CN115551828A - 一种香料组合物 - Google Patents
一种香料组合物 Download PDFInfo
- Publication number
- CN115551828A CN115551828A CN202180033983.7A CN202180033983A CN115551828A CN 115551828 A CN115551828 A CN 115551828A CN 202180033983 A CN202180033983 A CN 202180033983A CN 115551828 A CN115551828 A CN 115551828A
- Authority
- CN
- China
- Prior art keywords
- peg
- acid
- polydimethylsiloxane
- sodium
- ppg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- SLBXZQMMERXQAL-UHFFFAOYSA-M sodium;1-dodecoxy-4-hydroxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O SLBXZQMMERXQAL-UHFFFAOYSA-M 0.000 description 1
- UIGBPGNEWMRLGK-UHFFFAOYSA-M sodium;2-(2-hydroxydodecoxy)acetate Chemical compound [Na+].CCCCCCCCCCC(O)COCC([O-])=O UIGBPGNEWMRLGK-UHFFFAOYSA-M 0.000 description 1
- IKGKWKGYFJBGQJ-UHFFFAOYSA-M sodium;2-(dodecanoylamino)acetate Chemical compound [Na+].CCCCCCCCCCCC(=O)NCC([O-])=O IKGKWKGYFJBGQJ-UHFFFAOYSA-M 0.000 description 1
- BCISDMIQYBCHAT-UHFFFAOYSA-M sodium;2-(dodecanoylamino)ethanesulfonate Chemical compound [Na+].CCCCCCCCCCCC(=O)NCCS([O-])(=O)=O BCISDMIQYBCHAT-UHFFFAOYSA-M 0.000 description 1
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- CAVXVRQDZKMZDB-UHFFFAOYSA-M sodium;2-[dodecanoyl(methyl)amino]ethanesulfonate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CCS([O-])(=O)=O CAVXVRQDZKMZDB-UHFFFAOYSA-M 0.000 description 1
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- BRMSVEGRHOZCAM-UHFFFAOYSA-M sodium;2-dodecanoyloxyethanesulfonate Chemical compound [Na+].CCCCCCCCCCCC(=O)OCCS([O-])(=O)=O BRMSVEGRHOZCAM-UHFFFAOYSA-M 0.000 description 1
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- C07C255/00—Carboxylic acid nitriles
- C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
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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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/07—Mononitriles
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- C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
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- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
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Abstract
提出一种香料组合物含有或由选择的特定腈组成,其表现出改进的抗分解和抗变色稳定性。
Description
发明领域
本发明涉及香料领域并且涉及具有改进稳定性的具有腈结构的选择的特定腈香料以及包含它们的化妆品、个人护理和洗涤剂组合物。
背景发明
芳香腈类是化学工业[见March’s Advanced Organic Chemistry,Reactions,Mecha-nisms and Structure,John Wiley and Sons,Inc.,New York,2007]和香水工业的众所周知的合成中间体。
获得芳族腈类的合适方法包括使用氰化物源,例如CuCN、KCN、NaCN、Zn(CN)2、TMSCN,或将芳基卤化物转化为腈[参见Kim等人,Angewandte Chemie,Vol.124,p 12114ff(2012)]。
尽管腈类是一组非常突出的香料,提供各种不同的香调,但它们表现出两个严重的缺点:首先,它们的稳定性通常很差,因为它们很容易分解,特别是在透明瓶中和/或在较高温度下储存时;其次,由于分解,它们会使最终配方变色并使其外观呈黄色。
相关现有技术
EP 0550762 A1(KAO)涉及一种通过在一种或多种选自碱金属氢氧化物、碱金属醇盐、碱土金属氢氧化物和碱土金属醇盐的存在下加热醛肟,并从反应体系中蒸馏掉反应过程中形成的水,制备腈。
EP 2979682 A1(SYMRISE)公开了多种苄腈类例如3,4-二甲基苄腈、4(2-甲基丙基)苄腈、3-甲基苄腈、2-甲氧基苄腈、3,4-二甲氧基苄腈和4-甲氧基苄腈与各种载体作为香豆素替代品。
US 4,040,986(NAARDEN INT)涉及4-甲氧基苄腈作为香豆素的替代物在制造香料组合物或加香产品中的用途。根据实施例1,该组合物尤其包含4-甲氧基苄腈和依兰油。
发明主题
因此,本发明的目的是提供具有腈结构的香料,特别是具有肉桂、绿色和柑橘香调的香料,其在油性或水性组合物中稳定并且在储存期间不分解。特别地,那些香料应该避免所述组合物的任何变色。
本发明的另一个目的是鉴定能够以低剂量增强其他香料或香料油组合物的感觉和/或嗅觉印象的分子。
发明内容
本发明的第一个目的涉及一种香料组合物,其包含或由至少一种式(I)的腈组成
R-CN (I)
其中R代表
(i)取代的苯基;
(ii)任选取代的降冰片基;
(iii)任选取代的环戊(烯)基;和/或
(iv)-(CH2)n-CH=CH2基团,其中n表示1至10的整数;
条件是形成组(i)的腈选自下组:
·2,3-二甲基苄腈
·2,4,5-三甲基苄腈
·4-乙基苄腈
·4-丙基苄腈
·4-苯基苄腈。
令人惊讶地发现,选择的特定腈类香料在化妆品组合物中特别稳定,无论是油基产品还是水基产品。即使在20至40℃的温度下储存至少两周,香味的强度仍保持在较高水平。与许多其他具有腈结构的香料不同,它们不会显示出任何使组合物变色的趋势。当向所述腈类化合物添加溶剂,优选乙醇和/或柠檬酸三乙酯时,获得了特别高的稳定性。
最后观察到,所述腈分子可以在例如0.01至0.1重量%的低浓度下—以组合物中香料的总量计—改善许多香料和香料油的感官和嗅觉印象。
腈类香料
根据本发明的选择的腈类包括组(i)至(iv)。
组(i)代表式(I)的腈类,其中R代表取代的苯基,这意味着组(i)代表选择的五种苄腈,即
·2,3-二甲基苄腈
·2,4,5-三甲基苄腈
·4-乙基苄腈
·4-丙基苄腈
·4-苯基苄腈。
当添加到其他香料或香料油中时,显示出特别高的促进效果。在根据本发明的一个优选实施方案中,式(I)的组(i)选自2,3-二甲基苄腈。
组(ii)是指腈基连接到降冰片烷基的结构,其还可以带有其他取代基,优选C1-C5烷基、烷氧基或烷氧基烷基。该组的优选代表是3,3-二甲基降冰片烷-2-甲腈,包括所有相关的立体异构体,例如(1R)(2S)(4S)和(1R)(2R)(4S)产物。
组(iii)是指腈基连接到环戊基或环戊烯基的结构,其还可以带有其他取代基,优选C1-C5烷基、烷氧基或烷氧基烷基。该组的优选代表是2-[3-(甲氧基-甲基)-2-2-二甲基-环戊-3-烯-1-基]乙腈。
最后,组(iv)是指腈符合式(I)的结构
NC–(CH2)n-CH=CH2 (II)
其中n代表1至20的整数,优选10至15。优选的物质是十三-12-烯腈。
在根据本发明的最优选实施方案中,香料组合物包含或由至少一种式(I)的腈组成
R-CN (I),
其中式(I)的腈选自2,3-二甲基苄腈。换言之,在根据本发明的最优选实施方案中,香料组合物包含2,3-二甲基苄腈或由其组成。
次要香料
在另一个优选的实施方案中,根据本发明的香料组合物可以包含至少一种除所述腈类以外的额外香料(下文称为“次要香料”),优选重量比为约10:90至约90:10,优选约25:75至约75:25,更优选约50:60至约60:40。优选地,这些次要香料表现出木质、琥珀、水果或麝香气味。与单独使用次要香料相比,即使在高温下储存数周后,这些混合物也显示出改善的颜色稳定性。
带有木质气味的香料
合适的具有木质气味的香料选自组包括:
带有琥珀气味的香料
合适的具有琥珀气味的香料选自组包括:
带有水果气味的香料
合适的具有水果气味的香料选自组包括:
带有麝香气味的香料
合适的具有麝香气味的香料选自组包括:
香料油
在另一个实施方案中,香料组合物可以代表香料油,其中掺入少量例如0.01至0.1重量%的腈类香料。如上所述,根据本发明的腈类代表香味增强剂,这意味着它们特别加强了对香料油的前调的识别。
合适的香料油是天然和合成香料的混合物并且可以包括30、50或甚至超过100种不同的组分。天然香料包括花朵(百合、薰衣草、玫瑰、茉莉、橙花、依兰)、茎和叶(天竺葵、广藿香、苦橙叶)、果实(茴香、香菜、香菜、杜松)、果皮(佛手柑、柠檬、橙)、根(肉豆蔻、当归、芹菜、豆蔻、科斯图斯、鸢尾、菖蒲)、木材(松木、檀香、愈创木、雪松、花梨木)、草本植物(龙蒿、柠檬草、鼠尾草、百里香))、针叶和树枝(云杉、冷杉、松树、矮松)、树脂和香脂(格蓬、榄香脂、安息香、没药、乳香、红没药)。也可以使用动物原料,例如麝猫香和海狸香。
溶剂
根据本发明的香料组合物——包括如上所述还掺入次要香料的那些——也可以含有香料级的溶剂或载体,例如苯甲醇、苯甲酸苄酯、邻苯二甲酸二乙酯、二丙二醇、乙醇、肉豆蔻酸异丙酯、柠檬酸三乙酯、downol DPM、IsoPar L、三醋精及其混合物。然而,最优选的溶剂是乙醇和/或柠檬酸三乙酯。
通常,化合物(a)和(b)以约10:1至约1:10,优选约5:1至约1:5,更优选约2:1至1:2的重量比存在于所述组合物中。化合物(a)是指根据式(I)的香料加上次要香料(如果有的话。
本发明的另一个目的涉及一种香料制剂,其包含(a)至少一种根据式(I)的腈和(b)乙醇和/或柠檬酸三乙酯,适用与上述相同的优选比例。
如上面已经解释的,根据本发明选择的腈类包括组(i)至(iv)。
组(i)代表式(I)的腈类,其中R代表取代的苯基,这意味着组(i)代表选择的五种苄腈,即
·2,3-二甲基苄腈
·2,4,5-三甲基苄腈
·4-乙基苄腈
·4-丙基苄腈
·4-苯基苄腈。
当添加到其他香料或香料油中时,显示出特别高的促进效果。在根据本发明的一个优选实施方案中,式(I)的组(i)选自2,3-二甲基苄腈。
组(ii)是指腈基连接到降冰片烷基的结构,其可以带有其他取代基,优选C1-C5烷基、烷氧基或烷氧基烷基。该组的优选代表是3,3-二甲基降冰片烷-2-甲腈,包括所有相关的立体异构体,例如(1R)(2S)(4S)和(1R)(2R)(4S)产物。
组(iii)是指腈基连接至环戊基或环戊烯基的结构,其还可以带有其它取代基,优选C1-C5烷基、烷氧基或烷氧基烷基。该组的优选代表是2-[3-(甲氧基-甲基)-2-2-二甲基-环戊-3-烯-1-基]乙腈。
最后,组(iv)是指腈符合式(I)的结构
NC–(CH2)n-CH=CH2 (II)
其中n代表1至20的整数,优选10至15。优选的物质是十三-12-烯腈。
在根据本发明的最优选实施方案中,香料组合物包含或由至少一种式(I)的腈类组成
R-CN (I),
其中式(I)的腈类选自2,3-二甲基苄腈。换言之,在根据本发明的最优选实施方案中,香料组合物包含2,3-二甲基苄腈或由其组成。
化妆和个人护理组合物
本发明的另一个主题涉及含有上述香料组合物或香料制剂的化妆和/或个人护理组合物,优选含量为约0.1至约5重量%,并且更优选约0.5至约2重量%。
根据本发明的组合物可以含有去头屑剂、防刺激剂、抑制刺激剂,抗氧化剂、收敛剂、抑汗剂、杀菌剂、抗静电剂、粘合剂、缓冲剂、载体、螯合剂、细胞刺激剂、清洗剂、护理剂、除臭剂、止汗剂、软化剂、乳化剂、酶、精油、纤维、成膜剂、固色剂、泡沫形成剂、泡沫稳定剂、消泡剂、泡沫促进剂、胶凝剂、凝胶形成剂、头发护理剂、毛发定型剂、头发拉直剂、增湿剂、润湿剂、保湿剂、漂白剂、加强剂、驱污剂、光学增亮剂、浸溃剂、驱污剂、减摩剂、润滑剂、保湿霜、软膏、遮光剂、增塑剂、覆盖剂、上光剂、光泽剂、聚合物、粉末、蛋白质、加脂剂(re-oiling agents)、磨蚀剂、硅酮、生发剂、清凉剂、皮肤清凉剂、加温剂、皮肤升温剂、稳定剂、紫外线吸收剂、UV滤光剂、洗涤剂、增稠剂、维生素、油、蜡、脂肪、磷脂、饱和脂肪酸、单或多不饱和脂肪酸、α-羟基酸、多羟基脂肪酸、液化剂、染料、颜色保护剂、颜料、芳香物质、多元醇、表面活性剂、电解质、有机溶剂或硅酮衍生物等作为额外助剂和添加剂。
表面活性剂
优选的助剂和添加剂是阴离子和/或两性或两性离子表面活性剂。非离子和阳离子表面活性剂也可存在于组合物中。在涉及乳化剂的段落中提到了适当的例子。
阴离子和两性离子表面活性剂的典型实例包括:杏仁油酰胺丙基胺氧化物、杏仁油酰胺丙基甜菜碱、氨丙基月桂基谷氨酰胺、C12-15烷醇硫酸酯铵、C12-16烷醇硫酸酯铵、辛醇聚醚硫酸酯铵、单椰油酸甘油酯硫酸铵、椰油醇硫酸酯铵、椰油酰羟乙磺铵、椰油酰肌氨酸铵、C12-15链烷醇聚醚硫酸酯铵、C9-10全氟代烷基磺酸铵、磺基琥珀酸磺基琥珀酸二壬酯铵、十二烷基苯磺酸铵、异硬脂酸铵、月桂醇聚醚-6羧酸铵、月桂醇聚醚-8羧酸铵、月桂醇聚醚硫酸酯铵、月桂醇聚醚-5硫酸酯铵、月桂醇聚醚-7硫酸酯铵、月桂醇聚醚-9硫酸酯铵、月桂醇聚醚-12硫酸酯铵、月桂酰肌氨酸铵、月桂醇硫酸酯铵、月桂醇磺基琥珀酸酯铵、肉豆蔻醇聚醚硫酸酯铵、肉豆蔻基硫酸铵、壬基苯酚聚醚-4硫酸酯铵、壬基苯酚聚醚-30硫酸酯铵、油酸铵、棕榈仁油醇硫酸酯铵、硬脂酸铵、妥尔油酸铵、异硬脂酰水解胶原AMPD盐、松香(酰)水解胶原AMPD盐、异硬脂酰水解胶原AMP盐、异硬脂酰水解角蛋白AMP盐、异硬脂酰水解大豆蛋白AMP盐、异硬脂酰水解小麦蛋白AMP盐、野杏油酰胺基丙基甜菜碱、花生酸、己基癸醇磷酸酯精氨酸盐、鳄梨油酰胺丙基甜菜碱、鳄梨油甘油聚醚-8酯类、巴巴苏籽油酸、巴巴苏油酰胺丙基胺氧化物、巴巴苏油酰胺丙基甜菜碱、蜂蜡酸、山嵛酰胺丙基甜菜碱、山嵛胺氧化物、山嵛醇聚醚-25、山嵛醇聚醚-30、山嵛酸、山嵛基甜菜碱、双-丁基聚二甲基硅氧烷聚甘油-3、丁基苯酚聚醚-5羧酸、丁基苯酚聚醚-19羧酸、丁基二甲基(羟丙基丁基葡糖苷)氯化铵、丁基二甲基(羟丙基月桂基葡糖苷)氯化铵、丁基葡糖苷、丁基葡糖苷癸酸酯、丁基葡糖苷类羟丙基三甲基氯化铵、丁基辛酸、C18-36酸、C20-40酸、C30-50酸、C16-22酸酰胺MEA、十二烷基苯磺酸钙、月桂酰牛磺酸钙、C9-16烷/环烷、C10-14烷基苯磺酸、C12-14烷基二(氨基乙基)甘氨酸HCl、C9-15醇磷酸酯、假丝酵母/葡萄糖/油菜籽油酸甲酯发酵产物、低芥酸菜子油酰胺丙基甜菜碱、癸酸、己酸、己酰基乙基葡糖苷、辛酰/癸酰氨丙基甜菜碱、辛醇聚醚-4羧酸、辛醇聚醚-6羧酸、辛醇聚醚-9羧酸、辛酸、辛酰胶原氨基酸类、辛酰甘氨酸、辛酰水解胶原、辛酰水解角蛋白、辛酰角蛋白氨基酸类、辛酰蚕丝氨基酸类、辛基/癸基葡糖苷、辛基/癸基小麦麸/秸苷类、辛基葡糖苷、辛基甘油基醚、辛基吡咯烷酮、肉碱、鲸蜡硬脂醇聚醚-20、鲸蜡硬脂醇聚醚-23、鲸蜡硬脂醇聚醚-24、鲸蜡硬脂醇聚醚-25、鲸蜡硬脂醇聚醚-27、鲸蜡硬脂醇聚醚-28、鲸蜡硬脂醇聚醚-29、鲸蜡硬脂醇聚醚-30、鲸蜡硬脂醇聚醚-33、鲸蜡硬脂醇聚醚-34、鲸蜡硬脂醇聚醚-40、鲸蜡硬脂醇聚醚-50、鲸蜡硬脂醇聚醚-55、鲸蜡硬脂醇聚醚-60、鲸蜡硬脂醇聚醚-80、鲸蜡硬脂醇聚醚-100、鲸蜡硬脂醇聚醚-25羧酸、鲸蜡硬脂醇聚醚-2磷酸酯、鲸蜡硬脂醇聚醚-4磷酸酯、鲸蜡硬脂醇聚醚-5磷酸酯、二鲸蜡硬脂醇聚醚-10磷酸酯、鲸蜡醇聚醚-20、鲸蜡醇聚醚-23、鲸蜡醇聚醚-24、鲸蜡醇聚醚-25、鲸蜡醇聚醚-30、鲸蜡醇聚醚-40、鲸蜡醇聚醚-45、鲸蜡醇聚醚-150、鲸蜡醇聚醚-8磷酸酯、鲸蜡醇聚醚-10磷酸酯、鲸蜡醇聚醚-20磷酸酯、鲸蜡油醇聚醚-22、鲸蜡油醇聚醚-24、鲸蜡油醇聚醚-25、鲸蜡油醇聚醚-30、鲸蜡基甜菜碱、毛华菊(CHRYSANTHEMUM