier and has significantly improved sedimentation. It is extremely useful as a raw material for cosmetics such as paints and nail colors, and a raw material for paints. It is particularly useful as a raw material for producing nail colors that are gentle on nails, depending on the types of resin components and solvents used.
[0011]
(6) Production example of powder-resin composite composition
Hereinafter, the present invention will be described in more detail with reference to Production Examples. Needless to say, the raw materials of the composition of the present invention are not limited to these Production Examples.
[0012]
<Reference Example 1>
Preparation of hydrophilic resin
50 parts by weight of isopropyl alcohol was weighed into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, and nitrogen gas was blown thereinto to remove dissolved oxygen. From the dropping funnel, 30 parts by weight of isopropanol, 15 parts by weight of styrene, 47 parts by weight of α-methylstyrene, 28 parts by weight of acrylic acid, 10 parts by weight of butyl acrylate, and 0.2 parts by weight of azobisisobutyronitrile were stirred. The mixture was dropped into a reactor heated to 80 ° C. After completion of the dropwise addition of the monomer, the mixture was stirred at 80 ° C. for 2 hours, and a liquid in which 0.2 parts by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was added dropwise. After stirring at 80 ° C. for 3 hours, a solution in which 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was added dropwise, and stirring was continued at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was returned to room temperature, neutralized by adding 95% aqueous ammonia, added with 300 parts by weight of water, and concentrated under reduced pressure to obtain a hydrophilic resin dispersion 1 having a solid content of 30%.
[0013]
<Reference Example 2>
Preparation of hydrophilic resin
50 parts by weight of isopropyl alcohol was weighed into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, and nitrogen gas was blown thereinto to remove dissolved oxygen. From a dropping funnel, 30 parts by weight of isopropanol, 15 parts by weight of styrene, 47 parts by weight of α-methylstyrene, 10 parts by weight of butyl acrylate, 28 parts by weight of acrylic acid, and 0.2 parts by weight of azobisisobutyronitrile were stirred. The mixture was dropped into a reactor heated to 80 ° C. After completion of the dropwise addition of the monomer, the mixture was stirred at 80 ° C. for 2 hours, and a liquid in which 0.2 parts by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was added dropwise. After stirring at 80 ° C. for 3 hours, a solution in which 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was added dropwise, and stirring was continued at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was returned to room temperature, 300 parts by weight of water was added, and the mixture was dried under reduced pressure and pulverized to obtain a hydrophilic resin 2 as a powder.
[0014]
<Production Example 1>
Rutile type titanium oxide coated with 3% aluminum stearate is baked at 600 ° C. to form alumina coated titanium oxide, and 97 parts by weight of this is mixed with 30 parts by weight of a 10% hydrogen methylpolysiloxane / ethanol solution and kneaded well. After distilling off the solvent, the powder was baked at 130 ° C. for 12 hours to obtain a hydrophobic powder. 100 parts by weight of this hydrophobized powder was weighed, and 15 parts by weight of a styrene-butyl acrylate-α-methylstyrene-acrylic acid copolymer (monomer composition ratio 15: 10: 47: 28, hydrophilic resin 2) was added. In addition, 200 r. p. m. After treating for 4 hours, the mixture was purged with nitrogen, added with 35 parts by weight of water, neutralized with concentrated aqueous ammonia, added with 2 parts by weight of diethylene glycol monobutyl ether, replaced with nitrogen, and stirred, and stirred with 50 parts by weight of 2-ethylhexyl acrylate. The temperature was raised to 75 ° C, and 0.5 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water and added dropwise, and stirring was continued at 70 to 75 ° C for 2 hours. 0.2 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water, and the mixture was stirred for 2 hours to stop the reaction. Thus, a powder-resin composite composition 1 was obtained. It did not settle after standing at 40 ° C. for one week. As a control, 100 parts by weight of the same powder were mixed with 65 parts by weight of water, 15 parts by weight of a styrene-α-methylstyrene-butyl acrylate-acrylic acid copolymer (constituent ratio of monomers: 15: 47: 10: 28) and diethylene glycol monoester. When 2 parts by weight of butyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate were treated with a planetary ball mill, they were completely separated into two layers when left at 40 ° C. for 1 week.
