CN1422147A - 稳定的含水表面活性剂组合物 - Google Patents
稳定的含水表面活性剂组合物 Download PDFInfo
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- CN1422147A CN1422147A CN01807965A CN01807965A CN1422147A CN 1422147 A CN1422147 A CN 1422147A CN 01807965 A CN01807965 A CN 01807965A CN 01807965 A CN01807965 A CN 01807965A CN 1422147 A CN1422147 A CN 1422147A
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Classifications
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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- A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
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Abstract
一种稳定的、含水组合物,其含有基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂、表面活性剂、碱性物料和各种化合物,例如需要悬浮或稳定化的基本上不溶性物料,如硅氧烷、油性物料或珠光物料。此外,本发明还涉及流变性稳定和相稳定的阳离子头发染料组合物的配制。本发明还涉及在添加碱性物料之后掺加酸性物料,以降低组合物的pH同时不负面影响组合物的粘度和流变性。
Description
发明领域
本发明涉及稳定的、含水组合物的配制,所说的组合物含有基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂、表面活性剂、碱性物料和各种化合物,例如作为需要悬浮或稳定化的基本上不溶性物料,如硅氧烷、油性物料或珠光物料。此外,本发明还涉及流变性稳定和相稳定的阳离子头发染料组合物的配制。本发明还涉及在添加碱性物料之后掺加酸性物料,以降低组合物的pH同时不负面影响组合物的粘度和流变性。
发明背景
此前,在含有表面活性剂的含水组合物中,各种基本上不溶性化合物都不能充分地得到稳定。例如,各种含有硅氧烷添加剂如头发或皮肤调理剂的含水表面活性剂组合物,都会与它们的表面活性剂基料分离和/或出现乳油分层。经常用来提供珠光色外观的各种珠光物料都具有较短的保质期并且产生退色的珠光色外观(″失去光泽″)或者竟然沉降。换句话说,在掺加硅氧烷和珠光色物料时通常存在不稳定性的问题。
尽管人们在洗发液中使用了用于头发的阳离子或碱性染料,以便给头发临时性染色或者增亮,但这些阳离子染料通常与传统洗发液制剂中典型使用的阴离子表面活性剂不相容。因此,人们使用两性表面活性剂来赋予洗发液清洁和去污特性,但这种表面活性剂不能充分地增稠,以提供合意的产品流变性。尽管人们使用了传统的聚合型流变改良剂,如carbomers和/或丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物,来用于增加粘度,但这些组合物的流变稳定性通常仍很差。
为弥补上述问题,人们作出了各种尝试。
例如,US专利5,656,257涉及一种阴离子洗发液和调理用组合物,其中含有油性调理剂、洗发剂、丙烯酸酯共聚物、阳离子调理剂和水。它还涉及掺加C8-C18脂肪酸。此组合物利用了油性和阳离子调理剂与阴离子丙烯酸酯共聚物的组合来保持稳定性和分散性。
WO99/21530涉及一种护发组合物,含有约1.00wt%至约80.00wt%选自阴离子、非离子、阳离子和两性离子表面活性剂及其混合物的一种或多种表面活性剂;约0.05wt%至约15.00wt%至少一种具有10至约30个碳原子的脂肪醇;约0.10wt%至约15.00wt%非挥发性硅氧烷和约1.35wt%至约2.70wt%非交联的聚合悬浮剂。
EP0463,780涉及一种稳定的、带珠光色洗发液组合物,其含有不溶性的、非挥发性硅氧烷,此组合物可以通过包括悬浮剂聚合物来获得,所说的悬浮剂聚合物用以防止在储存期间硅氧烷″乳油分层″到瓶子的顶部,并且还用以防止涂敷有二氧化钛的云母颗粒沉淀。此组合物还涉及含水洗发液组合物,其除水之外还含有:
(a)2-40wt%选自阴离子、非离子或两性表面活性剂或其混合物的表面活性剂;
(b)0.01-10wt%不溶性的、非挥发性硅氧烷;
(c)0.1-5wt%悬浮剂聚合物,所说的聚合物选自聚丙烯酸、丙烯酸的交联的聚合物、丙烯酸与疏水单体的共聚物,含羧酸的单体和丙烯酸的酯的共聚物、丙烯酸和丙烯酸酯的交联共聚物以及杂多糖树胶;和
(d)0.01-5wt%涂敷有二氧化钛的云母。
US专利4,529,773涉及含有缔合性增稠剂(疏水改性的可碱溶性乳液聚合物)的组合物,其中通过中和至pH大于6.5,接着在表面活性剂的存在下酸化使所说的增稠剂活化。
然而,以上的现有技术不能产生充分稳定的含水表面活性剂组合物,如针对各种硅氧烷、油性物料、珠光物料、阳离子头发染料和其它基本上不溶性的物料而言。
发明概述
一种稳定的含水组合物含有基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂、水、碱性物料和有效量的表面活性剂,以便使基本上不溶性的化合物稳定或者悬浮在组合物中。该组合物是稳定的,其中可以含有各种挥发性和非挥发性硅油、油性物料等等。含珠光物料的组合物可以是稳定的并且给组合物进一步带来增强的珠光色外观。此外,可以获得含阳离子染料的组合物并且其保持可接受的流变性。此外,可以利用″回酸(Back-Acid)″配制技术来得到低pH组合物。这些稳定的含水表面活性剂组合物,在45℃下经过如至少一个月的长时间过程,通常来说可以保持光滑、可接受的流变性,同时其粘度或pH没有明显增加或降低,没有分离、沉淀或乳油析出。聚合型流变改良剂通常是由一种或多种羧酸单体、乙烯基单体和多不饱和单体制成。表面活性剂可以是阴离子、两性、两性离子、非离子或阳离子表面活性剂或者其的组合。
附图简介
图1是实施例2A(带珠光色二合一调理洗发液)的容器显示的在45℃下稳定性测试10周的照片;
图2是实施例2C(含云母的带珠光色二合一调理洗发液)的容器显示的在45℃下稳定性测试8周的照片;
图3是实施例2C(含云母的带珠光色二合一调理洗发液)的容器显示的开始阶段时的外观的照片;
图4是实施例2C(含云母的带珠光色二合一调理洗发液)的容器显示的开始阶段时的外观(上面)和12小时后的外观(下面)的照片;
图5是实施例4A(水杨酸脸部用擦洗液)的容器显示的在45℃下稳定性测试8周的照片;
图6是实施例4B(含云母的水杨酸洗发液)的容器显示的在45℃下稳定性测试8周的照片;
图7是实施例5(带珠光色的温和体用洗液)的容器显示的在45℃下稳定性测试10周的照片;
图8是实施例6(含悬浮珠的澄清浴用凝胶)的容器显示的在室温下稳定性测试8周的照片。
发明详述
本文中给出的标题是起举例说明作用的,不以任何方式限定本发明。
聚合型流变改良剂
聚合型流变改良剂提供各种流变性能,诸如流动性能、增稠或粘度、垂直粘着性、悬浮能力和屈服值。屈服值,也称作屈服应力,在本文中定义为在应力条件下对流动的初始抗性。它可以使用许多技术来测定,诸如通过使用恒定应力型流变仪或通过使用布鲁克菲尔德粘度计的外推法。这些技术和屈服值测定的有用性在可得自B.F.Goodrich公司的第244号技术数据单(Technical Data SheetNumber 244)中有进一步的解释,其引入本文作为参考。除此之外,此聚合物还可用于提供制剂中不溶性物料如粒状物质或油性物料的稳定化以及为整个制剂提供稳定性。
本发明的基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂通常可以通过各种聚合途径来制备,如乳液、溶液、沉淀聚合等等,通常优选乳液聚合。乳液聚合通常在pH约2.5至约5.0下、用至少三种本质上是烯键式不饱和的组分来完成。此外,这些单体中没有一种是缔合性单体,缔合性单体是指能够非特定性疏水缔合的可共的聚表面活性剂,类似于常规表面活性剂。
本发明的聚合型流变改良剂通常含有三种结构组分。第一种组分是一种或多种具有约3至约10个碳原子总数的羧酸单体。这种单体的实例包括(但不限于)丙烯酸,甲基丙烯酸,衣康酸,富马酸,巴豆酸,马来酸或乌头酸。此外,可以使用多元酸如马来酸、富马酸、衣康酸或乌头酸等等与C1-4链烷醇的半酯,特别是当它少量与丙烯酸或甲基丙烯酸联用时。
这种羧酸单体的量,以单体的总重量计,通常为约20wt%-80wt%,合意地是约25wt%至约70wt%并且优选约35wt%至约65wt%。
第二种组分是一种或多种非酸乙烯基单体,其使用量以单体的总重量计为约80wt%至约15wt%,合意地是约75wt%至约25wt%,并且优选约65wt%-35wt%。这种乙烯基单体是具有下式的α,β-烯键式不饱和单体:
1)CH2=CXY,
其中X是H并且Y是-COOR、-C6H4R’、-CN、-CONH2、-Cl、-NC4H6O、-NH(CH2)3COOH、-NHCOCH3、-CONHC(CH3)3、-CO-N(CH3)2,
或者X是CH3并且Y是-COOR、-C6H4R’、-CN或-CH=CH2;或者X是Cl并且Y是Cl,且
R是C1-C18烷基或羟基C2-C18烷基,
R’是H或C1-C18烷基
或者具有下式:
2)CH2=CH(OCOR1);其中R1是C1-C18烷基;
或者具有下式:
3)CH2=CH2或CH2=CHCH3。
典型的这种乙烯基单体或单体的混合物是其中酯部分具有1-10个碳原子的各种丙烯酸酯或羟基丙烯酸酯,如丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯,丙烯酸2-羟基乙酯或各种乙酸乙烯酯或苯乙烯或氯乙烯或偏二氯乙烯或丙烯腈、丙烯酰胺、N,N,-二甲基丙烯酰胺,叔丁基-丙烯酰胺及它们的甲基丙烯酸酯类似物。
形成丙烯酸酯流变改良剂用的第三种组分是一种或多种多不饱和化合物。也可以使用带有反应性基团的单体型不饱和化合物,其中所说的反应性基团能够引起所形成的共聚物在聚合发生之前、当中或之后交联。
使用各种多不饱和化合物来产生部分交联或者基本上交联的三维网络结构。这种多不饱和化合物的实例是蔗糖或多元醇的聚链烯基醚;邻苯二甲酸二烯丙酯,二乙烯苯,(甲基)丙烯酸烯丙酯,乙二醇二(甲基)丙烯酸酯,亚甲基双丙烯酰胺,三(甲基)丙烯酸三羟甲基丙烷酯,衣康酸二烯丙酯,富马酸二烯丙酯,马来酸二烯丙酯,(甲基)丙烯酸锌,蓖麻油或由烯键式不饱和羧酸等制作的多元醇的衍生物,甲基丙烯酸缩水甘油酯,N-羟甲基丙烯酰胺或N-烷氧基甲基丙烯酰胺,烷氧基是C1-C18醇;羟基(甲基)丙烯酸酯或(甲基)丙烯酸酯封端的己内酯。
对制作不饱和衍生物的本领域技术人员来说,诸如由环氧乙烷或环氧丙烷或其组合制成的多元醇与不饱和酸如丙烯酸、甲基丙烯酸或与不饱和酸酐如马来酸酐、柠康酸酐、衣康酸酐的酯化反应,或者与不饱和异氰酸酯如3-异丙烯基-α-α-二甲基苯异氰酸酯的加成反应的这些反应方案,也属于本发明的范围。当使用″(甲基)″时,其含义指甲基的使用是任选的。
此第三种组分的使用量,以形成所说丙烯酸酯共聚物流变改良剂用的所有单体的总重量计,可以为约0.01至约5wt%,合意地是约0.03至约3wt%,并且优选约0.05至约1wt%。
此外,此交联共聚物流变改良剂中通常不含任何得自于缔合性单体(即,可共的聚表面活性剂)的部分。通常来说,″不含″定义为含有少于约1wt%、合意地是少于约0.5wt%、并且优选少于约0.2wt%。
本发明的部分交联或基本上交联的三维网络结构可以按任何常规方式来制作,如US专利4,138,380或US专利4,110,291中所述,其整体引入本文作为参考。通常来说,将上述提及的羧酸单体、乙烯基单体和多不饱和单体的一种或多种单体添加到其中装有水的反应容器中。添加适宜量的常规或典型的乳液聚合表面活性剂如月桂基硫酸钠以及乳液型引发剂例如过硫酸钠或钾、氧化还原引发剂等等。此反应容器中还可以含有链转移剂。然后,将温度从约60℃增加至约100℃并且使聚合开始。任选地,在反应期间,在一段时期内添加附加的单体。当添加完单体之后,允许聚合反应进行至完,通常是通过添加附加的引发剂。
