CN1334717A - 包含羧酸/羧酸酯共聚物和易碎可见颗粒的头发调理组合物 - Google Patents
包含羧酸/羧酸酯共聚物和易碎可见颗粒的头发调理组合物 Download PDFInfo
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- CN1334717A CN1334717A CN99816186A CN99816186A CN1334717A CN 1334717 A CN1334717 A CN 1334717A CN 99816186 A CN99816186 A CN 99816186A CN 99816186 A CN99816186 A CN 99816186A CN 1334717 A CN1334717 A CN 1334717A
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- COXJMKGEQAWXNP-UHFFFAOYSA-N tris(14-methylpentadecyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CC(C)CCCCCCCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCCCCCCCC(C)C)CC(=O)OCCCCCCCCCCCCCC(C)C COXJMKGEQAWXNP-UHFFFAOYSA-N 0.000 description 1
- UMQCZSNKDUWJRI-UHFFFAOYSA-M tris(2-hydroxyethyl)-octadecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](CCO)(CCO)CCO UMQCZSNKDUWJRI-UHFFFAOYSA-M 0.000 description 1
- BIEMOBPNIWQLMF-UHFFFAOYSA-N tris(2-octyldodecyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCCCCC(CCCCCCCC)COC(=O)CC(O)(C(=O)OCC(CCCCCCCC)CCCCCCCCCC)CC(=O)OCC(CCCCCCCC)CCCCCCCCCC BIEMOBPNIWQLMF-UHFFFAOYSA-N 0.000 description 1
- GUIWIPNQQLZJIE-UHFFFAOYSA-K tris[2-(2-hydroxyethoxy)ethyl]-octadecylazanium;phosphate Chemical compound [O-]P([O-])([O-])=O.CCCCCCCCCCCCCCCCCC[N+](CCOCCO)(CCOCCO)CCOCCO GUIWIPNQQLZJIE-UHFFFAOYSA-K 0.000 description 1
- 229960000281 trometamol Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
- 229940118846 witch hazel Drugs 0.000 description 1
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- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
- 229940106668 yucca extract Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- WIBCVGUGRCGRSG-UHFFFAOYSA-N zinc oxygen(2-) 1H-pyridine-2-thione Chemical compound [O-2].[Zn+2].SC1=NC=CC=C1 WIBCVGUGRCGRSG-UHFFFAOYSA-N 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- 244000089265 zong er cha Species 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
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Abstract
本发明公开的是一种头发调理组合物,包含:(1)羧酸/羧酸酯共聚物;(2)易碎的可见颗粒,包含一结构材料,选自合成聚合物、合成的无定型二氧化硅、蜡化合物,以及它们的混合物;和(3)含水载体。
Description
技术领域
本发明涉及包含羧酸/羧酸酯共聚物和易碎可见颗粒的头发调理组合物。
发明背景
头发由于与周围环境接触并且因头皮分泌皮脂,所以会变得脏污。头发脏污后会使头发有肮脏和油腻的感觉,外观不雅。头发的脏污需要有规律地洗头。
洗头通过除去过量的污物和皮脂而清洁头发。但是,洗头会使头发处于湿的、紊乱的并且通常难于处理的状态。一旦头发干了,就会由于除去了头发的天然油和其它天然的调理和润湿成分而使头发处于干燥、粗糙、无光泽或卷曲起毛状态。另外,由于干燥,还会增加头发的静电,因而影响梳理并使头发处于通常所称的“头发飞扬(fly-away hair)”的状态;或者带来一种不希望出现的“末端分叉(split ends)”现象,对长头发尤其如此。
为减轻这些洗头之后存在的问题,已经开发了各种各样的方法。这些方法从洗头之后施用头发调理剂,如免洗型(leave-on)和漂洗型(rinse-off)产品,到靠单个产品来同时清洁和调理头发的头发调理香波。尽管一些消费者更倾向于使用包含调理剂的香波的容易和方便使用性,但是大部分消费者喜欢更常规的调理剂配方,即与洗头分开,通常是在洗发后使用调理剂。那些喜欢常规调理剂配方的消费者重视相对较高的调理效果或者是喜欢根据头发或部分头发的状况而改变调理量的方便性。
调理配方可以是漂洗型产品也可以是免洗型产品,而且可以是乳剂、霜剂、凝胶、喷剂和摩丝型产品。霜剂、凝胶和摩丝型产品使消费者能容易地控制产品的用量和分布。正因为如此,这些产品特别适合于免洗型产品。
给头发带来调理益处的普通方法是使用头发调理剂,如阳离子表面活性剂和聚合物、硅氧烷调理剂、烃油和脂肪醇。已知阳离子表面活性剂和聚合物、烃油和脂肪醇可以增强头发的光泽,并给头发带来湿润性、柔软性和抑制静电性。但是,这些组分也会带来油腻或蜡样的感觉。而且,还知道硅氧烷调理剂因硅氧烷化合物的表面张力低而带来如光滑和易于梳理的调理益处。然而,硅氧烷调理剂又会使头发感觉干燥或处于紊乱状态,而且当免洗型产品包含这些调理剂时,它们还会在手上留下又粘又脏的感觉。
基于上述原因,仍需要提供适于免洗用途的头发调理组合物,希望这样的头发调理组合物可提供改进的调理益处如光滑性、柔软性、减少摩擦、容易应用到头发上,并且使头发和手感觉清洁。
没有任何现有技术可提供本发明的全部优点和益处。
发明概述
本发明涉及一种头发调理组合物,该组合物包含:
(1)羧酸/羧酸酯共聚物;
(2)易碎的可见颗粒,包含一结构材料,选自合成聚合物、合成的无定型二氧化硅、蜡化合物,以及它们的混合物;和
(3)含水载体。
通过阅读本发明的公开内容,本领域的普通技术人员会清楚地明白本发明的这些及其它特征、目的和优点。
发明详述
尽管本说明书用权利要求的总结来具体地指出并清楚地阐述要求保护的发明,但是可以相信,下面的描述使本发明将会更好地被理解。
在本发明中,所有的引用文献均全文引入本发明中作为参考。任何文献的引用并不承认是将任何要求保护的发明确定为可以得到的现有技术。
在本发明中,“包含”是指可以加入的而且不影响最终结果的其它步骤和其它成分。这个术语包括了术语“由……组成”和“基本上由……组成”。
除非另有说明,所有的百分数、份数和比例均是以本发明的组合物的总重量为基础的。当涉及列出的成分时,所有这些重量均按活性量计,因此不包括市售材料中可能包含的载体或副产物。
在本文中陈述的本发明的特征和实施方案具有很多优点。举例来说,本发明的头发调理组合物可提供:改进头发调理的益处,如光滑性、柔软性,降低了摩擦,容易在头发上使用,使头发和手有清洁感。在本发明的一个实施方案中,可以提供透明的头发调理组合物。羧酸/羧酸酯共聚物
本发明的组合物包含羧酸/羧酸酯共聚物。在本发明中,该羧酸/羧酸酯共聚物是羧酸和羧酸烷基酯的疏水改性的交联共聚物,并具有两亲性。这些羧酸/羧酸酯共聚物由下列物质共聚得到:1)羧酸单体,如丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸、反丁烯二酸、巴豆酸或α-氯代丙烯酸;2)具有1至约30个碳原子烷基链的羧酸酯,以及优选3)下式代表的交联剂:其中R52为氢或具有约1至约30个碳原子的烷基基团;Y1独立地为氧、CH2O、COO、OCO、
其中R53为氢或具有约1至约30个碳原子的烷基基团;Y2选自(CH2)m"、(CH2CH2O)m"、(CH2CH2CH2O)m",且m"为1至约30的整数。相信本发明的羧酸/羧酸酯共聚物可赋予本发明的组合物合适的粘度和流变学特性,并将组合物中的某些调理剂乳化和稳定化。还相信,由于共聚的物中包含烷基基团,所以该羧酸/羧酸酯共聚物不会使组合物产生令人不希望存在粘性。
按重量计,本发明组合物中所包含的羧酸/羧酸酯共聚物的含量优选为约0.01%至约10%,更优选为约0.1%至约2%。
适用于本发明的羧酸/羧酸酯共聚物是具有下式结构的丙烯酸/丙烯酸酯共聚物:其中,R51独立地为氢或1至30个碳的烷基,且至少一个R51为氢;R52的定义同上;n、n'、m和m'是整数,且n+n'+m+m'为约40至约100;n"为1至约30的整数;C的定义使得共聚物的分子量为约500,000至约3,000,000。
用于本发明的商业上可得到的羧酸/羧酸酯共聚物包括:CTFA命名为丙烯酸酯/丙烯酸C10-30烷基酯交联聚合物,其商品名为Pemulene TR-1、Pemulene TR-2、Carbopol 1342、Carbopol 1382和Carbopol ETD 2020,均可从B.F.Goodrich公司得到。
在本发明中,可以包括中和剂以中和羧酸/羧酸酯共聚物。这种中和剂的非限定性实例有氢氧化钠、氢氧化钾、氢氧化铵、单乙醇胺、二乙醇胺、三乙醇胺、二异丙醇胺、氨基甲基丙醇、三甲胺(tromethamine)、四羟基丙基乙二胺以及它们的混合物。
易碎的可见颗粒
本发明的组合物包含易碎的可见颗粒。“易碎的可见颗粒”定义为当包含在本发明的组合物中时,通过肉眼能够清楚地辨识出单个颗粒的颗粒,每个颗粒在本发明的组合物中是稳定的,但在使用时破碎。依据所需要的产品特性,只要通过肉眼能一粒一粒地清楚地辨识,该易碎的可见颗粒的大小、形状和颜色可以是任意的。一般来讲,该易碎的可见颗粒的平均粒径为约50至约3,000μm,优选约100至约1,000μm,更优选约300至约1,000μm。“稳定”的意思是指该易碎的可见颗粒在正常贮存条件下不碎裂、不凝聚也不分离。“易碎”指的是该易碎的可见颗粒在使用时在手上用手指施以很小的剪切就碎裂。
本发明的易碎可见颗粒的用量是使本发明的组合物具有受人欢迎的美学益处的量。根据所需的产品特性,通常高达组合物重量的约10%,优选约0.01%至约5%。
本发明的易碎的可见颗粒包含一种结构材料(structural material),以及优选一种包围材料(encompassed material)。
结构材料为易碎的可见颗粒提供一定的强度,以便在正常贮存条件下,它们在本发明的组合物中保持可清楚辨识的结构,同时它们还能在使用时在手上通过手指所施加的很小的剪切而碎裂。优选,易碎的看见颗粒的压缩强度对于每个颗粒为约1至约200克。压缩强度可以使用Stable MicroSystems Ltd.供应的TA-XT2 Texture Analyzer在下列条件下通过每批测量20个颗粒而进行合适地测量:
模式:压缩下测量的力
测试速度:0.1毫米/秒
距离:0.8毫米
触发器类型:自动-10克
附件:使用5千克测力传感器在丙烯酸树脂上的25毫米的圆柱探测器(P/25)而且,在易碎的可见颗粒碎裂后,在手上有很少或没有残余物感,优选没有超过大于约10微米的颗粒碎片。
结构材料包含选自合成聚合物、合成的无定型二氧化硅、蜡化合物,以及它们的混合物的组分。
用于制备结构材料的例举的合成聚合物包含:丙烯酸类聚合物和共聚物包括聚丙烯酰胺、聚(氰基丙烯酸烷基酯)、聚(乙烯-乙酸乙烯酯)和羧乙烯基聚合物、聚酰胺、聚(甲基乙烯基醚-马来酸酐)、聚(己二酰-L-赖氨酸)、聚碳酸酯、聚对苯二甲酰胺、聚乙酸乙烯酯邻苯二甲酸酯、聚(对苯二甲酰-L-赖氨酸)、聚芳基砜、聚(甲基丙烯酸甲酯)、聚(ε-己内酯)、聚乙烯基吡咯烷酮、聚氧乙烯、聚酯、聚乙醇酸、聚乳酸、聚谷氨酸、聚赖氨酸、聚苯乙烯、聚(苯乙烯-丙烯腈)、聚酰亚胺和聚乙烯醇。
用于制备结构材料的例举的蜡材料包含:蜂蜡、巴西棕榈蜡、鲸蜡、石蜡、小烛树蜡、角鲨烷、氢化牛油、甘油单棕榈酸酯、甘油二棕榈酸酯、氢化蓖麻油、甘油单硬脂酸酯、甘油二硬脂酸酯、甘油三硬脂酸酯、12-羟基硬脂醇,以及和在本说明书其它部分中讲述的高熔点化合物相同的组分。但是,此处所述的组分基本上包含在易碎的可见颗粒内,并且在正常贮存条件下基本上不溶解于本发明组合物的本体(bulk)中。