[0015]
<Production Example 2>
3% aluminum stearate-coated rutile-type titanium oxide is baked at 600 ° C. to form an alumina-coated titanium oxide, and 97 parts by weight of this is added with 30 parts by weight of a 10% dimethylpolysiloxane / ethanol solution, and kneaded well. Was distilled off and baked at 130 ° C. for 12 hours to obtain a hydrophobized powder. 100 parts by weight of the hydrophobized powder was weighed, and 15 parts by weight of polyvinyl alcohol was added. p. m. After the treatment for 4 hours, the mixture was replaced with nitrogen, 35 parts by weight of water and 2 parts by weight of diethylene glycol monobutyl ether were added, the mixture was replaced with nitrogen, 50 parts by weight of 2-ethylhexyl acrylate was added dropwise with stirring, and the temperature was raised to 75 ° C. 0.5 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water and added dropwise, and stirring was continued at 70 to 75 ° C. for 2 hours. 0.2 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water, and the mixture was stirred for 2 hours to stop the reaction. Thus, a powder-resin composite composition 2 was obtained. It did not settle after standing at 40 ° C. for one week. As a control, 100 parts by weight of the same powder was treated with 65 parts by weight of water, 15 parts by weight of polyvinyl alcohol, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate in a planetary ball mill at 40 ° C. After standing for a week, two layers were completely separated.
[0016]
<Production Example 3>
3% aluminum stearate-coated rutile-type titanium oxide is baked at 600 ° C. to form alumina-coated titanium oxide, weighed at 50 parts by weight, added 1.6 parts by weight of sodium stearate, and added to 30 parts by weight of water. After dispersing, 0.3 parts by weight of aluminum chloride dissolved in 3 parts by weight of water were added, and the solid was collected by filtration. The solid was dispersed in 30 parts by weight of water in a wet state, and 30 parts by weight of the hydrophilic resin dispersion 1 of Reference Example and 2 parts by weight of diethylene glycol monobutyl ether were added. Was added dropwise, the temperature was raised to 75 ° C., 0.5 part by weight of ammonium persulfate was dissolved in 10 parts by weight of water and added dropwise, and stirring was continued at 70 to 75 ° C. for 2 hours. 0.2 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water, and the mixture was stirred for 2 hours to stop the reaction and neutralized to obtain a powder-resin composite composition 3. It did not settle after standing at 40 ° C. for one week. As a control, 50 parts by weight of the same powder was similarly treated with a metal soap, and 50 parts by weight of water, 30 parts by weight of the hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether, and 50 parts by weight of poly-2-ethylhexyl acrylate were used. One that had been treated by a planetary ball mill was completely separated into two layers when left at 40 ° C. for one week.
[0017]
<Production Example 4>
Powder-resin composite composition 4 was obtained in the same manner as in Production Example 3, except that the powder was replaced with Bengala. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate were treated with a planetary ball mill. When left at 40 ° C. for one week, two layers were completely separated.
[0018]
<Production Example 5>
Powder-resin composite composition 5 was obtained in the same manner as in Production Example 3 except that the powder was replaced with yellow iron oxide. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate were treated with a planetary ball mill. When left at 40 ° C. for one week, two layers were completely separated.
[0019]
<Production Example 6>
Powder-resin composite composition 6 was obtained in the same manner as in Production Example 3 except that the powder was replaced with navy blue. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder was treated with 50 parts by weight of water, 30 parts by weight of the hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether, and 50 parts by weight of poly-2-ethylhexyl acrylate in a planetary ball mill. When left at 40 ° C. for one week, the resulting product completely separated into two layers.
[0020]
<Production Example 7>
Powder-resin composite composition 7 was obtained in the same manner as in Production Example 3, except that the powder was replaced with ultramarine blue. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate were treated with a planetary ball mill. When left at 40 ° C. for one week, two layers were completely separated.
[0021]
<Production Example 8>
The powder of Production Example 3 was replaced with talc and treated in the same manner to obtain a powder-resin composite composition 8. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of the hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and poly-2-ethylhexyl acrylate were treated with a planetary ball mill at 40 ° C. For one week, completely separated into two layers.
[0022]
<Production Example 9>
The powder of Production Example 3 was replaced with talc and treated in the same manner to obtain a powder-resin composite composition 9. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate were treated with a planetary ball mill. When left at 40 ° C. for one week, two layers were completely separated.
[0023]
<Production Example 10>
The powder of Production Example 3 was replaced with sericite and treated in the same manner to obtain a powder-resin composite composition 10. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate were treated with a planetary ball mill. When left at 40 ° C. for one week, two layers were completely separated.
[0024]
<Production Example 11>
The powder of Production Example 3 was replaced with titanium mica and treated in the same manner to obtain a powder-resin composite composition 11. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poly-2-ethylhexyl acrylate were treated with a planetary ball mill. When left at 40 ° C. for one week, two layers were completely separated.