本发明的聚合型流变改良剂可以按Acrylates Crosspolymer(丙烯酸酯交联聚合物)的商品名称商购得自B.F.Goodrich公司。优选的聚合物是以1%活性聚合物浓度在pH6-8下在水中的粘度达500-10,000cP(布鲁克菲尔德RVT,20rpm)的聚合物。
以组合物的总重量计,一种或多种基本上交联的可碱溶胀性丙烯酸酯共聚物通常占活性聚合物的约0.1%至约10%、合意地是约0.3%至约5%、并且优选约0.5%至约3%。
表面活性剂
稳定的组合物中含有各种表面活性剂,如阴离子、两性、两性离子、非离子、阳离子表面活性剂或者其的组合。
阴离子表面活性剂可以是任何已知的或先前在含水表面活性剂组合物中使用过的阴离子表面活性剂。适宜阴离子表面活性剂包括(但不限于)烷基硫酸盐,烷基醚硫酸盐,烷芳基磺酸盐,烷基琥珀酸盐,烷基磺基琥珀酸盐,N-烷酰基肌氨酸盐,烷基磷酸盐,烷基醚磷酸盐,烷基醚羧酸盐,烷基氨基酸,烷基肽,烷酰基牛磺酸盐,羧酸,酰基和烷基谷氨酸盐,烷基羟乙基磺酸盐和α-烯烃磺酸盐,特别是它们的钠、钾、镁、铵及一-、二-和三乙醇胺盐。烷基通常含有8-18个碳原子并且可以是不饱和的。烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐中每分子可以含有1-10个环氧乙烷或环氧丙烷单元,并且优选每分子含有1-3个环氧乙烷单元。
适宜的阴离子表面活性剂的实例包括月桂基醚硫酸钠和铵(具有1、2和3摩尔环氧乙烷),月桂基硫酸钠、铵和三乙醇胺盐,月桂基醚磺基琥珀酸二钠,椰油基羟乙基磺酸钠,C12-14烯烃磺酸钠,月桂基醚-6羧酸钠,C12-15 pareth硫酸钠,甲基椰油基牛磺酸钠,十二烷基苯磺酸钠,椰油基肌氨酸钠,一月桂基磷酸三乙醇胺盐和脂肪酸皂。
非离子表面活性剂可以是任何已知的或先前在含水表面活性剂组合物中使用过的非离子表面活性剂。适宜非离子表面活性剂包括(但不限于)脂族(C6-C18)伯或仲直链或支链酸、醇或酚,烷基乙氧基化物,烷基酚烷氧基化物(特别是乙氧基化物和混合的乙氧基/丙氧基),烷基酚的嵌段氧化亚烷基缩合物,链烷醇的氧化亚烷基缩合物,环氧乙烷/环氧丙烷嵌段共聚物,半极性非离子化合物(例如,氧化胺和氧化膦),以及烷基氧化胺。其它适宜的非离子包括一或二烷基链烷醇酰胺和烷基多糖,脱水山梨糖醇脂肪酸酯,聚氧化乙烯脱水山梨糖醇脂肪酸酯,聚氧化乙烯山梨糖醇酯,聚氧化乙烯酸和聚氧化乙烯醇。适宜的非离子表面活性剂的实例包括椰油一或二乙醇酰胺,椰油二葡糖苷,烷基聚葡糖苷,椰油酰胺基丙基和月桂基氧化胺,聚山梨酸酯20,乙氧基化直链醇,鲸蜡硬脂基(cetearyl)醇,羊毛脂醇,硬脂酸,甘油硬脂酸酯,PEG-100硬脂酸酯和oleth 20。
两性和两性离子表面活性剂是能够起酸作用或者起碱作用的化合物。这些表面活性剂可以是任何已知的或先前在含水表面活性剂组合物中使用过的表面活性剂。适宜物料包括(但不限于)烷基甜菜碱,烷基酰胺基丙基甜菜碱,烷基磺基甜菜碱,烷基甘氨酸盐,烷基羧基甘氨酸盐,烷基两性丙酸盐,烷基酰胺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8-18个碳原子。实例包括椰油酰胺基丙基甜菜碱,椰油两性乙酸钠,椰油酰胺基丙基羟基磺基甜菜碱和椰油两性丙酸钠。
阳离子表面活性剂可以是任何已知的或先前在含水表面活性剂组合物中使用过的阳离子表面活性剂。适宜的阳离子表面活性剂包括(但不限于)烷基胺,烷基咪唑啉,乙氧基化胺,季铵化合物和季铵化酯。除此之外,烷基氧化胺可以在低pH下起阳离子表面活性剂的作用。实例包括月桂氧化胺,双十六烷基二甲基氯化铵(dicetyldimoniumchloride),十六烷三甲基氯化铵(cetrimoniumchloride)。
其它本发明可以利用的表面活性剂可详细见WO99/21530,US专利3,929,678,US专利4,565,647,US专利5,720,964和US专利5,858,948。其它适宜的表面活性剂描述于《McCutcheon乳化剂和洗涤剂》(北美和国际版,Schwartz、Perry和Berch),其引入本文作为参考。
表面活性剂的量可以在很宽的范围内变化,但通常的使用量的范围以组合物的总重量计为约1wt%至约80wt%,合意地是约5wt%至约65wt%,并且优选约6wt%至约30wt%或者首选约8wt%-20wt%。
不含脂肪酸,脂肪酸酯和脂肪醇
本发明的稳定的、含有表面活性剂的含水组合物中通常不含“脂肪”化合物,诸如脂肪酸、脂肪酸酯和脂肪醇。脂肪酸通常可以分类成通过脂肪水解获得的一元羧酸,其通常具有至少8或10个碳原子并且经常具有至少14个碳原子或更多,如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸等等。脂肪酸酯由这些脂肪酸制成。脂肪醇,通常具有至少10或12个碳原子并且更经常是约14至约24个碳原子,包括月桂醇、肉豆蔻醇、鲸蜡醇、硬脂醇、油醇等等。术语″不含″通常是指本发明的组合物通常含有少于约5wt%、2wt%或约1wt%,合意地少于约0.5wt%、0.2wt%或约0.1wt%,并且优选少于约0.05wt%、0.03wt%或0.01wt%或更少的脂肪酸和/或脂肪醇。
不溶性物料或化合物
需要稳定化的物料或化合物可以是水溶性的或水不溶性的。这种化合物包括不溶性硅氧烷,硅氧烷树胶,挥发性和非挥发性硅油,珠光物料及其它类型的以下列举的化合物。
硅氧烷和不溶性油性化合物
硅氧烷和油性化合物经常掺入制剂中用于调理,特别是针对头发和皮肤,并且用于改进或赋予光亮,光泽,防水性和/或润滑性。这些物料还可以起防潮剂或防护剂。
硅氧烷化合物可以是水不溶性或水溶性的。
适宜的水不溶性、非挥发性硅氧烷物料包括氨基聚二甲基硅氧烷(amodimethicone),氨基聚二甲基硅氧烷粗乳液或微乳液,聚烷基硅氧烷,聚-芳基硅氧烷,聚烷基芳基硅氧烷,聚硅氧烷树胶和聚醚硅氧烷共聚物。优选高分子量聚(二甲基硅氧烷)及其乳液,低分子量至高分子量的聚二甲基硅氧烷,例如粘度约5至约100,000厘沲(cS)的直链聚(二甲基硅氧烷)(聚二甲基硅氧烷)和其它硅氧烷类物料,如聚二甲基硅氧烷醇,聚二甲基硅氧烷醇粗乳液或微乳液,苯基聚二甲基硅氧烷,聚甲基苯基聚硅氧烷,有机聚硅氧烷,alkoyxy硅氧烷,聚二有机基硅氧烷,聚(二甲基硅氧烷)共聚物和聚氨基官能的硅氧烷,即聚烷基芳基硅氧烷聚烷基硅氧烷等等。水不溶性硅氧烷物料还可以被认为是油质调理剂。关于适宜的水溶性和水不溶性硅氧烷物料的教导参见US专利4,788,006;4,341,799;4,152,416;3,964,500;3,208,911;4,364,837和4,465,619,所有引入本文作为参考。
其它可以使用的非溶性硅氧烷物料包括挥发性硅氧烷,例如环甲基聚硅氧烷或粘度为10cS或更少的聚二甲基硅氧烷。
适宜的水溶性硅氧烷包括聚醚/聚硅氧烷嵌段共聚物,如聚二甲基硅氧烷共聚醇及其衍生物。
可商购获得的硅氧烷物料的实例包括Dow Corning 200、345、3225C、929乳液,949乳液,1664乳液,1692乳液,1784乳液,21894微乳液,184乳液;及General Electric SF1202,SF18(350),SF2169,Viscasil 60M,SM2658;和来自B.F.Goodrich的物料,如B.F.Goodrich蜡S、C和F等等。
优选用作油质调理剂的硅氧烷物料是CTFA命名为聚二甲基硅氧烷且25℃下的粘度范围为5-100,000cS的聚(二甲基硅氧烷)以及聚二甲基硅氧烷醇及其乳液。优选的聚二甲基硅氧烷的粘度为约60,000cS并且可得自Dow Corning或General Electric。
其它适宜的油性物料或调理剂包括(但不限于)以下:矿物油和饱和或不饱和植物油,如大豆油,巴西棕榈仁油,蓖麻油,棉籽油,乌桕油,两节荠油,紫苏油,丹麦菜籽油,米糠油,棕榈油,棕榈仁油,橄榄油,亚麻籽油,椰子油,向日葵油,红花油,花生油,玉米油,芝麻油和鳄梨油,以及矿脂;d-苧烯,润肤剂,维生素E和维生素A及诸如棕榈酸异丙酯,辛酸鲸蜡硬脂(cetearyl)酯,C12-15烷基苯甲酸酯,硬脂酸辛酯的酯和其它物料,如PPG-2肉豆蔻基醚丙酸酯等等。
硅氧烷或油性调理剂或其组合占组合物的约0.1wt%至约20wt%,更优选约0.3wt%至约7wt%并且首选约0.5wt%至约5wt%。珠光物料
一些制剂经常要通过在其中故意掺加珠光物料来遮光,以便达到美容上具吸引力的类似珍珠的外观,其已知是珠光色。本领域技术人员都知道配制者在一致性地制备具有珠光色制剂的所面临的问题。其详细的讨论可见Hunting的文章″洗发液中的遮光剂和珠光剂″,Cosmetic and Toiletries,Vol.96,第65-78页(1981年7月),引入本文作为参考。
珠光物料包括涂敷有二氧化钛的云母,涂敷有氧化铁的云母,乙二醇一硬脂酸酯,乙二醇二硬脂酸酯,聚乙二醇二硬脂酸酯,涂敷有氯氧化铋的云母,肉豆蔻酸肉豆蔻酯,鸟嘌呤,闪光剂(glitter)(聚酯和金属类的)及其混合物。其它珠光物料可见US专利4,654,207和US专利5,019,376,其引入本文作为参考。
出人意料的是,当掺入所说的基本上交联的可碱溶胀性丙烯酸酯聚合物时,观察到了改进的或增强的珠光色外观。与没有含此聚合物的组合物相比,开始阶段、特别是在将组合物放置24小时老化之后,观察到了视觉上可感觉出的改进的外观。此外,此聚合物还防止珠光物料的沉积或沉淀,由此明显降低了珠光色外观的″失去光泽″作用。此外,据信此聚合型流变改良剂起使珠光色颗粒或小片保持其最佳构型以便保持最大珠光色外观的作用。
以稳定的组合物的总重量计,珠光物料的使用量通常可以是约0.05wt%至约10wt%并且合意地是约0.15wt%至约3wt%。
其它不溶性化合物
除上述通常情况下不溶性的化合物外,还可以使用许多其它非必须的需要稳定化的基本上不溶性的化合物。这些其它的不溶性化合物的实例包括二氧化钛;浮石;碳酸钙;滑石;马铃薯淀粉;木薯淀粉;西蒙得木油珠;聚乙烯珠;核桃壳;丝瓜络;杏籽;杏仁粉;玉米粉;石蜡;燕麦麸/燕麦皮;明胶珠;藻酸盐珠;不锈钢纤维;氧化铁颜料;空气泡;涂敷有云母的氧化铁;高岭粘土;羟基吡啶硫酮锌;水杨酸;氧化锌;沸石;苯乙烯类泡沫塑料珠;磷酸盐;二氧化硅等等。其它通常情况下不溶性的化合物包括茶树粉末,微海绵,confetti(UnitedGuardian公司的一个商标名称),滑石,蜂蜡等等。
需要稳定化的各种不溶性化合物的量根据其用途、所需的最终结果和其功效而有很大变化。因此用量可以有很宽范围的变化,但经常是在约0.1wt%至约50wt%的通常范围内,以稳定的组合物的总重量计。
用于头发着色的阳离子染料
可以在临时性染发或护色用洗发液中使用的染料通常是可溶性的。这种染料通常是本领域和文献中已知的并且通常被称作阳离子或碱性染料。这些染料一般按两种不同的方式来描述。染料的名称(例如碱性棕16)涉及其INCI名称(化妆品用成分国际命名法)和/或其CTFA名称(化妆品、盥洗用品和香料协会名称)。另一种方式是通过其颜色索引号来指出这些染料(例如CI12250),这种颜色索引号为欧共体所使用。例如,″国际化妆品用成分字典和手册″第7版,1997,化妆品、盥洗用品和香料协会出版,华盛顿特区,美国,中给出了该两套数字。这些阳离子染料可以商品名称Arianor商购获得自Warner.Jenkinson。可以使用的具体的阳离子染料包括各种偶氮染料,如碱性棕16(CI12250),碱性棕17(CI12251),碱性红76(Cl12245),碱性黄57(Cl12719),以及各种蒽醌染料,如碱性蓝99(CI56059)等等。
头发染料的量,当在典型的临时性染色洗发液中使用时,以稳定的组合物的总重量计通常为约0.1至约5wt%。
碱性物料
本发明的聚合型流变改良剂通常是以其酸性的形式提供。这些聚合物通过随后的聚合物羧基的中和,改善了制剂的流变性。这样引起离子排斥和微凝胶网络的三维扩张,由此导致粘度和其它流变性能的增加。与缔合性增稠机理相比,这在文献中也称作″空间填充″机理。
因此,需要掺加碱性物料来中和聚合物并且优选是中和剂。本发明中可以使用很多类型的中和剂,包括无机和有机中和剂。无机碱的实例包括(但不限于)碱性氢氧化物(特别是钠、钾和铵)。有机碱的实例包括(但不限于)三乙醇胺(TEA),L-精氨酸,氨基甲基丙醇,tromethamine(2-氨基2-羟基甲基-1,3-丙二醇),PEG15椰油胺,二异丙醇胺,三异丙醇胺或四羟基丙基乙二胺。或者,可以使用其它碱性物料,诸如预中和的表面活性剂或其中掺加有中和剂的物料或任何其它能够增加组合物pH的物料。
酸性物料
本发明中可以使用各种酸性物料,如有机酸,例如柠檬酸,乙酸,α-羟基酸,β-羟基酸,水杨酸,乳酸,羟基乙酸或天然水果酸或无机酸,例如盐酸,硝酸,硫酸,氨基磺酸,磷酸及其组合。可以在工艺的各种时间点添加酸性物料,然而,在添加碱性中和剂之后添加酸性物料可以明显得到改善的流变特性。此将在″回酸″配制技术部分中作更详细的讨论。
