CN100551999C - 作为遮光剂的具有1,3-二亚胺基的水溶性聚氨基酰胺 - Google Patents
作为遮光剂的具有1,3-二亚胺基的水溶性聚氨基酰胺 Download PDFInfo
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- CN100551999C CN100551999C CNB2004800324772A CN200480032477A CN100551999C CN 100551999 C CN100551999 C CN 100551999C CN B2004800324772 A CNB2004800324772 A CN B2004800324772A CN 200480032477 A CN200480032477 A CN 200480032477A CN 100551999 C CN100551999 C CN 100551999C
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- Prior art keywords
- hair
- composition
- imidogen
- polyaminoamide
- agent
- Prior art date
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Abstract
一种含有具有1,3-二亚胺基的水溶性聚氨基酰胺的紫外防护组合物,其中具有1,3-二亚胺基的聚氨基酰胺吸收波长为大约200nm到大约420nm的紫外辐射;和用具有1,3-二亚胺基的紫外防护聚氨基酰胺处理基底的方法。
Description
技术领域
本发明涉及含有具有1,3-二亚胺基的聚氨基酰胺的组合物和使用该组合物保护基底免受紫外辐射的有害影响的方法。
背景技术
已知紫外线(UV)辐射是损害木材、涂料和其它保护性或装饰性涂层、塑料、天然和人造纤维制成的各种织物、以及包括人类皮肤和毛发的角蛋白基底的因素。对人类皮肤的伤害,例如,可以包括皮肤弹性的丧失和皱纹的出现、红斑和皮肤灼伤以及光毒性的诱导或者光过敏反应。紫外线带来的毛发损伤被感知为干燥、强度降低、表面纹理粗糙、色彩和光泽的损失、变硬和变脆。
在塑料的情况下,紫外线照射会导致抗拉强度损失、变脆和变色。紫外线照射还会导致油漆表面或者染色织物的退色。为了有助于防止这种劣化,经常向被用作底层物质的上保护层的聚合物组合物中加入紫外光稳定剂。
可以通过将含有紫外吸收分子部分的制剂直接涂覆在皮肤和毛发上来得到保护暴露的皮肤和毛发免受紫外辐照的结果。通常,涂覆在毛发上的遮光剂需要直接(粘附)作用于毛发,并且需要与通常是水基的毛发护理制剂相容。然而,许多遮光剂不完全符合这些要求。因此,可以加入到毛发护理制剂中的遮光剂的水平和/或可以沉积在毛发上的遮光剂的水平是有限的。因此,迫切需要新型遮光剂,其具有直接性和水溶性以便加入到水性制剂中。
皮肤和毛发也能够通过用衣物遮盖从而避免毛发和皮肤直接暴露在阳光下而得到保护。然而,绝大多数天然和合成的织物物质至少可以被阳光中的紫外组分分子部分穿透。因此,仅仅穿着衣物不会必然地为衣物之下的皮肤提供对于紫外辐照伤害的充分保护。尽管含有深色染料和/或纹理织造紧密的衣物可以为其下的皮肤提供合理水平的保护,然而从穿着者个人的舒适的角度来看,这样的衣物在阳光充沛的热天气中是不实用的。因此,还需要为包括轻薄的夏季衣物(其未染色或者仅仅染了淡色)在内的衣物之下的皮肤提供对紫外辐照的保护。例如苯并三唑和二苯甲酮的常用紫外吸收剂在其紫外吸收容量方面是高效的。然而,其非常昂贵,并且可以证实其难以加入到目标介质中。此外,这种类型的紫外吸收剂表现出对毛发没有直接性,并且存在通常以粉末形式制造和利用以及熔点相对低的操作困难。另一方面,液体更容易操作,无需溶解,并且提供在整个目标物质中更有效和彻底的混合。
因此,存在对于有效的液体紫外吸收组合物的持续性需要,该液体紫外吸收组合物表现出足够的多功能性以被加入或涂覆到不同的多种介质和底物上。
发明内容
本发明是用于保护基底免受紫外线影响的含有有效紫外防护(UV-protective)量的一种或多种具有1,3-二亚胺基的水溶性聚氨基酰胺的组合物,其中具有1,3-二亚胺基的聚氨基酰胺吸收波长为大约200nm到大约420nm的紫外辐射。
本发明还涉及保护基底免受紫外线影响的方法,包括在基底上涂覆有效紫外防护量的含有有效紫外防护量的一种或多种具有1,3-二亚胺基的水溶性聚氨基酰胺的组合物,其中具有1,3-二亚胺基的聚氨基酰胺吸收波长为大约200nm到大约420nm的紫外辐射。
具体实施方式
本发明是用于保护基底免受紫外线影响的含有有效紫外防护量的一种或多种具有1,3-二亚胺基的新型水溶性聚氨基酰胺的组合物。
“具有1,3-二亚胺基的聚氨基酰胺”指的是如本文所述制备的具有一种或多种结构式(1)的基团的聚氨基酰胺,该基团是通过在相对于聚氨基酰胺的形成温度来说升高的温度(elevated temperature)下持续加热聚氨基酰胺而产生的。
具有1,3-二亚胺基的聚氨基酰胺的合成包括两个反应阶段。第一阶段是在没有形成目标的咪唑啉和亚胺基的情况下形成聚氨基酰胺。第二阶段是在远远高于第一阶段的缩合反应所需的温度(通常低于160℃)的升高的温度下持续加热,从而形成咪唑啉环和1,3-二亚胺基结构。在较高温度下加热促进咪唑啉环和亚胺基的形成。
1,3-二亚胺基可以通过分子内反应或者分子间反应形成。由含有重复的二亚乙基三胺(DETA)基的聚氨基酰胺的分子内反应得到的具有双环1,3-二亚胺基的聚氨基酰胺的形成如方案1所示。由含有重复的二亚乙基三胺(DETA)基的聚氨基酰胺的分子间反应得到的具有1,3-二亚胺基的聚氨基酰胺的形成如方案2所示。
方案1
紫外吸收:280-350nm
方案2
紫外吸收:280-350nm
双环和环外的1,3-二亚胺结构的形成通过NMR研究证明。常规的聚氨基酰胺聚合物和具有1,3-二亚胺结构的聚氨基酰胺之间的区别可以通过其13C NMR的三个新峰而容易地区别开来。由于缺乏1,3-二亚胺结构,常规的聚氨基酰胺在280至350nm处不显示紫外吸收,1,3-二亚胺的存在还可以通过其烯胺-亚胺的互变平衡所导致的在300至350nm附近的强紫外吸收来识别。
用作具有1,3-二亚胺基的聚氨基酰胺的起始材料的水溶性聚氨基酰胺在本领域内是公知的,并且可以通过一种或多种有机二酸衍生物和一种或多种二胺的缩聚来制备。适用于转化成具有1,3-二亚胺基的聚氨基酰胺的代表性的聚氨基酰胺包括:美国专利4,201,776、4,866,159、5,350,796、6,222,006、6,352,613、EP 0320121和2003年9月4日申请的申请号为10/665,163的普通申请。
有机二酸衍生物包括脂肪族或芳香族二酸及其相应的二酰氯、酐和酯。代表性的有机二酸衍生物包括马来酸、琥珀酸、戊二酸、己二酸、庚二酸、软木酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二甲酸、马来酸二甲酯、丙二酸二甲酯、琥珀酸二甲酯、戊二酸二乙酯、己二酸二甲酯、癸二酸二甲酯、邻苯二甲酸二甲酯、间苯二甲酸二甲酯、对苯二甲酸二甲酯、萘二甲酸二甲酯、二元酸酯(DBE)、聚(乙二醇)双(羧甲基)醚、琥珀酰氯、戊二酰氯、己二酰氯、癸二酸酯、邻苯二甲酰氯、间苯二甲酰氯、对苯二甲酰氯、萘二甲酸酯、马来酸酐、琥珀酸酐、戊二酸酐、邻苯二甲酸酐、1,8-萘二甲酸酐等。优选对苯二甲酸二甲酯、己二酸、DBE-2二元酸酯。
二胺选自具有至少两个氨基(-NH2)的脂肪族或者芳香族有机化合物。代表性的二胺包括乙二胺、1,2-二氨基丙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、己二胺(HMDA)、1,10-二氨基癸烷、苯二胺(所有异构体)、萘二胺(所有异构体)、JEFFAMINETM二胺、双(氨基乙基)-N,N’-哌嗪、双(氨基丙基)-N,N’-哌嗪、聚烷撑胺(例如二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)等。优选二亚乙基三胺。
在本发明的一个方面,聚氨基酰胺起始材料或者具有1,3-二亚胺基的聚氨基酰胺的末端氨基(-NH2)可以用具有紫外吸收分子部分的分子来封端。
代表性的具有紫外吸收分子部分的分子包括芳酰基或磺酰基衍生物,例如被一种或多种烷氧基任选地取代的肉桂酰,对二烷基氨基苯甲酰,水杨酰,来源于衍生自苯亚甲基樟脑的羧酸或者磺酸的酰基残基,来源于衍生自2-芳基苯并咪唑、2-芳基苯并噁唑(arylbenzoxazole)、2-芳基苯并三唑、2-芳基苯并呋喃、2-芳基吲哚(arylindole)的羧酸或者磺酸的酰基残基,衍生自香豆羧酸(coumarinic carboxylic)结构的吸收剂的酰基残基,来源于对苯二亚甲基樟脑的磺酰残基,在芳香环上用一个或者多个低级烷氧基取代的衍生自苯亚甲基樟脑的磺酰残基,来源于衍生自2-芳基苯并三唑的羧酸或者磺酸的酰基残基,衍生自单-或二-苯基氰基丙烯酸结构的吸收剂的磺基残基,衍生自任选取代的二苯甲酰甲烷结构的吸收剂的酰基残基等。
优选的具有紫外吸收分子部分的分子包括取代和非取代的肉桂酰、水杨酰和对-二烷基氨基苯甲酰。
在本发明的优选方面,紫外吸收分子部分(moiety)吸收波长为大约280nm到大约400nm的紫外辐射。
