CN1089580C - 抗菌头发处理组合物 - Google Patents

抗菌头发处理组合物 Download PDF

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CN1089580C
CN1089580C CN96196742A CN96196742A CN1089580C CN 1089580 C CN1089580 C CN 1089580C CN 96196742 A CN96196742 A CN 96196742A CN 96196742 A CN96196742 A CN 96196742A CN 1089580 C CN1089580 C CN 1089580C
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P·A·鲍瑟尔
J·D·哈古伊
A·M·慕累
R·L·B·谭怀克
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Abstract

本发明提供了局部用于人体头发以处理例如头皮屑的抗菌头发处理组合物,该组合物含有:(a)至少一种表面活性剂;(b)细颗粒的不溶性颗粒状金属羟基吡啶硫酮,其中至少约90%(重量)的颗粒粒度为5微米或更低;以及(c)所述细颗粒的聚合水溶性阳离子沉积助剂。该组合物具有好的机械稳定性、光学性质和去头屑作用。

Description

抗菌头发处理组合物
发明领域
本发明涉及抗菌头发处理组合物,该组合物局部用于人体头发以处理例如头皮屑。具体地说,本发明涉及含水头发处理组合物,其包含表面活性剂、具有特定粒度分布的水不溶性抗菌颗粒和增强组合物中的抗菌颗粒在头发和/或头皮上沉积和滞留的阳离子聚合物。
背景和现有技术
不溶性颗粒状金属羟基吡啶硫酮是已知抗菌剂,它们可以掺入抗菌组合物例如去头屑洗发香波和调理剂中。其中普遍使用了锌盐(下文称作ZnPTO)。通常,分散的ZnPTO颗粒悬浮在组合物中,然后将组合物用在头发上使ZnPTO沉积在头发和头皮上。
该组合物存在的问题是难以得到含有ZnPTO的稳定分散液,因为ZnPTO的密度会导致其在贮藏过程中分离。迄今为止,防止ZnPTO颗粒分离所采取的步骤包括将配方基质限制为高粘度的乳液或凝胶,例如掺入增稠剂或增量剂如粘土或珠光剂以得到适于该系统的结构粘度,并防止ZnPTO沉降。这种方法对于香波组合物来说经常是不切实际的,并会得到浑浊、不美观的产物。
EP-A-0173259描述了为何该细颗粒ZnPTO的稳定性问题是特别尖锐的,据说细颗粒ZnPTO对分散液的液体基质条件特别敏感,并且在电解质如盐、香波表面活性剂和阳离子聚合物存在下趋于凝集。该参考文献公开了用特定的分散剂稳定在水中的细颗粒ZnPTO的方法,所述分散剂包括部分季铵化的羟烷基纤维素衍生物、或者特定类型的掺有至少一种无机盐的共聚季铵化阳离子聚合物。该参考文献仅仅讨论了悬浮液的稳定性,而没有涉及在使用过程中ZnPTO活性成分有效地沉积在头发上的问题。
理所当然,将ZnPTO颗粒掺入头发处理组合物中时,可得到的去头屑作用总是受到限制,这是由于该颗粒在所需部位例如头发和/或头皮上的沉积量少,也就是说大部分颗粒仍然悬浮在组合物中,并且在从头发上淋洗该组合物时被洗掉。
EP-A-136914描述了含有ZnPTO的去头屑护发组合物,该组合物增加了ZnPTO在头皮上的沉积。据说,这首先是由于使用了较大粒度的附聚物,该附聚物中至少20%的粒度至少为5微米,其次是由于在该组合物中不存在“影响沉积的聚合物和粘土型悬浮剂”。
