201249466 六、發明說明： 【發明所屬之技術領域】 本發明係關於染髮劑、其使用方法以及染髮劑用品。 更具體而言’本發明涉及染髮劑、將該染髮劑應用於頭髮 的使用方法、以及含有該染髮劑及非氣溶膠發泡器容器而 構成的染髮劑用品，所述染髮劑係包含含有鹼劑的第1劑 及含有氧化劑的第2劑而構成的，將第1劑與第2劑的混 合液從非氣溶膠發泡器容器以泡沫狀排出而使用的染髮劑 ’其中前述混合液排出時的泡沫形成，排出後的泡沫於頭 髮上的泡沫持久性沒有問題，且實現了作爲泡沫狀劑型的 適宜的表面張力。 【先前技術】 傳統上已知以包含含有鹼劑的第1劑及含有氧化劑的 第2劑的雙劑式或三劑式等多劑式構成之製爲膏狀、凝膠 狀等劑型之氧化染髮劑、毛髮脫色劑、毛髮脫染劑等染髮 劑。前述染髮劑係使用梳子或刷子等將其各劑的混合物應 用於頭髮以進行染髮處理。但是，由於前述染髮劑爲高黏 度，故雖可在染髮處理時間中有效地防止液體的懸滴，但 卻難以均勻地應用於頭髮整體。特別是對於使用者自身的 後頭部等，即使利用鏡子也難以進行染髮劑的均勻塗抹操 作。另外，還需要花功夫進行所謂的毛髮分區等。 與此相對，提出了使多劑式染髮劑的各劑混合物成爲 泡沫狀而使用的染髮劑。這些染髮劑可以用手揉搓排出的 -5- 201249466 泡沫而均勻地應用於頭髮整體。例如下述專利文獻1、2 Φ揭示使用氣溶膠式的發泡器容器以泡沫狀排出而應用於 毛髮的染髮劑’後述專利文獻3〜5中揭示使用泵發泡器 或擠ϋ發泡器等非氣溶膠式的發泡器容器以泡沫狀排出而 應用於毛髮的染髮劑。 〔先前技術文獻〕 專利文獻 專利文獻1 :日本特開平9 - 1 3 6 8 1 8號公報 專利文獻2:日本特開平10-287534號公報 專利文獻3:日本特開2007-291015號公報 專利文獻4:日本特開2008-291020號公報 專利文獻5:日本特開2006-124279號公報 【發明內容】 發明所欲解決之課題 然而，以泡沫狀劑型使用的染髮劑雖然已知可以如前 述均勻地應用於頭髮整體，但就確保前述優點的觀點上， 爲了使從發泡器容器排出時的泡沫的形成良好、或將排出 的泡沫於頭髮上用手揉搓起泡時之起泡性良好，通常摻混 有界面活性劑。 但是，對於這類染髮劑，由於染髮劑在頭皮上的擴散 ，從而引起大範圍內發生皮膚污染的問題。該問題在例如 氧化染髮劑中表現爲皮膚的染色，在例如毛髮脫色劑或毛 -6- 201249466 髮脫染劑中則表現爲皮膚的損傷。 因此本發明欲解決之課題係提供染髮劑，其從非氣溶 膠發泡器容器排出時的泡沫形成、或排出後的泡沫於頭髮 上的起泡沒有問題，同時不會發生皮膚污染。 作爲前述課題的解決方法，本專利申請人著眼於調整 染髮劑中的表面張力。其原因是認爲前述不良情況與後述 事實有關：染髮劑的表面張力因摻混界面活性劑等而降低 ，一方面雖然可獲得如前述之泡沬形成或者起泡的改良效 果，但另一方面染髮劑於頭皮上會變得容易擴散。 並且，本專利申請者對各式各樣的染髮劑的試製例， 反複進行試驗性硏究，結果發現非氣溶膠發泡器容器用染 髮劑中，滿足“排出前的第1劑與第2劑的混合液的表面 張力於特定的測定條件下爲30〜50mN/m的範圍內”的條 件係解決上述課題的方法，從而完成了本申請發明。 課題之解決手段 (第1發明的構成） 用於解決前述課題的本申請書第1發明的構成是染髮 劑’其係包含含有鹼劑的第1劑及含有氧化劑的第2劑而 構成的以水爲介質的染髮劑，將其各劑的混合液從非氣溶 膠發泡器容器以泡沬狀排出而使用的染髮劑，其中，排出 前各劑的混合液的表面張力於特定的測定條件下爲3 0〜5 0 mN/m的範圍內。 該第1發明中，測定排出前各劑的混合液的表面張力 201249466 的“特定的測定條件下”係指如下內容。 亦即’該表面張力的測定是使用泡壓法（Bubble Pressure Method)而由楊-拉普拉斯公式（Y〇ung_Laplace equation)算出表面張力。前述測定方法及計算公式係公 知的。具體地1將排出前的各劑的混合液利用例如SIT A 社制的SITA pro line tl5之類的利用泡壓法算出表面張力 的裝置以求出氣泡的內部與外部的壓力之差Δρ (單位： mN/m2 )。接著，基於下述式（1)所示的楊-拉普拉斯公 式求出泡沫的表面張力σ (單位：mN/m)。 σ = ( Δρ · r ) /2.....式（1) 前述式（η中，“ r (單位：n〇 ”係產生氣泡的毛 細管的半徑，是恒定的，因此通過求出Δρ來求出σ。該 測定時，雖然直接求出動態表面張力，但實際上由於是採 用該張力彙聚而達到平衡時的値，因而大致作爲靜態表面 張力的値算出，與利用作爲靜態表面張力測定法的代表性 的環法或吊片法的測定値大致相同。 (第2發明的構成） 用於解決前述課題的本申請書第2發明的構成是將第 1發明所述的染髮劑從非氣溶膠發泡器容器以泡沬狀排出 而應用於頭髮的染髮劑的使用方法。 該第2發明中，將以泡沬狀排出的染髮劑“應用於頭 髮”的方法通常是“用手揉搓來應用”的情形，但並不限 定於這樣的應用方法。 -8 - 201249466 (第3發明的構成） 用於解決前述課題的本申請書第3發明的構成係包含 第1發明所述的染髮劑、以及用於將該染髮劑以泡沫狀排 出的非氣溶膠發泡器容器而構成的染髮劑用品。 發明之功效 根據第1發明，基於“排出前各劑的混合液的表面張 力於特定的測定條件下爲30〜50mN/m的範圍內”這一客 觀指標，提供可以解決“從非氣溶膠發泡器容器排出時的 泡沫形成、或排出後的泡沫於頭髮上的起泡沒有問題，同 時不會引起皮膚污染”此一課題的染髮劑。 亦即，爲包含含有鹼劑的第1劑及含有氧化劑的第2 劑而構成的以水爲介質的染髮劑，爲將其各劑的混合液從 非氣溶膠發泡器容器以泡沫狀排出而使用的染髮劑，只要 排出前各劑的混合液的表面張力於特定的測定條件下爲30 〜5 0mN/m的範圍內，則從非氣溶膠發泡器容器排出時的 泡沫形成、或排出後的泡沫於頭髮上的起泡沒有問題，同 時不會引起皮膚污染。 前述表面張力小於30mN/m時，則該染髮劑以泡沫狀 排出並應用於頭髮上後，會在頭皮上擴散而在大範圍內引 起皮膚污染。相反，表面張力超過50mN/m時，則從非氣 溶膠發泡器容器排出時的泡沬形成、或排出後的泡沫於頭 髮上的起泡會變得不充分。 -9 - 201249466 第1發明從不同見解出發也可以理解後述發明。亦即 ，爲包含含有鹼劑的第1劑及含有氧化劑的第2劑而構成 的以水爲介質的染髮劑，爲將其各劑的混合液從非氣溶膠 發泡器容器以泡沫狀排出而使用的染髮劑，對於符合“排 出前各劑的混合液的表面張力於特定的測定條件下爲30〜 50mN/m的範圍內”此一·指標，即使不對其各種摻混成分 進行具體硏究，也可以判斷爲可解決“從非氣溶膠發泡器 容器排出時的泡沫形成、或排出後的泡沫於頭髮上的起泡 沒有問題，同時不會引起皮膚污染”此一新課題的染髮劑 。此點係藉由後述多個责施例得到確認》 因此，提供基於新的、客觀的且簡易的指標所選擇之 可以解決前述課題的有用的染髮劑。或者，提供用於提供 可以有效地解決前述課題之染髮劑之穎新的、客觀的且簡 易的指標。 根據第2發明，以提供第I發明所述的染髮劑的使用 方法爲宜。 根據第3發明，以提供包含第1發明所述的染髮劑、 以及用於將該染髮劑以泡沫狀排出的非氣溶膠發泡器容器 而構成的染髮劑用品爲且。 用以實施發明之最佳型態 接著，對包含其最佳方式的用於實施本發明的方式進 行說明。 201249466 〔染髮劑〕 本發明所述的染髮劑係包含含有鹼劑的第1劑及含有 氧化劑的第2劑而構成的以水爲介質的染髮劑’將各劑的 混合液從非氣溶膠發泡器容器以泡沫狀排出而使用的染髮 劑。非氣溶膠發泡器容器可以使用任意氣液混合比的非氣 溶膠發泡器容器，但以使氣液混合比於氣體：液體=7: 1 〜20: 1的範圍內爲宜，以使氣液混合比於氣體：液體=9 :1〜16: 1的範圍內尤佳。 染髮劑的各劑於發泡前的劑型並無特別的限定，可以 任意選擇例如以水爲介質的凝膠狀、膏狀或乳化物狀劑型 、水溶液狀劑型、固體狀劑型、其他劑型。作爲固體狀的 劑型，列舉以分散性優異的粉末狀爲宜。例如使第1劑爲 固體狀的劑型時，使第2劑爲含有水的劑型。總之，只要 各劑在混合時成爲以水爲介質的流動性的混合液，則對各 劑的劑型沒有特別限定。 以下陳述的染髮劑的各種成分，除了第1劑中所含有 的鹼劑及第2劑中所含有的氧化劑之外，若無特別記載， 則可以僅摻混於第1劑、第2劑等中的任意一劑中，也可 以分散摻混於不同的2種以上的劑中。 染髮劑的種類只要是包含含有鹼劑的第1劑及含有氧 化劑的第2劑而構成，則沒有限定，例如包含氧化染髮劑 、毛髮脫色劑、毛髮脫染劑等。另外，染髮劑中，除了由 前述第1劑及第2劑構成的雙劑式染髮劑之外，也包含除 前述各劑外’還添加了例如含有氧化助劑等之第3劑的三 201249466 劑式染髮劑等之多劑式染髮劑。 另外，本發明的染髮劑的必要條件係排出前各劑 合液的表面張力於特定的測定條件下爲30〜5 0mN/m 圍內。該表面張力特別於30〜35mN/m的範圍內爲宜 〔染髮劑中之已知必要成分〕 本發明的染髮劑爲例如氧化染髮劑、毛髮脫色劑 髮脫染劑等，均包含含有鹼劑的第1劑及含有氧化劑 2劑而構成。 氧化染髮劑藉由第1劑中的鹼劑使毛髮膨潤，而 化染料中間體及第2劑中的氧化劑滲透至毛髮內部， 藉由基於鹼劑的pH變化來促進氧化劑的作用，利用 劑使毛髮中所含的黑色素分解•脫色，同時使摻混於 劑中的氧化染料中間體進行氧化聚合而發色》毛髮脫 係於前述氧化染髮劑中的第1劑中不含氧化染料中間 僅進行黑色素的分解•脫色。毛髮脫染劑於毛髮脫色 組成中再摻混作爲氧化助劑的各種過硫酸鹽，亦進行 於毛髮中的氧化染料中間體的聚合物的分解·脫色。 染料中間體包含主要中間體、或包含主要中間體及偶 。氧化染髮劑中’爲了調整染髮色調，有時再摻混直 料。 作爲鹼劑’可例示氨、烷醇胺（單乙醇胺、二乙 、三乙醇胺、單異丙醇胺、二異丙醇胺、三異丙醇胺 、銨鹽、有機胺類（2-胺基-2-甲基-1-丙醇、2-胺基· 的混 的範 、毛 的第 使氧 同時 氧化 第1 色劑 體， 劑的 存在 氧化 合劑 接染 醇胺 等） 2-甲 -12- 201249466 基-1，3·丙二醇、胍等）、無機鹼（氫氧化鈉、氫氧化鉀、 碳酸鈉、碳酸鉀、碳酸銨、碳酸氫銨、碳酸氫鈉等）、鹼 性胺基酸（精胺酸、賴胺酸等）以及此等之鹽等。鹼劑的 含量係可以因應需要而適當設定。 氧化劑爲溴酸鉀、溴酸鈉、過硼酸鈉、過氧化氫、過 氧化物等。作爲過氧化物，可列舉過氧化脲、過氧化三聚 氰胺、過碳酸鈉、過碳酸鉀、過硼酸鈉、過硼酸鉀、過硫 酸鉸、過氧化鈉、過氧化鉀、過氧化鎂、過氧化鋇、過氧 化鈣、過氧化緦、硫酸鹽的過氧化氫加成物、磷酸鹽的過 氧化氣加成物、焦磷酸鹽的過氧化氫加成物等。氧化劑的 含量係可以因應需要而適當設定。 氧化染料中間體之中，作爲主要中間體，主要可舉出 鄰或對苯二胺類或者胺基苯酚類，具體可例示對苯二胺、 甲苯-2,5-二胺（對甲苯二胺）、N-苯基-對苯二胺、4，4，-二胺基二苯基胺、對胺基苯酚、鄰氨胺苯酚、對甲胺基苯 酚、N，N-雙（2-羥基乙基）-對苯二胺、2·羥基乙基-對苯 二胺、鄰氯對苯二胺、4·胺基-間甲酚、2-胺基-4_經基乙 基胺基苯甲醚、2,4-二胺基苯酚和它們的鹽類等。作爲鹽 類，可例示鹽酸鹽、硫酸鹽、乙酸鹽等。主要中間體的含 量可以根據需要適宜設定。 作爲偶合劑，主要可舉出間二胺類、胺基苯酣類或二 苯酚類，具體可列舉間苯二酚、兒茶酚、焦酚 '間苯三酣 、沒食子酸、氫醌、5-胺基鄰甲酚、間胺基苯酌、5_ ( 2-羥基乙基胺基）-2-甲基苯酚、間苯二胺、2,4-二胺基苯氧 -13- 201249466 基乙醇、甲苯-3,4-二胺、α -萘酚、2，6-二胺基吡啶、二苯 基胺、3,3’-亞胺基聯苯、ι,5-二羥基萘及鞣酸以及它們的 鹽等。偶合劑的含量係可以因應需要而適當設定。 作爲直接染料，可列舉各種酸性染料、鹼性染料、硝 基染料、分散染料等。此等中，作爲酸性染料，可舉出藍 色1號、紫色401號、黑色401號、橙色205號、紅色 227號、紅色106號、黃色203號、酸性橙3等，作爲鹼 性染料’可舉出鹼性藍9 9、鹼性棕1 6、鹼性棕1 7、鹼性 紅7 6、鹼性紅5 1、鹼性黃5 7、鹼性黃8 7、鹼性橙3 1等 ，作爲硝基染料，2-硝基對苯二胺、2-胺基-6-氯-4-硝基 苯酚、3-硝基對羥基乙蕋胺基苯酚、4-硝基鄰苯二胺、4-胺基-3-硝基苯酚、4 -羥基丙基胺基-3-硝基苯酚、HC藍 No.2、HC 橙 No.l、HC 紅 No.l、HC 黃 No.2、HC 黃 No.4 、HC 黃 Νο·5、HC 紅 Νο·3、N，N-雙（2-羥乙基）-2-硝基 對苯二胺等，作爲分散染料，可舉出分散紫1、分散藍1 、分散黑9等。直接染料的含量係可以因應需要而適當設 定。 〔染髮劑的主要成分〕 (界面活性劑） 本發明的染髮劑中，在使前述排出前各劑的混合液的 表面張力爲30〜50mN/m的範圍內的方面，含有的界面活 性劑的總量以1 〇質量％以上爲宜，以總計在1 5質量％以 上尤佳。 -14- 201249466 應予說明，本發明中，將成分的含量表示爲“質量％ ，’時，只要沒有特別說明，則指雙劑式或三劑式以上的染 髮劑中各劑於混合液中的含量。 作爲前述各種界面活性劑，在使前述表面張力爲3 0〜 5 0mN/m的範圍內的方面，以常溫下爲固體的界面活性劑 尤佳。 (陽離子性界面活性劑） 本發明的染髮劑在使前述表面張力爲30〜50mN/m的 範圍內的方面，以含有陽離子性界面活性劑作爲（A )成 分爲宜。 作爲（A )成分的陽離子性界面活性劑的含量係以於 0.05〜10質量％的範圍內爲宜，於0.1〜5質量％的範圍內 尤佳。 作爲陽離子性界面活性劑，可舉例如氯化十二烷基三 甲基銨、氯化十六烷基三甲基銨（Cetrimonium Chloride )、氯化硬脂基三甲基錢（Steartrimonium Chloride)、 氯化烷基三甲基銨、氯化二十二烷基三甲基銨（ B ehentr imonium Chloride)、氯化二硬脂基二甲基銨（ Distearyldimonium Chloride)、氯化二椰油醯基二甲基銨 、溴化十六烷基三甲基銨、溴化硬脂基三甲基銨、乙基硫 酸羊毛脂脂肪酸胺基丙基乙基二甲基銨 '硬脂基三甲基銨 糖精、十六烷基三甲基銨糖精、甲基硫酸二十二烷基三甲 基銨、和四級銨鹽-91 ( QUATERNIUM-91 )等，但並不限 -15- 201249466 定於此。陽離子性界面活性劑可以單獨使用1種、或並用 2種以上。 (陰離子性界面活性劑） 另外，本發明的染髮劑在使前述表面張力爲30〜 5 OmN/m的範圍內的方面，以含有陰離子性界面活性劑作 爲（B)成分爲宜》 作爲（B )成分的陰離子性界面活性劑的含量係以於 〇.〇5〜10質量％的範圍內爲宜，以於0.1〜5質量％的範圍 內尤佳。 作爲陰離子性界面活性劑，可舉例如聚氧乙烯（以下 ，稱爲POE)十二烷基醚硫酸鈉等烷基醚硫酸鹽、十二烷 基硫酸鈉、鯨脂基硫酸鈉、十六烷基硫酸鈉等烷基硫酸鹽 、烯基醚硫酸鹽、烯基硫酸鹽、烯烴磺酸鹽、烷磺酸鹽、 飽和或不飽和脂肪酸鹽、烷基或烯基醚羧酸酸鹽、α-磺 基脂肪酸鹽、椰油醯麩胺酸三乙醇胺（椰油醯麩胺酸TEA )等N-醯蕋胺基酸型界面活性劑、磷酸單或二酯型界面 活性劑、以及磺基琥珀酸酯等。作爲前述界面活性劑的陰 離子基團的平衡離子，可舉例如鈉離子、鉀離子、以及三 乙醇胺。陰離子性界面活性劑可以單獨使用1種、或併用 2種以上。 ((A)成分及（B)成分的關係） 對於（A)成分與（B)成分的關係，兩者含量的質量 -16- 201249466 比A/B爲0.2以上，特別爲1以上且100以下，在使 表面張力爲30〜50mN/m的範圍內的方面爲宜。另外 染髮劑中所含的界面活性劑的總配合量設爲1 00質量 ，以（A)成分及（B)成分占其中的5〜50質量份左 宜。 (其他界面活性劑） 作爲（A)成分及（B)成分以外的界面活性劑， 有非離子性界面活性劑爲宜。非離子性界面活性劑的 係以1 1〜4 0質量％爲宜，以1 1〜2 0質量％的範圍內 作爲非離子性界面活性劑，可列舉下述（1 )〜 )之非離子性界面活性劑，可以單獨使用其1種，也 倂用2種以上。 (1 ) POE十六烷基醚、POE硬脂基醚、POE二 烷基醚、POE油烯基醚、POE十二烷基醚' POE十三 醚、POE辛基十二烷基醚、POE己基癸基醚、POE異 基醚、POE癸基十五烷基醚、POE癸基十四烷基醚、 烷基（C12〜14)醚等之POE烷基醚。（2) POE壬 基醚、POE辛基苯基醚等之POE烷基苯基醚。（3) 酸POE山梨糖醇酐酯、單硬脂酸POE山梨糖醇酐酯 棕櫚酸POE山梨糖醇酐酯、單月桂酸POE山梨糖醇 、三油酸POE山梨糖醇酐酯等之POE山梨糖醇酐脂 酯。（4 )單硬脂酸POE甘油酯、單肉豆蔻酸POE甘 前述 ，將 份時 右爲 以含 含量 尤佳 (17 可以 十二 院基 硬脂 POE 基苯 單油 、單 酐酯 肪酸 油酯 -17- 201249466 等之POE甘油基單脂肪酸酯。（5)四油酸P0E山 酯、六硬脂酸POE山梨糖醇酯、單月桂酸POE山 酯、POE山梨糖醇酯蜂躐等之POE山梨糖醇脂肪酸 6 ) POE氫化蓖麻油、POE蓖麻油。（7 )單油酸聚 酯、單硬脂酸聚乙二醇酯、單月桂酸聚乙二醇酯。 親油型單油酸甘油酯、親油型單硬脂酸甘油酯、自 單硬脂酸甘油酯等之高級脂肪酸甘油酯。（9)單 梨糖醇酐酯、倍半油酸山梨糖醇酐酯、三油酸山梨 酯、單硬脂酸山梨糖醇酐酯、單棕櫚酸山梨糖醇酐 月桂酸山梨糖醇酐酯等山梨糖醇酐脂肪酸酯。（1C 羊毛脂、POE羊毛脂醇、POE山梨糖醇羊毛脂等之 衍生物。（11)月桂酸二乙醇醯胺、椰油脂肪酸二 胺等之烷醇醯胺。（1 2 ) POE硬脂醯胺等P0E脂肪 (13)蔗糖脂肪酸酯》(14)二甲基十二烷基胺氧 月桂胺氧化物、椰油烷基二甲基胺氧化物等之烷基 物》(15)十二烷基葡糖苷、烷基（8〜16)葡糖 基葡糖苷。（1 6 )卵磷脂衍生物氫化大豆卵磷脂、 黃卵磷脂等。（17 ) P0E .聚氧丙烯（以下簡稱爲 十六烷基醚等之POE · POP烷基醚。 各種界面活性劑中，可在不妨礙本發明效果的 摻混兩性界面活性劑。 作爲兩性界面活性劑，可列舉下述之（1 )〜（ 兩性界面活性劑，可以單獨使用其1種，也可以併 以上。 梨糖醇 梨糖醇 酯。（ 乙二醇 (8 ) 乳化型 油酸山 糖醇酐 酯、單 I ) POE 羊毛脂 乙醇醯 醯胺。 化物、 胺氧化 苷等烷 氫化蛋 POP ) 範圍內 5 )之 电2種 -18- 201249466 (i)椰油脂肪醯胺丙基二甲基胺基乙酸甜菜鹼、棕 櫚油脂肪醯胺丙基二甲基胺基乙酸甜菜鹼、月桂醯胺丙基 二甲基胺基乙酸甜菜鹼（月桂醯胺丙基甜菜鹼）、蓖麻油 醯胺丙基二甲基胺基乙酸甜菜鹼等之脂肪醯胺丙基二甲基 胺基乙酸甜菜鹼、以及此等之鈉鹽、鉀鹽或三乙醇胺鹽。 (2)癸基二甲基胺基乙酸甜菜鹼、十二烷基二甲基胺基 乙酸甜菜鹼、肉豆蔻基二甲基胺基乙酸甜菜鹼、十六烷基 二甲基胺基乙酸甜菜鹼、硬脂基二甲基胺基乙酸甜菜鹼、 油烯基二甲基胺基乙酸甜菜鹼、二十二烷基二甲基胺基乙 酸甜菜鹼、椰油烷基二甲基胺基乙酸甜菜鹼等烷基二甲基 胺基乙酸甜菜鹼、以及此等之鈉鹽、鉀鹽或三乙醇胺鹽。 (3 )椰油醯兩性基乙酸Na ( N-椰油脂肪醯基-N，-羧甲基-Ν’_羥乙基伸乙基二胺）、椰油兩性基丙酸Na(N -椰油脂 肪醯基-Ν’_羧乙基-Ν’-羥乙基亞乙基二胺）、月桂醯兩性 基乙酸Na(N-月桂醯-Ν’-羧甲基-Ν’-羥乙基伸乙基二胺） 、橄攬油醯兩性基乙酸Na、可可脂醯兩性基乙酸Na、芝 麻油醯兩性基乙酸Na、甜扁桃油醯兩性基乙酸Na、硬脂 醯兩性基乙酸鹽、棕櫚醯兩性基乙酸Na、花生油醯兩性 基乙酸Na、葵花籽油醯兩性基乙酸Na、棉子油醯兩性基 乙酸Na等N-醯基胺基乙基-N-2-羥乙基胺基羧酸鹽。（4 )椰油兩性基二乙酸Na、椰油兩性基二丙酸Na、以及月 桂醯兩性基二乙酸Na等N-醯基胺基乙基-N-羧基甲氧基 乙基胺基羧酸鹽。（5)羥基烷基（C12-14)羥乙基肌胺 酸。 -19- 201249466 (溶劑） 本發明的染髮劑係含有揮發性溶劑作爲溶劑，對使前 述表面張力爲30〜50mN/m的範圍內的方面是適合的。揮 發性溶劑的含量沒有限定，於0.1〜2 0質量％的範圍內爲 宜’以0.5〜1 5質量％的範圍內尤佳。揮發性溶劑的含量 高於前述範園時，染髮性能有可能變得不充分。 作爲揮發性溶劑，可列舉乙醇、異丙醇、丙醇、丁醇 、苯甲醇等’可以單獨使用其1種，也可以並用2種以上 〔染髮劑中的其他有效成分〕 本發明的染髮劑中，除前述各成分之外，還可摻混高 級醇、不揮發性溶劑、矽酮類、陽離子化聚合物、以及至 少含有二烯丙基四級銨鹽及丙烯酸作爲構成單元的共聚物 中各1種或2種以上爲宜。 (局級醇） 本發明的染髮劑中可以含有0.01〜1 5質量％的高級醇 。染髮劑中高級醇的含量超過前述範園而過量時，則有可 能發生黏度上升導致泡沫的排出不良、或泡沫變得容易消 失。 作爲高级醇，只要是碳數爲1 0〜3 0，則没有特别限定 ’其碳骨架部分可以爲直鏈狀、支鏈狀、環狀、前述的組 -20- 201249466 合，飽和•不飽和的區别也没有限定。作 例如選自十六烷醇（鯨蠟醇）、2-己基癸 烷醇、硬脂醇、異硬脂醇、鯨脂醇、油醇 二烷醇 '月桂醇、肉豆蔻醇、癸基十四院 以及氫化羊毛脂醇等中的1種以上。以選 飽和的直鍵狀或支鍵狀的筒級醇的肉豆寇 硬脂醇、2-己基癸醇、以及2-辛基十二烷 爲宜。 (不揮發性溶劑） 本發明的染髮劑中可以含有〇.〇1〜1C 性溶劑。染髮劑中的不揮發性溶劑的含量 過量時’泡沫有可能變得容易消失。 作爲不揮發性溶劑，可舉例如二醇及 ，可舉例如乙二醇、二乙二醇、三乙二醇 二醇、二丙二醇、異戊二醇、以及h 3 -丁 ’例如可舉出甘油、雙甘油、及聚甘油. (矽酮類） 本發明的染髮劑中可以含有〇.〇1〜3 。染髮劑中的矽酮類的含量超過上述範圍 有可能變得容易消失。 作爲矽酮類，可舉出二甲基聚矽孽 dimethicone )、具有羥基末端基團的二 爲高級醇，可舉 醇、2-辛基十二 、花生醇、二十 醇、羊毛脂醇、 自作爲飽和或不 醇、十六烷醇、 醇中的1種以上 質量％的不揮發 超過前述範圍而 甘油。作爲二醇 、聚乙二醇、丙 二醇。作爲甘油 質量％的矽酮類 而過量時，泡沫 ，烷（INCI 名： 甲基聚矽氧烷（ -21 - 201249466 INCI名：dimethiconol)、甲基苯基聚砂氧院、十甲基環 戊矽氧烷、十二甲基環己矽氧烷、聚醚改性矽酮、胺基改 性矽酮、甜菜鹼改性矽酮、烷基改性矽酮、烷氧基改性砂 酮、毓基改性矽酮、羧基改性矽酮、氟改性矽酮等。作爲 胺基改性矽酮，以列舉胺基乙基胺基丙基甲基矽氧烷•二 甲基矽氧烷共聚物爲宜。作爲聚醚改性矽酮，以列舉 PEG-10二甲基聚矽氧烷、PEG-11二甲蕋聚矽氧烷爲宜。 (陽離子化聚合物、以及至少含有二烯丙基四級銨鹽及丙 烯酸作爲構成單元的共聚物） 本發明的染髮劑中可以含有〇.〇 1〜2質量％的選自陽 離子化聚合物、以及至少含有二烯丙基四級銨鹽及丙烯酸 作爲構成單元的共聚物中的丨種以上。染髮劑中的選自陽 離子化聚合物、以及至少含有二烯丙基四級銨鹽及丙烯酸 作爲構成單元的共聚物中的1種以上的含量超過上述範園 而過量時，則有可能在從發泡器容器排出時發生不良狀況 〇201249466 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to hair dyes, methods of use thereof, and hair dye articles. More specifically, the present invention relates to a hair dye, a method of applying the hair dye to hair, and a hair dye article comprising the hair dye and a non-aerosol foamer container, the hair dye comprising a base a first agent of the agent and a second agent containing an oxidizing agent, wherein the mixed solution of the first agent and the second agent is discharged from the non-aerosol foamer container in a foam form, wherein the mixed solution is discharged When the foam is formed, there is no problem in the foam durability of the discharged foam on the hair, and a suitable surface tension as a foamy dosage form is achieved. [Prior Art] Oxidation of a dosage form including a two-part or a three-part formula including a first agent containing an alkali agent and a second agent containing an oxidizing agent is conventionally known as a paste or a gel. Hair dyes such as hair dyes, hair bleaching agents, and hair dye removers. The aforementioned hair dye is applied to a hair for hair dyeing treatment using a comb or a brush or the like. However, since the aforementioned hair dye has a high viscosity, it is possible to effectively prevent the dripping of the liquid during the hair dyeing treatment time, but it is difficult to apply it uniformly to the entire hair. Especially for the user's own back head and the like, it is difficult to perform uniform application of the hair dye even with a mirror. In addition, it takes a lot of effort to perform so-called hair zoning and the like. On the other hand, a hair dye which is used in a foam form of a mixture of various agents of a multi-dose hair dye has been proposed. These hair dyes can be applied evenly to the hair as a whole by the foam of -5-201249466. For example, Patent Literatures 1 and 2 below disclose a hair dye which is applied to hair using a foam type foamer container and discharged in a foam shape. Patent Documents 3 to 5, which will be described later, disclose the use of a pump foamer or a squeeze foamer. A non-aerosol type foamer container is discharged as a hair dye for hair by discharging it in a foam form. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. 2006-124279. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, hair dyes used in a foam form are known to be uniformly as described above. It is applied to the entire hair, but in order to ensure the aforementioned advantages, the foaming property is good in order to make the foam formation from the foamer container discharge, or to foam the discharged foam on the hair by hand, usually A surfactant is blended. However, for such hair dyes, the problem of skin contamination occurs in a wide range due to the spread of the hair dye on the scalp. This problem manifests itself in the dyeing of the skin in, for example, oxidative hair dyes, and is manifested as damage to the skin in, for example, a hair bleaching agent or a hair dyeing agent of -6-201249466. Therefore, the subject of the present invention is to provide a hair dye which has no problem in foam formation when discharged from a non-aerosol foamer container, or foaming on the hair after discharge, without skin contamination. As a solution to the aforementioned problems, the applicant of this patent has focused on adjusting the surface tension in hair dyes. The reason for this is that the above-mentioned adverse conditions are related to the facts described later: the surface tension of the hair dye is lowered by blending the surfactant, etc., on the one hand, although the above-mentioned effect of foam formation or foaming can be obtained, on the other hand, the hair dye is obtained. The agent will spread easily on the scalp. Further, the present inventors have repeatedly conducted experimental investigations on trial production examples of various hair dyes, and found that the hair dye for non-aerosol foamer containers satisfies "the first agent and the second before discharge". The condition that the surface tension of the mixed liquid of the agent is in the range of 30 to 50 mN/m under specific measurement conditions is a method for solving the above problems, and the present invention has been completed. Solution to Problem (Configuration of First Invention) The first invention of the present invention for solving the above-mentioned problems is a hair dye comprising a first agent containing an alkali agent and a second agent containing an oxidizing agent. A hair dye containing water as a medium, and a hair dye used for discharging a mixture of the respective agents from a non-aerosol foamer container in a bubble form, wherein the surface tension of the mixture of the respective agents before discharge is subjected to specific measurement conditions The lower is in the range of 3 0 to 5 0 mN/m. In the first invention, the surface tension of the mixed liquid of each agent before the discharge is measured. "Under the specific measurement conditions" of 201249466 is as follows. That is, the surface tension was measured by using the Bubble Pressure Method and calculating the surface tension by the Y〇ung_Laplace equation. The aforementioned measurement methods and calculation formulas are well known. Specifically, the mixture of the respective agents before discharge is used to calculate the surface tension by a bubble pressure method such as SITA pro line tl5 manufactured by SIT A Co., Ltd. to determine the difference Δρ between the pressure inside and outside the bubble (unit : mN/m2 ). Next, the surface tension σ (unit: mN/m) of the foam was determined based on the Young-Laplace formula shown by the following formula (1). σ = ( Δρ · r ) /2.. (1) In the above formula (η, "r (unit: n〇" is the radius of the capillary in which the bubble is generated, and is constant, so by obtaining Δρ σ is obtained. In the measurement, although the dynamic surface