JP4564707B2 - Hair composition - Google Patents

Description

【００２３】
本発明の「消色型」又は「変色型」の毛髪用組成物に用いられる「消色剤」とは、熱力学的に、発色剤よりも強く顕色剤と相互作用することにより、発色状態にある発色剤から顕色剤を奪い取り、発色状態にある発色剤を非発色状態にする物質をいう。消色剤は、発色剤の発色状態においてはマトリックス材料中に、また、非発色状態においては加熱により溶融、膨潤又は溶解し、かつ凝固した、発色剤、顕色剤及びマトリックス材料の混合物中に、微粒子（消色剤が結晶の場合）ないしミクロ相分離状態（消色剤がアモルファス状態の場合）として分散して存在することが可能な化合物である。
【００２４】
消色剤と顕色剤の間に働き得る分子間相互作用としては、水素結合、イオン結合、疎水性結合、立体化学的な包接現象等を利用することができる。すなわち、分子中に１個以上のアルコール性水酸基、遊離のカルボン酸基、カルボン酸塩残基、環式飽和炭化水素残基等を有する化合物の中から、使用するマトリックス材料への溶解性及びその温度依存性を目安として、消色剤として利用可能なものを選択することができる。
【００２５】
本発明で使用される消色剤の具体例としては、例えば、コーンスターチ、タピオカスターチ等のデンプン、疎水化デンプン、デキストリン、シクロデキストリン、コール酸、リトコール酸、テストステロン、コルチゾン等、並びにこれらの誘導体、すなわち、コール酸メチルエステル、リトコール酸メチルエステル、ヒドロキシコール酸、ヒドロキシコール酸メチルエステル、メチルテストステロン、11α-ヒドロキシメチルテストステロン、ヒドロコルチゾン等が挙げられる。
【００２６】
本発明の毛髪用組成物中におけるこれら消色剤の微粒子ないしミクロ相分離状態の大きさは、その形状を球で近似したときの平均直径として、10nm〜20μmが好ましい。
【００２７】
〈非変色色素〉
本発明の変色型の毛髪用組成物に用いられる「非変色色素」としては、顔料、及び通常のヘアマニキュアにおいて用いられる染料が挙げられる。具体的には、水不溶性の顔料、油溶性染料、建染染料、レーキ染料等が挙げられる。顔料としては、カーボンブラック、タルク、カオリン、マイカ、雲母チタン、ベンガラ、珪酸マグネシウム、酸化チタン等の無機顔料、赤色202号、赤色204号、赤色205号、赤色206号、赤色219号、赤色228号、赤色404号、黄色205号、黄色401号、だいだい色401号、青色404号等の有機顔料が挙げられ、染料としては、赤色505号、赤色501号、赤色225号、黄色404号、黄色405号、黄色204号、だいだい色403号、青色403号、緑色202号、紫色201号、赤色226号、青色204号、青色201号、種々の酸性染料をアルミニウムやバリウムでレーキしたもの等が挙げられる。非変色色素は、２種以上を併用してもよい。
【００２８】
〈熱変色〉
熱変色材料の熱変色の起こる温度範囲は、室温、及び毛髪用組成物が製造、保管、輸送され、店頭に展示され、消費者の元で保管される過程（以下、「保存環境」という）で晒されうる温度よりも高い温度域である必要がある。具体的には熱変色材料は、保存環境の温度40〜50℃において数ヶ月間保管しても熱変色しないことが好ましい。一方、熱変色材料の熱変色の起こる温度範囲は、毛髪の熱分解開始温度を超えず、更に、毛髪の生え際の頭皮に短時間には熱の影響を与えない程度の高温である必要がある。具体的には、60〜100℃、特に70〜90℃が好ましい。
【００２９】
本発明の毛髪用組成物が熱変色を起こすための、上記の好ましい温度範囲を簡便かつ確実に実現するために用いられる加熱手段としては、通常のヘアドライアーを好適に使用することができる。その他、アイパーなどの毛髪加熱手段を用いることもできる。
【００３０】
本発明の毛髪用組成物が熱変色を起こす速度は速いほど好ましい。具体的にはヘアドライアーによって60〜100℃で加熱したときに、３分以内で熱変色が完了することが好ましく、更には１分以内に完了することが好ましい。
【００３１】
〈マトリックス材料〉
本発明の毛髪用組成物が、毛髪や頭皮に熱の悪影響を与えない温度範囲で迅速に熱変色を完了し、一方、40〜50℃の保存環境においては熱変色を起こさないという、相反する要求を同時に満足させるため、熱変色材料の全て又は一部は、マトリックス材料中に分散された造粒物の状態で使用される。マトリックス材料は、毛髪用組成物を毛髪に塗布し加熱されるまでの間においては、「発色型」の場合は発色剤と顕色剤、「消色型」の場合は発色状態の色素と消色剤との相互作用を妨げる役割を有すると共に、加熱後においては、溶融して流動状態となることにより、両者の反応による熱変色を起こさせるという役割を有する。このような熱変色材料を分散したマトリックス材料は、本発明の毛髪用組成物を例えばスプレー、フォーム剤、ミスト、ゲル、ローション、トニック、ブロー剤、クリーム、後発泡性ゲル等の形態に調製して使用する際の分散安定性及び貯蔵安定性付与の観点より、混練、粉砕、分級により、数平均粒子径で0.1〜30μm、特に１〜20μm、体積平均粒子径で0.1〜30μm、特に１〜20μmの微粒子に造粒するのが好ましい。マトリックス材料は、毛髪用組成物を毛髪に付着させるためのバインダー樹脂と同一であっても、異種であってもよい。
【００３２】
マトリックス材料としては、有機高分子化合物（高分子マトリックス材料）又は低分子化合物（低分子マトリックス材料）を使用することができる。
【００３３】
高分子マトリックス材料としては、人体及び自然環境に対して無害であって、有害な残留モノマーを含まないものが好ましい。具体的には、ケトン樹脂、ノルボルネン樹脂、ポリスチレン、ポリ(α-メチルスチレン)、ポリインデン、ポリ(4-メチル-1-ペンテン)、ポリビニルピリジン、ポリアセタール、ポリビニルホルマール、ポリビニルアセタール、ポリビニルブチラール、ポリ酢酸ビニル、ポリプロピオン酸ビニル、ポリビニルアルコール、ポリエチレン、ポリプロピレン、ポリブタジエン、ポリメチルペンテン、ポリビニルメチルエーテル、ポリビニルエチルエーテル、ポリビニルベンジルエーテル、ポリビニルメチルケトン、ポリ(N-ビニルカルバゾール)、ポリ(N-ビニルピロリドン)、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ブチル、ポリメタクリル酸ベンジル、ポリメタクリル酸シクロヘキシル、ポリメタクリル酸アミド、ポリアセトアルデヒド、ポリエチレンオキシド、ポリプロピレンオキシド、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート類（ビスフェノール類＋炭酸）、ポリサルホン、ポリエーテルサルホン、ポリフェニレンサルファイド、ポリ（ジエチレングリコール・ビスアリルカーボネート）類、6-ナイロン、6,6-ナイロン、12-ナイロン、6,12-ナイロン、ポリアスパラギン酸エチル、ポリグルタミン酸エチル、ポリリジン、ポリプロリン、ポリ(γ-ベンジル-L-グルタメート)、メチルセルロース、エチルセルロース、ベンジルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、アセチルセルロース、セルローストリアセテート、セルローストリブチレート等の熱可塑性樹脂が挙げられる。
【００３４】
低分子マトリックス材料としては、低分子可塑剤、低分子滑剤、低分子ワックス等の低分子化合物を用いることができる。すなわち、熱変色材料の変色温度範囲において、発色剤及び顕色剤を固溶化（溶解し分子分散させる）することができ、かつ、50℃以下の温度域では粒子としての形態を維持することのできる低分子化合物を適宜選択して低分子マトリックス材料として使用することができる。
具体的には、長鎖アルキル基を有する尿素誘導体やアルコール類など、例えば、1-ドコサノールを好適に使用することができる。
【００３５】
〈マトリックス材料、熱変色材料及び非変色色素の使用量・比率〉
マトリックス材料の使用量は、発色剤１重量部に対して0.1〜1000重量部の割合が好ましく、更には0.5〜100重量部、特に１〜20重量部の割合が好ましい。顕色剤の使用量は、発色剤との相互作用による発色を十分なものにするとともに、「消色型」又は「変色型」の場合に消色剤によって発色剤との相互作用を十分に減少させる観点より、発色剤１重量部に対して0.1〜10重量部、特に１〜２重量部の割合が好ましい。消色剤の使用量は、発色状態から消色状態への状態変化を容易にするとともに、発色剤の発色を十分にする観点より、発色剤１重量部に対して、１〜200重量部、特に10〜100重量部の割合が好ましい。「変色型」の場合、非変色色素の使用量は、発色剤１重量部に対して0.1〜1000重量部が好ましく、更には0.5〜100重量部、特に１〜20重量部の割合が好ましい。
【００３６】
熱変色材料は、発色剤、顕色剤及び消色剤を含んだ合計量として、毛髪用組成物中に0.1〜100重量％含有することが好ましく、更には1.5〜50重量％、特に２〜20重量％含有することが好ましい。非変色色素は、毛髪用組成物中に0.01〜10重量％含有することが好ましく、更には0.05〜５重量％、特に0.1〜３重量％含有することが好ましい。
【００３７】
〈バインダー樹脂〉
本発明の毛髪用組成物には、熱変色材料を毛髪の表面に付着させるため、バインダー樹脂を含有させる。バインダー樹脂としては、毛髪に付着して皮膜を形成し得るものであれば特に制限されず、両性ポリマー、アニオンポリマー、カチオンポリマー、ノニオンポリマー、天然高分子及びそれらの誘導体のいずれでもよく、更に水分散性ポリエステル樹脂を使用することもできる。
