CN1268047A - 用于个人卫生产品的防腐剂体系 - Google Patents
用于个人卫生产品的防腐剂体系 Download PDFInfo
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- CN1268047A CN1268047A CN98808494A CN98808494A CN1268047A CN 1268047 A CN1268047 A CN 1268047A CN 98808494 A CN98808494 A CN 98808494A CN 98808494 A CN98808494 A CN 98808494A CN 1268047 A CN1268047 A CN 1268047A
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- Prior art keywords
- acid
- application
- anion
- antiseptic
- quaternary ammonium
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Abstract
本发明涉及至少一种季铵化合物和至少一种阴离子防腐剂和/或至少一种α-羟基羧酸的混合物作为人体护理组合物的防腐剂体系的应用,以及一种含重量比为1∶20—100∶1的至少一种季酯化合物(Esterquat)和至少一种水杨酸碱金属盐的防腐剂体系。
Description
本发明涉及人体护理组合物的防腐,更特别涉及护发剂的防腐,其中使用了季铵化合物和阴离子防腐剂和/或α-羟基羧酸。本发明也涉及特定的季铵化合物(所谓的esterquats)和水杨酸钠的混合物以及其作为人体护理组合物防腐剂的应用。
如今人体、特别是头发用化妆品制剂(头发处理组合物)以各种方法来处理。这些处理包括例如用香波和淋浴制剂来清洁身体和头发,用卷发水、染发组合物和美发制剂来进行头发的漂白、染色和成型。
配制成调理剂或润丝的头发处理组合物通常是各种水溶性或脂溶性组分的含水乳液。这种乳液的防腐要保持其性能、特别是长时期贮存后的性能常常是困难的。用于一些人体护理组合物中的季铵化合物确实在这些组合物中有杀微生物的作用,但其本身用来防腐是不足的。
现已发现,如果将至少一种季铵化合物和至少一种阴离子防腐剂和/或至少一种α-羟基羧酸的组合用作防腐剂体系,就可完成人体护理组合物、特别是护发剂非常有效的防腐。这些组分意外的互补作用使之得到了在效果上的协同增加。
因此,本发明涉及下列组分的混合物作为人体护理组合物的防腐剂体系的用途:--至少一种季铵化合物和--至少一种阴离子防腐剂和/或--至少一种α-羟基羧酸。
优选的人体护理组合物是护发剂。在本发明的上下文中,护发剂也包括那些只是想得到头发装饰上的改变的头发处理组合物,例如头发染色剂或长效卷发制剂。
适合的季铵化合物是聚合物质或单体物质。适合于本发明使用的聚合物一般是含有铵基的阳离子聚合物。优选的阳离子聚合物是,例如--可从市场上得到的以Celquat和Polymer JR为商品名的季铵化纤维素衍生物,其中化合物CelquatH 100、CelquatL 200和Polymer JR400是优选的季铵化纤维素衍生物;--含季铵基的聚硅氧烷;--聚合的二甲基二烯丙基铵盐和它们与丙烯酸和甲基丙烯酸的酯和酰胺的共聚物;名为Merquat100(聚二甲基二烯丙基氯化铵)和Merquat550(二甲基二烯丙基氯化铵/丙烯酰胺共聚物)是这类阳离子聚合物之实例;--乙烯基吡咯烷酮与二烷基氨基丙烯酸酯和甲基丙烯酸酯的季铵化衍生物的共聚物,例如用硫酸二乙酯季铵化的乙烯基吡咯烷酮/二甲基氨基甲基丙烯酸酯共聚物;诸如此类的化合物有市场供应,其商品名为Gafquat734和Gafquat755的化合物;--乙烯基吡咯烷酮/氯化甲基咪唑啉鎓(Methoimidazoliniumchlorid)共聚物,其商品供应名为Luviquat;--季铵化的聚乙烯醇和在聚合物主链中含有季氮原子的聚合物,其商名有--polyquaternium 2--polyquaternium 17--polyquaternium 18和--polyquaternium 27
然而使用阳离子表面活性剂一类化合物作为季铵化合物一般是有利的。在这些阳离子表面活性剂中,季铵化合物是优选的。优选的季铵化合物有卤化铵,更特别是氯化铵和溴化铵,诸如烷基三甲基氯化铵、二烷基二甲基氯化铵和三烷基甲基氯化铵,例如鲸蜡基三甲基氯化铵、鲸蜡基三甲基溴化铵、二鲸蜡基二甲基氯化铵、二鲸蜡基二甲基溴化铵、硬脂基三甲基氯化铵、二硬脂基二甲基氯化铵、二月桂基二甲基氯化铵、月桂基二甲基苄基氯化铵和三鲸蜡基甲基氯化铵。
其它的适合季铵化合物有季酯化合物,即所谓“esterquats”,由于它们易于生物降解,所以是优先选择的。为此请参考例如WO91/01295,在此文献中是用脂肪酸在次磷酸的存在下将三乙醇胺进行部分酯化,并在通入空气后将混合物用硫酸二甲酯或环氧乙烷季铵化。在这方面现列举下面的专利作为大量的现有技术的代表:US3,915,867,US 4,370,272,EP-A 0 239 910,EP-A 0 293 955 A2,EP-A0 295 739 EP-A 0 309 052。有关这一内容的综述已经公开在例如:R.Puchta等人,Tens.Surf.Det.,30,186(1993);M.Brock,Tens.Surf.Det.,30,394(1993);以及R.Lagerman等,美国油化学学会会志(J.Am.Oil.Chem.Soc.)71,97(1994)。