SINENSE)花提取物、C12-14羟烷基羟乙基β-丙氨酸、C12-14羟烷基羟乙基肌氨酸、椰油酰胺乙基甜菜碱、椰油酰胺丙基胺氧化物、椰油酰胺丙基甜菜碱酰胺MEA氯化物、椰油酰胺丙基甜菜碱、椰油酰胺丙基羟基磺基甜菜碱、椰油胺氧化物、椰油氨基丁酸、椰油氨基丙酸、椰油醇聚醚-7羧酸、椰油醇聚醚-4葡糖苷、椰油酰两性基丙酸、椰油基甜菜碱酰胺基两性基丙酸盐、椰油基甜菜碱、椰油基二甲基铵羟丙基水解大米蛋白、椰油基二甲基铵羟丙基水解大豆蛋白、椰油基二甲基铵羟丙基水解小麦蛋白、椰油基葡糖苷、椰油基葡糖苷羟丙基三甲基氯化铵、椰油基羟基磺基甜菜碱、椰油基吗啉氧化物、椰油酸、椰子油甘油聚醚-8酯类、椰油酰/油酰胺丙基甜菜碱、椰油基-磺基甜菜碱、(椰油/葵花籽油)酰胺丙基甜菜碱、椰油酰胆碱甲基硫酸盐、椰油酰谷氨酸、椰油酰基水解胶原、椰油酰基水解角蛋白、椰油酰基水解燕麦蛋白、椰油酰水解大米蛋白、椰油酰基水解蚕丝、椰油酰基水解大豆蛋白、椰油酰基水解小麦蛋白、椰油酰肌氨酸、玉米油脂酸、棉籽油酸、棉籽油甘油聚醚-8酯类、C10-16链烷醇聚醚-1、C10-16链烷醇聚醚-2、C11-13链烷醇聚醚-6、C11-13链烷醇聚醚-9、C11-13链烷醇聚醚-10、C11-15链烷醇聚醚-30、C11-15链烷醇聚醚-40、C12-13链烷醇聚醚-1、C12-13链烷醇聚醚-23、C12-14链烷醇聚醚-5、C12-14链烷醇聚醚-9、C13-15链烷醇聚醚-21、C14-15链烷醇聚醚-8、C20-22链烷醇聚醚-30、C20-40链烷醇聚醚-40、C20-40链烷醇聚醚-95、C22-24链烷醇聚醚-33、C30-50链烷醇聚醚-40、C9-11链烷醇聚醚-6羧酸、C9-11链烷醇聚醚-8羧酸、C11-15链烷醇聚醚-7羧酸、C12-13链烷醇聚醚-5羧酸、C12-13链烷醇聚醚-7羧酸、C12-13链烷醇聚醚-8羧酸、C12-13链烷醇聚醚-12羧酸、C12-15链烷醇聚醚-7羧酸、C12-15链烷醇聚醚-8羧酸、C12-15链烷醇聚醚-12羧酸、C14-15链烷醇聚醚-8羧酸、C6-10链烷醇聚醚-4磷酸酯、C12-13链烷醇聚醚-2磷酸酯、C12-13链烷醇聚醚-10磷酸酯、C12-15链烷醇聚醚-6磷酸酯、C12-15链烷醇聚醚-8磷酸酯、C12-15链烷醇聚醚-10磷酸酯、C12-16链烷醇聚醚-6磷酸酯、C4-18全氟代烷基乙基巯丙基三甲基氯化铵、大花可可脂肪酰胺丙基甜菜碱、C12-13醇硫酸酯DEA盐、C12-15醇硫酸酯DEA盐、鲸蜡硬脂醇聚醚-2磷酸酯DEA盐、鲸蜡醇硫酸酯DEA盐、椰油酰两性基二丙酸DEA盐、C12-13链烷醇聚醚-3硫酸酯DEA盐、环羧丙基油酸DEA盐、十二烷基苯磺酸DEA盐、异硬脂酸DEA盐、月桂醇聚醚硫酸酯DEA盐、月桂醇硫酸酯DEA盐、亚油酸DEA盐、肉豆蔻酸甲酯磺酸DEA盐、肉豆蔻醇醚硫酸酯DEA盐、肉豆蔻酸DEA盐、肉豆蔻醇硫酸酯DEA盐、油醇聚醚-5磷酸酯DEA盐、油醇聚醚-20磷酸酯DEA盐、DEA PG-油酸酯、癸醇聚醚-7羧酸、癸醇聚醚-7葡糖苷、癸醇聚醚-9磷酸酯、癸基胺氧化物、癸基甜菜碱、十一烷基葡糖苷、癸基十四醇聚醚-30、癸基十四胺氧化物、月桂酰胺-MEA磺基琥珀酸酯二铵、月桂醇磺基琥珀酸酯二铵、油酰胺基PEG-2磺基琥珀酸酯二铵、二丁氧基甲烷、二C12-15链烷醇聚醚-2磷酸酯、二C12-15链烷醇聚醚-4磷酸酯、二C12-15链烷醇聚醚-6磷酸酯、二C12-15链烷醇聚醚-8磷酸酯、二C12-15链烷醇聚醚-10磷酸酯、双十二醇丁烷四甲酸酯、月桂醇聚醚硫酸酯二乙胺盐、磺基琥珀酸二乙基己酯钠、二(羟乙基)C8-10烷氧丙基胺氧化物、二(羟乙基)C9-11烷氧丙基胺氧化物、二(羟乙基)C12-15烷氧丙基胺氧化物、二(羟乙基)椰油胺氧化物、二(羟乙基)月桂基胺氧化物、二(羟乙基)硬脂胺氧化物、二(羟乙基)牛脂基胺氧化物、聚二甲基硅氧烷PEG-7磷酸酯、聚二甲基硅氧烷PEG-10磷酸酯、聚二甲基硅氧烷PEG/PPG-7/4磷酸酯、聚二甲基硅氧烷PEG/PPG-12/4磷酸酯、聚二甲基硅氧烷/聚甘油-3交联聚合物、聚二甲基硅氧烷丙基PG-甜菜碱、二肉豆蔻醇磷酸酯、二油酰胺乙基羟乙基甲基铵甲基硫酸盐、氢化椰油酸DIPA盐、羊毛脂酸DIPA盐、肉豆蔻酸DIPA盐、辛酰谷氨酸二钾、月桂醇磺基琥珀酸酯二钾、十一碳烯酰谷氨酸二钾、巴巴苏油酰胺基MEA-磺基琥珀酸二钠、癸酰两性基二乙酸二钠、癸酰两性基二丙酸二钠、辛酰两性基二乙酸二钠、辛酰两性基二丙酸二钠、辛酰谷氨酸二钠、鲸蜡硬脂醇磺基琥珀酸酯二钠、鲸蜡基苯基醚二磺酸二钠、鲸蜡醇磺基琥珀酸酯二钠、椰油酰胺基MEA-磺基琥珀酸酯二钠、椰油酰胺基MIPA PEG-4磺基琥珀酸酯二钠、椰油酰胺基MIPA-磺基琥珀酸酯二钠、椰油酰胺基PEG-3磺基琥珀酸酯二钠、椰油醇聚醚-3磺基琥珀酸酯二钠、椰油酰两性基羧乙基羟丙基磺酸二钠、椰油酰两性基二乙酸二钠、椰油酰两性基二丙酸二钠、椰油基-葡糖苷磺基琥珀酸酯二钠、椰油基-磺基琥珀酸酯二钠、椰油酰基丁基葡糖醇聚醚-10磺基琥珀酸酯二钠、椰油酰谷氨酸二钠、C12-14链烷醇聚醚-1磺基琥珀酸酯二钠、C12-14链烷醇聚醚-2磺基琥珀酸酯二钠、C12-15链烷醇聚醚磺基琥珀酸酯二钠、C12-14仲链烷醇聚醚-3磺基琥珀酸酯二钠、C12-14仲链烷醇聚醚-5磺基琥珀酸酯二钠、C12-14仲链烷醇聚醚-7磺基琥珀酸酯二钠、C12-14仲链烷醇聚醚-9磺基琥珀酸酯二钠、C12-14仲链烷醇聚醚-12磺基琥珀酸酯二钠、癸醇聚醚-5磺基琥珀酸酯二钠、癸醇聚醚-6磺基琥珀酸酯二钠、癸基苯基醚二磺酸二钠、二羟乙基磺基琥珀酰十一烯酸二钠、二椰油酰乙二胺PEG-15二硫酸酯二钠、氢化棉籽油甘油酯磺基琥珀酸酯二钠、氢化牛脂酰谷氨酸二钠、羟癸基山梨醇柠檬酸酯二钠、磺基琥珀酸异癸酯二钠、异硬脂酰胺MEA-磺基琥珀酸二钠、异硬脂酰胺MIPA-MEA-磺基琥珀酸二钠、异硬脂两性基二乙酸二钠、异硬脂两性基二丙酸二钠、异硬脂基磺基琥珀酸二钠、羊毛脂醇醚-5磺基琥珀酸酯二钠、月桂酰胺基MEA-磺基琥珀酸酯二钠、月桂酰胺基MIPA乙二醇磺基琥珀酸酯二钠、月桂酰胺基PEG-2磺基琥珀酸酯二钠、月桂酰胺基PEG-5磺基琥珀酸酯二钠、月桂醇聚醚-5羧基两性基二乙酸二钠、月桂醇聚醚-7柠檬酸酯二钠、月桂醇聚醚磺基琥珀酸酯二钠、月桂醇聚醚-6磺基琥珀酸酯二钠、月桂醇聚醚-9磺基琥珀酸酯二钠、月桂醇聚醚-12磺基琥珀酸酯二钠、月桂亚氨基双羟丙基磺酸二钠、月桂亚氨基二乙酸二钠、月桂亚氨基二丙酸二钠、月桂亚氨基二丙酸生育酚磷酸酯盐二钠、月桂酰两性基二乙酸二钠、月桂酰两性基二丙酸二钠、N-月桂酰基天冬氨酸二钠、月桂酰谷氨酸二钠、月桂基苯基醚二磺酸二钠、月桂醇磺基琥珀酸酯二铵、肉豆蔻酰胺MEA-磺基琥珀酸酯二钠、壬基苯酚聚醚-10磺基琥珀酸酯二钠、油酰胺MEA磺基琥珀酸酯二钠、油酰胺MIPA磺基琥珀酸酯二钠、油酰胺PEG-2磺基琥珀酸酯二钠、油酰两性基二丙酸二钠、油醇聚醚-3磺基琥珀酸酯二钠、油醇磷酸酯二钠、油醇磺基琥珀酸酯二钠、棕榈酰胺PEG-2磺基琥珀酸酯二钠、棕榈油酰胺基PEG-2磺基琥珀酸酯二钠、PEG-4椰油酰胺MIPA-磺基琥珀酸酯二钠、PEG-12聚二甲基硅氧烷磺基琥珀酸酯二钠、PEG-8棕榈油脂酸甘油酯类磺基琥珀酸酯二钠、PPG-2-异癸醇聚醚-7羧基两性基二乙酸钠、蓖麻醇酸酰胺MEA磺基琥珀酸酯二钠、谷甾醇聚醚-14磺基琥珀酸酯二钠、大豆油酰两性基二乙酸二钠、硬脂酰胺MEA-磺基琥珀酸酯二钠、硬脂亚氨基二丙酸二钠、硬脂酰两性基二乙酸二钠、硬脂酰谷氨酸二钠、磺基琥珀酸单酰硬脂胺二钠、硬脂醇磺基琥珀酸酯二钠、2-磺基月桂酸二钠、2-磺基棕榈酸二钠、妥尔油酰胺MEA磺基琥珀酸酯二钠、牛脂酰胺MEA磺基琥珀酸酯二钠、牛脂酰两性基二乙酸二钠、牛脂亚氨基双丙酸二钠、磺基琥珀酸单酰牛脂胺二钠、十三醇磺基琥珀酸酯二钠、十一碳烯酰胺MEA磺基琥珀酸酯二钠、十一碳烯酰胺PEG-2磺基琥珀酸酯二钠、十一碳烯酰谷氨酸二钠、单小麦胚油酰MEA磺基琥珀酸酯二钠、单小麦胚油酰胺PEG-2磺基琥珀酸酯二钠、麦胚油酰两性基二乙酸二钠、椰油酰胺二乙酸二-TEA盐、油酰胺基PEG-2磺基琥珀酸酯二-TEA盐、棕榈酰天冬氨酸二-TEA盐、双十三醇磺基琥珀酸酯钠、十二烷基苯磺酸、芥酸酰胺丙基羟基磺基甜菜碱、乙基己醇聚醚-3羧酸、乙基PEG-15椰油胺硫酸酯盐、辛基甘油基醚、己基癸酸、氢化椰油酸、氢化羊毛脂醇聚醚-25、氢化鲱油脂肪酸、氢化棕榈油酸、氢化棕榈仁油胺氧化物、氢化牛脂酸、氢化牛脂基胺氧化物、氢化牛脂基甜菜碱、氢化牛脂醇聚醚-25、氢化牛脂酰谷氨酸、氢化假丝酵母提取物、羟鲸蜡醇聚醚-60、羟乙基乙酰氧基甲基铵PG-聚二甲基硅氧烷、月桂醇聚醚硫酸酯羟乙基丁胺盐、羟乙基羧甲基椰油酰胺基丙胺、羟乙基羟丙基C12-15烷氧基丙胺氧化物、羟月桂基/羟肉豆蔻基甜菜碱、羟基硬脂酸、酰胺基羟基琥珀酰亚胺C10-40异烷酸乙基己酯、酰胺基羟基琥珀酰亚胺C21-22异烷酸乙基己酯、羟基磺基甜菜碱、IPDI/PEG-15大豆油胺氧化物、IPDI/PEG-15大豆油胺乙醇硫酸甲酯共聚物、IPDI/PEG-15大豆油甘氨酸酯共聚物、lsoceteth-30、异月桂醚-4磷酸酯、异聚甘油-3聚二甲基硅氧烷、异聚甘油-3聚二甲基硅氧烷、羊毛脂酸异丙醇胺酯、十二烷基苯磺酸异丙醇胺盐、异硬脂酰胺丙基胺氧化物、异硬脂酰胺丙基甜菜碱、异硬脂酰胺丙基吗啉氧化物、异硬脂醇聚醚-8、异硬脂醇聚醚-16、异硬脂醇聚醚-22、异硬脂醇聚醚-25、异硬脂醇聚醚-50、异硬脂酸、异硬脂酰基水解胶原、霍霍巴油PEG-150酯类、霍霍巴蜡PEG-80酯类、霍霍巴蜡PEG-120酯类、羊毛脂醇聚醚-20、羊毛脂醇聚醚-25、羊毛脂醇聚醚-40、羊毛脂醇聚醚-50、羊毛脂醇聚醚-60、羊毛脂醇聚醚-75、羊毛脂酸、月桂酰胺丙基胺氧化物、月桂酰胺丙基甜菜碱、月桂酰胺丙基羟磺基甜菜碱、月桂基胺氧化物、月桂氨基丙酸、月桂基二甲基羟丙基癸基葡糖苷氯化铵、月桂基二甲基月桂基葡糖苷羟丙基氯化铵、月桂醇聚醚-16、月桂醇聚醚-20、月桂醇聚醚-21、月桂醇聚醚-23、月桂醇聚醚-25、月桂醇聚醚-30、月桂醇聚醚-38、月桂醇聚醚-40、月桂醇聚醚-3羧酸、月桂醇聚醚-4羧酸、月桂醇聚醚-5羧酸、月桂醇聚醚-6羧酸、月桂醇聚醚-8羧酸、月桂醇聚醚-10羧酸、月桂醇聚醚-11羧酸、月桂醇聚醚-12羧酸、月桂醇聚醚-13羧酸、月桂醇聚醚-14羧酸、月桂醇聚醚-17羧酸、月桂醇聚醚-6柠檬酸酯、月桂醇聚醚-7柠檬酸酯、月桂醇聚醚-1磷酸酯、月桂醇聚醚-2磷酸酯、月桂醇聚醚-3磷酸酯、月桂醇聚醚-4磷酸酯、月桂醇聚醚-7磷酸酯、月桂醇聚醚-8磷酸酯、月桂醇聚醚-7酒石酸酯、月桂酸、月桂亚氨基双丙二醇、月桂亚氨基二丙酸、月桂酰两性基二丙酸、月桂酰β-氨基丙酸、月桂酰基胶原氨基酸、月桂酰乙基三甲基铵甲基硫酸酯盐、月桂酰水解胶原、月桂酰水解弹性蛋白、月桂酰甲基葡糖酰胺、月桂酰肌氨酸、月桂酰蚕丝氨基酸、月桂基甜菜碱、月桂基聚二甲基硅氧烷/聚甘油-3交联聚合物、月桂基二甲基羟丙基椰油基葡糖苷氯化铵、月桂基葡糖苷、月桂基葡糖苷羟丙基三甲基氯化铵、月桂甘醇羟丙基醚、月桂基羟基磺基甜菜碱、月桂基苹果酰胺、月桂基甲基萄糖胺、(月桂/肉豆蔻)基二醇羟丙基醚、(月桂/肉豆蔻)基小麦麸/秸苷类、月桂基聚甘油-3聚二甲基硅氧乙基聚二甲基硅氧烷、月桂基吡咯烷酮、月桂基二甲基磺基甜菜碱、亚油酸、亚麻酸、亚麻油酸、赖氨酸椰油酸盐、澳洲坚果籽油甘油聚醚-8酯类、椰油醇聚醚硫酸酯镁、椰油醇硫酸酯镁、异十二烷基苯基磺酸镁、月桂醇聚醚-11羧酸镁、月桂醇聚醚硫酸酯镁、月桂醇聚醚-5硫酸酯镁、月桂醇聚醚-8硫酸酯镁、月桂醇聚醚-16硫酸酯镁、月桂醇聚醚-3磺基琥珀酸酯镁、月桂基羟丙基磺酸镁、月桂醇硫酸酯镁、甲基椰油基牛磺酸镁、肉豆蔻醇聚醚硫酸酯镁、油醇聚醚硫酸酯镁、椰油醇硫酸酯镁/TEA盐、曼尼古根冰河泥、椰油酸MEA盐、月桂醇聚醚-6羧酸MEA、盐桂醇聚醚硫酸酯MEA盐,月桂醇硫酸酯MEA盐、PPG-6-月桂醇聚醚-7羧酸MEA盐、PPG-8-硬脂醇聚醚-7羧酸MEA盐、十一碳烯酸MEA盐、美罗沙波108、美罗沙波174、美罗沙波178、美罗沙波254、美罗沙波255、美罗沙波258、美罗沙波314、甲氧基PEG-450酰胺基戊二酰琥珀酰胺、甲氧基PEG-450酰胺基羟基琥珀酰亚胺琥珀酸酯、甲氧基PEG-450马来酰亚胺、甲基吗啉氧化物、牛奶酰胺丙基胺氧化物、牛奶酰胺丙基甜菜碱、貂油酰胺丙胺氧化物、貂油酰胺丙基甜菜碱、C12-15链烷醇聚醚硫酸酯MIPA盐、十二烷基苯磺酸MIPA盐、月桂醇聚醚硫酸酯MIPA盐、月桂醇硫酸酯MIPA盐、混合异丙醇胺羊毛脂酸盐、混合异丙醇胺月桂基硫酸盐、混合异丙醇胺肉豆蔻酸盐、吗啉油酸盐、吗啉硬脂酸盐、肉豆蔻醇聚醚-3羧酸、肉豆蔻醇聚醚-5羧酸、肉豆蔻基苄基二甲基氯化铵、肉豆蔻酰胺丙基胺氧化物、肉豆蔻酰胺丙基甜菜碱、肉豆蔻酰胺丙基二甲胺磷酸盐、肉豆蔻酰胺丙基羟磺基甜菜碱、肉豆蔻酰胺丙基PG-二甲基氯化铵磷酸酯、肉豆蔻胺氧化物、肉豆蔻氨基丙酸、肉豆蔻酸、肉豆蔻酰乙基三甲基铵甲基硫酸酯盐、肉豆蔻酰基谷氨酸、肉豆蔻酰基水解胶原、肉豆蔻酰肌氨酸、肉豆蔻基甜菜碱、肉豆蔻基/鲸蜡基胺氧化物、肉豆蔻基二甲基羟丙基椰油基葡糖苷氯化铵、肉豆蔻基葡糖苷、肉豆蔻醇磷酸酯、壬基酚聚醚-20、壬基酚聚醚-23、壬基酚聚醚-25、壬基酚聚醚-30、壬基酚聚醚-35、壬基酚聚醚-40、壬基酚聚醚-44、壬基酚聚醚-50、壬基酚聚醚-100、壬基酚聚醚-120、壬基酚聚醚-5羧酸、壬基酚聚醚-8羧酸、壬基酚聚醚-10羧酸、壬基酚聚醚-3磷酸酯、壬基酚聚醚-4磷酸酯、壬基酚聚醚-6磷酸酯、壬基酚聚醚-9磷酸酯、壬基酚聚醚-10磷酸酯、二壬基酚聚醚-30、二壬基酚聚醚-49、二壬基酚聚醚-100、二壬基酚聚醚-150、二壬基酚聚醚-7磷酸酯、二壬基酚聚醚-8磷酸酯、二壬基酚聚醚-9磷酸酯、二壬基酚聚醚-10磷酸酯、二壬基酚聚醚-11磷酸酯、二壬基酚聚醚-15磷酸酯、二壬基酚聚醚-24磷酸酯、燕麦油酰胺丙基甜菜碱、辛苯酚聚醚-16、辛苯酚聚醚-25、辛苯酚聚醚-30、辛苯酚聚醚-33、辛苯酚聚醚-40、辛苯酚聚醚-70、辛苯酚聚醚-20羧酸、辛基十二醇聚醚-20、辛基十二醇聚醚-25、辛基十二醇聚醚-30、油酰胺基丙胺氧化物、油酰胺丙基甜菜碱、油酰胺丙基(羟基磺基)丙基二甲基铵、油胺氧化物、油酸、油酰基水解胶原、油酰肌氨酸、油醇聚醚-20、油醇聚醚-23、油醇聚醚-24、油醇聚醚-25、油醇聚醚-30、油醇聚醚-35、油醇聚醚-40、油醇聚醚-44、油醇聚醚-50、油醇聚醚-3羧酸、油醇聚醚-6羧酸、油醇聚醚-10羧酸、油基甜菜碱、橄榄油酰胺丙胺氧化物、橄榄油酰胺丙基甜菜碱、橄榄油酸、橄榄油酰基水解小麦蛋白、麦冬提取物硬脂酸酯、臭氧化油醇聚醚-10、臭氧化PEG-10油酸酯、臭氧化PEG-14油酸酯、臭氧化聚山梨醇酯80、棕榈油酸、棕榈油酰胺丙基甜菜碱、棕榈油醇聚醚-2磷酸酯、棕榈酰胺丙基胺氧化物、棕榈酰胺丙基甜菜碱、棕榈胺氧化物、棕榈酸、棕榈酰胶原氨基酸类、棕榈酰甘氨酸、棕榈酰水解胶原、棕榈酰水解牛奶蛋白、棕榈酰水解小麦蛋白、棕榈酰角蛋白氨基酸类、棕榈酰寡肽、棕榈酰蚕丝氨基酸类、棕榈仁油酸、棕榈仁油酰胺丙基甜菜碱、桃仁油甘油聚醚-8酯类、花生油酸、PEG-10蓖麻油、PEG-40蓖麻油、PEG-44蓖麻油、PEG-50蓖麻油、PEG-54蓖麻油、PEG-55蓖麻油、PEG-60蓖麻油、PEG-80蓖麻油、PEG-100蓖麻油、PEG-200蓖麻油、PEG-11椰油酰胺、PEG-6椰油酰胺磷酸酯、PEG-4椰油胺、PEG-8椰油胺、PEG-12椰油胺、PEG-150二山嵛酸酯、PEG-90二异硬脂酸酯、PEG-75二月桂酸酯、PEG-150二月桂酸酯、PEG-75二油酸酯、PEG-150二油酸酯、PEG-75二硬脂酸酯、PEG-120二硬脂酸酯、PEG-150二硬脂酸酯、PEG-175二硬脂酸酯、PEG-190二硬脂酸酯、PEG-250二硬脂酸酯、PEG-30甘油椰油酸酯、PEG-40甘油椰油酸酯、PEG-78甘油椰油酸酯、PEG-80甘油椰油酸酯、PEG-30甘油异硬脂酸酯、PEG-40甘油异硬脂酸酯、PEG-50甘油异硬脂酸酯、PEG-60甘油异硬脂酸酯、PEG-90甘油异硬脂酸酯、PEG-23甘油月桂酸酯、PEG-30甘油月桂酸酯、PEG-25甘油油酸酯、PEG-30甘油油酸酯、PEG-30甘油大豆油酸酯、PEG-25甘油硬脂酸酯、PEG-30甘油硬脂酸酯、PEG-40甘油硬脂酸酯、PEG-120甘油硬脂酸酯、PEG-200甘油硬脂酸酯、PEG-28甘油脂牛油酸酯、PEG-80甘油脂牛油酸酯、PEG-82甘油脂牛油酸酯、PEG-130甘油脂牛油酸酯、PEG-200甘油脂牛油酸酯、PEG-45氢化蓖麻油、PEG-50氢化蓖麻油、PEG-54氢化蓖麻油、PEG-55氢化蓖麻油、PEG-60氢化蓖麻油、PEG-80氢化蓖麻油、PEG-100氢化蓖麻油、PEG-200氢化蓖麻油、PEG-30氢化羊毛脂、PEG-70氢化羊毛脂、PEG-50氢化棕榈油酰胺、PEG-2异硬脂酸酯、PEG-3异硬脂酸酯、PEG-4异硬脂酸酯、PEG-6异硬脂酸酯、PEG-8异硬脂酸酯、PEG-10异硬脂酸酯、PEG-12异硬脂酸酯、PEG-20异硬脂酸酯、PEG-30异硬脂酸酯、PEG-40异硬脂酸酯、PEG-26霍霍巴酸、PEG-40霍霍巴酸、PEG-15霍霍巴醇、PEG-26霍霍巴醇、PEG-40霍霍巴醇、PEG-35羊毛脂、PEG-40羊毛脂、PEG-50羊毛脂、PEG-55羊毛脂、PEG-60羊毛脂、PEG-70羊毛脂、PEG-75羊毛脂、PEG-85羊毛脂、PEG-100羊毛脂、PEG-150羊毛脂、PEG-75羊毛脂油、PEG-2月桂酰胺、PEG-3月桂基胺氧化物、PEG-20月桂酸酯、PEG-32月桂酸酯、PEG-75月桂酸酯、PEG-150月桂酸酯、PEG-70芒果籽油甘油酯类、PEG-20一缩甘露醇月桂酸酯、PEG-8甲基醚聚二甲基硅氧烷、PEG-120甲基葡糖二油酸酯、PEG-80甲基葡糖月桂酸酯、PEG-120甲基葡糖三油酸酯、PEG-4褐煤酸酯、PEG-30油胺、PEG-20油酸酯、PEG-23油酸酯、PEG-32油酸酯、PEG-36油酸酯、PEG-75油酸酯、PEG-150油酸酯、PEG-20棕榈酸酯、PEG-150聚甘油-2三硬脂酸酯、PEG/PPG-28/21乙酸酯聚二甲基硅氧烷、PEG/PPG-24/18丁基醚聚二甲基硅氧烷、PEG/PPG-3/17共聚物、PEG/PPG-5/35共聚物、PEG/PPG-8/55共聚物、PEG/PPG-10/30共聚物、PEG/PPG-10/65共聚物、PEG/PPG-12/35共聚物、PEG/PPG-16/17共聚物、PEG/PPG-20/9共聚物、PEG/PPG-20/20共聚物、PEG/PPG-20/60共聚物、PEG/PPG-20/65共聚物、PEG/PPG-22/25共聚物、PEG/PPG-28/30共聚物、PEG/PPG-30-35共聚物、PEG/PPG-30/55共聚物、PEG/PPG-35/40共聚物、PEG/PPG-50/40共聚物、PEG/PPG-150/35共聚物、PEG/PPG-160/30共聚物、PEG/PPG-190/60共聚物、PEG/PPG-200/40共聚物、PEG/PPG-300/55共聚物、PEG/PPG-20/22甲基醚聚二甲基硅氧烷、PEG-26-PPG-30磷酸酯、PEG/PPG-4/2丙基庚醚、PEG/PPG-6/2丙基庚醚、PEG-7/PPG-2丙基庚醚、PEG/PPG-8/2丙基庚醚、PEG/PPG-10/2丙基庚醚、PEG/PPG-14/2丙基庚醚、PEG/PPG-40/2丙基庚醚、PEG/PPG-10/2蓖麻醇酸酯、PEG/PPG-32/3蓖麻醇酸酯、PEG-55丙二醇油酸酯、PEG-25丙二醇硬脂酸酯、PEG-75丙二醇硬脂酸酯、PEG-120丙二醇硬脂酸酯、PEG-5油菜籽甾醇、PEG-10油菜籽甾醇、PEG-40蓖麻油酰胺、PEG-75牛油树脂甘油酯类、PEG-75娑罗双树脂甘油酯类、PEG-20失水山梨醇椰油酸酯、PEG-20失水山梨醇异硬脂酸酯、PEG-40失水山梨醇羊毛脂酸酯、PEG-75失水山梨醇羊毛脂酸酯、PEG-10失水山梨醇月桂酸酯、PEG-40失水山梨醇月桂酸酯、PEG-44失水山梨醇月桂酸酯、PEG-75失水山梨醇月桂酸酯、PEG-80失水山梨醇月桂酸酯、PEG-20失水山梨醇油酸酯、PEG-80失水山梨醇棕榈酸酯、PEG-40山梨坦硬脂酸酯、PEG-60山梨坦硬脂酸酯、PEG-160失水山梨醇三异硬脂酸酯、PEG-40大豆甾醇、PEG-2硬脂酰胺羧酸、PEG-9硬脂酰胺羧酸、PEG-20硬脂酸酯、PEG-23硬脂酸酯、PEG-25硬脂酸酯、PEG-30硬脂酸酯、PEG-32硬脂酸酯、PEG-35硬脂酸酯、PEG-36硬脂酸酯、PEG-40硬脂酸酯、PEG-45硬脂酸酯、PEG-50硬脂酸酯、PEG-55硬脂酸酯、PEG-75硬脂酸酯、PEG-90硬脂酸酯、PEG-100硬脂酸酯、PEG-120硬脂酸酯、PEG-150硬脂酸酯、PEG-45硬脂酸酯磷酸酯、PEG-20妥尔酸酯、PEG-50牛脂酰胺、PEG-2牛脂酰胺DEA、PEG-20牛脂酸酯、PEG-66三羟硬脂精、PEG-200三羟硬脂精、PEG-60山茶油酸酯甘油酯类、壬酸、十五烷基苯酚聚醚-200、苯酚聚醚-6磷酸酯、泊洛沙姆105、泊洛沙姆108、泊洛沙姆182、泊洛沙姆183、泊洛沙姆184、泊洛沙姆188、泊洛沙姆217、泊洛沙姆234、泊洛沙姆235、泊洛沙姆237、泊洛沙姆238、泊洛沙姆288、泊洛沙姆334、泊洛沙姆335、泊洛沙姆338、泊洛沙胺908、泊洛沙胺1508,聚二甲基硅氧PEG/PPG-24/19丁基醚硅倍半氧烷、聚二甲基硅氧PPG-13丁基醚硅倍半氧烷、聚甘油-6癸酸酯、聚甘油-10二月桂酸酯、聚甘油-20七辛酸酯、聚甘油-20六辛酸酯、聚甘油-2月桂醚、聚甘油-10月桂醚、Polyglyceryl-20Octaisononanoate、聚甘油-6五辛酸酯、聚甘油-10五辛酸酯、月桂基聚甘油-3聚二甲基硅氧乙基聚二甲基硅氧烷、聚甘油-6四辛酸酯、聚甘油-10四月桂酸酯、聚甘油-6三辛酸酯、聚甘油-10三月桂酸酯、聚季铵盐-77、聚季铵盐-78、聚季铵盐-79、聚季铵盐-80、聚季铵盐-81、聚季铵盐-82、库氏安匝木(POMADERRIS