还可以包含在结构材料中的组分包含:多糖和糖衍生物,如结晶纤维素、乙酸纤维素、乙酸丁酸纤维素、乙酸邻苯二甲酸纤维素、硝酸纤维素、乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素、邻苯二甲酸羟丙基甲基纤维素、甲基纤维素、羧甲基纤维素钠、阿拉伯胶(gum arabic)、琼脂、琼脂糖、麦芽糖糊精、藻酸钠、藻酸钙、葡聚糖、淀粉、半乳糖、葡糖胺、环糊精、甲壳质、直链淀粉、支链淀粉、糖原、海带多糖(laminaran)、地衣淀粉、凝胶多糖、菊粉、果聚糖、果胶、甘露聚糖、木聚糖、藻酸、阿拉伯酸、葡甘露聚糖、琼脂糖、琼脂胶、prophyran、角叉菜胶、岩藻依聚糖、糖胺聚糖、透明质酸、软骨素、肽聚糖、脂多糖、瓜尔胶、淀粉及淀粉衍生物;寡糖,如蔗糖、乳糖、麦芽糖、糖醛酸、胞壁酸、纤维二糖、异麦芽糖、车前糖、松三糖、龙胆三糖、麦芽三糖、水苏糖、葡糖苷和多聚葡糖苷;单糖,如葡萄糖、果糖和麦芽糖,以及其它材料如乳类固体(milksolids)、糖蜜、凝胶、谷蛋白、白蛋白、紫胶、酪蛋白酸盐、蜂蜡、巴西棕榈蜡、鲸蜡、氢化牛油、甘油单棕榈酸酯、甘油二棕榈酸酯、氢化蓖麻油、甘油单硬脂酸酯、甘油二硬脂酸酯、甘油三硬脂酸酯、12-羟基硬脂醇、蛋白质和蛋白质衍生物;以及它们的混合物。此处所述的组分也可在其它部分中作为本发明组合物的有用组分描述。但是,此处所述的组分主要是用于制备易碎的可见颗粒的结构,并且在正常贮存条件下基本上不溶解于本发明组合物的本体中。
易碎的可见颗粒可以包围、包含或充满被包含的材料。这种被包含的材料可以是水溶性的也可以是非水溶性的,而且包含这样的组分,如:维生素、抗氧化剂、清爽剂、蛋白质及其衍生物、草本植物提取物、颜料、染料、抗微生物剂、螯合剂、紫外线吸收剂、荧光增白剂、聚硅氧烷化合物、香料、保湿剂(通常可溶于水)、附加的调理剂(通常不溶于水),以及它们的混合物。在一个实施方案中,水溶性组分是优选的被包含的材料。在这样一个实施方案中,可以使用非挥发性的聚硅氧烷化合物作为易碎可见颗粒的包覆材料,用以避免被包含的材料泄露,进入组合物本体中。
本发明中用作被包含的材料的维生素和氨基酸包括:水溶性的维生素,如维生素B1、B2、B6、B12、C、泛酸、泛基乙基醚、泛醇、生物素、以及它们的衍生物;水溶性的氨基酸,如天冬酰胺、丙氨酸(alanin)、吲哚、谷氨酸以及它们的盐;非水溶性的维生素,如维生素A、D、E、以及它们的衍生物;非水溶性的氨基酸,如酪氨酸、色胺、以及它们的盐。
本发明中用作被包含的材料的抗氧化剂包含:芝麻酚、芝麻啉、棉子酚、BHA(丁基羟基茴香醚)、BHT(二丁基羟基甲苯)、去甲二氢愈创木酸、没食子酸丙酯、植酸、guajacum resin。用于这些抗氧化剂的配合剂可以包含:如柠檬酸、抗坏血酸、苹果酸。
本发明中用作被包含的材料的清爽剂包括d-型和d1-型的薄荷醇和樟脑。
本发明中用作被包含的材料的颜料包括:无机、亚硝基、单偶氮基、双偶氮基、类葫萝卜素、三苯基甲烷、三芳基甲烷、呫吨、喹啉色料、噁嗪色料、吖嗪色料、蒽醌、靛类、硫代靛类(thionindigoid)、喹吖啶酮(quinacridone)、酞菁(phthalocianine)、植物性物质、天然染料,包括:水溶性组分,如C.I.名称如下的那些:酸性红18,26,27,33,51,52,87,88,92,94,95、酸性黄1,3,11,23,36,40,73、食品黄3、食品绿3、食品蓝2、食品红1,6、酸性蓝5,9,74、颜料红57-1,53(Na)、碱性紫10、溶剂红49、酸性橙7,20,24、酸性绿1,3,5,25、溶剂绿7、酸性紫9,43;非水溶性的组分,如那些C.I.名称如下的组分:颜料红53(Ba),49(Na),49(Ca),49(Ba),49(Sr),57、溶剂红23,24,43,48,72,73、溶剂橙2,7、颜料红4,24,48,63(Ca)3,64、瓮红1、瓮蓝1,6、颜料橙1,5,13、溶剂黄5,6,33、颜料黄1,12、溶剂绿3、溶剂紫13、溶剂蓝63、颜料蓝15、二氧化钛、叶绿酸铜络合物、群青、铝粉、膨润土、碳酸钙、硫酸钡、三氢化铋、硫酸钙、碳黑、骨炭、铬酸、钴蓝、金、氧化铁、水合氧化铁、亚铁氰化铁、碳酸镁、磷酸锰、银、以及氧化锌。
本发明中用作被包含的材料的抗微生物剂包括:那些化妆品用的杀菌剂和去头屑止痒剂,包括:水溶性组分如羟甲辛吡酮油胺(piroctoneolamine),非水溶性组分如3,4,4′-三氯代对称二苯脲(三氯森)、三氯卡班(triclocarban)、硫氧吡啶锌(zinc pyrithione)、二硫化硒、烷基异喹啉嗡溴化物、联非那明、thianthol、干斑蝥酊剂、姜酊剂、辣椒酊剂。
本发明中用作被包含的材料的螯合剂包括:2,2′-联吡啶胺;1,10-菲咯啉{邻菲咯啉};二-2-吡啶基酮;2,3-二(2-吡啶基)吡嗪;2,3-二(2-吡啶基)-5,6-二氢吡嗪;1,1′-羰基二咪唑;2,4-二(5,6-二苯基-1,2,4-三嗪-3-基)吡啶;2,4,6-三(2-吡啶基)-1,3,5-三嗪;4,4′-二甲基-2,2′-联吡啶;2,2′-联喹啉;二-2-吡啶基乙二醛{2,2′-pyridil};2-(2-吡啶基)苯并咪唑;2,2′-联吡嗪;3-(2-吡啶基)-5,6-二苯基-1,2,4-三嗪;3-(4-苯基-2-吡啶基)-5-苯基-1,2,4-三嗪;3-(4-苯基-2-吡啶基)-5,6-二苯基-1,2,4-三嗪;2,3,5,6-四-(2′-吡啶基)-吡嗪;2,6-吡啶二羧酸;2,4,5-三羟基嘧啶;苯基2-吡啶基酮肟;3-氨基-5,6-二甲基-1,2,4-三嗪;6-羟基-2-苯基-3(2H)-哒嗪酮;2,4-蝶啶二醇{2,4-二氧四氢蝶啶};2,2′-联吡啶和2,3-二羟基吡啶。
用作被包含的材料的有用的硅氧烷化合物、保湿剂、附加调理剂、紫外线吸收剂、荧光增白剂和草本植物提取物,与本说明书其它部分所列举的那些例子相同。但是,这里所述的组分基本上保留在易碎的可见颗粒之内,并且在正常的贮存条件下不溶解于本发明的组合物的本体。
本发明特别有用的易碎的可见颗粒由用量分别为易碎的可见颗粒重量的20-70%、5-40%、10-50%和0.1-10%重量的石蜡、巴西棕榈蜡、小烛树蜡和液体油的混合物制备。市售的易碎可见颗粒包括购自Crosfield的商品名为Neosil CBT 60、70、71、72和CBG60的在结构材料中包含无定型二氧化硅的那些。使用时,在手上用手指以很小的剪切就可以将这些颗粒弄碎,操作时没有阻力,并且它们容易溶于组合物中。
含水载体
本发明的组合物包含一种含水载体。根据与其它组分的兼容性和所期望的产品的其它特性,选择所述载体的用量和种类。
用于本发明的载体包括水和低级烷醇的水溶液。这里所用的低级烷醇为1至6个碳的一元醇,更优选乙醇和异丙醇。
优选,含水载体基本上是水。优选使用去离子水。依据所需的产品特性,含有无机阳离子的天然水也是可以使用的。一般来讲,本发明的组合物含有约20%至约99%的水,优选约40%至约98%的水,更优选约50%至约98%的水。
本发明的组合物的pH优选为约4至约9,更优选为约4.5至约7.5。为获得所需要的pH,本发明的组合物可以包含缓冲剂或其它pH调节剂。
硅氧烷化合物
本发明的组合物还可以包含硅氧烷化合物(silicone compound)。这里所用的硅氧烷化合物包括挥发性的可溶的或不可溶的、或不挥发性的可溶的或不可溶的硅氧烷调理剂。“可溶”的意思是指,该硅氧烷化合物可与组合物的载体相混溶,构成同一相的一部分。“不溶”的意思是指,该硅氧烷化合物形成一个独立于载体的不连续相,如硅氧烷液滴的乳液或悬浮液形式。这里的硅氧烷化合物可以通过本领域中已知的任何适宜的方法包括乳液聚合法来制备。硅氧烷化合物还可以以乳液的形式混入本发明的组合物,其中所述的乳液是或不是借助于选自阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂以及它们的混合物的表面活性剂,通过机械混合而制备;或者是处于乳液聚合的合成阶段的乳液。
本发明所使用的硅氧烷化合物在25℃时的粘度优选为约1,000至约2,000,000厘沲,更优选约10,000至约1,800,000厘沲,最优选约100,000至约1.500,000厘沲。该粘度可以通过1970年7月20日的Dow Corning公司试验方法CTM0004中所讲述的玻璃毛细管粘度计来测量。可以通过乳液聚合法制备高分子量的硅氧烷化合物。适宜的硅氧烷流体(silicone fluid)包括聚烷基硅氧烷、聚芳基硅氧烷、聚烷基芳基硅氧烷、聚醚硅氧烷共聚物以及它们的混合物。其它具有调理头发性能的非挥发性硅氧烷化合物也可以使用。
在本发明中,按组合物的重量计,硅氧烷化合物的用量优选为约0.1%至约60%,更优选约0.1%至约40%。
在本发明中,硅氧烷化合物还包括具有下列结构(I)的聚烷基或聚芳基硅氧烷:其中R93为烷基或芳基;x为约7至约8000的整数。Z8代表硅氧烷链的封端基团。只要所产生的硅氧烷在室温下是流体、是可分散的、施用于头发时既无毒无刺激又无伤害性、与组合物中的其它组分兼容、在正常使用和贮存条件下具有化学稳定性、并且能够沉积于头发上并调理头发,那么取代于硅氧烷链上(R93)的或硅氧烷链末端(Z8)的烷基或芳基基团可以具有任何结构。适宜的Z8基团包括羟基、甲基、甲氧基、乙氧基、丙氧基和芳氧基。硅原子上的两个R93基团可以是相同的基团或不同的基团。优选两个R93基团为相同的基团。适宜的R93基团包括甲基、乙基、丙基、苯基、甲基苯基和苯基甲基。优选的硅氧烷化合物是聚二甲基硅氧烷、聚二乙基硅氧烷和聚甲基苯基硅氧烷。聚二甲基硅氧烷,也称作聚二甲基硅酮,是特别优选的。可使用的聚烷基硅氧烷包括,例如,聚二甲基硅氧烷。这些硅氧烷化合物是可以得到的,例如产自the General Electric Company的Viscasil和SF96系列产品和产自Dow Corning的Dow Corning 200系列产品。
也可以使用的聚烷基芳基硅氧烷流体包括,例如,聚甲基苯基硅氧烷。这些硅氧烷是可以得到的,例如产自the General Electric Company的SF 1075甲基苯基流体或产自Dow Coming的556化妆品级流体。
为了增强头发的光亮特性,特别优选高度芳基化的硅氧烷化合物,如折光指数约1.46或更高的,特别是折光指数约1.52或更高的高度苯基化的聚乙基硅氧烷。使用这些高折光指数的硅氧烷化合物时,应按下面描述的那样,将它们与铺展剂如表面活性剂或硅氧烷树脂混合,以降低表面张力并增强材料的成膜能力。
可使用的硅氧烷化合物包括,例如,聚氧化丙烯改性的聚二甲基硅氧烷,当然也可以使用氧化乙烯或氧化乙烯与氧化丙烯的混合物进行改性的聚二甲基硅氧烷。氧化乙烯和氧化丙烯的量要足够低,以不妨碍硅氧烷的可分散性特性。这些材料也称作聚二甲基硅氧烷共聚醇。
其它的硅氧烷化合物包括氨基取代的硅氧烷。适宜的烷氨基取代的硅氧烷化合物包括具有下列结构(II)的那些:其中R94为H、CH3或OH,p1、p2、q1和q2是取决于分子量的整数,平均分子量近似介于5,000和10,000之间。这种聚合物也称作“氨基取代的二甲基硅氧烷(amodimethicone)”。
适宜的氨基取代的硅氧烷流体包括下式(III)所代表的那些:(R97)aG3-a-Si-(OSiG2)p3-(OSiGb(R97)2-b)p4-O-SiG3-a(R97)a(III)其中G选自氢、苯基、OH、C1-C8的烷基,并优选甲基;a代表0或1至3的整数,并优选0;b代表0或1,并优选等于1;p3与p4之和为1至2000的数,并优选50至150,p3可以代表0至1999的数,并优选49至149,p4可以代表1至2000的整数并优选1至10;R97为如式Cq3H2q3L的一价基团,其中q3为2至8的整数,而L选自下面的基团
-N(R96)CH2-CH2-N(R96)2
-N(R96)2
-N(R96)3X′
-N(R96)CH2-CH2-NR96H2X′,其中R96选自氢、苯基、苄基、饱和的烃基,优选含1至20个碳原子的烷基基团,而X′表示卤离子。
特别优选的对应于式(II)的氨基取代的硅氧烷,被称作“三甲基甲硅烷基氨基取代的聚二甲基硅氧烷(trimethylsilylamodimethcone)”的聚合物,其中的R94为甲基。
其它的可使用的氨基取代的硅氧烷聚合物如式(V)所示:其中的R98代表具有1至18个碳原子的一价烃基基团,优选烷基或链烯基基团,如甲基;R99代表烃基基团,优选C1-C18的亚烷基基团或C1-C18、更优选C1-C8的亚烷氧基基团;Q-为卤离子,优选氯离子;p5代表从2至20、优选2至8的统计平均值;p6代表从20至200、优选20至50的统计平均值。这种类型的优选的聚合物可从Union Carbide得到,名称为“UCARSILICONE ALE56”。
公开了适宜的不挥发性的分散的硅氧烷化合物的参考文献,包括授予Geen的US 2826551、1976年6月22日颁予Drakoff的US 3964500、授予Pader的US 4364837、以及授予Woolston的英国专利第849433号。PetrarchSystems公司于1984年发行的“Silicon Compounds(硅化合物)”提供了广泛的(但是不是排它的)适宜的硅氧烷化合物的清单。
另一种可能特别有用的不挥发性的分散的硅氧烷是硅橡胶纯胶料(silicone gum)。这里所用的术语“硅橡胶纯胶料”是指一种聚有机硅氧烷材料,其粘度在25℃时大于等于1000000厘沲。可以看出此处描述的硅橡胶纯胶料与前述的硅氧烷化合物可能有些重叠。这种重叠并不是对任何这些材料的限制。硅橡胶纯胶料被描述于Petrarch和其它文献,包括1979年5月1日授予Spitzer等人的US 4152416和Noll,Walter所著的Chemistry andTechnology of Silicones,New York:Academic Press 1968。另外,描述硅橡胶纯胶料的还有General Electric Silicone Rubber Product Data Sheets SE 30、SE 33、SE 54和SE76。典型的“硅橡胶纯胶料”的总体分子量(mass molecularweight)超过约200,000,一般介于约200,000至约1,000,000之间。这种材料的具体实例包括聚二甲基硅氧烷、聚(二甲基硅氧烷,甲基乙烯基硅氧烷)共聚物、聚(二甲基硅氧烷,二苯基硅氧烷,甲基乙烯基硅氧烷)共聚物以及它们的混合物。