【００３８】
両性ポリマーとしては、ユカフォーマーAM-75、同SM、同202（以上、三菱化学社）等のジアルキルアミノエチルメタクリレート／メタクリル酸アルキルエステル共重合体のモノクロル酢酸両性化物；アンフォマー28-4910、同LV-71（以上、ナショナル・スターチ社）等のアクリル酸ヒドロキシプロピル／メタクリル酸ブチルアミノエチル／アクリル酸オクチルアミド共重合体などが挙げられ、中でもユカフォーマーSM及び202が好ましい。
【００３９】
アニオンポリマーとしては、ガントレッツES-225、同ES-425、同SP-215（以上、ISP社）等のメチルビニルエーテル／無水マレイン酸アルキルハーフエステル共重合体；レジン28-1310（ナショナル・スターチ社）、ルビセットCA（BASF社）等の酢酸ビニル／クロトン酸共重合体；レジン28-2930（ナショナル・スターチ社）等の酢酸ビニル／クロトン酸／ネオデカン酸ビニル共重合体；ルビセットCAP（BASF社）等の酢酸ビニル／クロトン酸／プロピオン酸ビニル共重合体；ADVANTAGE CP（ISP社）等の酢酸ビニル／マレイン酸モノブチルエステル／イソボロニルアクリレート共重合体；プラスサイズL53D（カラー用Ａ）、同L-75CB（以上、互応化学社）、ダイヤホールド（三菱化学社）等の（メタ）アクリル酸／（メタ）アクリル酸アルキルエステル共重合体；ウルトラホールド８、ウルトラホールド・ストロング（以上、BASF社）、アンフォマーV-42（ナショナル・スターチ社）等のアクリル酸／アクリル酸アルキルエステル／アルキルアクリルアミド共重合体；ルビフレックスVBM35（BASF社）等のポリビニルピロリドン／アクリレート／（メタ）アクリル酸共重合体などが挙げられ、中でもプラスサイズL-75CBが好ましい。
【００４０】
カチオンポリマーとしては、ルビカットFC370、同FC550、同FC905、同HM552、同MonoCP（以上、BASF社）等のビニルイミダゾリウムトリクロライド／ビニルピロリドン共重合体；セルカットH-100、同L-200（以上、ナショナル・スターチ社）等のヒドロキシエチルセルロース／ジメチルジアリルアンモニウムクロリド；ガフカット734、同755N（以上、ISP社）、PQ-11（BASF社）等のビニルピロリドン／四級化ジメチルアミノエチルメタクリレート共重合体；コポリマー845、同937、同958（以上、ISP社）等のポリビニルピロリドン／アルキルアミノアクリレート共重合体；コポリマーVC-713（ISP社）等のポリビニルピロリドン／アルキルアミノアクリレート／ビニルカプロラクタム共重合体；ガフカットHS-100（ISP社）等のビニルピロリドン／メタクリルアミドプロピル塩化トリメチルアンモニウム共重合体；特開平2-180911号公報に記載の水溶性高分子化合物等のアルキルアクリルアミド／アクリレート／アルキルアミノアルキルアクリルアミド／ポリエチレングリコールメタクリレート共重合体等が挙げられ、特にガフカット755Nが好ましい。
【００４１】
ノニオンポリマーとしては、ルビスコールK12、同17、同30、同60、同80、同90（以上、BASF社）、PVP K15、同30、同60、同90（以上、ISP社）等のポリビニルピロリドン；ルビスコールVA28E、同37E、同55E、同64E、同73E（以上、BASF社）、PVP/VA E-735、同E-635、同E-535、同E-335、同S-630、同W-735（以上、ISP社）等のポリビニルピロリドン／酢酸ビニル共重合体；ルビスコールVAP343（BASF社）等のポリビニルピロリドン／酢酸ビニル／プロピオン酸ビニル三元共重合体；Dowlex（ダウ・ケミカル社）等の酢酸ビニル／N-ビニル-5-メチル-2-オキサゾリン共重合体等が挙げられ、中でもルビスコールVA55E、PVP/VA E-535が好ましい。
【００４２】
天然高分子又はその誘導体の具体例としては、グアーガム、ローカストビーンガム、アラビアガム、プルラン、カラギーナン等の天然多糖類；キトサン塩、カルボキシメチルキチン、ヒドロキシプロピルキトサン等のキチン誘導体；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のデンプン系高分子化合物、メチルセルロース、ニトロセルロース、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ナトリウム、ポリマーJR400（ユニオンカーバイド社）などのカチオン化セルロース、結晶セルロース、セルロース末等のセルロース系高分子化合物；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のアルギン酸系高分子化合物などが挙げられ、中でもカチオン化セルロース、ヒドロキシプロピルキトサンが好ましい。
【００４３】
なお、これらのバインダー樹脂のうち、酸性基又は塩基性基を有するものについては、洗髪性等の点から、これらの一部又は全部を中和して塩に変換したものが好ましい。酸性基の塩としては、ナトリウム、カリウム等のアルカリ金属塩；アンモニウム塩、エタノールアミン、ジエタノールアミン、トリエタノールアミン、2-アミノ-2-メチルプロパノール、2-アミノ-2-メチル-1,3-プロパンジオール、アミノメルカプトプロパンジオール、トリイソプロパノールアミン、グリシン、ヒスチジン、アルギニン等の有機塩基塩が挙げられ、中でも2-アミノ-2-メチルプロパノール、2-アミノ-2-メチル-1,3-プロパンジオールの塩が好ましい。
また、塩基性基の塩としては、無機酸塩としては塩酸、硫酸、リン酸等の塩が好ましく、有機酸塩としては、酢酸、乳酸、グリコール酸、ジメチロールプロピオン酸、酒石酸、クエン酸、マレイン酸、リンゴ酸、ピロリドンカルボン酸等の塩が好ましい。
【００４４】
水分散性ポリエステル樹脂としては、水不溶性で水に分散可能なものであれば特に制限されないが、例えば、水に分散するのに十分な量の−ＳＯ₃Ｍ基（Ｍは水素原子又は金属イオンを示す）を有するポリエステルが挙げられる。このようなポリエステルとしては、一種以上のジカルボン酸化合物と、重合にあずかる官能基以外にスルホン酸基を芳香核上に有する二官能モノマーの一種以上とを縮合させて得られるものが挙げられ、特にジエチレングリコール、シクロヘキサンジメタノール、イソフタル酸及びスルホイソフタル酸を縮合させて得られたものが好ましい。このようなポリエステルの市販品としては、Eastman AQ 38S、同55S（イーストマン・ケミカルプロダクツ社）等が挙げられる。
【００４５】
以上のバインダー樹脂のうち、（メタ）アクリル酸−（メタ）アクリル酸アルキルエステル共重合体が最も好ましく用いられる。
【００４６】
バインダー樹脂の含有量は、本発明の毛髪用組成物中に、好ましくは0.05〜10重量％、より好ましくは0.05〜５重量％、更に好ましくは0.1〜３重量％、特に好ましくは0.2〜２重量％である。また、熱変色材料の全部又は一部を含有するマトリックス材料の微粒子とバインダー樹脂との比率は、重量比で微粒子１に対しバインダー樹脂0.2〜２が好ましい。
【００４７】
〈毛髪用組成物の形状及びその他の成分〉
本発明の毛髪用組成物には、前記成分のほか、通常の毛髪化粧料に用いられる成分、例えばカチオン界面活性剤、アニオン界面活性剤、非イオン界面活性剤、両性界面活性剤等の界面活性剤；高級アルコール類；流動パラフィン、ワセリン等の炭化水素類；液状ラノリン、ラノリン脂肪酸等のラノリン誘導体；レシチン等のリン脂質；コレステロール等のステロール及びその誘導体；コラーゲン分解ペプチド誘導体；パーフルオロポリエーテル；高級アルコール高級脂肪酸エステル類、高級脂肪酸類等の油脂類；ミンクオイル、オリーブ油等の動植物性油脂類；抗フケ剤、殺菌剤、ビタミン類等の薬効剤；グリセリン、エタノール等の溶剤；パラベン類等の防腐剤；その他、紫外線吸収剤、植物抽出物、収れん剤、香料等を、目的に応じて、適宜配合又は粒子中に内包することができる。
【００４８】
本発明の毛髪用組成物は、常法に従って製造することができ、各種剤型、例えばスプレー、フォーム剤、ミスト、ゲル、ローション、トニック、ブロー剤、クリーム、後発泡性ゲル、粉末等の形態に調製することができる。中でも、操作性の点で噴射剤を含有させエアゾール剤型とすることが望ましい。噴射剤としては、プロパン、イソブタン、ブタン、これらの混合物（液化石油ガス；LPG）等の低級飽和炭化水素；ジメチルエーテル等のエーテル類；二酸化炭素、窒素、空気、亜酸化窒素等の圧縮ガスなどが挙げられる。これらは２種以上を併用することができる。これらの中でも、LPG、ジメチルエーテル又はこれらの混合物が好ましい。
【００４９】
毛髪用組成物中の噴射剤の含有量は、使用目的等に応じて適宜決定することができるが、噴射剤として、LPG、ジメチルエーテル又はこれらの混合物を使用したエアゾール型フォーム剤の場合には、１〜30重量％、特に１〜20重量％が好ましい。なお、毛髪用組成物中の噴射剤のガス圧は20℃において0.14〜0.69MPaが好ましい。
【００５０】
〈毛髪用組成物の製造方法〉
「発色型」の毛髪用組成物を製造するに際しては、発色剤が非発色状態を保つよう、諸工程の条件を設定する必要がある。例えば、発色剤を溶融状態のマトリックス材料中に溶解ないし微分散させた混練物を冷却後、粉砕・分級し、例えば平均粒子径10μmとし、一方、エタノールに溶解した顕色剤溶液を水に混合して再沈殿させて微結晶化した顕色剤の水−エタノール懸濁液を得、これらを混合する方法が挙げられる。
