TWI515018B - 潤髮組合物 - Google Patents
潤髮組合物 Download PDFInfo
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- TWI515018B TWI515018B TW100123727A TW100123727A TWI515018B TW I515018 B TWI515018 B TW I515018B TW 100123727 A TW100123727 A TW 100123727A TW 100123727 A TW100123727 A TW 100123727A TW I515018 B TWI515018 B TW I515018B
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229940032044 quaternium-18 Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/31—Hydrocarbons
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
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- Dermatology (AREA)
- Cosmetics (AREA)
Description
本發明係關於一種包含油摻合物之潤髮組合物。
WO 01/95866(Unilever)揭示一種包含礦物油及椰子油之髮油。該揭示內容表明在椰子油中加入礦物油減小了油脂性及提高了總油於毛髮中之滲透。
J. Cosmetic Sci.,56,283-295(2005九月/十月)揭示應用於毛髮上的油留下一層油膜且油在毛髮纖維之間形成毛細管橋進而使纖維「黏附」在一起。隨著時間推移,由於油被毛髮吸收(僅滲透油顯示此效果),油膜厚度減小且黏附性減小。纖維與厚油膜間的黏附導致油膩感及過重外觀。
儘管存在先前技術,但仍需改良的調理組合物。
吾人意外地發現於潤髮乳調配物之礦物油中添加椰子油較僅用礦物油使毛髮增重減少。甚至更為意外地是油與聚矽氧之組合使用較僅用聚矽氧使毛髮增重減少且使毛髮端更為順滑。
因此,本發明提供一種如技術方案1之組合物。
第一油性組分可以單一物質或摻合物存在於本發明之毛髮油摻合物中。
第一油性組分在本發明之毛髮油摻合物中之總含量宜為組合物總重量之10%至95重量%,較佳20%至80重量%。
適宜烴油包括環烴、直鏈脂肪烴(飽和或不飽和)、及支鏈脂肪烴(飽和或不飽和)。直鏈烴油一般包含約6至約16個碳原子,較佳約8至約14個碳原子。支鏈烴油可且一般會包含更高數量之碳原子,例如,約6至約20個碳原子,較佳約8至約18個碳原子。
本發明之適宜烴油一般具有在周溫(25至30℃)下由Carri-Med CSL2 100控制應力流變儀(TA Instruments Inc.,New Castle,Delaware(USA))量測之0.001至0.5 Pa.s之黏度,較佳0.001至0.05 Pa.s,更佳0.001至0.02 Pa.s。