然而,该方法存在的问题是,使用ZnPTO的大附聚物会导致难以配制美观的产品。而且,由于该附聚物以粘性大块的形式沉积在头发上,所以让使用者感觉不好。结果是沉积不均匀,并且头发对活性物质的生物利用率下降,导致丧失去头屑作用。
US 3580853(Parran)描述了洗涤剂组合物,例如香波组合物,该组合物含有阴离子表面活性剂、水不溶性颗粒和阳离子聚合物。在该专利所述的洗涤剂组合物中,阳离子聚合物是水溶性含氮阳离子聚合物、特别是季氮取代的纤维素醚衍生物。显然,由于存在阴离子表面活性剂与阳离子聚合物的配合物(该配合物一经稀释洗涤剂组合物即形成),该水不溶性颗粒的沉积作用加强了。在EP 93601中描述了洗涤组合物,该组合物含有阴离子表面活性剂、水不溶性颗粒物质和水溶性阳离子聚合物,该阳离子聚合物为非纤维素阳离子聚合物。
无论US 3580853还是EP 93601都没有涉及有关所含颗粒物质的性质或粒度的具体指导,该物质可以是抗菌剂例如ZnPTO,并且可以具有的颗粒直径范围是约0.2至约50微米。
WO-A-9502389公开了头发清洗组合物,该组合物含有表面活性剂、聚合阳离子试剂和ZnPTO。根据平均粒度描述ZnPTO颗粒,平均粒度为高达20微米。
目前发现,通过使用细颗粒的不溶性颗粒状金属羟基吡啶硫酮、并结合使用沉积助剂,可以得到具有好的机械稳定性和极好的去头屑能力的抗菌头发处理组合物。
发明概述
因此,本发明一方面提供了抗菌头发处理组合物,该组合物含有:(a)至少一种表面活性剂;(b)细颗粒的不溶性颗粒状金属羟基吡啶硫酮,其中至少约90%(重量)的颗粒粒度为1微米或更低;以及(c)所述细颗粒的聚合水溶性阳离子沉积助剂。详细描述与优选实施方案
不溶性颗粒状金属羟基吡啶硫酮可以用下列通式表示:其中M是多价金属离子,n与M的价态相对应。
M的优选实例包括镁、钡、锶、锌、镉、锡和锆。特别优选的是锌。
细颗粒的金属羟基吡啶硫酮的粒度分布为,其中至少90%的颗粒粒度为1微米或更低。可以认为,这种小的粒度使得抗菌颗粒被释放至毛囊处,从而导致了较好的功效。
在例如EP-A-0173259中描述了制备细颗粒金属羟基吡啶硫酮的各种方法。
掺入本发明组合物中的金属羟基吡啶硫酮的量取决于组合物的类型和所用材料的确切性质。金属羟基吡啶硫酮的优选用量为组合物总重量的约0.001至约5%,更优选的是约0.1至约3%(重量)。
本发明组合物含有至少一种表面活性剂,优选地选自阴离子、阳离子、非离子、两性和两性离子表面活性剂及其混合物。
特别优选的本发明头发处理组合物是香波组合物,其中至少一种表面活性剂提供了清洁作用。清洁用表面活性剂优选选自阴离子、非离子、两性和两性离子表面活性剂及其混合物。
合适的阴离子表面活性剂包括烷基硫酸盐、烷基醚硫酸盐、烷芳基磺酸盐、链烷醇酰羟乙磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷醇(alkoyl)肌氨酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐和α-烯烃磺酸盐,特别是其钠、镁、铵盐和一-、二-及三乙醇胺盐。烷基和酰基通常含有8-18个碳原子,并且可以是不饱和的。烷基醚硫酸盐、烷基醚磺酸盐和烷基醚羧酸盐的每个分子中可以含有1-10个环氧乙烷或环氧丙烷单元,优选每分子含有2-3个环氧乙烷单元。
合适的阴离子表面活性剂的实例包括油基琥珀酸钠、十二烷基磺基琥珀酸铵、十二烷基硫酸铵、十二烷基苯磺酸钠、十二烷基苯磺酸三乙醇胺、椰子酰基(cocoyl)羟乙磺酸钠、月桂酰基羟乙磺酸钠和N-十二烷基肌氨酸钠。最优选的阴离子表面活性剂是十二烷基硫酸钠、十二烷基硫酸三乙醇胺、单十二烷基磷酸三乙醇胺、十二烷基醚硫酸钠1EO、2EO和3EO、十二烷基硫酸铵和十二烷基醚硫酸铵1EO、2EO和3EO。