tension is directly obtained, actually, the enthalpy at the time of equilibrium is achieved by the concentration of the tension, and thus is roughly calculated as the static surface tension and used as the static surface tension measurement method. The measurement method of the representative ring method or the hanging sheet method is substantially the same. (Configuration of the second invention) The second invention of the present invention for solving the above problems is a configuration in which the hair dye according to the first aspect of the invention is non-gas. A method of using a hair dye which is applied to a hair by discharging a foaming device container in a bubble shape. In the second invention, a method of "applying a hair dye which is discharged in a bubble shape to a hair" is usually "hand rubbing" The application of the invention is not limited to the application method. -8 - 201249466 (Configuration of the third invention) The configuration of the third invention of the present application for solving the above problems includes the hair dye according to the first invention. And for dyeing A hair dye product comprising a non-aerosol foamer container which is discharged in a foam form. According to the first invention, the surface tension of the mixed liquid of each agent before discharge is 30 to a specific measurement condition. This objective index in the range of 50 mN/m provides a solution to the problem of "foam formation from the non-aerosol foamer container, or foaming of the discharged foam on the hair without causing skin contamination." The hair dye of this subject is a water-based hair dye comprising a first agent containing an alkali agent and a second agent containing an oxidizing agent, and the mixture of the respective agents is a non-aerosol. The hair dye used for discharging the foamer container in a foam form is a non-aerosol foamer as long as the surface tension of the mixture of the respective agents before discharge is in the range of 30 to 50 mN/m under specific measurement conditions. The foam formed at the time of discharge of the container or the foaming of the discharged foam on the hair has no problem and does not cause skin pollution. When the surface tension is less than 30 mN/m, the hair dye is discharged and applied as a foam. After the hair is spread, it will spread on the scalp and cause skin pollution in a wide range. On the contrary, when the surface tension exceeds 50 mN/m, the foam is discharged from the non-aerosol foamer container, or the foam after discharge is The blistering of the hair is not sufficient. -9 - 201249466 The first invention can be understood from the different findings, that is, the first agent containing the alkali agent and the second agent containing the oxidizing agent. A hair dye which uses water as a medium, and is a hair dye which is used for discharging a mixture of the respective agents from a non-aerosol foamer container in a foam form, and is compatible with the surface tension of the mixture of the respective agents before discharge. In the range of 30 to 50 mN/m under the measurement conditions, the index can be judged as "foam formation when discharged from a non-aerosol foamer container" without specifically examining the various blending components. The hair foam after discharge or the foam on the hair has no problem, and does not cause skin pollution. This new topic of hair dye. This point is confirmed by a plurality of examples of the following description. Therefore, a useful hair dye which can be solved based on a new, objective and simple index can be provided. Alternatively, it provides a new, objective and simple indicator for providing a hair dye which can effectively solve the aforementioned problems. According to the second invention, it is preferred to provide a method of using the hair dye according to the first aspect of the invention. According to a third aspect of the invention, there is provided a hair dye article comprising the hair dye according to the first aspect of the invention and a non-aerosol foamer container for discharging the hair dye in a foam form. BEST MODE FOR CARRYING OUT THE INVENTION Next, the mode for carrying out the invention including the best mode thereof will be described. 201249466 [dyeing agent] The hair dye according to the present invention comprises a water-based hair dye comprising a first agent containing an alkali agent and a second agent containing an oxidizing agent, and the mixture of the agents is sent from a non-aerosol. The hair dye container is used as a hair dye for discharging the foam container. The non-aerosol foamer container may use a non-aerosol foamer container of any gas-liquid mixture ratio, so that the gas-liquid mixture ratio is preferably in the range of gas: liquid = 7:1 to 20:1, so that The gas-liquid mixture ratio is particularly preferable in the range of gas: liquid = 9:1 to 16:1. The dosage form of each of the hair dyes before foaming is not particularly limited, and for example, a gel form, a paste form, or an emulsion form, an aqueous solution form, a solid form, or another dosage form containing water as a medium can be arbitrarily selected. The solid dosage form is preferably a powder having excellent dispersibility. For example, when the first agent is in the form of a solid, the second agent is a form containing water. In short, the dosage form of each agent is not particularly limited as long as the respective agents become a mixed liquid having a fluidity of water as a medium during mixing. The various components of the hair dye described below may be blended only with the first agent, the second agent, etc., unless otherwise specified, in addition to the alkali agent contained in the first agent and the oxidizing agent contained in the second agent. In any of the above agents, it may be dispersed and blended in two or more different agents. The type of the hair dye is not particularly limited as long as it is composed of a first agent containing an alkali agent and a second agent containing an oxidizing agent, and includes, for example, an oxidative hair dye, a hair bleaching agent, and a hair dyeing agent. Further, in the hair dye, in addition to the two-component hair dye comprising the first agent and the second agent, a third agent containing, for example, an oxidation aid or the like is added in addition to the above-mentioned respective agents. A multi-dose hair dye such as a dosage form hair dye. Further, the hair dye of the present invention is required to have a surface tension of 30 to 50 mN/m in the respective measurement conditions before discharge. The surface tension is particularly preferably in the range of 30 to 35 mN/m. [The known essential components in the hair dye] The hair dyes of the present invention are, for example, oxidative hair dyes, hair bleaching agents, hair dye removers, etc., all of which contain an alkali agent. The first agent and the oxidizing agent 2 are used. The oxidative hair dye swells the hair by the alkali agent in the first agent, and the oxidizing agent in the dye intermediate and the second agent penetrates into the hair, and promotes the action of the oxidizing agent by the pH change of the alkali agent. The melanin contained in the hair is decomposed and decolored, and the oxidative dye intermediate incorporated in the agent is oxidatively polymerized to develop color. The hair is removed from the first agent of the aforementioned oxidative hair dye without the oxidation dye. Decomposition and decolorization of melanin. The hair decoloring agent is further blended with various persulfates as an oxidizing aid in the hair bleaching composition, and is also decomposed and decolored by the polymer of the oxidative dye intermediate in the hair. The dye intermediate contains the main intermediate or contains the main intermediate and the couple. In