如果需要,聚氨基酰胺起始材料或者具有1,3-二亚胺基的聚氨基酰胺可以用一种或者多种交联剂交联。优选的交联剂包括二环氧化物、二酐、二卤代衍生物、二酯、二酸、表卤醇(epihalohydrin)和表卤醇/胺低聚物。更优选的交联剂包括聚(乙二醇)二缩水甘油醚、聚(丙二醇)二缩水甘油醚、表氯醇和表氯醇/胺低聚物。
具有1,3-二亚胺基的聚氨基酰胺也可以与一种或多种选自具有阳离子官能团的分子部分、具有阴离子官能团的分子部分和具有取代或非取代脂肪烃的分子部分的改性剂反应,从而将阳离子、阴离子或者两性性能引入聚合物中。
“具有阳离子官能团的分子部分”包括任何具有阳离子官能团并且还具有足以与聚氨基酰胺的一个或者多个仲氨基反应形成共价键的基团的分子。优选的具有阳离子官能团的分子部分包括缩水甘油基三甲基氯化铵、N-(3-氯-2-羟丙基)三甲基氯化铵等。
“具有阴离子官能团的分子部分”包括任何具有阴离子官能团并且还具有足以与聚氨基酰胺的一个或者多个仲氨基反应形成共价键的基团的分子。优选的具有阴离子官能团的分子部分包括氯乙酸及其盐、1,3-丙烷磺内酯、1,4-丁烷磺内酯等。
具有取代或非取代脂肪烃的分子部分典型地具有化学式R-X,其中X是卤素、环氧化物、酰基、酐、酸、酯、卤代醇,R是任意的直链或支链的、饱和或不饱和的、取代或非取代的脂肪烃。优选具有取代或非取代脂肪烃的分子部分包括C6-C18脂肪醇的缩水甘油醚。
在另一方面,本发明是用于保护基底免受紫外线影响的含有有效紫外防护量的一种或多种具有1,3-二亚胺基的水溶性聚氨基酰胺的组合物,其中具有1,3-二亚胺基的聚氨基酰胺吸收波长为大约200nm到大约420nm的紫外辐射。
在本发明的优选方面,聚氨基酰胺与一种或者多种化妆品可接受的赋形剂掺和以制备用于涂覆在包括毛发、皮肤和指甲在内的角蛋白基底上的组合物。
基于该组合物的重量,用于涂覆在角蛋白基底上的典型的组合物含有大约0.1到大约10wt%的水溶性聚氨基酰胺。
在本发明的一个优选方面,角蛋白基底为皮肤。
在本发明的另一个优选方面,角蛋白基底为毛发。
本发明的聚氨基酰胺的优点在于该聚合物可以选择性地具有阳离子、阴离子和/或两亲(两性)特性,从而得到“多功能”的性质,这种“多功能”的性质为毛发和皮肤提供调理的好处,并且改善聚合物在调理、染色保留等方面的性能。
“化妆品可接受的赋形剂”指的是这样一种无毒、无刺激性的物质:当其与本发明的紫外吸收聚合物混合时,可以便聚合物更适于涂覆在皮肤或者毛发上。
在另一个优选方面,赋形剂选自糖类、表面活性试剂(surface activeagent)、保湿剂、凡士林、矿物油、脂肪醇、脂肪酸酯软化剂、蜡和含聚硅氧烷的蜡、硅油、硅树脂液、聚硅氧烷表面活性剂、挥发性烃油、季氮化合物、胺官能化的硅氧烷、调理聚合物、流变改性剂、抗氧化剂、遮光活性剂、大约C10到C22的二长链胺、大约C10到C22的长链脂肪胺、脂肪醇、乙氧基化的脂肪醇和二尾磷脂。代表性的糖类包括非离子或阳离子糖类,例如琼脂糖、支链淀粉、直链淀粉、阿拉伯多糖、阿拉伯半乳聚糖、阿糖基木聚糖、鹿角菜胶、阿拉伯树胶、羧甲基瓜尔豆胶、羧甲基(羟丙基)瓜尔豆胶、羟乙基瓜尔豆胶、羧甲基纤维素、阳离子瓜尔豆胶、包括甲基纤维素的纤维素醚、软骨素、壳多糖、壳聚糖、壳聚糖吡咯烷酮羧化物、壳聚糖羟乙酸酯、壳聚糖乳酸酯、椰油基二甲基铵羟丙基乙氧基纤维素(cocodimoniumhydroxypropyl oxyethyl cellulose)、多聚乙酰神经氨糖酸([聚-N-乙酰基-神经氨酸])、玉米淀粉、凝胶多糖、硫酸皮肤素、葡聚糖、furcellaran、葡聚糖、交联的葡聚糖、糊精、emulsan、乙基羟乙基纤维素、亚麻子糖(酸性)、半乳葡甘露聚糖、半乳甘露聚糖、葡甘露聚糖、糖原、瓜尔豆胶、羟乙基淀粉、羟丙基甲基纤维素、羟乙基纤维素、羟丙基纤维素、羟丙基淀粉、羟丙基化的瓜尔豆胶、结冷胶(gellan gum)、结冷(gellan)、印度树胶、卡拉牙胶、黄蓍胶(黄蓍糖)、肝磷脂、透明质酸、菊粉、硫酸角蛋白、魔芋葡苷聚糖、改性淀粉、海带多糖、月桂基二甲基铵羟丙基乙氧基纤维素(laurdimonium hydroxypropyloxyethyl cellulose)、秋葵胶、氧化淀粉、果胶酸、果胶、聚葡萄糖、聚季铵盐-4、聚季铵盐-10、聚季铵盐-28、马铃薯淀粉、原生果胶、洋车前子胶(psyllium seed)、支链淀粉、透明质酸钠、淀粉二乙氨基乙基醚、硬脂基二甲基铵羟乙基纤维素(steardimonium hydroxyethylcellulose)、棉子糖、鼠李糖胶、木薯淀粉、whelan、果聚糖、硬葡聚糖、藻酸钠、stachylose、琥珀酰聚糖、小麦淀粉、黄原凝胶、木聚糖、木糖葡萄糖及其混合物。微生物糖类可以在Kirk-Othmer Encyclopediaof Chemical Technology(化学技术百科全书),第四版,第16卷,JohnWiley and Sons,NY,第578-611页(1994)中查到,其在此全部引入作为参考。复合碳水化合物可以在Kirk-Othmer Encyclopedia ofChemical Technology(化学技术百科全书),第四版,第16卷,John Wileyand Sons,NY,第930-948页(1995)中查到,其在此引入作为参考。
基于聚合物活性物,用于涂覆在角蛋白基底上的典型的组合物含有大约1到大约3wt%的本发明的具有1,3-二亚胺基的聚氨基酰胺。
本发明的化妆品可接受的组合物可以包括表面活性试剂。表面活性试剂包括通常为制剂提供清洁功能或者只是仅仅作为润湿剂的表面活性剂。表面活性试剂通常可以分成阴离子表面活性试剂、阳离子表面活性试剂、非离子表面活性试剂、两性表面活性试剂和两性离子表面活性试剂、以及分散聚合物。
本文中可使用的阴离子表面活性试剂包括美国专利5,573,709中公开的那些,其在此并入作为参考。例子包括烷基硫酸盐和烷基醚硫酸盐。可用于本发明的烷基醚硫酸盐的具体例子是月桂基硫酸、月桂醚硫酸、椰子烷基三甘醇醚硫酸、牛脂(tallow)烷基三甘醇醚硫酸和牛脂烷基六氧乙烯基(hexaoxyethylene)硫酸的钠盐和铵盐。高度优选的烷基醚硫酸盐是含有个别的化合物的混合物的那些,所述混合物的平均烷基链的长度为大约12到16个碳原子,并且平均乙氧基化度为大约1到大约6摩尔的环氧乙烷。
另一类适合的阴离子表面活性剂是烷基硫酸盐。重要的例子是包括异、新、ineso-和正石蜡在内的甲烷系烃类与包括例如SO3、H2SO4、发烟硫酸的磺化剂通过包括漂白和水解在内的已知磺化方法获得的有机硫酸反应产物的盐,其中该甲烷系烃类具有大约8到大约24个碳原子,优选大约12到大约18个碳原子。优选硫酸化的C12-38正石蜡的碱金属盐和铵盐。
另外的合成阴离子表面活性试剂包括烯烃磺酸盐、β-烷氧基链烷磺酸盐、脂肪酸用羟基乙磺酸酯化和用氢氧化钠中和的反应产物、以及琥珀酰胺酸盐。琥珀酰胺酸盐的具体例子包括N-十八烷基磺基琥珀酰胺酸二钠、N-(1,2-羧基乙基)-N-十八烷基磺基琥珀酰胺酸四钠、磺基琥珀酸钠的二戊酯、磺基琥珀酸钠的二己酯、磺基琥珀酸钠的二辛酯。
可用于本发明的化妆品可接受的组合物的优选的阴离子表面活性试剂包括月桂基硫酸铵、月桂醇聚醚硫酸铵、月桂基硫酸三乙胺、月桂醇聚醚硫酸三乙胺、月桂基硫酸三乙醇胺、月桂醇聚醚硫酸三乙醇胺、月桂基硫酸单乙醇胺、月桂醇聚醚硫酸单乙醇胺、月桂基硫酸二乙醇胺、月桂醇聚醚硫酸二乙醇胺、甘油单月桂酸酯硫酸钠(lauricmonoglyceride sodium sulfate)、月桂基硫酸钠、月桂醇聚醚硫酸钠、月桂基硫酸钾、月桂醇聚醚硫酸钾、月桂基肌氨酸钠、月桂酰肌氨酸钠、月桂基肌氨酸、椰油基肌氨酸、椰油基硫酸铵、月桂酰硫酸铵、椰油基硫酸钠、月桂酰硫酸钠、椰油基硫酸钾、月桂基硫酸钾、trlethanolaminelauryl sulfate、月桂基硫酸三乙醇胺、椰油基硫酸单乙醇胺、月桂基硫酸单乙醇胺、十三烷基苯磺酸钠和月桂基苯磺酸钠。
可用于本发明的化妆品可接受的组合物的两性表面活性试剂包括脂肪族仲胺和叔胺的衍生物,其中脂肪族取代基含有大约8到18个碳原子和阴离子水溶性基团,例如羧基、磺酸盐基、硫酸盐基、磷酸盐基或膦酸盐基。代表性的例子包括3-月桂基氨基丙酸钠、3-月桂基氨基丙磺酸钠、月桂基肌氨酸钠、例如美国专利2,658,072所述的通过使十二胺和羟乙基磺酸钠反应而制备的N-烷基氨基乙磺酸、美国专利2,438,091所述的N-高级烷基天冬氨酸、以及美国专利2,528,378所述的以MIRANOLTM为商品名出售的产品。其它的肌氨酸和肌氨酸衍生物可以在CTFA Cosmetic Ingredient Handbook(CTFA化妆品成分手册),第五版,1988,第42页找到,其在此引入作为参考。
季铵化合物也可以用于本发明的化妆品可接受的组合物,只要其与本发明的组合物相容,其中其结构可以在CTFA Cosmetic IngredientHandbook(CTFA化妆品成分手册),第五版,1988,第40页找到。阳离子表面活性试剂通常包括但不限于具有大约8到大约18个碳原子的脂肪季铵化合物。季铵化合物的阴离子可以是普通的离子,例如氯化物、乙基硫酸盐(ethosulfate)、甲基硫酸盐(methosulfate)、醋酸盐、溴化物、乳酸盐、硝酸盐、磷酸盐或甲苯磺酸盐及其混合物。长链烷基可以包括另外的或者替换的碳或氢原子或者其它的醚键。季氮上的其它取代基可以是氢、苄基或短链烷基或羟烷基,例如甲基、乙基、羟甲基或羟乙基、羟丙基或其组合。