較佳烴油為輕質礦物油。礦物油為從石油中獲取之透明油性液體,其中蠟已移除,及更多揮髮性餾份藉由蒸餾移除。250℃至300℃下之蒸餾餾份稱為礦物油,且其包含烴混合物,其中每個烴分子之碳原子數一般為C10至C40。礦物油特徵在於其黏度,其中輕質礦物油黏度較重質礦物油相對較低,且此等術語更具體地定義於U.S. Pharmacopoeia,第22修訂版,899頁(1990)中。用於本發明之適宜輕質礦物油之市售實例係Sirius M40(碳鏈長度C10-C28,主要為C12-C20,黏度4.3×10-3 Pa.s),購自Silkolene。
可用於本發明之其他烴油包含相對較低分子量烴,包括直鏈飽和烴(如十四烷、十六烷、及十八烷)、環烴(如二辛基環己烷(例如,購自Henkel之CETIOL S)、支鏈烴(例如,購自Exxon Corp.之ISOPAR L及ISOPAR V)。
烴油可以單一物質或摻合物存在於本發明之毛髮油摻合物中。
烴油在本發明之毛髮油摻合物中之總含量宜為毛髮油摻合物總重量的5%至90重量%,較佳20%至80重量%。
在本發明組合物中第一油性組分:烴油之重量比宜為95:5至5:95,較佳90:10至10:90,最佳80:20至20:80。以[椰子油及/或向日葵油及/或杏仁油]與輕質礦物油之摻合物尤佳,其中[椰子油及/或向日葵油及/或杏仁油]:輕質礦物油之重量比係60:40。
其他油性物質亦可以與烴油及甘油脂肪酸酯之組合形式存在於本發明之毛髮油摻合物中。其他適宜油性物質包括其他脂肪酸酯、脂肪醇及脂肪醚。
一般而言,脂肪酸酯、脂肪醇及醚特徵在於具有至少10個碳原子,且包含具有自脂肪酸或醇得到的烴基鏈之酯及醚,例如單羧酸酯、多元醇酯、及二-及三羧酸酯及醚,及具有10至18之碳鏈長度之脂肪醇,例如月桂醇、鯨蠟醇或鯨臘硬脂醇。
實例包括肉豆蔻酸異丙酯、棕櫚酸異丙酯、異壬酸蠟鯨硬脂酯、辛酸蠟鯨硬脂酯、二乙二醇單乙醚油酸酯、二辛醯基醚、辛酸/癸酸丙二醇二酯及以上任意之混合物。
其他油性物質於本發明組合物中之總含量宜為毛髮油摻合物總重量之0.01%至50重量%,較佳1.0%至20重量%。
油摻合物於組合物中的存在量為0.01至10重量%,更佳0.1至2重量%。
適宜調理表面活性劑係選自陽離子型表面活性劑,單獨使用或以混合物的形式使用。實例包括四級氫氧化銨或其鹽,如氯化物。
宜用於本發明之潤髮乳中之適宜陽離子型表面活性劑包括十六烷基三甲基氯化銨、二十二烷基三甲基氯化銨、十六烷基氯化吡啶、四甲基氯化銨、四乙基氯化銨、辛基三甲基氯化銨、十二烷基三甲基氯化銨、十六烷基三甲基氯化銨、辛基二甲基苄基氯化銨、癸基二甲基苄基氯化銨、硬脂醯基二甲基苄基氯化銨、雙十二烷基二甲基氯化銨、雙十八烷基三甲基氯化銨、牛脂三甲基氯化銨、可可三甲基氯化銨、及其對應氫氧化物。其它適宜陽離子型表面活性劑包括具有CTFA名稱Quaternium-5、Quaternium-31及及Quaternium-18之彼等物質。任意前述物質之混合物亦可適宜。特適用於本發明之潤髮乳中之陽離子型表面活性劑係十六烷基三甲基氯化銨,市售(例如)DEHYQUART,購自Henkel。
在本發明之潤髮乳中,陽離子型表面活性劑的含量較佳係組合物的0.01至10重量%,更佳0.05至5重量%,最佳0.1至2重量%。
本發明組合物較佳係專用潤髮組合物且包括少於5重量%陰離子型表面活性劑,較佳少於5重量%清潔表面活性劑,更佳少於2重量%陰離子型表面活性劑,較佳少於2重量%清潔表面活性劑,且最佳不含清潔表面活性劑。
本發明組合物可包含潤髮調配物中常用的任何其它成分。此等其它成分可包括黏度調理劑、防腐劑、著色劑、多元醇(諸如甘油及聚丙二醇)、螯合劑如EDTA、抗氧化劑如BHT(丁羥甲苯)、維生素E乙酸鹽、香料、抗菌劑及防曬劑及脂溶性成分(例如脂肪酸或脂醇)。此等成分中各者係以達到其目的的有效量存在。