KUMERAHOU)花/叶提取物、茯苓(PORIA COCOS)提取物、枞酰水解胶原钾、巴巴苏油酸钾、山嵛酸钾、C9-15醇磷酸酯钾、C11-15醇磷酸酯钾、C12-13醇磷酸酯钾、C12-14醇磷酸酯钾、癸酸钾、辛酰谷氨酸二钾、辛酰基水解大米蛋白钾、蓖麻油酸钾、椰油酸钾、椰油酰谷氨酸钾、椰油酰甘氨酸钾、椰油酰水解酪蛋白钾、椰油酰水解胶原钾、椰油酰水解玉米蛋白钾、椰油酰水解角蛋白钾、椰油酰水解燕麦蛋白钾、椰油酰水解马铃薯蛋白钾、椰油酰水解米糠蛋白钾、椰油酰水解大米蛋白钾、椰油酰水解蚕丝钾、椰油酰水解大豆蛋白钾、椰油酰水解小麦蛋白钾、椰油酰水解酵母蛋白钾、椰油酰PCA钾、椰油酰肌氨酸钾、椰油酰牛磺酸钾、玉米油酸钾、环羧丙基油酸钾、二羟乙基椰油胺氧化物磷酸酯钾、聚二甲基硅氧烷PEG-7磷酸酯钾、十二烷基苯磺酸钾、大麻籽油酸钾、氢化椰油酸钾、氢化棕榈油酸钾、氢化牛脂酸钾、羟基硬脂酸钾、羟基硬脂酸钾、羊毛脂酸钾、月桂酸钾、月桂醇聚醚-3羧酸钾、月桂醇聚醚-4羧酸钾、月桂醇聚醚-5羧酸钾、月桂醇聚醚-6羧酸钾、月桂醇聚醚-10羧酸钾、月桂醇聚醚磷酸钾、月桂酰胶原氨基酸钾、月桂酰谷氨酸钾、月桂酰水解胶原钾、月桂酰水解豌豆蛋白钾、月桂酰水解大豆蛋白钾、月桂酰PCA钾、月桂酰豌豆氨基酸钾、月桂酰肌氨酸钾、月桂酰蚕丝氨基酸钾、月桂酰小麦氨基酸钾、月桂醇磷酸酯钾、月桂醇硫酸酯钾、亚油酸钾、偏磷酸钾、甲基椰油酰基牛磺酸钾、肉豆蔻酸钾、肉豆蔻酰谷氨酸钾、肉豆蔻酰水解胶原钾、辛基酚聚醚-12磷酸酯钾、油酸钾、油酰水解胶原钾、橄榄油酸钾、橄榄油酰水解燕麦蛋白钾、橄榄油酰水解小麦蛋白钾、橄榄油酰/月桂酰小麦氨基酸钾、橄榄油酰PCA钾、棕榈油酸钾、棕榈酸钾、棕榈酰水解玉米蛋白钾、棕榈酰水解燕麦蛋白钾、棕榈酰水解大米蛋白钾、棕榈酰水解甜杏仁蛋白钾、棕榈酰水解小麦蛋白钾、棕榈仁油酸钾、花生油酸钾、油菜籽油酸钾、蓖麻醇酸钾、红花油酸钾、大豆油酸钾、硬脂酸钾、硬脂酰水解胶原钾、妥尔油酸钾、牛脂酸钾、牛磺酸钾、牛磺酸钾月桂酸盐、十三醇聚醚-3羧酸钾、十三醇聚醚-4羧酸钾、十三醇聚醚-7羧酸钾、十三醇聚醚-15羧酸钾、十三醇聚醚-19羧酸钾、十三醇聚醚-6磷酸钾、十三醇聚醚-7磷酸钾、山茶油酸钾、十一烯酸钾、十一碳烯酰基水解胶原钾、十一碳烯酰水解大米蛋白钾、PPG-30-丁醇聚醚-30、PPG-36-丁醇聚醚-36、PPG-38-丁醇聚醚-37、PPG-30-辛醇聚醚-4磷酸酯、PPG-10鲸蜡基醚磷酸酯、PPG-2C9-11醇聚醚-8、PPG-1-癸醇聚醚-5、PPG-3-癸醇聚醚-2羧酸、PPG-30-乙基己醇聚醚-4磷酸酯、PPG-20-甘油聚醚-30、PPG-2羟乙基椰油/异硬脂酰胺、PPG-2-异癸醇聚醚-8、PPG-2-异癸醇聚醚-10、PPG-2-异癸醇聚醚-18、PPG-2-癸醇聚醚-25、PPG-4-癸醇聚醚-10、丙基三甲基铵水解胶原、季铵盐-24、季铵盐-52、季铵盐-87、油菜籽油酸、米糠酸、稻米油甘油聚醚-8酯类、蓖麻醇酸酰胺丙基甜菜碱、蓖麻醇酸、蓖麻油醇聚醚-40、红花油酸、Sapindus Oahuensis水果提取物、肥皂草(SAPONARIA OFFICINALIS)根粉、皂苷、钾皂、钠/钾皂、皂基、钾皂基、芝麻油甘油聚醚-8酯类、芝麻油酰胺丙基胺氧化物、芝麻酰胺丙基甜菜碱、牛油树脂酰胺丙基甜菜碱、牛油树脂甘油聚醚-8酯类、花生酸钠、Sodium Arganampohoacetate、木鲁星果棕油酸钠、鳄梨油酸钠、巴巴苏油酰基两性基乙酸钠、巴巴苏油酸钠、巴巴苏油硫酸酯钠、山嵛酸钠、双甘醇蓖麻醇酸基磺基琥珀酸酯钠、双羟乙基甘氨酸钠椰油基葡糖苷交联共聚物、双羟乙基甘氨酸钠月桂基葡糖苷交联共聚物、玻璃苣油酰胺丙基PG-二甲基氯化铵磷酸酯钠、丁基苯酚聚醚-12硫酸酯钠、丁基葡萄糖苷羟丙基磷酸钠、C13-17烷磺酸钠、C14-18烷磺酸钠、C12-15烷氧丙基亚氨基二丙酸钠、C10-16醇硫酸酯钠、C11-15烷基硫酸钠、C12-13烷基硫酸钠、C12-15烷基硫酸钠、C12-18烷基硫酸钠、C16-20烷基硫酸钠、C9-22仲烷基磺酸钠、C14-17仲烷基磺酸钠、癸酸钠、癸酰两性基乙酸钠、癸酰两性基羟丙基磺酸钠、癸酰两性基丙酸钠、癸酰甲基牛磺酸钠、辛酸钠、辛醇聚醚-2羧酸钠、辛醇聚醚-9羧酸钠、辛酰两性基乙酸钠、辛酰两性基羟丙基磺酸钠、辛酰两性基丙酸钠、辛酰谷氨酸二钠、辛酰水解小麦蛋白钠、辛基PG-磺酸钠、辛基磺酸钠、蓖麻油酸钠、鲸蜡硬脂醇聚醚-13羧酸钠、鲸蜡硬脂醇硫酸酯钠、鲸蜡醇聚醚-13羧酸钠、鲸蜡醇硫酸酯钠、椰油酰胺丙基PG-二甲基氯化铵磷酸酯钠、椰油基氨基丙酸钠、椰油醇聚醚硫酸酯钠、椰油醇聚醚-30硫酸酯钠、可可脂酰两性基乙酸钠、可可脂酸酯钠、椰油酰两性基乙酸钠、椰油酰两性基羟丙基磺酸钠、椰油酰两性基丙酸钠、椰油酸钠、椰油醇/巴巴苏油醇/安迪拉巴醇硫酸酯钠、椰油醇/巴巴苏油醇硫酸酯钠、椰油基葡糖苷羟丙基磷酸钠、椰油基葡糖苷羟丙基磺酸钠、椰油基-葡糖苷酒石酸酯钠、椰油醇甘油醚磺酸钠、椰油醇/氢化牛脂醇硫酸酯钠、椰油基亚氨基二乙酸钠、椰油酸单甘油酯硫酸酯钠、椰油酸单甘油酯磺酸酯钠、椰油脂基PG-二甲基氯化铵磷酸酯钠、椰油醇硫酸酯钠、椰油醇磺基乙酸酯钠、椰油酰氨基丙酸钠、椰油酰基氨基酸钠、椰油酰胶原氨基酸钠、椰油酰谷氨酸二钠、椰油酰谷氨酸钠、椰油酰甘氨酸钠、椰油酰/氢化牛脂谷氨酸钠、椰油酰解胶原钠、椰油酰水解角蛋白钠、椰油酰水解大米蛋白钠、椰油酰水解蚕丝钠、椰油酰水解大豆蛋白钠、椰油酰水解甜扁桃蛋白钠、椰油酰水解小麦蛋白谷氨酸钠、椰油酰水解小麦蛋白谷氨酸钠、椰油酰羟乙磺酸酯钠、椰油酰甲氨基丙酸钠、椰油酰燕麦氨基酸钠、Sodium椰油酰基/棕榈油酰基/Sunfloweroyl谷氨酸钠、椰油酰脯氨酸钠、椰油酰肌氨酸钠、椰油酰牛磺酸钠、椰油酰苏氨酸钠、椰油酰小麦氨基酸钠、C12-14烯烃磺酸钠、C14-16烯烃磺酸钠、C14-18烯烃磺酸钠、C16-18烯烃磺酸钠、玉米油酰两性基丙酸钠、棉花籽油酰基两性基乙酸钠、C13-15烷醇聚醚-8丁醇磷酸酯钠、C9-11烷醇聚醚-6羧酸钠、C11-15烷醇聚醚-7羧酸钠、C12-13烷醇聚醚-5羧酸钠、C12-13烷醇聚醚-8羧酸钠、C12-13烷醇聚醚-12羧酸钠、C12-15烷醇聚醚-6羧酸钠、C12-15烷醇聚醚-7羧酸钠、C12-15烷醇聚醚-8羧酸钠、C14-15烷醇聚醚-8羧酸钠、C12-14仲烷醇聚醚-8羧酸钠、C14-15烷醇聚醚-PG磺酸钠、C12-13烷醇聚醚-2磷酸钠、C13-15烷醇聚醚-8磷酸钠、C9-15烷醇聚醚-3硫酸钠、C10-15烷醇聚醚硫酸钠、C10-16烷醇聚醚-2硫酸钠、C12-13烷醇聚醚硫酸钠、C12-15烷醇聚醚硫酸钠、C12-15烷醇聚醚-3硫酸钠、C13-15烷醇聚醚-3硫酸钠、C12-14仲烷醇聚醚-3硫酸钠、C12-15烷醇聚醚-3磺酸钠、C12-15烷醇聚醚-7磺酸钠、C12-15烷醇聚醚-15磺酸钠、癸醇聚醚-2羧酸钠、癸醇聚醚硫酸酯钠、癸基苯磺酸钠、癸基葡萄糖苷羟丙基磷酸钠、癸基葡萄糖苷羟丙基磺酸钠、二(月桂醇聚醚-7)柠檬酸酯钠、二(月桂醇聚醚-10)磷酸酯钠、二亚油酰胺丙基PG-二甲基氯化铵磷酸酯钠、二聚亚油酸钠、二(油醇聚醚-8)磷酸酯钠、十二烷基苯磺酸钠、2-磺基月桂酸乙酯钠、甘油油酸酯磷酸酯钠、葡萄籽油酰胺丙基PG-二甲基氯化铵磷酸酯钠、葡萄籽油酰基两性基乙酸钠、葡萄籽油酸钠、大麻籽油酰两性基乙酸钠、己醇聚醚-4羧酸钠、氢化椰油酸钠、氢化椰油酰基甲基羟乙基磺酸钠、氢化棕榈油酸钠、氢化牛脂酸钠、氢化牛脂酰谷氨酸钠、羟月桂基二甲基铵乙基磷酸钠、棕榈仁油酸羟丙酯磺酸钠、磷酸羟丙酯癸基葡糖苷交联聚合物钠、磷酸羟丙酯月桂基葡糖苷交联聚合物钠、磺酸羟丙酯椰油基葡糖苷交联聚合物钠、磺酸羟丙酯癸基葡糖苷交联聚合物钠、磺酸羟丙酯月桂基葡糖苷交联聚合物钠、羟基硬脂酸钠、异硬脂酸钠、异硬脂醇聚醚-6羧酸钠、异硬脂醇聚醚-11羧酸钠、异硬脂酰两性基乙酸钠、异硬脂酰两性基丙酸钠、N-异硬脂酰甲基牛磺酸钠、羊毛脂醇聚醚硫酸酯钠、羊毛脂酸钠、猪油酸钠、月桂酰胺基二乙酸钠、月桂氨基丙酸钠、月桂酸钠、月桂醇聚醚-3羧酸钠、月桂醇聚醚-4羧酸钠、月桂醇聚醚-5羧酸钠、月桂醇聚醚-6羧酸钠、月桂醇聚醚-8羧酸钠、月桂醇聚醚-11羧酸钠、月桂醇聚醚-12羧酸钠、月桂醇聚醚-13羧酸钠、月桂醇聚醚-14羧酸钠、月桂醇聚醚-16羧酸钠、月桂醇聚醚-17羧酸钠、月桂醇聚醚硫酸酯钠、月桂醇聚醚-5硫酸酯钠、月桂醇聚醚-7硫酸酯钠、月桂醇聚醚-8硫酸酯钠、月桂醇聚醚-12硫酸酯钠、月桂醇聚醚-40硫酸酯钠,月桂醇聚醚-7酒石酸酯钠,月桂亚氨基二丙酸二钠、月桂亚氨基二丙酸二钠,月桂酰两性基羟丙基磺酸钠、月桂酰两性基PG-乙酸盐磷酸酯钠、月桂酰两性基丙酸钠、月桂酰天冬氨酸钠、月桂酰胶原氨基酸钠、月桂酰甘氨酸丙酸钠、月桂酰水解胶原钠、月桂酰水解蚕丝钠、月桂酰羟丙基磺酸钠、月桂酰羟乙磺酸钠、月桂酰基甲基氨基丙酸钠、月桂酰甲基羟乙基磺酸钠、月桂酰Millet氨基酸钠、月桂酰/肉豆蔻酰天冬氨酸钠、月桂酰燕麦氨基酸钠、月桂酰肌氨酸钠、月桂酰蚕丝氨基酸钠、月桂酰牛磺酸钠、月桂酰小麦氨基酸钠、月桂基二(亚乙基二氨基)氨基乙酸钠、月桂基葡萄糖羧酸钠、月桂基葡糖苷羟丙基磷酸钠、月桂基葡糖苷羟丙基磺酸钠、月桂基甘醇羧酸钠、月桂基羟乙酰胺硫酸酯钠、月桂醇磷酸酯二钠、月桂醇硫酸酯钠、月桂醇磺基乙酸酯钠、亚油酸钠、澳洲坚果籽油酸钠、芒果油酰两性基乙酸钠、芒果籽油酯钠盐、月桂醇聚醚-2磺基琥珀酸酯钠/MEA、甲氧基PPG-2乙酸钠、甲基椰油酰基牛磺酸钠、甲基月桂酰基牛磺酸钠、甲基肉豆蔻酰基牛磺酸钠、甲基油酰基牛磺酸钠、甲基棕榈酰基牛磺酸钠、甲基硬脂酰基牛磺酸钠、2-磺基月桂酸甲酯钠、2-磺基棕榈酸甲酯钠、异棕榈酰甲基牛磺酸钠、甲基牛磺酸椰油酰甲基牛磺酸酯钠、肉豆蔻醇聚醚硫酸钠、肉豆蔻酸钠、肉豆蔻酰两性基乙酸钠、肉豆蔻酰谷氨酸钠、肉豆蔻酰水解胶原钠、肉豆蔻酰羟乙磺酸钠、肉豆蔻酰肌氨酸钠、肉豆蔻醇硫酸酯钠、壬苯酚聚醚-6磷酸酯钠、壬苯酚聚醚-9磷酸酯钠、壬苯酚聚醚-1硫酸酯钠、壬苯酚聚醚-3硫酸酯钠、壬基酚聚醚-4硫酸酯钠、壬苯酚聚醚-6硫酸酯钠、壬苯酚聚醚-8硫酸酯钠、壬苯酚聚醚-10硫酸酯钠、壬苯酚聚醚-25硫酸酯钠、辛苯酚聚醚-2乙磺酸酯钠、辛苯酚聚醚-2硫酸酯钠、辛苯酚聚醚-6硫酸酯钠、辛苯酚聚醚-9硫酸酯钠、油酸钠、油酰两性基乙酸钠、油酰两性基羟丙基磺酸钠、油酰两性基丙酸钠、油酰水解胶原钠、油酰羟乙磺酸钠、油醇聚醚硫酸酯钠、油酰基甲基羟乙磺酸钠、油醇硫酸酯钠、橄榄油酰两性基乙酸钠、橄榄油酸钠、橄榄油酰谷氨酸钠、棕榈油酰两性基乙酸钠、棕榈油酸钠、棕榈油酸甘油酯磺酸钠、棕榈酸钠、棕榈酰水解胶原钠、棕榈酰水解小麦蛋白钠、棕榈酰肌氨酸钠、棕榈仁油酸钠、棕榈油酰羟乙磺酸钠、棕榈油酰谷氨酸钠、西番莲籽油酸钠、花生油酰两性基乙酸钠、花生油酸钠、PEG-6椰油酰胺羧酸钠、PEG-8椰油酰胺羧酸钠、PEG-4椰油酰胺硫酸酯钠、PEG-3月桂酰胺羧酸钠、PEG-4月桂酰胺羧酸钠、PEG-8棕榈油甘油酯类羧酸钠、季戊四醇羟丙基亚氨基二乙酸钠树形聚合物、丙氧基PPG-2乙酸钠、油菜籽油酸钠、米糠油酰两性基乙酸钠、蓖麻醇酸钠、蓖麻醇酸酰两性基乙酸钠、Sodium RoseHipsamphoacetate、松脂酸钠、红花油酸钠、Saffloweroyl水解大豆蛋白钠、芝麻籽油酸钠、芝麻油酰两性基乙酸钠、牛油树脂酰两性基乙酸钠、大豆油酸钠、大豆油酰水解胶原钠、硬酯酸钠、硬脂酰两性基乙酸钠、硬脂酰两性基羟丙基磺酸钠、硬脂酰两性基丙酸钠、硬脂酰酪蛋白钠、硬脂酰谷氨酸钠、硬脂酰透明质酸钠、硬脂酰水解胶原钠、硬脂酰水解玉米蛋白钠、硬脂酰水解蚕丝钠、硬脂酰水解大豆蛋白钠、硬脂酰水解小麦蛋白钠、硬脂酰乳清蛋白钠、Sodium硬脂酰甲基羟乙磺酸钠、硬脂酰燕麦蛋白钠、硬脂酰豌豆蛋白钠、硬脂酰大豆蛋白钠、硬脂基二甲基甘氨酸钠、硬脂醇硫酸酯钠、葵花籽油酰基两性基乙酸钠、枯草菌脂肽钠、甜扁桃油酰基两性基乙酸钠、甜杏仁油酸钠、妥尔油酰两性基丙酸钠、妥尔油酸钠、牛脂酰两性基乙酸钠、牛脂酸钠、牛脂醇硫酸酯钠、胡桐(CALLOPHYLLUM INOPHYLLUM)籽油酸钠、牛磺酸钠、椰油酰甲基牛磺酸牛磺酸钠、月桂酸牛磺酸钠、月桂酰胶原氨基酸钠/TEA盐、月桂酰水解胶原钠/TEA盐、月桂酰水解角蛋白盐钠/TEA盐、月桂酰基角蛋白氨基酸钠/TEA盐、十一碳烯酰胶原氨基酸钠/TEA盐、十一碳烯酰水解胶原钠/TEA盐、十一碳烯酰水解玉米蛋白钠/TEA盐、十一碳烯酰水解大豆蛋白钠/TEA盐、十一碳烯酰水解小麦蛋白钠/TEA盐、大花可可树(THEOBROMA GRANDIFLORUM)籽油酸钠、十三烷醇聚醚-3羧酸钠、十三烷醇聚醚-4羧酸钠、十三烷醇聚醚-6羧酸钠、十三烷醇聚醚-7羧酸钠、十三烷醇聚醚-8羧酸钠、十三烷醇聚醚-12羧酸钠、十三烷醇聚醚-15羧酸钠、十三烷醇聚醚-19羧酸钠、十三烷醇聚醚硫酸钠、十三烷基苯磺酸钠、十三烷醇硫酸酯钠、三羟甲基丙烷羟丙基亚氨基二乙酸钠树形聚合物、十一烷醇聚醚-5羧酸钠、十一碳烯酸钠、十一碳烯酰两性基乙酸钠、十一碳烯酰两性基丙酸钠、十一碳烯酰谷氨酸二钠、小麦胚油酰两性基乙酸钠、山梨醇聚醚-160三硬脂酸酯、大豆油酸、大豆油酰胺基丙胺氧化物、大豆油酰胺丙基甜菜碱、大豆油甘油聚醚-8酯类、异硬脂酰胺基丙胺氧化物、硬脂酰胺丙基甜菜碱、硬脂胺氧化物、硬脂醇聚醚-15、硬脂醇聚醚-16、硬脂醇聚醚-20、硬脂醇聚醚-21、硬脂醇聚醚-25、硬脂醇聚醚-27、硬脂醇聚醚-30、硬脂醇聚醚-40、硬脂醇聚醚-50、硬脂醇聚醚-80、硬脂醇聚醚-100、硬脂醇聚醚-2磷酸酯、硬脂醇聚醚-3磷酸酯、硬脂酸、硬脂氧丙基三甲基氯化铵、硬脂酰谷氨酸、硬脂酰肌氨酸、硬脂基甜菜碱、硬脂基二甲基丁基葡糖苷羟丙基氯化铵、硬脂基二甲基癸基葡糖苷羟丙基氯化铵、硬脂基二甲基月桂基葡糖苷羟丙基氯化铵、硫酸化蓖麻油、硫酸化椰油、硫酸化甘油油酸酯、硫酸化橄榄油、硫酸化花生油、葵花油酰胺MEA、葵花籽油酸、葵花籽油酰胺丙基羟乙基二甲基氯化铵、葵花籽油甘油聚醚-8酯类、妥尔油酸、牛脂酸、牛脂酰胺基丙基胺氧化物、牛脂酰胺基丙基甜菜碱、牛脂酰胺基丙基羟基磺基甜菜碱、牛脂基胺氧化物、牛脂基甜菜碱、牛脂基二羟乙基甜菜碱、牛脂酰乙基葡糖苷、枞酰水解胶原TEA盐、C12-14醇磷酸酯TEA盐、C10-15烷基硫酸TEA盐、C11-15醇硫酸酯TEA盐、C12-13烷基硫酸TEA盐、TEA-C12-14烷基硫酸TEA盐、TEA-C12-15烷基硫酸TEA盐、TEA C14-17仲烷基磺酸TEA盐、低芥酸菜子油酸TEA盐、椰油酰胺二乙酸TEA盐、椰油酸TEA盐、椰油醇硫酸酯TEA盐、椰油酰基丙氨酸TEA盐、椰油酰基谷氨酸TEA盐、椰油酰基谷氨酰胺TEA盐、椰油酰基甘氨酸TEA盐、椰油酰基水解胶原TEA盐、椰油酰基水解大豆蛋白TEA盐、椰油酰基肌氨酸TEA盐、聚二甲基硅氧烷PEG-7磷酸TEA盐、十二烷基苯磺酸TEA盐、氢化椰油酸TEA盐、氢化牛脂酰谷氨酸TEA盐、异硬脂酸TEA盐、TEA-异硬脂酰基水解胶原TEA盐、月桂氨基丙酸TEA盐、月桂酸TEA盐、月桂酸/肉豆蔻酸TEA盐、月桂醇聚醚硫酸酯TEA盐、月桂酰基胶原氨基酸TEA盐、月桂酰谷氨酸TEA盐、月桂酰水解胶原TEA盐、月桂酰基角蛋白氨基酸TEA盐、月桂酰基甲氨基丙酸TEA盐、月桂酰基/肉豆蔻酰基天冬氨酸TEA盐、月桂酰基肌氨酸TEA盐、月桂醇磷酸酯TEA盐、月桂醇硫酸酯TEA盐、肉豆蔻氨基丙酸TEA盐、肉豆蔻酸TEA盐、肉豆蔻酰基水解胶原TEA盐、油酸TEA盐、油酰基水解胶原TEA盐、油酰基肌氨酸TEA盐、油醇硫酸酯TEA盐、棕榈酸TEA盐、棕榈仁肌氨酸TEA盐、PEG-3椰油酰胺硫酸酯TEA盐、松脂酸TEA盐、硬脂酸TEA盐、妥尔酸TEA盐、十三烷基苯磺酸TEA盐、十一碳烯酸TEA盐、十一碳烯酰水解胶原TEA盐、四甲基癸炔二醇、二羧乙基硬脂基磺基琥珀酰胺酸四钠、月桂醇聚醚硫酸酯TIPA盐、月桂醇硫酸酯TIPA盐、肉豆蔻酸TIPA盐、硬脂酸TIPA盐、生育酚磷酸酯、海藻糖十一烯酸酯、TM-C12-15链烷醇聚醚-2磷酸酯、TM-C12-15链烷醇聚醚-6磷酸酯、TM-C12-15链烷醇聚醚-8磷酸酯、TM-C12-15链烷醇聚醚-10磷酸酯、十三醇聚醚-20、十三醇聚醚-50、十三醇聚醚-3羧酸、十三醇聚醚-4羧酸、十三醇聚醚-7羧酸、十三醇聚醚-8羧酸、十三醇聚醚-15羧酸、十三醇聚醚-19羧酸、十三醇聚醚-10磷酸酯、十三烷基苯磺酸、三(月桂醇聚醚-9)柠檬酸酯、三羟甲基丙烷羟丙基双羟乙胺树形聚合物、三(月桂酰两性基PG-乙酸钠氯化物)磷酸酯、十一烷酸、十一烷醇聚醚-5羧酸、十一碳烯酰胺丙基胺氧化物、十一碳烯酰胺丙基甜菜碱、十一烯酸、十一烯酰胶原氨基酸、十一碳烯酰甘氨酸、十一碳烯酰基水解胶原、十一碳烯酰基小麦氨基酸类、十一烷基葡糖苷、小麦胚芽油脂酸、小麦胚芽油酰胺丙基胺氧化物、小麦胚芽油酰胺丙基甜菜碱、西地格丝兰(YUCCA SCHIDIGERA)叶/根/茎提取物、西地格丝兰(YUCCA SCHIDIGERA)茎提取物、椰油醇聚醚硫酸酯锌和椰油醇硫酸酯锌。
优选的是选自组包括月桂醇聚醚硫酸酯钠、椰油酰胺丙基甜菜碱、椰油酰两性基乙酸钠、椰油基葡糖苷和月桂醇磺基琥珀酸酯铵的一种或更多种化合物。
表面活性剂在制剂中的百分比含量可以为0.1至10重量%,并且优选为0.5至5重量%,基于制剂计。
油体