the oxidative hair dye, 'in order to adjust the color tone, sometimes a straightener is blended. As the alkali agent, ammonia, an alkanolamine (monoethanolamine, diethylamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ammonium salt, organic amine (2-amino group) can be exemplified. a mixture of -2-methyl-1-propanol and 2-amino group, the first oxygen of the hair, the first colorant body, the presence of the agent, the oxidizing agent, the alcoholamine, etc.) 2-methyl-12 - 201249466 keto-1,3·propylene glycol, hydrazine, etc.), inorganic base (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, ammonium hydrogencarbonate, sodium hydrogencarbonate, etc.), basic amino acid ( Arginine, lysine, etc.) and such salts. The content of the alkaline agent can be appropriately set as needed. The oxidizing agent is potassium bromate, sodium bromate, sodium perborate, hydrogen peroxide, peroxide or the like. Examples of the peroxide include carbamide peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, persulfate hinge, sodium peroxide, potassium peroxide, magnesium peroxide, and barium peroxide. Calcium peroxide, ruthenium peroxide, a hydrogen peroxide adduct of sulfate, a peroxidic gas adduct of phosphate, a hydrogen peroxide adduct of pyrophosphate, and the like. The content of the oxidizing agent can be appropriately set as needed. Among the oxidative dye intermediates, as the main intermediates, o- or p-phenylenediamines or aminophenols are mainly exemplified, and specific examples thereof include p-phenylenediamine and toluene-2,5-diamine (p-toluenediamine). ), N-phenyl-p-phenylenediamine, 4,4,-diaminodiphenylamine, p-aminophenol, o-aminoamine phenol, p-methylaminophenol, N,N-bis(2-hydroxyl) Ethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chloro-p-phenylenediamine, 4-amino-m-cresol, 2-amino-4-transethylethylaminobenzene Methyl ether, 2,4-diaminophenol, and salts thereof, and the like. As the salt, a hydrochloride, a sulfate, an acetate or the like can be exemplified. The content of the main intermediate can be appropriately set as needed. The coupling agent is mainly m-diamine, amino benzoquinone or diphenol, and specific examples thereof include resorcin, catechol, pyrogallol, meta-benzoic acid, and hydroquinone. , 5-Amino o-cresol, m-aminobenzene, 5-(2-hydroxyethylamino)-2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxy-13- 201249466 Ethanol, toluene-3,4-diamine, α-naphthol, 2,6-diaminopyridine, diphenylamine, 3,3'-iminobiphenyl, iota, 5-dihydroxynaphthalene and Tannin and their salts, etc. The content of the coupling agent can be appropriately set as needed. Examples of the direct dye include various acid dyes, basic dyes, nitro dyes, disperse dyes, and the like. In the above, examples of the acid dye include blue No. 1, purple No. 401, black No. 401, orange No. 205, red No. 227, red No. 106, yellow No. 203, and acidic orange 3 as basic dyes. It can be mentioned that basic blue 9 9 , alkaline brown 16 , alkaline brown 17 , alkaline red 7 6 , basic red 5 1 , basic yellow 5 7 , basic yellow 8 7 , alkaline orange 3 1 Et, as a nitro dye, 2-nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, 4-nitro-o-phenylene Amine, 4-amino-3-nitrophenol, 4-hydroxypropylamino-3-nitrophenol, HC Blue No. 2, HC Orange No. 1, HC Red No. 1, HC Yellow No. 2 , HC Yellow No. 4, HC Ν Ν · 5, HC Ν Ν 、 3, N, N-bis (2-hydroxyethyl)-2-nitro-p-phenylenediamine, etc., as a disperse dye, may be exemplified Purple 1, Disperse Blue 1, Disperse Black 9, etc. The content of the direct dye can be appropriately set as needed. [Main component of hair dye] (surfactant) In the hair dye of the present invention, the surfactant contained in the range of 30 to 50 mN/m of the mixed liquid of each of the agents before the discharge is contained. The total amount is preferably 1% by mass or more, and more preferably 15% by mass or more. In the present invention, when the content of the component is expressed as "% by mass,", unless otherwise specified, it means that each of the two or more doses of the hair dye is in the mixed solution. In the above-mentioned various surfactants, a surfactant which is solid at normal temperature is particularly preferable insofar as the surface tension is in the range of 30 to 50 mN/m. (Cational surfactant) The present invention The hair dye preferably contains a cationic surfactant as the component (A) in terms of the surface tension of 30 to 50 mN/m. The content of the cationic surfactant as the component (A) is It is preferably in the range of 0.05 to 10% by mass, more preferably in the range of 0.1 to 5% by mass. Examples of the cationic surfactant include lauryl trimethylammonium chloride and hexadecane chloride. Cetrimonium Chloride, Steartrimonium Chloride, alkyltrimethylammonium chloride, B ehentr imonium Chloride Distearyl chloride Distearyldimonium Chloride, dicocoyldimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium bromide, ethyl lanthanide lanolin fatty acid aminopropyl Ethyl dimethyl ammonium 'stearyl trimethyl ammonium saccharin, cetyl trimethyl ammonium saccharin, behenyl trimethyl ammonium methyl sulfate, and quaternary ammonium salt - 91 ( QUATERNIUM-91 In addition, the cationic surfactant may be used singly or in combination of two or more kinds. (Anionic surfactant) Further, the hair dye of the present invention makes the aforementioned surface The content of the anionic surfactant containing the anionic surfactant as the component (B) is preferably in the range of 30 to 5 OmN/m, and the content of the anionic surfactant as the component (B) is 〇.〇5~ In the range of 10% by mass, it is preferably in the range of 0.1 to 5% by mass. The anionic surfactant may, for example, be polyoxyethylene (hereinafter referred to as POE) sodium lauryl ether sulfate or the like. Alkyl ether sulfate, sodium lauryl sulfate, sodium bromide, sixteen Alkyl sulfates such as sodium sulfite, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α- N-nonylamino acid type surfactant, sulfonate mono- or diester type surfactant, and sulfosuccinic acid, such as sulfo fatty acid salt, coco glutamic acid triethanolamine (coco glutamic acid TEA) Examples of the counter ion of the anionic group of the surfactant include, for example, sodium ion, potassium ion, and triethanolamine. The anionic surfactant may be used alone or in combination of two or more. (Relationship between (A) component and (B) component) The relationship between the component (A) and the component (B) is such that the mass of the content of the two components is -16, and the ratio of A/B is 0.2 or more, particularly preferably 1 or more and 100 or less. It is preferable to make the surface tension into the range of 30 to 50 mN/m. Further, the total amount of the surfactant contained in the hair dye is set to 100% by mass, and 5 to 50 parts by mass of the component (A) and the component (B) are preferably used. (Other Surfactant) As the surfactant other than the component (A) and the component (B), a nonionic surfactant is preferred. The nonionic surfactant is preferably used in an amount of from 1 to 40% by mass, and in a range of from 1 to 20% by mass, as a nonionic surfactant, and the following (1) to nonionic surfactants are mentioned. The surfactant may be used singly or in combination of two or more. (1) POE cetyl ether, POE stearyl ether, POE dialkyl ether, POE oleyl ether, POE lauryl ether 'POE tridecyl ether, POE octyl lauryl ether, POE POE alkyl ethers such as hexyl decyl ether, POE isobutyl ether, POE decyl pentadecyl ether, POE decyl decyl ether, alkyl (C 12 14) ether, and the like. (2) POE alkylphenyl ethers such as POE mercapto ether and POE octylphenyl ether. (3) POE of acid POE sorbitan ester, monostearic acid POE sorbitan ester palmitate POE sorbitan ester, monolauric acid POE sorbitol, trioleic acid POE sorbitan ester, etc. Sorbitol ester ester. (4) Monostearic acid POE