硅氧烷树脂也是有用的,它们为高度交联的聚合硅氧烷体系。这种交联是在制造硅氧烷树脂的过程中,通过将三官能或四官能的硅烷混入单官能或二官能的硅烷,或单官能和二官能的硅烷中而引入的。在本领域中很好理解,为得到硅氧烷树脂所需要的交联度,将随混入该硅氧烷树脂中特定的硅烷单元的变化而变化。一般来讲,具有足够量的三官能和四官能硅氧烷单体单元,从而具有足够的交联程度,以致于干燥后变成坚硬或坚固的薄膜,这样的硅氧烷材料就被认为是硅氧烷树脂。对于具体的硅氧烷材料,其中的氧原子与硅原子的比例就表示着交联的水平。本发明中,每个硅原子至少具有约1.1个氧原子的硅氧烷材料通常即为硅氧烷树脂。优选氧原子:硅原子的比例至少为约1.2∶1.0。制造硅氧烷树脂时所使用的硅烷包括单甲基硅烷、二甲基硅烷、三甲基硅烷、单苯基硅烷、二苯基硅烷、甲基苯基硅烷、单乙烯基硅烷、甲基乙烯基氯代硅烷和四氯代硅烷,最常用的是甲基取代硅烷。优选的树脂是General Electric提供的GE SS4230和SS4267。一般地,市售品的硅氧烷树脂是以溶解成低粘度的挥发性或非挥发性的硅氧烷流体的形式提供的。这里所用的硅氧烷树脂,就是以这种形式提供并混入本发明的组合物中的,这对于本领域的普通技术人员而言是很明白的。不局限于理论的限制,可以相信硅氧烷树脂能够增强其它硅氧烷化合物在头发上的沉积,并能够以高折光指数增强头发的光亮性。
其它有用的硅氧烷树脂是硅氧烷树脂粉末,如CTFA给出的命名为polymethylsilsequioxane的材料,可以购自Toshiba Silicones,为TospearlTM。
制造这些硅氧烷化合物的方法可见于“聚合物科学和工程百科全书(Encyclopedia ofPolymer Science and Engineering)”,15卷,第二版,204-308页,John Wiley & Sons,Inc.,1989。
可根据简写命名系统方便地识别硅氧烷材料,特别是硅氧烷树脂,这就是该技术领域的技术人员公知的“MTDQ”命名法。在此命名系统中,根据所出现的构成硅氧烷的各种硅氧烷单体单元来描述硅氧烷。简单地讲,符号M代表单官能单元(CH3)3SiO0.5;D代表二官能单元(CH3)2SiO;T代表三官能单元(CH3)SiO1.5;Q代表四官能单元SiO2。单元符号上的撇号,如M′、D′、T′、和Q′代表非甲基的取代基,并且在每次出现时都必须专门定义。典型的可供选择的取代基包括乙烯基、苯基、氨基、羟基等基团。在MDTQ命名系统中,各种单元的摩尔比,或者以指出硅氧烷中每种类型单元总数(或其平均数)的符号下脚标表示,或者以具体指明的比例结合分子量表示,从而完成了对硅氧烷材料的描述。在硅氧烷树脂中,如果T、Q、T′和/或Q′相对于D、D′、M和/或M′的摩尔量高,就表示交联水平较高。但是,如前所述,也可以用氧对硅的比例表示交联的总体水平。
本发明所用的优选的硅氧烷树脂为MQ、MT、MTQ、MQ和MDTQ树脂。因此,优选的硅氧烷取代基是甲基。特别优选MQ树脂,其中M∶Q的比例为约0.5∶1.0至约1.5∶1.0,并且该树脂的平均分子量为约1,000至约10,000。
在本发明中,特别适合的硅氧烷化合物是分子量为约200,000至约600,000的非挥发性的硅氧烷油(silicone oil),如聚二甲基硅氧烷和聚二甲基硅氧烷醇。这些硅氧烷化合物可以混入本发明的组合物中作为硅氧烷油溶液,该硅氧烷油是挥发性的或非挥发性的。
在本发明中,有用的可购得的硅氧烷化合物包括产自Dow Corning公司商品名为DC345的聚二甲基硅氧烷、产自General Electric商品名为SE30,SE 33,SE54和SE 76的聚二甲基硅氧烷胶料溶液、产自Dow Corning公司商品名为DCQ2-1403和DCQ2-1401的聚二甲基硅氧烷醇、以及如英国专利申请2303857所描述的产自Toshiba Silicone的乳液聚合的聚二甲基硅氧烷醇。
两性调理聚合物
本发明的组合物可以包含一种两性调理聚合物。此处所述的两性调理聚合物为与羧酸/羧酸酯共聚物相容,并为头发提供调理益处的两性调理聚合物。尽管此处所述的一些两性调理聚合物具有一定的支持头发或固定头发的功能,但是这种支持头发或固定头发的功能不是本发明对两性调理聚合物的要求。用于本发明的两性调理聚合物,是那些包含至少一种阳离子单体和至少一种阴离子单体的聚合物;该阳离子单体为季铵,优选二烷基二烯丙基氯化铵或羧酰胺基烷基三烷基氯化铵;而该阴离子单体为羧酸。本发明的两性调理聚合物可以包括非离子单体,如丙烯酰胺、甲基丙烯酸酯或乙基丙烯酸酯。另外,本发明所用的两性调理聚合物不包含甜菜碱化(betanized)的单体。
按重量计,本发明的组合物所包含的两性调理聚合物的含量优选为约0.01%至约10%,更优选约0.1%至约5%。
本发明中有用的聚合物是CTFA名称为Polyquaternium 22、Polyquaternium 39和Polyquaternium 74的聚合物。举例来说,这些聚合物是由二甲基二烯丙基氯化铵和丙烯酸组成的共聚物,由二甲基二烯丙基氯化铵和丙烯酰胺组成的三元共聚物和由丙烯酸、甲基丙烯酰胺基丙基三甲基氯化铵与丙烯酸甲酯组成的三元共聚物,如下面式子所表示的那些,其中的比例n6∶n7∶n8为45∶45∶10:
在本发明中,特别优选的两性调理聚合物市售品包含Polyquaternium22,其商品名为MERQUAT 280、MERQUAT 295;Polyquaternium 39,其商品名为MERQUAT PLUS 3330、MERQUAT PLUS 3331;和Polyquaternium47,其商品名为MERQUAT2001、MERQUAT2001N,均产自Calgon公司。
此处也可以使用由乙烯基单体和碱性单体共聚所产生的聚合物。所述的乙烯基单体至少带有一个羧基基团,如丙烯酸、甲基丙烯酸、马来酸、衣康酸、反丁烯二酸、巴豆酸或α-氯代丙烯酸;所述的碱性单体是至少含有一个碱性氮原子的取代的乙烯基化合物,如二烷基氨基烷基甲基丙烯酸酯和丙烯酸酯以及二烷基氨基烷基甲基丙烯酰胺和丙烯酰胺。
此处还可以使用这样的聚合物,该聚合物包含衍生自下列的单元:
i)至少一种选自丙烯酰胺或甲基丙烯酰胺的单体,所述的丙烯酰胺或
甲基丙烯酰胺上的氮原子被烷基取代;
ii)至少一种酸性共聚单体,该酸性共聚单体含有一个或多个具有反应
活性的羧基基团;和
iii)至少一种碱性共聚单体,如带有伯胺、仲胺和叔胺取代基以及季铵
取代基的丙烯酸和甲基丙烯酸的酯,以及二甲基氨基乙基甲基丙烯酸
酯与硫酸二甲酯或二乙酯季铵化反应的产物。
最优选的N-取代的丙烯酰胺或甲基丙烯酰胺,是那些烷基基团含有2至12个碳原子的N-取代的丙烯酰胺或甲基丙烯酰胺,尤其是N-乙基丙烯酰胺、N-叔丁基丙烯酰胺、N-叔辛基丙烯酰胺、N-辛基丙烯酰胺、N-癸基丙烯酰胺和N-十二烷基丙烯酰胺,以及相应的甲基丙烯酰胺。更特别地,所述的酸性共聚单体选自丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、马来酸和反丁烯二酸,以及马来酸或反丁烯二酸的烷基(具有1至4个碳原子)单酯。
优选的碱性共聚单体是甲基丙烯酸的氨基乙酯、丁基氨基乙酯、N,N'-二甲基氨基乙酯和N-叔丁基氨基乙酯。
此处所述的两性调理聚合物的市售品包括:辛基丙烯胺/丙烯酸酯/甲基丙烯酸丁基氨基乙酯的共聚物,其商品名为AMPHOMER、AMPHOMERSH701、AMPHOMER 28-4910、AMPHOMER LV71和AMPHOMER LV47,由National Starch & Chemical提供。
保湿剂
本发明的组合物还可以包含保湿剂(humectant)。本发明的保湿剂选自多元醇、水溶性烷氧基化的非离子聚合物、以及它们的混合物。本发明中,保湿剂的含量优选占组合物重量的约0.1%至约20%,更优选占组合物重量的约0.5%至约5%。
在本发明中,有用的多元醇包括甘油、山梨醇、丙二醇、丁二醇、己二醇、乙氧基化葡萄糖、1,2-己二醇、己三醇、双丙甘醇、赤藓醇、海藻糖、双甘油、木糖醇、麦芽糖醇、麦芽糖、葡萄糖、果糖、软骨素硫酸钠、透明质酸钠、腺苷磷酸钠、乳酸钠、吡咯烷酮碳酸盐、葡糖胺、环糊精、以及它们的混合物。
本发明所使用的水溶性的烷氧基化的非离子聚合物,包括分子量高至约1000的聚乙二醇和聚丙二醇,如CTFA名称如下的那些:PEG-200、PEG-400、PEG-600、PEG-1000、以及它们的混合物。
在本发明中,可购得的保湿剂包括:产自The Procter & Gamble公司商品名为STAR和SUPEROL、产自Croda Universal有限公司商品名为CRODEROL GA7000、产自Unichema商品名为PRECERIN系列、以及产自NOF商品名与化学名称相同的甘油;产自Inolex商品名为LEXOL PG-865/855、产自BASF商品名为1,2-PROPYLENE GLYCOL USP的丙二醇;产自Lipo商品名为LIPONIC系列、产自ICI商品名为SORBO,ALEX,A-625和A-641、以及产自UPI商品名为UNISWEET 70,UNISWEET CONC的山梨醇;产自BASF商品名同为双丙甘醇的双丙甘醇;产自Solvay GmbH商品名为DIGLYCEROL的双甘油;产自Kyowa和Eizai商品名同为木糖醇的木糖醇;产自Hayashibara商品名为MALBIT的麦芽糖醇;产自Freeman andBioiberica商品名同为软骨素硫酸钠、以及产自Atomergic Chemetals商品名为ATOMERGIC SODIUM CHONDROITIN SULFATE的软骨素硫酸钠;产自Active Oganics商品名为ACTIMOIST、产自Intergen的AVIAN SODIUMHYALURONATE系列以及产自Ichimaru Pharcos商品名为HYALURONICACID Na的透明质酸钠;产自Asahikasei,Kyowa and Daiichi Seiyaku商品名同为腺苷磷酸钠的腺苷磷酸钠;产自Merck,Wako和Showa Kako商品名同为乳酸钠的乳酸钠;产自American Maize商品名为CAVITRON、产自Rhone-Poulenc的RHODOCAP系列、以及产自Tomen的DEXPEARL的环糊精;以及产自Union Carbide商品名为CARBOWAX系列的聚乙二醇。
附加的粘度调节剂(ADDITIONAL VISCOSITY MODIFIER)
本发明的组合物还可以包含附加的粘度调节剂。这里所述的附加粘度调节剂是水溶性的或可与水混溶的聚合物,能够增加组合物的粘度,并与羧酸/羧酸酯共聚物相容。该附加粘度调节剂的选择应使本发明的组合物具有适宜的粘度,优选使组合物具有约1,000至约100,000cps,更优选使组合物具有约2000至约50,000cps的粘度。如果没有附加粘度调节剂就得到这样的粘度,那么就不需要附加粘度调节剂了。这里所述的粘度可以通过布洛克菲尔德旋转粘度计(Brookfield RVT),用4#、5#、6#或7#(取决于组合物的粘度和特性)锭子,在20℃以每分钟20转的速度进行适当的测量。在本发明中,附加粘度调节剂的用量优选占组合物重量的约0.001%至约5%,更优选占组合物重量的约0.05%至约3%。
本发明所用的附加粘度调节剂包括阴离子聚合物和非离子聚合物。这里可用的附加粘度调节剂为乙烯基聚合物如CTFA名称为Carbomer的交联的丙烯酸聚合物、纤维素衍生物和改性纤维素聚合物如甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基甲基纤维素、硝基纤维素、硫酸纤维素钠、羧甲基纤维素钠、结晶纤维素、纤维素粉末、聚乙烯基吡咯烷酮、聚乙烯醇、瓜尔胶、羟丙基瓜尔胶、黄原胶、阿拉伯树胶、黄蓍胶、半乳聚糖、角豆树胶、瓜尔胶、刺梧桐树胶、角叉菜胶、果胶、琼脂、温泊子(Cydoniaoblonga Mill)、淀粉(稻米、玉米、马铃薯、小麦)、藻类胶体(藻类提取物)、微生物聚合物如葡聚糖、琥珀酰葡聚糖、pulleran,淀粉基聚合物如羧甲基淀粉、甲基羟丙基淀粉),藻酸基聚合物,如藻酸钠、藻酸丙二醇酯,丙烯酸类聚合物如聚丙烯酸钠、聚乙基丙烯酸酯、聚丙烯酰胺、聚乙烯亚胺、以及无机水溶性材料如膨润土、硅酸铝镁盐、合成锂皂石、锂蒙脱石(hectonite)、及无水硅酸。