其它可选的流变改良剂
组合物中可以选择性地含有其它流变改良剂,与基本上交联的可碱溶胀性丙烯酸酯共聚物联合使用。这些聚合物是本领域公知的并且可以包括天然、半合成(例如粘土)或合成聚合物。天然或改性的天然聚合物的实例包括(但不限于)树胶(例如,黄原胶),纤维素类,改性纤维素类,淀粉或多糖。其它合成聚合物的实例包括(但不限于)交联的聚丙烯酸酯,疏水改性的碱溶性聚合物或疏水改性的非离子氨基甲酸酯聚合物。此外,通过掺混盐来调整粘度也是公知的并且可以在本发明中使用。如果组合物中存在,这些流变改良剂的使用量通常为稳定的组合物的约0.01至约5wt%。
生物活性物料
本发明的稳定的、含有表面活性剂的含水组合物中还可以含有基本上不溶性的生物活性物料,这些生物活性物料具有药物、兽医用、杀生物、除草、杀虫或其它生物学活性。这种生物活性化合物的具体实例包括乙酰唑胺;七叶素;aesculi hippocastan;尿囊素;二乙胺苯酮;氨基propylon;阿莫罗芬;雄甾烷醇酮;山金车花;硫酸丁酚胺;苯丙哌林(benproperinembonate);苯扎氯胺;苯佐卡因;过氧化苯酰;烟酸苄酯;倍他米松;盐酸倍他洛尔;盐酸布酚宁;咖啡因;金盏花;樟脑;氯化十六烷基吡啶鎓;磷酸氯喹;克红霉素;富马酸氯苯苄咯氢(clemastin hydrogene fumarate);氯林可霉素-2-二氢磷酸酯;丙酸氯氟美松;三甲苯咪唑;磷酸可待因;氯康唑;克鲁米能;乙酸氟美松;d-泛醇;双氯酚酸;二乙胺水杨酸;二氟米松;戊酸二氟米松;二氟米松,双氯甲喹啉;difluoroprednate;二甲基亚砜;聚二甲基硅氧烷350-二氧化硅;二甲茚定;dimetindenmaleat丙吡啶;丙哌双苯醚酮;麦角毒;雌二醇;雌三醇;依托芬那酯;联苯乙酸;氟苯哒唑;氟芬那酸;氟轻松;醋酸氟轻松;氟考龙;褐霉酸;gelacturoglycani;肝素;氢化可的松;水杨酸羟乙酯;布洛芬;碘苷;咪唑水杨酸酯;吲哚美辛;硫酸异丙肾上腺素;酮洛芬;左旋薄荷醇;盐酸利多卡因;林旦;薄荷醇;甲氧苄二胺;5-氨基水杨酸;烟酸甲酯;水杨酸甲酯;甲硝唑;二氯苯咪唑;米诺地尔;桂萘甲胺;萘啶酮酸;萘普生;尼氟灭酸;呋喃巯唑酮;呋喃巯唑酮制霉素;硝呋酚酰肼;硝酸甘油;香草壬酰胺;制霉素呋喃巯唑酮;硝酸双醚康唑;o-芸香苷;苯咪唑嗪;oxerutin;羟基保泰松;胰酶;戊聚糖多硫酸酯;酚酞;苯基丁氮酮哌嗪;苯福林;毛果芸香碱;吡氧噻嗪;植物提取物;聚乙二醇单十二醚;聚丙烯酸树脂;多糖;磷酸钾;泼尼松龙;丙胺卡因;普利霉素硫酸盐利多卡因;黄体酮;蛋白质;消旋樟脑(racem.campher);retacnyl tritinoine;棕榈酸维生素A;水杨酰胺;水杨酸;水合蒎醇;藻酸钠;碳酸氢钠;氟化钠;戊聚糖多硫酸钠;磷酸钠;萜品;茶碱;凝血致活酶;麝香草酚;乙酸生育酚;托尔米丁;视黄酸;羟乙芦丁;维拉帕米;乙氧苯氧甲基吗啉;维生素b6;木糖醇;丁苄唑啉和透明质酸锌(zincum hyaluronicum)以及其的组合。
可以使用的其它化合物包括如下:水杨酸2-乙基己酯;adapalene;丙硫苯咪唑;avobenzone;苯扎氯胺;苯佐卡因;过氧化苯甲酰;二丙酸倍他米松,盐酸倍他洛尔;樟脑;辣椒辣素;克红霉素;磷酸克林霉素;丙酸氯倍他索;氯氟土龙特戊酸酯;克罗米能;去羟米松;聚二甲基硅氧烷;二羟苯酮;红霉素;对甲氧基肉桂酸乙基己酯;fentoin;氟轻松醋酸酯;愈创木酚甘油醚;水杨酸三甲环己酯;氢化可的松;戊酸氢化可的松;对苯二酚;高岭土;利多卡因;薄荷醇;mesalamine;烟酸甲酯;水杨酸甲酯;甲硝唑;盐酸萘替芬;萘啶酮酸;硝基呋喃妥因一水合物;甲氧基肉桂酸辛酯;羟甲氧苯酮;二甲氨苯戊酯;果胶;海尔地斯;苯基苯并咪唑磺酸;盐酸苯基丙醇胺;盐酸毛果芸香碱;胡椒基(piperonyl)丁氧化物;丙胺卡因;黄体酮;除虫菊提取物;双甲丙酰龙;二甲基硅油(simethicone);磺胺噁唑;视黄酸和氯化锌以及其的组合。可以配制到控释片中并且可以与本发明联用的其它化合物包括:抗坏血酸;阿斯匹林;阿替洛尔;盐酸咳美芬;马来酸氯苯吡胺;右旋氯苯吡胺;盐酸二乙胺苯酮;苯海拉明;盐酸麻黄碱;呋苯胺酸;愈创木酚甘油醚;二硝酸异山梨酯;Isoanizid;碳酸锂;马来酸(Meleate)甲氧苄二胺;盐酸美沙酮;甲氧氯普胺;硝基呋喃妥因;盐酸苯基丙醇胺;假麻黄碱;奎尼丁葡萄糖酸盐;硫酸奎尼丁;丙戊酸钠;磺胺甲噻唑;茶碱;硫胺素;十三胺;盐酸维拉帕米和乙氧苯氧甲基吗啉以及其的组合。这些化合物是可以使用的化合物的举例。也可以使用本领域技术人员已知的其它化合物。
其它成分
除上述提及的化合物外,本发明的稳定组合物中还可以非必须地使用各种其它的成分,如芳香剂,香料,防腐剂,消毒剂,抗氧化剂,抗再沉淀剂,载体,螯合剂和多价螯合剂,染料和颜料,季铵型调理剂,阳离子调理聚合物,如羟丙基三甲基氯化铵瓜尔豆胶,季化羟乙基纤维素-4(polyquaternium-4),李化羟乙基纤维素-6,李化羟乙基纤维素-7,季化羟乙基纤维素-10,季化羟乙基纤维素-11,季化羟乙基纤维素-16,季化羟乙基纤维素-24和季化羟乙基纤维素-39,腐蚀抑制剂,水溶助长剂,偶合剂,消泡剂,增效助剂,分散剂,润肤剂,提取物,维生素,酶,增泡剂,絮凝剂,增白剂,固定剂聚合物如PVP,保温剂,遮光剂,增塑剂,粉剂,增溶剂,溶剂,蜡,UV吸收剂/UV光稳定剂,水解蛋白,角蛋白,胶原等等。
用途
本发明的稳定的、含有表面活性剂的含水组合物具有广泛的许多用途,如个人护理用途,家庭护理用途,工业和公共机构用途,药物用途,织物配料等等。
各种个人护理用途的实例包括诸如以下的产品:
洗发液,例如二合一洗发液;婴儿洗发液;调理用洗发液;头发增密用(bodifying)洗发液;增湿用洗发液;临时性染发用洗发液;三合一洗发液;去头屑洗发液;发色保持用洗发液;酸(中和用)洗发液;水杨酸洗发液;
皮肤和体用清洁剂,例如增湿性体用洗液;抗菌性体用洗液;浴用凝胶;淋浴用凝胶;洗手皂;条皂;体用擦洗液;泡泡浴;脸部用擦洗液;足用擦洗液;
霜和露,例如α-羟基酸露和霜;β-羟基酸霜和露;皮肤增白剂;自身晒褐用露;防晒露;防护露;增湿剂;发型霜;维生素C霜;液体滑石制品和抗菌性露以及其它增湿用露和霜;
皮肤和头发用凝胶,例如脸部用面膜;体用膜;水醇凝胶;发胶;体用凝胶;防晒凝胶等等,以及其它个人护理用途,如长效染发等等。
家庭护理用途的实例包括诸如以下的产品:家庭护理及工业和公共机构用途,如洗衣用洗涤剂;洗餐具用洗涤剂(自动和手洗);硬表面清洁剂;洗手皂,清洁剂和卫生洗涤剂;擦亮剂(鞋,家具,金属等);汽车用蜡、擦亮剂、防护剂和清洁剂等等。
药物用途的实例包括以霜、露、软膏或凝胶形式的局部用制剂,其中表面活性剂可以用作药物活性物料的润湿助剂或用作皮肤渗透增强剂或用作具有美学效果的溶剂相的乳化剂,或者为增强药物活性物料的溶解性和生物利用性而存在。可以使用类似的制剂,以便用于在活体内的内部使用或口服给药或通过机械方式给药。
可以将这些制剂施用或应用于人或兽的可通过药物治疗的完全范围的适应症,如发热、刺激、皮炎、疹、病毒、真菌、细菌感染、器官疾病等。
药物活性剂可以具有任何适合治疗疾病的功能,并且可以是一种或多种的药物活性物料的混合物,所说的药物活性物料例如催吐剂,止吐剂,退热剂,杀真菌剂,杀生物剂,杀菌剂,抗生素,解热剂,NSAID,润肤剂,止痛剂,抗肿瘤剂,心血管剂,CNS刺激剂,CNS抑制剂,酶,蛋白质,激素,类固醇,止痒剂,抗风湿剂,生物制剂,咳嗽和感冒治疗剂,皮屑产品,胃肠治疗剂,肌肉松弛剂,心理治疗剂,皮肤和粘膜剂,护肤产品,阴道制剂,伤口护理剂和其它合适种类的能够通过剂量形式适当给药的药物活性剂。
配制技术
本发明可以用许多方式来制作。通常是,将一种或多种基本上交联的可碱溶胀性丙烯酸酯共聚物添加到水中并且混合。接着,将表面活性剂添加到此聚合物的水溶液中并且混合。(另一种方式是,可以首先将表面活性剂添加到水中,随后添加聚合物)。然后,添加碱性物料,优选中和剂例如氢氧化钠、三乙醇胺等,并且混合,以便将溶液中和。然后边混合边加入其余的添加剂,包括欲稳定的化合物,得到合意的最终产品。
″回酸″配制技术
本发明的聚合型流变改良剂不是开始便产生实质性的粘度,而是直至pH达到约5或6时。然而,有一些家庭和个人护理用途,它们要求pH少于6才达到最佳和合意的性能。因此这种聚合物在这类组合物中使用受到限制。此外,在如此较低pH范围下很难配制稳定的用品。
出人意料的是,现在发现如果将这些组合物的pH提高至近中性、甚至碱性,然后再降低pH,则粘度和屈服值通常保持不变或者经常是事实上增加。这种配制技术在本文中称作″回酸″增稠。这种配制技术因此拓宽了这些聚合物的用途范围并且现在允许用于在酸性pH条件下配制。此外,″回酸″增稠的过程还可以用于进一步增强在微酸性和在碱性pH条件下配制的组合物的粘度和稳定性。
将一种或多种丙烯酸酯共聚物、聚合物等等添加到水中并且混合。接着将表面活性剂添加到此聚合物的水溶液中并且混合。然后,添加碱性物料并且混合以便将组合物的pH增加到至少约5,优选至少约6,并且首选至少约6.5。碱性物料优选是中和剂,如氢氧化钠、氢氧化钾、三乙醇胺或在所说的用途中常用的另一种脂肪酸胺中和剂。或者是,可以使用其它碱性物料,如预中和的表面活性剂。合意地,其pH应当比组合物的最终目标pH高至少约0.5或2个pH单位并且优选至少3、4或甚至5个pH单位。然后,添加酸性物料,以便降低组合物的pH。
用于降低用品pH的物料是酸性物料,优选是有机酸,如柠檬酸,乙酸,α-羟基酸,β-羟基酸,水杨酸,乳酸,羟基乙酸,天然水果酸或者其的组合。除此之外,可以使用无机酸,例如盐酸,硝酸,硫酸,氨基磺酸,磷酸及其组合。以稳定的组合物的总重量计,这种酸的使用量通常为约0.1至约20wt%,合意地是约0.2wt%-15wt%,并且优选约0.25wt%至约10wt%。
使本发明组合物稳定的合意的pH显而易见地取决于具体的用途。通常来说,个人护理用途的所需pH范围为约3至约7.5,约4至约6是合意的。通常来说,家庭护理用途的所需pH范围为约1至约12,并且约3至约10是合意的。更具体说,当使用通常情况下是不溶性的硅氧烷或珠光色化合物时,所需的pH是约5.5至约12,而当稳定头发染料时,pH为约5至约9。
稳定性
使用本发明的基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂制作的各种个人护理、家庭护理、工业、公共机构等产品或组合物是稳定的。对特定组合物的稳定性要求将随其最终的市场用途以及将要购买和出售其的地点而有所不同。接下来测定每种组合物的可接受的″保质期″。″保质期″是指组合物在其整个正常贮藏和处置条件下应当是稳定的时间的量,测定的是将组合物生产出来和当将其最终出售用于消费之间的时间。通常来说,个人护理组合物需要3年保质期,而家庭护理组合物需要1年保质期。
为消除必需进行超过一年的稳定性研究,配制者可以在应力条件下进行稳定性测试,以便预测组合物的保质期。一般来说,在较高静态温度下进行加速测试,通常是45-50℃。在45℃下,组合物应当在至少2周内是稳定的,1个月是合意的,优选2或3个月,并且首选4或5个月。此外,经常使用冷冻-解冻循环操作,其中将组合物在结冻温度(通常是0℃)和常温(通常是20-25℃)之间循环。组合物应当可以通过最少1次冷冻解冻循环,优选3次循环,并且首选5次循环。
根据本发明制作的产品或组合物,如果它们满足以下条件的一项或多项,则认为它们是稳定的:
1.组合物中没有任何物料的相分离、沉淀或乳油分层。组合物的整体应当保持完全均匀。本文中,分离定义为在制剂中可以从视觉上看到存在有2层或更多层任何组分的不同的层或相,包括(但不限于)不溶性物质,可溶性物质,油质物等等。
2.组合物的粘度不随时间而有明显增加或降低,通常是增加或降低50%以下,优选35%以下,并且首选20%以下。
3.组合物的pH增加或降低不超过两个pH单位,优选不超过一个pH单位,并且首选不超过半个单位。
4.组合物的流变性和质地不随时间而有变化至其是不可接受的明显变化。
如果它们不满足上述所列条件的一项或多项,则根据本发明制作的产品或组合物认为是不稳定的。
关于稳定性测试要求的其它信息可见″稳定性测试的基本原理;IFSCC2号专刊″,以国际美容化学家协会联盟的名义出版,MicellePress,Weymouth,Dorset,英格兰和Cranford,新泽西,美国,并且其引入本文作为参考。
关于生物活性制剂稳定性的其它信息可见:欧盟对医药产品的评价/文件部分/ICH准则:
http://www.eudra.orq/humandocs/humans/ich.htm.(论题Q1A,步骤2)关于新药物质和产品稳定性测试的指南的注释(CPMP/ICH/380/95的修订版,99年11月发行供评议)。
实施例
本发明通过参考以下的实施例将会更好理解,以下实施例是举例说明性的,但不限制本发明的范围。
在以下的一些实施例中,如下制备制剂。将所提及的丙烯酸酯共聚物添加到水中并且混合。然后,将表面活性剂添加到此含水聚合物组合物中并且混合。接着,添加所示的中和剂如氢氧化钠并且混合。然后,按所列的顺序添加其余的化合物或成分,通常情况下在添加每种成分后进行混合。任选地,随后添加诸如柠檬酸的酸并且混合。
制剂实施例
实施例1:带珠光色的三合一调理洗发液
此制剂显示了:
1)使用″回酸″配制技术的稳定化的、含水表面活性剂组合物,
2)不溶性、高分子量非挥发性硅氧烷乳液的稳定化
3)珠光物料的悬浮和稳定化
4)增强的珠光色外观
特性:外观 缎子似光泽,带珠光色的粘性液体pH 5.5-5.8粘度*(cP) 8,000-10,000屈服值**(达因/cm2) 140-160表面活性剂活性物(%) 13.7稳定性 加速,45℃下,经过3个月
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%)月桂基醚硫酸钠(2mol,25%)氢氧化钠(18%) | 适量4.0025.000.75 | 稀释剂流变改良剂主要表面活性剂中和剂 | (BFGoodrich)StandapolES-2(Henkel) |
B部分去离子水NaOH(18%)羟丙基三甲基氯化铵瓜尔豆胶 | 5.000.050.30 | 稀释剂pH调节剂调理剂 | Cosmedia Guar C-261N(Henkel) |
C部分月桂基葡糖苷(50%)月桂基硫酸钠(29%)乙二醇二硬脂酸酯(和)月桂基醚-4(和)椰油酰胺基丙基甜菜碱 | 4.0015.003.00 | 辅助表面活性剂辅助表面活性剂珠光剂 | Plantaren1 200N(Henkel)StandapolWAQ-Special(Henkel)EuperlanPK-3000(Henkel) |
聚二甲基硅氧烷(和)月桂基醚-4(和)月桂基醚-23椰油酰胺基丙基甜菜碱(35%)椰油-葡糖苷(和)甘油油酸酯芳香剂苯氧基乙醇(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丁酯(和)对羟基苯甲酸乙酯(和)对羟基苯甲酸丙酯柠檬酸(50%) | 3.003.001.000.500.500.40 | 调理剂增泡剂增湿剂美学增强剂防腐剂pH调节剂 | DC1664乳液(DowCorning)VelvetexBA-35(Henkel)LamesoftPO-65(Henkel)Phenonip(Nipa) |
冷冻/解冻,通过5次循环*布鲁克菲尔德DV-II+(或RVT)@20;#5锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例2A、2B和2C:带珠光色的二合一调理洗发液
这些制剂显示了:
1)使用″回酸″配制技术的稳定化的、含水表面活性剂组合物,
2)不溶性、高分子量非挥发性硅氧烷的稳定化
3)三种不同类型的珠光物料的悬浮和稳定化:鸟嘌呤,乙二醇二硬脂酸酯和云母
4)增强的珠光色外观
特性:外观 粘性,缎子似光泽,带珠光色的液体pH 5.4-5.7粘度*(cP) 2A=3,600-6,000
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%)月桂基醚硫酸钠(3mol,28%)氢氧化钠(18%)椰油酰胺基丙基羟基磺基甜菜碱(50%)月桂基醚磺基琥珀酸二钠(40%) | 适量5.0030.001.0010.0010.00 | 稀释剂流变改良剂主要表面活性剂中和剂辅助表面活性剂辅助表面活性剂 | (BFGoodrich)StandapolES-3(Henkel)MirataineCBS(Rhodia)MackanateEL(McIntyre) |
B部分去离子水珠光剂:实施例2A:鸟嘌呤实施例2B:乙二醇二硬脂酸酯表面活性剂共混物实施例2C:云母(和)二氧化钛 | 适量0.153.000.20 | 稀释剂美学增强剂美学增强剂美学增强剂 | MearlmaidAAEuperlanPK3000TimironMP115 |
C部分聚二甲基硅氧烷芳香剂苯氧基乙醇(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丁酯(和)对羟基苯甲酸乙酯(和)对羟基苯甲酸丙酯柠檬酸(50%) | 3.000.500.500.35 | 调理剂美学增强剂防腐剂pH调节剂 | DowCorning200流体(60,000cS)Phenonip(Nipa) |
2B=5,300-8,200
2C=3,600-6,000屈服值**(达因/cm2) 80-150表面活性剂活性物(%) 17.4稳定性 加速,45℃下,经过3个月
冷冻/解冻,通过5次循环*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#4RV锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例3A和3B:澄清或闪亮的金色带珠光色二合一调理洗发液
这两种制剂是使用″回酸″技术配制的二合一调理洗发液的实例。它们也显示了不溶性、非挥发性高分子量胺官能团的硅氧烷微乳液的稳定化。
实施例3A是一种低pH(约5)的澄清制剂。
实施例3B中还含有珠光物料,其是悬浮的和稳定化的。此实施例也显示了流变性改良聚合物增强制剂珠光色外观的能力。
特性:外观 3A=澄清,粘性液体
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%)月桂基硫酸铵(30%)月桂基醚硫酸铵(3mol,27%)NaOH(18%)二甲苯磺酸铵(40%)PPG-2羟基乙基椰油酰胺(100%)椰油两性乙酸二钠(50%) | 适量5.0040.0020.001.402.504.004.00 | 稀释剂流变改良剂主要表面活性剂主要表面活性剂中和剂水溶助长剂增泡剂温和表面活性剂 | (BFGoodrich)stepanolAM(Stepan)StandapolEA-3(Henkel)StepanateAXS(Stepan)PromidiumCO(Mona)MonatericCLV(Mona) |
B部分去离子水实施例3A:不含云母实施例3B:云母、二氧化钛和氧化铁 | 适量0.20 | 稀释剂美学增强剂 | Cloisonne SparkleGold#222J(Englehard) |
C部分氨基聚二甲基硅氧烷(和)Trideceth-12(和)十六烷三甲基氯化铵芳香剂苯氧基乙醇(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丁酯(和)对羟基苯甲酸乙酯(和)对羟基苯甲酸丙酯柠檬酸(50%) | 3.000.500.501.70 | 调理剂美学增强剂防腐剂pH调节剂 | DowCorning2-8194微乳液Phenonip(Nipa) |
3B=粘性,金色,带珠光色的液体
柠檬酸添加之前
柠檬酸添加之后pH 6.5 5.0粘度*(cP) 3,300 7,800屈服值**(达因/cm2) 22 180表面活性剂活性物(%) 24.4稳定性 加速,45℃下,经过3个月
冷冻/解冻,通过5次循环*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#5RV锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例4A和4B:水杨酸脸部用擦洗液或洗发液
这两种制剂是使用″回酸″技术配制的非常低pH的水杨酸脸部用擦洗液的实例。
实施例4A显示了不溶性物料,西蒙得木油珠,在非常低pH(约4)下的悬浮和稳定化
实施例4B中含有珠光物料,其是悬浮的和稳定化的。此实施例也显示了流变性改良聚合物增强制剂的珠光色外观的能力。
特性:外观 4A=半透明,粘性液体,含有悬浮的珠
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%)α-烯烃磺酸盐(40%)氢氧化钠(18%)柠檬酸(50%) | 适量5.0015.001.000.50 | 稀释剂流变改良剂主要表面活性剂中和剂pH调节剂 | (BFGoodrich)BiotergeAS-40(Stepan) |
B部分去离子水α-烯烃磺酸盐(40%)甘油水杨酸(USP) | 15.0010.002.002.00 | 稀释剂主要表面活性剂润肤剂活性物 | BiotergeAS-40(Stepan) |
C部分椰油酰胺基丙基甜菜碱(35%)实施例4A:C12-13磷酸钾(40%)FD&C#33红(0.1%)FD&C#6黄(0.1%)西蒙得木油珠实施例4B:去离子水云母(和)二氧化钛 | 10.002.000.100.202.00适量0.20 | 增泡剂温和表面活性剂美学增强剂美学增强剂美学增强剂稀释剂美学增强剂 | VelvetexBA-35(Henkel)MonafaxMAP230(Mona)(BFG Hilton Davis)(BFG Hilton Davis)Florabeads(Floratech)Timiron MP115(Rona) |
4B=缎子似光泽,白色,带珠光色的粘性液体pH 3.8-4.0粘度*(cP) 5,500-10,000屈服值**(达因/cm2) 200-350表面活性剂活性物(%) 14.3稳定性 加速,45℃下,经过3个月
冷冻/解冻,通过5次循环*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#4RV锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例5:带珠光色的温和体用洗液
以下制剂是带珠光色的温和体用洗液的实例。这种制剂显示了以下:
1)使用″回酸″配制技术的稳定化的、含水表面活性剂组合物
2)不溶性、高分子量非挥发性硅氧烷树胶乳液的稳定化
3)珠光物料的悬浮和稳定化
4)增强的珠光色外观
特性:外观 粘性,缎子似光泽,带珠光色的液体pH 6.4-6.8粘度*(cP) 17,000-22,000屈服值**(达因/cm2) 100-150表面活性剂活性物(%) 23.0稳定性 加速,45℃下,经过3个月
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%)椰油基羟乙基磺酸盐(和)月桂基两性乙酸钠(和)甲基椰油基牛磺酸钠(和)二甲苯磺酸钠(38%)月桂基醚硫酸钠(2mol,27%) | 14.455.0045.0015.00 | 稀释剂流变改良剂主要表面活性剂共混物主要表面活性剂 | (BFGoodrich)MiracareUM-140(Rhodia)RhodapexES-2(Rhodia) |
B部分去离子水NaOH(18%)羟丙基三甲基氯化铵瓜尔豆胶柠檬酸(50%) | 5.000.050.150.05 | 稀释剂pH调节剂调理剂pH调节剂 | JaguarC-14S(Rhodia) |
C部分椰油两性乙酸钠(37%)季化羟乙基纤维素-7聚二甲基硅氧烷醇(和)TEA-十二烷基苯磺酸盐 | 5.002.004.00 | 辅助表面活性剂调理剂调理剂 | Miranol Ultra C37(Rhodia)Mirapo1550(Rhodia)DC1784乳液(DowCorning) |
D部分去离子水云母(和)二氧化钛 | 2.500.20 | 稀释剂美学增强剂 | Flamenco Satin Pearl3500(Englehard) |
E部分芳香剂苯氧基乙醇(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丁酯(和)对羟基苯甲酸乙酯(和)对羟基苯甲酸丙酯柠檬酸(50%) | 0.500.500.60 | 美学增强剂防腐剂pH调节剂 | Phenonip(Nipa) |
冷冻/解冻,通过5次循环*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#6RV锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例6:含有悬浮珠的澄清浴用凝胶
以下制剂是含有悬浮的珠的澄清浴用凝胶的实例。这种制剂显示了以下:
1)稳定化的、含水表面活性剂组合物
2)不溶性物料明胶珠在矿物油中的悬浮和稳定化