glyceride, monomyristate POE, the above, the right part of the content is particularly good (17 can be 12 yards of hard fat POE benzene benzene oil, monoanhydride fatty acid oil Ester-17- 201249466 and other POE glyceryl mono-fatty acid esters. (5) Tetra-oleic acid P0E sorbate, hexasuccinic acid POE sorbitol ester, monolauric acid POE sulphate, POE sorbitol ester bee sting, etc. POE sorbitol fatty acid 6) POE hydrogenated castor oil, POE castor oil. (7) Monooleic acid polyester, polyethylene glycol monostearate, and polyethylene glycol monolaurate. A lipophilic monoglyceride, a lipophilic glyceryl monostearate, a higher fatty acid glyceride such as glyceryl monostearate. (9) sorbitan ester, sorbitan sesquioleate, sorbitan trioleate, sorbitan monostearate, sorbitan monolaurate, sorbitan laurate Is a sorbitan fatty acid ester. (1C lanolin, POE lanolin alcohol, POE sorbitol lanolin, etc.. (11) Alcohol decylamine such as lauric acid diethanolamine, coconut fatty acid diamine, etc. (1 2 ) POE hard fat P0E fat (13) sucrose fatty acid ester such as guanamine (14) alkyl group such as dimethyldodecylamineoxylaurylamine oxide, cocoalkyl dimethylamine oxide (15) Dialkyl glucoside, alkyl (8~16) glucosyl glucoside. (16) Lecithin derivative hydrogenated soybean lecithin, yellow lecithin, etc. (17) P0E. Polyoxypropylene (hereinafter referred to as ten POE · POP alkyl ether such as hexaalkyl ether. Among the various surfactants, the amphoteric surfactant can be blended without impairing the effects of the present invention. As the amphoteric surfactant, the following (1) to (1) can be cited. The amphoteric surfactant may be used alone or in combination. The sorbitol sorbitol ester (ethylene glycol (8) emulsified oleic acid sorbitan ester, single I) POE lanolin alcohol oxime Indole amines, alkoxylated eggs such as amine glucosides, POP) range 5) electricity 2 species -18- 201249466 (i) coconut oil fat 醯Aminopropyldimethylaminoacetic acid betaine, palm oil fat amidoxime dimethylaminoacetate betaine, lauryl propyl dimethylaminoacetate betaine (lauric acid propyl betaine) , castor oil, amidoxime dimethylaminoacetate, betaine, etc., and the like, sodium, potassium or triethanolamine salts. Dimethylaminoacetic acid betaine, dodecyldimethylaminoacetic acid betaine, myristyl dimethylaminoacetic acid betaine, cetyldimethylaminoacetic acid betaine, stearyl Alkyl groups such as dimethylaminoacetic acid betaine, oleyl dimethylaminoacetic acid betaine, behenyldimethylaminoacetic acid betaine, and cocoalkyl dimethylaminoacetic acid betaine Dimethylaminoacetic acid betaine, and such sodium, potassium or triethanolamine salts. (3) Cocoon amphoteric acid Na (N-cocoyl fatty thiol-N,-carboxymethyl-oxime) '_Hydroxyethyl-extension ethyldiamine), coconut oil amphoteric propionic acid Na(N-cocoate fatty decyl-Ν'_carboxyethyl-Ν'-hydroxyethylethylenediamine , Laurel, Amphoteric Acid, Na(N-Laurylhydra-Ν'-carboxymethyl-Ν'-hydroxyethylethylidene diamine), Olive oil, Amphoteric acid, Na, Cocoa butter, Amidoacetic acid, Na, Sesame oil Amidine-based alkanoic acid Na, sweet almond oil, amphoteric acid, Na, stearic acid amidoacetate, palmitoyl amidoacetic acid, Na, peanut oil, amidoacetic acid, Na, sunflower seed oil, amphoteric acid, Na, cottonseed oil N-mercaptoaminoethyl-N-2-hydroxyethylaminocarboxylate such as amphoteric acetic acid Na. (4) Cocoamphodiacetate Na, Cocoamphodipropionate Na, and Laurel N-mercaptoaminoethyl-N-carboxymethoxyethylaminocarboxylate such as amphoteric diacetate. (5) Hydroxyalkyl (C12-14) hydroxyethyl creatinine. -19- 201249466 (Solvent) The hair dye of the present invention contains a volatile solvent as a solvent, and is suitable for the above surface tension of 30 to 50 mN/m. The content of the volatile solvent is not limited, and it is preferably in the range of 0.1 to 20% by mass in terms of 0.5 to 15% by mass. When the content of the volatile solvent is higher than the above-mentioned range, the hair dyeing performance may become insufficient. Examples of the volatile solvent include ethanol, isopropyl alcohol, propanol, butanol, benzyl alcohol, and the like. One type may be used alone or two or more types (other active ingredients in the hair dye) may be used in combination. The hair dye of the present invention In addition to the foregoing components, a higher alcohol, a nonvolatile solvent, an anthrone, a cationized polymer, and a copolymer containing at least a diallyl quaternary ammonium salt and acrylic acid as a constituent unit may be blended. One type or two or more types are preferable. (Local alcohol) The hair dye of the present invention may contain 0.01 to 15% by mass of a higher alcohol. When the content of the higher alcohol in the hair dye is more than the above-mentioned range, there is a possibility that the viscosity rises to cause the discharge of the foam to be poor, or the foam is easily lost. The higher alcohol is not particularly limited as long as it has a carbon number of 10 to 30. The carbon skeleton portion may be linear, branched or cyclic, and the above-mentioned group is a group of -20-201249466, saturated or unsaturated. The difference is not limited. For example, selected from the group consisting of cetyl alcohol (cetyl alcohol), 2-hexyl decyl alcohol, stearyl alcohol, isostearyl alcohol, whale alcohol, oleyl dialkyl alcohol 'lauryl alcohol, myristyl alcohol, decyl decyl One or more of the four hospitals and hydrogenated lanolin alcohol. It is preferred to select a saturated linear or branched-type tubular alcoholic nutmeg, stearyl alcohol, 2-hexyl decyl alcohol, and 2-octyldodecane. (Non-volatile solvent) The hair dye of the present invention may contain a solvent of 〇.〇1~1C. When the content of the non-volatile solvent in the hair dye is excessive, the foam may become easily disappeared. Examples of the nonvolatile solvent include glycols, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol glycol, dipropylene glycol, isoprene glycol, and h 3 -butyl group. Glycerin, diglycerin, and polyglycerol. (Indolones) The hair dye of the present invention may contain 〇.〇1~3. When the content of the anthrone in the hair dye exceeds the above range, it may become easy to disappear. Examples of the anthrones include dimethyl polyfluorene dimethicone and two hydroxyl group-containing groups, and examples thereof include alcohols, 2-octyldane, arachidyl alcohol, eicosyl alcohol, and lanolin alcohol. The glycerin which is not more than one of the above-mentioned range is not more than 1% by mass of the saturated or non-alcohol, cetyl alcohol or alcohol. As diol, polyethylene glycol, propylene glycol. When used as an anthrone of glycerol in excess, foam, alkane (INCI name: methyl polyoxyalkylene (-21 - 201249466 INCI name: dimethiconol), methyl phenyl polyoxalate, decamethylcyclopentane Alkoxysilane, dodecamethylcyclohexanoxane, polyether modified anthrone, amine modified anthrone, betaine modified anthrone, alkyl modified anthrone, alkoxy modified ketone, A mercapto-modified anthrone, a carboxyl-modified anthrone, a fluorine-modified anthrone, etc. As an amino-modified anthrone, an aminoethylaminopropylmethyloxane/dimethyloxane is exemplified Copolymers are preferred. As the polyether modified anthrone, PEG-10 dimethyl polyoxane and PEG-11 dimethyl hydrazine polyoxyalkylene are preferred. (Cationized polymer, and at least diene a propyl quaternary ammonium salt and a copolymer of acrylic acid as a constituent unit) The hair dye of the present invention may contain 〜.〇1 to 2% by mass of a selected cationized polymer and at least a diallyl quaternary ammonium salt. And a type of ruthenium or the like in the copolymer of acrylic acid as a constituent unit. The hair dye is selected from the group consisting of a cationized polymer, and at least When the excess of allyl methacrylate as a quaternary ammonium salt and one or more kinds of the constituting unit content of the copolymer exceeds the Park range, there may occur inconvenience square foaming when discharged from the vessel