【００５１】
「消色型」の毛髪用組成物を製造するに際しては、発色剤が顕色剤と作用して発色状態として、微粒子ないしミクロ相分離状態の消色剤とともに存在するよう、諸工程の条件を設定する必要がある。例えば、所定の大きさに予め粉砕ないし微細化された微粒子ないしミクロ相分離状態の消色剤を、顕色剤と発色剤との反応により生成した色素及びマトリックス材料の混練物中に分散させた後、粉砕・分級し、例えば平均粒子径10μmとし、これをバインダー樹脂の水−エタノール溶液中に分散させる方法が挙げられる。
【００５２】
また「発色型」又は「消色型」の毛髪用組成物に非変色色素を混合することで「変色型」の毛髪用組成物を製造することができる。非変色色素を混合する方法としては、前記マトリックス材料中に溶解又は分散させる方法、あるいは、前記懸濁液中に溶解ないし分散させる方法を用いることができる。
【００５３】
【実施例】
以下の実施例において、粒子径は、分散剤としてドデシルベンゼンスルホン酸ナトリウムを用いて電解質を含んだ水中に超音波分散させた試料をコールターカウンターTA-II型（コールター社）にて測定して求めた。
なお、実施例５及び６は参考例であって、特許請求の範囲に含まれるものではない。
【００５４】
実施例１ 発色型毛髪用組成物（無色→黒色）
発色剤として未発色状態のロイコ色素S-205（山田化学工業社）６重量部、及びマトリックス材料として94重量部のポリスチレンを予め混合し、ニーダーを用いて75℃を超えない温度で十分に混練した後、冷却した。この混練物を、カッター刃回転式粉砕機で粒子外径１mmまで粗粉砕し、次いでサイクロン式分級機を備えた循環式エアジェット粉砕機で最大粒子径20μm以下まで粉砕し、更に、別のサイクロン式分級機を用いて分級し、数平均粒子径８μmかつ体積平均粒子径10μmの無色の微粒子を得た。
一方、顕色剤として没食子酸ステアリル４重量部をエタノール20重量部に分散・溶解した溶液を、バインダー樹脂としてユカフォーマーSM（三菱化学社）２重量部を水72重量部に溶解させた溶液中によくかき混ぜながら注入し、没食子酸ステアリルの微結晶懸濁液を得た。この懸濁液中に上記の微粒子２重量部を混合、分散して毛髪用組成物を得た。
この毛髪用組成物５ｇを、櫛を用いて白色の毛髪５ｇに塗布し、ヒーターの容量１kWのヘアドライヤーにて毛髪の温度が80℃以上になるよう加熱したところ、約30秒以上の熱処理によって、毛髪は黒色に着色された。
【００５５】
実施例２ 発色型毛髪用組成物（無色→黒色）
発色剤として未発色のロイコ色素S-205（山田化学工業社）６重量部及びマトリックス材料として94重量部のポリスチレンを用い、実施例１と同様にして、同サイズの発色剤を含有する無色の微粒子を得た。
また、顕色剤として没食子酸ステアリル30重量部及びマトリックス材料として70重量部のポリスチレンを予め混合し、ニーダーを用いて75℃を超えない温度で十分に混練した後、冷却した。この混練物を、カッター刃回転式粉砕機で粒子外径１mmまで粗粉砕し、次いでサイクロン式分級機を備えた循環式エアジェット粉砕機で最大粒子径20μm以下まで粉砕し、更に、別のサイクロン式分級機を用いて分級し、数平均粒子径８μmかつ体積平均粒子径10μmの顕色剤を含有する無色の微粒子を得た。
一方、バインダー樹脂としてユカフォーマーSM（三菱化学社）２重量部をエタノール20重量部及び水78重量部に溶解させた。この溶液中に上記の発色剤を含有する微粒子１重量部および顕色剤を含有する微粒子１重量部を混合、分散して毛髪用組成物を得た。
この毛髪用組成物５ｇを、櫛を用いて白色の毛髪５ｇに塗布し、ヒーターの容量１kWのヘアドライヤーにて毛髪の温度が80℃以上になるよう加熱したところ、約30秒以上の熱処理によって、毛髪は黒色に着色された。
【００５６】
実施例３ 発色型毛髪用組成物（無色→黒色）
実施例２の顕色剤を含有する微粒子の製造において、顕色剤として没食子酸ステアリルの代わりにL(+)-アスコルビン酸（ビタミンＣ）20重量部を使用し、ポリスチレンを80重量部とする以外は実施例２と同様にして、毛髪用組成物を得た。
この毛髪用組成物を用いて、実施例２と同様に白色の毛髪を処理したところ、約30秒以上の熱処理によって、毛髪は黒色に着色された。
【００５７】
実施例４ 変色型毛髪用組成物（金色→黒色）
発色剤として未発色状態のロイコ色素S-205（山田化学工業社）６重量部、非変色色素としてベンガラ被覆雲母チタン（金色；Imperial Gold 222X，エンゲルハード社）６重量部及びマトリックス材料として86重量部のポリスチレンを予め混合し、ニーダーを用いて75℃を超えない温度で十分に混練した後、冷却した。
この混練物を、カッター刃回転式粉砕機で粒子外径１mmまで粗粉砕し、次いでサイクロン式分級機を備えた循環式エアジェット粉砕機で最大粒子径20μm以下まで粉砕し、更に、別のサイクロン式分級機を用いて分級し、数平均粒子径８μmかつ体積平均粒子径10μmの金色の微粒子を得た。
一方、顕色剤として没食子酸ステアリル10重量部をエタノール20重量部に分散・溶解した溶液を、バインダー樹脂としてガフカット755N（ISP社）２重量部を水68重量部に溶解させた溶液中によくかき混ぜながら注入し、没食子酸ステアリルの微結晶懸濁液を得た。この懸濁液中に上記の微粒子２重量部を混合、分散して毛髪用組成物を得た。
この毛髪用組成物を、櫛を用いて白色の毛髪に塗布し、60℃以下の温風で乾燥したところ、毛髪は金色に着色された。この毛髪を、更に、ヒーターの容量１kWのヘアドライヤーにて毛髪の温度が80℃以上になるよう加熱したところ、約30秒以上の熱処理によって、毛髪は黒色に着色された。
【００５８】
実施例５ 消色型毛髪用組成物（黒色→無色）
消色剤として、市販のコーンスターチ（粒子の外径約10〜20μm）を、サイクロン式分級機を備えた循環式エアジェット粉砕機で粉砕・分級したものを用いた。
発色剤として未発色状態のロイコ色素S-205（山田化学工業社）６重量部及び顕色剤として没食子酸プロピル２重量部を混合し、100℃に加熱融解させることにより、黒色に発色させた。このものに、上記のコーンスターチ微粒子17重量部、及びマトリックス材料として75重量部のポリスチレンを混合し、ニーダーを用いて75℃を超えない温度で十分に混練した後、冷却し、黒色の混練物を得た。この混練物を、実施例１と同様に粗粉砕、粉砕及び分級し、同サイズの黒色微粒子を得た。
バインダー樹脂としてポリマーJR400（ユニオンカーバイド社）２重量部を水98重量部に溶解させた溶液中に、上記の微粒子２重量部を混合、分散して黒色の毛髪用組成物を得た。
この毛髪用組成物を、櫛を用いて白色の毛髪に塗布し、60℃以下の温風で乾燥したところ、毛髪は黒色に着色された。この毛髪を、更に、ヒーターの容量１kWのヘアドライヤーにて毛髪の温度が80℃以上になるよう加熱したところ、約30秒以上の熱処理によって、毛髪は白色に戻った。
【００５９】
実施例６ 変色型毛髪用組成物（黒色→銅色）
実施例５の微粒子の製造において、更に非変色色素としてベンガラ被覆雲母チタン（銅色；Copper 340X，エンゲルハード社）８重量％を加え、ポリスチレンを67重量部のポリスチレンとする以外は同様にして、同サイズの黒色微粒子を得た。バインダー樹脂としてユカフォーマー202（三菱化学社）３重量部を水97重量部に溶解させた溶液中に上記の微粒子３重量部を混合、分散して黒色の毛髪用組成物を得た。
この毛髪用組成物を、櫛を用いて白色の毛髪に塗布し、60℃以下の温風で乾燥したところ、毛髪は黒色に着色された。この毛髪を、更に、ヒーターの容量１kWのヘアドライヤーにて毛髪の温度が80℃以上になるよう加熱したところ、約30秒以上の熱処理によって、毛髪は銅色に変色した。
【００６０】
実施例７ 発色型毛髪用組成物（白色→黒色；エアゾール）
発色剤として非発色状態のロイコ色素S-205（白色；山田化学工業社）６重量部、及びマトリックス材料として94重量部のポリスチレンを予め混合し、ニーダーを用いて75℃を超えない温度で十分に混練した後、冷却した。この混練物を、カッター刃回転式粉砕機で粒子外径１mmまで粗粉砕し、次いでサイクロン式分級機を備えた循環式エアジェット粉砕機で最大粒子径20μm以下まで粉砕し、更に、別のサイクロン式分級機を用いて分級し、数平均粒子径８μmかつ体積平均粒子径10μmの微粒子を得た。
一方、顕色剤として没食子酸ステアリル４重量部をエタノール20重量部に分散・溶解した溶液を、バインダー樹脂としてユカフォーマーSM（三菱化学社）２重量部、起泡剤として塩化セチルトリメチルアンモニウム0.025重量部を水72重量部に溶解させた溶液中によくかき混ぜながら注入し、没食子酸ステアリルの微結晶懸濁液を得た。この懸濁液中に上記の微粒子２重量部を混合、分散して毛髪用組成物を得た。
エアゾール用容器に、原液として上記毛髪用組成物を90重量％、噴射剤としてLPG（0.44Mpa）を10重量％の割合で充填し、エアゾール剤を得た。
このエアゾール型の毛髪用組成物５ｇを、櫛を用いて白色の毛髪５ｇに塗布し、ヒーターの容量１kWのヘアドライヤーにて毛髪の温度が80℃以上になるよう加熱したところ、約30秒以上の熱処理によって、毛髪は黒色に着色された。
【００６１】
【発明の効果】