季铵化合物的例子包括但不限于:山嵛基三甲基氯化铵、椰油基三甲基氯化铵、鲸蜡醇聚醚基乙基二甲基溴化铵(cethethyldimoniumbromide)、二山嵛基二甲基氯化铵、二氢化牛脂基苄基甲基氯化铵、二大豆基二甲基氯化铵、二牛脂基二甲基氯化铵、羟基鲸蜡基羟乙基二甲基氯化铵、羟乙基山嵛酰胺基二甲基氯化铵、羟乙基鲸蜡基二甲基氯化铵、羟乙基牛脂基二甲基氯化铵、肉豆蔻基二甲基苄基氯化铵(myristalkonium chloride)、PEG-2油烯基甲基氯化铵(PEG-2oleamonium chloride)、PEG-5硬脂基甲基氯化铵、PEG-15椰油基季铵盐-4、PEG-2硬脂基二甲基苄基铵-4、月桂基三甲基氯化铵、季铵盐-16、季铵盐-18、月桂基二甲基苄基氯化铵、油酰基二甲基苄基氯化铵、鲸蜡基氯化吡啶鎓、聚季铵盐-5、聚季铵盐-6、聚季铵盐-7、聚季铵盐-10、聚季铵盐-22、聚季铵盐-37、聚季铵盐-39、聚季铵盐-47、鲸蜡基三甲基氯化铵、二月桂基二甲基氯化铵、鲸蜡基二甲基苄基氯化铵、二鲸蜡基二甲基氯化铵、大豆基三甲基氯化铵、硬脂基辛基二甲基(甲基硫酸)铵及其混合物。其它的季铵化合物在CTFA Cosmetic IngredientHandbook(CTFA化妆品成分手册),第五版,1988,第41-42页中列出,其并入本文作为参考。
化妆品可接受的组合物可以包括大约C10到C22的二-长链胺、大约C10到C22的二-长链脂肪胺及其混合物。具体例子包括二软脂胺、月桂酰胺基丙基二甲胺、硬脂酰胺基丙基二甲胺。本发明的化妆品可接受的组合物还可以包括脂肪醇(通常是一元脂肪醇)、乙氧基化的脂肪醇和二尾磷脂,这些物质可以用于稳定乳液或分散体形式的化妆品可接受的组合物。其还提供化妆品可接受的粘性。脂肪醇的选择不苛刻,但是通常采用特征在于具有C10到C32的脂肪链的那些醇,优选C14到C22,其基本上是饱和链烷醇。例子包括硬脂醇、鲸蜡醇、鲸蜡硬脂醇、肉豆蔻醇、山嵛醇、花生醇、异硬脂醇和异鲸蜡醇。鲸蜡醇是优选的,其可以单独使用或者与其它脂肪醇组合使用,优选与硬脂醇组合使用。使用时,本发明的制剂中优选含有浓度在大约1到大约8wt%的范围内的脂肪醇,更优选大约2到大约6wt%。脂肪醇也可以乙氧基化。具体例子包括鲸蜡醇聚醚-20、硬脂醇聚醚-20、硬脂醇聚醚-21及其混合物。还可以含有例如磷脂酰丝氨酸和卵磷脂及其混合物的磷脂。当使用时,制剂中含有浓度为大约1到大约10wt%的脂肪醇组分,更优选大约2到大约7wt%。
可用于本发明的化妆品可接受的组合物的非离子表面活性试剂包括那些被广泛地定义为通过氧化烯基(本质上是亲水的)和有机疏水化合物的缩合而制备的化合物,其本质上可以是脂肪族或烷基芳香族。非离子表面活性是剂的优选例子为:长链链烷醇酰胺、烷基酚的聚环氧乙烷缩合物、具有大约8到大约18个碳原子的直链或者支链构造的脂肪醇与环氧乙烷的缩合产物、长链叔胺氧化物、长链叔膦氧化物、具有一个含有大约1到大约3个碳原子的短链烷基或羟烷基的长链二烷基亚砜、以及例如烷基多代糖苷的烷基多糖(APS)表面活性剂、聚乙二醇(PEG)甘油脂肪酸酯。
例如甜菜碱的两性离子表面活性试剂也可以用于本发明的化妆品可接受的组合物中。本文所使用的甜菜碱的例子包括高级烷基甜菜碱,例如椰油基二甲基羧甲基甜菜碱、椰油酰胺基丙基甜菜碱、椰油基甜菜碱、月桂酰胺基丙基甜菜碱、油烯基甜菜碱、月桂基二甲基羧甲基甜菜碱、月桂基二甲基α-羧乙基甜菜碱、鲸蜡基二甲基羧甲基甜菜碱、月桂基双-(2-羟乙基)羧甲基甜菜碱、硬脂基双-(2-羟丙基)羧甲基甜菜碱、油烯基二甲基γ-羧丙基甜菜碱和月桂基双-(2-羟丙基)α-羧乙基甜菜碱。磺基甜菜碱的代表是:椰油基二甲基磺丙基甜菜碱、硬脂基二甲基磺丙基甜菜碱、月桂基二甲基磺乙基甜菜碱、月桂基双-(2-羟乙基)磺丙基甜菜碱等;其中的RCONH(CH2)3基连接到甜菜碱的氮原子上的酰胺基甜菜碱和氨基磺基甜菜碱也可以用于本发明。
本发明的化妆品可接受的组合物中使用的阴离子、阳离子、非离子、两性或者两性离子表面活性试剂使用量通常为大约0.1到50wt%,优选大约0.5到大约40wt%,更优选大约1到大约20wt%。
本发明的化妆品可接受的组合物可以包括保湿剂,其充当吸湿剂以增加吸水、控水和保水量。适用于本发明制剂的保湿剂包括但不限于:乙酰胺MEA、乳酸铵、壳聚糖及其衍生物、胶态燕麦、galactoarabinan、葡萄糖谷氨酸酯、glerecyth-7、glerecyth-12、glerecyth-26、glerecyth-31、甘油、乳酰胺MEA、乳酰胺DEA、乳酸、甲基葡萄糖聚醚-10、甲基葡萄糖聚醚-20、泛醇、丙二醇、山梨醇、聚乙二醇、1,3-丁二醇、1,2,6-己三醇、氢化淀粉水解物、肌醇、甘露醇、PEG-5季戊四醇醚、聚甘油基山梨醇、木糖醇、蔗糖、透明质酸钠、PCA钠及其组合。甘油是特别优选的保湿剂。组合物中保湿剂的存在浓度为大约0.5到40wt%,优选大约0.5到大约20wt%,更优选大约0.5到大约12wt%。
本发明的化妆品可接受的组合物可以包括凡士林或者矿物油组分,其在选择时通常为USP或者NF级。凡士林可以为白色或者黄色。凡士林的粘度或稠度等级并不精确严格。凡士林可以用能够调配为外观和稠度与凡士林类似的烃类物质的混合物部分替代。例如,凡士林或矿物油与不同的蜡及类似物质的混合物可以组合。优选的蜡包括杨梅蜡、小烛树蜡、纯地蜡(ceresin)、霍霍巴脂、羊毛脂蜡、褐煤蜡、地蜡(ozokerite)、聚甘油基-3-蜂蜡、聚甘油基-6-五硬脂酸酯、微晶蜡、石蜡、异石蜡、凡士林固体石蜡、鲨烯、低聚烯、蜂蜡、合成小烛树蜡、合成巴西棕榈蜡、合成蜂蜡等可以掺和在一起。具有不同取代度的烷基甲基硅氧烷(siloxane)可以用于增加皮肤的保水量。硅氧烷例如被称为2503蜡的硬脂基聚二甲基硅氧烷、被称为AMS-C30蜡的C30-45烷基聚甲基硅氧烷、被称为580蜡的硬脂氧基三甲基硅烷(和)硬脂醇,均可得自DowMidland,MI,USA。另外的烷基和苯基聚硅氧烷可以用于提高补水性能。例如聚二甲基硅氧烷(和)被称为Dow593或环甲基硅酮的三甲基甲烷硅氧基硅酸酯(trimethylsoiloxysilicate)(和)被称为Dow749液体的三甲基甲烷硅氧基硅酸酯的树脂可以用于强化护肤产品的成膜。当使用时,制剂中含有的凡士林、蜡或烃类或者油组分的浓度为大约1到大约20wt%,更优选大约1到大约12wt%。当使用时,聚硅氧烷树脂的含量为大约0.1到大约10.0wt%。
软化剂定义为有助于保持皮肤的柔软、光滑和柔韧外观的试剂。软化剂通过其保留在皮肤表面或角质层中的能力而起作用。本发明的化妆品可接受的组合物可以包括脂肪酸酯软化剂,其在InternationalCosmetic Ingredient Dictionary(国际化妆品成分辞典),第8版,2000,第1768到1773页中列出。适用于本发明制剂的脂肪酸酯的具体例子包括肉豆蔻酸异丙酯、棕榈酸异丙酯、甘油辛酸/癸酸三酯、乳酸鲸蜡酯、棕榈酸鲸蜡酯、氢化蓖麻油、甘油酯、异硬脂酸羟基鲸蜡酯、磷酸羟基鲸蜡酯、异硬脂酸异丙酯、异硬脂酸异硬脂酯、癸二酸二异丙酯、PPG-5-鲸蜡醇聚醚-20、异壬酸-2-乙基己酯、硬脂酸-2-乙基己酯、C12-C16脂肪醇乳酸酯、羊毛脂酸异丙酯、水杨酸-2-乙基己酯及其混合物。目前优选的脂肪酸酯是肉豆蔻酸异丙酯、棕榈酸异丙酯、PPG-5-鲸蜡醇聚醚-20和甘油辛酸/癸酸三酯。当使用时,本发明制剂中含有的脂肪酸酯软化剂的浓度优选为大约1到大约8wt%,更优选大约2到大约5wt%。
本发明的组合物还可以包括聚硅氧烷化合物。优选聚硅氧烷组分的粘度在25℃下为大约0.5到大约12,500cps。适合的材料的例子是二甲基聚硅氧烷、二乙基聚硅氧烷、二甲基聚硅氧烷-二苯基聚硅氧烷、环甲基硅酮、三甲基聚硅氧烷、二苯基聚硅氧烷及其混合物。一个优选的例子是二甲硅油(dimethicone),一种用三甲基单元封闭的二甲基聚硅氧烷。特别优选粘度在50和1,000cps之间的二甲硅油。当使用时,本发明制剂中含有的硅油的浓度优选为0.1到5wt%,更优选1到2wt%。
本发明的化妆品可接受的组合物可以包括挥发性和非挥发性的硅油或硅树脂液。聚硅氧烷化合物可以是粘度为大约0.5到大约100厘沲的直链或环状的聚二甲基硅氧烷。最优选的直链聚二甲基硅氧烷化合物的粘度范围在大约0.5到大约50厘沲。直链、低分子量、挥发性的聚二甲基硅氧烷的一个例子是八甲基三硅氧烷,商品名为Dow200液体,粘度为大约1厘沲。当使用时,本发明制剂中含有的硅油浓度优选为0.1到30wt%,更优选1到20wt%。
本发明的化妆品可接受的组合物可以包括挥发性、环状、低分子量的聚二甲基硅氧烷(环甲基硅酮)。优选的环状挥发性聚硅氧烷可以是平均重复单元为4到6,粘度为大约2.0到大约7.0厘沲的聚二甲基环硅氧烷及其混合物。优选的环甲基硅酮是可得自DowMidland,MI,USA的商品名为Dow244液体、Dow245液体、Dow246、Dow344液体和Dow345液体;和可得自General Electric,Waterford,NY,USA的聚硅氧烷SF-1173和聚硅氧烷SF-1202。当使用时,本发明制剂中含有的硅油浓度优选为0.1到30wt%,更优选1到20wt%。
具有聚氧化乙烯或聚氧化丙烯侧链的聚硅氧烷表面活性剂或乳化剂也可以用于本发明的组合物中。优选的例子包括聚二甲基硅氧烷共聚醇、可得自DowMidland,MI,USA的Dow3225C和5225C制剂助剂、和可得自General Electric,Waterford,NY,USA的聚硅氧烷SF-1528。侧链还可以包括烷基,例如月桂基或硬脂基。优选被称为Dow5200制剂助剂的月桂基聚甲基硅氧烷共聚醇,和可得自Goldschmidt Chemical Corporation,Hopewell,VA的被称为Abil EM-90的鲸蜡基聚二甲基硅氧烷共聚醇。还优选可得自Wacker-Chemie,Munchen,GER的被称为Belsil LDM 3107VP的月桂基聚二甲基硅氧烷。当使用时,本发明制剂中含有的聚硅氧烷表面活性剂的浓度优选为0.1到30wt%,更优选1到15wt%。