作爲陽離子化聚合物’以水溶性的陽離子化聚合物爲 宜。作爲水溶性的陽離子化聚合物，可舉出作爲陽離子化 多糖類的陽離子化纖維素、陽離子性澱粉、陽離子化瓜爾 豆膠等，以及二甲基二烯丙基氯化銨聚合物（聚四級銨 鹽-6(POLYQUATERNIUM-6)、例如 MERQUAT 100 ； Nalco公司）、二甲基二烯丙基氯化銨/丙烯醯胺共聚物（ 聚四級銨鹽- 7(POLYQUATERNIUM-7) ’例如 MERQUAT •22- 201249466 5 50 ; Nalco公司）、四級銨化聚乙烯吡咯烷酮等。 作爲陽離子化纖維素的具體例，可舉出羥乙基纖維素 加成氯化縮水甘油基三甲基銨而得的四級銨鹽的聚合物（ 聚四級銨鹽-10 ( POLYQUATERNIUM-10 )，例如 CATINAL HC-100、CATINAL HC-200、CATINAL LC-100 、CATINAL LC-200 ;東邦化學工業（股）、CELQUAT SC-23M ； Akzo Nobel 公司、LEOGARD G、LEOGARD GP ;Lion (股）、Polymer JR-125 、Polymer JR-400、 Polymer JR-30M、Polymer LR-400、Polymer LR-30M ； Amerchol公司）、羥乙基纖維素/二甲基二烯丙基氯化銨 共聚物（聚四級銨鹽-4 ( POLYQUATERNIUM-4 )，例如 CELQUAT L-200 : Akzo Nobel 公司）等。 作爲陽離子化瓜爾豆膠的具體例，可舉出氯化0·[2-羥基- 3-(三甲基銨）丙基]瓜爾豆膠等。 作爲四級銨化聚乙烯吡咯烷酮的具體例，可舉出由乙 烯基吡咯烷酮（VP)和甲基丙烯酸二甲基胺基乙基的共聚 物與硫酸二乙酯而得的四級銨鹽（聚四級銨鹽-11 ( POLYQUATERNIUM-1 1 )、例如 GAFQUAT 734、GAFQUAT 75 5 ' GAFQUAT 75 5N ； ISP. Japan 公司）等。 作爲至少含有二烯丙基四級銨鹽及丙烯酸作爲構成單 元的共聚物的具體例，可舉出二甲基二烯丙基氯化銨/丙 烯酸共聚物（聚四級銨鹽-22 ( POLYQUATERNIUM-22 ) ，例如 MERQUAT 280、MERQUAT 295 ; Nalco 公司）、 丙烯酸/二甲基二烯丙基氯化铵/丙烯醯胺共聚物（聚四級 -23- 201249466 銨鹽-39 ( POL YQUATERNIUM-39 )、例如 MERQUAT PLUS 3 3 3 0、MERQUAT PLUS 3 3 3 1、MERQUAT 3 3 3 0、 MERQUAT 3 3 3 1 ; Nalco 公司）等。 此等中，考量毛髮化妝品組合物的黏度上升時，以陽 離子化多糖類、以及至少含有二烯丙基四級銨鹽作爲構成 單元的聚合物及共聚物爲宜。 〔染髮劑中的其他成分〕 本發明所述的染髮劑中，除前述各成分外，只要不妨 礙本發明的效果，則可添加適當量的可配合於該種染髮劑 中的各種成分。這類成分的數個例子陳述如下。 (油性成分） 作爲油性成分，可舉例如與之符合的前述成分以外之 油脂、烴、高級脂肪酸、蠟類、酯類等。 作爲油脂，可列舉橄欖油 '薔薇果油、山茶油、牛油 樹脂、夏威夷火山豆油、杏仁油等。 作爲烴，可列舉α-烯烴低聚物、輕質異鏈烷烴、輕質 液體異鏈烷烴、液體異鏈烷烴、液體鏈烷烴、角鯊烷、聚 丁烯、鏈烷烴、聚乙烯粉末、微晶蠟、凡士林等。 作爲高級脂肪酸，可列舉月桂酸、肉豆蔻酸、棕櫚酸 、硬脂酸、二十二烷酸、異硬脂酸、羥基硬脂酸、12-羥 基硬脂酸、油酸、十一碳烯酸、亞油酸、蓖麻醇酸、羊毛 脂脂肪酸等》 -24- 201249466 作爲蠟類，可列舉蜂蠘、小燭樹蠟、巴西棕櫚蠟、荷 荷巴油、羊毛脂等。 作爲酯類，可列舉肉豆蔻酸異丙基酯、己二酸二異丙 基酯、辛酸十六烷基酯、棕櫚酸異丙基酯、硬脂酸丁基酯 、異辛酸異十六烷基酯、異壬酸異壬基酯、肉豆蔻酸丁基 酯、肉豆蔻酸異十三烷基酯、肉豆蔻酸辛基十二烷基酯、 棕櫚酸2 -乙基己基酯、蓖麻醇酸辛基十二烷基酯 '辛酸十 六烷基酯、蘋果酸二異硬脂酯、琥珀酸二辛基酯、2 -乙基 己酸十六烷基酯、硬脂酸硬脂酯、肉豆蔻酸肉豆蔻酯、具 有10〜30的碳數的脂肪酸瞻固醇酯/羊毛固醇酯、乳酸十 六烷基酯、乙酸羊毛脂酯、二-2-乙基己酸乙二醇酯、季戊 四醇脂肪酸酯、二季戊四醇脂肪酸酯、癸酸十六烷基酯、 三辛酸甘油酯等。 (烷基甘油醚） 作爲烷基甘油醚，可列舉鯊肝醇（單硬脂基甘油醚） '鮫肝醇（單十六烷基甘油醚）、鯊油醇（單油烯基甘油 醚）等。 (肽、胺基酸系成分） 作爲肽、胺基酸系成分，可列舉膠原、角蛋白、彈性 蛋白、絲蛋白、絲、酪蛋白、明膠等動物系蛋白質，由小 麥、大麥、燕麥、大豆、杏仁等植物得到的蛋白質，將前 述蛋白質利用酸 '鹼、酶等水解而得的物質等。 -25- 201249466 (高分子化合物） 作爲高分子化合物，可列舉前述陽離子化聚合物以外 之羧基乙烯基聚合物等陰離子性聚合物、水溶性聚合物等 。作爲水溶性聚合物的具體例，可列舉阿拉伯膠、黃原膠 、鹿角菜膠、果膠、瓊脂、澱粉、海藻膠（褐藻提取物） 等植物性高分子、葡聚糖、支鏈澱粉等微生物系高分子、 羧甲基澱粉、甲基羥丙蕋澱粉等澱粉系高分子、甲基纖維 素、乙基纖維素、硝基纖維素、羥乙基纖維素等纖維素系 高分子、藻酸鈉等藻酸系高分子、羧基乙烯基聚合物等乙 烯基系高分子等。 (pH緩衝成分） pH緩衝成分包含作爲無機酸或有機酸的酸成分、與 作爲無機鹼或有機鹼的鹼成分。以包含有機酸及有機鹼的 pH緩衝成分尤佳。 作爲有機酸，可列舉羥基羧酸（乙醇酸、乳酸、蘋果 酸、檸檬酸、酒石酸等）、二羧酸（琥珀酸等）。 作爲有機鹼，可列舉嗎啉等揮發性鹼成分、L-組胺酸 等鹼性胺基酸。 〔染髮劑的使用方法〕 本發明所述的毛髮化妝品組合物的使用方法係將上述 染髮劑從非氣溶膠發泡器容器以泡沫狀排出而應用於頭髮 -26- 201249466 的方法。 作爲非氣溶膠發泡器容器，只要是具有對毛髮化妝品 組合物進行非氣溶膠類型的發泡和排出的功能即可，並無 限定。以可使用後述的非氣溶膠發泡器容器進行發泡爲宜 〔染髮劑用品〕 本發明所述的染髮劑用品係包含前述染髮劑、與用於 將該染髮劑以泡沫狀排出的非氣溶膠發泡器容器而構成的 0 作爲非氣溶膠發泡器容器的代表例，可舉出泵發泡器 或擠壓發泡器。泵發泡器是指藉由對泵壓頭部進行擠壓操 作而將容納液（例如染髮劑的第1劑/第2劑混合液）以 泡沫狀排出的裝置，是將容納液與空氣混合而以泡沫狀排 出的泡沫排出器安裝在容器主體的口頸部的裝置。泵發泡 器係已知如日本特開2007-275777號公報等中所揭示。擠 壓發泡器係指藉由用手擠壓軟質合成樹脂製的容器主體（ 重複容器的壓縮操作與解除壓縮操作），將同上的容納液 及空氣導入至發泡器用排出頭的氣液混合室中進行混合， 並將由泡沫排出器形成的泡沫從噴嘴排出的裝置。擠壓發 泡器係已知如日本特開 2008-29 1 024號公報或雜誌“ Fragrance Journal”的2009年6月號所揭不的文獻“染髮 技術之新趨勢（-泡沫状染髮技術的開發-)”等中所記載 -27- 201249466 非氣溶膠發泡器容器的泡沫排出器具有1張或多張用 於形成泡沫的多孔膜。作爲多孔膜的材質，可列舉尼龍、 聚酯、聚乙烯、聚丙烯等。作爲多孔膜的篩孔數，例如以 50〜300篩孔爲宜。 【實施方式】 〔實施例〕 以下係對本發明的實施例及比較例進行說明。本發明 的技術範圍並不局限於此等實施例及比較例。 〔染髮劑的第1劑和第2劑〕 分別製備最後的表1所示的編號1〜9所述的氧化染 髮劑的第〗劑、最後的表2所示的編號1〜8所述的氧化 染髮劑的第2劑。此等第1劑及第2劑按照常法均製備爲 液狀或水溶液狀。表1、2中，表示成分組成的數値的單 位爲"質量％” ，這些數値是第1劑或第2劑中的質量％ 數，並不是第1劑及第2劑的混合時的質量％數。 〔實施例及比較例所述的染髮劑〕 從表1所示編號1〜9所述的第1劑與表2所示編號1 〜8所述的第2劑中，藉由選擇組合分別示於表3的"第 1劑”、“第2劑”一欄中的特定編號所述的第]劑與第 2劑，來構成表3的實施例1〜實施例8、比較例1〜比較 例5所示的雙劑式的氧化染髮劑。 -28- 201249466 〔實施例及比較例所述的染髮劑之評估〕 (表面張力的測定） 對於實施例1〜實施例8、比較例1〜比較例 染髮劑，分別將表3所示的第1劑及第2劑以 量比進行混合，接著如前“第1發明的構成”一 在“特定的測定條件下”測定排出前各劑的混合 張力。將對各實施例、比較例的表面張力（單ί )的測定結果如表3的“表面張力”一欄所示。 (泡質之評估） 將實施例1〜實施例8、比較例1〜比較例5 髮劑的第1劑及第2劑以1 : 1的質量比容納於 發泡器容器（泵發泡器）中製爲混合液，並藉由 頭部進行擠壓操作而將前述混合液以泡沫劑型排 泵發泡器，使用了（股）吉野工業所製之商品名 、WP泡沫泵 L噴嘴型（氣/液混合比：13/1、 〇.9g(l次擠壓）、多孔膜：90目的聚乙烯製網 )° 對於該評估，將“排出時的泡沫紋理細緻， 髮時的起泡良好”的情形記爲“ ◎” 、將“排出 紋理細緻，應用於頭髮時的起泡稍好”、或“排 沬紋理稍微細緻、應用於頭髮時的起泡良好”的 “〇”、將“排出時泡齧多，應用於頭髮時的起 5所述的 1 : 1的質 欄所述， 液的表面 立：m N/m 所述的染 非氣溶膠 對其泵壓 出。作爲 3 W-5 72 1 排出量： 孔環2片 應用於頭 時的泡沫 出時的泡 情形記爲 泡稍差” -29- 201249466 、或“排出時有泡齧，應用於頭髮時的起泡差”的情形記 爲“△” 、將“排出時泡齧多，應用於頭髮時的起泡差” 的情形記爲“ X ” 。將對各實施例、比較例的泡質的評估 結果示於表3的“泡質”一欄。 應予說明，"泡齧”係指不是"泡沫的大小均一，所 謂紋理整齊的狀態”，泡沫包含大氣泡而從發泡器容器排 出的狀況。 (皮膚污染之評估） 將實施例1〜實施例8、比較例1〜比較例5所述的染 髮劑的第1劑及第2劑以1 : 1的質量比進行混合，並從 與前述相同的非氣溶膠發泡器容器以泡沫狀排出，將排出 的泡沫狀的染髮劑塗布於手腕內側部表皮的直徑1 . 5 cm的 圓形區域，放置3 0分鐘後用溫水沖洗。然後，使用肥皂 用手指輕輕擦拭前述圓形區域1分鐘，用溫水沖洗後對該 區域的皮膚污染狀況進行評估》 對於該評估，將“皮膚污染少，污染的範圍狹小”的 情形記爲“ ◎” 、將“皮膚污染少、污染的範圍稍狹小” 或“皮廚污染稍少，污染的範圍狹小”的情形記爲“〇” 、將“皮0污染多，污染的範圍稍寬”或“皮膚污染稍多 ，污染的範圍寬”的情形記爲“ △” 、將“皮膚污染多， 污染的範圍寬的情形記爲“ X ” 。將對各實施例、比較例 的皮10污染的評估結果如表3的“皮膺污染”一欄所示。 -30- 201249466 "«】 CD ΙΛ d I 1 1 OJ I 1 ΙΛ 1 1 1 1 CO 1 3 1 1 〇.15__ 1 1 <Μ Ο ο ΙΛ ο ιό ο 剩餘量 100 GO ΙΛ d I 1 1 π CM 1 1 ΙΛ >r~ 1 1 1 1 CO 1 04 in O 1 Ο CO ΙΛ CSJ Ο Ο ΙΟ ο ΙΛ Ο •«r ο 剩餘量 100 卜 ΙΛ d I • 1 CsJ 1 1 1 1 1 麵 1 ΙΟ 1 1 ΙΛ Ο 1 ΙΛ ΙΛ CSJ Ci Ο ιη ο ΙΟ Ο •«r a 剩餘量 100 (D in 〇 I 1 1 1 1 1 1 ίΛ 1 翁 1 1 C0 1 CM ΙΟ ο 1 ΙΛ ΙΛ Ο ο ΙΛ ο ΙΟ ο <r 〇 1剩餘量1 100 in ID d 1 1 1 1 I \ in 1 1 1 1 C0 I CM ΙΟ ο 1 ΙΛ ΙΛ CM Ο ο ΙΛ ο \ό ο ^=T 剩餘量 100 V ID 〇 •r*· 1 , 1 Cs) 1 1 1 1 1 1 1 1 1 1 ιτ> ο 1 ΙΟ ιη C^J Ο ο ΙΟ ο ΙΛ ο o 丨剩餘量1 100 CO \n o 1 1 1 OJ 1 I Csj 1 1 1 1 ΙΟ 〇 1 ΙΛ C) ιη c> 1 ΙΟ to OJ ο ΙΟ ο ΙΟ ο ^r 〇 1剩餘量丨 100 C\l I I T— 5 o' 1 1 ΙΛ ο 1 卜 卜 w~· - 1 - CSI 1 ΙΛ a ιη ιη <\ί Ο ο ΙΟ ο ΙΛ ο 〇 丨剩餘量1 100 V- ΙΛ 〇 1 1 1 <M 1 1 in 1 翁 1 1 CO I <N ΙΛ Ο I ΙΛ ιη <Μ Ο ο ιη Ο ΙΟ ο •=r 〇 丨剩餘量1 100 丨第1劑 肉豆蔻醇 馳 II + m Cvl 油醇 1異硬脂醇 己基癸醇 氯化十二烷基三甲基銨 1氯化硬脂基三甲基銨 乙基硫酸羊毛脂脂肪酸胺基丙基乙基 二甲基銨 繼 艇 趦 Κ1 m 狴 m ffi- 11 m 遐 11 七 憩 m 蹈 11 十 Q. 想 稍 ss •1C 十 g* CO UJ o CL 想 m 伽 5 © in 6 Ο CL 聚氧乙烯聚氧丙烯十六烷基醚（20_Ε.Ο·) (4.Ρ.Ο.) |ΡΟΕ(3)院基(C12〜14)酸 m i CM ο m 越 in UJ Ο |POE(9)十二烷基醚 1烷基葡糖苷 丙二醇 甘油 丨無水乙醇 1 ι異丙醇 1二伸乙基三胺五乙酸五鈉 1 1單乙醇胺溶液（70%) 1 丨濃氯水(28%) 對甲苯二胺 丨香料 純水 總計 -31 - 201249466 【CNm】 00 ir> d CM r- I ΙΛ CM Ο I I I I 1 OJ d Τ Ο <ΝΙ Ο 剩餘量 100 in 〇 CM 1 I 〇 CM Ο I I 0.05 I 1 <M C) »— d OJ d <〇 剩餘量 100 <D iO O 1 1 卜 I in CsJ Ο I I 0.05 I 1 CM 〇 d OJ 〇 (D y— 剩餘量 100 ΙΛ in 〇 1 卜 I IT) Csl ο I I 0.05 I 1 OJ 〇 δ CM 〇 <〇 剩餘量 100 啼 ir> 〇 Csl 1 I I CM d I I 0.05 I 1 CSJ 〇 δ <N d (O 剩餘量 100 CQ in c> CS1 ^―· I ΙΛ Ο CM o I I 0.05 I 1 CM 〇 5 <N d <D 剩餘量 100 CM in O OsJ ▼— 1 r- ΙΛ I S δ I 5 〇 <NJ 〇 v— Ο CM d i〇 剩餘量 100 r· to d τ— r- I ΙΟ CM o I I 0.05 I 1 CsJ d δ <N d <D 剩餘量 100 第2劑 肉豆蔻醇 趙 痗 想 m 11 t s UJ o Q. 十六烷基硫酸鈉 POE(21)十二院基醚 POE(30>十六烷基醚 Ρ〇Ε(5)烷基（C12〜14)醚 ffi- II o ό UJ Ϊ m 抹 碱 訟 m m •遯 NO訟 祕嵌 嵌猢 &· I! 5 出 I 嵌 祕 Κ m •遐 线祕 κι訟 賴 胺基乙基胺基丙基甲基矽氧烷·二甲基矽氧烷 共聚物 氯化〇-[2-羥基-3-(三甲基錢)丙基]羥基乙 基纖維素 MERQUAT 100 〇 Η < α Pi 1 苯氧乙醇 經基乙院雙膦酸 苯甲酸銷 過氧化氫水（35%) 純水 總計 -32- 201249466As the cationized polymer, a water-soluble cationized polymer is preferred. Examples of the water-soluble cationized polymer include cationized cellulose, cationic starch, cationized guar gum, and the like, and dimethyl diallyl ammonium chloride polymer (polymerized). Quaternary ammonium salt-6 (POLYQUATERNIUM-6), such as MERQUAT 100; Nalco), dimethyl diallyl ammonium chloride / acrylamide copolymer (polyquaternary ammonium salt - 7 (POLYQUATERNIUM-7) ' For example, MERQUAT • 22- 201249466 5 50 ; Nalco), quaternized ammonium polyvinylpyrrolidone. Specific examples of the cationized cellulose include a quaternary ammonium salt polymer obtained by adding hydroxyethyl cellulose to glycidyl trimethylammonium chloride (poly quaternary ammonium salt-10 ( POLYQUATERNIUM-10) ), such as CATINAL HC-100, CATINAL HC-200, CATINAL LC-100, CATINAL LC-200; Toho Chemical Industry Co., Ltd., CELQUAT SC-23M; Akzo Nobel, LEOGARD G, LEOGARD GP; Lion Polymer JR-125, Polymer JR-400, Polymer JR-30M, Polymer LR-400, Polymer LR-30M; Amerchol), Hydroxyethyl Cellulose/Dimethyldiallyl Ammonium Chloride Copolymer (Polymer 4) Gradeum-4 ( POLYQUATERNIUM-4), such as CELQUAT L-200: Akzo Nobel, etc. Specific examples of the cationized guar gum include 0·[2-hydroxy-3-(trimethylammonium)propyl]guar gum. Specific examples