以上詳述したように、本発明の毛髪用組成物を用いれば、毛髪用組成物を塗布した毛髪部分のみを着色することができる。また、本発明の毛髪用組成物によって着色された毛髪を洗髪することなく簡便かつ迅速に脱色し、本来の毛髪の色に戻すことができる。更に、本発明の毛髪用組成物によって着色された毛髪を、洗髪及び再着色することなく、簡便かつ迅速に色彩変化させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composition for hair that contains a thermochromic material and can be colored, decolored or discolored by heating after application to hair.
[0002]
[Prior art]
One method of coloring hair is to apply hair nail polish to the hair surface. Since the hair manicure method does not act chemically on the hair itself, the hair manicure method has features such that the hair is not damaged, the hair can be colored relatively easily, and the hair can be decolored by washing.
[0003]
However, since the composition for hair used for the conventional hair manicure uses the pigment | dye which is in a coloring state permanently, it will also color skin other than hair, Therefore In using, very care is required . In the unlikely event that it adheres to the skin, it is necessary to prepare another means for removing the hair nail polish from the skin. Moreover, in order to remove the color of the hair colored with hair manicure, it is necessary to carefully wash the hair. In addition, if you coat the next hair nail polish with another color on top of the first hair nail polish, the two types of colors will melt together, resulting in an unintended color or uneven color. In order to change the color of the colored hair, it is necessary to wash out what was used first and then use a hair nail polish of another color again.
[0004]
On the other hand, in thermal recording paper for word processors, facsimiles, various office automation equipment, etc., a thermal layer containing leuco dye, developer and decolorizer is provided, and the printed characters are naturally erased over time and repeated. It has been proposed to enable use (see Patent Document 1). However, the idea of applying leuco dyes to hair compositions has never existed.
[0005]
[Patent Document 1]
Japanese Laid-Open Patent Publication No.4-14482
[0006]
[Problems to be solved by the invention]
An object of this invention is to provide the composition for hair which can color only the hair part which apply | coated the composition for hair. It is another object of the present invention to provide a hair composition that can be easily and quickly decolored after coloring without returning to the original hair color. Furthermore, an object of the present invention is to provide a hair composition that can be easily and quickly changed in color without being washed and recolored after coloring.
[0007]
[Means for Solving the Problems]
The present inventors have conceived that a reversible reaction by a combination of a color former (leuco dye) and a developer used in heat-sensitive recording paper and the like is used for a hair composition and satisfies the above requirements. I succeeded in getting things.
[0008]
  The present invention relates to a thermochromic material comprising a color former and a developer.And a binder resin, a part of the thermochromic material,Granules dispersed in matrix materialIs in the stateA composition for hair is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
<Aspects of hair composition>
Examples of the hair composition of the present invention include “color developing type”, “decoloring type” and “discoloring type”.
[0011]
The “color-forming” hair composition contains, as a thermochromic material, a color former and a developer that are in an uncolored state, and is applied to the hair and then colored by heating. By selectively heating the coloring type hair composition applied to the hair by a heating means such as a hair dryer, only the hair can be selectively colored without coloring the scalp or facial skin. It becomes possible.
[0012]
The “decoloring type” hair composition contains, as a thermochromic material, a pigment generated by the reaction of a color former and a developer and a decoloring agent, and is applied to the hair and then heated. The color is to be erased. By heating the color-erasable hair composition applied to the hair with a heating means such as a hair dryer, the hair colored with the hair composition can be easily and quickly decolored without washing the hair. It becomes possible to return to the color of.