特性:外观 粘性,澄清液体pH 6.3-6.7粘度*(cP) 4,000-6,000cP屈服值**(达因/cm2) 120-220表面活性剂活性物(%) 11.1稳定性 经过3月加速的45℃
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
去离子水丙烯酸酯交联聚合物(30%)月桂基醚硫酸钠(2mol,28%)氢氧化钠(18%)椰油酰胺基丙基甜菜碱(30%)季化羟乙基纤维素-39EDTA四钠芳香剂聚山梨酸酯20含维生素E的白色珠 | 适量8.0037.301.322.102.100.050.500.501.00 | 稀释剂流变改良剂主要表面活性剂中和剂增泡剂调理剂鳌合剂芳香剂增溶剂增湿剂 | (BFGoodrich)TexaponNSO(Henkel)TegobetaineL(Goldschmidtl)Merquat3330(Calgon)吐温-20Lipopearls(LipoTechnologies) |
冷冻/解冻,通过5次循环*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃#4RV锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例7:临时性染发用洗发液(中等棕色)
以下制剂是临时性染发用洗发液或发色保持用洗发液的实例。这种制剂显示了以下:
1)使用阳离子染料的稳定化的粘性临时性染发用组合物
2)珠光物料的悬浮和稳定化
3)增强的珠光色外观
4)改进的流变特性
特性:外观 暗棕色,珠光色粘性液体pH 6.8-7.4粘度*(cP) 5,000-7,000屈服值**(达因/cm2) 300-400表面活性剂活性物(%) 8.6稳定性 加速,45℃下,经过3个月
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%) | 41.8510.00 | 稀释剂流变改良剂 | (BFGoodrich) |
B部分去离子水(加热至50℃)EDTA二钠丁二醇椰油两性乙酸钠(37%)椰油酰胺基丙基甜菜碱(35%)季化羟乙基纤维素-39丙二醇(和)二偶氮利定脲(diazolidinyl urea)(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丙酯氢氧化钠(18%) | 15.000.055.0015.003.000.800.450.25 | 稀释剂鳌合剂溶剂表面活性剂表面活性剂头发调理剂防腐剂中和剂 | Miranol Ultra C-37(Rhodia)ProtericCAB(Protameen)Merquat Plus 3330(Calgon)GermabenII(ISP) |
C部分去离子水(加热至50℃)碱性棕17/CI12251碱性蓝99/CI56059碱性红76/Cl12245聚二甲基硅氧烷共聚醇 | 10.000.250.1250.1250.20 | 稀释剂染料染料染料头发调理剂 | Arianor Sienna Brown(Tri-K/WarnerJenkinson)Arianor Steel Blue(Tri-K/WarnerJenkinson)Arianor Madder Red(Tri-K/WarnerJenkinson)DC193表面活性剂(DowCorning) |
D部分癸基葡糖苷(50%)去离子水云母(和)二氧化钛 | 4.003.000.20 | 表面活性剂稀释剂珠光剂 | Planaren2000(HenkelCospha)TimironMP-149DiamondCluster(Rona) |
冷冻/解冻,通过7次*布鲁克菲尔德DV-II+(或RVT)@20rpm,#4锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例8:去头屑用洗发液
以下制剂是调理型去头屑用洗发液的实例。这种制剂显示了以下:
1)使用″回酸″配制技术的稳定化的、含水表面活性剂组合物
2)不溶性、高分子量非挥发性硅氧烷树胶乳液的稳定化
3)不溶性去头屑物料羟基吡啶硫酮锌的悬浮和稳定化;
特性:外观 蓝色,不透明,粘性液体pH 5.4-5.7粘度*(cP) 3,500-5,000屈服值**(达因/cm2) 120-170表面活性剂活性物 11.5稳定性 加速,45℃下,经过1个月*布鲁克菲尔德DV-II(或RVT)@20rpm,25℃,#4锭子**布鲁克菲尔德DV-II(或RVT)@1和0.5rpm
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%)月桂基硫酸钠(29%)月桂基醚硫酸钠(2mol,25%)氢氧化钠(18%) | 适量5.0016.0016.000.65 | 稀释剂流变改良剂主要表面活性剂主要表面活性剂中和剂 | (BFGoodrich)StandapolWAQ-LC(Henkel)StandapolES-2(Henkel) |
B部分去离子水季化羟乙基纤维素-10DMDM乙内酰脲 | 10.000.250.30 | 稀释剂头发调理剂防腐剂 | UcarePolymerJR-400(Amerchol)Glydant(Lonza) |
C部分椰油酰胺基丙基甜菜碱柠檬酸(50%)羟基吡啶硫酮锌(48%)聚二甲基硅氧烷醇(和)TEA-十二烷基苯磺酸盐FD&C#1蓝(0.1%)芳香剂氯化钠 | 4.000.752.503.001.000.500.60 | 泡沫增强剂pH调节剂活性物调理剂染料芳香剂粘度增强剂 | VelvetexBA-35(Henkel)Zinc Omadine(Arch Chemical)DC1784乳液(DowCorning)(BFG Hilton Davis) |
实施例9:含有悬浮珠的澄清浴用凝胶
以下制剂是含有悬浮珠的澄清浴用凝胶的实例。这种制剂显示了以下:
1)稳定化的、含水表面活性剂组合物
2)不溶性物料明胶珠在矿物油中的悬浮和稳定化
特性:外观 粘性,澄清液体
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水丙烯酸酯交联聚合物(30%)月桂基醚硫酸钠(3mol,28%)氢氧化钠(18%)丙二醇 | 42.0310.0030.001.902.00 | 稀释剂流变改良剂主要表面活性剂中和剂保湿剂 | (BFGoodrich)StandapolES-3(Henkel) |
B部分去离子水二苯甲酮-4EDTA二钠 | 5.000.020.10 | 稀释剂UV吸收剂鳌合剂 | UvinulMS-40(BASF) |
C部分椰油酰胺基丙基甜菜碱(35%) | 4.00 | 泡沫增强剂 | Incronam30(Croda) |
D部分聚山梨酸酯-20芳香剂丙二醇、二偶氮利定脲、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯白色珠w/维生素EFD&C#1蓝(0.1%)FD&C#5绿(0.1%) | 0.800.601.001.000.051.50 | 增溶剂芳香剂防腐剂增湿剂染料染料 | 吐温20(ICI)GermabenII(Sutton)Lipopearis(LipoTechnolgioes)(BFG Hilton Davis)(BFG Hilton Davis) |
柠檬酸添加之前
柠檬酸添加之后pH 6.5 4.5粘度*(cP) 4,600 5,500屈服值**(达因/cm2) 270 440表面活性剂活性物(%) 10.6稳定性 加速,45℃下,经过3个月
冷冻/解冻,通过5次循环*布鲁克菲尔德DV-I)+(或RVT)@20rpm,25℃,#4RV锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例10:α-羟基酸霜
以下制剂是AHA(α-羟基酸)露的实例。这种制剂显示了以下:
1)使用″回酸″配制技术的稳定化的、含水的以表面活性剂为基料的乳液组合物。
2)高含量α-羟基酸(约6%)的pH非常低(约4)下的乳液的流变性改良和稳定化。
3)不溶性、非挥发性硅氧烷(聚二甲基硅氧烷)和其它油性物料(棕榈酸异丙酯和矿物油)在乳液中的稳定化。
特性:外观 浓稠,白色霜pH 3.8-4.1粘度*(cP) 16,000-18,000表面活性剂活性物(%) 5.7稳定性 加速,45℃下,经过1月
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水甘油三乙醇胺(99%) | 51.554.800.75 | 稀释剂保湿剂中和剂 | |
B部分鲸蜡基醇硬脂酸甘油酯(和)PEG-100硬脂酸酯硬脂酸(3X)棕榈酸异丙酯矿物油(和)羊毛脂醇聚二甲基硅氧烷 | 2.854.251.454.254.251.45 | 遮光剂乳化剂乳化剂润肤剂润肤剂润肤剂 | Arlacel165(ICI表面活性剂)Amerchol101(Amerchol)DC200Fluid(350cS)(DowCorning) |
C部分丙烯酸酯交联聚合物(30%)乳酸(45%溶液)三乙醇胺丙二醇(和)二偶氮利定脲(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丙酯 | 5.0013.405.001.00 | 流变改良剂活性物中和剂防腐剂 | (BFGoodrich)GermabenII(Sutton) |
冷冻/解冻,通过3次循环*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#6RV锭子
制备过程:
1.A部分:将甘油和三乙醇胺添加到去离子水中。加热至65℃。
2.B部分:将所有的成分在单独的容器中合并并且加热直至熔融。边剧烈搅拌边添加到A部分。冷却至约40℃同时混合。
3.缓慢加入到丙烯酸酯交联聚合物中,同时混合。
4.缓慢添加乳酸溶液,同时混合。
5.用三乙醇胺调节pH至4.0。
6.添加防腐剂。
实施例11:脸部用霜
以下制剂是脸部用霜的实例。这种制剂显示了以下:
1)含水的以表面活性剂为基料的乳液组合物
2)不溶性、挥发性硅氧烷(环二甲基聚硅氧烷),非挥发性硅氧烷(聚二甲基硅氧烷)和其它油性物料(向日葵油,鲸蜡硬脂基辛酸酯和PPG-2肉豆蔻基醚丙酸盐)在乳液中的稳定化
特性:外观 白色,粘性乳液pH 6.0-7.0粘度*(cP) 10,000-20,000表面活性剂活性物(%) 4.5*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#6锭子
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分(加热至55℃)去离子水甘油 | 76.802.50 | 稀释剂保湿剂 | |
B部分(加热至55C)PPG-2肉豆蔻基醚丙酸盐鲸蜡硬脂基辛酸酯向日葵油鲸蜡基醇鲸蜡硬脂基醇/Ceteareth-20 | 2.003.253.001.503.00 | 润肤剂润肤剂润肤剂乳化剂乳化剂 | CrodamolPMP(Croda)CrodamolCAP(Croda)Lanette16NF(Henkel)Emulgade1000NI(Henkel) |
C部分丙烯酸酯交联聚合物(30%)氢氧化钠(18%)(至pH6.5) | 5.000.95 | 流变性改良剂中和剂 | (BFGoodrich) |
D部分(40℃下添加)环二甲基聚硅氧烷(和)聚二甲基硅氧烷 | 1.00 | 润滑剂 | DC1401Fluid(DowCorning) |
E部分丙二醇(和)二偶氮利定脲(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丙酯 | 1.00 | 防腐剂 | GermabenII-E(Sutton) |
实施例12:体用露以下制剂是体用露的实例。这种制剂显示了以下:
1)含水的以表面活性剂为基料的乳液
2)不溶性、挥发性硅氧烷(环二甲基聚硅氧烷),非挥发性硅氧烷(聚二甲基硅氧烷)和其它油性物料(C12-15烷基苯甲酸酯,硬脂酸辛酯和矿物油)的稳定化。
特性:外观 白色露pH 6.0-7.0粘度*(cP) 15,000-25,000表面活性剂活性物(%) 4.5*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#6锭子
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
A部分去离子水甘油 | 76.802.50 | 稀释剂保湿剂 | |