Esterquats的一个实例是相应于通式I的季铵化脂肪酸三乙醇胺酯盐:式中R1CO是含总数为6-22个碳原子的酰基,R2和R3各互相独立地代表氢或与R1CO的含义相同,R4是含1-4个碳原子的烷基或是一(CH2CH2O-)qH基,m,n和p共同代表0或1-12的数,q是1-12的数,X-是卤化物离子、烷基硫酸根或烷基磷酸根。
可在本发明中使用的季铵化脂肪酸三乙醇胺酯盐的典型实例有基于己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、异硬脂酸、硬脂酸、油酸、反油酸、花生酸、山嵛酸和芥酸的产品,以及它们的工业混合物,例如得自天然油脂的加压水解产品。工业C12-18椰油脂肪酸和特别是部分氢化的C16-18牛油或棕榈油脂肪酸和富含反油酸的C16-C18脂肪酸馏分是优选使用的。
生产相应于通式I的季铵化脂肪酸三乙醇胺酯盐时,脂肪酸和三乙醇胺的摩尔比可用1.1∶1-3∶1。考虑到esterquats的应用性能,用1.2∶1-2.2∶1、优选1.5∶1-1.9∶1的脂肪酸和三乙醇胺摩尔比被证明是特别有利的。优选的相应于通式I的季铵化脂肪酸三乙醇胺酯盐是单-、二-和三酯的工业混合物,平均酯化度为1.5-1.9,且衍生自工业C16/18牛油或棕榈油脂肪酸(碘值为0-40)。
从应用性能观点出发,使用这样的相应于通式I的季铵化脂肪酸三乙醇胺酯盐是特别有利的,其中的R1CO是含16-18个碳原子的酰基、R2的含义与R1CO相同、R3是氢、R4是甲基、m,n和p代表O、X-代表甲基硫酸根。
除了相应于通式I的季铵化的脂肪酸三乙醇胺酯盐外,其它适合的esterquats有相应于通式II的脂肪酸与二乙醇烷基胺的季铵化的酯盐:式中R5CO是含总数为6-22个碳原子的酰基,R6是氢或含义与R5CO同,R7和R8是互相独立的含1-4个碳原子的烷基,m和n共同代表0或1-12的数,X-是卤化物离子、烷基硫酸根或烷基磷酸根。
最后,适合的另一组esterquats有相应于式III的脂肪酸与1,2-二羟丙基二烷基胺的季铵化酯盐:式中R9CO是含总数为6-22个碳原子的酰基,R10是氢或含义与R9CO同,R11、R12和R13是互相独立的含1-4个碳原子的烷基,m和n共同代表0或1-12的数,X-是卤化物离子、烷基硫酸根或烷基磷酸根。
就优选的脂肪酸和最佳酯化度的选择而言,对式I提及的实例也适用于相应于式II和式III的esterquats。Esterquats通常是以50-90%(重量)的醇溶液销售的,如需要可方便地用水稀释。
虽然相应于式I-III的化合物是单独的化合物,但一般说来这些化合物的混合物也可用于本发明的目的。通过生产过程得到的组成变化的工业混合物也是可以使用的。如果季铵化合物不是esterquats,根据本发明,优选的季铵化合物应为鲸蜡基三甲基溴化铵或鲸蜡基三甲基氯化铵或这两种化合物的混合物。
有机酸的碱金属盐或一种或多种有机酸的碱金属盐混合物优选被用作阴离子防腐剂。可以用作抗微生物防腐剂的有机酸盐(例如在食品和/或化妆品中防腐使用的)是为本发明目的所优选使用的。
这些盐包括例如甲酸盐、乙酸盐、丙酸盐、乳酸盐、山梨酸盐、苯甲酸盐、水杨酸盐或乙酰丙酸盐或两种或多种这些盐的混合物。
所述的酸与锂、钠、钾、铷或铯的任何盐原则上都可以用作碱金属盐。但所述酸的钠盐或钾盐是优选的,而钠盐又是特别优选的。
在阴离子防腐剂中,水杨酸碱金属盐、更特别是水杨酸钠盐是优选的。
作为至少一种阴离子防腐剂的替代或补充,根据本发明可以使用至少一种α-羟基羧酸。优选的α-羟基羧酸是乳酸、酒石酸、苹果酸和柠檬酸。乳酸、苹果酸和酒石酸是特别优先选择的。当然α-羟基羧酸也可以其生理相容盐的形式使用,更特别是它们的碱金属、碱土金属和铝盐。
根据本发明,使用季铵化合物、阴离子防腐剂和α-羟基羧酸的组合作为防腐剂体系是有利的。如果使用二元混合物,用季铵化合物与一阴离子溶剂组合是有利的。
季铵化合物与阴离子防腐剂或α-羟基羧酸的重量比一般约为1∶20-100∶1。
季铵化合物的一般使用浓度约为0.1-10%(重量),基于本发明组合物总体计算。优选的量约为0.5-7%(重量),特别优选0.8-5%(重量)。
阴离子防腐剂的使用浓度一般约为0.1-2%(重量),优选0.5-1%,基于含阴离子防腐剂的组合物总体计算。
α-羟基羧酸的优选用量约为0.1-0.5%(重量),基于制剂总体计算。
在某些国家,上述限定可受法定的上限所限制。
鉴于所用防腐剂体系的易生物降解性,使用季酯化合物作为季铵化合物是有利的。在本发明的上下文中,esterquats应理解为上述相应于通式I、II和III的季铵化合物。
Esterquats与水杨酸碱金属盐结合使用是优选的,更优选与水杨酸钠结合使用。
因此,本发明涉及含重量比约为1∶20-100∶1的至少一种季酯化合物(esterquat)和至少一种水杨酸碱金属盐作为活性组分的防腐剂体系。
优选用作水杨酸碱金属盐的是水杨酸钠盐。
本发明也涉及上述的防腐剂体系,其中是用二硬脂酰基乙基羟乙基甲硫酸铵(INCI名:DistearoylethylHydroxyethylmoniummethosulfate,例如以DehyquartF 75商品名出售,制造商为Henkel KGaA,Düsseldorf)作为季酯化合物。