[0013]
The “color-changing type” hair composition is obtained by adding a non-color-changing dye to the above “coloring type” or “decoloring type” composition. The form of “color-forming type + non-color-changing dye” contains a color-developing agent and a developer in an uncolored state, and a non-color-changing dye, and is for hair exhibiting a first color (the color of the non-color-changing dye) After the composition is attached to the hair, the color former is colored by heating to change the color to the second color (mixture of the dye formed by the reaction between the color former and the developer and the non-color-changing dye). Is. The form of “color-erasing type + non-color-changing dye” contains a color produced by the reaction between the color former and the developer, the color-erasing agent, and the non-color-changing dye. The hair composition exhibiting a color mixture of a pigment generated by the reaction of the agent and a non-color-changing pigment) is attached to the hair and then heated to change to the second color (color of the non-color-changing pigment). In any case, it is possible to change the color of the hair colored with the hair composition before discoloration easily and quickly without washing and recoloring the hair.
[0014]
<Heat discoloration material>
In the present invention, the thermochromic material refers to a combination of compounds that cause a reversible chemical reaction accompanied by a color change by heating.
[0015]
Examples of the color former include leuco dyes such as triarylmethane compounds, diphenylmethane compounds, xanthene compounds, thiazine compounds, and spiropyran compounds. Specifically, as a triarylmethane color former, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (commonly known as crystal violet lactone), 3,3-bis (p-dimethylamino) Phenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole-3- Yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylamino Phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1-methylpyrrol-2-yl ) -6-dimethylaminophthalide and the like.
[0016]
Examples of the diphenylmethane color former include 4,4′-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl leucooramine, N-2,4,5-trichlorophenyl leucooramine and the like.
[0017]
Xanthene color formers include rhodamine B-anilinolactam, rhodamine- (p-nitroanilino) lactam, rhodamine B (p-chloroanilino) lactam, 3-dimethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxy. Fluorane, 3-diethylamino-7-chloro-6-methylfluorane, 3-diethylamino-7- (acetylmethylamino) fluorane, 3-diethylamino-7- (dibenzylamino) fluorane, 3-diethylamino-7- ( Methylbenzylamino) fluorane, 3-diethylamino-7- (chloroethylmethylamino) fluorane, 3-diethylamino-7- (diethylamino) fluorane, etc.
[0018]
Examples of thiazine color formers include benzoyl leucomethylene blue and p-nitrobenzyl leucomethylene blue.
[0019]
Spiropyran-based color formers include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho (3 -Methoxybenzo) spiropyran, 3-propyl-spiro-dibenzodipyran and the like.
[0020]
The developer has a function of coloring when in contact with the above leuco dye (coloring agent). Examples thereof include inorganic acid such as activated clay, acid clay, attapulgite, bentonite, colloidal silica, and aluminum silicate. Substance: Vitamins such as ascorbic acid; phenol, 4-tert-butylphenol, 4-hydroxydiphenoxide, α-naphthol, β-naphthol, 4-hydroxyacetophenol, 4-tert-octylcatechol, 2,2'-dihydroxy Diphenol, 2,2'-methylenebis (4-methyl-6-tert-isobutylphenol), 4,4'-isopropylidenebis (2-tert-butylphenol), 4,4'-sec-butylidenediphenol, 4 -Phenylphenol, 4,4'-isopropylidene diphenol (bisphenol A), 4,4'-ethylidene diphenol (bisphenol F), 4,4 '-(1-cyclohex Ruethylidene) diphenol, 2,2'-methylenebis (4-chlorophenol), hydroquinone, 4,4'-cyclohexylidenediphenol, gallic acid, gallic acid esters (propyl gallate, stearyl gallate, etc.), 4-hydroxy Such as benzyl benzoate, dimethyl 4-hydroxyphthalate, hydroquinone monobenzyl ether, 4-hydroxyphenyl-4'-isopropyloxyphenyl sulfone, bis (4-hydroxyphenylthioethoxy) methylene, novolac-type phenolic resin, phenol polymer, etc. Phenolic compounds; benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl- 4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalic Lithic acid, 3-benzylsalicylic acid, 3- (α-methylbenzyl) salicylic acid, 3-chloro-5- (α-methylbenzyl) salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5- ( (α, α-dimethylbenzyl) salicylic acid, 3,5-di-α-methylbenzylsalicylic acid and other aromatic carboxylic acids; the above phenolic compounds or aromatic carboxylic acids and zinc, magnesium, aluminum, calcium, titanium, manganese, Organic acidic substances such as salts with polyvalent metals such as tin and nickel are listed.
[0021]
These color developers can stabilize the colored state by, for example, interacting between the carboxylic acid residues of the color former and molecules to form hydrogen bonds as shown in the chemical formula below. Such intermolecular interaction between the color former and the developer can occur even when both of them are solid solution (dissolved and molecularly dispersed) in the matrix material.
[0022]
[Chemical 1]

[0023]
The “decoloring agent” used in the “decoloring type” or “discoloring type” hair composition of the present invention is a thermodynamically stronger color developer than interacting with the color developing agent. A substance that takes a developer from a color former in a state to make the color former in a color development state into a non-color development state. The color erasing agent is in the matrix material in the color developing state of the color former, or in the mixture of the color developing agent, the developer and the matrix material which is melted, swollen or dissolved by heating and solidified in the non-color developing state. These compounds can exist in a dispersed state as fine particles (when the color erasing agent is in a crystal state) or in a microphase separation state (when the color erasing agent is in an amorphous state).
[0024]
As an intermolecular interaction that can act between the color erasing agent and the color developer, a hydrogen bond, an ionic bond, a hydrophobic bond, a stereochemical inclusion phenomenon, or the like can be used. That is, the solubility in a matrix material to be used from among compounds having one or more alcoholic hydroxyl groups, free carboxylic acid groups, carboxylate residues, cyclic saturated hydrocarbon residues, etc. in the molecule and its With reference to the temperature dependence, one that can be used as a decoloring agent can be selected.
[0025]
Specific examples of the color erasing agent used in the present invention include, for example, starch such as corn starch and tapioca starch, hydrophobized starch, dextrin, cyclodextrin, cholic acid, lithocholic acid, testosterone, cortisone, and derivatives thereof, That is, cholic acid methyl ester, lithocholic acid methyl ester, hydroxycholic acid, hydroxycholic acid methyl ester, methyl testosterone, 11α-hydroxymethyl testosterone, hydrocortisone, and the like.
[0026]
In the hair composition of the present invention, the size of fine particles or microphase separation state of these decolorizers is preferably 10 nm to 20 μm as an average diameter when the shape is approximated by a sphere.
[0027]
<Non-discoloring dye>
Examples of the “non-discoloring pigment” used in the color-changing hair composition of the present invention include pigments and dyes used in ordinary hair manicure. Specific examples include water-insoluble pigments, oil-soluble dyes, vat dyes, lake dyes and the like. As pigments, inorganic pigments such as carbon black, talc, kaolin, mica, mica titanium, bengara, magnesium silicate, titanium oxide, red 202, red 204, red 205, red 206, red 219, red 228 No., red No. 404, yellow No. 205, yellow No. 401, orange No. 401, blue No. 404, and other organic pigments, and as dyes, red No. 505, red No. 501, red No. 225, yellow No. 404, Yellow 405, yellow 204, orange 403, blue 403, green 202, purple 201, red 226, blue 204, blue 201, various acid dyes raked with aluminum or barium, etc. Is mentioned. Two or more non-discoloring dyes may be used in combination.
[0028]
<Heat discoloration>
The temperature range in which the thermochromic material undergoes thermal discoloration is room temperature, and the process in which the hair composition is manufactured, stored, transported, displayed at the storefront, and stored at the consumer (hereinafter referred to as “preservation environment”). It must be in a higher temperature range than can be exposed to. Specifically, it is preferable that the thermochromic material does not undergo thermal discoloration even when stored for several months at a storage environment temperature of 40 to 50 ° C. On the other hand, the temperature range where the thermochromic material undergoes thermal discoloration does not exceed the thermal decomposition start temperature of the hair, and it is necessary to be a high temperature that does not affect the scalp at the hair growth in a short time. . Specifically, 60 to 100 ° C., particularly 70 to 90 ° C. is preferable.