B部分矿物油C12-15烷基苯甲酸酯硬脂酸辛酯鲸蜡基醇鲸蜡硬脂基醇/Ceteareth-20 | 4.002.501.751.503.00 | 润肤剂润肤剂润肤剂乳化剂乳化剂 | Drakeol21(Penreco)FinsolvTN(Finetex)Cetiol868(Henkel)Lanette16NF(Henkel)Emulgade1000NI(Henkel) |
C部分丙烯酸酯交联聚合物(30%)氢氧化钠(18%) | 5.000.95 | 流变性改良剂中和剂 | (BFGoodrich) |
D部分环二甲基聚硅氧烷(和)聚二甲基硅氧烷 | 1.00 | 润滑剂 | DC1401Fluid(DowCorning) |
E部分丙二醇(和)二偶氮利定脲(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丙酯 | 1.00 | 防腐剂 | GermabenII-E(Sutton) |
实施例13:d-苧烯清洁剂
以下制剂是苧烯清洁剂的实例。这种制剂显示了以下:
1)使用″回酸″配制技术的含水的以表面活性剂为基料的乳液组合物
2)不溶性油性物料(d-苧烯)在含非常少表面活性剂的乳液中稳定化和共乳化
特性:外观 不透明,白色,低粘度,可喷的露
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
去离子水丙烯酸酯交联聚合物(30%)d-苧烯丙二醇甘油C12-15Pareth-7丙二醇(和)二偶氮利定脲(和)对羟基苯甲酸甲酯(和)对羟基苯甲酸丙酯氢氧化钠(18%)柠檬酸(50%) | 适量4.0025.001.002.001.001.001.200.25 | 稀释剂稳定剂溶剂保湿剂保湿剂表面活性剂防腐剂中和剂pH调节剂 | (BFGoodrich)ArylessenceNeodol25-7(Shell)GermabenII-E(SuttonLabs) |
柠檬酸添加之前
柠檬酸添加之后pH 7.8 6.8粘度*(cP) 6,500 11,300屈服值**(达因/cm2) 520 1,380表面活性剂活性物(%) 1.0*布鲁克菲尔德DV-II+(或RVT)@20rpm,25℃,#3锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
实施例14:液体洗涤剂
以下制剂是可用于各种清洁用途的组合物的实例,如用于手洗洗餐具用的组合物。这种制剂显示了用″回酸″配制技术来明显增加粘度的作用。此外,通过″回酸″配制技术获得的屈服值的明显增加允许不溶性化合物的悬浮。
特性:外观 粘性液体
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
去离子水丙烯酸酯交联聚合物(30%)月桂基硫酸铵(28%)月桂基醚硫酸钠(2mol,25%)氢氧化钠(18%)柠檬酸(50%) | 适量5.5025.0025.001.00适量 | 稀释剂流变改良剂表面活性剂表面活性剂pH调节剂pH调节剂 | (BFGoodrich)StandapolA(Henkel)StandapolES-2(Henkel) |
柠檬酸添加之前
柠檬酸添加之后pH 7.0 5.0粘度*(cP) 1,825 4,550屈服值**(达因/cm2) 25 170表面活性剂活性物(%) 13.3*布鲁克菲尔德DV-II+(或RVT)@20,#5锭子**布鲁克菲尔德DV-11+(或RVT)@1和0.5rpm
实施例15:重役型液体洗涤剂
以下制剂是可用于各种清洁用途的组合物的实例,如用于手洗洗餐具或洗织物用的组合物。这种制剂显示了″回酸″配制技术来明显增加粘度的作用。此外,通过″回酸″配制技术获得的屈服值的明显增加允许不溶性化合物的悬浮。
特性:外观 粘性液体pH 3.0-4.0粘度*(cP) 9,000-10,000表面活性剂活性物(%) 21.0*布鲁克菲尔德DV-II+(或RVT)@20,#5锭子
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
去离子水丙烯酸酯交联聚合物(30%)月桂基醚硫酸钠3molEO(28%)C12-13乙氧基化直链醇1molEO氢氧化钠(18%)柠檬酸(50%) | 适量5.0075.002.001.004.00 | 稀释剂流变改良剂表面活性剂表面活性剂pH调节剂pH调节剂 | (BFGoodrich)StandapolES-3(Henkel)Neodol23-1(Shell) |
实施例16:重役型液体洗涤剂
以下制剂是可用于各种清洁其它的组合物的实例,如手洗洗餐具用或织物洗涤用的组合物。此制剂合并了基本上交联的可碱溶胀性丙烯酸酯流变改良剂与标准交联的聚丙烯酸酯聚合物。此制剂进一步显示了″回酸″配制技术来明显增加粘度的作用。此外,通过″回酸″配制技术获得的屈服值的明显增加允许不溶性化合物的悬浮。
特性:外观 粘性液体pH 4.0粘度*(cP) 42,000表面活性剂活性物(%) 17.5*布鲁克菲尔德DV-II+(或RVT)@20,#5锭子
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
去离子水丙烯酸酯交联聚合物(30%)Carbomer月桂基醚硫酸钠2摩尔EO(25%)氢氧化钠(18%)柠檬酸(50%) | 适量5.000.7570.001.004.00 | 稀释剂流变改良剂流变改良剂表面活性剂pH调节剂pH调节剂 | (BFGoodrich)CarbopolEZ-1(BFGoodrich)StandapolES-2(Henkel) |
实施例17:重役型液体洗涤剂
以下制剂是可用于各种清洁用途的组合物的实例,如用于织物洗涤用的组合物。这种制剂显示了″回酸″配制技术来明显增加粘度的作用。该实施例,然而,显示了将组合物的pH增加至非常碱性的pH,然后通过降低至近中性pH的能力。此外,通过″回酸″配制技术获得的屈服值的明显增加允许不溶性化合物的悬浮。
特性:外观 粘性凝胶柠檬酸添加之前的pH 13.0柠檬酸添加之后的pH 8.0粘度*(cP) 15,000屈服值**(达因/cm2) 180表面活性剂活性物 23.2*布鲁克菲尔德DV-II+(或RVT)@20,#5锭子**布鲁克菲尔德DV-II+(或RVT)@1和0.5rpm
成分 | 重量百分比 | 功能 | 商品名称(供应商) |
水丙烯酸酯交联聚合物(30%)烷基苯磺酸(97%)月桂基硫酸钠(29%)月桂基醚硫酸钠2摩尔EO(25%)烷基聚葡糖苷(50%)椰油脂肪酸三乙醇胺(99%)甘油NaOH(50%)柠檬酸(50%) | 适量7.0013.507.507.505.003.507.002.008.608.00 | 稀释剂流变改良剂表面活性剂表面活性剂表面活性剂表面活性剂表面活性剂pH调节剂溶剂pH调节剂pH调节剂 | (BFGoodrich)BiosoftS-100(Stepan)StandapolWAQ(Henkel)StandapolES-2(Henkel)Glucopon600CS(Henkel) |
对比稳定性测试
用不同的聚合型流变改良剂配制所选择的实施例制剂:样品 聚合物代码 描述A ″W″ 丙烯酸酯交联聚合物(本发明)B 没有聚合物C ″X″ 丙烯酸酯/Ceteth-20甲基丙烯酸酯共聚物D ″Y″ 丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物
将用″不含聚合物″所作的实验的粘度调节至使用氯化钠的每一制剂的所需粘度范围。每一制剂中使用等重量的″聚合物W″和″聚合物X″。通过所需的制剂粘度确定″聚合物Y″的量。表1
解答:STAB=稳定/不稳定评价S=稳定的U=不稳定的LV=低粘度(开始阶段)NT=没有测试PR=差的流变性和质地SEP=相分离评价等级
实施例# | 样品A | 样品B | 样品C | 样品D | ||||||||
STAB | SEP | DAY | STAB | SEP | DAY | STAB | SEP | DAY | STAB | SEP | DAY | |
1 | S | 0 | 84 | U | 10 | 14 | U | 2 | 7 | U | 10 | 21 |
2A | S | 0 | 84 | U | 6 | 7 | U | 2 | 21 | U | 6 | 14 |
2B | S | 0 | 84 | U | 10 | 7 | U | 2 | 7 | U | 2 | 91 |
2C | S | 0 | 70 | U | 10 | 7 | U | 4 | 7 | U | 4 | 7 |
3A | S | 0 | 84 | S,LV | 0 | 8 | S | 0 | 77 | U | 2 | 56 |
3B | S | 0 | 84 | U | 10 | 1 | U | 10 | 1 | U | 10 | 14 |
4A | S | 0 | 84 | U | 10 | 1 | U | 10 | 1 | U | 10 | 1 |
4B | S | 0 | 84 | U | 10 | 14 | NT | U | 10 | 7 | ||
5 | S | 0 | 70 | U | 10 | 14 | NT | U | 5 | 21 | ||
6 | S | 0 | 84 | U | 10 | 1 | U | 10 | 7 | U | 5 | 7 |
7 | S | 0 | 84 | NT | NT | U,PR | -- | 14 |
以数字表示的评价
视觉分离
稳定性解释
0 没有分离 稳定的
1 乳油分层 处于不稳定边界
2 分离(0.1-0.2cm) 不稳定
5 分离(0.5cm) 不稳定
10 分离(4+cm) 不稳定DAY=在45℃下的天数
正如从表1所示的数据明显看出的,针对实施例1至7而言,本发明的流变性改良用聚合物(各实施例的样品A)产生改进的稳定性,而不含聚合物或者使用聚合物X和Y中任一种没有产生稳定的系统。
″回酸″增稠数据
使用″回酸″配制技术制备选择的实施例制剂。记录下开始阶段时高pH下的粘度和屈服值测量值。再记录下随后添加酸性物料之后的测量值。如表2所示,注意到使用本发明的聚合物W,粘度值和屈服值在添加酸之后有所增加。注意到用聚合物X和聚合物Y的粘度和屈服值没有增加。表2
*布鲁克菲尔德粘度@20rpm,锭子4**布鲁克菲尔德屈服值@1和0.5rpm
实施例# | 聚合物 | 读数 | pH | 粘度*(cP) | 屈服值**(达因/cm2) |
2B | W | 柠檬酸添加之前柠檬酸添加之后 | 6.25.5 | 1,8007,400 | 20160 |
3A | W | 柠檬酸添加之前柠檬酸添加之后 | 6.55.0 | 3,3007,800 | 22180 |
X | 柠檬酸添加之前柠檬酸添加之后 | 6.55.2 | 11,000700 | 2828 | |
9 | W | 柠檬酸添加之前柠檬酸添加之后 | 6.54.5 | 4,6005,500 | 270440 |
X | 柠檬酸添加之前柠檬酸添加之后 | 6.54.5 | 11,000700 | 10025 | |
Y | 柠檬酸添加之前柠檬酸添加之后 | 6.54.5 | 6,0002,900 | 300100 | |
13 | W | 柠檬酸添加之前柠檬酸添加之后 | 7.86.8 | 6,50011,300 | 5201,380 |
14 | W | 柠檬酸添加之前柠檬酸添加之后 | 7.05.0 | 1,8254,550 | 25170 |
改进的珠光色外观
根据以下制剂的珠光色外观给它们以等级评价。在开始阶段(制作完之后立即)观察这些制剂,并且在45℃烘箱中稳定性测试一周后再观察。用本发明聚合物(聚合物W)的制剂相比其它聚合物(聚合物X和Y)提供改进的珠光色外观并且还稳定地保持此外观。
表3
实施例制剂的珠光色外观评价
注释NT=没有测试珠光色外观的评分等级
实施例# | 开始阶段的评价 | 45℃下老化一周后的评价 | ||||||
聚合物 | W | 不含 | X | Y | W | 不含 | X | Y |
2A | 9 | 9 | 9 | 2 | 9 | 1 | 1 | 0 |
2B | 8 | 8 | 8 | 1 | 8 | 0 | 0 | 0 |
2C | 10 | 10 | 10 | 3 | 10 | 0 | 0 | 0 |
3B | 10 | 9 | 9 | 5 | 10 | 0 | 0 | 0 |
4B | 10 | 10 | NT | 6 | 10 | 0 | NT | 0 |
评分 | 描述 |
10 | 极具珠光色外观,非常强眼和夺目,缎子似光泽,优雅,发光亮并且有光泽。 |
9 | |
8 | 良好的珠光色外观。 |