一般而言,此等可選成份各係以佔整個組合物至高達約5重量%之含量存在。
較佳地,該組合物包含一種選自脂肪醇及調理性聚矽氧之調理性活性成分。
有利地,本發明之調理劑併入脂肪醇物質。調理組合物中使用脂肪醇物質與陽離子型表面活性劑之組合據信尤為有利,因為其導致了層狀相的形成,讓陽離子型表面活性劑分散於其中。
代表性脂肪醇包括8至22個,更佳為16至20個碳原子。適宜脂肪醇之實例包括鯨蠟醇、硬脂醇及其混合物。此等物質之應用亦有利,因其等有助於本發明組合物之整體調理性。
脂肪醇物質於本發明調理劑中之含量宜佔組合物的0.01至10重量%,較佳0.1至5重量%。陽離子型表面活性劑與脂肪醇之重量比宜為10:1至1:10,較佳4:1至1:8,最佳1:1至1:4。
聚矽氧為本發明之毛髮處理組合物中之極佳成分。特定言之,本發明之調理劑較佳亦包含聚矽氧之乳化粒子,用以提高調理性能。聚矽氧不溶於組合物的水性基質中,且因此以乳化形式存在,聚矽氧以分散粒子存在。
適宜聚矽氧包括聚二有機矽氧烷,特定言之CTFA名稱為二甲基矽酮(dimethicone)之聚二甲基矽氧烷。具有羥基端基之聚二甲基矽氧烷亦適用於本發明組合物,其CTFA名稱為二甲聚矽氧烷醇(dimethiconol)。具有輕度交聯之聚矽氧膠亦適用於本發明組合物,其如WO 96/31188所述。此等材料可賦予毛髮以濃密感、豐盈及定型性、及良好的乾濕調理性。
乳化聚矽氧本身之黏度(非乳液或最終毛髮調理組合物)一般為至少10,000 cst。一般而言,吾人已發現調理性能隨黏度增加而增加。因此,聚矽氧本身之黏度較佳為至少60,000 cst,最佳至少500,000 cst,理想地為至少1,000,000 cst。較佳地,便於調配物,黏度不超過109 cst。
用於本發明調理劑中之乳化聚矽氧一般於組合物中具有小於30之平均聚矽氧粒徑,較佳小於20,更佳小於10微米。吾人已發現減小粒徑一般改良調理性能。更佳地,組合物中乳化聚矽氧之平均聚矽氧粒徑小於2微米,理想地係在0.01至1微米範圍內。平均聚矽氧粒徑0.15微米之聚矽氧乳液一般稱為微乳液。
粒徑可利用購自Malvern Instruments之2600D粒徑分析儀藉由雷射光散射技術測量。
用於本發明之適宜聚矽氧乳液亦係以預乳化形式購得。
適宜預成型乳液之實例包括乳液DC2-1766、DC2-1784、及微乳液DC2-1865及DC2-1870,以上所有均購自Dow Corning。此等皆為二甲聚矽氧烷醇之乳液/微乳液。交聯聚矽氧膠亦係以預乳化形式購得,其有利於調配物。較佳實例為以DC X2-1787購自Dow Corning之物質,其為交聯二甲聚矽氧烷醇膠之乳液。更佳實例為以DC X2-1391購自Dow Corning之物質,其為交聯二甲聚矽氧烷醇膠之微乳液。
本發明調理劑所包含的更佳一類聚矽氧為胺基官能基聚矽氧。「胺基官能基聚矽氧」意為包含至少一第一、第二或第三胺基,或第四銨基團之聚矽氧。
適宜胺基官能基聚矽氧之實例包括:
(i) 具有CTFA名稱「胺基矽油」且通式如下之聚矽氧烷:
HO-[Si(CH3)2-O-]x-[Si(OH)(CH2CH2CH2-NH-CH2CH2NH2)-O-]y-H
其中x及y係取決於聚合物分子量之數值,一般為使分子量介於約5,000至500,000之間的數值。
(ii) 具有如下通式的聚矽氧烷:
R'aG3-a-Si(OSiG2)n-(OSiGbR'2-b)m-O-SiG3-a-R'a
其中:G係選自H、苯基、OH或C1-8烷基,例如甲基;a為0或1至3之整數,較佳為0;b為0或1,較佳為1;m及n為使(m+n)可介於1至2000之間,較佳介於50至150之間的數值;m為1至2000,較佳1至10的數值;n為0至1999,較佳49至149的數值,及R'係式-CqH2qL之單價基團,其中q係2至8的數值及L為選自以下的胺基官能基基團:
-NR"-CH2-CH2-N(R")2
-N(R")2
-N+(R")2A-
-N+H(R")2A-
-N+H2(R")A-
-NR"-CH2-CH2-N+H2(R")A-
其中R"選自H、苯基、苄基、或飽和單價烴基,例如C1-20烷基,及;A為鹵素離子,例如氯或溴。
對應上式之適宜胺基官能基聚矽氧包括如下所述之稱為「三甲基甲矽烷基胺基矽油」之彼等聚矽氧烷,其水不溶性足以用於本發明組合物中:
Si(CH3)3-O-[Si(CH3)2-O-]x-[Si(CH3)(R-NH-CH2CH2NH2)-O-]y-[Si(CH3)3
其中x+y為約50至約500之數值,及其中R為具有2至5個碳原子之伸烷基。較佳地,數值x+y係介於約100至約300之間。
(iii) 具有以下通式的四級聚矽氧聚合物:
{(R1)(R2)(R3)N+CH2CH(OH)CH2O(CH2)3[Si(R4)(R5)-O-]n-Si(R6)(R7)-(CH2)3-O-CH2CH(OH)CH2N+(R8)(R9)(R10)}(X-)2
其中R1及R10可相同或不同且可獨立地選自H、飽和或不飽和長或短鏈烷(烯)基、支鏈烷(烯)基及C5-C8環形系統;R2至R9可相同或不同且可獨立地選自H、直鏈或支鏈低碳數烷(烯)基、及C5-C8環形系統;n為約60至約120範圍內之數值,較佳約80,及X-較佳為醋酸根,但可另為例如鹵素、有機羧酸根、有機磺酸根或類似物。
此類適宜四級聚矽氧聚合物係闡述於EP-A-0 530 974中。
適用於本發明調理劑的胺基官能基聚矽氧一般具有約0.1至約8.0莫耳%的莫耳%胺官能度,較佳約0.1至約5.0莫耳%,最佳約0.1至約2.0莫耳%。一般而言,胺基濃度不應超過約8.0莫耳%,原因在於吾人已發現過高胺濃度不利於總聚矽氧沉積及因此之調理性能。
胺基官能基聚矽氧黏度並非特別關鍵且可宜為約100至約500,000 cst。
適用於本發明之胺基官能基聚矽氧之具體實例為胺基聚矽氧油DC2-8220、DC2-8166、DC2-8466、及DC2-8950-114(均購自Dow Corning),及GE 1149-75,(購自General Electric Silicones)。
胺基官能基聚矽氧油與非離子及/或陽離子型表面活性劑之乳液亦適宜。
適宜之該等預成型乳液於組合物中具有小於30,較佳小於20,更佳小於10微米的平均胺基官能基聚矽氧粒徑。又,我們已發現減小粒徑一般改良調理性能。最佳地,組合物中平均胺基官能基聚矽氧粒徑係小於2微米,理想地,其係介於0.01至1微米之間。平均聚矽氧粒徑0.15微米之聚矽氧乳液一般稱為微乳液。
胺基官能基聚矽氧之預成型乳液亦可購自聚矽氧油供應商,諸如Dow Corning及General Electric。具體實例包括DC929陽離子型乳液、DC939陽離子型乳液、及非離子型乳液DC2-7224、DC2-8467、DC2-8177及DC2-8154(均購自Dow Corning).