适当的油体,其为O/W乳液的成分,是例如基于含有6至18个,优选8至10个碳原子的Guerbet醇,直链C6-C22-脂肪酸与直链或支链C6-C22-脂肪族醇的酯或支链C6-C13-羧酸与直链或支链C6-C22-脂肪族醇的酯,如例如肉豆蔻酸十四烷酯、棕榈酸十四烷酯、硬脂酸十四烷酯、异硬脂酸十四烷酯、油酸十四烷酯、山嵛酸十四烷酯、芥酸十四烷酯、肉豆蔻酸十六烷酯、棕榈酸十六烷酯、硬脂酸十六烷酯、异硬脂酸十六烷酯、油酸十六烷酯、山嵛酸十六烷酯、芥酸十六烷酯、肉豆蔻酸十八烷酯、棕榈酸十八烷酯、硬脂酸十八烷酯、异硬脂酸十八烷酯、油酸十八烷酯、山嵛酸十八烷酯、芥酸十八烷酯、肉豆蔻酸异十八烷酯、棕榈酸异十八烷酯、硬脂酸异十八烷酯、异硬脂酸异十八烷酯、油酸异十八烷酯、山嵛酸异十八烷酯、油酸异十八烷酯、油醇肉豆蔻酸酯、棕榈酸油醇酯、油醇硬脂酸酯、油醇异硬脂酸酯、油酸油醇酯、山嵛酸油醇酯、芥酸油醇酯、肉豆蔻酸二十二烷酯、棕榈酸二十二烷酯、硬脂酸二十二烷酯、异硬脂酸二十二烷酯、油酸二十二烷酯、山嵛酸二十二烷酯、芥酸二十二烷酯、肉豆蔻酸芥醇酯、棕榈酸芥醇酯、硬脂酸芥醇酯、异硬脂酸芥醇酯、油酸芥醇酯、山嵛酸芥醇酯和芥酸芥醇酯。此外适当的是直链C6-C22-脂肪酸与支链醇,特别是2-乙基己醇的酯、C18-C38-烷基羟基羧酸与直链或支链C6-C22-脂肪族醇的酯,特别是苹果酸二辛酯、直链和/或支链脂肪酸与多元醇(如例如丙二醇、二聚二元醇(Dimerdiol)或三聚三元醇(Trimertriol))和/或Guerbet醇的酯、基于C6-C10-脂肪酸的甘油三酯、基于C6-C18-脂肪酸的液态单-/二-/三酸甘油酯混合物、C6-C22-脂肪族醇和/或Guerbet醇与芳族羧酸,特别是苯甲酸的酯、C2-C12-二羧酸与具有1至22个碳原子的直链或支链醇或者具有2至10个碳原子和2至6个羟基的多元醇的酯、植物油、支链伯醇、取代环己烷、直链和支链C6-C22-脂肪族醇的碳酸酯,如例如碳酸二辛酯(CC)、基于具有6至18个优选8至10个碳原子的脂肪族醇的Guerbet碳酸酯、苯甲酸与直链和/或支链C6-C22-醇的酯(例如TN)、每个烷基具有6至22个碳原子的直链或支链、对称或非对称的二烷基醚,如例如二辛酰基醚(OE)、环氧化脂肪酸酯与多元醇的开环产物、硅油(环聚二甲基硅氧烷、硅酮甲基硅油等级等)和/或脂肪烃或环烷烃,如例如角鲨烷、角鲨烯或二烷基环己烷。
乳化剂
其他非离子或阳离子表面活性剂也可以作为乳化剂添加到制剂中,包括例如:
·2至30摩尔环氧乙烷和/或0至5摩尔环氧丙烷与直链C8-22脂肪族醇、与C12-22脂肪酸、与烷基中具有8-15个碳原子的烷基苯酚的加成产物;
·1至30摩尔环氧乙烷在甘油上的加成产物的C12/18脂肪酸单酯和二酯;
·含有6至22个碳原子的饱和和不饱和脂肪酸甘油单酯和二酯和脱水山梨糖醇单酯和二酯和它们的环氧乙烷加成产物;
·15至60摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·多元醇酯,尤其是聚甘油酯例如,聚甘油聚蓖麻醇酸酯、聚甘油聚-12-羟基硬脂酸酯或聚甘油二聚合油异硬脂酸酯。同样适用的是多个这类化合物的混合物;
·2至15摩尔环氧乙烷与蓖麻油和/或氢化蓖麻油的加成产物;
·基于直链、支链、不饱和或饱和C6/22脂肪酸、蓖麻油酸以及12-羟基硬脂酸和甘油、聚甘油、季戊四醇、二季戊四醇、糖醇(例如山梨糖醇)、烷基葡糖苷(例如:甲基葡糖苷、丁基葡糖苷、月桂基葡糖苷)以及多葡糖苷(例如纤维素)的偏酯;
·磷酸单-、二-和三烷酯类以及磷酸单-、二-和/或三-PEG烷酯类及其盐;
·羊毛蜡醇类;
·聚硅氧烷/聚烷基聚醚共聚物及相应衍生物;
·季戊四醇、脂肪酸、柠檬酸和脂肪族醇的混合脂和/或C6-22脂肪酸、甲基葡萄糖和多元醇,优选丙三醇或聚甘油的混合脂;
·聚二醇类以及
·碳酸甘油酯。
环氧乙烷和/或环氧丙烷与脂肪族醇、脂肪酸和烷基酚的加成产物,脂肪酸或蓖麻油的甘油单酯和二酯和脱水山梨糖醇单酯和二酯是市场上可以买到的产品。在这里是指同系混合物,其平均烷氧基化度相当于进行加成反应的环氧乙烷和/或环氧丙烷和基质的用量比例。环氧乙烷与甘油加成产物的C12/18脂肪酸单酯和二酯已知用作化妆制剂的富脂剂。优选的乳化剂在下文详细列出:
偏甘油酯。适当的偏甘油酯的典型实例是羟基硬脂酸单甘油酯、羟基硬脂酸二甘油酯、异硬脂酸单甘油酯、异硬脂酸二甘油酯、油酸单甘油酯、油酸二甘油酯、蓖麻酸单甘油酯、蓖麻酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、亚油酸单甘油酯、亚油酸二甘油酯、芥酸单甘油酯、芥酸二甘油酯、酒石酸单甘油酯、酒石酸二甘油酯、柠檬酸单甘油酯、柠檬酸二甘油酯、苹果酸单甘油酯、苹果酸二甘油酯及其仍含有少量源自生产过程的甘油三酯的技术混合物。1至30且优选5至10摩尔环氧乙烷与上述偏甘油酯的加成产物同样适当。
脱水山梨醇酯。适当的脱水山梨醇酯是脱水山梨醇单异硬脂酸酯、脱水山梨醇倍半异硬脂酸酯、脱水山梨醇二异硬脂酸酯、脱水山梨醇三异硬脂酸酯、脱水山梨醇单油酸酯、脱水山梨醇倍半油酸酯、脱水山梨醇二油酸酯、脱水山梨醇三油酸酯、脱水山梨醇单芥酸酯、脱水山梨醇倍半芥酸酯、脱水山梨醇二芥酸酯、脱水山梨醇三芥酸酯、脱水山梨醇单蓖麻酸酯、脱水山梨醇倍半蓖麻酸酯、脱水山梨醇二蓖麻酸酯、脱水山梨醇三蓖麻酸酯、脱水山梨醇单羟基硬脂酸酯、脱水山梨醇倍半羟基硬脂酸酯、脱水山梨醇二羟基硬脂酸酯、脱水山梨醇三羟基硬脂酸酯、脱水山梨醇单酒石酸酯、脱水山梨醇倍半酒石酸酯、脱水山梨醇二酒石酸酯、脱水山梨醇三酒石酸酯、脱水山梨醇单柠檬酸酯、脱水山梨醇倍半柠檬酸酯、脱水山梨醇二柠檬酸酯、脱水山梨醇三柠檬酸酯、脱水山梨醇单马来酸酯、脱水山梨醇倍半马来酸酯、脱水山梨醇二马来酸酯、脱水山梨醇三马来酸酯及其技术混合物。1至30且优选5至10摩尔环氧乙烷与上述脱水山梨醇酯的加成产物同样适当。
聚甘油酯。适当的聚甘油酯的典型实例是聚甘油-2二聚羟基硬脂酸酯(PGPH)、聚甘油-3-二异硬脂酸酯(TGI)、聚甘油-4异硬脂酸酯(GI 34)、聚甘油-3油酸酯、聚甘油-3二异硬脂酸酯(PDI)、聚甘油-3甲基葡糖二硬脂酸酯(Tego450)、聚甘油-3蜂蜡(Cera)、聚甘油-4癸酸酯(聚甘油癸酸酯T2010/90)、聚甘油-3鲸蜡基醚(NL)、聚甘油-3二硬脂酸酯(GS 32)和聚甘油聚蓖麻酸酯(WOL 1403)、聚甘油二异硬脂酸(polyglyceryl dimerate isostearate)酯及其混合物。其它适当的多元醇酯的实例是任选与1至30摩尔环氧乙烷反应的月桂酸、椰油酸、牛油酸、棕榈酸、硬脂酸、油酸、山嵛酸等与三羟甲基丙烷或季戊四醇的单酯、二酯和三酯。
四烷基季铵盐。水溶液中阳离子活性表面活性剂含有解离阳离子中表面活性所需的疏水高分子基团。阳离子表面活性剂的重要代表是通式(R1R2R3R4N+)X-的四烷基季铵盐。其中R1代表C1-C8烷(烯)基,R2、R3和R4,相互独立地代表含有1至22个碳原子的烷(烯)基。X是反离子,优选自卤素、烷基硫酸盐和烷基碳酸盐。特别优选阳离子表面活性剂,其中氮原子被两个长酰基和两个短烷(烯)基取代。
酯季铵盐。特别用作本发明的助表面活性剂的一组阳离子表面活性剂是所谓的酯季铵盐。酯季铵盐通常是指季铵化脂肪酸三乙醇胺酯盐。它们是已知化合物,可以通过制备有机化学的相关方法得到。在这方面参考国际专利申请WO 91/01295 A1,其中在次磷酸存在下三乙醇胺被脂肪酸部分酯化,将空气通过反应混合物,随后整体用硫酸二甲酯或环氧乙烷季铵化。此外,德国专利DE 4308794 C1记载了一种制备固体酯季铵盐的方法,其中三乙醇胺酯的季铵化在适当分散剂,优选脂肪醇的存在下进行。
根据本发明适当使用的酯季铵盐的典型实例是一种产品,其酰基成分源自对应于式RCOOH的单羧酸,其中RCO是含有6至10个碳原子的酰基,并且氨基成分是三乙醇胺(TEA)。这类单羧酸的实例是己酸、辛酸、癸酸及其技术混合物,如例如所谓的头分馏脂肪酸。优选使用的酯季铵盐,其酰基成分源自含有8至10个碳原子的单羧酸。其他酯季铵盐是那些产物,其酰基成分源自二元碳酸如丙二酸、琥珀酸、马来酸、富马酸、戊二酸、山梨酸、庚二酸、壬二酸、癸二酸和/或十二烷二酸,但优选己二酸。总之优选其酰基源自含有6至22个碳原子的单羧酸和己二酸的混合物的酯季铵盐。在最终的酯季铵盐中单羧酸和二元羧酸的摩尔比为1:99至99:1并且优选50:50至90:10并且特别是70:30至80:20。除了季铵化脂肪酸三乙醇胺酯盐,其他适当的酯季铵盐是单/二元羧酸混合物与二乙醇烷基胺或1,2-二羟基丙基二烷基胺。酯季铵盐可以由脂肪酸和相应的甘油三酯与相应二元羧酸混合得到。一种这类方法,其可以为被看为相关现有技术的代表,记载于欧洲专利EP 0750606 B1。为了生产季铵化酯,单和二元羧酸和三乙醇胺的混合物—基于可用的羧基功能—摩尔比可以为1.1:1至3:1。考虑到酯季铵盐的性能,已经证明特别有利的比例是1.2:1至2.2:1,并且优选1.5:1至1.9:1。优选的酯季铵盐是平均酯化度为1.5至1.9的单、二和三酯的技术混合物。
富脂剂和稠度因子
富脂剂可以选自物质如,例如羊毛脂和卵磷脂以及聚乙氧基化或酰基化羊毛脂和卵磷脂衍生物、多元醇脂肪酸酯、单甘油酯和脂肪酸烷醇酰胺,其中脂肪酸烷醇酰胺也可用作泡沫稳定剂。
使用的主要稠度因子是含有12至22个并且优选16至18个碳原子的脂肪族醇或羟基脂肪族醇以及偏甘油酯、脂肪酸或羟基脂肪酸。优选使用这些物质与烷基寡葡萄糖苷和/或相同链长的脂肪酸N-甲基葡糖酰胺和/或聚甘油聚-12-羟基硬脂酸酯的结合物。
增稠剂和流变添加剂
适当的增稠剂是聚合物增稠剂,如类(亲水性二氧化硅)、多糖,更特别是黄原胶、瓜尔胶、琼脂、藻酸盐和纤基乙酸钠(tyloses)、羧甲基纤维素和羟乙基和羟丙基纤维素、以及脂肪酸的相对高分子量聚乙二醇单酯和二酯、聚丙烯酸酯(例如[Goodrich]或[Sigma])、聚丙烯酰胺、聚乙烯醇和聚乙烯吡咯烷酮、表面活性剂如,例如乙氧基化脂肪酸甘油酯、脂肪酸与多元醇,如季戊四醇或三羟甲基丙烷的酯、窄同系物分布的脂肪族醇乙氧基化物和电解质,如氯化钠和氯化铵。
聚合物
合适的阳离子聚合物是例如阳离子纤维素衍生物,例如可从Amerchol以PolymerJR的名称获得的季铵化羟乙基纤维素、阳离子淀粉、二烯丙基铵盐和丙烯酰胺的共聚物、季铵化乙烯基吡咯烷酮/乙烯基咪唑聚合物,例如(BASF)、聚乙二醇和胺的缩合物、季铵化胶原多肽,例如月桂基二铵羟丙基水解胶原蛋白(L,Grünau)、季铵化小麦多肽、聚乙烯亚胺、阳离子有机硅聚合物,例如氨基聚二甲基硅氧烷、己二酸和二甲氨基羟丙基二亚乙基三胺的共聚物(Sandoz)、丙烯酸与二甲基二烯丙基氯化铵的共聚物(550,Chemviron)、聚氨基聚酰胺及其交联水溶性聚合物、阳离子几丁质衍生物,例如季铵化壳聚糖,任选微晶分布、二卤代烷,例如二溴丁烷,与双二烷基胺,例如双二甲氨基-1,3-丙烷的缩合产物、阳离子瓜尔胶如,的CBS、C-17、C-16、季铵盐聚合物,例如Miranol的A-15、AD-1、AZ-1、和可以在市场上以商品名CC或300找到的各种聚季铵盐类型(例如6、7、32或37)。
合适的阴离子、两性离子、两性和非离子聚合物是例如乙酸乙烯酯/巴豆酸共聚物、乙烯基吡咯烷酮/丙烯酸乙烯酯共聚物、乙酸乙烯酯/马来酸丁酯/丙烯酸异冰片酯共聚物、甲基乙烯基醚/马来酸酐共聚物及其酯、未交联和多元醇交联的聚丙烯酸、丙烯酰胺丙基三甲基氯化铵/丙烯酸酯共聚物、辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁基氨基乙酯/甲基丙烯酸2-羟丙酯共聚物、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯/乙烯基己内酰胺三元共聚物和任选衍生的纤维素醚和有机硅。
珠光蜡
适当的珠光蜡是例如,烷二醇酯,尤其是乙二醇二硬脂酸酯;脂肪酸烷醇酰胺,尤其是椰油脂肪酸二乙醇酰胺;偏甘油酯,尤其是硬脂酸单甘油酯;多元、任选羟基取代的羧酸与具有6-22个碳原子的脂肪族醇的酯,尤其是酒石酸的长链酯;具有总计至少24个碳原子的脂肪物质,如例如脂肪族醇、脂肪酮、脂肪醛、脂肪醚和脂肪碳酸酯,尤其是月桂酮和二硬脂醚;脂肪酸如硬脂酸、羟基硬脂酸或山嵛酸、具有12-22个碳原子的环氧烯烃与具有12-22个碳原子的脂肪族醇和/或具有2-15个碳原子和2-10个羟基的多元醇的开环产物、及其混合物。
硅酮
适当的硅酮选自组包括:茶碱甲基硅烷醇甘露糖醛酸酯、乙酰甲硫氨酰基甲基硅烷醇弹性蛋白酯丙烯酸(酯)类/山嵛醇丙烯酸酯、丙烯酸(酯)类/山嵛醇甲基丙烯酸酯/聚二甲基硅氧烷甲基丙烯酸酯共聚物、丙烯酸(酯)类/山嵛醇甲基丙烯酸酯/聚二甲基硅氧烷甲基丙烯酸酯共聚物、丙烯酸(酯)类/双羟丙基聚二甲基硅氧烷交联聚合物、丙烯酸(酯)类/聚二甲基硅氧烷共聚物、丙烯酸(酯)类/聚二甲基硅氧烷甲基丙烯酸酯/丙烯酸乙基己酯共聚物、丙烯酸(酯)类/聚二甲基硅氧烷醇丙烯酸酯共聚物、丙烯酸(酯)类/丙烯酸乙基己酯/聚二甲基硅氧烷甲基丙烯酸酯共聚物、丙烯酸(酯)类/辛基丙烯酰胺/二苯基氨端聚二甲基硅氧烷共聚物、丙烯酸(酯)类/聚三甲基硅氧烷甲基丙烯酸酯共聚物、丙烯酸(酯)类/丙基聚三甲基硅氧烷甲基丙烯酸酯共聚物、丙烯酸(酯)类/硬脂醇丙烯酸酯/聚二甲基硅氧烷甲基丙烯酸酯共聚物、丙烯酸(酯)类/十三醇丙烯酸酯/三乙氧基甲硅烷基丙醇甲基丙烯酸酯/聚二甲基硅氧烷甲基丙烯酸酯共聚物、丙烯酸(酯)类/甲基丙烯酸三氟丙酯/聚三甲基硅氧烷甲基丙烯酸酯共聚物、氨基双丙基聚二甲基硅氧烷、氨乙基氨丙基聚二甲基硅氧烷、氨丙基聚二甲硅氧烷、氨丙基苯基聚三甲基硅氧烷、氨丙基三乙氧基硅烷、聚二甲基硅氧烷PEG-7硫酸酯铵、氨端聚二甲基硅氧烷、氨端聚二甲基硅氧烷羟基硬脂酸盐、氨端聚二甲基硅氧烷/硅倍半氧烷共聚物、抗坏血酸羧癸基三硅氧烷、抗坏血酸甲基硅烷醇果胶酸酯、山嵛氧基聚二甲基硅氧烷、山嵛基三甲基铵聚二甲基硅氧烷PEG-8邻苯二甲酸酯、山嵛基聚二甲基硅氧烷、双氨基PEG/PPG-41/3氨乙基PG-丙基聚二甲基硅氧烷、双-氨丙基/乙氧基氨丙基聚二甲基硅氧烷、双(苯甲酸丁酯)二氨基三嗪氨丙基三硅氧烷、双-丁基聚二甲基硅氧烷聚甘油-3、双-丁氧基氨端聚二甲基硅氧烷/PEG-60共聚物、双(C13-15烷氧基)羟基丁酰胺基氨端聚二甲基硅氧烷、双(C13-15烷氧基)PG-氨端聚二甲基硅氧烷、双-(C1-8烷基月桂酰赖氨酸癸基甲酰胺)聚二甲基硅氧烷、双-鲸蜡基鲸蜡基聚二甲基硅氧烷、双-鲸蜡基/PEG-8鲸蜡基PEG-8二甲基硅氧烷、双-二苯乙基二聚硅氧烷、双-乙基乙基聚甲基硅氧烷、双-葡糖酰胺乙基-氨丙基二聚硅氧烷、双-氢聚二甲基硅氧烷、双-羟基乙氧基丙基二聚硅氧烷双-羟月桂基、聚二甲基硅氧烷/IPDI共聚物、双-羟基/甲氧基氨端聚二甲基硅氧烷、双-羟基丙基二甲基硅氧烷山嵛酸酯、双-羟基丙基聚二甲基硅氧烷/SMDI共聚物、双-异丁基PEG-14/聚二甲基硅氧烷共聚物、双-异丁基PEG-15/聚二甲基硅氧烷共聚物、双-异丁基PEG/PPG-20/35/聚二甲基硅氧烷共聚物、双-异丁基PEG/PPG-10/7/聚二甲基硅氧烷共聚物、双-异丁基PEG-24/PPG-7/二聚二甲基硅氧烷共聚物、双-PEG-1聚二甲基硅氧烷、双-PEG-4聚二甲基硅氧烷、双-PEG-8聚二甲基硅氧烷、双-PEG-12聚二甲基硅氧烷、双-PEG-20聚二甲基硅氧烷、双-PEG-12聚二甲基硅氧烷蜂蜡酸酯、双-PEG-12聚二甲基硅氧烷坎地利拉蜡酸酯、双-PEG-15聚二甲基硅氧烷/IPDI共聚物、双-PEG-15甲醚聚二甲基硅氧烷、双-PEG-18甲基醚二甲基硅烷、双-PEG/PPG-14/14聚二甲基硅氧烷、双-PEG/PPG-15/5聚二甲基硅氧烷、双-PEG/PPG-18/6聚二甲基硅氧烷、双-PEG/PPG-20/20聚二甲基硅氧烷、双-PEG/PPG-16/16PEG/PPG-16/16聚二甲基硅氧烷、双-PEG/PPG-20/5PEG/PPG-20/5聚二甲基硅氧烷、双苯基六甲基硅氧烷、双-苯丙基聚二甲基硅氧烷、双聚乙烯聚二甲基硅氧烷、双(聚甘油-3羟苯基丙基)聚二甲硅氧烷、双-(聚甘油-7羟苯基丙基)聚二甲基硅氧烷、双-PPG-15聚二甲基硅氧烷/IPDI共聚物、双(PPG-7十一碳烯醇聚醚-21)聚二甲基硅氧烷、双-硬脂基聚二甲基硅氧烷、双-三甲氧硅乙基四甲基二硅氧乙基聚二甲基硅氧烷、双-乙烯基聚二甲基硅氧烷、双-乙烯基聚二甲基硅氧烷/聚二甲基硅氧烷共聚物、玻璃苣籽油PEG-7聚二甲基硅氧烷酯类、丙烯酸丁酯/C6-14全氟代烷基乙醇丙烯酸酯/巯丙基聚二甲基硅氧烷共聚物、丙烯酸丁酯/羟丙基聚二甲基硅氧烷丙烯酸酯共聚物、丁基聚二甲基硅氧烷丙烯酸酯/甲基丙烯酸环己酯/丙烯酸乙基己酯共聚物、丁基聚二甲基硅氧烷甲基丙烯酸酯/甲基丙烯酸甲酯交联聚合物、叔丁基二甲基甲硅烷葡萄籽提取物、丁基聚二甲基硅氧烷乙烯/丙烯/乙烯降冰片烯共聚物、C6-8烷基C3-6烷基葡糖苷聚二甲基硅氧烷、C20-24烷基聚二甲基硅氧烷、C24-28烷基聚二甲基硅氧烷、C26-28烷基聚二甲基硅氧烷、C30-45烷基聚二甲基硅氧烷、C30-60烷基聚二甲基硅氧烷、C32烷基聚二甲基硅氧烷、C30-45烷基聚二甲基硅氧烷/聚环己烯氧化物交联聚合物、C26-28烷醇二甲基甲硅烷聚丙基硅倍半氧烷、C30-45烷醇二甲基甲硅烷聚丙基硅倍半氧烷、C20-24烷基聚甲基硅氧烷、C24-28烷基聚甲基硅氧烷、C26-28烷基聚甲基硅氧烷、C30-45烷基聚甲基硅氧烷、C20-28烷基全氟癸基乙氧基聚二甲基硅氧烷、C26-54烷基十四烷剂聚二甲基硅氧烷、辛基聚二甲基硅氧烷、辛基聚二甲基硅氧烷乙氧基葡糖苷、辛基聚甲基硅氧烷、辛基聚三甲基硅氧烷、羧癸基三硅氧烷、蓖麻油双-羟丙基聚二甲基硅氧烷酯类、蜡基聚二甲基硅氧烷、鲸蜡硬脂基聚二甲基硅氧烷交联聚合物、鲸蜡硬脂基聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物、鲸蜡硬脂基聚甲基硅氧烷、西曲铵羧癸基PEG-8聚二甲基硅氧烷盐、西曲铵聚二甲基硅氧烷PEG-7邻苯二甲酸酯盐、鲸蜡基山嵛醇聚二甲基硅氧烷盐、鲸蜡基聚二甲基硅氧烷、鲸蜡基聚二甲基硅氧烷/双乙烯基聚二甲硅氧烷交联聚合物、鲸蜡基二十六烷基聚二甲基硅氧烷、鲸蜡氧基聚二甲基硅氧烷、鲸蜡基PEG-8聚二甲基硅氧烷、鲸蜡基PEG/PPG-15/15丁基醚聚二甲基硅氧烷、鲸蜡基PEG/PPG-7/3聚二甲基硅氧烷、鲸蜡基PEG/PPG-10/1聚二甲基硅氧烷、鲸蜡基三乙基铵聚二甲基硅氧烷PEG-8邻苯二甲酸酯、鲸蜡基三乙基铵聚二甲基硅氧烷PEG-8琥珀酸酯、乙酰酪氨酸铜甲基硅烷醇、PCA甲基硅烷醇铜、C4-14全氟代烷基乙氧基聚二甲基硅氧烷、环乙氧基聚甲基硅氧烷、环庚硅氧烷、环己硅氧烷、环聚二甲基硅氧烷、环五聚二甲基硅氧烷、环苯基聚甲基硅氧烷、环四聚二甲基硅氧烷、环乙烯基聚甲氧基硅烷、胱氨酸双-PG-丙基硅烷三醇、DEA