7 | |
6 | |
5 | 中等的珠光色外观。不强眼或无光泽。 |
4 | |
3 | 略微珠光色外观。 |
2 | |
1 | |
0 | 没有珠光色外观。完全不透明并且单调 |
数据表1所示的所选择的制剂的对比稳定性测试的照片示于各附图中。样品 聚合物代码 描述A ″W″ 丙烯酸酯交联聚合物(本发明)B 没有聚合物C ″X″ 丙烯酸酯/Ceteth-20甲基丙烯酸酯共聚物D ″Y″ 丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物
图1涉及实施例2A(带珠光色二合一调理洗发液)在45℃下稳定性测试10周。此照片显示了样品A的稳定性,和样品B、C和D的乳油分层不稳定性。注意到样品B、C和D中的珠光色-外观也消失。
图2涉及实施例2C(含云母的带珠光色二合一调理洗发液)在45℃下稳定性8周。此照片显示了样品A的增强的珠光色外观和稳定性。在样品C中观察到乳油分层不稳定性和阴暗的外观。
图3涉及实施例2C(含云母的带珠光色二合一调理洗发液)的珠光色外观。注意到样品A的闪亮外观(评分10)以及样品D的阴暗、单调外观(评分0)。
图4涉及实施例2C(含云母的带珠光色二合一调理洗发液)的珠光色外观。上面的照片是开始阶段的外观,下面的照片是12小时后的外观。注意到样品B、C和D在12小时后的阴暗外观。样品A保持闪亮珠光色外观。
图5涉及实施例4A(水杨酸脸部用擦洗液)在45℃下稳定性测试8周。此照片显示了样品A中西蒙得木油珠的稳定性和悬浮。在样品B、C和D中,观察到极不稳定性和西蒙得木油珠的分离。
图6涉及实施例4B(含云母的水杨酸洗发液)在45℃下稳定性测试8周。此照片显示了样品A的稳定性以及增强的珠光色外观。在样品B、和D中观察到云母的极不稳定性和沉积。
图7涉及实施例5(带珠光色温和体用洗液)在45℃下稳定性测试10周。此照片显示了样品A的稳定性以及样品B和D的清晰的相分离(不稳定)和沉积。
图8涉及实施例6(含悬浮珠的澄清浴用凝胶)在室温下稳定性测试8周。此照片显示了样品A的稳定性和油珠的悬浮。在样品C和D中观察到不稳定性和和油珠的分离。
尽管本发明根据专利法给出了最佳方式和优选的实施方案,但本发明的范围不限于此而由权利要求书的范围所限定。
Claims (60)
1.一种稳定的、含有表面活性剂的含水组合物,该组合物含有:
a.至少一种阴离子、两性离子、两性、非离子或阳离子表面活性剂或者其的组合;
b.至少一种基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂;
c.水;
d.有效量的至少一种碱性物料,以便使组合物的pH为约5至约14;和
e.有效量的随后添加的酸性物料,以便使组合物的pH降低至约1至约12。
2.根据权利要求1的组合物,其中所说的共聚物得自:
a.约20wt%至约80wt%的至少一种羧酸单体,包括丙烯酸、甲基丙烯酸、衣康酸、富马酸、巴豆酸、乌头酸或马来酸或者其的组合;
b.约80wt%至约15wt%的至少一种α,β-烯键式不饱和单体,其中所说的单体具有下式:
i)CH2=CXY,其中X是H并且Y是-COOR,-C6H4R’,-CN,-CONH2,-Cl,-NC4H6O,NH(CH2)3COOH,-NHCOCH3,-CONHC(CH3)3,-CO-N(CH3)2或X是CH3并且Y是-COOR,-C6H4R’,-CN;或-CH=CH2;或者X是Cl并且Y是Cl,并且R是C1-C18烷基或羟基C2-C18烷基,R’是H或C1-C18烷基,或下式:
ii)CH2=CH(OCOR1);其中R1是C1-C18烷基;或具有下式:
iii)CH2=CH2或CH2=CHCH3,和
c.约0.01至约5wt%的至少一种可用于形成部分交联或者基本上交联的三维网络结构的多不饱和化合物。
3.根据权利要求2的组合物,其中所说的共聚物的量以所说的稳定的组合物的总重量计为约0.1wt%至约10wt%,并且其中所说的表面活性剂的量以所说的稳定的组合物的总重量计为约1wt%至约80wt%。
4.根据权利要求3的组合物,其中所说的酸性物料是柠檬酸,乙酸,β-羟基酸,水杨酸,α-羟基酸,乳酸,羟基乙酸,盐酸,硫酸,硝酸,氨基磺酸,磷酸或天然水果酸或者其的组合。
5.根据权利要求4的组合物,其中所说的共聚物得自:
a.约35wt%至约65wt%的丙烯酸或甲基丙烯酸或者其的组合,
b.约65wt%至约35wt%的丙烯酸乙酯或丙烯酸甲酯酯或者其的组合,和
c.约0.03wt%至约3wt%的蔗糖或多元醇的聚链烯基醚或者三(甲基)丙烯酸三羟甲基丙烷酯,甲基丙烯酸缩水甘油酯,N-羟甲基丙烯酰胺,或者其的组合。
6.根据权利要求5的组合物,含有至少一种具有药物、兽医用、杀生物、除草、杀虫或其它生物学活性的″生物活性″物料。
7.根据权利要求5的组合物,含有至少一种需要悬浮或稳定化的基本上不溶性的物料。
8.根据权利要求7的组合物,其中所说的基本上不溶性物料是具有药物、兽医用、杀生物、除草、杀虫或其它生物学活性的″生物活性″物料。
9.根据权利要求7的组合物,其中所说的基本上不溶性物料是硅氧烷或油性物料或珠光物料或者其的组合。
10.根据权利要求9的组合物,其中所说的不溶性硅氧烷是聚(二甲基硅氧烷),氨基聚二甲基硅氧烷,氨基聚二甲基硅氧烷粗乳液或微乳液,聚二甲基硅氧烷,聚二甲基硅氧烷醇(硅氧烷树胶),环二甲基聚硅氧烷,苯基三甲基聚硅氧烷,聚二甲基硅氧烷或聚二甲基硅氧烷醇微乳液或粗乳液,有机聚硅氧烷,烷氧基硅氧烷或其的任何组合,其中所说的硅氧烷的量以所说的稳定的组合物的总重量计为约0.1至约20wt%。
11.根据权利要求9的组合物,其中所说的不溶性珠光物料是涂敷有二氧化钛的云母,涂敷有氧化铁的云母,乙二醇一硬脂酸酯,乙二醇二硬脂酸酯,聚乙二醇二硬脂酸酯,涂敷有氯氧化铋的云母,肉豆蔻酸肉豆蔻酯,鸟嘌呤(鱼鳞)或闪光剂(聚酯或金属类的)或者其的组合,其中所说的珠光物料的量以所说的稳定的组合物的总重量计为约0.05%至约10wt%。
12.根据权利要求10的组合物,其中所说的组合物基本上不含脂肪酸,脂肪酸酯,脂肪醇或者其的组合。
13.一种稳定的、含有表面活性剂的含水组合物,该组合物含有:
a.至少一种阴离子、两性离子、两性、非离子或阳离子表面活性剂或者其的组合;
b.至少一种基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂;
c.水;
d.至少一种化合物,其是不溶性硅氧烷或不溶性油性物料或者其的组合;和
e.有效量的至少一种中和剂,以便使最终的pH为约5.5至约12。
14.根据权利要求13的组合物,其中所说的共聚物得自:
a.约20wt%至约80wt%的至少一种羧酸单体,包括丙烯酸、甲基丙烯酸、衣康酸、富马酸、巴豆酸、乌头酸或马来酸或者其的组合;
b.约80wt%至约15wt%的至少一种α,β-烯键式不饱和单体,其中所说的单体具有下式:
i)CH2=CXY,其中X是H并且Y是-COOR,-C6H4R’,-CN,-CONH2,-Cl,-NC4H6O,-NH(CH2)3COOH,-NHCOCH3,-CONHC(CH3)3,-CO-N(CH3)2或X是CH3并且Y是-COOR,-C6H4R’,-CN;或-CH=CH2;或者X是Cl并且Y是Cl,并且R是C1-C18烷基或羟基C2-C18烷基,R’是H或C1-C18烷基,或下式:
ii)CH2=CH(OCOR1);其中R1是C1-C18烷基;或具有下式:
iii)CH2=CH2或CH2=CHCH3,和
c.约0.01至约5wt%的至少一种可用于形成部分交联或者基本上交联的三维网络结构的多不饱和化合物。
15.根据权利要求14的组合物,其中所说的表面活性剂的量以所说的稳定的组合物的总重量计为约1wt%至约80wt%,并且其中所说的共聚物的量以所说的含水组合物的总重量计为约0.1wt%至约10wt%。
16.权利要求15的稳定的、含水表面活性剂,其中所说的共聚物得自
a.约35wt%至约65wt%的丙烯酸或甲基丙烯酸或者其的组合,
b.约65wt%至约35wt%的丙烯酸乙酯或丙烯酸甲酯或者其的组合,和
c.约0.03wt%至约3wt%的蔗糖或多元醇的聚链烯基醚或者三(甲基)丙烯酸三羟甲基丙烷酯,乙基丙烯酸缩水甘油酯,N-羟甲基丙烯酰胺,或者其的组合。
17.根据权利要求14的组合物,其中所说的不溶性硅氧烷是聚(二甲基硅氧烷),氨基聚二甲基硅氧烷,氨基聚二甲基硅氧烷粗乳液或微乳液,聚二甲基硅氧烷,聚二甲基硅氧烷醇(硅氧烷树胶),环二甲基聚硅氧烷,苯基三甲基聚硅氧烷,聚二甲基硅氧烷或聚二甲基硅氧烷醇微乳液或粗乳液,有机聚硅氧烷,烷氧基硅氧烷或其的任何组合,并且其中所说的硅氧烷的量以所说的稳定的组合物的总重量计为约0.1至约20wt%。
18.根据权利要求16的组合物,其中所说的不溶性硅氧烷是聚(二甲基硅氧烷),氨基聚二甲基硅氧烷,氨基聚二甲基硅氧烷粗乳液或微乳液,聚二甲基硅氧烷,聚二甲基硅氧烷醇(硅氧烷树胶),环二甲基聚硅氧烷,苯基三甲基聚硅氧烷,聚二甲基硅氧烷或聚二甲基硅氧烷醇微乳液或粗乳液,有机聚硅氧烷,烷氧基硅氧烷或其的任何组合,并且其中所说的硅氧烷的量以所说的稳定的组合物的总重量计为约0.1至约20wt%。
19.根据权利要求18的组合物,其中所说的组合物基本上不合脂肪酸,脂肪醇,脂肪酸酯或者其的组合。
20.一种具有改进或增强的珠光色外观的稳定的、含有表面活性剂的含水组合物,该组合物含有:
a.至少一种阴离子、两性离子、两性、非离子或阳离子表面活性剂或者其的组合;
b.至少一种基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂;
c.水;
d.至少一种珠光色物料;和
e.有效量的至少一种中和剂,以便使最终的pH为约5.5至约12。
21.根据权利要求20的组合物,其中所说的共聚物得自:
a.约20wt%至约80wt%的至少一种羧酸单体,包括丙烯酸、甲基丙烯酸、衣康酸、富马酸、巴豆酸、乌头酸或马来酸或者其的组合;
b.约80wt%至约15wt%的至少一种α,β-烯键式不饱和单体,其中所说的单体具有下式:
i)CH2=CXY,其中X是H并且Y是-COOR,-C6H4R’,-CN,-CONH2,-Cl,-NC4H6O,-NH(CH2)3COOH,-NHCOCH3,-CONHC(CH3)3,-CO-N(CH3)2或X是CH3并且Y是-COOR,-C6H4R’,-CN;或-CH=CH2;或者X是Cl并且Y是Cl,并且R是C1-C18烷基或羟基C2-C18烷基,R’是H或C1-C18烷基,或具有下式:
ii)CH2=CH(OCOR1);其中R1是C1-C18烷基;或具有下式:
iii)CH2=CH2或CH2=CHCH3,和
c.约0.01至约5wt%的至少一种可用于形成部分交联或者基本上交联的三维网络结构的多不饱和化合物。
22.根据权利要求21的组合物,其中所说的表面活性剂的量以所说的稳定的组合物的总重量计为约1%至约80wt%,并且其中所说的共聚物的量以所说的含水组合物的总重量计为约0.1wt%至约10wt%。
23.根据权利要求22的组合物,其中所说的共聚物得自
a.约35wt%至约65wt%的丙烯酸或甲基丙烯酸或者其的组合,
b.约65wt%至约35wt%的丙烯酸乙酯或丙烯酸甲酯或者其的组合,和
c.约0.03wt%至约3wt%的蔗糖或多元醇的聚链烯基醚或者三(甲基)丙烯酸三羟甲基丙烷酯,甲基丙烯酸缩水甘油酯,N-羟甲基丙烯酰胺,或者其的组合。
24.根据权利要求21的组合物,其中所说的珠光物料是涂敷有二氧化钛的云母,涂敷有氧化铁的云母,乙二醇一硬脂酸酯,乙二醇二硬脂酸酯,聚乙二醇二硬脂酸酯,涂敷有氯氧化铋的云母,肉豆蔻酸肉豆蔻酯,鸟嘌呤(鱼鳞)或闪光剂(聚酯或金属类的)或者其的组合,其中所说的珠光物料的量以所说的稳定的组合物的总重量计为约0.05%至约10wt%。
25.根据权利要求23的组合物,其中所说的珠光物料是涂敷有二氧化钛的云母,涂敷有氧化铁的云母,乙二醇一硬脂酸酯,乙二醇二硬脂酸酯,聚乙二醇二硬脂酸酯,涂敷有氯氧化铋的云母,肉豆蔻酸肉豆蔻酯,鸟嘌呤(鱼鳞)或闪光剂(聚酯或金属类的)或者其的组合,其中所说的珠光物料的量以所说的稳定的组合物的总重量计为约0.05%至约10wt%。
26.根据权利要求25的组合物,其中所说的珠光物料是平均颗粒粒度为约2至约150微米直径的涂敷有二氧化钛的云母。
27.一种稳定的、含水临时性头发染料组合物,该组合物含有:
a.至少一种两性离子、两性、非离子或阳离子表面活性剂或者其的组合;
b.至少一种基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂;
c.水;
d.至少一种阳离子头发染料;和
e.有效量的至少一种中和剂,以便使最终的pH为约5至约9。