用於本發明之四級聚矽氧聚合物實例係物質K3474,購自Goldschmidt。
併入本發明組合物之聚矽氧之總量取決於所需調理程度及所用物質。較佳量為佔整個組合物之0.01至約10重量%,儘管該限值並非絕對值。下限值取決於獲得調理性之最小量且上限值取決於避免毛髮及/或皮膚出現無法接受之油膩感時之最大量。
吾人已發現聚矽氧總量佔整個組合物的0.3至5%,較佳0.5至3重量%為適宜含量。
其他成分可包括黏度調理劑、防腐劑、著色劑、多元醇(諸如甘油及聚丙二醇)、螯合劑如EDTA、抗氧化劑如維生素E乙酸酯、香料、抗菌劑及防曬劑。此等成分各係以達到其目標之有效量存在。一般而言,此等可選成份各係以佔整個組合物至高約5重量%之含量存在。
較佳地,本發明組合物亦含有適於毛髮護理之佐劑。一般而言,此等成分各係以佔整個組合物至高2重量%,較佳至高1重量%之含量存在。
適宜毛髮護理佐劑為:
(i) 天然髮根營養素,諸如胺基酸及糖類。適宜胺基酸實例包括精胺酸、半胱胺酸、穀胺醯胺、穀胺酸、異亮胺酸、亮胺酸、甲硫胺酸、絲胺酸及纈胺酸、及/或其前驅體及衍生物。胺基酸可單獨,以混合物或以肽的形式(如二肽及三肽)添加。胺基酸亦可以蛋白質水解產物(諸如角蛋白或膠原蛋白水解產物)的形式添加。適宜糖類係葡萄糖、右旋糖及果糖。此等物質可單獨或以(例如)水果提取物的形式添加。
(ii) 毛髮纖維生效劑。實例為:神經醯胺,其用於潤濕纖維及維持表皮完整性。神經醯胺可自天然來源中提取獲得,或以合成神經醯胺及假神經醯胺獲得。較佳神經醯胺係Ceramide Ⅱ,購自Quest。神經醯胺混合物亦適宜,諸如Ceramides LS,購自Laboratoires Serobiologiques。
- 游離脂肪酸,用以表皮修復及防止損傷。實例係支鏈脂肪酸(諸如18-甲基花生酸及此系列之其它同系物),直鏈脂肪酸(諸如硬脂酸、肉豆蔻酸及棕櫚酸),及不飽和脂肪酸(諸如油酸、亞油酸、亞麻酸及花生四烯酸)。較佳脂肪酸係油酸。該脂肪酸可單獨,以混合物,或以(例如)羊毛脂提取物得到之摻合物形式添加。
亦可用以上活性成分之任意混合物。
較佳地,該組合物係漂淨型調理組合物。
本發明藉由以下實例進行進一步闡述,其中所有百分比為基於總重量之重量比,除非另說明。
以下調配物係藉由標準製程製得。調配物1為本發明調配物而調配物A及B為對比調配物。
在一盲性單一試驗中,要求使用者在如實例1之調配物一周使用三次並持續兩周後比較毛髮重量。
結果顯示如實例1之組合物比對比組效果更佳。
在頭兩盒子上,調配物1亦優於A與B,其意指標記頭兩盒子(即,4與5)的消費者之絕大部分為認為實例1超A與B者。
Claims (6)
- 一種包含陽離子型表面活性劑及油摻合物的潤髮組合物,該摻合物包括:(i)佔該油摻合物總重量之10%至95重量%之第一油性組分,其係選自椰子油、向日葵油、杏仁油及其等混合物,及(ii)佔該油摻合物總重量之5%至90重量%之第二油性組分,其為平均碳鏈長度小於20個碳原子之一或多種烴油,其中該油摻合物於組合物中的存在量為0.1至2重量%。
- 如請求項1之組合物,其中該第一油性組分之總含量係佔該油摻合物總重量之20%至80重量%。
- 如請求項1或2之組合物,其中該烴油係輕質礦物油。
- 如請求項1或2之組合物,其中該烴油之總含量係佔該油摻合物總重量之20%至80重量%。
- 如請求項1或2之組合物,其中第一油性組分:烴油重量比係90:10至10:90。
- 如請求項1或2之組合物,其中第一油性組分:烴油重量比係80:20至20:80。
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| JP2017523145A (ja) * | 2014-06-16 | 2017-08-17 | ザ プロクター アンド ギャンブル カンパニー | 濃縮コンディショナーを用いて毛髪を処理する方法 |
| FR3113459B1 (fr) * | 2020-08-18 | 2022-09-23 | Oreal | Compositions aerosolisees, systemes, necessaires, et procedes pour substrats keratineux |
| WO2022005811A1 (en) * | 2020-06-29 | 2022-01-06 | L'oreal | Aerosolized compositions, systems, kits, and methods for keratinous substrates |
| JP2025539952A (ja) | 2022-12-19 | 2025-12-10 | ユニリーバー・アイピー・ホールディングス・ベスローテン・ヴェンノーツハップ | コンディショニング組成物 |
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| CH272709A (fr) * | 1950-08-22 | 1950-12-31 | Tempia Caliera Pierre | Produit pour les soins des poils. |
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| GB9507130D0 (en) | 1995-04-06 | 1995-05-31 | Unilever Plc | Hair treatment composition |
| BR9610319A (pt) * | 1995-09-01 | 1999-07-06 | Procter & Gamble | Xampus para modelar o cabelo que contêm óleo orgânico |
| US5935561A (en) * | 1996-03-27 | 1999-08-10 | Procter & Gamble Company | Conditioning shampoo compositions containing select hair conditioning agents |