适用于本发明组合物的非离子表面活性剂包括脂族(C8-C18)直链或支链伯或仲醇或酚与烯化氧(通常是环氧乙烷并且一般具有6-30个环氧乙烷基团)的缩合产物。其他合适的非离子表面活性剂包括一-或二-烷基链烷醇酰胺,其实例包括椰子一-或二-乙醇酰胺和椰子一-异丙醇酰胺。
适用于本发明组合物的两性和两性离子表面活性剂包括烷基胺氧化物、烷基甜菜碱、烷基酰氨基丙基甜菜碱、烷基磺基甜菜碱(磺基甜菜碱)、烷基甘氨酸盐、烷基羧基甘氨酸盐、烷基两性丙酸盐、烷基两性甘氨酸盐、烷基酰氨基丙基羟基磺基甜菜碱、酰基牛磺酸盐和酰基谷氨酸盐,其中烷基和酰基具有8-19个碳原子。实例包括十二烷基胺氧化物、椰子二甲基磺基丙基甜菜碱,优选十二烷基甜菜碱、椰子酰氨基丙基甜菜碱和椰子两性丙酸钠。
表面活性剂在本发明香波组合物中的含量为0.1至50%(重量),优选为0.5至30%(重量)。
本发明的头发处理组合物也可以是头发调理组合物,其中优选含有一种或多种阳离子表面活性剂。特别优选使用阳离子表面活性剂,因为这些成分能够为头发提供调理作用。
阳离子表面活性剂的实例包括:季铵氢氧化物,例如四甲基氢氧化铵、烷基三甲基氢氧化铵(其中烷基具有约8至约22个碳原子),例如辛基三甲基氢氧化铵、十二烷基三甲基氢氧化铵、十六烷基三甲基氢氧化铵、十六烷基三甲基氢氧化铵、辛基二甲基苄基氢氧化铵、癸基二甲基苄基氢氧化铵、硬脂基二甲基苄基氢氧化铵、双十二烷基二甲基氢氧化铵、双十八烷基二甲基氢氧化铵、牛脂三甲基氢氧化铵、椰子三甲基氢氧化铵和其相应的盐,例如氯化物;十六烷基氢氧化吡啶或其盐,例如氯化物季铵-5季铵-31季铵-18及其混合物。
在本发明的头发调理组合物中,阳离子表面活性剂的含量优选为组合物重量的0.01-10%,更优选为0.05-5%,最优选为0.1-2%。
本发明的头发处理组合物也可以含有一种或多种本领域公知的调理剂。调理剂可以包括聚硅氧烷、蛋白水解产物、季铵化的蛋白水解产物以及本领域已知的具有所需头发调理性质的其他物质。
聚硅氧烷是最优选的调理剂。
合适的聚硅氧烷包括挥发性和非挥发性聚硅氧烷,例如聚烷基硅氧烷、聚烷芳基硅氧烷、硅氧烷胶和硅氧烷树脂、环甲聚硅氧烷、氨基官能的聚硅氧烷、季聚硅氧烷及其混合物。硅油是特别优选的头发调理剂。聚硅氧烷可以是溶液形式的低粘度的油,其中可以含有高粘度的油或胶。或者,高粘度的物质可以是在水中的乳液形式。乳液可以由高粘度的油或在低粘度油中的胶的溶液形成。油相的粒度可以在30纳米至20微米的平均粒度范围内。
可以使用的硅油是平均粒度小于20微米的聚二甲基硅氧烷,优选平均粒度小于2微米。小的粒度能够使同样浓度的聚硅氧烷在组合物中有更均匀的聚硅氧烷调理剂分布。优选的是,使用粘度在1-20兆cst范围内的聚硅氧烷。优选将聚硅氧烷乳液聚合,因为这样可以使聚硅氧烷的粘度非常高而更易于加工。聚硅氧烷可以是交联的。
合适的蛋白水解产物包括十二烷基dimonium羟基丙氨基水解的动物蛋白(以商品名LAMEQUAT L出售),和含有带硫氨基酸的水解角蛋白(以商品名CROQUAT WKP出售)。
本发明的头发处理组合物含有细颗粒的聚合水溶性阳离子沉积助剂。术语“沉积助剂”是指可促进金属羟基吡啶硫酮细致颗粒在所需部位,即头发和/或头皮上沉积的试剂。
沉积助剂的含量通常为0.01-5%(重量),优选为约0.5-1%(重量),更优选为约0.08%至约0.5%(重量)。
优选的沉积助剂的阳离子电荷密度(阳离子电荷密度被定义为含1个电荷的聚合物单体单元的分子量的倒数)至少为0.1meq/g,优选大于0.8或更高。阳离子电荷密度不应超过4meq/g,优选小于3,更优选小于2meq/g。电荷密度可以采用电导分析进行测量,并且在使用时所需的pH下应在上述范围内,所述pH值一般为约3-9,优选4-8。