这里可以使用分子量超过约1,000的聚亚烷基二醇。可用的聚亚烷基二醇具有如下的通式:其中R95选自氢、甲基、以及它们的混合物。当R95为氢时,这些材料为氧化乙烯的聚合物,也称作聚环氧乙烷、聚氧乙烯和聚乙二醇。当R95为甲基时,这些材料为氧化丙烯的聚合物,也称作聚环氧丙烷、聚氧丙烯和聚丙二醇。另外应当知道,当R95为甲基时,所得到的聚合物可能存在多种位置异构体。在上面的结构中,x3的平均值为约1,500至约25,000,优选约2,500至约20,000,更优选约3,500至约15,000。其它可用的聚合物包括聚丙二醇和聚乙二醇与聚丙二醇的混合物,或聚氧乙烯-聚氧丙烯的共聚物。本发明所使用的聚乙二醇聚合物有PEG-2M,其中的R95是氢且x3的平均值约2,000(PEG-2M也称作Polyox WSRN-10,产自Union Carbide并称为PEG-2,000);PEG-5M,其中的R95是氢且x3的平均值约5,000(PEG-5M也称作Polyox WSRN-35和Polyox WSRN-80,二者都产自Union Carbide并分别称为PEG-5,000和聚乙二醇300,000);PEG-7M,其中的R95是氢且x3的平均值约7,000(PEG-7M也称作Polyox WSRN-750,产自Union Carbide);PEG-9M,其中的R95是氢且x3的平均值约9,000(PEG-9M也称作Polyox WSRN-3333,产自Union Carbide);以及PEG-14M,其中的R95是氢且x3的平均值约14,000(PEG-14M也称作Polyox WSRN-3000,产自Union Carbide)。
此处特别有用的市售的附加粘度调节剂,包括产自B.F.Goodrich公司商品名为Carbopol 934、Carbopol 940、Carbopol 950、Carbopol 980和Carbopol981的Carbomer,产自Rohm and Hass商品名为ACRYSOL 22的丙烯酸酯/十八烷基聚氧乙烯醚-20甲基丙烯酸酯共聚物,产自Amerchol商品名为AMERCELL POLYMERHM-1500的nonoxynyl羟乙基纤维素,产自Herculus商品名为BENECEL的甲基纤维素、商品名为NATROSOL的羟乙基纤维素、商品名为KLUCEL的羟丙基纤维素、商品名为POLYSURF 67的十六烷基羟乙基纤维素,产自Amerchol商品名为CARBOWAX PEGs、POLYOXWASRs和UCON FLUIDS的基于氧化乙烯和/或氧化丙烯的聚合物。
荧光增白剂
本发明的组合物还可以包含荧光增白剂。荧光增白剂是吸收紫外光并以可见光的形式再发射能量的化合物。具体地讲,本发明所用的荧光增白剂在约1nm和约420nm的波长之间有一个吸收峰,优选是主吸收峰;在约360nm和约830nm的波长之间有一个发射峰,优选是主发射峰;其中主吸收峰的波长比主发射峰的波长短。更优选地,本发明所用的荧光增白剂在约200nm和约420nm的波长之间有一个主吸收峰,在约400nm和约780nm的波长之间有一个主发射峰。荧光增白剂在波长为约360nm至约830nm之间的可见光范围可以有、也可以没有次级吸收峰。在本技术领域和其它工业中,荧光增白剂也可以以其它的名称来描述,如荧光增亮剂、荧光光亮剂和荧光染料。
当通过适宜的载体施用于头发时,本发明的荧光增白剂为头发提供三方面的益处。首先,本发明的荧光增白剂通过发射可见光而改变头发的颜色;其次,本发明的荧光增白剂通过发射可见光而增强头发的光泽;再次,本发明的荧光增白剂通过吸收紫外光而保护头发,使头发免于紫外光的伤害。
一般来讲,荧光增白剂是以芳族化合物和芳香杂环体系的结构为基础的,该芳族化合物和芳香杂环体系提供这种独特的特性。本发明所用的荧光增白剂可以是水溶性的和非水溶性的,并可以根据它们的基本结构来分类,如下面所述。在本发明中,优选的荧光增白剂包括聚苯乙烯基二苯乙烯、三嗪二苯乙烯、羟基香豆素、氨基香豆素、三唑、吡唑啉、噁唑、芘、卟啉和咪唑。
在本发明中,有用的荧光增白剂的用量,优选占组合物重量的0.001%至10%。
聚苯乙烯基二苯乙烯
在本发明中,有用的聚苯乙烯基二苯乙烯包括具有下面式(1)、(2)和(3)的那些:这里R101为H、OH、SO3M、COOM、OSO3M、OPO(OH)OM,其中M是H、Na、K、Ca、Mg、铵、一-、二-、三-或四-(C1-C30烷基)铵、一-、二-或三-(C1-C30羟烷基)铵或由C1-C30烷基和C1-C30羟烷基混合物二或三取代的铵;或者为SO2N(C1-C30烷基)2、O-(C1-C30烷基)、CN、Cl、COO(C1-C30烷基)、CON(C1-C30烷基)2或O(CH2)3N+(CH3)2X-,其中X-是氯、溴、碘、甲酸、乙酸、丙酸、羟乙酸、乳酸、丙烯酸、甲烷膦酸、亚磷酸、二甲基或二乙基亚磷酸的阴离子,CN、或1至30个碳原子的烷基,R102和R103独立地为H、SO3M,其中M的定义同前;x为0或1;其中该化合物具有反式-共面取向或顺式-共面取向;优选x为1,R101为SO3Na,R102和R103为H;其中该化合物具有反式-共面取向;其中,R104和R105独立地为CN、COO(C1-C30烷基)、CONH(C1-C4烷基)或CON(C1-C4烷基)2,其中该化合物具有反式-共面取向或顺式-共面取向;优选为R104和R1052-氰基,其中该化合物具有反式-共面取向;和其中,每个R106独立地为H或1至30个碳原子的烷基;其中该化合物具有反式-共面取向或顺式-共面取向,优选反式-共面取向。
适宜的聚苯乙烯基二苯乙烯包括1,4′-二(2-磺基苯乙烯基)联苯二钠(C.I.荧光光亮剂351),其商品名为Tinopal CBS-X,产自Ciba SpecialtyChemicals;1,4-二(2-氰基苯乙烯基)苯(C.I.荧光光亮剂199),其商品名为Ultraphor RN,产自BASF。
三嗪二苯乙烯
三嗪二苯乙烯是在同一分子中既有三嗪结构又有二苯乙烯结构的一类化合物。在本发明中,有用的三嗪二苯乙烯包括具有式(4)结构的那些三嗪二苯乙烯:这里,R107和R108独立地为苯基氨基、一或二磺化的苯基氨基、吗啉代、N(CH2CH2OH)2、N(CH3)(CH2CH2OH)、NH2、N(C1-C4烷基)2、OCH3、Cl、NH-(CH2)1-4SO3H或NH-(CH2)1-4OH;An-为羧酸、硫酸、磺酸或磷酸阴离子,而M的定义同前,其中该化合物具有反式-共面取向或顺式-共面取向;优选地,R107为2,5-二磺基苯基氨基,每个R108为吗啉代;或每个R107为2,5-二磺基苯基氨基,每个R108为N(C2H5)2;或每个R107为3-磺基苯基,每个R108为NH(CH2CH2OH)或N(CH2CH2OH)2;或每个R107为4-磺基苯基,每个R108为N(CH2CH2OH)2;每种情况下,磺基均为SO3M,其中M为Na;其中该化合物具有反式-共面取向。
适宜的三嗪二苯乙烯包括4,4′-二-[(4-苯胺基-6-二(2-羟乙基)氨基-1,3,5-三嗪-2-基)氨基]二苯乙烯-2,2′-二磺酸,商品名为Tinopal UNPA-GX,产自Ciba Specialty Chemicals;4,4′-二-[(4-苯胺基-6-吗啉-1,3,5-三嗪-2-基)氨基]二苯乙烯-2,2′-二磺酸钠,商品名为Tinopal AMS-GX,产自CibaSpecialty Chemicals;4,4′-二-[(4-苯胺基-6-二(2-羟乙基)甲基氨基-1,3,5-三嗪-2-基)氨基]二苯乙烯-2,2′-二磺酸钠,商品名为Tinopal 5BM-GX,产自Ciba Specialty Chemicals;4,4′-二-[(4,6-二苯胺基-1,3,5-三嗪-2-基)氨基]二苯乙烯-2,2′-二磺酸钠;4,4′-二-[(4-苯胺基-6-甲基氨基-1,3,5-三嗪-2-基)氨基]二苯乙烯-2,2′-二磺酸钠;4,4′-二-[(4-苯胺基-6-乙基氨基-1,3,5-三嗪-2-基)氨基]二苯乙烯-2,2′-二磺酸钠和4,4′-二-(4-苯基-1,2,3-三唑基-2-基)二苯乙烯-2,2′-二磺酸。
羟基香豆素
本发明的羟基香豆素包括具有下面式(5)结构的那些:这里,R201为H、OH、Cl、CH3、CH2COOH、CH2SO3H、CH2OSO3H或CH2OPO(OH)OH,R202为H、苯基、COO-C1-C30-烷基、葡萄糖或如下面式(6)的基团:而R203为OH或O-C1-C30-烷基,并且R204为OH或O-C1-C30-烷基、葡糖苷或如下面式(7)的基团:其中R205和R206独立地为苯基氨基、一或二磺化的苯基氨基、吗啉代、N(CH2CH2OH)2、N(CH3)(CH2CH2OH)、NH2、N(C1-C30烷基)2、OCH3、Cl、NH-(CH2)1-4SO3H或NH-(CH2)1-4OH。
适宜的羟基香豆素包括产自Wako Chemicals的6,7-二羟基香豆素、4-甲基-7-羟基香豆素和4-甲基-6,7-二羟基香豆素,以及产自Wako Chemicals的七叶苷和伞形酮(4-羟基香豆素)。
氨基香豆素
氨基香豆素是具有下面基本香豆素结构并至少具有一个氨基部分的一类化合物。
本发明的氨基香豆素包括具有下面式(8)结构的那些:这里,R207为H、Cl、CH3、CH2COOH、CH2SO3H、CH2OSO3H或CH2OPO(OH)OH,R208为H、苯基或COO-C1-C30-烷基,R209和R210独立地为H、NH2、N(C1-C30烷基)2、NHC1-C30烷基或NHCOC1-C30烷基。
适宜的氨基香豆素包括产自BASF商品名为Calcofluor-RWP的4-甲基-7,7′-二乙基氨基香豆素;产自BASF商品名为Calcofluor-LD的4-甲基-7,7-二甲基氨基香豆素。
三唑
本发明的三唑包括具有式(9)至式(12)和式(15)至式(20)结构的那些:这里,R301和R302独立地为H、C1-C30的烷基、苯基或单磺化的苯基;An-和M的定义同前,其中该化合物具有反式-共面取向或顺式-共面取向;优选地,R301为苯基,R302为H,而M为钠;这里该化合物具有反式-共面取向;其中,R303为H或Cl;R304为SO3M、SO2N(C1-C30烷基)2、SO2O-苯基或CN;R305为H、SO3M、COOM、OSO3M或OPO(OH)OM;并且M的定义同前,其中该化合物具有反式-共面取向或顺式-共面取向;优选地,R303和R305为H,R304为SO3M其中M为Na;这里该化合物具有反式-共面取向;这里,每个R306和R312均独立地为H、磺酸基或其盐或其酯或其酰胺、羧酸基或其盐或其酯或其酰胺、氰基、卤原子、未取代的或取代的烷基磺酰基、芳基磺酰基、烷基、烷氧基、芳烷基、芳基、芳氧基、芳烷氧基或环烷基基团、未取代的或取代的五员杂环(含2-3个氮原子或1个氧原子和1个或2个氮原子),或者与R307和R313一起,它们代表亚甲二氧基、亚乙二氧基、亚甲氧基亚甲氧基、三亚甲基、四亚甲基、亚丙烯基、亚丁烯基或亚丁二烯基(butadienylene)基团;每个R307和R313独立地为H、磺酸基或其盐或其酯或其酰胺、羧酸基或其盐或其酯或其酰胺、氰基、卤原子、未取代的或取代的烷基或烷氧基基团,或者与R306和R312一起,代表亚甲二氧基、亚乙二氧基、亚甲氧基亚甲氧基、三亚甲基、四亚甲基、亚丙烯基、亚丁烯基或亚丁二烯基基团;每个R308和R314独立地为H、卤原子、未取代的或取代的烷基基团;每个R309和R311独立地为H、卤原子、氰基基团、磺酸基或其盐或其酯或其酰胺、或者羧酸基或其盐或其酯或其酰胺;而R310独立地为H、卤原子、氰基基团、磺酸基或其盐、烷基基团,优选被羟基、1-30个碳原子的烷氧基、氰基、卤素、羧基、磺酸基、烷氧基部分有1-30个碳原子的烷酯基、苯基、苯氧基取代;烷氧基基团,可以被羟基、1-30个碳原子的烷氧基、氰基、卤素、羧基、烷氧基部分有1-30个碳原子的烷酯基、苯基或苯氧基取代;苯基、苯基烷基或苯氧基基团,可以被卤素、氰基、羧基、烷氧基部分有1-30个碳原子的烷酯基、磺基、或具有1-30个碳原子的烷基或烷氧基取代;其中该化合物具有反式-共面取向或顺式-共面取向;可能的环烷基基团优选可以被1-30个碳原子的烷基取代的环己基和环戊基基团;可能的五员杂环是v-三唑、噁唑或1,3,4-噁二唑基团,这些基团可包含具有1-4个碳原子的烷基、卤素、苯基、羧基、烷氧基部分有1-30个碳原子的烷酯基、氰基、苄基、1-30个碳原子的烷氧基、苯氧基或磺基作为取代基,其中三唑和噁唑基团上的两个相邻的取代基可以一起形成取代的或未取代的稠合苯核;其中该化合物具有反式-共面取向;这里,Q1代表环系(13)或(14)之一;这里,R317代表H、1-30个碳原子的烷基、环己基、烷基部分具有1-30个碳原子的苯基烷基、苯基、1-30个碳原子的烷氧基、或Cl,或者与R318一起代表3-30碳原子的链烯基;R318代表H或1-30个碳原子的烷基,或者与R317一起代表3-30个碳原子的亚烷基;R319代表H或甲基;R320代表H、1-30个碳原子的烷基、苯基、1-30个碳原子的烷氧基、或Cl,或者与R321一起代表稠合苯环;R321代表H或Cl,或者与R320一起代表稠合苯环;R315代表H、1-30个碳原子的烷基、1-30个碳原子的烷氧基或Cl,R315代表H或Cl;Q2代表H、Cl、1-30个碳原子的烷基、或苯基;而Q3代表H或Cl;其中该化合物具有反式-共面取向或顺式-共面取向;优选反式-共面取向;这里,R322代表H、Cl、甲基、苯基、苄基、环己基或甲氧基;R323代表H或甲基;而Z代表O或S;其中该化合物具有反式-共面取向或顺式-共面取向;优选反式-共面取向;和这里,R324代表H、Cl、1-30个碳原子的烷基、1-30个碳原子的苯基烷基、苯基、或1-30个碳原子的烷氧基,或者R324与R325一起代表稠合苯基团;R325代表H或甲基,或者R325与R324一起代表稠合苯基团;R326代表H、1-30个碳原子的烷基、1-30个碳原子的烷氧基、Cl、1-30个碳原子的烷酯基、或1-30个碳原子的烷基磺酰基;而R327代表H、Cl、甲基或甲氧基;其中该化合物具有反式-共面取向或顺式-共面取向;优选反式-共面取向。
适宜的三唑包括产自Ciba Specialty Chemicals商品名为Tinopal RBS的2-(4-苯乙烯基-3-磺基苯基)-2H-萘并[1,2-d]三唑(C.I.荧光光亮剂46)。