胺官能化的聚硅氧烷和乳化剂也可以在本发明中使用。优选的例子包括Dow8220、Dow939、Dow949、Dow2-8194,均可得自DowMidland,MI,USA。还优选可得自General Electric,Waterford,NY,USA的聚硅氧烷SM253。当使用时,本发明制剂中含有的胺官能化的聚硅氧烷的浓度优选为0.1到5wt%,更优选0.1到2.0wt%。
本发明的化妆品可接受的组合物可以包括挥发性烃油。挥发烃含有大约C6到C22个原子。优选的挥发烃是链长为C6到C16个碳原子的脂肪烃。这样的化合物的例子包括可得自Presperse,South Plainfield,NJ,USA的商品名为Permethyl 101A的异十六烷。优选挥发烃的另一个例子是可得自Exxon,Baytown,TX,USA的商品名为Isopar M的C12到C14的异链烷烃。当使用时,本发明制剂中含有的挥发烃浓度优选为0.1到30wt%,更优选1到20wt%。
本发明的化妆品可接受的组合物可以包括阳离子和两性调理聚合物。其例子包括但不限于Cosmetic,Toiletry,and Fragrance Association(化妆品、盥洗品和香料委员会)(CTFA),1101 17th街,N.W.,Suite 300,华盛顿特区20036,出版的CTFA Cosmetic Ingredient Dictionary(化妆品成分辞典)。常用的例子包括纤维素醚的四级衍生物、瓜尔胶的四级衍生物、DADMAC的均聚物和共聚物、MAPTAC的均聚物和共聚物、以及淀粉的四级衍生物。使用CTFA命名方法的具体例子包括但不限于聚季铵-10、瓜尔胶羟丙基三甲基氯化铵、淀粉羟丙基三甲基氯化铵、聚季铵-4、聚季铵-5、聚季铵-6、聚季铵-7、聚季铵-14、聚季铵-15、聚季铵-22、聚季铵-24、聚季铵-28、聚季铵-32、聚季铵-33、聚季铵-36、聚季铵-37、聚季铵-39、聚季铵-45、聚季铵-47和聚甲基丙烯酰胺基丙基三甲基氯化铵及其混合物。当使用时,本发明的化妆品可接受的组合物中含有的调理聚合物浓度优选为0.1到10wt%,更优选0.2到6wt%,最优选0.2到5wt%。
本发明的化妆品可接受的组合物可以包括一种或多种流变改性剂。可用于本发明的流变改性剂包括但不限于丙烯酸的高分子量交联均聚物,以及丙烯酸盐/C10-30丙烯酸烷基酯交联聚合物,例如和系列,二者均可得自B.F.Goodrich,Akron,OH,USA;例如AST的阴离子丙烯酸聚合物和例如SC96的阳离子丙烯酸聚合物,可得自Ciba Specialties,High Point,NC,USA;丙烯酰胺基丙基三甲基氯化铵/丙烯酰胺;甲基丙烯酸羟乙酯聚合物、硬脂醇聚醚-10烯丙基醚/丙烯酸酯共聚物;可得自InternationalSpecialties,Wayne,NJ,USA的被称作28的丙烯酸酯/山嵛醇聚醚-25甲基丙烯酸酯;甘油聚甲基丙烯酸酯、丙烯酸酯/硬脂醇聚醚-20甲基丙烯酸酯共聚物;膨润土;胶,例如藻酸盐、鹿角菜胶、阿拉伯树胶、阿拉伯胶、印度树胶、卡拉牙胶、黄蓍胶、瓜尔豆胶;瓜尔胶羟丙基三甲基氯化铵、黄原胶或结冷胶;纤维素衍生物,例如羧甲基纤维素钠、羟乙基纤维素、羟甲基羧乙基纤维素、羟甲基羧丙基纤维素、乙基纤维素、硫酸化的纤维素、羟丙基纤维素、甲基纤维素、羟丙基甲基纤维素、微晶纤维素;琼脂;果胶;明胶;淀粉及其衍生物;壳聚糖及其衍生物,例如羟乙基壳聚糖;聚乙烯醇、PVM/MA共聚物、PVM/MA癸二烯交联聚合物、聚(氧化乙烯)基增稠剂、卡波姆钠(sodium carbomer)及其混合物。当使用时,本发明的化妆品可接受的组合物中含有的流变改性剂浓度优选为0.01到12wt%,更优选0.05到10wt%,最优选0.1到6wt%。
本发明的化妆品可接受的组合物可以包括一种或多种抗氧化剂,其包括但不限于抗坏血酸、BHT、BHA、异抗坏血酸、亚硫酸氢盐、巯基乙酸盐、生育酚、偏亚硫酸氢钠、维生素E醋酸盐和抗坏血酸棕榈酸酯。化妆品可接受的组合物中存在的抗氧化剂量为0.01到5wt%,优选0.1到3wt%,最优选0.2到2wt%。
本发明的化妆品可接受的组合物可以包括一种或者多种遮光活性剂。遮光活性剂包括但不限于甲氧基肉桂酸辛酯(对甲氧基肉桂酸乙基己酯)、水杨酸辛酯氧苯酮(二苯甲酮-3)、二苯甲酮-4、氨基苯甲酸薄荷酯、二氧苯酮、氨基苯甲酸、戊基二甲基PABA、对甲氧基肉桂酸二乙醇胺、4-双(羟丙基)氨基苯甲酸乙酯、1-2-氰基-3,3-二苯基丙烯酸-2-乙基己酯、水杨酸同薄荷酯(homomentyl salicylate)、氨基苯甲酸甘油酯、二羟基丙酮、辛基二甲基PABA、2-苯基苯并咪唑-5-磺酸、水杨酸三乙醇胺、氧化锌和氧化钛、及其混合物。本发明的化妆品可接受的组合物中使用的遮光剂量根据所使用的具体遮光活性物的具体紫外吸收波长而改变,可以是0.1到10wt%,2到8wt%。
本发明的化妆品可接受的组合物可以包括一种或多种防腐剂。可以使用的防腐剂的例子包括但不限于1,2-二溴-2,4-二氰基丁烷(甲基二溴戊二腈,被称为Ondeo Nalco Company,Naperville,IL,USA)、苯甲醇、咪唑烷基脲、1,3-双(羟甲基)-5,5-二甲基-2,3-咪唑烷二酮(例如,DMDM Hydantoin,被称为Lonza,Fairlawn,NJ,USA.)、甲基氯代异噻唑啉酮和甲基异噻唑啉酮(例如,Rohm&Haas Co.,Philadephia,PA,USA)、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯、苯氧基乙醇、和苯甲酸钠、及其混合物。
本发明的化妆品可接受的组合物可以包括任何其它常用于化妆品的成分。这样的成分的例子包括但不限于缓冲剂、香料成分、螯合剂可用于使组合物自身或角蛋白染色的着色剂或染料、多价螯合剂、软化剂、泡沫增效剂、泡沫稳定剂、滤光剂和胶溶剂。
例如二氧化钛、氧化锌、滑石、碳酸钙或高岭土的颜料的表面,可以用本文描述的不饱和季铵化合物处理,然后用于本发明的化妆品可接受的组合物。由此,处理过的颜料作为遮光活性剂将更为有效,并可用于例如粉底和睫毛膏的彩妆品。
本发明的化妆品可接受的组合物可以以各种形式存在。这样的形式包括但不限于溶液、液体、膏、乳剂、分散剂、凝胶、增稠乳液。
本发明的化妆品可接受的组合物可以含有水,还可以含有任意化妆品可接受的溶剂。可接受的溶剂的例子包括但不限于一元醇,例如具有1到8个碳原子的链烷醇(像乙醇、异丙醇、苯甲醇和苯乙醇);多醇,例如亚烷基二醇(像甘油、乙二醇和丙二醇);和二醇醚,例如一-、二-和三-乙二醇单烷基醚,例如乙二醇一甲醚和二甘醇一甲醚,其可以单独使用或组合使用。相对于总的组合物重量,这些溶剂的存在比例可以达到差不多70wt%,例如0.1到70wt%。
本发明的化妆品可接受的组合物还可以包装成气溶胶,在这种情况下其可以以气溶胶喷雾或者气溶胶泡沫的形式应用。作为用于这些气溶胶的喷射剂,具体地说,可以使用二甲醚,二氧化碳,氮气,一氧化二氮,空气和例如丁烷、异丁烷和丙烷的挥发烃。
本发明的化妆品可接受的组合物还可以含有电解质,例如水合氯化铝;碱金属盐,例如钠、钾或锂盐,这些盐优选是例如氯化物或溴化物的卤化物和硫酸盐或者例如醋酸盐或乳酸盐的有机酸盐;以及碱土金属盐,优选钙、镁和锶的碳酸盐、硅酸盐、硝酸盐、醋酸盐、葡糖酸盐、泛酸盐和乳酸盐。
在一个优选方面,本发明的化妆品可接受的组合物选自用于处理毛发的制品,包括洗发剂、遮光剂、护发素(conditioner)、烫发剂(permanent waves)、顺发剂(hair relaxer)、毛发漂白剂、毛发柔顺露(hair detangling lotion)、定型凝胶、定型发釉、喷雾泡沫、定型膏、定型蜡、定型乳液、摩丝、喷雾凝胶、润发油、染发制剂、短效和长效染发剂、染后护发素、亮发素、染后和非染后毛发润丝精(hair rinse)、染发剂(hair tint)、烫发剂(hair wave set)、烫发剂、卷发剂、直发剂、毛发修饰助剂(hair grooming aid)、毛发营养剂、美发剂和氧化产物、针剂(spritze)、定型蜡和香脂。
在另一个优选方面,化妆品可接受的组合物选自用于处理皮肤的组合物,包括免洗或洗去式皮肤护理产品,例如乳液、手霜和体霜、液体皂、固体皂、浴油皂(bath oil bar)、洁面乳、须后水、剃须凝胶或剃须膏、睫毛膏、眼部凝胶、眼部乳液、沐浴露、除臭剂、防汗剂、遮光剂、遮光露、晒后凝胶、泡沫浴、以及手洗和机洗洗涤剂组合物等。除了聚合物外,皮肤护理组合物可以包括常用于皮肤护理制剂的组分。这样的组分包括,例如:(a)保湿剂、(b)凡士林或矿物油、(c)脂肪醇、(d)脂肪酸酯软化剂、(e)硅油或硅树脂液、以及(f)防腐剂。通常这些组分涂覆在人体皮肤上必须是安全的,并且必须与制剂中的其它组分相容。这些组分的选择通常是在本领域的技术范围内。皮肤护理组合物还可以含有其它用于化妆品皮肤护理制剂的常规添加剂。这样的添加剂包括美观增强剂、芳香油、染料和例如薄荷醇的药物等。
本发明的皮肤护理组合物可以制备成水包油乳剂、油包水乳剂、三重乳剂或分散体。