[0029]
A normal hair dryer can be suitably used as the heating means used to easily and reliably realize the above preferred temperature range for causing thermal discoloration of the hair composition of the present invention. In addition, hair heating means such as an eyeper can be used.
[0030]
The faster the rate at which the hair composition of the present invention causes thermal discoloration, the better. Specifically, when it is heated at 60 to 100 ° C. by a hair dryer, it is preferable that the thermal discoloration is completed within 3 minutes, and more preferably within 1 minute.
[0031]
<Matrix material>
  The composition for hair according to the present invention has a contradictory effect that heat discoloration is completed quickly in a temperature range that does not adversely affect heat on the hair and scalp, while it does not cause heat discoloration in a storage environment of 40 to 50 ° C. In order to satisfy the requirements at the same time, all or part of the thermochromic material is in the form of a granulate dispersed in the matrix materialUsed in. The matrix material is a color former and a developer in the case of “coloring type” and a colorant and a colorant in the case of “decoloring type” until the hair composition is applied to the hair and heated. In addition to having the role of hindering the interaction with the colorant, it has the role of causing thermal discoloration due to the reaction between the two by melting into a fluid state after heating. Such a matrix material in which the thermochromic material is dispersed is prepared by preparing the hair composition of the present invention in the form of, for example, a spray, foam, mist, gel, lotion, tonic, blow agent, cream, post-foaming gel or the like. From the viewpoint of imparting dispersion stability and storage stability during use, the number average particle size is 0.1 to 30 μm, especially 1 to 20 μm, and the volume average particle size is 0.1 to 30 μm, particularly 1 to 3, by kneading, pulverization, and classification. It is preferable to granulate into 20 μm fine particles. The matrix material may be the same as or different from the binder resin for attaching the hair composition to the hair.
[0032]
As the matrix material, an organic polymer compound (polymer matrix material) or a low molecular compound (low molecule matrix material) can be used.
[0033]
As the polymer matrix material, a material that is harmless to the human body and the natural environment and does not contain harmful residual monomers is preferable. Specifically, ketone resin, norbornene resin, polystyrene, poly (α-methylstyrene), polyindene, poly (4-methyl-1-pentene), polyvinylpyridine, polyacetal, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyacetic acid Vinyl, vinyl polypropionate, polyvinyl alcohol, polyethylene, polypropylene, polybutadiene, polymethylpentene, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl benzyl ether, polyvinyl methyl ketone, poly (N-vinyl carbazole), poly (N-vinyl pyrrolidone) ), Polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybenzyl methacrylate, polymethacrylate Hexyl, polymethacrylamide, polyacetaldehyde, polyethylene oxide, polypropylene oxide, polyethylene terephthalate, polybutylene terephthalate, polycarbonates (bisphenols + carbonate), polysulfone, polyethersulfone, polyphenylene sulfide, poly (diethylene glycol bisallyl carbonate) 6-nylon, 6,6-nylon, 12-nylon, 6,12-nylon, polyethylaspartate, ethyl polyglutamate, polylysine, polyproline, poly (γ-benzyl-L-glutamate), methylcellulose, ethylcellulose , Benzylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, acetylcellulose, cellulose triacetate, cellulose tributyrate It includes thermoplastic resins.
[0034]
As the low-molecular matrix material, low-molecular compounds such as low-molecular plasticizers, low-molecular lubricants, and low-molecular waxes can be used. That is, the color former and developer can be dissolved (dissolved and molecularly dispersed) in the color change temperature range of the thermochromic material, and the form as particles can be maintained in the temperature range of 50 ° C. or lower. A low molecular compound that can be used is appropriately selected and used as a low molecular matrix material.
Specifically, urea derivatives and alcohols having a long-chain alkyl group such as 1-docosanol can be preferably used.
[0035]
<Amounts and ratios of matrix materials, thermochromic materials and non-chromic pigments>
The amount of the matrix material used is preferably 0.1 to 1000 parts by weight, more preferably 0.5 to 100 parts by weight, and particularly preferably 1 to 20 parts by weight with respect to 1 part by weight of the color former. The amount of the developer used is sufficient to cause color development due to interaction with the color former, and in the case of the “decoloring type” or “discoloring type”, sufficient interaction with the color developing agent is achieved by the decoloring agent. From the viewpoint of reducing, a ratio of 0.1 to 10 parts by weight, particularly 1 to 2 parts by weight is preferable with respect to 1 part by weight of the color former. The amount of the decolorizer used is 1 to 200 parts by weight with respect to 1 part by weight of the color former from the viewpoint of facilitating the state change from the colored state to the decolored state and sufficient color development of the color former. A ratio of 10 to 100 parts by weight is particularly preferable. In the case of the “color-changing type”, the amount of the non-color-changing dye is preferably 0.1 to 1000 parts by weight, more preferably 0.5 to 100 parts by weight, and particularly preferably 1 to 20 parts by weight with respect to 1 part by weight of the color former.
[0036]
The thermochromic material is preferably contained in the hair composition in an amount of 0.1 to 100% by weight, more preferably 1.5 to 50% by weight, particularly 2 to 2, in terms of the total amount including the color former, the developer and the color erasing agent. It is preferable to contain 20% by weight. The non-discoloring pigment is preferably contained in the hair composition in an amount of 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, and particularly preferably 0.1 to 3% by weight.
[0037]
<Binder resin>
  In the hair composition of the present invention,In order to attach the thermochromic material to the hair surface, a binder resin is used.Contain. The binder resin is not particularly limited as long as it can adhere to hair and form a film, and may be any of an amphoteric polymer, an anionic polymer, a cationic polymer, a nonionic polymer, a natural polymer, and derivatives thereof, and water. A dispersible polyester resin can also be used.
[0038]
Examples of amphoteric polymers include dialkylaminoethyl methacrylate / methacrylic acid alkyl ester copolymer monochloroacetic acid amphoteric products such as Yucaformer AM-75, SM, and 202 (Mitsubishi Chemical); Amphomer 28-4910, LV- Examples thereof include hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers such as 71 (National Starch Co., Ltd.), among which Yucaformer SM and 202 are preferred.
[0039]
Anionic polymers include methyl vinyl ether / maleic anhydride alkyl half ester copolymers such as Gantrez ES-225, ES-425, and SP-215 (ISP); Resin 28-1310 (National Starch) , Vinyl acetate / crotonic acid copolymers such as Ruby Set CA (BASF); vinyl acetate / crotonic acid / vinyl neodecanoate copolymers such as Resin 28-2930 (National Starch); Ruby Set CAP (BASF), etc. Vinyl acetate / crotonic acid / vinyl propionate copolymer; vinyl acetate / maleic acid monobutyl ester / isoboronyl acrylate copolymer such as ADVANTAGE CP (ISP); plus size L53D (color A), L -Methacrylic acid / (meth) acrylic acid alkyl ester copolymers such as -75CB (above, Kyodo Chemical Co., Ltd.) and Diamond Hold (Mitsubishi Chemical Corporation); Ultra Acrylic acid / alkyl acrylate / alkyl acrylamide copolymers such as Hold 8, Ultrahold Strong (above BASF) and Amphomer V-42 (National Starch); Polyvinyl such as Rubiflex VBM35 (BASF) Examples include pyrrolidone / acrylate / (meth) acrylic acid copolymer, and among them, plus size L-75CB is preferable.
[0040]
As the cationic polymer, vinyl imidazolium trichloride / vinyl pyrrolidone copolymers such as Rubycut FC370, FC550, FC905, HM552, MonoCP (above, BASF); Cellcut H-100, L-200 ( (National Starch Co., Ltd.) Hydroxyethyl cellulose / dimethyldiallylammonium chloride such as GAFCAT 734, 755N (ISP), PQ-11 (BASF), etc. Vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer Polyvinylpyrrolidone / alkylaminoacrylate copolymer such as copolymers 845, 937, and 958 (above ISP); polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer such as copolymer VC-713 (ISP) ; Vinylpyrrolidone / methacrylamide propyl such as Guffcut HS-100 (ISP) Trimethylammonium hydride copolymer; alkyl acrylamide / acrylate / alkyl aminoalkyl acrylamide / polyethylene glycol methacrylate copolymer such as water-soluble polymer compound described in JP-A-2-809911, etc., and particularly, Guffcut 755N is preferable. .