吡唑啉
吡唑啉是一类具有下列基本结构的化合物:本发明的吡唑啉包括具有式(21)至式(23)结构的那些:这里,R401为H、Cl或N(C1-C30-烷基)2;R402为H、Cl、SO3M、SO2NH2、SO2NH-(C1-C30-烷基)、COO-C1-C30烷基、SO2-C1-C30烷基、SO2NH(CH2)1-4N+(CH3)3或SO2(CH2)1-4N+H(C1-C30烷基)2An-;R403和R404相同或不同,每个为H、C1-C30的烷基或苯基;而R405为H或Cl;An-和M的定义同前;优选R401为Cl,R402为SO2CH2CH2N+H(C1-C4烷基)2An-(其中An-为亚磷酸根),R403、R404和R405每个均为H;并且式(22)和式(23)如下所示。
适宜的吡唑啉有1-(4-酰胺基磺酰基苯基)-3-(4-氯代苯基)-2-吡唑啉(C.I.荧光光亮剂121),商品名为Blankophor DCB的,产自Bayer;1-[4-(2-磺基乙基磺酰基)苯基]-3-(4-氯代苯基)-2-吡唑啉,1-[4-(2-磺基乙基磺酰基)苯基]-3-(3,4-二氯代-6-甲基苯基)-2-吡唑啉,1-<4-{N-[3-(N,N,N-三甲基氨)丙基]-酰胺基磺酰基}苯基>-3-(4氯代苯基)-2-吡唑啉硫酸甲酯,和1-<4-{2-[1-甲基-2-(N,N-二甲基氨基)乙氧基]乙基磺酰基}苯基>-3-(4-氯代苯基)-2-吡唑啉硫酸甲酯。
噁唑
本发明的噁唑包括具有式(24)、(25)、(26)和(27)结构的那些:这里,R501和R502独立地为H、Cl、C1-C30的烷基或SO2-C1-C30-烷基,其中该化合物具有反式-共面取向或顺式-共面取向;优选R501为4-CH3而R502为2-CH3,其中该化合物具有反式-共面取向;这里,R503独立地为H、C(CH3)3、C(CH3)2-苯基、C1-C30的烷基或COO-C1-C30的烷基,优选R503为H而Q4为-CH=CH-;优选或每个环中的一个R503基团为2-甲基,而其它的R503为H,并且Q4为-CH=CH-;或每个环中的一个R503基团为2-C(CH3)3,而其它的R503为H;其中该化合物具有反式-共面取向或顺式-共面取向,优选反式-共面取向;这里,R504为CN、Cl、COO-C1-C30的烷基或苯基;R505和R506是形成稠合苯环所需的原子,或R506和R508独立地为H或C1-C30的烷基;而R507为H、C1-C30的烷基或苯基;其中该化合物具有反式-共面取向或顺式-共面取向;优选R504为4-苯基而每个R505至R508为H;其中该化合物具有反式-共面取向;和这里,R509代表H、Cl、1-30个碳原子的烷基、环己基、烷基部分有1-3个碳原子的苯基烷基、苯基或1-30个碳原子的烷氧基;R510代表H或1-30个碳原子的烷基;而Q5代表基团:这里,R511表示H、1-30个碳原子的烷基、1-30个碳原子的烷氧基、Cl、1-30个碳原子的烷酯基、未取代的氨磺酰基、或被1-30个碳原子的烷基或羟烷基一取代或二取代的氨磺酰基,或表示1-30个碳原子的烷基磺酰基;其中该化合物具有反式-共面取向或顺式-共面取向,优选反式-共面取向。
适宜的噁唑包括4,4′-二(5-甲基苯并噁唑-2-基)二苯乙烯,和2-(4-甲氧基羰基苯乙烯基)苯并噁唑。
芘
适宜的芘包括2,4-二甲氧基-6-(1′-芘基)-1,3,5-三嗪(C.I.荧光光亮剂179),商品名为Fluolite XMF;8-羟基-1,3,6-芘三磺酸(D&C Green No.8);和3-羟基-5,8,10-三磺基苯胺芘(trisulphanilic pyrene)。
卟啉
本发明的卟啉包括具有下面式(30)、(31)和(32)结构的那些:这里,R701为CH3或CHO;R702为H或COOC1-C30烷基,而R703为H或1-30个碳原子的烷基;和这里,每个R704独立地为H、SO3M、COOM、OSO3M或OPO(OH)OM(其中M的定义同前)、卤素或1-30个碳原子的烷基;而Q6为Cu、Mg、Fe、Cr、Co或它们的带正电荷的混合物。
适宜的卟啉包括产自Wako Chemicals的卟啉和酞菁铜II。
适宜的咪唑包括那些产自Ciba Specialty Chemical商品名为C.I.荧光光亮剂352或Uvtex AT的咪唑。
紫外线吸收剂
本发明的组合物还可包含紫外线吸收剂。紫外线吸收剂对于基本上透明的本发明组合物是特别有用的。本发明的紫外线吸收剂的用量优选占组合物重量的约0.01%至约10%。
这里所使用的紫外线吸收剂可以是水溶性的或非水溶性的,包括对-氨基苯甲酸及其盐和衍生物(乙酯、异丁酯、甘油酯,对二甲氨基苯甲酸);氨茴酸酯(即邻-氨基苯甲酸酯;甲基、基、苯基、苄基、苯乙基、里哪基、萜品基和环己烯基酯);水杨酸酯(戊基、苯基、苄基、基、甘油基和双丙甘醇酯);肉桂酸衍生物(基和苄基酯、-苯基肉桂腈;丁基肉桂酰基丙酮酸酯;三羟基肉桂酸衍生物(6,7-二羟基香豆素、甲基-6,7-二羟基香豆素、7,8-二羟基香豆素、葡糖苷、七叶苷、瑞香苷);二亚苄基丙酮和亚苄基乙酰苯;萘酚磺酸盐(2-萘酚-3,6-二磺酸钠盐和2-萘酚-6,8-二磺酸钠盐);二羟基-萘甲酸及其盐;邻-和对-羟基联苯二磺酸酯;奎宁盐(硫酸氢盐、硫酸盐、氯化物、油酸盐和单宁酸盐);喹啉衍生物(8-羟基喹啉盐、2-苯基喹啉);羟基或甲氧基取代的二苯酮;尿酸和vilouric酸;单宁酸及其衍生物(如六乙基醚);(丁基卡必基(carbityl))(6-丙基胡椒基)醚;对苯二酚;二苯酮(羟苯、sulisobenzone、dioxybenzone、苯并雷琐酚(benzoresorcinol)、2,2′,4,4′-四羟基二苯酮、2,2′-二羟基-4,4′-二甲氧基二苯酮、octabenzone);4-异丙基二苯甲酰基甲烷;丁基甲氧基二苯甲酰基甲烷;etocrylene;和4-异丙基-二-苯甲酰基甲烷。此外,还有对-甲氧基肉桂酸2-乙基己酯、4,4′-叔丁基甲氧基二苯甲酰基甲烷、2-羟基-4-甲氧基二苯酮、辛基二甲基对-氨基苯甲酸、双倍酰基三油酸酯、2,2-二羟基-4-甲氧基二苯酮、4-[二(羟丙基)]氨基苯甲酸乙酯、2-氰基-3,3-二苯基丙烯酸2-乙基己酯、水杨酸2-乙基己酯、对-氨基苯甲酸甘油酯、3,3,5-三甲基环己基水杨酸酯、邻-氨基苯甲酸甲酯、对-二甲氨基苯甲酸或氨基苯甲酸酯、对-二甲氨基苯甲酸2-乙基己酯、2-苯基苯并咪唑-5-磺酸、2-(对-二甲氨基苯基)-5-磺酸基苯并噁唑酸(sulfonicbenzoxazoic acid)以及它们的混合物。本发明组合物中的优选的防晒剂,对-甲氧基肉桂酸2-乙基己酯、丁基甲氧基二苯甲酰基甲烷、2-羟基-4-甲氧基二苯酮、辛基二甲基对-氨基苯甲酸以及它们的混合物。
草本植物提取物
本发明的组合物还可以包含草本植物提取物。用于本发明的草本植物提取物包括那些水溶性的提取物和那些非水溶性的提取物。这里所用的草本植物提取物包括:何首乌提取物(Polygonum multiflori Extract)、蕺菜提取物(Houttuynia cordate extract)、黄柏树皮提取物(Phellodendron Bark Pxtract)、草木犀提取物、野芝麻提取物、甘草根提取物、草本芍药提取物、肥皂草提取物、丝瓜提取物、金鸡纳树提取物、匍匐虎耳草提取物(creeping saxifrageextract)、窄叶槐提取物(Sophora angustifolia extract)、睡莲提取物、小茴香提取物、报春花提取物、玫瑰提取物、Rehmannia glutinosa提取物、柠檬提取物、shikon提取物、芦荟(alloe)提取物、鸢尾鳞茎(iris bulb)提取物、桉树提取物、问荆提取物、鼠尾草提取物、百里香提取物、茶叶提取物、甘紫菜提取物、黄瓜提取物、丁香(clove)提取物、树莓提取物、蜜蜂花提取物、人参提取物、胡萝卜提取物、七叶树提取物、桃子提取物、桃叶提取物、桑树提取物、矢车菊提取物、金缕梅(hamamelis)提取物、胎座提取物、百里香(thymus)提取物、蚕丝提取物、藻类提取物、蜀葵提取物、兴安白芷(angelica dahurica)提取物、苹果提取物、杏仁提取物、山金车花提取物、茵陈蒿(Artemisia capillaris)提取物、黄芪(astragal)提取物、柠檬薄荷(balm mint)提取物、紫苏提取物、桦树皮提取物、苦橙皮提取物、甜山茶(Thea sinensis)提取物、牛蒡根提取物、地榆提取物、假叶树提取物、金线吊乌龟(Stephaniacepharantha)提取物、母菊提取物、菊花提取物、citrus unshiu peel提取物、蛇床提取物、薏苡籽提取物、款冬提取物、聚合草叶(comfrey leaf)提取物、山楂(crataegus)提取物、月见草油、黑儿茶(gimbir)提取物、灵芝提取物、栀子提取物、龙胆提取物、天竺葵提取物、银杏提取物、葡萄叶提取物、苹卷(crataegus)提取物、散沫花提取物、忍冬提取物、金银花提取物、茯苓(hoelen)提取物、蛇麻子提取物、问荆提取物、绣球(hydrangea)提取物、金丝桃(hypericum)提取物、isodonis提取物、常春藤提取物、日本当归(Japaneseangelica)提取物、日本黄连(Japanese coptis)提取物、柏提取物、枣提取物、羽衣草(Lady’s mantle)提取物、熏衣草提取物、莴苣提取物、甘草提取物、椴提取物、紫草提取物、枇杷提取物、丝瓜提取物、malloti提取物、锦葵提取物、金盏花提取物、牡丹树皮提取物、槲寄生提取物、mukurossi提取物、艾蒿提取物、桑树根提取物、荨麻提取物、肉豆蔻提取物、橙子提取物、欧芹(Parsely)提取物、水解壳(hydrolyzed conchiorin)蛋白、芍药根提取物、胡椒薄荷提取物、喜林芋提取物、松果提取物、桔梗提取物、黄精(Polygonatum)提取物、地黄提取物、米糠提取物、大黄提取物、营实(rose fruit)提取物、迷迭香提取物、蜂王浆提取物、红花提取物、藏红花提取物、接骨木(花)提取物、肥皂草提取物、Sasa albo marginata提取物、虎耳草(Saxifragastolonifera)提取物、黄芩根提取物、香菇小丝膜菌(Cortinellus shiitake)提取物、紫草提取物、槐提取物、月桂提取物、菖蒲根提取物、獐牙菜提取物、百里香提取物、菩提树提取物、西红柿提取物、姜黄提取物、钩藤提取物、水芹提取物、洋苏木树提取物、葡萄提取物、白百合提取物、蔷薇果提取物、野生百里香提取物、美洲金缕梅提取物、蓍提取物、酵母提取物、丝兰提取物、花椒提取物以及它们的混合物。
用于本发明的商业上可得到的草本植物提取物包括:产自Institute ofOccupational Medicine,CAPM,China National Light Industry和Maruzen的水溶性何首乌提取物,以及上面所列出的、产自Maruzen的其它草本植物提取物。
附加的调理剂
本发明的组合物还可以包含附加调理剂,该附加调理剂选自高熔点化合物、阳离子表面活性剂、高分子量酯油、阳离子聚合物、附加的油性化合物,以及它们的混合物。附加的调理剂是根据与其它组分的兼容性和所期望的产品特性来选择的。例如,阳离子性组分的包含量不使阴离子和/或两性的基本组分产生分离。此处所用的附加调理剂的优选用量为组合物重量的约0.01%至约10%。
高熔点化合物
用于本发明的高熔点化合物的熔点至少为约25℃,并选自脂肪醇、脂肪酸、脂肪醇衍生物、脂肪酸衍生物、烃、甾族化合物以及它们的混合物。本领域的技术人员明白,在本说明书这一部分所公开的化合物在某些情况下可以归为不止一类中,例如一些脂肪醇衍生物也可以归类于脂肪酸衍生物。但是,归类并不是打算限定那些特殊的化合物,之所以这样做,只是为了方便分类和命名。另外,本领域的技术人员还明白,取决于双键的数目和位置、支链的长度和位置,某些具有某种所需的碳原子数的化合物的熔点可能低于约25℃。这一部分不打算包括这种低熔点化合物。可以在1993年第5版的International Cosmetic Ingredient Dictionary以及1992年第2版的CTFA Cosmetic Ingredient Handbook中查到本发明的高熔点化合物的非限定性例子。
据信,这些高熔点化合物覆盖头发的表面并减小摩擦,因此,使头发感觉起来光滑并且易于梳理。
这里所用的脂肪醇具有约14至约30个碳原子,优选具有约16至约22个碳原子。这些脂肪醇可以是直链的或支链的,也可以是饱和的或不饱和的。脂肪醇的非限定性例子包括鲸蜡醇、硬脂醇、二十二烷醇以及它们的混合物。
这里所用的脂肪酸具有约10至约30个碳原子,优选具有约12至约22个碳原子,更优选具有约16至约22个碳原子。这些脂肪酸可以是直链的或支链的,也可以是饱和的或不饱和的。也包括那些符合本发明要求的二元酸、三元酸及其它多元酸。这里还包括这些脂肪酸的盐。脂肪酸的非限定性例子包括月桂酸、棕榈酸、硬脂酸、二十二烷酸、癸二酸以及它们的混合物。