PG-丙基PEG/PPG-18/21聚二甲基硅氧烷、二异硬脂酰基三羟甲基丙烷硅烷氧基硅酸酯、二月桂酰基三羟甲基丙烷硅氧烷基硅酸酯、二聚亚油酰胺丙基二甲胺聚二甲硅氧烷PEG-7磷酸酯、聚二甲基硅氧烷、聚二甲基硅氧烷交联聚合物、聚二甲基硅氧烷交联聚合物-3、聚二甲基硅氧烷/二乙烯基聚二甲硅氧烷/硅倍半氧烷交联聚合物、聚二甲基硅氧烷乙氧基葡糖苷、聚二甲基硅氧烷羟丙基三甲基氯化铵、聚二甲基硅氧烷/巯丙基聚甲基硅氧烷共聚物、聚二甲基硅氧烷PEG-15乙酸酯、聚二甲基硅氧烷PEG-8己二酸酯,聚二甲基硅氧烷PEG-7鳄梨油酸酯、聚二甲基硅氧烷PEG-8鳄梨油酸酯、聚二甲基硅氧烷PEG-8蜂蜡酸酯、聚二甲基硅氧烷PEG-8苯甲酸酯、聚二甲基硅氧烷PEG-8玻璃苣油酸酯、聚二甲基硅氧烷PEG-7椰油酸酯、聚二甲基硅氧烷/PEG-10交联聚合物、聚二甲基硅氧烷PEG-10/15交联聚合物、聚二甲基硅氧烷PEG-15交联聚合物、聚二甲基硅氧烷PEG-7异硬脂酸酯、聚二甲基硅氧烷PEG-8异硬脂酸酯、聚二甲基硅氧烷PEG-7乳酸酯、聚二甲基硅氧烷PEG-8羊毛脂酸酯、聚二甲基硅氧烷PEG-8月桂酸酯、聚二甲基硅氧烷PEG-8白池花籽油酸酯、聚二甲基硅氧烷PEG-7辛基十二醇柠檬酸酯、聚二甲基硅氧烷PEG-7橄榄油酸酯、聚二甲基硅氧烷PEG-8橄榄油酸酯、聚二甲基硅氧烷PEG-7磷酸酯、聚二甲基硅氧烷PEG-8磷酸酯、聚二甲基硅氧烷PEG-10磷酸酯、聚二甲基硅氧烷PEG-7邻苯二甲酸酯、聚二甲基硅氧烷PEG-8邻苯二甲酸酯、聚二甲基硅氧烷PEG-8聚丙烯酸酯、聚二甲基硅氧烷PEG/PPG-20/23苯甲酸酯、聚二甲基硅氧烷PEG/PPG-7/4磷酸酯、聚二甲基硅氧烷PEG/PPG-12/4磷酸酯、聚二甲基硅氧烷PEG-7琥珀酸酯、聚二甲基硅氧烷PEG-8琥珀酸酯、聚二甲基硅氧烷PEG-7硫酸酯,聚二甲基硅氧烷PEG-7十一酸酯、聚二甲基硅氧烷PG-二乙基甲基氯化铵、聚二甲基硅氧烷/苯基乙烯基聚二甲硅氧烷交联聚合物、聚二甲基硅氧烷/聚甘油-3交联聚合物、聚二甲基硅氧烷/PPG-20交联聚合物、聚二甲基硅氧烷丙基乙二胺山嵛酸盐、聚二甲基硅氧烷丙基PG-甜菜碱、聚二甲基硅氧烷/硅倍半氧烷共聚物、甲硅烷基化聚二甲基硅氧烷、聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物、聚二甲基硅氧烷/乙烯基三甲基硅烷氧基硅酸酯交联聚合物、聚二甲基硅氧烷醇、聚二甲基硅氧烷醇精氨酸、聚二甲基硅氧烷醇蜂蜡酸酯、聚二甲基硅氧烷醇山嵛酸酯、聚二甲基硅氧烷醇玻璃苣酸酯、聚二甲基硅氧烷醇小烛树蜡酸酯、聚二甲基硅氧烷醇巴西棕榈酸酯、聚二甲基硅氧烷醇半胱氨酸、聚二甲基硅氧烷醇德鲁巴脂酸酯、聚二甲基硅氧烷醇氟代醇二聚亚油酸聚酯、聚二甲基硅氧烷醇羟基硬脂酸酯、聚二甲基硅氧烷醇印度赤铁树脂酸酯、聚二甲基硅氧烷醇/IPDI共聚物、聚二甲基硅氧烷醇异硬脂酸酯、聚二甲基硅氧烷醇烛果脂酸酯、聚二甲基硅氧烷醇乳酸酯、聚二甲基硅氧烷醇白池花籽油酸酯、聚二甲基硅氧烷醇蛋氨酸、聚二甲基硅氧烷醇/甲基硅烷醇/硅酸酯交联聚合物、聚二甲基硅氧烷醇长叶雾冰藜木脂酸酯、聚二甲基硅氧烷醇泛醇、聚二甲基硅氧烷醇柳安脂酸酯、聚二甲基硅氧烷/硅石交联聚合物、聚二甲基硅氧烷醇/硅倍半氧烷共聚物、聚二甲基硅氧烷醇硬脂酸酯、聚二甲基硅氧烷醇/硬脂基聚甲基硅氧烷/苯基聚三甲基硅氧烷共聚物、二甲氧硅烷基亚乙基二氨丙基聚二甲基硅氧烷、二甲氨基丙酰胺基PCA聚二甲基硅氧烷、二甲基氧代苯并二噁硅烷、二甲基甲硅烷醇透明质酸酯、二油基生育酚甲基硅烷醇、二苯基氨端聚二甲基硅氧烷、二苯基聚二甲基硅氧烷、二苯基聚二甲基硅氧烷交联聚合物、二苯基聚二甲基硅氧烷/乙烯基二苯基聚二甲基硅氧烷/硅倍半氧烷交联聚合物、二苯乙基苄氧基二甲基二硅氧烷、二苯基异丙基聚二甲基硅氧烷、二苯基甲硅烷氧基苯基/丙基聚三甲基硅氧烷、二苯基甲硅烷氧基苯基聚三甲基硅氧烷、二聚硅氧烷、氨端聚二甲基硅氧烷/二琥珀酰亚胺二钠、PEG-12聚二甲基硅氧烷磺基琥珀酸酯二钠,PEG-8月桂基聚二甲基硅氧烷磺基琥珀酸酯二钠、二乙烯基聚二甲基硅氧烷/聚二甲基硅氧烷共聚物、二乙烯基聚二甲基硅氧烷/聚二甲基硅氧烷交联聚合物、甲酚曲唑三硅氧烷、丙烯酸乙基己酯/VP/聚二甲基硅氧烷甲基丙烯酸酯共聚物、乙基聚甲基硅氧烷、乙基三硅氧烷、氟代C2-8烷基聚二甲基硅氧烷、葡糖酰胺丙基氨丙基聚二甲基硅氧烷、4-(2-β-吡喃葡糖甲硅氧基)丙氧基-2-羟基二苯甲酮、甘油十一烷基聚二甲基硅氧烷、环氧丙氧基聚二甲基硅氧烷、聚十六烷基甲基硅氧烷、己基聚二甲基硅氧烷、己基聚甲基硅氧烷、己基三甲氧基硅烷、氢化聚二甲基硅氧烷、氢化聚二甲基硅氧烷/辛基硅倍半氧烷共聚物、水解胶原PG-丙基聚二甲基硅氧烷醇、水解胶原PG-丙基甲基硅烷二醇、水解胶原PG-丙基硅烷三醇、水解角蛋白PG-丙基甲基硅烷二醇、水解芝麻蛋白PG-丙基甲基硅烷二醇、水解蚕丝PG-丙基甲基硅烷二醇、水解蚕丝PG-丙基甲基硅烷二醇交联聚合物、水解大豆蛋白/聚二甲基硅氧烷PEG-7乙酸酯、水解大豆蛋白PG-丙基甲基硅烷二醇、水解植物蛋白PG-丙基硅烷三醇、水解小麦(TRITICUM VULGARE)蛋白/胱氨酸双-PG-丙基硅烷三醇共聚物、水解小麦蛋白/聚二甲基硅氧烷PEG-7乙酸酯、水解小麦蛋白/聚二甲基硅氧烷PEG-7磷酸酯共聚物、水解小麦蛋白PG-丙基甲基硅烷二醇、水解小麦蛋白PG-丙基硅烷三醇、羟乙基乙酰氧基甲基铵PG-聚二甲基硅氧烷、羟丙基聚二甲基硅氧烷、羟丙基聚二甲基硅氧烷山嵛酸酯、羟丙基聚二甲基硅氧烷异硬脂酸酯、羟丙基聚二甲基硅氧烷硬脂酸酯、甲基丙烯酸异丁酯/双-羟丙基聚二甲基硅氧烷丙烯酸酯共聚物、甲基丙烯酸异丁酯/甲基丙烯酸三氟乙酯/双-羟丙基聚二甲基硅氧烷丙烯酸酯共聚物、异戊醇三甲氧基肉桂酸酯三硅氧烷、异聚甘油-3聚二甲基硅氧烷、异聚甘油-3聚二甲基硅氧烷醇、异丙基钛三异硬脂酸酯/三乙氧基甲硅烷基乙基、聚二甲基硅氧乙基聚二甲基硅氧烷交联聚合物、异硬脂基羧癸基PEG-8聚二甲基硅氧烷、乳酰基甲基硅烷醇弹性蛋白酯、月桂基聚二甲基硅氧烷、月桂基聚二甲基硅氧烷PEG-15交联聚合物、月桂基聚二甲基硅氧烷PEG-10磷酸酯、月桂基聚二甲基硅氧烷/聚甘油-3交联聚合物、月桂基聚甲基硅氧烷、月桂基PEG-8聚二甲基硅氧烷、桂基PEG-10甲醚聚二甲基硅氧烷、月桂基PEG-9聚二甲基硅氧乙基聚二甲基硅氧烷、月桂基PEG/PPG-18/18聚甲基硅氧烷、月桂基苯异丙基聚甲基硅氧烷、月桂基苯丙基聚甲基硅氧烷、月桂基聚二甲基硅氧乙基聚二甲基硅氧烷/双乙烯基聚二甲硅氧烷交联聚合物、月桂基聚甘油-3聚二甲基硅氧乙基聚二甲基硅氧烷、月桂基聚三甲基硅氧烷、亚油酰胺丙基PG-二甲基氯化铵磷酸酯聚二甲基硅氧烷、甲基丙烯酰基丙基三甲氧基硅烷、聚甲基硅氧烷、甲氧基氨端聚二甲基硅氧烷/硅倍半氧烷共聚物、甲氧基肉桂酰胺丙基聚硅倍半氧烷、甲氧基肉桂酰丙基硅倍半氧烷硅酸盐、甲氧基PEG-13乙基聚硅倍半氧烷、甲氧基PEG/PPG-7/3氨丙基聚二甲基硅氧烷、甲氧基PEG/PPG-25/4聚二甲基硅氧烷、甲氧基PEG-10丙基三甲氧基硅烷、甲基丁香酚PEG-8聚二甲基硅氧烷、甲基聚硅氧烷乳液、甲基硅烷醇乙酰蛋氨酸酯、甲基硅烷醇乙酰酪氨酸酯、甲基硅烷醇抗坏血酸、甲基硅烷醇羧甲基茶碱、甲基硅烷醇羧甲基茶碱藻酸盐、甲基硅烷醇弹性蛋白酯、甲基硅烷醇甘草酸酯、甲基硅烷醇羟脯氨酸酯、甲基硅烷醇羟脯氨酸酯天冬氨酸酯、甲基硅烷醇甘露糖醛酸酯、甲基硅烷醇PCA酯、甲基硅烷醇PEG-7甘油椰油酸酯、甲基硅烷醇/硅酸酯交联聚合物、甲基硅烷醇螺旋藻蛋白酯、甲基硅烷醇三-PEG-8甘油基椰油酸酯、甲基聚三甲基硅氧烷、甲基三甲氧基硅烷、肉豆蔻酰胺丙基二甲基胺聚二甲基硅氧烷PEG-7磷酸酯、肉豆蔻基聚甲基硅氧烷、肉豆蔻基三硅氧烷、锦纶-611/聚二甲基硅氧烷共聚物、PCA聚二甲基硅氧烷、PEG-7氨端聚二甲基硅氧烷、PEG-8氨端聚二甲基硅氧烷、PEG-8鲸蜡基聚二甲基硅氧烷、PEG-3聚二甲基硅氧烷、PEG-6聚二甲基硅氧烷、PEG-7聚二甲基硅氧烷、PEG-8聚二甲基硅氧烷、PEG-9聚二甲基硅氧烷、PEG-10聚二甲基硅氧烷、PEG-12聚二甲基硅氧烷、PEG-14聚二甲基硅氧烷、PEG-聚二甲基硅氧烷、PEG-10聚二甲基硅氧烷交联聚合物、PEG-12聚二甲基硅氧烷交联聚合物、PEG-8聚二甲基硅氧烷二聚亚油酸酯、PEG-8二聚亚油酸酯/二聚亚油酸共聚物、PEG-10聚二甲基硅氧烷/乙烯基聚二甲基硅氧烷交联聚合物、PEG-8二硬脂基甲基氯化铵PG-聚二甲基硅氧烷、PEG-10/月桂基聚二甲基硅氧烷交联聚合物、PEG-15/月桂基聚二甲基硅氧烷交联聚合物、PEG-15/月桂基聚二甲基硅氧乙基聚二甲基硅氧烷交联聚合物、PEG-8聚甲基硅氧烷、PEG-6聚甲基硅氧烷乙酸酯、PEG-6甲醚聚二甲基硅氧烷、PEG-7甲醚聚二甲基硅氧烷、PEG-8甲醚聚二甲基硅氧烷、PEG-9甲醚聚二甲基硅氧烷、PEG-10甲醚聚二甲基硅氧烷、PEG-11甲醚聚二甲基硅氧烷、PEG-32甲醚聚二甲基硅氧烷、PEG-8PEG-8甲基醚三乙氧基硅烷、PEG-10九氟代己基聚二甲基硅氧烷共聚物、PEG-4PEG-12聚二甲基硅氧烷、PEG-8PG椰油酰葡糖苷聚二甲基硅氧烷、PEG-9聚二甲基硅氧乙基聚二甲基硅氧烷、PEG/PPG-20/22丁醚聚二甲基硅氧烷、PEG/PPG-22/22丁醚聚二甲基硅氧烷、PEG/PPG-23/23丁醚聚二甲基硅氧烷、PEG/PPG-24/18丁醚聚二甲基硅氧烷、PEG/PPG-27/9丁醚聚二甲基硅氧烷、PEG/PPG-3/10聚二甲基硅氧烷、PEG/PPG-4/12聚二甲基硅氧烷、PEG/PPG-6/4聚二甲基硅氧烷、PEG/PPG-6/11聚二甲基硅氧烷、PEG/PPG-8/14聚二甲基硅氧烷、PEG/PPG-8/26聚二甲基硅氧烷、PEG/PPG-10/2聚二甲基硅氧烷、PEG/PPG-12/16聚二甲基硅氧烷、PEG/PPG-12/18聚二甲基硅氧烷、PEG/PPG-14/4聚二甲基硅氧烷、PEG/PPG-15/5聚二甲基硅氧烷、PEG/PPG-15/15聚二甲基硅氧烷、PEG/PPG-16/2聚二甲基硅氧烷、PEG/PPG-16/8聚二甲基硅氧烷、PEG/PPG-17/18聚二甲基硅氧烷、PEG/PPG-18/6聚二甲基硅氧烷、PEG/PPG-18/12聚二甲基硅氧烷、PEG/PPG-18/18聚二甲基硅氧烷、PEG/PPG-19/19聚二甲基硅氧烷、PEG/PPG-20/6聚二甲基硅氧烷、PEG/PPG-20/15聚二甲基硅氧烷、PEG/PPG-20/20聚二甲基硅氧烷、PEG/PPG-20/23聚二甲基硅氧烷、PEG/PPG-20/29聚二甲基硅氧烷、PEG/PPG-22/23聚二甲基硅氧烷、PEG/PPG-22/24聚二甲基硅氧烷、PEG/PPG-23/6聚二甲基硅氧烷、PEG/PPG-25/25聚二甲基硅氧烷、PEG/PPG-27/27聚二甲基硅氧烷、PEG/PPG-30/10聚二甲基硅氧烷、PEG/PPG-25/25聚二甲基硅氧烷/丙烯酸(酯)类共聚物、PEG/PPG-20/22甲醚聚二甲基硅氧烷、PEG/PPG-24/24甲基醚环氧丙氧基聚二甲基硅氧烷、PEG/PPG-10/3油基醚聚二甲基硅氧烷、PEG/PPG-5/3三硅氧烷、PEG-4三氟代丙基聚二甲基硅氧烷共聚物、PEG-8三氟代丙基聚二甲基硅氧烷共聚物、PEG-10三氟代丙基聚二甲基硅氧烷共聚物、PEG-8三硅氧烷、全氟辛烷基三乙氧基甲硅烷基乙基聚甲基硅氧烷、全氟壬基聚二甲基硅氧烷、全氟壬基聚二甲基硅氧烷/聚甲基硅氧烷/氨端聚二甲基硅氧烷交联聚合物、全氟壬基乙基羧癸基山嵛基聚二甲基硅氧烷、全氟壬基乙基羧癸基二十六烷基聚二甲基硅氧烷、全氟壬基乙基羧癸基月桂基/山嵛基聚二甲基硅氧烷、全氟壬基乙基羧癸基月桂基聚二甲基硅氧烷、全氟壬基乙基羧癸基PEG-8聚二甲基硅氧烷、全氟壬基乙基羧癸基PEG-10聚二甲基硅氧烷、全氟壬基乙基聚二甲基硅氧烷/聚甲基硅氧烷共聚物、全氟壬基乙基PEG-8聚二甲基硅氧烷、全氟壬基乙基硬脂基聚二甲基硅氧烷、全氟辛基乙基/二苯基聚二甲基硅氧烷共聚物、全氟辛基乙基三乙氧基硅烷、全氟辛基乙醇三甲氧基硅烷、全氟辛基乙基三硅氧烷、全氟辛基三乙氧基硅烷、PG-氨端聚二甲基硅氧烷、苯乙基聚二甲硅氧烷、苯乙基二硅氧烷、二苯基聚二甲基硅氧烷、二苯基异丙基聚二甲基硅氧烷、苯基聚甲基硅氧烷、苯基聚甲基硅氧烷醇、苯丙基二甲基硅烷氧基硅酸酯、苯丙基乙基聚甲基硅氧烷、苯基丙基聚三甲基硅氧烷、苯基丙基聚三甲基硅氧烷/二苯基聚甲基硅氧烷、苯基聚三甲基硅氧烷、二乙烯基二硅氧烷铂、聚丙烯酸酯-6、聚二乙基硅氧烷、聚二甲基硅羟乙基聚二甲基硅氧烷/双乙烯基聚二甲硅氧烷交联聚合物、聚二甲基硅氧乙基聚二甲基硅氧烷/聚甲基硅氧烷共聚物、聚二甲基硅氧PEG/PPG-24/19丁基醚硅倍半氧烷、聚二甲基硅氧PPG-13丁基醚硅倍半氧烷、聚甘油-3二硅氧烷聚二甲基硅氧烷、聚甘油-3/月桂基聚二甲基硅氧乙基聚二甲基硅氧烷交联聚合物、聚甘油-3聚二甲基硅羟乙基聚二甲基硅氧烷、聚(乙二醇己二酸酯)/双羟乙氧基丙基聚二甲基硅氧烷共聚物、聚甲基硅倍半氧烷、聚甲基硅倍半氧烷/三甲基硅氧基硅酸酯、聚苯基倍半硅氧烷、聚丙基硅倍半氧烷、聚硅氧烷-1、聚硅氧烷-2、聚硅氧烷-3、聚硅氧烷-4、聚硅氧烷-5、聚硅氧烷-6、聚硅氧烷-7、聚硅氧烷-8、聚硅氧烷-9、聚硅氧烷-10、聚硅氧烷-11、聚硅氧烷-12、聚硅氧烷-13、聚硅氧烷-14、聚硅氧烷-15、聚硅氧烷-16、聚硅氧烷-17、聚硅氧烷-18、聚硅氧烷-19、聚硅氧烷-20、聚硅氧烷-21、聚硅氧烷-18鲸蜡醇磷酸酯、聚硅氧烷-1交联聚合物、聚硅氧烷-18硬脂酸酯聚氨酯-10、甲基硅氧烷PEG-7泛醇磷酸酯钾、聚二甲基硅氧烷PEG-7磷酸酯钾、PPG-12丁醚聚二甲基硅氧烷、PPG-2聚二甲基硅氧烷、PPG-12聚二甲基硅氧烷、PPG-27聚二甲基硅氧烷、PPG-4油醇聚醚-10聚二甲基硅氧烷、丙氧基四甲基哌啶基聚二甲基硅氧烷、丙基聚三甲基硅氧烷、季铵盐-80、视黄氧基三甲基硅烷、硅烷二醇水杨酸酯、硅烷三醇、硅烷三醇精氨酸酯、硅烷三醇谷氨酸酯、硅烷三醇赖氨酸酯、硅烷三醇黑色素酯、硅烷三醇海藻糖醚、硅石、聚二甲基硅氧烷甲硅烷基化硅石、二甲基甲硅烷基化硅石、甲硅烷基化硅石、硅碳化物、聚硅氧烷季铵盐-1、聚硅氧烷季铵盐-2、聚硅氧烷季铵盐-2泛醇琥珀酸酯、聚硅氧烷季铵盐-3、聚硅氧烷季铵盐-4、聚硅氧烷季铵盐-5、聚硅氧烷季铵盐-6、聚硅氧烷季铵盐-7、聚硅氧烷季铵盐-8、聚硅氧烷季铵盐-9、聚硅氧烷季铵盐-10、聚硅氧烷季铵盐-11,聚硅氧烷季铵盐-12,聚硅氧烷季铵盐-15、聚硅氧烷季铵盐-16、聚硅氧烷季铵盐-16/环氧丙氧基聚二甲基硅氧烷交联聚合物、聚硅氧烷季铵盐-17、聚硅氧烷季铵盐-18、聚硅氧烷季铵盐-19、聚硅氧烷季铵盐-20、聚硅氧烷季铵盐-21、聚硅氧烷季铵盐-22、聚硅氧烷季铵盐-24、聚硅氧烷季铵盐-25、硅氧烷三醇藻酸酯、硅氧烷三醇植酸酯、有机硅树脂、羧癸基PEG-8聚二甲基硅氧烷钠、聚二甲基硅氧烷PEG-7乙酰甲基牛磺酸钠、二甲基硅烷醇透明质酸酯钠、乳酸钠甲基硅烷醇、甘露糖醛酸钠甲基硅烷醇、PCA钠甲基硅烷醇、PG-丙基聚二甲基硅氧烷硫代硫酸酯共聚物钠、PG-丙基硫代硫酸钠聚二甲基硅氧烷、丙氧基羟基丙基硫代硫酸酯钠硅石、山梨醇硅烷二醇、大豆三乙氧基甲硅烷基丙基二甲基氯化铵、司拉氯铵聚二甲基硅氧烷PEG-8邻苯二甲酸酯盐、硬脂酰胺丙基聚二甲硅氧烷、硬脂基二甲基铵羟丙基泛醇基PEG-7聚二甲基硅氧烷磷酸酯氯化物、硬脂基二甲基铵羟丙基PEG-7聚二甲基硅氧烷磷酸酯氯化物、硬脂氧基聚二甲硅氧烷、硬脂氧聚甲硅氧烷/聚二甲硅氧烷共聚物、硬脂氧基三甲基硅烷、硬脂基氨丙基聚甲基硅氧烷、硬脂基聚二甲硅氧烷、硬脂醇/月桂醇甲基丙烯酸酯交联聚合物、硬脂基聚甲基硅氧烷、硬脂基三乙氧基硅烷、硬脂基聚三甲基硅氧烷、苯乙烯/丙烯酸(酯)类/聚二甲基硅氧烷丙烯酸酯交联聚合物、苯乙烯/丙烯酸(酯)类/聚二甲基硅氧烷共聚物、聚二甲基硅氧烷PEG-7磷酸酯TEA盐、(四丁氧基)丙基三硅氧烷、四甲基六苯基四硅氧烷、四甲基四苯基三聚硅氧烷、生育酚氧丙基三硅氧烷、十三烷醇聚醚-9PG-氨端聚二甲基硅氧烷、三乙氧基辛基硅烷、聚二甲基硅氧烷/聚甲基硅氧烷共聚物、三乙氧基甲硅烷基乙基聚二甲基硅氧乙基聚二甲基硅氧烷、三乙氧基甲硅烷基乙基聚二甲基硅氧乙基己基聚二甲基硅氧烷、三乙氧基甲硅烷基丙基氨基甲酰乙氧基丙基丁基聚二甲基硅氧烷、三氟甲基C1-4烷基聚二甲基硅氧烷、三氟丙基环五硅氧烷、三氟丙基环四硅氧烷、三氟代丙基聚二甲基硅氧烷、三氟丙基聚二甲基硅氧烷/PEG-10交联聚合物、三氟丙基聚二甲基硅氧烷/三氟丙基二乙烯基聚二甲基硅氧烷交联聚合物、三氟丙基聚二甲基硅氧烷/乙烯基三氟丙基聚二甲基硅氧烷/硅倍半氧烷交联聚合物、三氟丙基聚二甲基硅氧烷醇、三氟丙基二甲基/三甲基硅氧基硅酸酯、三氟丙基聚甲基硅氧烷、三甲氧基辛基硅烷、三甲氧基甲硅烷基聚二甲基硅氧烷、三甲基五苯基三硅氧烷、三甲基甲硅烷氧基氨端聚二甲基硅氧烷、三甲基硅烷氧苯基聚二甲基硅氧烷、三甲基硅烷氧基硅酸酯、三甲基硅烷氧基硅酸酯/聚二甲基硅氧烷交联共聚物、三甲基硅烷氧基硅酸酯/聚二甲基硅氧烷醇交联聚合物、三甲基硅烷氧基甲硅烷基氨基甲酰支链淀粉、三甲基甲硅烷基水解贝壳硬蛋白PG-丙基甲基硅烷二醇交联聚合物、三甲基甲硅烷基水解蚕丝PG-丙基甲基硅烷二醇交联聚合物、三甲基甲硅烷基水解小麦蛋白PG-丙基甲基硅烷二醇交联聚合物、三甲基甲硅烷基支链淀粉、三甲基硅烷醇三硅甲烷氧基乙醇酸酯、三甲基甲硅烷醇三硅甲烷氧基乳酸酯、三甲基甲硅烷醇三硅甲烷氧基水杨酯、聚三苯基三甲基硅氧烷、三硅氧烷、三(三丁氧基甲硅烷氧基)甲基硅烷、十一碳烯聚二甲基硅氧烷、乙烯基聚二甲基硅氧烷、乙烯基聚二甲基硅氧烷/月桂基聚二甲基硅氧烷交联聚合物、乙烯基聚二甲基硅氧烷/聚甲基硅氧烷硅倍半氧烷交联聚合物、乙烯基二甲基/三甲基硅氧基硅酸酯/硬脂基聚二甲基硅氧烷交联聚合物、VP/甲基丙烯酸二甲氨基乙酯/聚氨基甲酸聚乙二醇酯、羧癸基三硅氧烷锌和聚二甲基硅氧烷PEG-8琥珀酸锌及其混合物。
根据本发明的混合物中所含的有机硅更优选为聚二甲基硅氧烷、环聚二甲基硅氧烷、苯基三甲基硅油,环己硅氧烷和环五聚二甲基硅氧烷。适当的挥发硅氧烷化合物的详细介绍见于Todd et al.in Cosm.Toil.91,27(1976)。
蜡和稳定剂
除了使用的天然油,制剂中还可以含有蜡,尤其是天然蜡例如,小烛树蜡、巴西棕榈蜡、日本蜡、芦华草腊(espartograss wax)、软木蜡、小冠椰子腊(guaruma wax)、米糠油蜡、糖甘蔗蜡、小冠巴西棕蜡(ouricury wax)、褐煤蜡、蜂蜡、紫胶蜡(shellac wax)、鲸蜡、羊毛脂(wool wax)、尾脂脂肪(uropygial fat)、(纯)地蜡、地蜡(石蜡)、凡士林、石油蜡和微蜡;化学改性的蜡类(硬蜡类)如例如,褐煤酯蜡(montan ester waxes)、沙索蜡(sasolwaxes)、氢化霍霍巴蜡(jojoba waxes)以及合成蜡类如例如聚亚烷基蜡类和聚乙二醇蜡类。
作为稳定剂可以使用脂肪酸的金属盐,如例如硬脂酸或蓖麻酸镁、铝和/或锌盐。
主要防晒剂
在本发明中主要防晒剂是,例如在室温下是液态或结晶的有机物质(光过滤物质),其能够吸收紫外辐射并又以长波辐射的形式释放吸收的能量,例如热量。
根据本发明的制剂有利地含有至少一种UV-A过滤物质和/或至少一种UV-B过滤物质和/或宽带过滤物质和/或至少一种无机染料。根据本发明的制剂优选含有至少一种UV-B过滤物质或一种宽带过滤物质,更特别是至少一种UV-A过滤物质和至少一种UV-B过滤物。
下文引用的可在本发明中使用的UV过滤物质是优选的,但不限于这些物质。优选使用的UV过滤剂选自以下种类中的一种、两种、三种、四种、五种或更多种
在一个优选的实施方案中,形成防晒过滤剂的组分(ii)代表UV-A-和UV-B-过滤剂的共混物,其选自高水杨酸盐、奥克立林、双-乙基己氧基苯酚甲氧基苯基三嗪、丁基甲氧基二苯并-基甲烷、水杨酸乙基己酯及其混合物。特别优选的是所有这些过滤剂的混合物,其可在市场上以商标Flat(SYMRISE)商购,其也为WO 2020 088778 A1的主题。
合适的颜料包括钛(TiO2)、锌(ZnO)、铁(Fe2O3)、锆(ZrO2)、硅(SiO2)、锰(例如MnO)、铝(Al2O3)、铈(例如Ce2O3)的氧化物和/或其混合物。
在进一步优选的实施方案中,根据本发明的制剂包含总量的防晒剂,即特别是UV过滤剂和/或无机颜料(UV过滤颜料),使得根据本发明的制剂具有光大于或等于5且至多50的保护因子。根据本发明的此类制剂特别适用于保护皮肤和头发。
二级防晒剂