优选的水包油乳剂如下制备:首先形成例如不饱和季铵化合物、保湿剂、水溶性防腐剂的水溶性组分的含水混合物,随后加入不溶于水的组分。不溶于水的组分包括乳化剂、不溶于水的防腐剂、凡士林或矿物油组分、脂肪醇组分、脂肪酯软化剂和硅油组分。输入高的混合能量,并且保持足以形成具有平滑外观的油包水乳剂(意味着在乳剂中存在相对小的胶体)的时间。优选的分散体通常如下制备:在施加不溶于水的物质的悬浮能的情况下,形成不溶于水的含水混合物,然后加入增稠剂。
用于处理毛发的组合物包括洗浴制剂,例如泡沫浴、肥皂和油、洗发水、护发素、毛发漂白剂、染发制剂、短效和长效染发剂、染后护发素、亮发素、染后和非染后毛发润丝精(hair rinse)、染发剂(hairtint)、烫发剂(hair wave set)、烫发剂、卷发剂、直发剂、毛发修饰助剂、毛发营养剂、美发剂和氧化产物。分散聚合物还可以与其它聚合物或结构剂组合用于例如凝胶、摩丝、针剂、定型膏、定型蜡、润发脂、香脂等的定型类免洗产品以便提供具有洁净、自然、不粘感觉的控制和毛发护理能力。
由于分散聚合物、挥发性聚硅氧烷、其它聚合物、表面活性剂或其它可以改变头发上物质沉积的化合物的存在,本发明的毛发护理组合物给出光滑的感觉,并且可以轻易地从毛发上冲洗掉。
在例如清洗毛发用的洗发水、或者液体洗手皂、或用于清洗皮肤的沐浴胶(shower gel)的清洁制剂中,组合物中含有的阴离子、阳离子、非离子、两性离子或两性表面活性试剂的量为大约3到大约50wt%,优选大约3到大约20wt%,其pH通常在大约3到大约10的范围内。
本发明优选的洗发水含有阴离子表面活性剂和两性离子表面活性剂和/或两性表面活性剂的组合。特别优选洗发水含有大约0到大约16wt%的烷基硫酸盐活性物、0到大约50wt%的乙氧化的烷基硫酸盐和0到大约50wt%的选自非离子、两性和两性离子表面活性试剂的任选的表面活性剂、和至少5wt%的烷基硫酸盐、乙氧化的烷基硫酸盐或者其混合物,总的表面活性剂的水平为大约10到大约25wt%。
清洗毛发用的洗发水还可以含有例如聚硅氧烷和常用于洗发水的其它调理聚合物的其它调理添加剂。美国专利5,573,709提供了可用于洗发水的非挥发性聚硅氧烷调理剂的名单。用于本发明的调理聚合物在Cosmetic,Toiletries and Fragrance Associations(CTFA)dictionary中列出。具体例子包括聚季铵(例如聚季铵-1到聚季铵-50)、瓜尔胶羟丙基三甲基氯化铵、淀粉羟丙基三甲基氯化铵和聚甲基丙烯酰胺基丙基三甲基氯化铵。
其它优选实施方式包括以润发剂(rinsing lotion)的形式主要在洗发之前或者之后使用。这些洗剂通常为水溶液或者水-醇溶液、乳剂、增稠洗剂或者凝胶。如果组合物以乳剂的形式存在,其可以是非离子、阴离子或者阳离子的。非离子乳剂主要包括油和/或脂肪醇与例如聚氧乙烯化的硬脂醇或鲸蜡醇/硬脂醇的聚氧乙烯化的醇,并且可以像这些组合物中加入阳离子表面活性试剂。这些阴离子乳剂基本由肥皂形成。
如果组合物以增稠洗剂或凝胶的形式存在,其含有存在或者不存在溶剂的增稠剂。可以使用的增稠剂特别是树脂、可得自B.F.Goodrich的丙烯酸增稠剂;黄原胶;藻酸钠;阿拉伯胶;纤维素衍生物和聚(氧乙烯)基增稠剂,可以通过聚乙二醇硬脂酸酯或聚乙二醇二硬脂酸酯混合物的方式或者磷酸酯和酰胺混合物的形式而实现增稠。增稠剂的浓度通常为0.05到15wt%。如果组合物以定型乳液(styling lotion)、造型乳液(shaping lotion)或固型乳液(setting lotion)的形式存在,其通常含有上述两性聚合物的水溶液、醇溶液或者水-醇溶液。
在毛发固定剂的情况下,组合物还可以含有一种或多种另外的毛发固定聚合物。当存在时,另外的毛发固定聚合物的存在总量为大约0.25到大约10wt%。另外的毛发固定树脂可以选自下列祖分,只要其与给定的分散聚合物相容:丙烯酰胺共聚物、丙烯酰胺/丙烯酸钠共聚物、丙烯酸酯/甲基丙烯酸铵共聚物、丙烯酸酯共聚物、丙烯酸/丙烯酸酯共聚物、己二酸/二甲氨基羟丙基二亚乙基三胺共聚物、己二酸/环氧基丙基二亚乙基三胺共聚物、硬脂酸烯丙酯/VA共聚物、磷酸丙烯酸氨基乙酯/丙烯酸酯共聚物、丙烯酸铵共聚物、乙烯基醋酸铵/丙烯酸酯共聚物、AMP丙烯酸酯/二丙酮丙烯酰胺共聚物、AMPD丙烯酸酯/二丙酮丙烯酰胺共聚物、乙烯丁基酯/马来酐共聚物、PVM丁基酯/MA共聚物、钙/钠PVM/MA共聚物、玉米淀粉/丙烯酰胺/丙烯酸钠共聚物、乙二醇胺/表氯醇/哌嗪共聚物、十二烷二酸/鲸蜡硬脂醇/乙二醇共聚物、PVM乙基酯/MA共聚物、PVM异丙酯/MA共聚物、卡拉牙胶、甲基丙烯酰基乙基甜菜碱/甲基丙烯酸酯共聚物、辛基丙烯酰胺/丙烯酸酯/甲基丙烯酸丁氨基乙酯共聚物、辛基丙烯酰胺/丙烯酸酯共聚物、邻苯二甲酸酐/甘油/癸酸缩水甘油酯共聚物、邻苯二甲酸/偏苯三甲酸/乙二醇共聚物、聚丙烯酰胺、聚丙烯酰胺基甲基丙磺酸、聚对苯二甲酸丁二酯、聚丙烯酸乙酯、聚乙烯、聚季铵-1、聚季铵-2、聚季铵-4、聚季铵-5、聚季铵-6、聚季铵-7、聚季铵-8、聚季铵-9、聚季铵-10、聚季铵-11、聚季铵-12、聚季铵-13、聚季铵-14、聚季铵-15、聚季铵-39、聚季铵-47、聚醋酸乙烯酯、聚乙烯基丁缩醛、聚醋酸乙烯咪唑啉鎓、聚乙烯基甲基醚、PVM/MA共聚物、PVP、PVP/甲基丙烯酸二甲氨基乙酯、PVP/二十碳烯共聚物、PVP/甲基丙烯酸乙酯/甲基丙烯酸共聚物、PVP/十六碳烯共聚物、PVP/VA共聚物、PVP/乙酸乙烯酯/衣康酸共聚物、虫胶、丙烯酸钠共聚物、丙烯酸钠/丙烯基氮共聚物、丙烯酸钠/乙烯醇共聚物、角叉菜聚糖钠、淀粉二乙氨乙基醚、硬脂基乙烯基醚/马来酐共聚物、苯甲酸蔗糖酯/蔗糖醋酸异丁酸酯/邻苯二甲酸丁基苄基酯共聚物、苯甲酸蔗糖酯/蔗糖醋酸异丁酸酯/邻苯二甲酸丁基苄基酯/甲基丙烯酸甲酯共聚物、蔗糖苯甲酸酯/蔗糖醋酸异丁酸酯共聚物、醋酸乙烯酯/巴豆酸酯共聚物、醋酸乙烯酯/巴豆酸共聚物、醋酸乙烯酯/巴豆酸/甲基丙烯酰氧基二苯甲酮-1共聚物、醋酸乙烯酯/巴豆酸/新癸酸乙烯酯共聚物及其混合物。用于制造定型助剂的合成聚合物在“The History of Polymers in Haircare”(毛发护理中的聚合物历史),Cosmetics and Toiletries,103(1988)中有所描述,其在此引入作为参考。可与本发明一起使用的合成聚合物参见CTFA辞典,第五版,2000,其在此作为参考引入。
如果本发明的组合物目的是用于角蛋白纤维的染色,特别是人类毛发的染色,除不饱和季铵化合物之外其含有至少一种氧化染料前体和/或一种直接染料。其还可以含有常用于此类型组合物中的任意其它辅料。
染色组合物的pH通常为7到11,并且可以通过添加碱性试剂以调节到期望的值。
根据本发明的组合物还可以用于卷发或者直发。在这种情况下,除了不饱和季铵化合物之外,组合物通常含有一种或多种还原剂,如果合适的话,含有常用于此类型组合物中的其它辅料;这样的组合物往往和中和剂组合使用。
如上所述,本发明的具有1,3-二亚胺基的新型聚氨基酰胺还可以用作用于稳定包括下列物质在内的多种物质的紫外吸收剂,例如各种聚合物(交联的和热塑性的)、照相材料和用于织物材料的染料溶液;以及用作紫外线遮光剂。具有1,3-二亚胺基的聚氨基酰胺可以以包括以下方式在内的各种常规方式中的任意一种加入到这些材料中,例如作为例如涂料或溶液的光稳定组合物中的组分、或者作为紫外遮光组合物中的组分,任选地与结合到该材料(通常是结合到聚合物)的化学品物理混合或掺和。
本发明的具有1,3-二亚胺基的聚氨基酰胺可以用于通过化学或物理方式将具有1,3-二亚胺基的聚氨基酰胺加入到聚合物质中而用于稳定聚合物质以及各种自然形成或者合成的遭受紫外线降解的有机物质。
可以被稳定的代表性聚合物包括但不限于:聚烯烃;聚酯;聚醚;聚酮;聚氨;天然橡胶和合成橡胶;聚氨酯;聚苯乙烯;耐冲击性聚苯乙烯;聚丙烯酸酯;聚甲基丙烯酸酯;聚乙缩醛;聚丙烯腈;聚丁二烯;聚苯乙烯;ABS;SAN(苯乙烯丙烯腈);ASA(丙烯酸苯乙烯丙烯腈);纤维素醋酸丁酸酯;纤维素聚合物;聚酰亚胺;聚酰胺酰亚胺;聚醚酰亚胺;聚苯硫醚;PPO;聚砜;聚醚砜;聚氯乙烯;聚碳酸酯;聚酮;脂肪族聚酮;热塑性TPO’s;氨基树脂交联的聚丙烯酸酯和聚酯;聚异氰酸酯交联的聚酯和聚丙烯酸酯;苯酚/甲醛、脲/甲醛和蜜胺/甲醛树脂;干性和非-干性醇酸树脂;醇酸树脂;聚酯树脂;与蜜胺树脂、脲树脂、异氰酸酯、异氰脲酸酯、氨基甲酸酯和环氧树脂交联的丙烯酸酯树脂;衍生自与酸酐或胺交联的脂肪族、脂环族、杂环和芳香族缩水甘油基化合物的交联的环氧树脂;聚硅氧烷;胺或嵌段胺与活化的不饱和亚甲基化合物Michael加成聚合物、酮亚胺与活化的不饱和亚甲基化合物的Michael加成聚合物、聚酮亚胺与不饱和丙烯酸聚乙酰乙酸酯树脂的Michael加成聚合物、以及聚酮亚胺与不饱和丙烯酸树脂的Michael加成聚合物;辐射固化组合物;以及环氧蜜胺树脂。
根据要稳定的物质和具体用途,本发明的具有1,3-二亚胺基的新型聚氨基酰胺的使用量可以广泛地变化。但是,当其用作用于例如有机聚合物的物质的稳定添加剂时,基于要稳定的原料的重量,本发明的聚氨基酰胺紫外吸收剂的典型用量为大约0.01到大约20wt%,优选大约0.1到大约10wt%,最优选大约0.1到大约5wt%。在例如遮光组合物的遮光剂用途中,聚氨基酰胺紫外吸收剂的用量与相对量相同,但是其是基于遮光剂的总重。
具有1,3-二亚胺基的聚氨基酰胺还可以以含有这些化合物的母料的形式加入到要稳定的聚合物中,例如,其浓度为聚合物的大约2.5到大约25wt%,优选大约5到大约20wt%。