本发明也涉及含重量比为1∶20-100∶1的至少一种季酯化合物(esterquat)和至少一种水杨酸碱金属盐作为活性成分的防腐剂体系在人体护理组合物中的应用。
上述适合作为防腐剂体系的季铵化合物和阴离子防腐剂的组合可用于许多人体护理组合物中,更特别是护发剂。
它们包括例如下面的护发剂:香波,润丝,调节剂,发尖液(Haarspitzenfluids),染发剂,发胶和卷发液。
因此,最后的制剂除了防腐的活性组分组合外还含有其它的一些化合物,例如有清洁、调节、着色或成型效果的化合物。
如果本发明的防腐剂体系用于例如香波时,除了防腐的活性物质组合外一般还有至少一种阴离子、两性离子、两性或非离子表面活性剂。
适合于人体使用的任何阴离子表面活性剂在原则上是可与本发明的防腐活性物质组合(防腐剂体系)一起使用的,只要它们不是与防腐剂体系中的阳离子组分不相容的。某些化合物的这种不相容性是否存在对专业技术人员来说是已知的,或可由简单的试验所确定。所说类型的阴离子表面活性剂是以赋予水溶性的阴离子基团诸如至少一个羧酸根、硫酸根、磺酸根、或磷酸根基团和至少一个烃基、优选至少一个含约10-22个碳原子的亲油烷基为特征的。此外,在分子中可存在乙二醇、聚乙二醇醚基、酯基、醚、酰胺和羟基。
适合的阴离子表面活性剂例如有:--含10-22个碳原子的直链脂肪酸(皂),--相应于式R14O(CH2CH2O)xCH2COOH(其中R14是含10-22个碳原子的直链烷基,x=0或1-16)的醚羧酸,--相应于式[R15NH(CH2CH2O)nCH2COO]mZ(式中R15是含2-29个碳原子的直链或支化的饱和或不饱和酰基,n是1-10的整数,m是1或2的数,Z是碱金属或碱土金属阳离子)的酰胺醚羧酸盐,--酰基中含10-18个碳原子的酰基肌氨酸化合物,酰基中含10-18个碳原子的酰基牛磺酸盐,--酰基中含10-18个碳原子的酰基羟乙基磺酸盐,--烷基中含8-18个碳原子的磺基琥珀酸单酯和二酯和烷基中含8-18个碳原子和含1-6个乙氧基的磺基琥珀酸单烷基聚氧乙基酯,--含12-18个碳原子的直链烷磺酸盐,--含12-18个碳原子的直链α-烯烃磺酸盐,--含12-18个碳原子的脂肪酸的α-磺基脂肪酸甲基,相应于式R16(CH2CH2O)xSO3H(式中R16优选含10-18个碳原子的直链烷基,x=0或1-12)的烷基硫酸盐和烷基聚乙二醇醚硫酸盐,--DE-A 37 23 354中的硫酸化羟烷基聚乙二醇醚和/或羟烷基聚丙二醇醚,--DE-A 39 26 344中的含12-24个碳原子和1-6个双键的不饱和脂肪酸的磺酸盐,--酒石酸和柠檬酸与醇的酯,该醇代表约2-15分子的环氧乙烷和/或环氧丙烷在8-22个碳原子的脂肪醇上的加合产物,分别以碱金属、碱土金属和/或铵盐的形式,优选的是它们的钠、钾、镁盐和/或铵盐以及烷醇基中含2或3个碳原子的单-、二-和/或三烷醇铵盐。
优选的阴离子表面活性剂有烷基硫酸盐、烷基聚乙二醇醚硫酸盐和烷基含10-18个碳原子和分子中含至多12个乙二醇醚基的醚羧酸,和烷基中含8-18个碳原子的磺基琥珀酸单烷基酯和二烷基酯以及烷基中含8-18个碳原子和含1-6个乙氧基的磺基琥珀酸单烷基聚乙氧基酯。
除所述的阴离子表面活性剂外,非离子表面活性剂也可存在于本发明含防腐剂体系的组合物中。
非离子表面活性剂含有例如多元醇基、聚亚烷基二醇醚基或多元醇与聚二醇醚基的组合作为它们的亲水基团。相应的化合物有例如:--2-30摩尔环氧乙烷和/或0-5摩尔环氧丙烷在含8-22个碳原子的直链脂肪醇或含12-22个碳原子的脂肪酸或烷基中含8-15个碳原子的烷基苯酚上的加合产物,--1-30摩尔环氧乙烷与甘油加合物的C12-22脂肪酸单酯和二酯,--C8-22烷基单-和低聚苷和其乙氧基化的类似物,--5-60摩尔环氧乙烷在蓖麻油和/或氢化蓖麻油上的加合产物。
在本发明的另一优选具体实施方案中,相应于通式R17O(-Z)X的烷基聚苷是被用作非离子表面活性剂的。在这些化合物中R17含6-22个碳原子,并且可以是直链或支化的。直链伯烷基或2-位甲基支化的烷基是优选的。烷基R17例如是1-辛基、1-癸基、1-月桂基、1-肉豆蔻基、1-鲸蜡基和1-硬脂基。1-辛基、1-癸基、1-月桂基和1-肉豆蔻基是特别优选的。当用所谓的羰基合成醇作为原料时,烷基链中含奇数碳原子的化合物是占优势的。
在本发明组合物中有用的烷基聚苷可含例如仅一种特定的烷基R17。但是烷基聚苷通常是用天然油、脂或矿物油制备的。在这种情况中,R17是对应于原料化合物的混合物或那些化合物的特殊加工的混合物。特别优选的烷基聚苷是其中R17主要是代表下列基团的那些烷基聚苷:--C8和C10烷基,--C12和C14烷基,--C8-C16烷基,--C12-C16烷基。
任何单糖或低聚糖都可用作糖单元Z。通常使用的是含5或6个碳原子的糖以及相应的低聚糖。这样的糖有例如葡萄糖、果糖、半乳糖、***糖、核糖、木糖、来苏糖、阿洛糖、阿卓糖、甘露糖、古洛糖、艾杜糖、塔罗糖和蔗糖。优选的糖单元是葡萄糖、果糖、半乳糖、***糖和蔗糖。特别优选的是葡萄糖。
适合于本发明使用的烷基聚苷含有平均1.1-5个糖单元。其中x值为1.1-1.6的烷基聚苷是优选的。x值为1.1-1.4的烷基聚苷是最特别优选的。
所述烷基聚苷的烷氧基化同系物也可按本发明使用。这些同系物中的每个烷基苷单元可含平均最高达10个环氧乙烷和/或环氧丙烷单元。