除了上述主要防晒剂组,也可以使用抗氧化剂型的二级防晒剂。抗氧化剂型的二级防晒剂阻断了当紫外线渗透进入皮肤时引发的光化学反应链。典型实例是氨基酸类(例如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物、咪唑类(例如尿刊酸)及其衍生物、肽类例如D,L-肌肽、D-肌肽,L-肌肽及其衍生物(例如鹅肌肽)、类胡萝卜素类、胡萝卜素类(例如α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物、氯原酸及其衍生物、硫辛酸及其衍生物(例如二氢硫辛酸)、金硫葡糖、丙基硫氧嘧啶和其他硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油烯基、α-亚油酰基、胆甾醇基和其甘油酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸双十八酯、硫代二丙酸及其衍生物(酯类、醚类、肽类、脂类、核苷酸类、核苷类和盐)以及非常低的耐药剂量的亚砜亚胺化合物(例如丁硫氨酸亚砜亚胺、同型半胱氨酸亚砜亚胺、丁硫氨酸砜、五-、六-和七-硫氨酸亚砜亚胺)、以及(金属)螯合剂类(例如,α-羟基脂肪酸类、棕榈酸、植酸、乳铁蛋白)、α-羟基酸类(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸及其衍生物(例如亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醇及其衍生物、维生素C及其衍生物(例如抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸乙酸酯)、生育酚及衍生物(例如维生素E乙酸酯)、维生素A及衍生物(维生素A棕榈酸酯)以及安息香树脂的苯甲酸松酯、芸香十烯酸及其衍生物、糖基芦丁、阿魏酸、亚糠基山梨醇、肌肽、丁基羟甲苯、丁基羟基茴香醚、去甲二氢愈创木酸木脂酸、去甲二氢愈创木酸、三羟基丁酰苯、尿酸及其衍生物、甘露糖及其衍生物、超氧化物歧化酶、二氧化钛(例如乙醇中的分散体)、锌及其衍生物(例如ZnO、ZnSO4)、硒及其衍生物(例如蛋氨酸硒)、芪类及其衍生物(例如均二苯乙烯氧化物、反-均二苯乙烯氧化物)及这些活性化合物的适合本发明目的的衍生物(盐类、酯类、醚类、糖类、核苷酸类、核苷类、肽类和脂类)。
有利的无机二级光保护颜料是精细分散的金属氧化物和金属盐,它们也在WO2005123101A1中提及。在根据本发明的成品化妆品制剂中无机颜料,特别是疏水性无机微颜料的总量有利地为0.1至30重量%,优选0.5至10.0重量%,在每种情况下基于制剂的总重量计。
还优选的是颗粒状UV过滤剂或无机颜料,它们可以任选地被疏水化,可以使用,例如钛(TiO2)、锌(ZnO)、铁(Fe2O3)、锆(ZrO2),硅(SiO2)、锰(例如MnO)、铝(Al2O3)、铈(例如Ce2O3)的氧化物和/或它们的混合物。
生物制剂和抗氧化剂
生物活性物质包括例如生育酚、生育酚乙酸酯、生育酚棕榈酸酯、抗坏血酸、(脱氧)核糖核酸及其断裂产物、β-葡聚糖、视黄醇、红没药醇、尿囊素、植烷三醇、泛醇、AHA酸、氨基酸、神经酰胺、假神经酰胺、精油、植物提取物,例如李子提取物、bambaranus提取物和维生素复合物。
抗氧化剂阻断了当紫外线渗透进入皮肤时引发的光化学反应链。典型实例是氨基酸类(例如甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物、咪唑类(例如尿刊酸)及其衍生物、肽类例如D,L-肌肽、D-肌肽,L-肌肽及其衍生物(例如鹅肌肽)、类胡萝卜素类、胡萝卜素类(例如α-胡萝卜素、β-胡萝卜素、番茄红素)及其衍生物、氯原酸及其衍生物、硫辛酸及其衍生物(例如二氢硫辛酸)、金硫葡糖、丙基硫氧嘧啶和其他硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺及其糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基和月桂基、棕榈酰基、油烯基、α-亚油酰基、胆甾醇基和其甘油酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸双十八酯、硫代二丙酸及其衍生物(酯类、醚类、肽类、脂类、核苷酸类、核苷类和盐)以及非常低的耐药剂量的亚砜亚胺化合物(例如丁硫氨酸亚砜亚胺、同型半胱氨酸亚砜亚胺、丁硫氨酸砜、五-、六-和七-硫氨酸亚砜亚胺)、以及(金属)螯合剂类(例如,α-羟基脂肪酸类、棕榈酸、植酸、乳铁蛋白)、α-羟基酸类(例如柠檬酸、乳酸、苹果酸)、腐殖酸、胆汁酸、胆汁提取物、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸及其衍生物(例如亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醇及其衍生物、维生素C及其衍生物(例如抗坏血酸棕榈酸酯、抗坏血酸磷酸镁、抗坏血酸乙酸酯)、生育酚及衍生物(例如维生素E乙酸酯)、维生素A及衍生物(维生素A棕榈酸酯)以及安息香树脂的苯甲酸松酯、芸香十烯酸及其衍生物、糖基芦丁、阿魏酸、亚糠基山梨醇、肌肽、丁基羟甲苯、丁基羟基茴香醚、去甲二氢愈创木酸木脂酸、去甲二氢愈创木酸、三羟基丁酰苯、尿酸及其衍生物、甘露糖及其衍生物、超氧化物歧化酶、二氧化钛(例如乙醇中的分散体)、锌及其衍生物(例如ZnO、ZnSO4)、硒及其衍生物(例如蛋氨酸硒)、芪类及其衍生物(例如均二苯乙烯氧化物、反-均二苯乙烯氧化物)及这些活性化合物的适合本发明目的的衍生物(盐类、酯类、醚类、糖类、核苷酸类、核苷类、肽类和脂类)。
调节毛发色素沉着的活性物质
用于毛发亮化的优选活性成分选自组包括:曲酸(5-羟基-2-羟基甲基-4-吡喃酮)、曲酸衍生物,优选地122178二棕榈酸酯、熊果苷、抗坏血酸,抗坏血酸衍生物、优选地抗坏血酸磷酸镁、氢醌、氢醌衍生物、间苯二酚、间苯二酚衍生物,优选4-烷基间苯二酚和4-(1-苯乙基)1,3-间苯二酚(苯乙基间苯二酚)、环己基氨基甲酸酯类(优选WO 2010/122178和WO 2010/097480中公开的一种或多种氨基甲酸环己基酯类),含硫分子,优选地谷胱甘肽或半胱氨酸、α-羟基酸类(优选柠檬酸、乳酸、苹果酸),其盐类和酯类、N-乙酰基酪氨酸和衍生物、十一碳烯酰基苯基丙氨酸、葡萄糖酸、色酮衍生物,优选芦荟苦素、黄酮类化合物、1-氨基乙基次膦酸、硫脲衍生物、鞣花酸、烟酰胺(niacinamide)、锌盐类,优选氯化锌或葡萄糖酸锌、崖柏素和衍生物、三萜类,优选山楂酸、甾醇类,优选地麦角甾醇、苯并呋喃酮类,优选川芎内酯、乙烯基愈疮木酚、乙基愈疮木酚、二酸类(dionic acids)、优选十八烯二酸和/或壬二酸,氮氧化物合成的抑制剂,优选地L-硝基精氨酸及其衍生物、2,7-二硝基吲唑或硫瓜氨酸、金属螯合剂(优选α-羟基脂肪酸类、植酸、腐殖酸、胆酸、胆汁提取物、EDTA、EGTA及其衍生物)、维甲酸类化合物、豆奶和提取物、丝氨酸蛋白酶抑制剂或硫辛酸或者用于皮肤和毛发亮化的其他合成或天然活性成分,后者优选地以取自植物的提取物的形式使用,优选熊果提取物、大米提取物、番木瓜提取物、姜黄提取物、桑果提取物、凉薯提取物、香附提取物、甘草根提取物或从其中浓缩或分离的组成成分,优选光甘草定或甘草查尔酮甲、桂木提取物、酸模属的提取物、松属(松树)的提取物、葡萄属的提取物或者从其中分离或浓缩的茋类衍生物、虎耳草提取物、黄芩提取物(scutelleria extract)、葡萄提取物和/或微藻提取物,尤其是四肩突四鞭藻提取物。
在此方面有利的皮肤和毛发晒黑活性成分是酪氨酸酶的底物或底物类似物,如L-酪氨酸、N-乙酰基酪氨酸、L-DOPA或L-二羟基苯基丙氨酸、黄嘌呤生物碱类,如咖啡因、可可碱和茶碱及其衍生物、阿黑皮素原肽类,如ACTH、α-MSH、其肽类似物、和与黑皮质素受体结合的其他物质、肽类如Val-Gly-Val-Ala-Pro-Gly、Lys-lle-Gly-Arg-Lys或Leu-Ile-Gly-Lys、嘌呤类、嘧啶类化合物、叶酸、铜盐类如葡萄糖酸铜、氯化铜或吡咯烷酸铜、1,3,4-噁二唑-2-硫醇如5-吡嗪-2-基-1,3,4-噁二唑-2-硫醇、姜黄素、锌二甘氨酸盐(Zn(GIy)2))、锰(II)二碳酸盐络合物(“pseudocat-alases”),如例如EP 0584178中所描述、四取代的环己烯衍生物,例如WO2005/032501中所描述、异戊二烯萜类,如WO 2005/102252和WO2006/010661中所描述、黑色素衍生物诸如Melasyn-100和MelanZe、二酰基丙三醇类、脂肪族或环状二醇类、补骨脂素类、前列腺素及其类似物、腺苷酸环化酶的活化剂和激活毛发黑色素小体转化成角蛋白细胞的化合物,如丝氨酸蛋白酶或PAR-2受体激动剂、菊属的植物和植物部分的提取物、地榆属的植物和植物部分的提取物、核桃提取物、urucum提取物、大黄提取物、微藻提取物,尤其是球等鞭金藻、海藻糖、赤藓酮糖和二羟基丙酮。也可以使用引起皮肤和毛发染色或变褐色的黄酮类化合物(例如槲皮素、鼠李醚、山奈酚、漆黄素、染料木黄酮、黄豆苷元、白杨素和芹菜素、表儿茶素、香叶木苷和香叶木素、桑色素、槲皮苷、柚皮素、橙皮苷、根皮苷、根皮素)。
根据本发明的产品中用于对皮肤和毛发色素沉着进行调整的其他活性成分(一种或多种化合物)的前述例子的量优选为0.00001至30重量%、优选0.0001至20重量%,尤其优选0.001至5重量%,基于制剂总量计。
毛发生长活化剂或抑制剂
根据本发明的制剂和产品还可含有一种或多种毛发生长活化剂,即刺激毛发生长的药剂。毛发生长活化剂优选自组包括嘧啶衍生物,如2,4-二氨基嘧啶-3-氧化物(Aminexil)、2,4-二氨基-6-哌啶并嘧啶-3-氧化物(Minoxidil)及其衍生物,6-氨基-1,2-二氢-1-羟基-2-亚氨基-4-哌啶并嘧啶及其衍生物、黄嘌呤生物碱类,如咖啡因,可可碱和茶碱及其衍生物、槲皮素及衍生物、二氢槲皮素(花旗松素)及衍生物、钾通道开放剂、抗雄激素药物、合成或天然的5-还原酶抑制剂、烟酸酯,如烟酸生育酚酯,烟酸苄酯和C1-C6烷基烟酸盐、蛋白质如三肽Lys-Pro-Val、diphencypren、激素、非那雄胺、度他雄胺、氟他胺、比卡鲁胺、孕烷衍生物、黄体酮及其衍生物、醋酸环丙孕酮、安体舒通和其他利尿剂、钙调磷酸酶抑制剂如FK506(他克莫司(Tacrolimus)、藤霉素(Fujimycin))及其衍生物,环孢菌素A及其衍生物、锌和锌盐、茶多酚、前花青素、原花青素、植物甾醇,如β-谷甾醇、生物素、丁子香酚、(±)-β-香茅醇、泛醇、糖原,例如源于贻贝、源于微生物、海藻、植物和植物的部分,例如以下属的植物:蒲公英(狮齿菊属或蒲公英属),鸡脚参、牡荆、咖啡、泡林藤、可可、萍叶细辛、南瓜属或槐、锯叶棕(锯棕榈)、苦参、非洲臀果木、猪黍、美类叶升麻、大豆、丁香、黄栌、扶桑、茶树、巴拉圭茶、球等鞭金藻、甘草、葡萄、苹果、大麦或啤酒花的提取物,或/和大米或小麦水解产物。
可选地,根据本发明的制剂和产品还可包含一种或多种毛发生长抑制剂(如上所述),即减缓或防止毛发生长的制剂。毛发生长抑制剂优选自组包括激活素、激活素衍生物或激活素激动剂、鸟氨酸脱羧酶抑制剂,例如α-二氟甲基鸟氨酸或五环三萜类化合物例如熊果酸、桦木醇、桦木酸、齐墩果酸及其衍生物、5α-还原酶抑制剂、雄激素受体拮抗剂、S-腺苷甲硫氨酸脱羧酶抑制剂、γ-谷氨酰转肽酶抑制剂、谷氨酰胺转胺酶抑制剂、大豆来源的丝氨酸蛋白酶抑制剂、来自微生物、海藻、不同微藻或植物和植物的部分,如豆科、茄科、禾本科、萝藦科或葫芦科、角叉菜属、海萝属、仙菜属、杜尔维勒属、大豆属、地榆属、金盏花属、金缕梅属、蒙大纳山金车属、白柳属、贯叶连翘属或匙羹藤属的提取物。
生理清凉剂和温热剂
生理清凉剂优选自以下列表:薄荷醇和薄荷醇衍生物(例如L-薄荷醇、D-薄荷醇、外消旋薄荷醇、异薄荷醇、新异薄荷醇、新薄荷醇)薄荷醚(例如(I-薄荷氧基)-1,2-丙二醇、(l-薄荷氧基)-2-甲基-1,2-丙二醇、l-薄荷基-甲基醚)、薄荷酯(例如,甲酸薄荷酯、乙酸薄荷酯、异丁酸薄荷酯、乳酸薄荷酯、L-乳酸-L-薄荷酯、D-乳酸-L-薄荷酯、薄荷基-(2-甲氧基)乙酸酯,薄荷基(2-甲氧基乙氧基)乙酸酯,焦谷氨酸薄荷酯)、碳酸薄荷酯(例如碳酸薄荷基丙二醇酯、碳酸薄荷基乙二醇酯、碳酸薄荷基甘油酯或其混合物)、薄荷醇与二羧酸或其衍生物的半酯(例如琥珀酸单薄荷酯、戊二酸单薄荷酯、丙二酸单薄荷酯、O-薄荷基琥珀酸酯-N,N-(二甲基)酰胺,O-薄荷基琥珀酸酯酰胺)、薄荷烷羧酸酰胺(在这种情况下优选薄荷烷羧酸-N-乙酰胺[WS3]或Nα-(薄荷羰基)甘氨酸乙酯[WS5],如US 4,150,052中所述,薄荷烷羧酸-N-(4-氰基苯基)酰胺或薄荷烷羧酸-N-(4-氰基甲基苯基)酰胺,如WO 2005049553 A1中所述,薄荷烷羧酸-N-(烷氧基烷基)酰胺)、薄荷酮和薄荷酮衍生物(例如L-薄荷酮甘油缩醛/缩酮)、2,3-二甲基-2-(2-丙基)-丁酸酸衍生物(例如2,3-二甲基-2-(2-丙基)-丁酸N-甲基酰胺[WS23])、异胡薄荷醇或其酯(I-(-)-异胡薄荷醇,I-(-)-异胡薄荷醇乙酸酯)、薄荷烷衍生物(例如对-薄荷烷-3,8-二醇)、苹澄茄醇(cubebol)或含有苹澄茄醇的合成或天然混合物、环烷基二酮衍生物的吡咯烷酮衍生物(例如3-甲基-2(1-吡咯烷基)-2-环戊烯-1-酮)或四氢嘧啶-2-酮(例如iciline或相关化合物,如WO 2004/026840中所记载)、其他甲酰胺(例如N-(2-(吡啶-2-基)-3-对-薄荷烷甲酰胺或相关的化合物)、(1R,2S,5R)-N-(4-甲氧基苯基)-5-甲基-2-(1-异丙基)环己烷-甲酰胺[WS12]、草酸酯(优选EP2033688 A2中描述的那些)和[(1R,2S,5R)-2-异丙基-5-甲基-环己基]2-(乙氨基)-2-氧代-乙酸酯。
生理温热剂可以选自组包括辣椒素、二氢辣椒素、去甲二氢辣椒素、高辣椒素、高二氢辣椒素、N-香草基壬酰胺(nonivamide)和辣椒提取物。
抗炎制剂
合适的抗炎制剂选自组包括:
(i)皮质类固醇类甾体抗炎物质,特别是氢化可的松、氢化可的松衍生物如氢化可的松17-丁酸酯、地塞米松、磷酸地塞米松、甲泼尼龙或可的松,
(ii)非甾体抗炎物质,特别是氧昔康如吡罗昔康或替诺昔康、水杨酸类如阿司匹林、双水杨酸酯、solprin或芬度柳、乙酸衍生物如双氯芬酸、fenclofenac、吲哚美辛、舒林酸、托麦汀或环氯弗酸(clindanac)、灭酸酯类如甲芬那酸、甲氯芬那酸、氟芬那酸或尼氟灭酸、丙酸衍生物如布洛芬、甲氧萘丙酸或苯恶洛芬、吡唑类如苯基丁氮酮、羟基保泰松、febrazone或阿扎丙酮
(iii)天然或天然产生的抗炎物质或缓解发红和/或瘙痒的物质,特别是甘菊、芦荟、没药属、茜草类、柳、柳草、燕麦、金盏花、山金车、圣约翰草、忍冬、迷迭香、西番莲(Passiflora incarnata)、金缕梅、姜或紫雏菊的提取物或馏分,或其单一活性化合物,
(iv)组胺受体拮抗剂、丝氨酸蛋白酶抑制剂(例如大豆提取物)、TRPV1拮抗剂(例如4-叔丁基环已醇)、NK1拮抗剂(例如阿瑞吡坦、羟苯基丙酰胺苯甲酸)、大麻素受体激动剂(例如棕榈酰乙醇胺)和TRPV3拮抗剂。
抗微生物剂
适当的抗微生物剂理论上是能够抵抗革兰氏阳性菌的所有物质,如例如4-羟基苯甲酸及其盐和酯、N-(4-氯苯基)-N'-(3,4-二氯苯基)脲、2,4,4'-三氯-2'-羟基-二苯基醚(三氯生)、4-氯-3,5-二甲基-苯酚、2,2'-亚甲基双(6-溴-4-氯苯酚)、3-甲基-4-(1-甲基乙基)苯酚、2-苄基-4-氯-苯酚、3-(4-氯苯氧基)-1,2-丙二醇、3-碘-2-丙炔氨基甲酸丁酯、氯己定、3,4,4'-三氯碳酰替苯胺(TTC)、抗菌芳香剂、麝香草酚、麝香草油、丁香酚、丁香油、薄荷醇、薄荷油、金合欢醇、苯氧乙醇、甘油单癸酸酯、单辛酸甘油酯、月桂酸单甘油酯(GML)、双甘油单癸酸酯(DMC)、水杨酸N-烷基胺,例如,正辛基水杨酰胺或正癸基水杨酰胺。
酶抑制剂
适当的酶抑制剂是例如酯酶抑制剂。这些酶抑制剂优选柠檬酸三烷酯,如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙酯、柠檬酸三丁酯和,特别是,柠檬酸三乙酯(HydagenCAT)。上述物质抑制酶活性,由此减少气味的生成。适合作为酯酶抑制剂的其它物质为甾醇硫酸酯或甾醇磷酸酯,例如,羊毛甾醇硫酸酯或磷酸酯、胆固醇硫酸酯或磷酸酯、菜油甾醇硫酸酯或磷酸酯、豆甾醇硫酸酯或磷酸酯和谷甾醇硫酸酯或磷酸酯;二羧酸和其酯,例如戊二酸、戊二酸单乙酯、戊二酸二乙酯、己二酸、己二酸单乙酯、己二酸二乙酯、丙二酸和丙二酸二乙酯、羟基羧酸及其酯,例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯,以及甘氨酸锌。
气味吸收剂和止汗活性剂
适当的气味吸收剂是能够吸收并在很大程度上保留形成味道的化合物的物质。它们降低各成分的分压,由此还可降低其扩散速率。重要的是在该过程中芳香剂必须保持未受损害。气味吸收剂对细菌没有作用。它们含有例如作为主成分的蓖麻油酸的复合锌盐,或作为“固香剂”为本领域技术人员所知晓的特定的主要中和气味的芳香剂,例如,岩蔷薇或苏合香的提取物或一些松香酸衍生物。气味掩蔽剂为芳香剂或芳香油,除了其作为气味掩蔽剂的功能之外,还向除臭剂提供其各自香味。可以提及的芳香油是例如天然和合成芳香剂的混合物。天然芳香剂为花、茎和叶、果实、果皮、根、木材、草本植物和禾本植物、松针和树枝以及树脂和香脂的提取物。还适当的是动物产品,例如麝猫香和海狸香。典型的合成芳香化合物为酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物是例如,乙酸苄基酯、乙酸p-叔丁基环己酯、乙酸芳樟酯、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类包括,例如苄基乙基醚;醛类包括,例如含有8至18个碳原子的直链烷醛、柠檬醛、香茅醛、香茅基氧基乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁红醛(bourgeonal);酮包括,例如紫罗兰酮和甲基柏木酮;醇包括茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇,苯乙醇和松油醇;烃类主要包括萜烯和香脂。通常用作芳香成分的挥发性较低的精油也适用作芳香油,例如鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、椴树花油、杜松子油、香根草油、乳香油、白松香油(galbanum oil)、岩蔷薇油和熏衣草油。优选单独使用或以混合物使用佛手柑油、二氢月桂烯醇、铃兰醛、新铃兰醛、香茅醇、苯乙醇、α-己基肉桂醛、香叶醇、苄丙酮、仙客来醛、芳樟醇、乙氧基甲氧基环十一烷(boisambrene forte)、龙涎呋喃、吲哚、二氢茉莉酮酸甲酯、sandelice、柠檬油、柑橘油、橙油、异戊氧基乙酸烯丙酯、cyclovertal、熏衣草油、鼠尾草油、β-大马酮、波旁香叶油、水杨酸环己酯、Vertofix Coeur、Iso-E-Super、Fixolide NP、evernyl、iraldein gamma、苯乙酸、乙酸香叶酯、乙酸苄酯、玫瑰醚、romilat、2-乙基-己酸乙酯(irotyl)和2-叔丁基环己基乙基碳酸酯(floramat)。