具有1,3-二亚胺基的聚氨基酰胺可以通过包括本领域常用的那些方法在内的任意方法加入到聚合物质中,例如:a)作为乳剂或分散体(例如晶格聚合物或乳液聚合物);(b)作为在与另外的成分混合时的干性混合物或聚合物混合物;(c直接加入到加工设备中(例如挤出机、密闭式混合机等);或(d)作为溶液或熔融体。加入物可以在定型之前或定型过程中通过以下方式容易地制成,例如将粉末成分混合或者将稳定剂加入到聚合物的熔融体或溶液中,或者在有或没有随后的溶剂蒸发步骤的情况下将溶解或分散的化合物加入到聚合物中。
加入了本发明的具有1,3-二亚胺基的聚氨基酰胺的聚合物可以通过包括模塑、挤出等的任意本领域常规方法加入到生产的产品中。
本发明的具有1,3-二亚胺基的聚氨基酰胺还适用于未染色、染色或印花的纤维材料的光化学稳定,该纤维材料包括丝、皮革、羊毛、聚丙烯、聚酯、聚乙烯、聚烯烃、聚酰胺或聚氨酯,特别是所有种类的含有纤维素的材料。纤维材料的例子是天然纤维素纤维,例如棉花、亚麻、黄麻和大麻,还有粘胶短纤维和再生纤维素。聚酰胺也适用于混纺织物中的含羟基纤维的光化学稳定,例如棉与聚酯纤维的混纺或棉与聚酰胺纤维的混纺。进一步优选的用途范围涉及阻碍或减少穿过上述织物材料的紫外辐射(紫外阻断),和增强这样的织物材料为人类皮肤提供的抵抗阳光的作用。另一个优选范围包括汽车用途,例如座舱安全带、headliner、地毯和汽车装潢。
具有1,3-二亚胺基的聚氨基酰胺以任何常规的染色方法应用于织物纤维材料,基于纤维材料的重量,其用量为0.01到5wt%。
具有1,3-二亚胺基的聚氨基酰胺可以以各种方式应用于纤维物质并固定在纤维上,特别是以含水分散体或印刷糊剂(printing paste)的形式。
用本发明的具有1,3-二亚胺基的聚氨基酰胺整理(finish)的织物纤维材料对于纤维的光化学破坏和发黄现象具有改进的保护,在染色纤维材料的情况下,耐光性增强。特别要强调的是,经处理过的织物纤维材料的光保护效果极大地改善,特别是对短波紫外线B射线的良好的保护作用。显然用具有1,3-二亚胺基的聚氨基酰胺整理的织物纤维材料相对于未处理的织物,防晒系数(SPF)极大地提高。
防晒系数定义为伤害受保护皮肤的紫外辐射剂量与伤害未受保护的皮肤的紫外辐射剂量的比值。因此,防晒系数也是未处理纤维材料和用具有1,3-二亚胺基的聚氨基酰胺处理的纤维材料对于紫外辐射的可透过程度的量度。织物纤维材料防晒系数的测定在例如WO94/04515或者J.Soc.Cosmet.Chem.40,127-133(1989)中有所说明,可以类似地实施。
本发明的具有1,3-二亚胺基的聚氨基酰胺可以用于涂料组合物,并且可以应用于任意的希望的基底上,例如金属、木材、塑料、玻璃纤维或陶瓷材料。涂料组合物可以是着色的单层涂层或多层系统(底层涂料/底涂层/透明涂层),典型的是汽车涂料。
涂料组合物可以通过常规方法涂覆于基底上,例如通过刷涂、喷涂、浇注、浸渍或电泳;也可以参见Ullmann’s Encyclopedia of IndustrialChemistru,第五版,第A18卷,第491-500页。
具有1,3-二亚胺基的聚氨基酰胺还可以通过用含有具有1,3-二亚胺基的聚氨基酰胺和例如溶剂、水包油型聚硅氧烷乳剂或汽车油漆蜡(例如巴西棕榈蜡)的惰性溶剂的组合物来抛光表面而局部应用。这些局部处理组合物可以用于稳定涂层膜、织物、皮革、乙烯和其它塑料和木材。
含有本发明的具有1,3-二亚胺基的聚氨基酰胺的混合物还可以用作涂层用成膜粘合剂的稳定剂,例如在例如美国专利4,619,956、4,740,542、4,826,978、4,962,142、5,106,891、5,198,498、5,298,067、5,322,868、5,354,794、5,369,140、5,420,204、5,461,151和5,476,937、EP-0434608和EP-A-0444323中公开的用于油漆,特别是用于汽车工业的涂层和油漆。
这样的成膜组合物通常含有大约0.01到大约20wt%的本发明的具有1,3-二亚胺基的聚氨基酰胺。
本发明的具有1,3-二亚胺基的聚氨基酰胺还可以用于各种类型的光敏材料。例如,其可以用于彩色相纸、彩色反转相纸、正像彩色材料、彩色底片、彩色正片、彩色反转胶片和其它材料。其优选用于,尤其是用于含有反转基底或者形成正片的光敏彩色材料。
具有1,3-二亚胺基的聚氨基酰胺可以与其它紫外吸收剂组合,特别是那些分散在水性凝胶中的材料,例如羟苯基苯并三唑(例如,美国专利4,853,471、4,973,702、4,921,966和4,973,701)、二苯甲酮、美国专利6,537,670中描述的双二苯甲酮、草酰替苯胺(oxanilide)、氰基丙烯酸酯、水杨酸酯或丙烯腈或噻唑啉。在这种情况下,在照相材料中与那些含有具有1,3-二亚胺基的聚氨基酰胺的物质不同的层中进一步应用这些紫外吸收剂是有利的。
本发明的具有1,3-二亚胺基的聚氨基酰胺还可以用于纤维素类纸制剂中,例如在新闻纸、纸板、海报、包装纸、标签、信纸、书籍和杂志用纸、粘结打印纸(bond typing paper)、多用途办公室用纸、计算机用纸、静电复印纸、激光和喷墨打印纸、胶版印纸、钞票纸等。
本发明的具有1,3-二亚胺基的聚氨基酰胺还适用于稳定墨水。
根据其最终用途,本发明的具有1,3-二亚胺基的聚氨基酰胺可以和一种或多种常规用于紫外线稳定技术领域的各种添加剂组合,包括抗氧化剂、紫外吸收剂、紫外稳定剂、金属钝化剂、亚磷酸盐、亚膦酸盐、羟胺、硝酮、硫代增效剂、过氧化物净化剂、聚酰胺稳定剂、成核剂、填充剂、增强剂、增塑剂、润滑剂、乳化剂、颜料、流变添加剂、阻燃剂、抗静电剂、发泡剂、苯并呋喃和吲哚满酮。
参考下列实施例可以更好地理解前述内容,提出这些实施例是为了说明的目的,而非限制本发明的范围。
实施例1
具有1,3-二亚胺基的二亚乙基三胺-DBE-2二元酸酯聚氨基酰胺
在装配有机械搅拌器、氮气吹扫管、温度控制器和冷凝器的1000ml五颈两件式树脂反应器中加入208.0g二亚乙基三胺(DETA,2.0摩尔)、327g(2.0摩尔)DBE-2二元酸酯和5g硫酸。将混合物加热至150℃,通过冷凝器收集甲醇。一旦没有更多的甲醇蒸馏出,则将温度升高至180℃。温度保持在180℃至少数小时,直到收集到大约15.0g的副产物水。随后停止加热,在低于大约140℃的温度下将395g水慢慢加入到反应器中以制备聚合物的水溶液。
实施例2
具有1,3-二亚胺基的二亚乙基三胺-对苯二甲酸二甲酯-DBE-2二元酸酯聚氨基酰胺
向实施例1所述的反应器中加入87.3g(0.45摩尔)对苯二甲酸二甲酯,并且用氮气吹扫反应器15分钟。向反应器中加入DETA(156.4g,1.5摩尔)、DBE-2二元酸酯和5.0g硫酸。将混合物在150℃加热大约2小时,直到没有甲醇蒸馏出。随后将温度升高至190℃。在高于或等于190℃的温度下保温数小时,直到收集到大约15.0g的副产物水。随后停止加热,在低于大约140℃的温度下将300g水慢慢加入到反应器中以制备聚合物的水溶液。
实施例3
具有1,3-二亚胺基的二亚乙基三胺-对苯二甲酸二甲酯-DBE-2二元酸酯-水杨酸甲酯聚氨基酰胺
向实施例1所述的反应器中加入58.3g(0.3摩尔)对苯二甲酸二甲酯,并且用氮气吹扫反应器15分钟。向反应器中加入DETA(171.6g,1.65摩尔)、196.2g(1.2摩尔)DBE-2二元酸酯和5.0g硫酸。将混合物在150℃加热,直至没有甲醇蒸馏出。向反应器中加入45.3g(0.3摩尔)水杨酸甲酯。混合物在150℃进一步加热直至没有甲醇蒸馏出。随后将温度升高至190℃,并在190℃或者更高温度下保温数小时直至收集到大约15.0g的副产物水。随后停止加热,并在低于大约140℃的温度下将300g水慢慢加入到反应器中以制备聚合物的水溶液。
实施例4
具有1,3-二亚胺基的二亚乙基三胺-己二酸聚氨基酰胺
向实施例1所述的反应器中加入208.0g(2.0摩尔)DETA和292g(2.0摩尔)己二酸。混合物加热至160℃,并通过冷凝器收集水。收集到大约72.0g(4.0摩尔)水后将温度升高到185℃。在至少185℃下保温,直至收集到大约15.0g副产物水。随后停止加热,在低于大约140℃的温度下慢慢将410g水加入反应器中以制备聚合物的水溶液。
实施例5
具有1,3-二亚胺基的四亚乙基五胺-己二酸聚氨基酰胺
向实施例1中所述的反应器中加入330.0g(1.65摩尔)四亚乙基五胺(TEPA)和219.0g(1.50摩尔)的己二酸。混合物加热至190℃,并通过冷凝器收集副产物水。在至少190℃下保温数小时,直至收集到72.0g(4.0摩尔)或者更多的副产物水。随后停止加热,在低于大约140℃的温度下慢慢将410g水加入反应器中以制备聚合物的水溶液。
实施例6
比较实施例
在本实施例中,除了按照如表1所示的时间和温度来加热之外,使用类似于实施例1-5中描述的方法将DETA与DBE-2二元酸酯或己二酸缩合。在150℃下加热2小时后,记录聚合物的紫外吸收(测量1cm测量池内的100ppm聚合物溶液,λmax=313nm)。随后聚合物在第4栏所示温度下再加热一段时间,并再次记录该聚合物的紫外吸收。
表1具有1,3-二亚胺基的聚氨基酰胺的紫外吸收和合成条件
实施例 | 原材料 | 预聚物的吸收 | 新聚合物的吸收 |
实施例A | DETA/DBE-2 | <0.01(150℃下2小时) | 0.507(180℃下4.5小时) |
实施例B | DETA/DBE-2 | <0.01(150℃下2小时) | 0.767(220℃下2.0小时) |
实施例C | DETA/己二酸 | <0.05(150℃下2.0小时) | 0.270(165℃下6.0小时) |