优选的沉积助剂是瓜尔胶的阳离子衍生物和阳离子聚丙烯酰胺。
合适的瓜尔胶的阳离子衍生物是JAGUAR C13S(其阳离子基团取代的程度低并且粘度高),JAGUAR C15(取代程度适中并且粘度低),JAGUAR C17(取代程度高并且粘度高),JAGUAR C16(羟丙基化的阳离子瓜尔胶衍生物,取代基和阳离子季铵基团的含量低),和JAGUAR 162(是取代程度低的高透明、中等粘度的瓜尔胶)。
特别优选的沉积助剂是Jaguar C13S,其阳离子电荷密度为0.8meq/g。其他特别适合的物质包括Jaguar C15、Jaguar C17和JaguarC16以及Jaguar 162。
在WO 95/22311中描述了合适的阳离子聚丙烯酰胺。
该组合物可以进一步含有0.1-5%的悬浮剂。实例是聚丙烯酸、丙烯酸的交联聚合物、丙烯酸与疏水单体的共聚物、含单体的羧酸与丙烯酸酯的共聚物、丙烯酸与丙烯酸酯的交联共聚物、杂多糖胶和晶形长链酰基衍生物。长链酰基衍生物优选选自乙二醇硬脂酸酯、具有16-22个碳原子的脂肪酸的链烷醇酰胺及其混合物。市售的聚丙烯酸有Carbopol420、Carbopol 488或Carbopol 493。也可以使用与多功能试剂交联的丙烯酸聚合物,市售的该聚合物有Carbopol 910、Carbopol 934、Carbopol 940、Carbopol 941和Carbopol 980。含单体的羧酸与丙烯酸酯的共聚物的实例是Carbopol 1342。所有的Carbopol物质均是由Goodrich提供的,Carbopol是商标。另一适合的悬浮剂是二氢化的牛酯邻苯二甲酸酰胺(由Stepan Chemical Co.以商标Stepan TAB-2出售)。
合适的丙烯酸与丙烯酸酯的交联聚合物是Pemulen TR1或PemulenTR2。合适的杂多糖胶是黄原胶,例如以Kelzan mu出售的。
优选的掺入本发明头发处理组合物中的另一成分是脂肪醇材料。这些物质特别优选用于本发明的调理组合物,尤其是含有一种或多种阳离子表面活性剂材料的调理组合物。据信,脂肪醇材料与阳离子表面活性剂结合用于调理组合物是特别有利的,因为这样可以形成层状相,其中分散有阳离子表面活性剂。
优选的脂肪醇含有8-22个碳原子,更优选16-20个碳原子。优选的脂肪醇的实例是鲸蜡醇和硬脂醇。这些物质的应用也是有利的,因为它们对本发明组合物的总体调理性质有贡献。
脂肪醇材料的含量通常占组合物重量的0.01-10%,优选0.1-5%。阳离子表面活性剂与脂肪醇的重量比优选为10∶1至1∶10,更优选为4∶1至1∶8,最优选1∶1至1∶4。
本发明的头发处理组合物优选是水基的。该组合物适当地包含占组合物总重量约20%至约99%的水。
本发明的组合物优选为可淋洗的组合物,即适于将其施用在头发和/或头皮上,使其在头发和/或头皮上保留适当的时间,然后用水淋洗掉。因此,香波是特别优选的本发明组合物的产品形式。
根据所用组合物的类型,在本发明组合物中可以包括通常掺入头发处理制剂中的一种或多种附加组分。这种附加组分包括遮光剂如聚乙二醇二硬脂酸酯和乙二醇硬脂酸酯、聚合物晶格、附加的抗菌剂、泡沫促进剂、香料、着色剂、防腐剂、粘度调节剂、蛋白质、聚合物、缓冲剂或pH调节剂、润湿剂、草药或其他植物提取物以及其他天然成分。
通过下列非限制性实施例对本发明做进一步说明。
实施例1&2
制备本发明的洗发香波组合物,该组合物含有细颗粒的金属羟基吡啶硫酮和沉积聚合物。两个组合物的配方如下。
            成分                          重量%