适当的收敛止汗活性成分主要是铝,锆或锌的盐。这类适当的antihydrotic活性成分是例如,氯化铝、氢氯酸铝、二氢氯酸铝、倍半氢氯酸铝及其络合物,例如与1,2-丙二醇的络合物、尿囊素羟基铝(aluminium hydroxyallantoinate)、酒石酸氯化铝、三氢氯酸铝锆、四氢氯酸铝锆、五氢氯酸铝锆及其络合物,例如与氨基酸如甘氨酸的络合物。
成膜剂和抗头屑剂
标准成膜剂是例如,壳聚糖、微晶壳聚糖、季铵壳聚糖、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、丙烯酸系聚合物、季纤维素衍生物、胶原、透明质酸及其盐和类似化合物。
适当的抗头屑剂是Pirocton Olamin(1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2-(1H)-吡啶酮单乙醇胺盐)、(氯咪巴唑)、(4-乙酰基-1-{4-[2-(2,4-二氯苯基)r-2-(1H-咪唑-1-基甲基)-1,3-二氧戊(dioxylan)-c-4-基甲氧基苯基}-哌嗪、酮康唑、新康唑、二硫化硒、胶体硫、硫聚乙二醇脱水山梨醇单油酸酯、硫蓖麻醇聚乙氧基化物、硫磺焦油馏分、水杨酸(或结合六氯酚)、十一碳烯酸、单乙醇酰胺磺基琥珀酸钠盐、UD(蛋白质/十一烯酸浓缩物)、吡啶硫酮锌、吡啶硫酮铝和吡啶硫酮镁/双吡硫翁硫酸镁。
载体和助水溶物
优选的化妆品载体材料在25℃和1013mbar下为固体或液体(包括高粘度物质),例如甘油、1,2-丙二醇、1,2-丁二醇、1,3-丙二醇、1,3-丁二醇、乙醇、水以及两种或多种所述液体载体物质与水的混合物。任选地,本发明的这些制剂可使用防腐剂或助溶剂制备。可作为本发明制剂的成分的其它优选的液体载体物质选自组包括油类,例如植物油、中性油和矿物油。
可作为本发明制剂的成分的优选的固体载体物质为水胶体,例如淀粉、降解淀粉、化学或物理改性淀粉、糊精、(粉末状)麦芽糊精(优选地具备葡糖值为5至25,优选10-20)、乳糖、二氧化硅、葡萄糖、改性纤维素、阿拉伯树胶、印度树胶、胺黄树胶、梧桐胶、卡拉胶、普鲁兰多糖、凝胶多糖、黄原胶、结冷胶、瓜尔豆胶、角豆粉、藻酸盐、琼脂、果胶和菊粉以及两种或两种以上这些固体物质的混合物,特别是麦芽糊精(优选地葡糖值为15至20)、乳糖,二氧化硅和/或葡萄糖。
此外,助水溶物,例如乙醇、异丙醇或多元醇,可用于改善流动性。适当的多元醇优选含有2至15个碳原子和至少两个羟基。这种多元醇可含有其它官能团,更具体地为氨基,或可被氮修饰。典型实例为:
·甘油;
·烷二醇,例如乙二醇、二乙二醇、丙二醇、丁二醇、己二醇和平均分子量为100至1000道尔顿的聚乙二醇;
·自缩合度为1.5至10的寡甘油技术混合物,如二甘油含量为40至50重量%的二甘油技术混合物;
·羟甲基化合物,特别是,例如三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、季戊四醇和二季戊四醇;
·低级烷基糖苷,尤其是烷基中含有1至8个碳原子的那些烷基糖苷,例如甲基糖苷和丁基糖苷;
·含有5至12个碳原子的糖醇,例如山梨醇或甘露糖醇;
·含有5至12个碳原子的糖,例如葡萄糖或蔗糖;
·氨基糖,例如葡糖胺;
·二醇胺,例如二乙醇胺或2-氨基丙烷-1,3-二醇。
防腐剂和/或产品保护剂
合适的防腐剂是,例如,苯氧乙醇、苯甲酸钠或山梨酸、上述成分的混合物以及Kosmetikverordnung(“Cosmetics Directive”)附录6A和B部分中列出的其他类别的化合物。可以改善产品保护的替代产品是例如1,2-链烷二醇,例如1,2-戊二醇、1,2-己二醇、1,2-辛二醇、1,2-癸二醇、1,2-十二烷二醇和其混合物,4-羟基苯乙酮。
染料
适合的染料是例如德国研究学会染料协会(Farbstoff-kommission derDeutschen Forschungsgemeinschaft)的公开物“Kosmetische”,VerlagChemie,Weinheim,1984,页81至106中列举的适于并批准用于化妆品的物质中的任何一种。实例包括胭脂红A(C.I.16255)、专利蓝V(C.I.42051)、靛蓝(C.I.73015)、叶绿酸(C.I.75810)、喹啉黄(C.I.47005)、二氧化钛(C.I.77891)、阴丹士林蓝RS(C.I.69800)和茜草红(C.I.58000)。鲁米诺(Luminol)也可用作荧光染料。有利的着色颜料是例如二氧化钛、云母、铁氧化物(例如Fe2O3、Fe3O4、FeO(OH))和/或氧化锡。有利的染料是例如胭脂红、柏林蓝、氧化铬绿、群青和/或锰紫。
制剂
根据本发明的优选组合物选自用于治疗、防护、护理和清洁皮肤和/或毛发的产品或作为化妆产品,优选地,作为免洗(leave-on)产品(是指与洗去(rinse-off)产品相比,一种或多种式(I)的化合物在皮肤和/或毛发上停留更长的时间)。
本发明的制剂优选以乳剂形式,例如W/O(油包水)、O/W(水包油)、W/O/W(水包油包水)、O/W/O(油包水包油)乳剂、PIT乳剂、皮克林(Picking)乳剂、油含量低的乳剂、微米乳剂或纳米乳剂、溶液,例如在油(脂肪油或脂肪酸酯,特别是C6-C32脂肪酸C2-C30酯)或硅油、分散体、悬浮液、乳霜、乳液或奶液中的溶液,取决于制备方法和成分、凝胶(包括水凝胶、水分散凝胶、油凝胶)、喷雾剂(例如泵喷雾剂或含有推进剂的喷雾剂)或用于擦拭化妆品的泡沫或浸渍溶液、洗涤剂,如肥皂、合成洗涤剂、洗涤液、淋浴和沐浴制剂、沐浴产品(胶囊、油剂、片剂、盐、浴盐、肥皂等);泡腾制剂、皮肤护理产品如乳剂(如上所述)、软膏剂、糊剂、凝胶(如上所述)、油、香油、乳清、粉末(如擦脸粉、身体粉)、面膜、眉笔、唇膏、走珠、泵剂、气雾剂(发泡、非发泡或后发泡)、除臭剂和/或止汗剂、漱口水和口腔清洗剂、足部护理产品(包括去角质、除臭剂)、驱虫剂、防晒霜、晒后用品、剃须产品、须后膏、剃须前和剃须后洗剂、脱毛剂、头发护理产品,如洗发香波(包括2合1香波,去屑香波,婴儿香波,干性发质香波,浓缩香波)、护发素、生发油、生发水、染发液、造型膏、润发油、烫发和卷发药水、发胶、定型助剂(如凝胶或蜡)、头发光滑剂(护发剂、松弛剂)、染发剂如短时直接染发剂、半永久性染发剂、永久性染发、护发素、护发摩丝、眼睛护理产品、化妆、卸妆或婴儿产品。
辅助物质和添加剂的含量为5至99%b.w.,优选10至80%b.w.,基于制剂总量计。本领域技术人员容易根据特定产品的性质通过简单试凑法确定在各情况下所使用的化妆品或护肤用品助剂和添加剂以及芳香剂的的量。
所述制剂还可至多含有99重量%,优选地,约5至约80重量%的水,更优选约10至约50或约60至约80重量%的水,基于制剂总量计。
洗涤剂组合物
本发明的另一个实施方案包括一种洗涤剂组合物,其含有上述香料组合物或香料制剂,优选含量为约0.1至约5重量%,并且更优选约0.5至约2重量%。
根据本发明的洗涤剂组合物可包含在此类组合物中常见的任何成分,例如阴离子、非离子、阳离子、两性或两性离子(助)表面活性剂、有机溶剂、助洗剂、酶以及其他助剂,例如防污剂、增稠剂、着色剂和香料等。
阴离子和两性离子表面活性剂
合适的阴离子和两性离子表面活性剂已经在上述化妆品组合物的上下文中公开。这些实施例适用于洗涤剂。
非离子表面活性剂
醇烷氧基化物。加入的非离子表面活性剂优选是烷氧基化和/或丙氧基化,特别是优选每摩尔醇含有8-18个碳原子以及平均1至12摩尔环氧乙烷(EO)和/或1至10摩尔环氧丙烷(PO)的伯醇。特别优选乙氧基化度为2至10,优选3至8,和/或丙氧基化度为1至6,优选1.5至5的C8-C16-醇烷氧基化物,有利的是乙氧基化物和/或丙氧基化物C10-C15-醇烷氧基化物,特别是C12-C14醇烷氧基化物。所述的乙氧基化度和丙氧基化度构成统计平均值,对于特定产物其可能为整数或分数。优选的醇乙氧基化物和丙氧基化物具有窄同系物分布(窄范围乙氧基化物/丙氧基化物,NRE/NRP)。除了这些非离子表面活性剂之外,也可使用具有大于12EO的脂肪醇。其实例为具有14EO、16EO、20EO、25EO、30EO或40EO的(牛油)脂肪醇。
烷基糖苷此外,作为额外的非离子表面活性剂,可以加入满足通式RO(G)x的烷基糖苷,例如作为化合物,特别是与非离子表面活性剂一起,其中R为直链或甲基-支化,尤其是2-甲基支化的,具有8至22,优选12至18个碳原子的脂族基团,G代表具有5或6个碳原子的单糖单元,优选葡萄糖。糖基化度x,其定义了单糖苷和低聚糖苷的分布,为1至10,优选1.1至1.4之间的数值。
脂肪酸酯烷氧基化物。另一类优选的非离子表面活性剂,其或作为单独的非离子表面活性剂或与其他非离子表面活性剂,特别是与烷氧基化脂肪醇和/或烷基糖苷结合使用,是烷氧基化,优选乙氧基化或乙氧基化和丙氧基化脂肪酸烷基酯,优选烷基链中含有1至4个碳原子,更特别地是,例如在日本专利申请中JP-A-58/217598记载的或优选通过国际专利申请WO-A-90/13533记载的方法制备的脂肪酸甲酯。特别优选含有平均3至15个EO,特别是含有约5至12个EO的C12-C18脂肪酸甲酯。
胺氧化物。胺氧化物类型的非离子表面活性剂,如N-椰油烷基-N,N-二甲基胺氧化物和N-牛油脂烷基-N,N-二羟乙胺氧化物,以及脂肪酸链烷醇酰胺类型也是适当的。这些非离子表面活性剂的量优选不大于乙氧基化脂肪醇的量,尤其是不大于其一半的量。
双子表面活性剂。其他的表面活性剂是所谓的双子表面活性剂。通常这类化合物是指每分子含有两个亲水基团和两个疏水基团的化合物。这些基团通常通过“间隔子”相互分隔。这种间隔子通常是碳链,其长度应足以使亲水基团有充足的距离能够相互独立的起作用。这类表面活性剂的特征通常在于非常小的临界浓度并且极大地降低水的表面张力。然而特殊情况下双子表面活性剂不仅指二聚也指三聚表面活性。适当的双子表面活性剂是例如德国专利申请DE 4321022 A1的硫酸化羟基混合醚,或根据国际专利申请96/23768 A1的二聚醇-双-和三聚醇-三-硫酸盐和-醚硫酸盐。根据德国专利申请DE 19513391 A1,封端的二聚和三聚混合醚的特征是其双官能性和多官能性。也可以使用如那些记载于国际专利申请WO 95/19953 A1、WO 95/19954 A1和WO 95/19955 A1中的双子聚羟基脂肪酸酰胺或聚羟基脂肪酸酰胺。
阳离子助表面活性剂
四烷基季铵盐。水溶液中阳离子活性表面活性剂含有解离阳离子中表面活性所需的疏水高分子基团。阳离子表面活性剂的重要代表是通式(R1R2R3R4N+)X-的四烷基季铵盐。其中R1代表C1-C8烷(烯)基,R2、R3和R4相互独立地代表含有1至22个碳原子的烷(烯)基。X是反离子,优选自卤素、烷基硫酸盐和烷基碳酸盐。特别优选阳离子表面活性剂,其中氮原子被两个长酰基和两个短烷(烯)基取代。
酯季铵盐。特别用作本发明的辅助表面活性剂的阳离子表面活性剂由所述酯季铵盐代表。酯季铵盐通常被理解为季铵化的脂肪酸三乙醇胺酯盐。这些是可以通过制备有机化学的相关方法得到的已知化合物。可以参考国际专利申请WO 91/01295A1,其中三乙醇胺在次磷酸的存在下使用脂肪酸部分酯化,将空气通入反应混合物,随后使用硫酸二甲酯或环氧乙烷整体季铵化。此外,德国专利DE 4308794 C1记载了制备固体酯季铵盐的方法,其中三乙醇胺酯的季铵化在适当分散剂,优选脂肪醇的存在下进行。
根据本发明适当使用的酯季铵盐的典型实例是一种产品,其酰基成分源自对应于式RCOOH的单羧酸,其中RCO是含有6至10个碳原子的酰基,并且氨基成分是三乙醇胺(TEA)。这类单羧酸的实例是己酸、辛酸、癸酸及其技术混合物,如例如所谓的头分馏脂肪酸。优选使用的酯季铵盐,其酰基成分源自含有8至10个碳原子的单羧酸。其他酯季铵盐是那些产物,其酰基成分源自二元碳酸如丙二酸、琥珀酸、马来酸、富马酸、戊二酸、山梨酸、庚二酸、壬二酸、癸二酸和/或十二烷二酸,但优选己二酸。总之优选其酰基源自含有6至22个碳原子的单羧酸和己二酸的混合物的酯季铵盐。在最终的酯季铵盐中单羧酸和二元羧酸的摩尔比为1:99至99:1并且优选50:50至90:10并且特别是70:30至80:20。除了季铵化脂肪酸三乙醇胺酯盐,其他适当的酯季铵盐是单/二元羧酸混合物与二乙醇烷基胺或1,2-二羟基丙基二烷基胺。酯季铵盐可以由脂肪酸和相应的甘油三酯与相应二元羧酸混合得到。一种这类方法,其可以为被看为相关现有技术的代表,记载于欧洲专利EP 0750606 B1。为了生产季铵化酯,单和二元羧酸和三乙醇胺的混合物—基于可用的羧基功能—摩尔比可以为1.1:1至3:1。考虑到酯季铵盐的性能,已经证明特别有利的比例是1.2:1至2.2:1,并且优选1.5:1至1.9:1。优选的酯季铵盐是平均酯化度为1.5至1.9的单、二和三酯的技术混合物。
两性表面活性剂
内铵盐。两性或两性离子表面活性剂具备多种可以在水溶液中离子化的官能团并从而—取决于介质条件—赋予化合物阴离子或阳离子属性(参见DIN 53900,1972年7月)。接近等电点(约pH4),两性表面活性剂形成内盐,从而在水中变得弱溶解或不溶。两性表面活性剂细分为两性物和内铵盐,后者在溶液中表现为两性离子。两性物是两性的电解质,即,同时具有酸性和碱性亲水基团,并因此依赖于条件表现为酸或表现为碱的化合物。尤其,内铵盐是已知的表面活性剂,其主要通过胺化合物的羧基烷基化,优选羧基甲基化生产。起始原料优选与卤代羧酸或其盐,尤其是氯乙酸钠缩合,每摩尔内铵盐形成一摩尔盐。不饱和羧酸,例如丙烯酸的加成也是可能的。适合的内铵盐的例子是仲胺,尤其是叔胺的羧基烷基化产物,其对应于通式R1R2R3N-(CH2)qCOOX,其中R1是具有6-22个碳原子的烷基基团,R2是氢或含有1-4个碳原子的烷基基团,R3是含有1-4个碳原子的烷基基团,q是1-6的数,以及X是碱和/或碱土金属或铵。典型的例子是己基甲基胺、己基二甲基胺、辛基二甲基胺、癸基二甲基胺、C12/14-椰子烷基二甲基胺、肉豆蔻基二甲基胺、鲸蜡基二甲基胺、硬脂基二甲基胺、硬脂基乙基甲基胺、油基二甲基胺、C16/18-牛脂烷基二甲基胺和它们的工业混合物,以及特别是十二烷基甲基胺、十二烷基二甲基胺、十二烷基乙基甲基胺和其工业混合物的羧基甲基化产物。
烷基酰胺基内铵盐。其它合适的内铵盐是酰胺基胺的羧基烷基化产物,其对应于通式R1CO(R3)(R4)-NH-(CH2)p-N-(CH2)qCOOX,其中R1CO是具有6-22个碳原子以及0或1至3个双键的脂族酰基基团,R2是氢或具有1-4个碳原子的烷基基团,R3是具有1-4个碳原子的烷基基团,P是1-6的数,q是1-3的数,和X是碱和/或碱土金属或铵。典型的例子是具有6-22个碳原子的脂肪酸,例如己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸,棕榈油酸、硬脂酸、异硬脂酸、油酸、反油酸、岩芹酸、亚油酸、亚麻酸、桐酸、花生四烯酸、顺(9)-二十碳烯酸、山嵛酸、芥酸和它们的工业混合物与N,N-二甲基氨基乙胺、N,N-二甲基氨基丙胺、N,N-二乙基氨基乙胺和N,N-二乙基氨基丙胺的反应产物,该产物与氯乙酸钠缩合。市售可得产品包括K和PK(Cognis Deutschland GmbH&Co.,KG)以及Betaine(Goldschmidt)。
咪唑啉。用于本发明目的的内铵盐的其它合适的起始原料是咪唑啉。这些物质也是已知的并且可以例如通过1或2摩尔的C6-C22脂肪酸与多官能胺例如氨基乙基乙醇胺(AEEA)或二亚乙基三胺的环化缩合获得。相应的羧基烷基化产物是不同的开链内铵盐的混合物。典型的实例是以上提及的脂肪酸与AEEA的缩合产物,优选基于月桂酸的咪唑啉,其随后用氯乙酸钠内铵盐化。市售可得产品包括G(Cognis Deutschland GmbH&Co.,KG)。
本发明的组合物中(辅助)表面活性剂的用量优选0.1至90重量%,特别是10至80重量%,并且特别优选20至70重量%。
有机溶剂
液态轻垢或重垢洗涤剂可以含有有机溶剂,优选那些与水互溶的。为此用量为0至90重量%,优选0.1至70重量%,特别是0.1至60重量%的聚二醇、醚、醇、酮、酰胺和/或酯优选用作有机溶剂。优选低分子量极性物质,如甲醇、乙醇、碳酸丙烯酯、丙酮、丙酮基丙酮、二丙酮醇、乙酸乙酯、2-丙醇、乙二醇、丙二醇、甘油、二乙二醇、二丙二醇单甲醚和二甲基甲酰胺或其混合物。
酶
纤维素酶。任选地,在本洗涤剂组合物中掺入纤维素酶,当使用该酶时,其优选以每克组合物足够提供最高达约5毫克,更优选约0.01毫克至约3毫克活性酶的含量掺入组合物中。除非另有说明,本发明组合物优选含有约0.001%(重量)至约5%(重量),优选0.01%-1%(重量)的市售酶制剂。
适用于本发明的纤维素酶包括细菌或真菌纤维素酶。优选它们具有5-9.5的最佳pH范围。适宜的纤维素酶是由Humicola insolens和腐植霉菌株DSM1800产生的真菌纤维素酶或者由属于气单胞菌属的真菌产生的纤维素酶212,和由海生软体动物(DolabellaAuricula Solander)的肝胰腺中提取的纤维素酶。适宜的纤维素酶也公开在GB 2,075,028A中。此外,特别适用于本发明的纤维素酶公开在WO 1992 013057A1中。最优选的,用于本洗涤剂组合物中的纤维素酶以产品名称CAREZYME和CELLUZYME从NOVOIndustries A/S商业购买。
其他酶。为了达到各种洗涤织物的目的,包括例如,除去蛋白质类、碳水化合物类或三甘油酯类污渍,以及为了避免脱落的染料迁移和为了织物的复原,在本发明的洗涤剂组合物中可以包括其他酶。可掺入的其他酶包括蛋白酶、淀粉酶、脂肪酶、和过氧化物酶,以及它们的混合物。也可以包括其它类型的酶。它们可以是任何适当的来源,如植物、动物、细菌、真菌和酵母源。然而,它们的选择由几个因素决定,如pH-活性和/或稳定性最佳值、热稳定性、对抗活性洗涤剂和助洗剂的稳定性,以及它们在使用中产生臭味的可能性。在该方面,细菌或真菌酶是优选的,如细菌淀粉酶和蛋白酶。
通常掺入足量的酶以提供每克组合物中最高达约5毫克重量,更典型的是约0.01毫克至约3毫克的活性酶。除非另有说明,本文中的组合物一般含有约0.001重量%至约5重量%,优选0.01重量%-1重量%的市售酶制品。蛋白酶在这种市售制品中通常以每克组合物提供0.005至0.1Anson单位(AU)活性度的含量存在。
适宜的蛋白酶实例为枯草杆菌蛋白酶,它是由枯草芽胞杆菌和地衣型芽胞杆菌的特殊菌株得到。另一种适当的蛋白酶是由芽孢杆菌菌株得到的,它在pH8-12范围内具有最大活性,是由Novo Industries A/S开发和销售的,它的注册商品名称为这种酶和类似酶的制备记载于Novo的英国专利GB 1,243,784中。市售可得的适合除去蛋白质基质污渍的蛋白水解酶包括由Novo Industries A/S出售的商品名为和和由International Bio-Synthitics,Inc.出售的那些。其它蛋白酶包括蛋白酶A、蛋白酶B和由Genencor International,Inc.,根据US 5,204,015和US 5,244,791。