在本发明中,有用的脂肪醇衍生物和脂肪酸衍生物,包括脂肪醇的烷基醚、烷氧基化的脂肪醇、烷氧基化的脂肪醇的烷基醚、脂肪醇的酯、具有可酯化羟基的化合物的脂肪酸酯、羟基取代的脂肪酸以及它们的混合物。脂肪醇衍生物和脂肪酸衍生物的非限定性例子所包括的材料如甲基硬脂基醚;十六烷基聚氧乙烯醚(cetech)系列化合物,如cetech-1至cetech-45,这些化合物是十六醇的乙二醇醚,其中的数字标记表示出现的乙二醇数目;十八烷基聚氧乙烯醚(steareth)系列化合物,如steareth-1至steareth-10,这些化合物是十八醇的乙二醇醚,其中的数字标记表示出现的乙二醇数目;ceteareth-1至ceteareth-10(十六/十八烷基聚氧乙烯醚),这些化合物是十六/十八醇(即主要含有十六醇和十八醇的脂肪醇混合物)的乙二醇醚,其中的数字标识表示出现的乙二醇数目;上面刚刚描述过的cetech、steareth和ceteareth化合物的C1-C30烷基醚;二十二烷醇的聚氧乙烯醚;硬脂酸乙酯、硬脂酸十六酯、棕榈酸十六酯、硬脂酸十八酯、肉豆蔻酸十四酯、聚氧乙烯十六基醚硬脂酸酯、聚氧乙烯十八基醚硬脂酸酯、聚氧乙烯月桂基醚硬脂酸酯、乙二醇单硬脂酸酯、聚氧乙烯单硬脂酸酯、聚氧乙烯二硬脂酸酯、丙二醇单硬脂酸酯、丙二醇二硬脂酸酯、三羟甲基丙烷二硬脂酸酯、失水山梨糖醇硬脂酸酯、聚硬脂酸甘油酯、甘油单硬脂酸酯、甘油二硬脂酸酯、甘油三硬脂酸酯以及它们的混合物。
本发明中所用的烃包括具有至少约20个碳的化合物。
本发明中所用的甾族化合物包括如胆甾醇的化合物。
优选单一的高纯度化合物作为高熔点化合物。选自纯十六醇、十八醇和二十二醇的纯脂肪醇的单一化合物是特别优选的。这里,“纯”的意思是指化合物的纯度至少为约90%,优选至少约95%。当消费者从头发上洗掉本发明的组合物时,这些高纯度的单一化合物提供良好的可漂洗性。
本发明中所用的可购得的高熔点化合物包括:产自Shin NihonRika(Osaka,Japan)商品名为KONOL系列,和产自NOF(Tokyo,Japan)商品名为NAA系列的十六醇、十八醇和二十二醇;产自WAKO(Osaka,Japan)商品名为1-DOCOSANOL的纯二十二醇;产自Akzo(Chicago Illinois,USA)商品名为NEO-FAT、产自Witco公司(Dublin Ohio,USA)商品名为HYSTRENE和产自Vevy(Genova,Italy)商品名为DERMA的各种脂肪酸;以及产自Nikko的商品名为NIKKOL AGUASOME LA的胆甾醇。
阳离子表面活性剂
在阳离子表面活性剂中,对本发明有用的是对应于下面通式(I)的那些:其中R71、R72、R73和R74中的至少一个选自8-30个碳原子的脂族基团或具有高至约22个碳原子的芳族基团、烷氧基、聚氧化烯、烷基酰胺基、羟烷基、芳基或烷芳基基团,剩下的R71、R72、R73和R74独立地选自1至约22个碳原子的脂族基团或具有高至约22个碳原子的芳族基团、烷氧基、聚氧化烯、烷基酰胺基、羟烷基、芳基或烷芳基基团;而X为成盐阴离子,如选自卤素(如氯、溴)、乙酸根、柠檬酸根、乳酸根、羟乙酸根、磷酸根、硝酸根、磺酸根、硫酸根、烷基硫酸根及烷基磺酸根的成盐离子。所述的脂族基团除了包含碳和氢原子之外,还可以包含醚键和其它基团,如氨基基团。链较长的脂族基团,如具有约12个或更多碳原子的脂族基团,可以是饱和的也可以是不饱和的。优选R71、R72、R73和R74独立地选自C1至约C22的烷基。可用于本发明的阳离子表面活性剂的非限定性实例包括具有下列CTFA名称的物质:quaternium-8、quaternium-14、quaternium-18、quaternium-18硫酸甲酯、quaternium-24,以及它们的混合物。
在通式(I)的阳离子表面活性剂中,优选那些分子中至少含有一条不低于16个碳原子的烷基链的阳离子表面活性剂。这样的优选的阳离子表面活性剂的非限定性实例包括二十二烷基三甲基氯化铵,如产自Croda商品名为INCROQUAT TMC-80的产品和产自Sanyo Kasei商品名为ECONOL TM22的产品;十六烷基三甲基氯化铵,如产自NikkoChemicals商品名为CA-2350的产品;氢化牛油烷基三甲基氯化铵、二烷基(14-18)二甲基氯化铵、二牛油烷基二甲基氯化铵、二氢化牛油烷基二甲基氯化铵、二硬脂基二甲基氯化铵、二鲸蜡基二甲基氯化铵、二(二十二烷基/花生基)二甲基氯化铵、二(二十二烷基)二甲基氯化铵、硬脂基二甲基苄基氯化铵、硬脂基磷酸丙二醇酯二甲基氯化铵、硬脂酰胺基丙基二甲基苄基氯化铵、硬脂酰胺基丙基二甲基(乙酸肉豆蔻酯)氯化铵,以及N-(硬脂酰基胆氨基甲酰基甲基)氯化吡啶鎓。
另外,优选的是亲水取代的阳离子表面活性剂,在该亲水化取代的阳离子表面活性剂中,至少一个取代基含有一个或多个芳族、醚、酯、酰胺基或氨基部分,它们在残基链中作为取代基或连接键存在,这里R71-R74中至少有一个含有一个或多个亲水部分,该亲水部分选自烷氧基(优选C1-C3的烷氧基)、聚氧化烯(优选C1-C3的聚氧化烯)、烷基酰胺基、羟烷基、烷基酯、以及它们的组合。优选,亲水化取代的阳离子调理表面活性剂,包含2至约10个定位于上述范围之内的非离子亲水部分。优选的亲水化取代的阳离子表面活性剂,包括具有下面式(II)至(VIII)结构的那些:其中n1为8至约28;m1+m2为2至约40;Z1为短链烷基,优选C1-C3的烷基,更优选甲基或(CH2CH2O)m3H,其中m1+m2+m3最高至60;而X的定义同前面的一样,为成盐阴离子;其中n2为1至5;R75、R76和R77中的一个或多个独立地为C1-C30烷基,余下的为CH2CH2OH;R78、R79和R80中的一个或两个独立地为C1-C30烷基,余下的为CH2CH2OH;X如上面提到的一样,为成盐阴离子;这里,对于式(IV)和式(V),Z2独立地为烷基,优选C1-C3的烷基,更优选甲基;而Z3独立地为短链羟烷基,优选羟甲基或羟乙基;n3和n4独立地为2至4的整数(含2和4),优选2至3的整数(含2和3),更优选2;R81和R82独立地为取代的或未取代的烃基、C12-C20的烷基或链烯基;X如上面定义的一样,为成盐阴离子;其中R83为烃基,优选C1-C3的烷基,更优选甲基;Z4和Z5独立地为短链烃基,优选C2-C4的烷基或链烯基,更优选乙基;m4为2至约40,优选7至约30;X如上面定义的一样,为成盐阴离子;其中R84和R85独立地为C1-C3的烷基,优选甲基;Z6为C12-C22的烃基、烷基羧基或烷基酰胺基;A为蛋白质,优选胶原蛋白、角蛋白、乳蛋白、丝蛋白、大豆蛋白、小麦蛋白或它们的水解形式;X如上面定义的一样,为成盐阴离子:其中n5为2或3;R86和R87独立地为C1-C3的烃基,优选甲基;X如上面定义的一样,为成盐离子。可用于本发明的亲水化取代的阳离子表面活性剂的非限定性实例包括具有下列CTFA名称的物质:quaternium-16、quaternium-26、quaternium-27、quaternium-30、quaternium-33、quaternium-43、quaternium-52、quaternium-53、quaternium-56、quaternium-60、quaternium-61、quaternium-62、quaternium-70、quaternium-71、quaternium-72、quaternium-75、quaternium-76水解胶原蛋白、quaternium-77、quaternium-78、quaternium-79水解胶原蛋白、quaternium-79水解角蛋白、quaternium-79水解乳蛋白、quaternium-79水解丝蛋白、quaternium-79水解大豆蛋白和quaternium-79水解小麦蛋白、quaternium-80、quaternium-81、quaternium-82、quaternium-83、quaternium-84、以及它们的混合物。
特别优选的亲水化取代的阳离子表面活性剂,包括二烷基酰胺基乙基羟乙基甲基铵盐、二烷基酰胺基乙基二甲基铵盐、二烷酰基乙基羟乙基甲基铵盐、二烷酰基乙基二甲基铵盐以及它们的混合物;例如商品名如下的市售品:产自WitcoChemical的VARISOFT 110、VARJSOFT222、VARIQUATK1215和VARIOUAT 638,产自Mclntyre的MACKPRO KLP、MACKPROWLW、MACKPROMLP、MACKPRONSP、MACKPRONLW、MACKPROWWP、MACKPRONLP和MACKPROSLP,产自Akzo的ETHOQUAD18/25、ETHOQUAD O/12PG、ETHOQUAD C/25、ETHOQUAD S/25和ETHODUOQUAD,产自Henkel的DEHYQUATSP,以及产自ICI Americas的ATLAS G265。
胺适合作为阳离子表面活性剂。有用的是伯、仲和叔脂肪胺。具有一个约12至约22个碳的烷基基团的叔酰胺基胺是特别有用的。示例性的叔酰胺基胺包括:硬脂酰胺基丙基二甲基胺、硬脂酰胺基丙基二乙基胺、硬脂酰胺基乙基二乙基胺、硬脂酰胺基乙基二甲基胺、棕榈酰胺基丙基二甲基胺、棕榈酰胺基丙基二乙基胺、棕榈酰胺基乙基二乙基胺、棕榈酰胺基乙基二甲基胺、二十二酰胺基丙基二甲基胺、二十二酰胺基丙基二乙基胺、二十二酰胺基乙基二乙基胺、二十二酰胺基乙基二甲基胺、花生酰胺基丙基二甲基胺、花生酰胺基丙基二乙基胺、花生酰胺基乙基二乙基胺、花生酰胺基乙基二甲基胺、二乙基氨基乙基硬脂酰胺。还有用的有二甲基硬脂族基团胺、二甲基大豆胺、大豆胺、肉豆蔻胺、十三胺、乙基硬脂族基团胺、N-牛油丙烷二胺、乙氧基化的(用5摩尔的环氧乙烷)硬脂胺、二羟基乙基硬脂基胺和花生基二十二烷基胺。授予Nachtigal等人的US 4275055公开了在本发明中有用的胺。
这些胺还可以和酸组合起来使用,所述的酸有C-谷氨酸、乳酸、盐酸、苹果酸、琥珀酸、乙酸、反丁烯二酸、酒石酸、柠檬酸、C-谷氨酸盐酸盐、马来酸以及它们的混合物;更优选C-谷氨酸、乳酸、柠檬酸。本发明的胺优选用任何一种酸,按胺与酸的摩尔比为约1∶0.3至约1∶2,更优选按约1∶0.4至约1∶1的摩尔比部分地中和。
高分子量酯油
在本发明中,高分子量酯油是有用的。本发明所使用的高分子量酯油是那些非水溶性的,分子量至少为约500,优选至少为约800,而且在25℃时为液态的高分子量酯油。本发明所使用的高分子量酯油,包括季戊四醇酯油、三羟甲基酯油、聚α-烯烃油、柠檬酸酯油、甘油酯油、以及它们的混合物。如这里所使用的那样,术语“非水溶性的”是指该化合物在25℃时基本上不溶于水;当该化合物按高于1.0%、优选高于0.5%的重量百分比浓度与水混合时,可以暂时分散于水中并形成不稳定的胶体,然后很快地从水中分离出来成为两相。
在本发明中,高分子量酯油提供各种调理益处,例如当头发处于干燥状态时的湿润感觉、光滑感觉和易控制梳理性,而不产生油腻的感觉。可以相信,非水溶性的油性材料一般可以沉积在头发上。不局限于理论的束缚,可以相信,高分子量酯油因其蓬松性(bulkiness)会覆盖于头发的表面,结果降低头发的摩擦,并赋予头发以光滑性和易控制梳理性。还可以相信,由于高分子量酯油具有一些亲水基团,因此可提供湿润的感觉;又由于它是液体,故不产生油腻的感觉。高分子量酯油在正常的使用和存储条件下,具有化学稳定性。
本发明中所用的季戊四醇酯油为具有下式的那些:其中R1、R2、R3和R4独立地为支链的、直链的、饱和的或不饱和的烷基、芳基和烷基芳基,具有1至约30个碳原子。优选R1、R2、R3和R4独立地为支链的、直链的、饱和的或不饱和的烷基,具有8至约22个碳原子。更优选这样限定的R1、R2、R3和R4,使该化合物的分子量为约800至约1200。
本发明中所用的三羟甲基酯油是具有下式的三羟甲基酯油:其中R11是具有1至约30个碳原子的烷基基团,而R12、R13和R14独立地为支链的、直链的、饱和的或不饱和的烷基、芳基和烷基芳基,具有1至约30个碳原子的。优选R11为乙基,而R12、R13和R14独立地为支链的、直链的、饱和的、不饱和的烷基,并具有8至约22个碳原子。更优选这样限定的R11、R12、R13和R14,使该化合物的分子量为约800至约1200。
本发明所使用的聚α-烯烃油是那些具有下式的结构、粘度为约1至约35,000厘沲、分子量为约200至约60,000、多分散性不超过约3的聚α-烯烃油;
其中R31为约4-14个碳原子的烷基,优选4-10个碳原子的烷基。在本发明中,有用的聚α-烯烃油的分子量至少为约800。据信,这些高分子量的聚α-烯烃油赋予头发长期持续的湿润感觉。在本发明中,分子量为低于约800的聚α-烯烃油也是有用的。据信,这些低分子量的聚α-烯烃油赋予头发光滑、明亮、清洁的感觉。
在本发明中,有用的柠檬酸酯油是分子量至少约500并具有下式结构的那些:其中R21为OH或CH3COO,而R22、R23和R24独立地为支链的、直链的、饱和的或不饱和的烷基、芳基和烷基芳基,具有1至约30个碳原子。优选R21为OH,而R22、R23和R24独立地为支链的、直链的、饱和的、不饱和的烷基、芳基和烷基芳基,具有约8至约22个碳原子。更优选这样限定的R21、R22、R23和R24,使该化合物的分子量至少为约800。
在本发明中,有用的甘油酯油是分子量至少约500并具有下式结构的那些:其中R41、R42和R43独立地为支链的、直链的、饱和的或不饱和的烷基、芳基和烷基芳基,具有1至约30个碳原子。优选R41、R42和R43独立地为支链的、直链的、饱和的或不饱和的烷基、芳基和烷基芳基,具有约8至约22个碳原子。更优选这样限定的R41、R42和R43,使该化合物的分子量至少为约800。
在本发明中,特别有用的季戊四醇酯油和三羟甲基酯油,包括季戊四醇四异硬脂酸酯、季戊四醇四油酸酯、三羟甲基丙烷三异硬脂酸酯、三羟甲基丙烷三油酸酯、以及它们的混合物。这些化合物可得自于KokyoAlcohol,商品名为KAKPTI、KAKTTI;以及得自于Shin-nihon Rika,商品名为PTO、ENUJERUBUTP3SO。
在本发明中,特别有用的聚α-烯烃油,包括数均分子量约500商品名为PURESYN 6、数均分子量约3000商品名为PURESYN100和数均分子量约6000商品名为PURESYN 300的聚癸烯,可从Mobil Chemical公司得到。