[0025]
<Production Example 12>
The powder of Production Example 3 was replaced with an iris foil and treated similarly to obtain a powder-resin composite composition 12. It maintained good dispersibility at 40 ° C. for one week. As a control, 50 parts by weight of the same powder, 50 parts by weight of water, 30 parts by weight of the hydrophilic resin dispersion 1, 2 parts by weight of diethylene glycol monobutyl ether and 50 parts by weight of poei-2-ethylhexyl acrylate were treated with a planetary ball mill. When left at 40 ° C. for one week, two layers were completely separated.
[0026]
<Production Example 13>
3% aluminum stearate-coated rutile-type titanium oxide is baked at 600 ° C. to form alumina-coated titanium oxide, weighed 50 parts by weight, added 1.6 parts by weight of sodium stearate, and dispersed in 30 parts by weight of water Then, 0.3 parts by weight of aluminum chloride dissolved in 3 parts by weight of water was added, and the solid was collected by filtration and dried at 80 ° C. for 24 hours. 15 parts by weight of the hydrophilic resin 2 was added, and 200 r. p. m. The mixture was treated for 4 hours, added with 35 parts by weight of water, neutralized with concentrated aqueous ammonia, and replaced with nitrogen. Then, 50 parts by weight of methyl methacrylate was added dropwise with stirring. 0.5 parts by weight was dissolved in 10 parts by weight of water and added dropwise, and stirring was continued at 70 to 75 ° C. for 2 hours. 0.2 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water, and the mixture was stirred for 2 hours to stop the reaction, whereby a powder-resin composite composition 13 was obtained. This product did not show sedimentation even when left at 40 ° C. for one week. The same powder was treated with 15 parts by weight of the aqueous resin 2 in the same manner as in Production Example 1, and 35 parts by weight of water was added thereto, followed by neutralization with concentrated aqueous ammonia. .
[0027]
<Reference example>
Preparation of hydrophilic resin
50 parts by weight of isopropyl alcohol was weighed into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, and nitrogen gas was blown thereinto to remove dissolved oxygen. From a dropping funnel, 30 parts by weight of isopropanol, 18 parts by weight of styrene, 53 parts by weight of α-methylstyrene, 25 parts by weight of acrylic acid, 4 parts by weight of butyl acrylate, and 0.2 parts by weight of azobisisobutyronitrile were stirred. The mixture was dropped into a reactor heated to 80 ° C. After completion of the dropwise addition of the monomer, the mixture was stirred at 80 ° C. for 2 hours, and a liquid in which 0.2 parts by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was added dropwise. After stirring at 80 ° C. for 3 hours, a solution in which 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was added dropwise, and stirring was continued at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was returned to room temperature, 300 parts by weight of water was added, and the mixture was dried under reduced pressure and pulverized to obtain a hydrophilic resin 3 as a powder.
[0028]
<Production Example 14>
30 parts by weight of a 10% hydrogen methylpolysiloxane / ethanol solution was added to 97 parts by weight of titanium oxide (titanium 100A) and kneaded well. After the solvent was distilled off, the mixture was baked at 130 ° C. for 12 hours to obtain a hydrophobic powder. . 15 parts by weight of the hydrophobized powder was weighed, and a styrene-butyl acrylate-α-methylstyrene-acrylic acid copolymer (hydrophilic resin 3: monomer ratio 18: 4: 53: 25, water-soluble resin) was used. 5 parts by weight, and 200 r. p. m. After the treatment for 4 hours, the atmosphere is replaced with nitrogen. After adding 40 parts by weight of water and neutralizing with concentrated aqueous ammonia, 2 parts by weight of methyl methacrylate and 1 part by weight of 2-ethylhexyl acrylate are added dropwise with stirring. The temperature was raised to 75 ° C, and 0.5 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water and added dropwise, and stirring was continued at 70 to 75 ° C for 2 hours. 0.2 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water, and the mixture was stirred for 2 hours to stop the reaction. Thus, a powder-resin composite composition 14 was obtained. It did not settle after standing at 40 ° C. for one week. As a control, 15 parts by weight of the same powder were mixed with 65 parts by weight of water and 28 parts by weight of a styrene-α-methylstyrene-butyl acrylate-acrylic acid copolymer (monomer composition ratio 15: 47: 10: 28) with a planetary ball mill. Was left at 40 ° C. for 1 week, completely separated into two layers.