实施例D | DETA/己二酸 | <0.05(150℃下2.0小时) | 1.374(185℃下5.0小时) |
表1显示了在较低温度下预先形成的聚合物在较高温度下加热后出现的紫外吸收。传统的聚氨基酰胺由于缺乏1,3-二亚胺基而不会在280-350nm处显示有意义的紫外吸收,1,3-二亚胺基的存在由于烯胺-亚胺的互变平衡通过300nm-350nm附近的强紫外吸收可以容易地识别出来。
实施例7
代表性的表面活性剂处理制剂
代表性的表面活性剂实验溶液在表2中示出。该制剂通过混合水和月桂基硫酸钠而制备。随后将聚合物加入到表面活性剂溶液中。用柠檬酸将表面活性剂溶液的pH调节到5.0+/-0.2。
表2代表性的表面活性剂实验溶液
组分(INCI名) | %w/w |
水 | 加到100 |
月桂基硫酸钠 | 10(固体) |
聚合遮光剂 | 2.0(固体) |
实施例8
代表性的护发素制剂
代表性的免洗护发素制剂如表3所示。该护发素如下制备:将纤维素羟乙基醚(Natrosol)分散在水中,加入聚合物并混合至均匀。随后加入泛醇和鲸蜡基三甲基氯化铵,并且在每次加入后混合。对羟苯甲酸酯与甘油结合并搅拌至均匀,随后加入到主料中。将聚山梨酸酯和任意香料结合并搅拌至均匀,随后加入到主料中。最后将主料的pH调节到大约5.3。
表3代表性的免洗护发素制剂
组分(INCI名) | %w/w |
水 | 加到100 |
羟乙基纤维素 | 0.8 |
聚合遮光剂 | 0.7 |
泛醇 | 0.7 |
鲸蜡基三甲基氯化铵 | 2.0 |
甘油 | 1.0 |
对羟基苯甲酸甲酯 | 0.2 |
对羟基苯甲酸丙酯 | 0.02 |
聚山梨酸酯20 | 0.5 |
实施例9
代表性的洗发水制剂
表4所示的组分按照所示顺序依次加入到水中并且以中等搅拌速度混合。随后加入聚合遮光剂,用柠檬酸(0.25-0.4wt%)将pH调节至大约6,并边搅拌边加入氯化钠以获得希望的粘度。
表4代表性的洗发水
组分 | INCI名称 | %w/w |
水 | 水 | 平衡量 |
Standapol EA-1 | 月桂醇聚醚硫酸铵 | 43 |
Mirataine CB | 椰油酰胺丙基甜菜碱 | 9.3 |
Hamposyl L-30 | 月桂酰肌氨酸钠 | 5.0 |
聚合遮光剂 | 聚合遮光剂 | 4 |
防腐剂 | 防腐剂 | 平衡量 |
柠檬酸 | 柠檬酸 | 加至pH=6 |
氯化钠 | 氯化钠 | 1.0 |
香料 | 香料 | 0.05 |
实施例10
检验用发绺的制备
此处描述的实验是在8英寸长的原始(virgin)/金发绺上进行的,该发绺得自International Hair Importers and Prodcuts Inc.,Bellerose,NewYork。
将发绺(每绺1.5g)绑在一起并用水润湿。用1克月桂醇聚醚硫酸钠从发绺的顶部到底部揉搓1分钟。随后用40℃的自来水漂洗1分钟,然后在去离子水中浸泡过夜并风干。
实施例11
检验用染色发绺的制备
使用得自International Hair Importers and Prodcuts Inc.,Bellerose,New York的8英寸长的中等褐色并漂白过的发绺。用得自欧莱雅公司的3级商业染发剂将毛发染成赭红色。染色过程按照染发剂的说明进行。
实施例12
紫外辐射
在紫外照射之前,发绺用上述实施例所示制剂处理5分钟,随后用去离子水漂洗30秒。将处理过的毛发风干。重复该处理3次。
处理后,将发绺从捆绑状态解开并在样品架上摊开成一层。样品放置在距离紫外灯10厘米处,在45℃和30%的相对湿度下在Q-Panel加速耐候实验机(Q-Panel Accelerated Weathering Tester)(Q-Panel LabProducts,26200First Street Cleveland,OH 44145)模拟的夏天正午的阳光中曝晒400到600小时。
实施例13
色度计测量
将从紫外耐候实验机上收集到的毛发样品捆绑在一起。将色度计(LabScan XE,HunterLab,Reston,VA)在实验前校正。将发束(hairbundle)放置在扫描部分的顶部,并读取毛发样品。使用HunterColorimeter LabScan XE设备来测量Hunter三色L、a、b值。报告的数据为在紫外辐射下发绺的未照射部分和照射部分之间的总色差ΔE=√(9Δl2+Δa2+Δb2)和色度差ΔC=√(Δa2+Δb2),其是几个位置上进行的测量的平均值。染色指数计算为CI=ΔE/ΔC。
实施例14
抗拉强度试验
毛发的抗拉强度是毛发光损伤程度的直接反应。毛发的强度可以使用适合的抗拉实验设备来测量。将单根的毛发固定在夹具中,并以且固定速率牵引到发生断裂。在计算机的控制下给每根毛发施加负载并且记录对抗拉伸的负载。利用测量的毛发直径和固定的标距长度,该数据可以转化成毛发纤维断裂所需的总功。用于测量毛发抗拉强度的仪器是DiaStron Miniature抗拉实验仪170/670(DiaStron,Hamphsire,UK)。
实施例15
FT-IR分析
用FTIR测定紫外线对于毛发的损伤程度。紫外伤害可以作为半胱氨酸或胱氨酸内S-S键的氧化的结果而通过SO波段观察到。通过在不同的时间点取得的1041cm-1的SO波段和1633cm-1的酰胺波段的波段比值,可以定量地测量SO波段强度的增加。在第一个800小时,SO波段的强度和紫外线照射长度成正比例。在800到1200小时的照射期,其达到平台。研究表明FTIR方法是定量测量SO波段的相对变化的可行方法。
FT-IR研究是通过加压器沿着与射束路径相同的轴给单反射单元上的原始发绺上加压而进行的。毛发用Nicolet Avatar 360 FTIR扫描128次。使用的检测器为DTGS。收集到的光谱作为照射0小时。随后在紫外线照射400、800和1200小时后按照相同方式在毛发上进行FTIR分析。测量1041cm-1的SO波段的峰高,并与1633cm-1的酰胺I波段比较。较高的峰比例意味着紫外损伤毛发的氧化程度更大。每个发绺均分成三份进行分析以获得平均值。
实施例16
毛发着色减少的证明
为了证明紫外吸收聚合物在紫外照射后在减少毛发着色方面的效果,测量了经照射的发绺和未照射的发绺之间的总色差的定量变化,以及用本发明的代表性的紫外吸收聚合物处理过的发绺和用使用聚季铵59和丁烯制备的比较产品(对比遮光剂A)处理过的发绺之间的总色差的定量变化。
表5着色指数的测量
样品名 | L | a | b | ΔE |
原始毛发 | 40.4 | 6.1 | 16.5 | |
对照 | 45.01 | 6.78 | 21.16 | 15.47 |
聚合遮光剂 | 44.15 | 7.01 | 20.89 | 12.94 |
比较遮光剂A | 45.21 | 6.86 | 20.62 | 15.90 |
如表5所示,通过使用本发明的紫外吸收聚合物制备的聚合遮光剂处理的毛发样品显示了比未处理毛发样品低得多的总色差(ΔE)。结果提示本发明的聚合遮光剂为毛发提供超强保护,使其免于在紫外线照射后改变颜色。
表6着色指数的测量
如表6所示,正如用该护发素处理过的发绺的总色彩变化所证实的,用本发明代表性的聚合遮光剂调制的护发素提供了比比较遮光剂A更好的防护阳光的作用。
实施例17
染色毛发的毛发着色降低的证明
测量经照射的发绺和未照射发绺之间的染色毛发的总色差的定量变化,以及用本发明代表性的紫外吸收聚合物处理过的发绺和用特别是商品名为和Clariol的聚季铵59和丁烯制备的比较产品(比较遮光剂A)处理过的发绺之间的总色差的定量变化。结果如表7所示。
表7染色毛发的总色彩变化的测量
在表7中,防止毛发色彩褪色的商业产品用作基准。表7的结果显示,用聚合遮光剂处理过的手工染色的发绺的ΔE比用比较遮光剂A和商业产品处理过的低得多,这意味着聚合遮光剂提供了更好的防止人造毛发染料的色彩褪色的作用。
实施例18
抗拉强度结果
单纤维的耐断裂性直接反应了阳光所致的毛发受损的程度。断裂单纤维所需的力量越大,毛发纤维遭受的伤害越小。下表总结了单纤维分析的实验结果,在该分析中使用了70根毛发纤维以使得每一项研究产生统计学上有意义的数据。
表8抗拉强度分析
样品名 | 总功(mJ) | %强化 |
未受损 | 6.69 | |
受损 | 4.12 | |
聚合物1 | 4.9 | 30.3 |
聚合物2 | 4.89 | 30.3 |
比较遮光剂A | 4.46 | 13.2 |
如表8所示,聚合遮光剂1和2显示出比比较遮光剂A高得多的断裂力。结果还证明聚合遮光剂1和2提供了比对照(受损)和基准更好的阳光防护作用。
实施例19
FT-IR分析
双硫键的氧化是毛发角蛋白光降解程度的指标。FT-IR分析使用来自毛发蛋白质的酰胺作为内标测量的S-O波段的吸收。结果(表9和10)显示用本发明的聚合遮光剂保护的发绺的SO/酰胺的比值比比较遮光剂和对照的低。检验了两套不同的用护发素制剂处理的发绺以观察可重复性。表9和10所示结果证明本发明的聚合遮光剂比对照和比较遮光剂A的效果更好。
表9FT-IR分析
样品名 | S-O/酰胺比例 | 平均 |
对照 | 0.574 | |
0.621 | ||
0.59 | 0.601 | |
0.581 |
0.641 | ||
聚合遮光剂 | 0.516 | |
0.509 | ||
0.482 | 0.502 | |
0.469 | ||
0.533 | ||
比较遮光剂 | 0.705 | |
0.654 | ||
0.722 | 0.673 | |