在本发明中,特别有用的柠檬酸酯油,包括产自Bernel商品名为CITMOL 316的柠檬酸三异鲸蜡酯、产自Phoenix商品名为PELEMOL TISC的柠檬酸三异硬脂酸酯和产自Bernel商品名为CITMOL 320的柠檬酸三辛基十二酯。
在本发明中,特别有用的甘油酯油,包括产自Taiyo Kagaku商品名为SUN ESPOL G-318的三异硬脂酸甘油酯、产自Croda Surfactants有限公司商品名为CITHROL GTO的三油酸甘油酯、产自Vevy商品名为EFADERMA-F或产自Brooks商品名为EFAGLYCERIDES的三亚麻酸甘油酯。
阳离子聚合物
阳离子聚合物可用于本发明中。这里所使用的术语“聚合物”,将包括通过一种类型的单体聚合或通过两种(即共聚物)或多种类型的单体聚合所制造的材料。
优选,阳离子聚合物是水溶性的阳离子聚合物。“水溶性的”阳离子聚合物的意思是指该聚合物能够充分溶解于水,并在25℃、水(蒸馏水或与蒸馏水相当的水)中和0.1%的浓度下,形成对肉眼来说基本上澄清的溶液。优选的聚合物在约0.5%的浓度下,将充分溶解于水,形成基本上澄清的溶液,更优选在约1.0%的浓度下形成基本上澄清的溶液的聚合物。
本发明阳离子聚合物的重均分子量一般至少为约5,000,典型地至少为约10,000,并且低于约10,000,000。优选分子量为约100,000至约2,000,000。通常该阳离子聚合物具有含氮的阳离子部分,如季铵或阳离子氨基部分,以及它们的混合物。
只要符合水溶解性准则,阳离子聚合物可以使用任何阴性抗衡离子。适宜的抗衡离子包括卤离子(如Cl、Br、I或F,优选Cl、Br或I)、硫酸根和甲基硫酸根(methylsulfate)。也可以使用其它抗衡离子,这里的列举并不是排它的。
含氮的阳离子部分通常以取代基的形式存在于阳离子头发调理聚合物的全部单体单元的一小部分上。因此,阳离子聚合物可以包含季铵或阳离子胺取代的单体单元和其它的这里称为间隔单体单元的非阳离子单元的二元共聚物、三元共聚物等。在本领域中,这种聚合物是已知的并且许多可以在由Estrin,Crosley and Haynes编辑的CTFA化妆品成分词典(CosmeticIngredient Dictionary)的第3版中(The Cosmetic,Toiletry,and FragranceAssociation,Inc.,Washington,D.C.,1982)查到。
该阳离子胺可以是伯、仲、叔胺,这取决于具体的物质和组合物的pH。一般来讲,优选仲和叔胺,特别是叔胺。
胺取代的乙烯基单体可以胺的形式聚合,然后可任选地通过季铵化反应转化成铵;同样也可以将胺季铵化,然后再形成聚合物。例如,叔胺官能团可通过与式R88X的盐反应而季铵化,其中R88是短链烷基,优选C1-C7的烷基,更优选C1-C3的烷基,而X如上面定义的一样,是一种成盐阴离子。
适宜的阳离子氨基和季铵单体包括,例如,由下列取代的乙烯基化合物:二烷基氨基烷基丙烯酸酯、二烷基氨基烷基甲基丙烯酸酯、一烷基氨基烷基丙烯酸酯、一烷基氨基烷基甲基丙烯酸酯、三烷基甲基丙烯酰氧基烷基铵盐、三烷基丙烯酰氧基烷基铵盐、二烯丙基季铵盐,和乙烯基季铵单体,该乙烯基季铵单体具有如吡啶鎓、咪唑鎓和季铵化吡咯烷酮的环状的含氮阳离子环,例如烷基乙烯基咪唑鎓、烷基乙烯基吡啶鎓、烷基乙烯基吡咯烷酮盐。这些单体的烷基部分优选如C1-C3烷基的低级烷基,更优选C1和C2的烷基。适用于本发明的胺取代的乙烯基单体,包括二烷基氨基烷基丙烯酸酯、二烷基氨基烷基甲基丙烯酸酯、二烷基氨基烷基丙烯酰胺和二烷基氨基烷基甲基丙烯酰胺,其中的烷基基团优选C1-C7的烃基,更优选的C1-C3烷基。
本发明的阳离子聚合物可以包含各种单体单元的混合物,所述的单体单元由胺和/或季铵取代的单体和/或可配伍的间隔单体衍生而来。
适宜的阳离子头发调理聚合物例如包括:1-乙烯基-2-吡咯烷酮和1-乙烯基-3-甲基咪唑鎓盐(如氯化物盐)的共聚物(工业上,the Cosmetic,Toiletryand Fragrance Association,“CTFA”,称为Polyquaternium-16),如产自BASFWyandotte公司(Parsippany,NJ,USA)商品名为LUVIQUAT(例如LUVIQUATFC 370)的那些;1-乙烯基-2-吡咯烷酮和二甲基氨基乙基甲基丙烯酸酯的共聚物(工业上,CTFA,称为Polyquaternium-11的工业品),如产自Gaf公司(Wayne,NJ,USA)商品名为GAFQUAT(例如QAFQUAT 755N)的那些;含二烯丙基季铵的阳离子聚合物,包括如二甲基二烯丙基氯化铵均聚物和丙烯酰胺与二甲基二烯丙基氯化铵的共聚物,工业上(CTFA)分别称为Polyquaternium 6和Polyquaternium 7;以及如US 4009256所述的不饱和羧酸的均聚物和共聚物的氨基-烷基酯的无机酸盐,该不饱和羧酸具有3-5个碳原子。
可以使用的其它阳离子聚合物包括多糖聚合物,如阳离子纤维素衍生物和阳离子淀粉衍生物。
适用于本发明的阳离子多糖聚合物材料,包括具有下式结构的那些:其中:Z7是失水葡萄糖残基,如淀粉或纤维素失水葡萄糖残基;R89是亚烷基氧基亚烷基、聚氧基亚烷基、或羟基亚烷基基团,或它们的组合;R90、R91、和R92独立地为烷基、芳基、烷基芳基、芳基烷基、烷氧基烷基、或烷氧基芳基基团,每个基团含有多至约18个碳原子,并且每个阳离子部分的碳原子总数(即R90、R91、和R92中的碳原子数之和)优选约为20或更低;X同前面所描述的一样。
阳离子纤维素,可从Amerchol公司(Edison,NJ,USA)的聚合物系列Polymer JR和LR中得到,是与三甲基铵取代的环氧化物反应过的羟乙基纤维素的盐,工业上(CTFA)称为Polyquaternium 10的那些。另一种类型的阳离子纤维素包括与月桂基二甲基铵取代的环氧化物反应过的羟乙基纤维素的聚合季铵盐,工业上(CTFA)称为Polyquaternium 24。这些材料可从Amerchol公司(Edison,NJ,USA)得到,商品名为Polymer LM-200。
可以使用的其它阳离子聚合物,包括阳离子瓜尔胶衍生物,如瓜尔羟丙基三甲基氯化铵(guar hydroxypropyltrimonium chloride),工业品为产自Celanese公司的Jaguar R系列产品。其它材料,包括如US 3962418所描述的含季氮的纤维素醚,和US 3958581所描述的醚化纤维素与淀粉的共聚物。
在本发明中,特别有用的阳离子聚合物包括Polyquaterniun-7、Polyquaterniun-10、Polyquaterniun-24,以及它们的混合物。
附加的油性化合物
本发明中,有用的附加油性化合物包括脂肪醇及其衍生物、脂肪酸及其衍生物以及烃类。本发明的附加油性化合物可以是挥发性的,也可以是非挥发性的,而且其熔点不超过约25℃。不受理论的限制,可以相信,该附加油性化合物可以渗透到头发里并修饰头发的羟基键,从而使头发具有柔软性和弹性。这部分的附加油性化合物应与前述的高熔点化合物区别开来。这种附加的油性化合物的非限定性实例,可以在1993年第5版的国际化妆品成分词典(International Cosmetic Ingredient Dictionary)和1992年第2版的CTFA化妆品成分手册(CTFA Cosmetic Ingredient Handbook)中查到。
本发明中所用的脂肪醇包括那些具有约10至约30个碳原子,优选约12至约22个碳原子,更优选约16至约22碳原子的脂肪醇。这些脂肪醇可以是直链的也可以是支链的,可以是饱和的也可以是不饱和的,优选不饱和的醇。这些化合物的非限定性实例包括油醇、棕榈油醇、异硬脂醇、异鲸蜡醇、十一醇、辛基十二醇、辛基癸醇、辛基醇、辛醇、癸醇和月桂醇。
本发明中所用的脂肪酸包括那些具有约10至约30个碳原子,优选约12至约22个碳原子,更优选约16至约22碳原子的脂肪酸。这些脂肪酸可以是直链的也可以是支链的,可以是饱和的也可以是不饱和的。举例来说,适宜的脂肪酸包括油酸、亚油酸、异硬脂酸、亚麻酸、乙基亚麻酸、花生四烯酸和蓖麻油酸。
这里所定义的脂肪酸衍生物和脂肪醇衍生物包括脂肪醇的酯、烷氧基化的脂肪醇、脂肪醇的烷基醚、烷氧基化脂肪醇的烷基醚和蓬松的酯油如季戊四醇酯油、三羟甲基酯油、柠檬酸酯油、甘油酯油,以及它们的混合物。举例来说,脂肪酸衍生物和脂肪醇衍生物的非限定性实例包括亚油酸甲酯、亚油酸乙酯、亚油酸异丙酯、油酸异癸酯、油酸异丙酯、油酸乙酯、油酸辛基十二酯、油酸油基酯、油酸癸酯、油酸丁酯、油酸甲酯、硬脂酸辛基十二酯、异硬脂酸辛基十二酯、异棕榈酸辛基十二酯、壬酸辛酯、异壬酸辛酯、异硬脂酸己酯、异硬脂酸异丙酯、异壬酸异癸酯、硬脂酸异丙酯、硬脂酸乙酯、硬脂酸甲酯和Oleth-2。这里所使用的蓬松酯油,如季戊四醇酯油、三羟甲基酯油、柠檬酸酯油和甘油酯油的分子量低于约800,优选低于约500。
本发明所使用的烃包括直链的、环状的和支链的烃,它们可以是饱和的,也可以是不饱和的,只要它们的熔点不超过约25℃。这些烃具有约12至约40个碳原子,优选具有约12至约30个碳原子,最优选约12至约22个碳原子。这里也包括由链烯基单体聚合而成的烃,如C2-6的链烯基单体的聚合物。这些聚合物可以是直链的,也可以是支链的。直链聚合物的链长度通常相对较短,具有的碳原子总数如上所述。支链聚合物大体上可以具有较高的链长度。这些材料的数均分子量的变化范围很宽,通常高至约500,优选约200至约400,更优选约300至约350。此外,还可以使用各种级别的矿物油。矿物油是从石油中得到的烃的液体混合物。适宜的烃材料的具体实例有石蜡油、矿物油、十二烷、异十二烷、十六烷、异十六烷、二十碳烯、异二十碳烯、十三烷、十四烷、聚丁烯、聚异丁烯、以及它们的混合物。本发明中优选使用的烃选自矿物油、聚α-烯烃油,如异十二烷、异十六烷、聚丁烯、聚异丁烯、以及它们的混合物。
本发明所使用的可购得的脂肪醇及其衍生物包括:产自Shin Nihon Rika商品名为UNJECOL 90BHR的油醇、产自Scher商品名为SCHERCEMOL系列的各种液体酯、产自Kokyu Alcohol商品名为HIS的异硬脂酸己酯和商品名为ZPIS的异硬脂酸异丙酯。本发明所使用的可购得的蓬松酯油包括:产自Mobil Chemical公司商品名为MOBIL ESTER P43的三羟甲基丙烷三辛酸酯/三癸酸酯。本发明所使用的可购得的烃包括:产自Presperse(SouthPlainfield New Jersey,USA)商品名为PERMETHYL 99A、PERMETHYL 101A和PERMETHYL 1082的异十二烷、异十六烷和异二十碳烯;产自AmocoChemical(Chicago Illinois,USA)商品名为INDOPOL H-100的异丁烯与正丁烯的共聚物;以及产自Witco商品名为BENOL的矿物油和产自ExxonChemical公司(Houston Texas,USA)商品名为ISOPAR的异链烷烃。
其它的附加组分
本发明的组合物可以包含其它的附加组分,所述的其它的附加组分由本领域的技术人员根据最终产品特性的需要来选择,它们适于赋予该组合物在美容或美观方面更可接受,或者为化妆品和美容用品提供额外的使用优点。这些其它的附加组分各自的量一般为组合物重量的约0.001%至约10%、优选约5%。
可配制到本发明的组合物中的其它附加组分的种类很多,其中包括:其它的调理剂,如产自Hormel商品名为Peptein 2000的水解胶原蛋白、产自Eisai商品名为Emix-d的维生素E、产自Roche的泛醇、产自Roche的泛基乙基醚,以及水解角蛋白、蛋白质、植物提取物和营养素;固定发形的聚合物,如两性的定形聚合物、阳离子型的定形聚合物、阴离子型的定形聚合物、非离子型的定形聚合物、和聚硅氧烷接枝共聚物;防腐剂,如苄醇、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯和咪唑烷基尿;pH调节剂,如柠檬酸、柠檬酸钠、琥珀酸、磷酸、氢氧化钠、碳酸钠;盐,一般地如乙酸钾和氯化钠;着色剂,如任何FD&C或F&C染料;毛发氧化(漂白)剂,如过氧化氢、过硼酸盐和过硫酸盐;毛发还原剂,如巯基乙酸盐;香料;以及多价螯合剂,如乙二胺四乙酸二钠;紫外和红外遮蔽与吸收剂,如水杨酸辛酯;去头屑剂,如2-巯基吡啶氧化锌(zinc pyridinethione);以及它们的混合物。
实施例
下面的实施例在本发明的范围内进一步描述和演示实施方案。这些实施例的给出只是为了说明的目的,不能解释成是对本发明的限制,因为在不脱离本发明的构思和范围的情况下,对本发明作出的很多变化都是可能的。用化学名称或CTFA名称标识各种成分,或另行规定于后面。
本发明的组合物适于制备制备乳液、霜膏、凝胶、喷剂或摩丝形式的产品,并且特别适于制备凝胶形式的免洗型产品。所述产品能够用在湿或干头发上。
组合物
组分的定义*1丙烯酸/丙烯酸烷基酯共聚物1:得自B.F.Goodrich的PEMULEN TR-1。*2丙烯酸/丙烯酸烷基酯共聚物2:得自B.F.Goodrich的PEMULEN TR-2。*3三乙醇胺:得自Nippon Shokubai的三乙醇胺。*4易碎的可见颗粒1:得自Crosfield的Neosil CBT 60。*5易碎的可见颗粒2:得自Crosfield的Neosil CBT 70。*6聚二甲基硅氧烷和聚二甲基硅氧烷醇:得自Dow Corning的DCQ2-1403。*7环状聚二甲基硅氧烷/聚二甲基硅氧烷醇:得自Dow Corning的DCQ2-