                                      实施例1  实施例2十二烷基醚硫酸钠2EO(28%活性物)              50      50椰子酰氨基丙基甜菜碱(30%活性物)             6.7     6.7Jaguar C13S                                  0.1     0.1羟基吡啶硫酮锌,细粒度(48%活性物)           2.08    2.08CARBOPOL 980                                 0.4     0.4乙二醇一硬脂酸酯                             3.0     3.0二甲基聚硅氧烷(60%含水乳液)                 3.34    1.7七水合硫酸锌                                 0.1     0.1维生素E乙酸酯                                0.05    0.05防腐剂,色料,香料                           -----适量------水                                             --至100%--
两种香波均对头发产生了极好的去头屑作用,并且在室温和45℃两种温度下贮存3个月后均无肉眼可见的分离,是稳定的。
实施例3
制备一系列组合物,以测定本发明制剂与不含沉积聚合物的对照制剂相比羟基吡啶硫酮锌在皮肤上的沉积量,并用于证明降低羟基吡啶硫酮锌粒度的作用。
组合物(重量%)     A     B     C
成分
十二烷基醚硫酸钠     14     14     14
椰子酰氨基丙基甜菜碱     2     2     2
二甲基聚硅氧烷乳液(1)     -     1     1
羟基吡啶硫酮锌(2)     -     -     1
羟基吡啶硫酮锌(3)     1     1     -
聚羧乙烯制剂     -     0.6     0.6
瓜耳羟丙基氯化三铵     -     0.1     0.1
Veegum(4)     0.6     -     -
(1)X2-1766胶,由Dow Corning提供(2)羟基吡啶硫酮锌,由Olin提供,90%的粒度小于1微米(3)羟基吡啶硫酮锌,由Olin提供,90%的粒度小于5微米(4)胶体硅酸镁铝,由R.T.Vanderbilt提供
在皮肤上对上述组合物A至C的每一个进行标准沉积实验,并采用X线荧光技术测量每种情况下羟基吡啶硫酮锌的沉积量。所用方法描述如下:评审对象的选择:
从不患有任何皮肤病如牛皮癣或湿疹的志愿者中招募10名评审对象(5男5女;年龄18-60岁)。实验方法:
用圆珠笔在每一前臂的内侧画六个直径25毫米的圆圈。施用产品之前,将每一前臂的一个圈用J-透明胶带粘住。在胶带粘贴的部位用橡胶压机压30秒。用此初始的胶带测定基础读数。a)校准:
为了进行校准实验,在每个剩余的圈上施用20微升稀释的ZnPTO
(细粒度级*,由Olin提供)并使其干燥。在每一部位施加的最终
ZnPTO的量为0、1、2、5和10微克/平方厘米的ZnPTO。然
后在另一手臂上重复此校准实验。
*(细粒度级:90%ZnPTO颗粒的粒度小于1微米)。b)组合物的施用:
在每一剩余的部位,如下施用每一组合物:
将内径25毫米的聚乙烯量筒置于标记的环上,并在皮肤上压出一个
印。将10倍稀释的100微升组合物(3克组合物用27克蒸馏水稀