of the quaternized ammonium polyvinylpyrrolidone include a quaternary ammonium salt obtained by copolymerizing vinylpyrrolidone (VP) and dimethylaminoethyl methacrylate with diethyl sulfate (poly Quaternary ammonium salt-11 ( POLYQUATERNIUM-1 1 ), such as GAFQUAT 734, GAFQUAT 75 5 'GAFQUAT 75 5N; ISP. Japan company) and the like. Specific examples of the copolymer containing at least a diallyl quaternary ammonium salt and acrylic acid as a constituent unit include dimethyl diallyl ammonium chloride/acrylic acid copolymer (poly quaternary ammonium salt-22 ( POLYQUATERNIUM) -22), for example MERQUAT 280, MERQUAT 295; Nalco), Acrylic/Dimethyldiallyl ammonium chloride/propylene amide copolymer (Poly Quaternary-23-201249466 Ammonium Salt-39 (POL YQUATERNIUM-39) ), for example, MERQUAT PLUS 3 3 3 0, MERQUAT PLUS 3 3 3 1 , MERQUAT 3 3 3 0, MERQUAT 3 3 3 1 ; Nalco Company). In the above, when the viscosity of the hair cosmetic composition is increased, it is preferred to use a cationic ionized polysaccharide and a polymer and a copolymer containing at least a diallyl quaternary ammonium salt as a constituent unit. [Other components in the hair dye] In the hair dye according to the present invention, in addition to the above-described respective components, an appropriate amount of various components which can be blended in the hair dye can be added as long as the effects of the present invention are not impaired. Several examples of such ingredients are set forth below. (Oil-based component) Examples of the oil-based component include oils and fats other than the above-mentioned components, hydrocarbons, higher fatty acids, waxes, esters and the like. Examples of the fats and oils include olive oil 'rose hip oil, camellia oil, shea butter, Hawaii volcanic soybean oil, almond oil, and the like. Examples of the hydrocarbon include an α-olefin oligomer, a light isoparaffin, a light liquid isoparaffin, a liquid isoparaffin, a liquid paraffin, a squalane, a polybutene, a paraffin, a polyethylene powder, and a micro Crystal wax, petroleum jelly, etc. As the higher fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecene can be cited. Acid, linoleic acid, ricinoleic acid, lanolin fatty acid, etc. -24- 201249466 Examples of the wax include bee sting, candelilla wax, carnauba wax, jojoba oil, lanolin, and the like. Examples of the esters include isopropyl myristate, diisopropyl adipate, cetyl octanoate, isopropyl palmitate, butyl stearate, and isohexadecane isooctanoate. Base ester, isodecyl isononanoate, butyl myristate, isotridecyl myristate, octyldodecyl myristate, 2-ethylhexyl palmitate, ricinole Octyl cyanate, 'cetyl octanoate, diisostearyl malate, dioctyl succinate, cetyl 2-ethylhexanoate, stearyl stearate, meat Myristate myristate, fatty acid glycol ester having a carbon number of 10 to 30, lanosterol ester, cetyl lactate, lanolin acetate, ethylene di-2-ethylhexanoate, Pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, cetyl citrate, tricaprylin, and the like. (Alkyl glyceryl ether) Examples of the alkyl glyceryl ether include squalyl alcohol (monostearyl glyceryl ether) ' 鲛 heparin (monohexadecyl glyceryl ether), squalyl alcohol (monooleyl glyceryl ether) Wait. (Peptide, Amino Acid-Based Component) Examples of the peptide and amino acid-based component include animal proteins such as collagen, keratin, elastin, silk protein, silk, casein, and gelatin, and wheat, barley, oats, and soybeans. A protein obtained by a plant such as an almond, a substance obtained by hydrolyzing the above-mentioned protein with an acid 'base, an enzyme, or the like. -25-201249466 (Polymer compound) The polymer compound may, for example, be an anionic polymer such as a carboxyvinyl polymer other than the cationized polymer, or a water-soluble polymer. Specific examples of the water-soluble polymer include plant polymers such as gum arabic, xanthan gum, carrageenan, pectin, agar, starch, and seaweed gum (fucoid extract), dextran, amylopectin, and the like. A starch-based polymer such as a microbial polymer, carboxymethyl starch or methylhydroxypropionin, or a cellulose-based polymer such as methylcellulose, ethylcellulose, nitrocellulose or hydroxyethylcellulose, or algae An alkyd-based polymer such as sodium acid or a vinyl-based polymer such as a carboxyvinyl polymer. (pH buffer component) The pH buffer component contains an acid component as an inorganic acid or an organic acid, and an alkali component as an inorganic base or an organic base. It is especially preferred to use a pH buffering component comprising an organic acid and an organic base. Examples of the organic acid include a hydroxycarboxylic acid (glycolic acid, lactic acid, malic acid, citric acid, tartaric acid, etc.), and a dicarboxylic acid (succinic acid or the like). The organic base may, for example, be a volatile base component such as morpholine or a basic amino acid such as L-histamine. [Method of Using Hair Coloring Agent] The method of using the hair cosmetic composition according to the present invention is a method of applying the above-mentioned hair dye to a hair -26-201249466 by discharging it from a non-aerosol foamer container in a foam form. The non-aerosol foamer container is not particularly limited as long as it has a function of non-aerosol type foaming and discharging of the hair cosmetic composition. It is preferred to use a non-aerosol foamer container to be described later for foaming. [Dyeing agent article] The hair dye article of the present invention comprises the aforementioned hair dye and non-gas for discharging the hair dye in a foam form. 0 of a sol foamer container As a representative example of a non-aerosol foamer container, a pump foamer or a squeeze foamer is mentioned. The pump foamer refers to a device for discharging a liquid (for example, a first agent/second agent mixture of a hair dye) in a foam form by pressing a pumping head, and mixing the containing liquid with air. The foam ejector which is discharged in the form of a foam is attached to the neck portion of the container body. A pump foamer is known as disclosed in Japanese Laid-Open Patent Publication No. 2007-275777. The squeeze foamer refers to a gas-liquid mixture in which the same liquid and air are introduced into the discharge head for the foamer by pressing the container body of the soft synthetic resin by hand (the compression operation and the decompression operation of the repeated container). A means of mixing in the chamber and discharging the foam formed by the foam ejector from the nozzle. The extrusion foaming machine is known as the new trend of hair dyeing technology (the development of foam hair dyeing technology) as disclosed in Japanese Unexamined Patent Publication No. 2008-29 1 024 or the magazine "Fragrance Journal", June 2009 issue. The foam ejector of the non-aerosol foamer container described in -27-201249466 has one or more porous membranes for forming a foam. Examples of the material of the porous film include nylon, polyester, polyethylene, and polypropylene. The number of mesh holes as the porous film is preferably, for example, 50 to 300 mesh openings. [Embodiment] [Examples] Hereinafter, examples and comparative examples of the present invention will be described. The technical scope of the present invention is not limited to these embodiments and comparative examples. [The first agent and the second agent of the hair dye] The first agent of the oxidative hair dyes described in Nos. 1 to 9 shown in the last Table 1 and the numbers 1 to 8 shown in the last Table 2 were respectively prepared. The second agent of the oxidative hair dye. These first agent and second agent are prepared in the form of a liquid or an aqueous solution according to a usual method. In Tables 1 and 2, the unit of the number of components is ""% by mass", and these numbers are the mass % of the first agent or the second