用作表面活性剂的含烷基的化合物可以是纯物质。但一般优选从天然植物或动物原料来生产这些化合物,因此得到的是决定于该具体原料的在烷基链中含不同碳原子数的混合物。
环氧乙烷和/或环氧丙烷与脂肪醇的加合物或这些加合物的衍生物的表面活性剂可以是有“正常”同系物分布的产物,也可以是有窄同系物分布的产物。有“正常”同系物分布的产物被认为是用碱金属、碱金属氢氧化物或碱金属醇盐作催化剂在脂肪醇和烯化氧的反应中得到的同系物混合物。与之对照,窄的同系物分布是用例如水滑石、醚羧酸的碱土金属盐、碱土金属氧化物、氢氧化物或醇盐作为催化剂得到的。使用具有窄同系物分布的产物是有利的。
用本发明防腐剂体系制备的组合物的优选含两性离子、阴离子和/或非离子表面活性剂的量为0.5-40%(重量),更优选0.5-20%(重量);在一特别优选具体实施方案中,其量为1-5%(重量),基于组合物总体计算。
含本发明防腐剂体系的组合物通常是以含水或水/醇溶液或分散液的形式存在。水基配方或基于配方总体计算含有低于15%(重量)的醇、特别是乙醇的配方是优选的。但是醇基配方、更特别是乙醇基的配方对于特种应用也可以是优选的。
除必须存在防腐活性物质的组合外,组合物可含维生素和/或维生素衍生物作为已列出的一种或多种其它化合物的替代或补充。原则上天然的、合成的、水溶性的或油溶性的维生素和维生素衍生物是适合的。
特别适合的维生素和维生素衍生物有例如维生素A、维生素E、维生素E乙酸酯、维生素E-烟酸酯、维生素F、维生素B3、维生素B6、烟酰胺、维生素H、维生素C、维生素B5和它们的衍生物,更特别是泛酰醇、泛酸、泛酸钙、泛基乙基醚、panthenyl hydroxypropylsteardimonium chloride(Panthequat,Innovachem)、双泛酰硫乙胺和panthenyltriacetate。类似的衍生物例如泛基丙基醚、泛基丁基醚和其它支化的或直链的饱和或不饱和同系物当然也是可以使用的。这同样适用于泛酸的盐,其可能的抗衡离子不限于钙离子,而是包括所有的生理可接受金属阳离子,例如碱金属和碱土金属离子、更特别是镁、钠或钾离子。本发明也包括使用各种维生素、特别是维生素B5和其衍生物的所有可能的立体异构体,D-型和L-型和二者的混合物都可根据本发明使用。
一般说来,用于本发明组合物的维生素或维生素衍生物的量为0.01-30%(重量),基于组合物总体计算。0.02-15%(重量)、更特别是0.02-8%(重量)的量对于含水的备用制剂的生产通常是特别有利的。在许多情况中,0.05-5%(重量)的量已足够。对于浓缩物而言,使用0.05-30%(重量)、更特别是1-25%(重量),并特别优选3-20%(重量)的维生素和/或维生素衍生物是有利的。
除组分A和B外,本发明的组合物也可含蛋白质水解产物(单独地或与一种或多种已列组分一起)。在本发明的上下文中蛋白质水解产物应理解为氨基酸、低聚肽和多肽以及它们的衍生物的混合物。
适合按本发明使用的氨基酸是例如精氨酸、赖氨酸、半光氨酸、谷氨酰胺、天冬酰胺和缬氨酸。动物或植物蛋白质已基本上完全用碱、酸或酶水解得到的氨基酸混合物也证明是适合的。
适合按本发明使用的低聚肽和多肽有例如动物或植物蛋白或它们的用酸、碱或酶水解得到的(部分)水解产物。适合的蛋白质有例如角蛋白、胶原蛋白、弹性蛋白、大豆蛋白、乳蛋白、酪蛋白、丝心蛋白、丝胶蛋白、小麦蛋白、丝蛋白和杏仁蛋白。根据本发明,角蛋白和植物蛋白是优选的。水解过程得到平均分子量约为400-50,000道尔顿的混合物。典型的平均分子量在约500-8,000道尔顿范围。按照本发明,角蛋白、丝蛋白和植物蛋白的水解物是优选的。
在本发明的上下文中,氨基酸、低聚肽和多肽的衍生物应理解为它们的阳离子衍生物和它们与脂肪酸的缩合物。
阳离子衍生物是与通常含季铵基的化合物反应或与相应的胺反应并随后季铵化得到的。
许多这样的季蛋白水解物是从市场得到的,它们包括例如:--阳离子胶原蛋白水解产物,例如市售产品LamequatL(INCI名:Lauryldimonium Hydroxypropyl Hydrolyzed Collagen;ChemischeFabrik Grünau),--阳离子角蛋白水解产物,例如市售产品Croquat(CTFA名:Cocodimonium Hydroxypropyl Hydrolyzed Keratin;Croda),--以HydrotriticumQL得到的阳离子小麦水解产物(CTFA名:Lauryldimonium Hydroxypropyl Hydrolyzed Wheat Protein;Croda),--以CroteinQ得到的产物(INCI名:HydroxypropyltrimoniumHydrolyzed Collagen;Croda)和--以LexeinQ X 3000(Inolex)得到的季铵化蛋白水解产物。
在蛋白质水解产物/脂肪酸缩合产物的生产中,以油酸、肉豆蔻酸、十一碳烯酸、椰油脂肪酸和松香酸用作酸组分是优选的。缩合物也可以以盐的形式存在,更特别是钠、钾和三乙醇胺盐。
基于胶原蛋白水解产物的缩合物也有CTFA名:油酰水解胶原蛋白,肉豆蔻酰水解胶原蛋白,油酰水解动物胶原蛋白,钾椰油水解动物蛋白,TEA松香酰水解胶原蛋白,钾十一碳烯酰水解胶原蛋白和TEA椰油水解胶原蛋白。市售产品有例如:LameponLPO、Lamepon4 SK、LameponUD、Lamepon460、LameponPA TR、LameponST 40和LameponS(Grünau)以及LexeinA 240,LexeinS 620和LexeinA 520(Inolex)。