[0041]
Nonionic polymers include: Rubiscol K12, 17, 30, 60, 80, 90 (above, BASF), PVP K15, 30, 30, 60, 90 (above, ISP), etc. Pyrrolidone: Lubiscol VA28E, 37E, 55E, 64E, 73E (BASF), PVP / VA E-735, E-635, E-535, E-335, S-630 Polyvinylpyrrolidone / vinyl acetate copolymer such as W-735 (above ISP); Polyvinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer such as Rubiscol VAP343 (BASF); Dowlex (Dow. Chemical Co.) and other vinyl acetate / N-vinyl-5-methyl-2-oxazoline copolymers, etc., among which rubiscol VA55E and PVP / VA E-535 are preferred.
[0042]
Specific examples of natural polymers or derivatives thereof include natural polysaccharides such as guar gum, locust bean gum, gum arabic, pullulan and carrageenan; chitin derivatives such as chitosan salt, carboxymethyl chitin and hydroxypropyl chitosan; carboxymethyl starch, methyl Starch polymer such as hydroxypropyl starch, cationized cellulose such as methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, polymer JR400 (Union Carbide) Cellulose polymer compounds such as cellulose acetate, cellulose powder, sodium alginate, propylene alginate Alginate-based polymer compound such as glycol esters, etc. Among them cationized cellulose, hydroxypropyl chitosan is preferred.
[0043]
Among these binder resins, those having an acidic group or a basic group are preferably those obtained by neutralizing a part or all of them and converting them to a salt from the viewpoint of hair washability. Examples of acidic group salts include alkali metal salts such as sodium and potassium; ammonium salts, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propane Examples include organic base salts such as diol, aminomercaptopropanediol, triisopropanolamine, glycine, histidine, and arginine. Among them, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol Salts are preferred.
In addition, as the salt of the basic group, the inorganic acid salt is preferably a salt of hydrochloric acid, sulfuric acid, phosphoric acid, and the organic acid salt is acetic acid, lactic acid, glycolic acid, dimethylolpropionic acid, tartaric acid, citric acid, Preferred are salts of maleic acid, malic acid, pyrrolidone carboxylic acid and the like.
[0044]
The water-dispersible polyester resin is not particularly limited as long as it is water-insoluble and dispersible in water. For example, a sufficient amount of -SO is sufficient to disperse in water._ThreeExamples thereof include polyesters having an M group (M represents a hydrogen atom or a metal ion). Examples of such polyesters include those obtained by condensing one or more dicarboxylic acid compounds and one or more bifunctional monomers having a sulfonic acid group on the aromatic nucleus in addition to the functional group involved in the polymerization. Those obtained by condensing diethylene glycol, cyclohexanedimethanol, isophthalic acid and sulfoisophthalic acid are preferred. Examples of such commercially available polyesters include Eastman AQ 38S and 55S (Eastman Chemical Products).
[0045]
Of the above binder resins, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymers are most preferably used.
[0046]
The content of the binder resin is preferably 0.05 to 10% by weight, more preferably 0.05 to 5% by weight, still more preferably 0.1 to 3% by weight, and particularly preferably 0.2 to 2% by weight in the hair composition of the present invention. %. The ratio of the fine particles of the matrix material containing all or part of the thermochromic material to the binder resin is preferably 0.2 to 2 binder resin with respect to the fine particles 1 in terms of weight ratio.
[0047]
<Hair composition shape and other ingredients>
In the hair composition of the present invention, in addition to the above-described components, surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants, which are used in ordinary hair cosmetics Agents; higher alcohols; hydrocarbons such as liquid paraffin and petrolatum; lanolin derivatives such as liquid lanolin and lanolin fatty acid; phospholipids such as lecithin; sterols and derivatives thereof such as cholesterol; collagen-degrading peptide derivatives; perfluoropolyether; Fats and oils such as higher alcohol higher fatty acid esters and higher fatty acids; Animal and vegetable oils and fats such as mink oil and olive oil; Medicinal agents such as anti-dandruff agents, fungicides and vitamins; Solvents such as glycerin and ethanol; Parabens and the like Preservatives: UV absorbers, plant extracts, astringents, fragrances, etc., depending on the purpose Yichun can be included in the formulation or particles.
[0048]
The hair composition of the present invention can be produced according to a conventional method, and various dosage forms such as sprays, foams, mists, gels, lotions, tonics, blow agents, creams, post-foaming gels, powders and the like. Can be prepared. Among these, it is desirable to contain a propellant from the viewpoint of operability to form an aerosol dosage form. Propellants include lower saturated hydrocarbons such as propane, isobutane, butane, and mixtures thereof (liquefied petroleum gas; LPG); ethers such as dimethyl ether; compressed gases such as carbon dioxide, nitrogen, air, and nitrous oxide. Can be mentioned. Two or more of these can be used in combination. Among these, LPG, dimethyl ether or a mixture thereof is preferable.
[0049]
The content of the propellant in the hair composition can be appropriately determined according to the purpose of use, etc., but in the case of an aerosol-type foam using LPG, dimethyl ether or a mixture thereof as a propellant, 1 to 30% by weight, particularly 1 to 20% by weight is preferred. The gas pressure of the propellant in the hair composition is preferably 0.14 to 0.69 MPa at 20 ° C.
[0050]
<Method for producing hair composition>
In producing a “color-forming” hair composition, it is necessary to set the conditions of the various steps so that the color former maintains a non-colored state. For example, a kneaded product in which a color former is dissolved or finely dispersed in a matrix material in a molten state is cooled, pulverized and classified, for example, an average particle diameter of 10 μm, while a developer solution dissolved in ethanol is mixed with water. Then, a method of obtaining a water-ethanol suspension of the developer that has been re-precipitated and microcrystallized, and mixing them is mentioned.
[0051]
When producing a “decolorizable” hair composition, the conditions of the various processes are set so that the color former acts as a color developer by the color developer and exists together with the fine color or microphase-separated color eraser. Must be set. For example, fine particles or microphase-separated decolorizers previously pulverized or refined to a predetermined size are dispersed in a kneaded mixture of a dye and a matrix material produced by the reaction of a developer and a color former. Thereafter, pulverization and classification are performed, for example, an average particle diameter of 10 μm, and this is dispersed in a water-ethanol solution of a binder resin.
[0052]
Further, a “color-changing” hair composition can be produced by mixing a “color-developing” or “decoloring-type” hair composition with a non-discoloring pigment. As a method of mixing the non-discoloring dye, a method of dissolving or dispersing in the matrix material or a method of dissolving or dispersing in the suspension can be used.
[0053]
【Example】
  In the following examples, the particle size is determined by measuring a sample dispersed ultrasonically in water containing electrolyte using sodium dodecylbenzenesulfonate as a dispersant, using Coulter Counter TA-II (Coulter). It was.
Examples 5 and 6 are reference examples and are not included in the scope of the claims.
[0054]
Example 1 Colorable hair composition (colorless to black)
6 parts by weight of uncolored leuco dye S-205 (Yamada Chemical Co., Ltd.) as a color former and 94 parts by weight of polystyrene as a matrix material are premixed and sufficiently kneaded at a temperature not exceeding 75 ° C. using a kneader. And then cooled. This kneaded product is coarsely pulverized to a particle outer diameter of 1 mm with a cutter blade rotary pulverizer, then pulverized to a maximum particle size of 20 μm or less with a circulating air jet pulverizer equipped with a cyclone classifier, and then another cyclone. Classification was carried out using a formula classifier to obtain colorless fine particles having a number average particle diameter of 8 μm and a volume average particle diameter of 10 μm.
On the other hand, a solution in which 4 parts by weight of stearyl gallate as a developer is dispersed and dissolved in 20 parts by weight of ethanol, and 2 parts by weight of Yuka Former SM (Mitsubishi Chemical) as a binder resin are dissolved in 72 parts by weight of water. Poured while stirring well to obtain a microcrystalline suspension of stearyl gallate. In this suspension, 2 parts by weight of the above fine particles were mixed and dispersed to obtain a hair composition.
When 5 g of this hair composition is applied to 5 g of white hair using a comb and heated so that the temperature of the hair becomes 80 ° C. or higher with a hair dryer having a heater capacity of 1 kW, heat treatment for about 30 seconds or more is performed. The hair was colored black.