0.595 | ||
0.692 |
表10FT-IR分析
样品名 | S-O/酰胺比例 | 平均 |
对照 | 0.605 | |
0.638 | ||
0.66 | 0.656 | |
0.74 | ||
0.639 | ||
聚合遮光剂 | 0.528 | |
0.506 | ||
0.529 | 0.519 | |
0.511 | ||
0.519 | ||
比较遮光剂 | 0.692 | |
0.619 | ||
0.588 | 0.624 | |
0.606 | ||
0.617 |
本文所述的本发明的组成、方法的操作和排列可以在不脱离权利要求所定义的本发明的概念和范围的情况下改变。
Claims (22)
1.用于保护基底免受紫外线影响的组合物,其特征在于含有有效紫外防护量的一种或者多种具有1,3-二亚胺基的水溶性聚氨基酰胺,其中所述具有1,3-二亚胺基的聚氨基酰胺吸收波长为200nm到420nm的紫外辐射。
2.如权利要求1所述的组合物,其中所述的聚氨基酰胺的特征在于具有吸收波长为280nm到350nm的紫外辐射的1,3-二亚胺基。
3.如权利要求1所述的组合物,其特征在于所述具有1,3-二亚胺基的聚氨基酰胺进一步含有一种或者多种选自取代或未取代的肉桂酰基、水杨酰基和对二烷基氨基苯甲酰基的另外的紫外吸收分子部分。
4.如权利要求1所述的组合物,其特征在于所述具有1,3-二亚胺基的聚氨基酰胺与一种或多种交联剂交联。
5.根据权利要求4所述的具有1,3-二亚胺基的交联聚氨基酰胺,其特征在于所述交联剂选自二环氧化物、二酐、二卤代衍生物、二酯、二酸、表卤醇和表卤醇/胺低聚物。
6.根据权利要求5所述的具有1,3-二亚胺基的交联聚氨基酰胺,其特征在于所述交联剂选自聚(乙二醇)二缩水甘油醚、聚(丙二醇)二缩水甘油醚、表氯醇、表氯醇/二甲胺低聚物。
7.改性聚氨基酰胺,其特征在于具有通过使如权利要求1所述的具有1,3-二亚胺基的聚氨基酰胺与一种或多种选自含有阳离子官能团的分子部分、含有阴离子官能团的分子部分和含有取代和非取代脂肪烃的分子部分的改性剂反应而制备的1,3-二亚胺基。
8.根据权利要求7所述的改性聚氨基酰胺,其中所述含有阳离子官能团的分子部分选自缩水甘油基三甲基氯化铵和N-(3-氯代-2-羟丙基)三甲基氯化铵。
9.根据权利要求7所述的改性聚氨基酰胺,其特征在于所述含有阴离子官能团的分子部分选自氯乙酸及其盐、1,3-丙烷磺内酯、1,4-丁烷磺内酯。
10.根据权利要求7所述的改性聚氨基酰胺,其中所述含有脂肪烃的分子部分选自C6-C18脂肪醇的缩水甘油醚。
11.如权利要求1所述的组合物,进一步含有一种或多种化妆品可接受的赋形剂。
12.如权利要求11所述的组合物,其特征在于所述赋形剂选自糖类、凡士林、矿物油、脂肪醇、蜡、硅油、硅树脂液、挥发性烃油、季氮化合物、胺官能化的聚硅氧烷、C10到C22的长链二胺、C10到C22的长链脂肪胺、乙氧基化的脂肪醇和二尾磷脂。
13.如权利要求12所述的组合物,其特征在于所述蜡包括含聚硅氧烷的蜡。
14.如权利要求11或12所述的组合物,其特征在于所述赋形剂选自表面活性试剂、保湿剂、脂肪酸酯软化剂、调理聚合物、流变改性剂、抗氧化剂和遮光活性剂。
15.如权利要求14所述的组合物,其特征在于所述表面活性试剂包括聚硅氧烷表面活性剂。
16.如权利要求11所述的组合物,其特征在于所述组合物选自洗发剂、遮光剂、护发素、烫发剂、顺发剂、毛发漂白剂、毛发柔顺露、定型凝胶、定型发釉、喷雾泡沫、定型膏、定型蜡、定型乳液、摩丝、喷雾凝胶、润发油、染发制剂、亮发素、卷发剂、直发剂、毛发修饰助剂、毛发营养剂、美发剂、针剂和香脂。
17.如权利要求16所述的组合物,其特征在于所述护发素包括染后护发素以及染后和非染后毛发润丝精;且所述染发制剂包括短效和长效染发剂。
18.如权利要求11所述的组合物,其特征在于所述组合物选自乳液、手霜和体霜、液体皂、固体皂、浴油皂、洁面乳、须后水、剃须凝胶或剃须膏、睫毛膏、眼部凝胶、沐浴露、除臭剂、防汗剂、遮光露、晒后凝胶、泡沫浴、以及手洗和机洗洗涤剂组合物。
19.如权利要求18所述的组合物,其特征在于所述乳液包括眼部乳液。
20.保护基底免受紫外线影响的方法,包括在该基底上涂覆有效紫外防护量的权利要求1所述的具有1,3-二亚胺基的聚氨基酰胺。
21.如权利要求20所述的方法,其特征在于所述基底为选自皮肤和毛发的角蛋白基底。
22.如权利要求20所述的方法,其特征在于所述基底选自织物纤维材料、金属、木头、陶瓷、塑料和油漆。
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US10/696,835 US6887400B1 (en) | 2003-10-30 | 2003-10-30 | Water-soluble polyaminoamides comprising 1,3-diimines as sunscreen agents |
US10/696,835 | 2003-10-30 |
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CN1875082A CN1875082A (zh) | 2006-12-06 |
CN100551999C true CN100551999C (zh) | 2009-10-21 |
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US (2) | US6887400B1 (zh) |
EP (1) | EP1716219B1 (zh) |
CN (1) | CN100551999C (zh) |
AU (1) | AU2004286932B2 (zh) |
BR (1) | BRPI0414922A (zh) |
CA (1) | CA2537583C (zh) |
ES (1) | ES2401480T3 (zh) |
WO (1) | WO2005044948A2 (zh) |
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-
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2004
- 2004-09-27 CA CA2537583A patent/CA2537583C/en not_active Expired - Lifetime
- 2004-09-27 CN CNB2004800324772A patent/CN100551999C/zh not_active Expired - Lifetime
- 2004-09-27 BR BRPI0414922-0A patent/BRPI0414922A/pt not_active IP Right Cessation
- 2004-09-27 EP EP04789105A patent/EP1716219B1/en not_active Expired - Lifetime
- 2004-09-27 AU AU2004286932A patent/AU2004286932B2/en active Active
- 2004-09-27 WO PCT/US2004/031693 patent/WO2005044948A2/en active Application Filing
- 2004-09-27 ES ES04789105T patent/ES2401480T3/es not_active Expired - Lifetime
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102770459A (zh) * | 2010-02-19 | 2012-11-07 | 丘比株式会社 | 修饰透明质酸和/或其盐、及其制造方法以及含有它的化妆品 |
CN102770459B (zh) * | 2010-02-19 | 2016-01-20 | 丘比株式会社 | 修饰透明质酸和/或其盐、及其制造方法以及含有它的化妆品 |
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ES2401480T3 (es) | 2013-04-22 |
BRPI0414922A (pt) | 2006-11-14 |
US20050180933A1 (en) | 2005-08-18 |
CA2537583A1 (en) | 2005-05-19 |
EP1716219B1 (en) | 2013-01-30 |
EP1716219A2 (en) | 2006-11-02 |
US6887400B1 (en) | 2005-05-03 |
WO2005044948A3 (en) | 2005-06-30 |
WO2005044948A2 (en) | 2005-05-19 |
CN1875082A (zh) | 2006-12-06 |
EP1716219A4 (en) | 2008-05-07 |
AU2004286932A1 (en) | 2005-05-19 |
US20050092970A1 (en) | 2005-05-05 |
CA2537583C (en) | 2013-04-16 |
AU2004286932B2 (en) | 2009-11-05 |
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