弹性蛋白水解产物与脂肪酸(例如月桂酸)的缩合产物(CTFA名:月桂酰水解弹性蛋白)也是可以使用的。其相应的商品是CrolastinAS(Croda)。
有商品供应的钾椰油基水解小麦蛋白是Promois EGCP(Seiwa)。
其它适合于按本发明使用的商品有LexeinA 200(Inolex),LameponPO-TR,LameponPA-K,LameponS-MV和LameponS-TR(Grünau)和CroteinCCT(Croda)。
本发明的季铵化合物与阴离子防腐剂的活性物质组合不仅可用于头发再生组合物,也可用于使头发产生纯装饰改变的产品,例如用于头发染色剂中。如用于头发染色剂中,除了至少一种季铵化合物和至少一种阴离子防腐剂外,还需有至少一种染料或染料前体以对角蛋白纤维染色。要取得染色效果,氧化染色剂一般要含已知为显示剂(Entwickler)和成色剂(Kuppler)的两组化合物。
根据本发明,优选的显示剂有对苯二胺、对亚甲苯基二胺、对氨基苯酚、邻氨基苯酚、1-(2’-羟乙基)-2,5-二氨基苯、N,N-双(2-羟乙基)对苯二胺、2-(2,5-二氨基苯氧基)乙醇、1-苯基-3-羧酰氨基-4-氨基-5-吡唑酮、4-氨基-3-甲基苯酚、2,4,5,6-四氨基嘧啶、2-羟基-4,5,6-三氨基嘧啶、4-羟基-2,5,6-三氨基嘧啶、2,4-二羟基-5,6-二氨基嘧啶、2-二甲基氨基-4,5,6-三氨基嘧啶、2-羟乙基氨基甲基-4-氨基苯酚、4,4’-二氨基二苯胺、4-氨基-3-氟苯酚、2-氨基甲基-4-氨基苯酚、2-羟基甲基-4-氨基苯酚、双(2-羟基-5-氨基苯基)甲烷、1,4-双(4-氨基苯基)二氮杂环庚烷、1,3-双(N-(2-羟乙基)-N-(4-氨基苯基氨基))-2-丙醇、4-氨基-2-(2-羟乙氧基)苯酚和根据EP 0 740 741或根据WO 94/089704的5-二氨基吡唑衍生物,例如4,5-二氨基-1-(2’-羟乙基)吡唑。
根据本发明,优选的成色剂有1-萘酚、1,2,3-苯三酚、1,5-、2,7-和1,7-二羟基萘、邻氨基苯酚、5-氨基-2-甲基苯酚、间氨基苯酚、间苯二酚、间苯二酚单甲醚、间苯二胺、1-苯基-3-甲基-5-吡唑酮、2,4-二氯-3-氨基苯酚、1,3-双(2,4-二氨基苯氧基)丙烷、4-氯间苯二酚、2-氯-6-甲基-3-氨基苯酚、2-甲基间苯二酚、5-甲基间苯二酚、2,5-二甲基间苯二酚、2,6-二羟基吡啶、2,6-二氨基吡啶、2-氨基-3-羟基吡啶、2,6-二羟基-3,4-二氨基吡啶、3-氨基-2-甲氨基-6-甲氧基吡啶、4-氨基-2-羟基甲苯、2,6-双(2-羟乙基氨基)甲苯、2,4-二氨基苯氧基乙醇、1-甲氧基-2-氨基-4-(2-羟乙基氨基)苯、2-甲基-4-氯-5-氨基苯酚、6-甲基-1,2,3,4-四氢喹喔啉、3,4-亚甲二氧基苯酚、3,4-亚甲二氧基苯胺、2,6-二甲基-3-氨基苯酚、3-氨基-6-甲氧基-2-甲氨基苯酚、2-羟基-4-氨基苯氧基乙醇、2-甲基-5-(2-羟乙基氨基)苯酚和2,6-二羟基-3,4-二甲基吡啶。
这些显示剂和成色剂常以游离形式使用,但在它们含有氨基时则优选使用其盐的形式,更特别是其盐酸盐和硫酸盐形式。
头发染色剂含显示剂和成色剂的量优选0.005-20%(重量),更优选0.1-5%(重量),分别基于氧化染发剂总体计算。显示剂和成色剂的用量一般基本上是等摩尔的。虽然使用基本上等摩尔量被证明是适合的,但使用过量的某一氧化染料前体是没有坏处的,所以显示剂和成色剂的摩尔比可以是1∶0.5-1∶3,更特别是1∶1-1∶2。
在另一具体实施方案中,染发剂除了氧化染料前体外也可含直接染料作为进一步改变色调的唯一染色组分。
典型的直接染料有硝基苯二胺、硝基氨基苯酚、偶氮染料、蒽醌或靛酚。优选的直接染料是国际名或商品名如下的化合物:HC黄2,HC黄4,HC黄5,HC黄6,碱性黄57,分散橙3、HC红3、HC红BN、碱性红76、HC兰2、HC兰12、分散兰3、碱性兰99、HC紫1、分散紫1、分散紫4、分散黑9、碱性棕16和碱性棕17以及4-氨基-2-硝基二苯胺-2’-羧酸、6-硝基-1,2,3,4-四氢喹喔啉、羟乙基-2-硝基甲苯胺、苦氨酸、2-氨基-6-氯-4-硝基苯酚、4-乙氨基-3-硝基苯甲酸和2-氯-6-乙氨基-1-羟基-4-硝基苯。此具体实施方案中的本发明制剂含直接染料的量优选为0.01-20%(重量),基于染色剂总体计算。
除此以外,本发明的组合物也可含天然染料,诸如散沫花红、散沫花灰、散沫花黑、春黄菊花、檀香木、黑茶、黑桤木、鼠尾草、苏木、茜草根、儿茶、sedre和柴草。
在本发明染发剂中存在的其它染料组分可以是吲哚和二氢吲哚以及它们的生理相容盐。优选的例子是5,6-二羟基吲哚、N-甲基-5,6-二羟基吲哚、N-乙基-5,6-二羟基吲哚、N-丙基-5,6-二羟基吲哚、N-丁基-5,6-二羟基吲哚、5,6-二羟基吲哚-2-羧酸、6-羟基吲哚、6-氨基吲哚和4-氨基吲哚。优选的还有5,6-二羟基二氢吲哚、N-甲基-5,6-二羟基二氢吲哚、N-乙基-5,6-二羟基二氢吲哚、N-丙基-5,6-二羟基二氢吲哚、N-丁基-5,6-二羟基二氢吲哚、5,6-二羟基二氢吲哚-2-羧酸、6-羟基二氢吲哚、6-氨基二氢吲哚和4-氨基二氢吲哚。