释)涂在标记区内,并用玻璃棒搅30秒。然后用注射器,用2×5
毫升蒸馏水直接冲洗涂覆组合物部位的该组合物。
将试验组合物均匀地涂在指定的部位,以使任何偏差减至最小。随
机排列位置后,重复进行同样的实验。
干燥15分钟后,将每个环用J-透明胶带粘住。在每一胶带粘贴的部
位用橡胶压机压30秒。用X线荧光光谱分析法测量胶带上锌的计
数。锌和硫含量的XRF荧光光谱分析
将胶带置于铝环上,并用Philips PW2400波长色散X线荧光光谱仪测量锌和硫。从空白胶带总锌的计数中减去所得到的计数,得到锌的净含量。
结果示于下面表1中:表1
    组合物     沉积的锌(Kcounts/s)
    A     0.23
    B     0.45
    C     0.63
通过对从组合物A和B中分别沉积的锌的量进行比较,显示出具有统计意义的显著差别,置信水平>99%,含有阳离子沉积聚合物的组合物B是有利的。
通过对从组合物B和C中分别沉积的锌的量进行比较,显示出具有统计意义的显著差别,置信水平>99%,含有较小粒度羟基吡啶硫酮锌的组合物C是有利的。

Claims (12)

1.一种抗菌头发处理组合物,该组合物含有:
(a)至少一种表面活性剂,其在组合物中的含量是0.1-50%(重量);
(b)细颗粒的不溶性颗粒状金属羟基吡啶硫酮,其中至少90%(重量)的颗粒粒度为1微米或更低,所述金属羟基吡啶硫酮在组合物中的含量是0.001-5%(重量);以及
(c)所述细颗粒的聚合水溶性阳离子沉积助剂,其在组合物中的含量是0.01-5%(重量)。
2.一种根据权利要求1的组合物,其中金属羟基吡啶硫酮是羟基吡啶硫酮锌。
3.一种根据权利要求1的组合物,其中金属羟基吡啶硫酮在组合物中的含量为0.1至3%(重量)。
4.一种根据权利要求2的组合物,其中金属羟基吡啶硫酮在组合物中的含量为0.1至3%(重量)。
5.一种根据权利要求1的组合物,其中沉积助剂是瓜耳胶的阳离子衍生物或阳离子聚丙烯酰胺。
6.一种根据权利要求2的组合物,其中沉积助剂是瓜耳胶的阳离子衍生物或阳离子聚丙烯酰胺。
7.一种根据权利要求3的组合物,其中沉积助剂是瓜耳胶的阳离子衍生物或阳离子聚丙烯酰胺。
8.一种根据权利要求4的组合物,其中沉积助剂是瓜耳胶的阳离子衍生物或阳离子聚丙烯酰胺。
9.一种根据前述任一权利要求的组合物,其是香波组合物,其中至少一种表面活性剂选自阴离子、非离子、两性和两性离子表面活性剂及其混合物,表面活性剂在组合物中的总含量为0.5至30%(重量)。
10.一种根据权利要求1-8任一项的组合物,还含有选自挥发性和非挥发性聚硅氧烷的调理剂。
11.一种根据权利要求9的组合物,还含有选自挥发性和非挥发性聚硅氧烷的调理剂。
12.根据权利要求1的抗菌头发处理组合物在制备去头屑处理产品中的用途。
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AR003457A1 (es) 1998-08-05
US5723112A (en) 1998-03-03
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CN1195283A (zh) 1998-10-07
ES2164905T3 (es) 2002-03-01
WO1997003637A1 (en) 1997-02-06
DE69616330D1 (de) 2001-11-29
EP0839022B1 (en) 2001-10-24
EP0839022A1 (en) 1998-05-06

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