28.根据权利要求27的组合物,其中所说的共聚物得自:
a.约20wt%至约80wt%的至少一种羧酸单体,包括丙烯酸、甲基丙烯酸、衣康酸、富马酸、巴豆酸、乌头酸或马来酸或者其的组合;
b.约80wt%至约15wt%的至少一种α,β-烯键式不饱和单体,其中所说的单体具有下式:
i)CH2=CXY,其中X是H并且Y是-COOR,-C6H4R’,-CN,-CONH2,-Cl,-NC4H6O,-NH(CH2)3COOH,-NHCOCH3,-CONHC(CH3)3,-CO-N(CH3)2或X是CH3并且Y是-COOR,-C6H4R’,-CN;或-CH=CH2;或者X是Cl并且Y是Cl,并且R是C1-C18烷基或羟基C2-C18烷基,R’是H或C1-C18烷基,或下式:
ii)CH2=CH(OCOR1);其中R1是C1-C18烷基;或具有下式:
iii)CH2=CH2或CH2=CHCH3,和
c.约0.01至约5wt%的至少一种可用于形成部分交联或者基本上交联的三维网络结构的多不饱和化合物。
29.根据权利要求28的组合物,其中所说的表面活性剂的量以所说的稳定的组合物的总重量计为约1wt%至约80wt%,并且其中所说的共聚物的量以所说的含水组合物的总重量计为约0.1wt%至约10wt%。
30.根据权利要求29的组合物,其中所说的共聚物得自
a.约35wt%至约65wt%的丙烯酸或甲基丙烯酸或者其的组合,
b.约65wt%至约35wt%的丙烯酸乙酯或丙烯酸甲酯或者其的组合,和
c.约0.03wt%至约3wt%的蔗糖或多元醇的聚链烯基醚或者三(甲基)丙烯酸三羟甲基丙烷酯,甲基丙烯酸缩水甘油酯,N-羟甲基丙烯酰胺,或者其的组合。
31.根据权利要求28的组合物,其中所说的阳离子头发染料是偶氮染料或蒽醌染料或者其的组合,并且其中所说的头发染料的量以稳定的组合物的总重量计为约0.1wt%至约5wt%。
32.根据权利要求31的组合物,其中所说的偶氮染料是碱性棕16(Cl12250),碱性棕17(Cl12251),碱性红76(12245),碱性黄57(Cl12719),并且其中所说的蒽醌染料是碱性蓝99(Cl56059)。
33.根据权利要求30的组合物,其中所说的阳离子头发染料是偶氮染料或蒽醌染料或者其的组合,并且其中所说的头发染料的量以稳定的组合物的总重量计为约0.1%至约5wt%。
34.根据权利要求33的组合物,其中所说的偶氮染料是碱性棕16(Cl12250),碱性棕17(Cl12251),碱性红76(12245),碱性黄57(Cl12719),并且其中所说的蒽醌染料是碱性蓝99(Cl56059)。
35.根据权利要求13的组合物,其中所说的组合物含有至少一种珠光物料或至少一种阳离子头发染料或者其的组合,并且所说的组合物是稳定的。
36.根据权利要求18的组合物,其中所说的组合物含有至少一种珠光物料或至少一种阳离子头发染料或者其的组合,并且所说的组合物是稳定的。
37.根据权利要求36的组合物,其中所说的珠光物料是涂敷有二氧化钛的云母,涂敷有氧化铁的云母,乙二醇一硬脂酸酯,乙二醇二硬脂酸酯,聚乙二醇二硬脂酸酯,涂敷有氯氧化铋的云母,肉豆蔻酸肉豆蔻酯,鸟嘌呤(鱼鳞)或闪光剂(聚酯或金属类的)或者其的组合,并且其中所说的珠光物料的量以所说的组合物的总重量计为约0.05%至约10wt%。
38.根据权利要求24的组合物,其中所说的组合物还至少一种不溶性硅氧烷或至少一种可溶性硅氧烷或至少一种可溶性阳离子头发染料或者其的组合,并且所说的组合物是稳定的。
39.根据权利要求31的组合物,其中所说的组合物还含有至少一种不溶性硅氧烷或至少一种可溶性硅氧烷或至少一种珠光物料或者其的组合,并且其中所说的组合物是稳定的。
40.根据权利要求5的组合物,其中所说的组合物是个人护理清洁用组合物,其中所说的酸是水杨酸或α-羟基酸,并且其中所说的酸的量为约0.2至约6wt%。
41.根据权利要求5的组合物,其中所说的组合物是个人护理用乳液组合物,其中所说的酸是α-羟基酸或β-羟基酸,并且其中所说的酸的量为约0.2%至约15wt%。
42.根据权利要求37的组合物,其中所说的组合物是个人护理清洁用组合物,并且其中所说的不溶性硅氧烷的量为约0.1wt%至约5wt%,并且其中所说的珠光物料的量为约0.05wt%至约3wt%。
43.根据权利要求17的组合物,含有至少一种阳离子调理聚合物,并且其中所说的阳离子聚合物的量为约0.01至5wt%。
44.根据权利要求43的组合物,其中所说的阳离子调理聚合物是阳离子瓜尔豆胶,季化羟乙基纤维素-4,季化羟乙基纤维素-6,季化羟乙基纤维素-7,季化羟乙基纤维素-10,季化羟乙基纤维素-11,季化羟乙基纤维素-16,季化羟乙基纤维素-24,季化羟乙基纤维素-39或者其的组合。
45.根据权利要求43的组合物,含有至少一种珠光物料。
46.根据权利要求45的组合物,其中所说的珠光物料是平均颗粒粒度为约2至约150微米直径的涂敷有二氧化钛的云母。
47.根据权利要求7的组合物,其中所说的组合物是去头屑用洗发液,其中所说的需要悬浮或稳定化的基本上不溶性物料是羟基吡啶硫酮锌,并且其中所说的羟基吡啶硫酮锌的量为约0.1wt%至5wt%。
48.根据权利要求2的组合物,含有至少一种需要悬浮或稳定化的基本上不溶性的物料。
49.根据权利要求48的组合物,其中所说的基本上不溶性的物料是硅氧烷或油性物料或珠光物料或者其的组合。
50.根据权利要求49的组合物,其中所说的不溶性硅氧烷是聚(二甲基硅氧烷),氨基聚二甲基硅氧烷,氨基聚二甲基硅氧烷粗乳液或微乳液,聚二甲基硅氧烷,聚二甲基硅氧烷醇(硅氧烷树胶),环二甲基聚硅氧烷,苯基三甲基聚硅氧烷,聚二甲基硅氧烷或聚二甲基硅氧烷醇微乳液或粗乳液,有机硅氧烷,烷氧基硅氧烷或其的任何组合,其中所说的硅氧烷的量以所说的稳定的组合物的总重量计为约0.1至约20wt%。
51.根据权利要求49的组合物,其中所说的不溶性珠光物料是涂敷有二氧化钛的云母,涂敷有氧化铁的云母,乙二醇一硬脂酸酯,乙二醇二硬脂酸酯,聚乙二醇二硬脂酸酯,涂敷有氯氧化铋的云母,肉豆蔻酸肉豆蔻酯,鸟嘌呤(鱼鳞)或闪光剂(聚酯或金属类的)或者其的组合,其中所说的珠光物料的量以所说的稳定的组合物的总重量计为约0.05wt%至约10wt%。
52.一种制备稳定的、含有表面活性剂的含水组合物的方法,包括以下步骤:
a.形成含有至少一种阴离子、两性离子、两性、非离子或阳离子表面活性剂或者其的组合;至少一种基本上交联的可碱溶胀性丙烯酸酯共聚物流变改良剂;和水的混合物;
b.用有效量的碱性物料中和所说的混合物,以便使所说的混合物的pH增加到至少约5;并且
c.添加有效量的酸性物料,以便使所说的混合物的pH降低约0.5至约5个pH单位。
53.根据权利要求52的方法,其中所说的共聚物得自:
a.约20wt%至约80wt%的至少一种羧酸单体,包括丙烯酸、甲基丙烯酸、衣康酸、富马酸、巴豆酸、乌头酸或马来酸或者其的组合;
b.约80wt%至约15wt%的至少一种α,β-烯键式不饱和单体,其中所说的单体具有下式:
i)CH2=CXY,其中X是H并且Y是-COOR,-C6H4R’,-CN,-CONH2,-Cl,-NC4H6O,-NH(CH2)3COOH,-NHCOCH3,-CONHC(CH3)3,-CO-N(CH3)2或X是CH3并且Y是-COOR,-C6H4R’,-CN;或-CH=CH2;或者X是Cl并且Y是Cl,并且R是C1-C18烷基或羟基C2-C18烷基,R’是H或C1-C18烷基,或具有下式:
ii)CH2=CH(OCOR1);其中R1是C1-C18烷基;或具有下式:
iii)CH2=CH2或CH2=CHCH3,和
c.约0.01至约5wt%的至少一种可用于形成部分交联或者基本上交联的三维网络结构的多不饱和化合物。
54.根据权利要求53的方法,其中所说的基本上可碱溶胀性交联的聚合物的量以所说的稳定的组合物的总重量计为约0.1wt%至约10wt%,并且其中所说的表面活性剂的量以所说的稳定的组合物的总重量计为约1wt%至约80wt%。
55.根据权利要求54的方法,其中所说的共聚物得自:
a.约35wt%至约65wt%的丙烯酸或甲基丙烯酸或者其的组合,
b.约65wt%至约35wt%的丙烯酸乙酯或丙烯酸甲酯或者其的组合,和
c.约0.03wt%至约3wt%的蔗糖或多元醇的聚链烯基醚或者三(甲基)丙烯酸三羟甲基丙烷酯,甲基丙烯酸缩水甘油酯,N-羟甲基丙烯酰胺,或者其的组合。
56.根据权利要求54的方法,其中所说的酸性物料是柠檬酸,乙酸,β-羟基酸,水杨酸,α-羟基酸,乳酸,羟基乙酸,盐酸,硫酸,硝酸,氨基磺酸或磷酸或天然水果酸或者其的组合。
57.根据权利要求56的方法,包括形成需要悬浮或稳定化的基本上不溶性的物料的稳定的组合物。
58.根据权利要求57的组合物,其中所说的基本上不溶性物料是硅氧烷或油性物料或珠光物料或者其的组合。
59.根据权利要求58的组合物,其中所说的不溶性硅氧烷是聚(二甲基硅氧烷),氨基聚二甲基硅氧烷,氨基聚二甲基硅氧烷粗乳液或微乳液,聚二甲基硅氧烷,聚二甲基硅氧烷醇(硅氧烷树胶),环二甲基聚硅氧烷,苯基三甲基聚硅氧烷,聚二甲基硅氧烷或聚二甲基硅氧烷醇微乳液或粗乳液,有机聚硅氧烷,烷氧基硅氧烷或其的任何组合,其中所说的硅氧烷的量以所说的稳定的组合物的总重量计为约0.1至约20wt%。
60.根据权利要求58的组合物,其中所说的不溶性珠光物料是涂敷有二氧化钛的云母,涂敷有氧化铁的云母,乙二醇一硬脂酸酯,乙二醇二硬脂酸酯,聚乙二醇二硬脂酸酯,涂敷有氯氧化铋的云母,肉豆蔻酸肉豆蔻酯,鸟嘌呤(鱼鳞)或闪光剂(聚酯或金属类的)或者其的组合,其中所说的珠光物料的量以所说的稳定的组合物的总重量计为约0.05wt%至约10wt%。
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CN114599335B (zh) * | 2019-07-26 | 2024-07-12 | 莱雅公司 | 用于清洁角蛋白材料和/或从角蛋白材料卸妆的组合物 |
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BRPI0109990B1 (pt) | 2015-11-17 |
CA2405222C (en) | 2008-04-08 |
ES2329872T3 (es) | 2009-12-02 |
ZA200208119B (en) | 2003-07-17 |
WO2001076552A3 (en) | 2002-09-19 |
KR100866186B1 (ko) | 2008-10-30 |
AU5759201A (en) | 2001-10-23 |
MXPA02009941A (es) | 2003-02-12 |
CZ20023712A3 (cs) | 2003-02-12 |
JP2014028957A (ja) | 2014-02-13 |
US7217752B2 (en) | 2007-05-15 |
WO2001076552A2 (en) | 2001-10-18 |
ATE440130T1 (de) | 2009-09-15 |
AU2001257592B2 (en) | 2006-02-23 |
CN100475178C (zh) | 2009-04-08 |
KR20030005275A (ko) | 2003-01-17 |
US20040087668A1 (en) | 2004-05-06 |
JP2003530446A (ja) | 2003-10-14 |
KR20080027396A (ko) | 2008-03-26 |
EP1272159B1 (en) | 2009-08-19 |
US6897253B2 (en) | 2005-05-24 |
EP2138561A1 (en) | 2009-12-30 |
DE60139613D1 (de) | 2009-10-01 |
EP1272159A2 (en) | 2003-01-08 |
US20050158268A1 (en) | 2005-07-21 |
KR20090088964A (ko) | 2009-08-20 |
JP5465820B2 (ja) | 2014-04-09 |
RU2002130255A (ru) | 2004-03-27 |
US6635702B1 (en) | 2003-10-21 |
BR0109990A (pt) | 2004-03-23 |
KR100947959B1 (ko) | 2010-03-15 |
CA2405222A1 (en) | 2001-10-18 |
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