组分 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
丙烯酸/丙烯酸烷基酯共聚物1*1 | 0.3 | - | - | 0.5 | - |
丙烯酸/丙烯酸烷基酯共聚物2*2 | - | 0.5 | 0.5 | - | 0.3 |
三乙醇胺*3 | 0.5 | 0.6 | 0.7 | 0.6 | 0.5 |
易碎的可见颗粒1*4 | 0.1 | - | 0.5 | - | 0.1 |
易碎的可见颗粒2*5 | - | 0.2 | - | 0.5 | 0.1 |
环状聚二甲基硅氧烷/聚二甲基硅氧烷醇*6 | 1.0 | 1.0 | - | 2.0 |
环状聚二甲基硅氧烷/聚二甲基硅氧烷醇*7 | 2.0 | ||||
环状聚二甲基硅氧烷/聚二甲基硅氧烷*8 | - | - | 2.0 | - | - |
环状聚二甲基硅氧烷*9 | - | - | 1.0 | - | - |
Polyquaternium-39*10 | 0.2 | 0.1 | - | - | - |
丙二醇 | 2.0 | - | - | 4.0 | - |
聚乙二醇200*11 | - | 2.0 | - | - | - |
Carbomer 1*12 | 0.1 | - | 0.2 | - | - |
Carbomer 2*13 | - | - | - | 0.5 | 0.3 |
2,4-二甲氧基-6-(1’-芘基)-1,3,5-三嗪*14 | - | - | - | - | 1.0 |
二苯酮-4*15 | 0.1 | - | 0.2 | - | - |
甲氧基肉桂酸辛酯*16 | 0.1 | - | 1.0 | - | |
芦荟提取物*17 | - | - | - | - | 1.0 |
泛醇(Pantenol)*18 | 0.1 | - | - | - | - |
对羟基苯甲酸甲酯 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
苯氧基乙醇 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
EDTA二钠 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
香料溶液 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
去离子水 | 适量至100% |
1401。*8环状聚二甲基硅氧烷/聚二甲基硅氧烷:得自GB的SE76。*9环状聚二甲基硅氧烷:得自Dow Corning的DC345。*10 Polyquaternium-39:得自Calgon的Merquat Plus3330。*11聚乙二醇200:得自Union Carbide的Carbowax PEG200。*12 Carbomer 1:得自B.F.Goodrich的Carbopol 981。*13 Carbomer 2:得自B.F.Goodrich的Carbopol Ultrez 10。*14 2,4-二甲氧基-6-(1’-芘基)-1,3,5-三嗪:2,4-二甲氧基-6-(1’-芘基)-1,
3,5-三嗪,得自Ciba Geigy。*15二苯酮-4:得自BASF的Uvnul MS-40。*16甲氧基肉桂酸辛酯:得自Roche的Parasol MCX。*17芦荟提取物:得自Ichimaru Farcos的Aloe Extract Vera。*18泛醇:得自Roche的泛醇。
制备方法
如果组合物中包括聚合的材料,如羧酸/羧酸酯共聚物和附加的粘度调节剂、增粘剂和两性调理聚合物,那么就将这些聚合的材料在室温下分散于水中,在强烈搅拌下混合,然后加热到50摄氏度。将得到的混合物冷却到40摄氏度以下,然后在混合物中加入中和剂。如果分散聚合物材料需要,可以使用三叶掺混机(triblender)。中和后,在该混合物中加入剩余的组分。
实施例1至5为本发明的头发调理组合物,该组合物特别适用于免洗型用途。这些实施例具有很多优点。例如,它们是透明的,可清楚地辩识出易碎的可见颗粒。而且它们还改进了头发的调理益处:如光滑性、柔软性,抗静电并降低了摩擦、易于使用在头发上、使头发和手具有清洁感。易碎的可见颗粒在手上用手指施以很小的剪切就会碎裂。
可以理解,这里所描述的实施例和实施方案仅仅是为了解释的目的,而在不脱离本发明的构思和范围的情况下,本领域的普通技术人员可以根据本发明提出多种修正或更改。
Claims (8)
1.一种头发调理组合物,包含:
(1)羧酸/羧酸酯共聚物;
(2)易碎的可见颗粒,包含一结构材料,选自合成聚合物、合成的无定型二氧化硅、蜡化合物,以及它们的混合物;和
(3)含水载体。
2.权利要求1的头发调理组合物,其中还包含聚硅氧烷化合物。
3.权利要求1的头发调理组合物,其中还包含两性调理聚合物。
4.权利要求1、2或3中的任一项的头发调理组合物,其中还包含保湿剂。
5.权利要求1、2或3中的任一项的头发调理组合物,其中还包含附加的粘度调节剂。
6.权利要求1、2或3中的任一项的头发调理组合物,其中还包含荧光增白剂。
7.权利要求1、2或3中的任一项的头发调理组合物,其中还包含紫外线吸收剂。
8.权利要求1、2或3中的任一项的头发调理组合物,其中还包含草本植物提取物。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/000010 WO2000040211A1 (en) | 1999-01-04 | 1999-01-04 | Hair conditioning composition comprising carboxylic acid/carboxylate copolymer and breakable visible particle |
Publications (1)
Publication Number | Publication Date |
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CN1334717A true CN1334717A (zh) | 2002-02-06 |
Family
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CN99816186A Pending CN1334717A (zh) | 1999-01-04 | 1999-01-04 | 包含羧酸/羧酸酯共聚物和易碎可见颗粒的头发调理组合物 |
Country Status (6)
Country | Link |
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EP (1) | EP1139984A1 (zh) |
JP (1) | JP2002534367A (zh) |
CN (1) | CN1334717A (zh) |
AU (1) | AU2100599A (zh) |
BR (1) | BR9916762A (zh) |
WO (1) | WO2000040211A1 (zh) |
Families Citing this family (8)
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DE19933452A1 (de) * | 1999-07-16 | 2000-02-17 | Wella Ag | Verkapselte Duft- oder Wirkstoffe enthaltendes Haarkonditioniermittel in Gelform |
DE10054215A1 (de) * | 2000-11-02 | 2002-06-06 | Goldwell Gmbh | Haarpflegemittel |
GB0027180D0 (en) | 2000-11-07 | 2000-12-27 | Unilever Plc | Cosmetic and personal care compositions |
FR2833486B1 (fr) * | 2001-12-18 | 2004-08-20 | Oreal | Composition cosmetique formant un gainage tackant comprenant un polymere a squelette non silicone et a fonctions reactives |
FR2833487B1 (fr) * | 2001-12-18 | 2004-08-27 | Oreal | Compositions cosmetiques comprenant des polymeres a fonctions chimiques complementaires |
US20130115320A1 (en) | 2007-03-30 | 2013-05-09 | Dynova Laboratories, Inc. | Therapeutic agent for intranasal administration and method of making and using same |
BRPI0909940A2 (pt) * | 2008-06-20 | 2015-10-20 | Unilever Nv | composição de condicionamento do cabelo |
WO2018076355A1 (en) * | 2016-10-31 | 2018-05-03 | L'oreal | Cosmetic composition with wax microbeads |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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IT1079004B (it) * | 1976-05-11 | 1985-05-08 | Rubinstein Inc H | Composizione di lavaggio e condizionamento di capelli |
FR2649608B1 (fr) * | 1989-07-12 | 1991-10-11 | Oreal | Composition cosmetique sous forme d'un gel aqueux contenant en suspension des spheroides d'une substance lipidique solide non hydrophile |
US6048520A (en) * | 1992-09-24 | 2000-04-11 | Helene Curtis, Inc. | Clear leave-on hair treatment composition and method |
GB9224563D0 (en) * | 1992-11-24 | 1993-01-13 | Unilever Plc | Cosmetic composition |
KR100234547B1 (ko) * | 1995-12-26 | 1999-12-15 | 손경식 | 유성물질이 충진된 캡슐을 함유하는 샴푸 조성물 |
US6001344A (en) * | 1996-03-06 | 1999-12-14 | Lever Brothers Company | Liquid cleansing compositions comprising xanthan gum and cross-linked polyacrylic acid polymers for enhanced suspension of large droplet oils |
-
1999
- 1999-01-04 CN CN99816186A patent/CN1334717A/zh active Pending
- 1999-01-04 BR BR9916762-0A patent/BR9916762A/pt not_active Application Discontinuation
- 1999-01-04 AU AU21005/99A patent/AU2100599A/en not_active Abandoned
- 1999-01-04 WO PCT/US1999/000010 patent/WO2000040211A1/en not_active Application Discontinuation
- 1999-01-04 JP JP2000591968A patent/JP2002534367A/ja active Pending
- 1999-01-04 EP EP99901265A patent/EP1139984A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
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EP1139984A1 (en) | 2001-10-10 |
AU2100599A (en) | 2000-07-24 |
WO2000040211A1 (en) | 2000-07-13 |
BR9916762A (pt) | 2001-09-25 |
JP2002534367A (ja) | 2002-10-15 |
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