关于适合在本发明头发染色和调色配方中使用的染料,也请具体参考下列文献:Ch.Zviak,头发护理科学(The Science of Hair Care),第7章,(PP.248-250;直接染料)和第8章,PP.264-267;氧化染料前体,作为皮肤病学(“Dermatology”)丛书的第7卷出版(编辑:Ch.Culnan和H.Maibach),Marcel Dekker Inc.,New York/Basel,(1986);以及欧洲化妆品原料目录(“Europaeische Inventar derKosmetik-Rohstoffe”),Europaeische Gemeinschaft出版。由Bundesverband Deutscher Industrie-und Hundelsunternehmenfuer Arzneimittel,Reformwaren und Koerperpflegemittel e.V.,Mannheim,Germany提供磁盘。
氧化染料前体或任选的直接染料不必是单一的化合物。与之相反本发明的染发剂(由于生产单个染料所用的方法所造成的)可含少量的其它组分,只要它们对染色结果不起不利作用或因其它原因(例如有毒性)而必须被除去。
生产染发剂时是将氧化染料前体掺入至少含组分A和组分B的本发明组合物中的。为用于染发目的,本发明的组合物可配制成例如乳剂、气溶胶、乳状液、凝胶,或者甚至是含表面活性剂的发泡溶液,例如香波、泡沫气溶胶或其它适合在头发上使用的制剂形式。
在原则上,可以用大气氧来进行氧化显色。但优选使用的是化学氧化剂,特别是在人发不仅需有染色也需要上光时。特别适合的氧化剂是过硫酸盐、亚氯酸盐和首先是过氧化氢或它们与脲、三聚氰胺或硼酸钠的加合产物。氧化也可以用酶来进行。在这种情况下,可用酶将空气氧转移至显示剂上或使少量存在的氧化剂的效果提高。酶催法的一实例是少量(例如1%或更低,基于配方总体计算)过氧化氢的作用被过氧化酶提高的措施。
氧化剂制剂最好是直接在染发之前才与氧化染料前体制剂混合。由此所形成的备用染发剂优选的pH值应在6-10的范围。染发剂在一弱碱性介质中使用是特别有利的。使用时的温度可在15-40℃范围。在接触约30分钟后进行漂洗以从被染头发上除去染发剂。当使用高表面活性剂载体例如染色香波时,头发无需再用香波洗涤。
本发明的防腐剂体系也可用于卷发制剂的生产。在本发明的上下文中,卷发制剂应理解为用于角蛋白纤维的永久成型的制剂。象这类成型一般是使纤维机械变形并用适合的助剂将变形固定。在变形前和/或后,纤维用还原角蛋白物质(卷发液)的含水制剂处理,并在接触一段时间后用水或含水溶液漂洗。第二步是用氧化剂(固定剂)的含水制剂处理纤维。在接触一定时间后,漂洗出固定剂并从纤维中除去机械成型助器(卷发器,卷子)。
卷发制剂含有可还原角蛋白的物质硫醇,例如巯基乙酸、硫羟乳酸、硫羟苹果酸、巯基乙磺酸以及它们的盐和酯、半光胺、半光氨酸、Bunte盐和亚硫酸碱金属盐。巯基乙酸和/或硫羟乳酸的碱金属或铵盐以及游离酸是优选的。它们用于卷发剂的优选浓度为0.5-1.0摩尔/公斤,基于卷发制剂总体计算,在pH值为5-10,更特别是7-8.5时。
氧化剂例如溴酸钠、溴酸钾或过氧化氢与典型的用于稳定含水的过氧化氢制剂的稳定剂一起用作固定剂。这种含水的过氧化氢制剂(常含约0.5-3.0%(重量)过氧化氢)的优选pH值在2-4范围,是用无机酸、优选磷酸调节的。
基于溴酸盐的固定剂含溴酸盐的浓度常为1-10,溶液的pH值被调至4-7。不含或只含少量氧化剂、特别是过氧化氢的基于酶(过氧化酶)的固定剂也是适合的。
卷发剂和固定剂都可配制成乳剂、凝胶或液体。组合物也可以配制成泡沫气溶胶,与液化气体(诸如丙烷/丁烷混合物、氮气、CO2、空气、N2O、二甲醚、氯氟烃推进剂或它们的混合物)一起包装在有泡沫阀的气溶胶容器中。固定剂也可以配制成固体,其中所含的氧化剂是固体形式,例如溴酸钾或钠,仅在应用前才在这些试剂中加水。将氧化剂配制成两组分体系也是有利的。这两种组分之一优选为过氧化氢溶液或另一氧化剂的水溶液,另一组分含其余的配料,它们也是在临用前混合在一起。
本发明的头发处理组合物可以是在接触一定时间(一般约1-45分钟)后可自头发漂洗掉的产品,也可以是保留在头发上的产品。
本发明的防腐剂体系可在不同的pH值下使用。例如洗发香波、润丝和卷发液的优选pH值为2.5-7.0,更特别是在4.0-6.0范围。与之对照,氧化染发剂的pH值一般是6.0-10.0范围,更特别是7.0-9.0范围。
实际上,用于化妆品的任何酸或碱都可用来调节pH值。如用酸调节pH值,使用食品级酸诸如乙酸、抗坏血酸和葡糖酸是有利的。但α-羟基羧酸(诸如乳酸、酒石酸、柠檬酸和苹果酸)除了用作防腐剂体系的组分外也可用来调节pH值。
根据设想的应用和制剂的种类,本发明的制剂可含任何为各种应用所常用的化妆品添加剂。