| US6235275B1 (en) * | 1999-06-25 | 2001-05-22 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Water-in-oil hair conditioner with lamellar dispersion in water phase |
| GB0014426D0 (en) * | 2000-06-13 | 2000-08-09 | Unilever Plc | Hair oils |
| US6939537B2 (en) * | 2001-03-12 | 2005-09-06 | San-Ei Kagaku Co., Ltd. | Composition for blending to hair treating agents and a hair treating agent |
| GB0210936D0 (en) * | 2002-05-13 | 2002-06-19 | Unilever Plc | Hair conditioning compositions |
| US20050069508A1 (en) * | 2003-08-06 | 2005-03-31 | Karl Pays | Cosmetic composition comprising a dispersion of at least one wax in at least one volatile oil |
| US20050069516A1 (en) * | 2003-09-30 | 2005-03-31 | Sidney Hornby | Hair conditioning products |
| US8709453B2 (en) * | 2004-06-21 | 2014-04-29 | Daniel S. Cap | Cosmetic product including vegetable oil blend |
| FR2873573B1 (fr) | 2004-08-02 | 2006-11-17 | Oreal | Emulsion eau-dans-huile comprenant une huile non-volatile non-siliconee, un tensioactif cationique, une polyolefine a partie's) polaire(s), et un alkylmonoglycoside ou alkylpolyglycoside |
| FR2878421B1 (fr) * | 2004-11-29 | 2008-10-31 | Michel Aude | Barbecue a double foyers verticaux securise |
| US20060127345A1 (en) * | 2004-12-10 | 2006-06-15 | Hilvert Jennifer E | Conditioning shampoo containing stabilized silicone particles |
| MX2007007736A (es) * | 2004-12-23 | 2007-08-14 | Unilever Nv | Microemulsiones agua-en-aceite para tratamiento de cabello. |
| MX2007007728A (es) * | 2004-12-23 | 2007-08-14 | Unilever Nv | Microemulsiones agua-en-aceite para tratamiento de cabello. |
| EP1827355B1 (en) * | 2004-12-23 | 2008-10-15 | Unilever Plc | Gelled water-in-oil microemulsions for hair treatment |
| MX2007007747A (es) * | 2004-12-23 | 2007-08-14 | Unilever Nv | Emulsiones agua-en-aceite para tratamiento de cabello. |
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| TWI418368B (zh) | 2006-08-23 | 2013-12-11 | 花王股份有限公司 | 水性毛髮化粧料 |
| JP5189807B2 (ja) * | 2006-08-23 | 2013-04-24 | 花王株式会社 | 水性毛髪化粧料 |
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| BR112013001852A2 (pt) | 2016-05-31 |
| MX2013002047A (es) | 2013-03-22 |
| EP2605743B1 (en) | 2015-05-20 |
| JP2013534230A (ja) | 2013-09-02 |
| ZA201300571B (en) | 2014-03-26 |
| WO2012022516A3 (en) | 2012-08-30 |
| WO2012022516A2 (en) | 2012-02-23 |
| US20130189213A1 (en) | 2013-07-25 |
| TW201208714A (en) | 2012-03-01 |
| PH12013500306A1 (en) | 2013-03-25 |
| CN103068361A (zh) | 2013-04-24 |
| EA201390261A1 (ru) | 2013-06-28 |
| EA023027B1 (ru) | 2016-04-29 |
| EP2605743A2 (en) | 2013-06-26 |
| EA023027B9 (ru) | 2016-09-30 |
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