[0029]
<Reference example>
50 parts by weight of isopropyl alcohol was weighed into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, and nitrogen gas was blown thereinto to remove dissolved oxygen. From a dropping funnel, 30 parts by weight of isopropanol, 18 parts by weight of styrene, 53 parts by weight of α-methylstyrene, 25 parts by weight of acrylic acid, 4 parts by weight of butyl acrylate, and 0.2 parts by weight of azobisisobutyronitrile were stirred. The mixture was dropped into a reactor heated to 80 ° C. After completion of the dropwise addition of the monomer, the mixture was stirred at 80 ° C. for 2 hours, and a liquid in which 0.2 parts by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was dropped. After stirring at 80 ° C. for 3 hours, a solution in which 0.1 part by weight of azobisisobutyronitrile was dissolved in 10 parts by weight of isopropanol was added dropwise, and stirring was continued at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was returned to room temperature, neutralized by adding 95% aqueous ammonia, added with 300 parts by weight of water, and concentrated under reduced pressure to obtain a hydrophilic resin dispersion 4 having a solid content of 30%.
[0030]
<Production Example 15>
15 parts by weight of titanium dioxide (titanium 100A) is weighed, 0.6 parts by weight of sodium stearate is added, dispersed in 30 parts by weight of water, and 0.1 part by weight of aluminum chloride is dissolved in 3 parts by weight of water. In addition, the solid was filtered off and 200 r. p. m. The mixture was treated for 8 hours, added with water, centrifuged, washed with water, and added with 30 ml of water. After this was replaced with nitrogen, a styrene-butyl acrylate-α-methylstyrene-acrylic acid copolymer (monomer composition ratio 18: 4: 53: 25, solid content of water-soluble resin 30%; hydrophilic resin dispersion liquid) 4) Add 14 parts by weight, and add 200 r. p. m. Treated for 1 hour. After adding 30 parts by weight of water and neutralizing with concentrated ammonia water, replacing with nitrogen, 2 parts by weight of methyl methacrylate and 1 part by weight of 2-ethylhexyl acrylate were added dropwise with stirring, and the temperature was raised to 75 ° C. 0.5 parts by weight of ammonium sulfate was dissolved in 10 parts by weight of water and added dropwise, and stirring was continued at 70 to 75 ° C. for 2 hours. 0.2 parts by weight of ammonium persulfate was dissolved in 10 parts by weight of water, and the mixture was stirred for 2 hours to stop the reaction. Thus, a powder-resin composite composition 15 was obtained. It did not settle after standing at 40 ° C. for one week. As a control, 15 parts by weight of the same powder were mixed with 65 parts by weight of water and 14 parts by weight of a styrene-α-methylstyrene-butyl acrylate-acrylic acid copolymer (monomer composition ratio 15: 47: 10: 28) with a planetary ball mill. Was left at 40 ° C. for one week, completely separated into two layers.
[0031]
(7) The coloring composition of the present invention
The coloring composition of the present invention is characterized by containing the above powder-resin composite composition. The type of the composition is not particularly limited as long as it is for coloring, and examples thereof include cosmetics such as paints, foundations, and manicures. Further, since coloring materials such as titanium dioxide and zinc oxide are also used as ultraviolet absorbers, they may be contained in cosmetics or pharmaceuticals for purposes other than coloring for the purpose of protecting contents and skin from ultraviolet rays. The composition belongs to the technical scope of the present invention, and such a composition also belongs to the composition of the present invention. Of these, particularly preferred are cosmetics. This is because the composition of the present invention has excellent dispersibility of the coloring material and excellent safety. This is because the coloring material is coated with the resin. The coloring composition of the present invention can contain, in addition to the powder-resin composite composition which is an essential component, an optional component usually used in cosmetics and paints. Such optional components include, for example, hydrocarbons such as petrolatum and microcrystalline wax, esters such as jojoba oil and gay wax, triglycerides such as tallow, olive oil, higher alcohols such as cetanol and oleyl alcohol, Fatty acids such as stearic acid and oleic acid, polyhydric alcohols such as glycerin and 1,3-butanediol, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, ethanol, carbopol, etc. Preferred examples include thickeners, preservatives, ultraviolet absorbers, antioxidants, pigments, and powders. The content of the powder-resin composite composition in the coloring composition of the present invention is preferably 0.01 to 50% by weight, more preferably 0.05 to 30% by weight in terms of dry weight. And more preferably 0.1 to 20% by weight. The coloring composition of the present invention can be produced according to a conventional method.
[0032]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited only to these Examples.
[0033]
<Examples 1 to 15>
A nail color was prepared according to the following prescription. That is, the ingredients were mixed well by a ball mill to obtain a nail color. In any of these, no abnormality was observed at 40 ° C. for one month. This indicates that the composition of the present invention is excellent in stability.