诸如此类的添加剂包括:--两性表面活性剂,例如烷基中分别含8-18个碳原子的N-烷基甘氨羧、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚氨基二丙酸、N-羟乙基-N-烷基酰氨基丙基甘氨羧、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基氨基丙酸和烷基氨基乙酸,--两性离子表面活性剂,例如所谓的甜菜碱和2-烷基-3-羧甲基-3-羟乙基咪唑啉,--阴离子聚合物,例如聚丙烯酸和聚甲基丙烯酸、它们的盐、它们与丙烯酸-和甲基丙烯酸-酯和-酰胺的共聚物和它们与多官能试剂交联得到的衍生物;此类化合物例如能以如下的商名得到的,例如Carbopol934、Carbopol934P、Carbopol940、Carbopol950、Carbopol980和CarbopolEDT类型(生产厂商均为BF Goodrich)和PNC400(生产厂商:3V Sigma);--非离子聚合物,例如乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物、聚乙烯吡咯烷酮和乙烯基吡咯烷酮/乙酸乙烯酯共聚物,--增稠剂,诸如琼脂、瓜耳胶、藻酸盐、纤维素醚、明胶、果胶和/或苫吨胶,--结构剂,诸如葡萄糖和马来酸,--头发调节化合物,诸如磷脂,例如大豆卵磷脂、鸡蛋卵磷脂和脑磷脂,以及硅油,--香精油,二甲基异山梨醇和环糊精,--增溶剂,诸如乙醇、异丙醇、乙二醇、丙二醇、甘油和二甘醇,--染料,--抗头皮屑剂,诸如Climbazol,Piroctone Olamine和Zinc Omadine,--其它调节pH值的物质,--活性物质,诸如红没药醇、尿囊素、和植物提取物,--紫外过滤剂,--脂肪和蜡,诸如鲸蜡、蜂蜡、褐煤蜡、石蜡、酯、甘油酯和脂肪醇,--脂肪酸烷醇酰胺,--膨胀和渗透剂,诸如PCA、甘油、丙二醇单乙基醚、碳酸盐、碳酸氢盐、胍、脲和一代-、二代-、三代磷酸盐,--遮光剂,诸如乳胶和苯乙烯/丙烯酰胺共聚物,--珠光剂,诸如乙二醇单-和二硬脂酸酯和PEG-3-二硬脂酸酯,--推进剂,诸如丙烷/丁烷混合物、N2O、二甲醚、CO2和空气,以及--抗氧化剂。
现以实施例对本发明进行说明。
实施例
为测试本发明活性物质组合的防腐效果,制备了有下列组分的两个配方:配方1:2.5% Stenol 1618 (Cetearyl Alcohol) Henkel0.5% Cutina GMS (硬脂酸甘油酯) Henkel0.4% Eumulgin B1 (Ceteareth-12) Henkel0.1% Cetiol OE (二辛醚) Henkel2.4% Dehyquart A (Cetrimomium Chloride) Henkel2.0% 葡萄糖适量 柠檬酸适量 水配方2:
与配方1相同,但另外加入0.57%水杨酸钠。
pH值(二配方):约2.8
配方1和2的防腐效果试验如下:
试验微生物:
用于试验的细菌培养物含下列的微生物:
-金黄色葡萄球菌 ATCC 6538
-Enterococcus faecium ATCC 6057
-大肠杆菌 ATCC 11229
-产气肠杆菌 DSM 30053
-绿脓杆菌 ATCC 15442
用于试验的真菌培养物含下列的微生物:
-白假丝酵母 ATCC 10231
-黑曲霉 ATCC 6275
-红色青霉 CMI 113729
-绿色木霉 BAM T 21
用上述的微生物制备各含108 CBU/毫升细菌和107CBU/毫升真菌的标准微生物悬浮液。在一消毒的器皿中分别用10克量的配方1和配方2与0.1毫升细菌悬浮液和0.1毫升真菌悬浮液进行试验。在玻璃匀化器中混合至少10个匀化器冲程以掺入微生物悬浮液。用两个接种圈将已加入微生物的配方直接施于THL标准I营养琼脂、THL麦芽汁琼脂、THL标准I营养肉汤和THL麦芽汁汤。
观察到的灭菌时间(天)如下:
细菌(2.5·106) 真菌(6·105)
配方1: >21 >35
配方2: 1 1
Claims (13)
1.下列组分的混合物作为人体护理组合物的防腐剂体系的应用,--至少一种季铵化合物和--至少一种阴离子防腐剂和/或--至少一种α-羟基羧酸。
2.权利要求1所述的应用,其特征在于人体护理组合物是护发剂。
3.权利要求1或2所述的应用,其特征在于季铵化合物是鲸蜡基三甲基溴化铵和/或鲸蜡基三甲基氯化铵。
4.前述任一项权利要求的应用,其特征在于季铵化合物是至少一种季酯化合物。
5.前述任一项权利要求的应用,其特征在于阴离子防腐剂是有机酸碱金属盐。
6.权利要求5所述的应用,其特征在于有机酸碱金属盐是甲酸、乙酸、丙酸、乳酸、山梨酸、苯甲酸、水杨酸和乙酰丙酸的盐。
7.前述任一项权利要求的应用,其特征在于水杨酸钠被用作至少一种阴离子防腐剂。
8.前述任一项权利要求的应用,其特征在于α-羟基羧酸选自乳酸、酒石酸、苹果酸和柠檬酸。
9.前述任一项权利要求的应用,其特征在于至少一种季铵化合物和至少一种阴离子防腐剂和/或α-羟基羧酸是以重量比1∶20-100∶1存在的。
10.前述任一项权利要求的应用,其特征在于鲸蜡基三甲基氯化铵被用作至少一种季铵化合物。
11.一种含重量比为1∶20-100∶1的至少一种季酯化合物和至少一种水杨酸碱金属盐作为活性物质的防腐剂体系。
12.权利要求11所述的防腐剂体系,其特征在于二硬脂酰基乙基羟乙基甲硫酸铵被用作至少一种季酯化合物。
13.权利要求11或12所述的防腐剂体系,其特征在于水杨酸钠被用作至少一种阴离子防腐剂。
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DE19733684.1 | 1997-08-04 | ||
DE19733684A DE19733684A1 (de) | 1997-08-04 | 1997-08-04 | Konservierungsmittelsystem für Körperpflegemittel |