agent, and are not the mixing of the first agent and the second agent. [% by mass of the hair dyes of the examples and the comparative examples] The first agent described in Nos. 1 to 9 shown in Table 1 and the second agent described in Nos. 1 to 8 shown in Table 2 were used. The first agent and the second agent described in the specific numbers in the "first agent" and "second agent" columns of Table 3 are selected and combined to form the first to eighth embodiments of Table 3. The two-part oxidative hair dyes shown in Comparative Examples 1 to 5 were used. -28-201249466 [Evaluation of hair dyes according to Examples and Comparative Examples] (Measurement of surface tension) For the hair dyes of Examples 1 to 8, and Comparative Examples 1 to Comparative Examples, Table 3 One dose and the second dose were mixed in an amount ratio, and then the mixing tension of each agent before discharge was measured under "specific measurement conditions" as in the "configuration of the first invention". The measurement results of the surface tension (single ί) of each of the examples and the comparative examples are shown in the column of "surface tension" in Table 3. (Evaluation of the foaming amount) The first agent and the second agent of the hairs of Examples 1 to 8 and Comparative Examples 1 to 5 were accommodated in a foamer container at a mass ratio of 1:1 (pumper) The mixture is made into a mixed liquid, and the mixture is pumped by a foaming type by a head pressing operation, and the product name of the Yoshino Industrial Co., Ltd., WP foam pump L nozzle type is used. Gas/liquid mixture ratio: 13/1, 〇.9g (1 time extrusion), porous film: 90 mesh polyethylene mesh) ° For this evaluation, "the foam texture at the time of discharge is fine, and the foaming at the time of hair generation is good. "The situation is marked as " ◎", "the texture is fine, the blistering when applied to the hair is slightly better", or "the sputum texture is slightly fine, and the blistering when applied to the hair is good", " When squirting, there are many blisterings. When applied to the hair, the surface of the liquid is as described in 5: The surface of the liquid stands: m N/m. The dyed non-aerosol is pumped out. As 3 W -5 72 1 Discharge: The bubble condition when the 2 pieces of the ring ring are applied to the head is marked as a slightly worse bubble -29- 201249466, or "discharge" Frothy Nie, foaming difference during application to the hair "case referred to as" △ ", the" bubble is discharged engagement plurality foaming difference is applied to hair "case referred to as" X ". The evaluation results of the foams of the respective examples and comparative examples are shown in the column of "foam" in Table 3. It should be noted that "foaming" means a condition in which the size of the foam is uniform, the texture is neat, and the foam contains large bubbles and is discharged from the foamer container. (Evaluation of Skin Contamination) The first agent and the second agent of the hair dyes described in Examples 1 to 8 and Comparative Examples 1 to 5 were mixed at a mass ratio of 1:1, and were the same as described above. The non-aerosol foamer container was discharged in a foam form, and the discharged foam-like hair dye was applied to a circular area having a diameter of 1.5 cm in the inner skin of the wrist, and left for 30 minutes, and then rinsed with warm water. Then, use soap to gently wipe the circular area with your finger for 1 minute, and rinse with warm water to evaluate the skin contamination of the area. For this evaluation, the situation of "small skin pollution and narrow contamination" is recorded as “ ◎”, the case of “small skin pollution, a narrow range of pollution” or “small skin pollution is small, the scope of pollution is narrow” is recorded as “〇”, “the skin is more polluted, and the scope of pollution is slightly wider” Or the case of "slightly contaminated skin, wide range of pollution" is described as "△", and "the skin is contaminated, and the range of contamination is wide" as "X". The skin 10 of each example and comparative example will be contaminated. The results of the assessment are shown in the column “Skin pollution” in Table 3. -30- 201249466 "«] CD ΙΛ d I 1 1 OJ I 1 ΙΛ 1 1 1 1 CO 1 3 1 1 〇.15__ 1 1 < ;Μ Ο ο ΙΛ ο ιό ο Remaining amount 100 GO ΙΛ d I 1 1 π CM 1 1 ΙΛ >r~ 1 1 1 1 CO 1 04 in O 1 Ο CO ΙΛ CSJ Ο Ο ΙΟ ο ΙΛ Ο •«r ο Remaining amount 100 Divination d I • 1 CsJ 1 1 1 1 1 Face 1 ΙΟ 1 1 ΙΛ Ο 1 ΙΛ ΙΛ CSJ Ci ι ιη ο ΙΟ Ο •«ra Remaining amount 100 (D in 〇I 1 1 1 1 1 1 ίΛ 1 翁1 1 C0 1 CM ΙΟ ο 1 ΙΛ Ο Ο ο ΙΛ ο ΙΟ ο <r 〇1 Remaining amount 1 100 In ID d 1 1 1 1 I \ in 1 1 1 1 C0 I CM ΙΟ ο 1 ΙΛ CM CM Ο ο ΙΛ ο \ό ο ^=T Remaining amount 100 V ID 〇•r*· 1 , 1 Cs) 1 1 1 ι ι C c> 1 ΙΟ to OJ ο ΙΟ ο ΙΟ ο ^r 〇1 Remaining amount 丨100 C\l IIT— 5 o' 1 1 ΙΛ ο 1 Bu Bu w~· - 1 - CSI 1 ΙΛ a ιη ιη <\ί Ο ο ΙΟ ο ΙΛ ο 〇丨 Remaining amount 1 100 V- ΙΛ 〇1 1 1 <M 1 1 in 1 翁1 1 CO I <N ΙΛ Ο I ΙΛ ιη <Μ Ο ο ιη Ο ΙΟ ο •= r 〇丨 Remaining amount 1 100 丨 1st dose of myristyl alcohol II + m Cvl oleyl alcohol 1 isostearyl hexyl decyl alcohol chlorinated lauryl trimethyl ammonium 1 chlorinated stearyl trimethyl ammonium Sulfonic acid lanolin fatty acid aminopropyl ethyl dimethyl ammonium submarine 趦Κ 1 m 狴m ffi- 11 m 遐11 憩m m 1111 十 Q. I want to ss •1C ten g* CO UJ o CL I want m gamma 5 © in 6 Ο CL polyoxyethylene polyoxypropylene cetyl ether (20_Ε.Ο·) (4. Ρ.Ο.) |ΡΟΕ(3)院基(C12~14) Acid mi CM ο m 越 in UJ Ο |POE(9) lauryl ether 1 alkyl glucoside propylene glycol glycerol hydrazine anhydrous ethanol 1 isopropyl Alcohol 1 di-ethyltriamine pentaacetic acid pentasodium 1 1 monoethanolamine solution (70%) 1 丨 concentrated chlorine water (28%) p-toluenediamine hydrazine pure water total -31 - 201249466 [CNm] 00 ir> d CM r- I ΙΛ CM Ο IIII 1 OJ d Τ Ο <ΝΙ 剩余 Remaining amount 100 in 〇CM 1 I 〇CM Ο II 0.05 I 1 <MC) »- d OJ d <〇 remaining amount 100 <D iO O 1 1 Bu I in CsJ Ο II 0.05 I 1 CM 〇d OJ 〇 (D y—remaining amount 100 ΙΛ in 〇1 I I) Csl ο II 0.05 I 1 OJ 〇δ CM 〇<〇 remaining amount 100啼ir> 〇Csl 1 II CM d II 0.05 I 1 CSJ 〇δ <N d (O residual amount 100 CQ in c> CS1 ^―· I ΙΛ Ο CM o II 0.05 I 1 CM 〇5 <N d < ;D Remaining amount 100 CM in O OsJ ▼— 1 r- ΙΛ IS δ I 5 〇<NJ 〇v— Ο CM di〇 Remaining amount 100 r· to d τ— r- I ΙΟ CM o II 0.05 I 1 CsJ d δ <N d <D Remaining amount 100 Second dose of myristyl alcohol Zhao Zhaoxiang m 11 Ts UJ o Q. Sodium hexadecyl sulfate POE (21) 12-yard ether POE (30 > cetyl ether oxime (5) alkyl (C12~14) ether ffi- II o ό UJ Ϊ m Soda 讼 遁 遁 讼 讼 讼 讼 嵌 猢 · · · 出 出 出 出 出 出 出 出 出 出 出 出 出 遐 遐 遐 遐 遐 遐 遐 遐 遐 遐 遐 遐 遐 遐 遐 遐 秘 秘 秘 秘 秘 秘 胺Oxyalkylene copolymer ruthenium chloride-[2-hydroxy-3-(trimethyl hydroxy)propyl]hydroxyethylcellulose MERQUAT 100 〇Η < α Pi 1 phenoxyethanol via bis-bisphosphonic acid benzoic acid Pin hydrogen peroxide water (35%) pure water total -32- 201249466
[表3] 組合 表面張力 評估 第1劑 第2劑 泡質 皮膚污染 實施例1 1 1 32.0 <2> 實施例2 2 1 31.2 <2) 實施例3 1 2 34.2 〇 實施例4 3 3 30.9 % ο 實施例5 4 4 30.2 ο 實施例6 7 7 30.2 ο 實施例7 1 8 31.0 <s) ο 實施例8 9 2 31.2 ο ο 比較例1 5 1 29.3 X 比較例2 6 1 28.7 © X 比較例3 1 5 29.5 Θ X 比較例4 1 6 28.7 <2> X 比較例5 8 2 26.9 X 產業上利用性 本發明係提供從非氣溶膠發泡器容器排出時的泡沫形 成、或排出後的泡沫於頭髮上的起泡沒有問題，同時不會 引起皮膚污染的染髮劑。 -33-[Table 3] Combined surface tension evaluation first dose second agent blister skin contamination Example 1 1 1 32.0 <2> Example 2 2 1 31.2 < 2) Example 3 1 2 34.2 〇 Example 4 3 3 30.9 % ο Example 5 4 4 30.2 ο Example 6 7 7 30.2 ο Example 7 1 8 31.0 < s) ο Example 8 9 2 31.2 ο ο Comparative Example 1 5 1 29.3 X Comparative Example 2 6 1 28.7 © X Comparative Example 3 1 5 29.5 Θ X Comparative Example 4 1 6 28.7 <2> X Comparative Example 5 8 2 26.9 X Industrial Applicability The present invention provides foam formation when discharged from a non-aerosol foamer container, or The hair foam after discharge has no problem in foaming on the hair, and does not cause skin contamination of the hair dye. -33-