Powder-resin composite composition * 50 parts by weight
Triethyl citrate 1 part by weight
1,3-butanediol 3 parts by weight
20 parts by weight of ethanol
26 parts by weight of water
* Details of the powder-resin composite composition are shown in Table 1.
[0034]
[Table 1]
<Example 16>
The manicures of the above Examples 1 to 15 were stuck on the back of a group of five Hartley-type guinea pigs (male 250 to 350 g) for 24 hours, and the skin reaction was observed. Skin reactions were determined according to Draize's criteria. That is, ++: reaction with edema, +: reaction with obvious erythema, ±: reaction with suspicious erythema, −: no response. As a result, all animals were non-reactive (-), which proved that the coloring composition of the present invention had excellent safety.
[0036]
<Example 17>
A foundation was prepared according to the following prescription. That is, the ingredients were charged into a ball mill and mixed well to obtain a foundation. It was stable at 40 ° C. for one month.
Powder-resin composite 3 12 parts by weight
Powder-resin composite 41 1 part by weight
Powder-resin composite 55 parts by weight
Powder-resin composite 7 0.1 parts by weight
8-7 parts by weight of powder-resin composite
1,3-butanediol 5 parts by weight
Ethanol 10 parts by weight
59.9 parts by weight of water
[0037]
<Example 18>
A pharmaceutical composition was prepared according to the following formulation. That is, the ingredients were charged in a ball mill and mixed well to obtain an anti-inflammatory skin external preparation. This product had suppressed phototoxicity.
Powder-resin composite 15 parts by weight
Indomethacin 1 part by weight
50 parts by weight of ethanol
44 parts by weight of water
[0038]
<Example 19>
A pharmaceutical composition was prepared according to the following formulation. That is, the ingredients were charged into a ball mill and mixed well to obtain an antifungal external preparation. This product had suppressed phototoxicity.
Powder-resin composite 15 parts by weight
Butenafine 1 parts by weight
50 parts by weight of ethanol
44 parts by weight of water
[0039]
<Examples 20 to 34>
A paint was prepared according to the following prescription. That is, the ingredients were mixed well by a ball mill to obtain a paint. These had excellent dispersibility as well as redispersibility.
Acrylic ester emulsion 50 parts by weight
Powder-resin composite composition ** 50 parts by weight
** Details of the powder-resin composite composition are shown in Table 2.
[0040]
[Table 2]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the composition for coloring which is excellent in the dispersion stability of a coloring material can be provided.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02769998A JP3554174B2 (en) | 1998-01-26 | 1998-01-26 | Powder-resin complex containing cosmetics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02769998A JP3554174B2 (en) | 1998-01-26 | 1998-01-26 | Powder-resin complex containing cosmetics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11209241A JPH11209241A (en) | 1999-08-03 |
| JP3554174B2 true JP3554174B2 (en) | 2004-08-18 |
Family
ID=12228239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02769998A Expired - Fee Related JP3554174B2 (en) | 1998-01-26 | 1998-01-26 | Powder-resin complex containing cosmetics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3554174B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363444A (en) * | 2001-06-05 | 2002-12-18 | Daito Kasei Kogyo Kk | Cosmetic pigment and cosmetic containing the same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033362B2 (en) * | 1978-03-28 | 1985-08-02 | カネボウ株式会社 | new nail enamel |
| JPH0717864B2 (en) * | 1987-02-12 | 1995-03-01 | 有限会社三好化成 | Moisturizing powder and cosmetics |
| JP2791122B2 (en) * | 1989-08-18 | 1998-08-27 | 鐘紡株式会社 | Nail polish |
| JP3080803B2 (en) * | 1993-01-11 | 2000-08-28 | 鐘紡株式会社 | Water based nail polish |
| JP3149291B2 (en) * | 1993-03-24 | 2001-03-26 | ユーホーケミカル株式会社 | Composition for beautiful nails |
| JPH06336558A (en) * | 1993-05-28 | 1994-12-06 | Kose Corp | Cosmetic |
| JP3513864B2 (en) * | 1995-06-30 | 2004-03-31 | 株式会社コーセー | Aqueous nail polish |
| JP3432979B2 (en) * | 1995-11-17 | 2003-08-04 | 花王株式会社 | Cosmetics |
| JP3434964B2 (en) * | 1996-03-07 | 2003-08-11 | 株式会社資生堂 | Composite powder and method for producing the same |
-
1998
- 1998-01-26 JP JP02769998A patent/JP3554174B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11209241A (en) | 1999-08-03 |
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