[0055]
Example 2 Colorable hair composition (colorless to black)
Using 6 parts by weight of uncolored leuco dye S-205 (Yamada Chemical Co., Ltd.) as the color former and 94 parts by weight of polystyrene as the matrix material, a colorless colorant containing the same size color former as in Example 1 was used. Fine particles were obtained.
Further, 30 parts by weight of stearyl gallate as a developer and 70 parts by weight of polystyrene as a matrix material were mixed in advance and sufficiently kneaded at a temperature not exceeding 75 ° C. using a kneader, and then cooled. This kneaded product is coarsely pulverized to a particle outer diameter of 1 mm with a cutter blade rotary pulverizer, then pulverized to a maximum particle size of 20 μm or less with a circulating air jet pulverizer equipped with a cyclone classifier, and then another cyclone. Classification was carried out using a formula classifier to obtain colorless fine particles containing a developer having a number average particle diameter of 8 μm and a volume average particle diameter of 10 μm.
On the other hand, 2 parts by weight of Yuka Former SM (Mitsubishi Chemical Corporation) as a binder resin was dissolved in 20 parts by weight of ethanol and 78 parts by weight of water. In this solution, 1 part by weight of the fine particles containing the color former and 1 part by weight of the fine particles containing the developer were mixed and dispersed to obtain a hair composition.
When 5 g of this hair composition is applied to 5 g of white hair using a comb and heated so that the temperature of the hair becomes 80 ° C. or higher with a hair dryer having a heater capacity of 1 kW, heat treatment for about 30 seconds or more is performed. The hair was colored black.
[0056]
Example 3 Colorable hair composition (colorless to black)
In the production of the microparticles containing the developer of Example 2, 20 parts by weight of L (+)-ascorbic acid (vitamin C) is used as the developer instead of stearyl gallate, and 80 parts by weight of polystyrene is used. Except for this, a hair composition was obtained in the same manner as in Example 2.
When this hair composition was used to treat white hair in the same manner as in Example 2, the hair was colored black by a heat treatment of about 30 seconds or more.
[0057]
Example 4 Color-changing hair composition (gold → black)
6 parts by weight of uncolored leuco dye S-205 (Yamada Chemical Co., Ltd.) as a color former, 6 parts by weight of Bengala-coated mica titanium (gold color; Imperial Gold 222X, Engelhard) as a non-discoloring dye, and 86 weights as a matrix material A portion of polystyrene was premixed and sufficiently kneaded at a temperature not exceeding 75 ° C. using a kneader, and then cooled.
This kneaded product is coarsely pulverized to a particle outer diameter of 1 mm with a cutter blade rotary pulverizer, then pulverized to a maximum particle size of 20 μm or less with a circulating air jet pulverizer equipped with a cyclone classifier, and then another cyclone. Classification was carried out using a formula classifier to obtain gold fine particles having a number average particle diameter of 8 μm and a volume average particle diameter of 10 μm.
On the other hand, a solution in which 10 parts by weight of stearyl gallate as a developer is dispersed and dissolved in 20 parts by weight of ethanol, and 2 parts by weight of Guffcut 755N (ISP) as a binder resin are dissolved in 68 parts by weight of water. The mixture was poured while stirring to obtain a microcrystalline suspension of stearyl gallate. In this suspension, 2 parts by weight of the above fine particles were mixed and dispersed to obtain a hair composition.
When this hair composition was applied to white hair using a comb and dried with warm air of 60 ° C. or lower, the hair was colored in gold. When this hair was further heated with a hair dryer having a heater capacity of 1 kW so that the temperature of the hair became 80 ° C. or higher, the hair was colored black by a heat treatment of about 30 seconds or more.
[0058]
Example 5 Decolorizable hair composition (black → colorless)
As the decoloring agent, a commercially available corn starch (particle outer diameter of about 10 to 20 μm) was pulverized and classified with a circulating air jet pulverizer equipped with a cyclone classifier.
6 parts by weight of uncolored leuco dye S-205 (Yamada Chemical Co., Ltd.) as a color former and 2 parts by weight of propyl gallate as a developer were mixed and heated to 100 ° C. to develop a black color. . To this, 17 parts by weight of the above-mentioned corn starch fine particles and 75 parts by weight of polystyrene as a matrix material were mixed, kneaded sufficiently at a temperature not exceeding 75 ° C. using a kneader, cooled, and a black kneaded product was obtained. Obtained. This kneaded product was coarsely pulverized, pulverized and classified in the same manner as in Example 1 to obtain black fine particles of the same size.
2 parts by weight of the above fine particles were mixed and dispersed in a solution obtained by dissolving 2 parts by weight of polymer JR400 (Union Carbide) in 98 parts by weight of water as a binder resin to obtain a black hair composition.
When this hair composition was applied to white hair using a comb and dried with warm air of 60 ° C. or lower, the hair was colored black. When this hair was further heated with a hair dryer having a heater capacity of 1 kW so that the temperature of the hair became 80 ° C. or higher, the hair returned to white by a heat treatment of about 30 seconds or more.
[0059]
Example 6 Color-changing hair composition (black → copper)
In the manufacture of the fine particles of Example 5, Bengala-coated mica titanium (copper color; Copper 340X, Engelhard) 8 wt% was further added as a non-discoloring pigment, and the polystyrene was changed to 67 parts by weight of polystyrene. Black fine particles of the same size were obtained. 3 parts by weight of the above fine particles were mixed and dispersed in a solution obtained by dissolving 3 parts by weight of Yuka Former 202 (Mitsubishi Chemical Corporation) in 97 parts by weight of water as a binder resin to obtain a black hair composition.
When this hair composition was applied to white hair using a comb and dried with warm air of 60 ° C. or lower, the hair was colored black. When this hair was further heated with a hair dryer having a heater capacity of 1 kW so that the temperature of the hair became 80 ° C. or higher, the hair turned copper color by heat treatment for about 30 seconds or more.
[0060]
Example 7 Colorable hair composition (white → black; aerosol)
6 parts by weight of leuco dye S-205 (white; Yamada Chemical Co., Ltd.) in a non-coloring state as a color former and 94 parts by weight of polystyrene as a matrix material are mixed in advance, and a temperature not exceeding 75 ° C. is sufficient using a kneader. And then cooled. This kneaded product is coarsely pulverized to a particle outer diameter of 1 mm with a cutter blade rotary pulverizer, then pulverized to a maximum particle size of 20 μm or less with a circulating air jet pulverizer equipped with a cyclone classifier, and then another cyclone. Classification was carried out using a formula classifier to obtain fine particles having a number average particle diameter of 8 μm and a volume average particle diameter of 10 μm.
On the other hand, a solution obtained by dispersing and dissolving 4 parts by weight of stearyl gallate as a developer in 20 parts by weight of ethanol, 2 parts by weight of Yucaformer SM (Mitsubishi Chemical) as a binder resin, and 0.025 parts by weight of cetyltrimethylammonium chloride as a foaming agent Was poured into a solution in which 72 parts by weight of water had been dissolved while stirring well to obtain a microcrystalline suspension of stearyl gallate. In this suspension, 2 parts by weight of the above fine particles were mixed and dispersed to obtain a hair composition.
An aerosol container was obtained by filling the aerosol container with 90% by weight of the hair composition as a stock solution and 10% by weight of LPG (0.44Mpa) as a propellant.
When 5 g of this aerosol-type hair composition is applied to 5 g of white hair using a comb and heated with a hair dryer with a heater capacity of 1 kW so that the hair temperature is 80 ° C. or higher, it takes about 30 seconds or longer. The hair was colored black by the heat treatment.
[0061]
【The invention's effect】
As described in detail above, when the hair composition of the present invention is used, only the hair portion to which the hair composition is applied can be colored. In addition, the hair colored with the hair composition of the present invention can be easily and quickly decolored without washing the hair, and returned to the original hair color. Furthermore, the color of the hair colored with the hair composition of the present invention can be changed easily and quickly without washing and recoloring.

Claims (2)

Thermochromic material consisting of color developer which develops color by contacting with the color former, and the coloring agent, and a hair compositions containing a binder resin, all color former is dispersed in a matrix material The developer is contained in the form of a granulated product, and all of the developer is contained in the hair composition in a form that is not contained in the granulated product. A composition for hair which prevents interaction with a colorant and causes thermal discoloration due to a reaction between the color former and the developer by melting and becoming fluid after heating .   Furthermore, the composition for hair of Claim 1 containing a non-color-change pigment | dye.