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JP (1) | JP2001513488A (zh) |
KR (1) | KR20010022607A (zh) |
CN (1) | CN1268047A (zh) |
AU (1) | AU8733198A (zh) |
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CA (1) | CA2299340A1 (zh) |
DE (1) | DE19733684A1 (zh) |
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PL (1) | PL338475A1 (zh) |
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DE10035248A1 (de) * | 2000-07-20 | 2002-01-31 | Cognis Deutschland Gmbh | Verwendung von Esterquats als mikrobizide Wirkstoffe |
TW201002201A (en) | 2001-03-01 | 2010-01-16 | Lonza Ag | Preservative blends containing quaternary ammonium compounds |
DE10223934B4 (de) * | 2002-05-29 | 2009-04-09 | Schülke & Mayr GmbH | Verwendung eines Desinfektionsmittels zur Inaktivierung von Hepatitis B-Virus |
US9028852B2 (en) | 2004-09-07 | 2015-05-12 | 3M Innovative Properties Company | Cationic antiseptic compositions and methods of use |
FR2992859B1 (fr) * | 2012-07-09 | 2014-10-03 | Fabre Pierre Dermo Cosmetique | Utilisation de coceth sulfate de zinc comme agent antibacterien vis a vis de propionibacterium acnes |
JP2014172894A (ja) * | 2013-03-12 | 2014-09-22 | Separator System Kogyo Kk | エアゾール型可食性除菌剤 |
KR101506185B1 (ko) | 2014-06-11 | 2015-03-26 | 주식회사 에스앤텍 | 4급 암모늄 화합물 내성균을 저해하는 방부조성물 |
KR101741981B1 (ko) * | 2015-04-22 | 2017-06-01 | 코스맥스 주식회사 | 리브온 타입의 에어로졸 화장료 조성물 |
JP6904979B2 (ja) | 2016-03-01 | 2021-07-21 | エコラボ ユーエスエー インコーポレイティド | 第4級アニオン性界面活性剤の相乗効果に基づく殺菌すすぎ |
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- 1998-07-30 BR BR9811843-9A patent/BR9811843A/pt not_active IP Right Cessation
- 1998-07-30 SK SK149-2000A patent/SK1492000A3/sk unknown
- 1998-07-30 PL PL98338475A patent/PL338475A1/xx unknown
- 1998-07-30 CN CN98808494A patent/CN1268047A/zh active Pending
- 1998-07-30 JP JP2000506926A patent/JP2001513488A/ja active Pending
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WO1999007331A1 (de) | 1999-02-18 |
DE19733684A1 (de) | 1999-02-11 |
AU8733198A (en) | 1999-03-01 |
KR20010022607A (ko) | 2001-03-26 |
TR200000270T2 (tr) | 2000-09-21 |
HUP0100333A2 (hu) | 2001-06-28 |
JP2001513488A (ja) | 2001-09-04 |
CA2299340A1 (en) | 1999-02-18 |
PL338475A1 (en) | 2000-11-06 |
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