洗涤剂可使用的适当脂肪酶包括由假单胞菌属族中的微生物,如司徒茨氏(stutzeri)假单胞菌ATCC 19154产生的那些脂肪酶。这种脂肪酶可由AmanoPharmacetical Co.Ltd.Nagoya,Japan买到,商品名为脂肪酶P“Amano”。其它市售脂肪酶包括Amano-CES、脂肪酶ex Chromobacter viscosum,例如,Chromobacter viscosum varlipolyticum NRRLB 3673,由Toyo Jozo Co.市售可得;和U.S.Biochemical Corp.和Disoynth Co.出售的其它色素杆菌viscosum脂肪酶,和脂肪酶ex唐菖蒲假单胞菌(Pseudomonas gladioli)。由腐植菌属胎毛菌(Humicola lanuginosa)得到的(由NovoIndustries A/S市售可得)买酶是本文中的优选脂肪酶。
过氧化物酶与氧源,例如过碳酸盐、过硼酸盐、过硫酸盐、过氧化氢等结合使用。它们用于“溶液漂白”,即避免在洗涤过程中从底物中脱落的染料或颜料迁移至洗涤溶液中的其它基物上。过氧化物酶在本技术领域中已知并包括例如辣根过氧化物酶、木质素酶,和卤代过氧化物酶,如氯代和溴代过氧化物酶。含有过氧化物酶的洗涤剂组合物公开在,例如WO1989 099813 A1。
酶稳定剂。本文中使用的酶可被在成品组合物中存在的水溶性钙和/或镁离子物源(其给酶提供这些离子)稳定化。(钙离子通常比镁离子更有效,如果只使用一种该类阳离子时本文优选使用钙离子)。其他的稳定性可通过在各种其它现有技术公开的稳定剂,尤其是硼酸盐类的存在获得,参见US 4,537,706,其再次全文引用。典型的洗涤剂,尤其是液体洗涤剂,每升成品组合物中含有约1至约30,优选约2至约20,更优选约5至约15,最优选约8至约12毫摩尔的钙离子。在固体洗涤剂组合物中,制剂可含有足够量的水溶性钙离子物源以提供在洗衣水溶液中所需的该物料量。另一方面,天然水的硬度是足够的。
应认识到,上述钙和/或镁离子的含量足以保证酶稳定性。可将更多的钙和/或镁离子加入组合物中以提供去除油脂的其他手段。因此,本发明的组合物的普通制剂可以含有约0.05重量%至约2重量%的水溶性钙或镁离子物源,或同时含有两者。当然该量可随组合物中所使用的酶的数量和类型而变化。
本发明组合物也可以任选地,但优选地含有各种其他的稳定剂,尤其是硼酸盐型稳定剂。通常,这种稳定剂在组合物中的用量为约0.25重量%至约10重量%,优选约0.5重量%至约5重量%,更优选约0.75重量%至约3重量%(基于硼酸计)。虽然,其它化合物,如氧化硼、硼砂和其它碱金属硼酸盐(例如原硼酸钠、偏硼酸钠和焦硼酸钠和戊硼酸钠)是适用的,但优选硼酸。取代的硼酸(例如,苯基硼酸、丁烷硼酸和对溴苯基硼酸)也可以用于代替硼酸。
助洗剂
沸石。含有结合水的细晶合成沸石,优选沸石A和/或沸石P可以用作助洗剂。特别优选的沸石P是沸石MAP.RTM.(Crosfield公司的市售产品)。然而,沸石X以及沸石A、X、Y和/或P的混合物也是适合的。特别优选以商品名RX(Condea Augusta S.p.A.的市售产品)可得的沸石X和沸石A的共结晶硅铝酸钠/钾。优选地可使用喷雾干燥粉末状的沸石。在以悬浮液形式加入沸石的情况下,可添加少量的非离子表面活性剂作为稳定剂,例如基于沸石计1至3重量%的、具有2至5个环氧乙烷基团的乙氧基化C12-C18脂肪醇、具有4至5个环氧乙烷基团的C12-C14脂肪醇或乙氧基化的异十三烷醇。合适的沸石具有的平均颗粒尺寸小于10微米(测量方法:体积分布Coulter计数器),并优选含有18至22重量%,更优选20至22重量%的结合水。此外,磷酸盐也可用作助洗剂。
层状硅酸盐。磷酸盐和沸石的适当替代品或部分替代品是结晶、层状硅酸钠。这类结晶层状硅酸钠记载于,例如欧洲专利申请EP 0164514 A1。优选的结晶层状硅酸盐是通过,例如国际专利申请WO 91/08171 A1中记载的方法得到的那些。
无定型硅酸盐。优选的助洗剂也包括模数(Na2O:SiO2比例)为1:2至1:3.3,优选1:2至1:2.8并且更优选1:2至1:2.6的无定型硅酸钠,其具有延时溶解和多次循环洗涤的特性。与传统的无定形硅酸钠相比这种延迟溶解特性可由各种方式获得,例如通过表面处理、复合、密实/压缩或通过过度干燥而获得。在本发明的范围内,术语“无定形”也指“X射线无定形”。换句话说在X射线衍射试验中,硅酸盐没有产生任何晶态物质的典型X射线反射,而是充其量具有一个或多个散射X射线的峰值,其具有几度衍射角的宽度。但是,当硅酸盐颗粒在电子衍射试验中产生不明显或者甚至清晰的衍射峰值时,可以实现特别好的助洗剂特性。这可理解为产品具有10至几百纳米的微晶范围,其中优选该值最大是50纳米,尤其最大为20纳米。在德国专利申请DE 4400024 A1中公开了与常规水玻璃相比,同样具有延迟溶解特性的这类X射线无定形硅酸盐。特别优选的是压缩/密实的无定形硅酸盐、复合的无定形硅酸盐和过度干燥的X射线无定形硅酸盐。
磷酸盐。也可使用通常已知的磷酸盐作为助洗剂,只要这种使用不会由于生态方面的原因而应当避免。特别合适的是正磷酸、焦磷酸以及尤其是三聚磷酸盐的钠盐。其含量通常不大于25重量%,优选不大于20重量%,基于最终组合物计。在有些情况下特别是三聚磷酸盐,在最大为10重量%的低含量下,基于最终组合物计,与其他助洗剂结合已经表现出二次洗涤功率的增效改善。磷酸盐的优选用量低于10重量%,特别是0重量%。
辅助助洗剂
聚羧酸。有用的有机辅助助洗剂是,例如可以其聚羧酸钠盐形式使用的聚羧酸,其中聚羧酸是指带有多于一个酸官能的羧酸。包括例如柠檬酸、己二酸、琥珀酸、戊二酸、苹果酸、酒石酸、马来酸、富马酸、糖酸、氨基羧酸、氨三乙酸(NTA)及其衍生物和混合物。优选的盐是聚羧酸如柠檬酸、己二酸、琥珀酸、戊二酸、酒石酸、糖酸的盐及其混合物。
有机酸。也可以使用酸本身。除了其助洗作用,酸通常也具有酸化成分的作用,因此可以在洗涤剂或清洁组合物中建立相对低和温和的pH值。特别可以提到柠檬酸、琥珀酸、戊二酸、己二酸、葡糖酸及其混合物。其他适当的酸化剂是已知的pH调节剂如碳酸氢钠和硫酸氢钠。
聚合物。特别适合的聚合物类辅助助洗剂是聚丙烯酸酯,其优选分子量为2000至20000g/mol。基于其出色的溶解性,本组中优选摩尔量为2000至10000g/mol,且特别优选3000至5000g/mol的短链聚丙烯酸酯。适当的聚合物也可以包括部分或完全由乙烯醇单元或其衍生物构成的物质。
其他适当的共聚羧酸盐特别是丙烯酸与甲基丙烯酸以及丙烯酸或甲基丙烯酸与马来酸的共聚物。已经证明丙烯酸与马来酸的共聚物,其含有50至90重量%的丙烯酸与50至10重量%的马来酸,特别合适。其相对分子量,基于自由酸计,通常为2000至70000g/mol,优选20000至50000g/mol并且尤其是30000至40000g/mol。(共)聚羧酸盐可以水溶液或优选以粉末加入。为了改善水溶解度,聚合物也可以含有烯丙基磺酸单体,如例如EP 0727448B1中的烯丙氧基苯磺酸和甲基烯丙基磺酸。
特别优选含有多于两种不同单体单元的可生物降解聚合物,实例是DE 4300772A1中含有丙烯酸盐和马来酸盐,以及乙烯醇或乙烯醇衍生物作为单体的那些,或含有丙烯酸和2-烷基烯丙基磺酸盐,以及糖衍生物作为单体的那些。其他优选的共聚物是记载于德国专利申请DE 4303320 A1和DE 4417734 A1中的那些并且优选包括丙烯醛和丙烯酸/丙烯酸盐或丙烯醛和乙酸乙烯酯作为单体。
同样地,其他优选的助洗剂是聚合物类氨基二羧酸,其盐或其前体物质。特别优选的是德国专利申请DE 19540086 A1中公开的聚天冬氨酸或其盐和衍生物,它们除了辅助助洗剂性能也具备漂白稳定作用。
其它适合的助洗剂是聚缩醛,它们是通过将二醛与具有5至7个碳原子和至少3个羟基的多羟基羧酸进行反应而获得的,如记载于欧洲专利申请EP 0280223 A1。优选的聚缩醛是由二醛例如乙二醛、戊二醛、对苯二甲醛及其混合物与多羟基羧酸,例如葡糖酸和/或葡庚糖酸获得的。
碳水化合物。其它合适的有机辅助助洗剂是糊精,例如碳水化合物的低聚物或聚合物,它们是通过淀粉部分水解而获得的。水解可以常规方法,例如酸催化或酶催化方法进行。优选的是平均摩尔量是400至500000g/mol的水解产物。优选一种具有葡萄糖当量(DE)为0.5至40,更特别是2至30的多糖,其中DE是与DE为100的葡萄糖相比,该多糖还原作用的可接受量度。可以使用DE是3至20的麦芽糊精和DE是20至37的干燥葡萄糖糖浆,以及所谓的具有2000至30000g/mol的较高分子量的黄糊精和白糊精。优选的糊精记载于英国专利申请94 19 091。
这类糊精的氧化衍生物涉及的是糊精与氧化剂的反应产物,其能至少使糖环的醇官能团氧化成羧酸官能团。这类氧化糊精和用于其制备的方法由例如欧洲专利申请EP0232202 A1已知。一种在糖环的C6上氧化的产物是特别优选的。
其它适合的辅助助洗剂是氧代二琥珀酸酯和二琥珀酸酯(Disuccinaten)的其它衍生物,优选乙基二胺二琥珀酸酯。优选使用钠盐或镁盐形式的乙二胺-N,N'-二琥珀酸(EDDS),其合成记载于例如US 3,158,615。在本文中特别优选的是甘油二琥珀酸酯和甘油三琥珀酸酯,如记载于US 4,524,009。在含有沸石和/或含有硅酸盐的制剂中加入量为3至15重量%。
内酯。其它可使用的有机辅助助洗剂例如是乙酰化的羟基羧酸或其盐,其任选也可以内酯的形式存在,且其含有至少4个碳原子,至少1个羟基以及至多2个酸基。这类辅助助洗剂记载于例如国际专利申请WO 1995 020029 A1。
漂白化合物、漂白制剂和漂白活化剂
本文的洗涤剂组合物可以任选地含有漂白制剂或含有漂白制剂和一种或多种的漂白活化剂的漂白组合物。如果存在,漂白制剂的含量通常至少为洗涤剂组合物的约1%至约30%,更特别为约5%至约20%,特别对于织物洗涤。如果含有漂白活化剂,其含量一般为包含漂白剂加漂白活化剂的漂白组合物的约0.1%至约60%,更优选为约0.5%至约40%。
本文中所用的漂白剂可以是适用于清洗织物,清洗硬表面,或其它现在已知或将已知的清洗用途的洗涤剂组合物中的任何漂白剂。这些包括氧漂白剂以及其它的漂白剂。本文中可以使用过硼酸盐漂白剂,例如过硼酸钠(例如一水合物或四水合物)。
可以不受限制地使用的另一类漂白剂包括过羧酸漂白剂和其盐。这类漂白剂的适当实例包括单过氧邻苯二甲酸镁六水合物,间氯过苯甲酸镁,4-壬基氨基-4-氧代过氧丁酸镁和二过氧十二烷二酸镁。
优选的过碳酸盐漂白剂包括具有平均颗粒度在约500至约1000微米范围的干燥颗粒,小于约200微米的所述颗粒不超过约10重量%,大于约1250微米的所述颗粒不超过约10重量%。任选地,过碳酸盐可以用硅酸盐、硼酸盐或水溶性表面活性剂涂覆。过碳酸盐可以从各种供应商得到。
也可以使用漂白剂的混合物。
过氧漂白剂,过硼酸盐,过碳酸盐等优选与漂白活化剂结合使用,这导致在水溶液(即在洗涤过程)中原位产生对应于漂白活化剂的过氧酸。壬酰氧基苯磺酸盐(NOBS)和四乙酰基乙二胺(TAED)活化剂是典型的活化剂,也可以使用它们的混合物。
优选的酰胺基衍生的漂白活化剂包括(6-辛酰氨基-己酰基)氧基苯磺酸盐、(6-壬酰氨基己酰基)氧基苯磺酸盐、(6-癸酰氨基-己酰基)氧基苯磺酸盐及其混合物。
另一类漂白活化剂包括US4966723中公开的苯并噁嗪类活化剂,其在此引用。
非常优选的内酰胺活化剂包括苯甲酰基己内酰胺,辛酰基己内酰胺,3,5,5-三甲基己酰基己内酰胺,壬酰基己内酰胺,癸酰基己内酰胺,十一碳烯酰基己内酰胺,苯甲酰基戊内酰胺,辛酰基戊内酰胺,癸酰基戊内酰胺,十一碳烯酰基戊内酰胺,壬酰基戊内酰胺,3,5,5-三甲基己酰基戊内酰胺和它们的混合物,任选吸附在固体载体上,例如酰基己内酰胺,优选苯甲酰基己内酰胺,它们被吸附到过硼酸钠中。
非常优选的内酰胺活化剂包括苯甲酰基己内酰胺,辛酰基己内酰胺,3,5,5-三甲基己酰基己内酰胺,壬酰基己内酰胺,癸酰基己内酰胺,十一碳烯酰基己内酰胺,苯甲酰基戊内酰胺,辛酰基戊内酰胺,癸酰基戊内酰胺,十一碳烯酰基戊内酰胺,壬酰基戊内酰胺,3,5,5-三甲基己酰基戊内酰胺和它们的混合物,任选吸附在固体载体上,例如酰基己内酰胺,优选苯甲酰基己内酰胺,它们被吸附到过硼酸钠中。
如果需要,漂白化合物可以用锰化合物来催化。该类基于锰的催化剂在本领域公知并且包括MnIV 2(u-O)3(1,4,7-三甲基-1,4,7-三氮杂环壬烷)2(PF6)2,MnIII 2(u-O)1(u-OAc)2(1,4,7-三甲基-1,4,7-三氮杂环壬烷)2(ClO4)2,MnIV 4(1,4,7-三氮杂环壬烷)4(ClO4)4,MnIIIMnIV 4(u-O)1(u-OAc)2(1,4,7-三甲基-1,4,7-三氮杂环壬烷)2(ClO4)3,MnIV(1,4,7-三甲基-1,4,7-三氮杂环壬烷)-(OCH3)3(PF6),和它们的混合物。
在实际应用中,不受局限性,本发明组合物和方法可以被调节以便在洗涤水溶液中提供至少约每千万分之一的活性漂白催化剂,优选在洗涤溶液中提供约0.1ppm至约700ppm,更优选约1ppm至约500ppm的催化剂物质。
聚合污垢解脱剂
在本发明的洗涤剂组合物和方法中可以采用任何本领域技术人员已知的聚合污垢解脱剂。聚合污垢解脱剂的特征在于含有亲水部分,用于使疏水织物如聚酯和尼龙的表面亲水化,以及疏水部分,其沉积在疏水纤维上并在整个洗涤过程中保持粘附其上,从而用作亲水部分的固定锚。这使得使用污垢解脱剂处理后的污渍在之后的清洗程序中更容易去除。
文中使用的聚合污垢解脱剂特别包括那些污垢解脱剂,其具备(a)一个或多个非离子亲水成分,主要由以下成分组成:(i)聚合度至少为2的聚氧乙烯片段,或(ii)氧化丙烯或聚合度为2至10的聚氧丙烯片段,其中所说的亲水片段不包含任何氧化丙烯单元除非它通过醚连接到每一端部的邻近部分处,或(iii)含有氧化乙烯和1至约30氧化丙烯单元的氧化烯单元的混合物,其中所说的混合物含有足够量的氧化乙烯单元以使亲水组份具有足够大的亲水性能以提高以污垢解脱剂在织物表面上的沉积来衡量的普通聚酯合成纤维表面的亲水性能,所说的亲水片段优选地包含至少约25%的氧化乙烯单元和更优选地,特别对这些具有约20至30氧化丙烯单元的组分,它们含有至少约50%氧化乙烯单元;或(b)一种或多种疏水组份,它们包含(i)C3氧化烯基对苯二酸酯片段,其中,如果所说的疏水组份还包含氧化乙烯基对苯二酸酯,则氧化乙烯基对苯二酸酯与C3氧化烯基对苯二酸酯单元的比率为约2∶1或更低,(ii)C4-C6亚烷基或氧化C4-C6烯片段,或它们的混合物,(iii)聚(乙烯酯)片段,优选的是聚合度至少为2的聚(乙酸乙烯酯)或(iv)C1-C4烷基醚或C4羟烷基醚取代基,或它们的混合物,其中所说的取代基是以C1-C4烷基醚或C4羟烷基醚纤维素衍生物或它们的混合物的形式存在,其中的纤维素衍生物是两性的,或(a)和(b)的结合,因此它们具有足够量的C1-C4烷基醚和/或C4羟烷基醚单元以沉积到普通的聚酯合成纤维表面之上和保持足够量的羟基—一旦它们粘结到普通的合成纤维表面—以提高纤维表面的亲水性能。
虽然更高的聚合度也可使用,但通常(a)(i)的聚氧化乙烯片段具有的聚合度为约200,优选的为3至约150,更优选的为6至约100。适用的氧C4-C6烯基疏水物片段包括,但并不只限于,聚合污垢解脱剂的封端。
可用于本发明的聚合污垢解脱剂也包括纤维素衍生物例如羟基醚纤维素聚合物,对苯二酸一乙二醇或对苯二酸一丙二醇与聚环氧乙烷或聚环氧丙烷对苯二甲酸酯的嵌段共聚物,和类似的物质。这类制剂市售可得并且包括纤维素的羟基醚,如(DOW)。本发明中使用的纤维素污垢解脱剂还包括C1-C4烷基和C4羟烷基纤维素。
以聚(乙烯基酯)疏水片段为特征的污垢解脱剂包括聚(乙烯基酯),如C1-C6乙烯基酯的接枝共聚物,优选的是聚(乙酸乙烯酯)接枝到聚烯化氧主链,如聚环氧乙烷主链上的共聚物,参见EP 0,219,048,其在此全文引用。市售可得的这类污垢解脱剂包括类物质,例如可从BASF得到的HP-22。
一类优选的污垢解脱剂是具有对苯二酸一乙二醇和聚环氧乙烷(PEO)对苯二甲酸酯的无规嵌段的共聚物。该聚合污垢解脱剂的分子量为约25,000至约55,000。
另一种优选的聚合污垢解脱剂是带有乙二醇对苯二甲酸酯重复单元的聚酯,其中含有10重量%-15重量%的乙二醇对苯二甲酸酯单元和90重量%-80重量%(重量)的聚氧乙烯对苯二甲酸酯单元,其从平均分子量为300-5000的聚氧化亚乙基二醇得到。这种聚合物的实例包括市售的5126(Dupont生产)和T(ICI生产)。
还有一种优选的聚合污垢解脱剂是基本上为直链酯低聚物的磺化产物,该低聚物含有对苯二酰基和氧亚烷基氧基重复单元低聚酯骨架,以及与该骨架共价相连的末端部分。US 4,968,451中对这些污垢解脱剂有完整的描述。其它适用的聚合污垢解脱剂包括US4,711,730中的对苯二甲酸酯聚酯,US 4,721,580中阴离子封端的低聚酯和US 4,702,857中的嵌段聚酯低聚物,以及US 4,877,896中的阴离子,特别是磺基芳酰基封端的对苯二甲酸酯,所有引用的专利全文引用。
另外优选的污垢解脱剂是具有以下重复单元的低聚物:对苯二酰单元、磺基间苯二酰单元、氧亚乙基氧和氧-1,2-亚丙基单元。这些重复单元构成了低聚物的骨架并优选用改性的羟乙磺酸盐封端。特别优选的此类污垢解脱剂包含约一个磺基间苯二酰单元,5个对苯二酰单元,比例为约1.7至约1.8的氧亚乙基氧和氧-1,2-亚丙基氧单元,和两个2-(2-羟乙氧基)乙烷磺酸钠的封端单元。所说的污垢解脱剂还包含按低聚物重量计约0.5重量%-20重量%降低结晶的稳定剂,该稳定剂优选选自二甲苯磺酸盐、枯烯磺酸盐、甲苯磺酸盐和其混合物。
如果使用污垢解脱剂,则其用量一般为本发明洗涤剂组合物重量的约0.01重量%-约10.0重量%,通常为约0.1重量%-约5重量%,优选约0.2重量%-约3.0重量%。
聚合物分散剂
在本发明的洗涤剂组合物中聚合物分散剂的用量有利的是约0.1重量%至约7重量%,特别是在沸石和/或层状硅酸盐助洗剂的存在下。适当的聚合物分散剂包括聚合的多羧酸盐和聚乙二醇,尽管本领域熟知的其它分散剂也可以使用。虽然不想受理论限制,但可以认为,聚合物分散剂当与其它助洗剂(包括低分子量聚羧酸盐)一起使用时,通过晶体增长抑制、颗粒污垢释放胶溶作用和抗再沉积作用,聚合物分散剂增强了整个洗涤助洗剂的性能。
通过聚合或共聚适当的不饱和单体,优选以酸的形式,可以制得聚合的多羧酸盐物质。可以聚合形成适当的聚合多羧酸盐的不饱和单体酸包括丙烯酸、马来酸(或马来酸酐)、富马酸、衣康酸、乌头酸、中康酸、柠康酸和亚甲基丙二酸。在聚合多羧酸盐中存在含非羧酸基如乙烯基甲基醚、苯乙烯、乙烯等的单体片段是适宜的,只要这些片段不占多于约40%重量。
特别适当的聚合的多羧酸盐可以由丙烯酸制得。本发明使用的这些丙烯酸为基的聚合物是聚合丙烯酸的水溶性盐。这些呈酸形式的聚合物的平均分子量优选为约2000-10,000,更优选地为约4,000-7,000,最优选的为约4,000-5,000。这些丙烯酸聚合物的水溶性盐可包括,如碱金属、铵和取代的铵盐。这种可溶聚合物是已知材料。例如US 3,308,067中已公开在洗涤剂组合物中使用这种聚丙烯酸盐。
丙烯酸/马来酸为基的共聚物也可用作分散/抗再沉积剂的优选成分。这些材料包括丙烯酸和马来酸共聚物的水溶性盐。这些呈酸形式的共聚物的平均分子量优选为约2,000-100,000,更优选的约5,000-75,000,最优选的约7,000-65,000。在这些共聚物中丙烯酸盐和马来酸盐片段的比值一般为约30:1至约1:1,更优选为约10:1至2:1。这些丙烯酸/马来酸共聚物的水溶性盐可包括,如碱金属、铵和取代的铵盐。这类水溶性的丙烯酸盐/马来酸盐共聚物是公开于EP 0193360 A1的已知物质,该申请也记载了该类聚合物含有羟丙基丙烯酸盐。其他有用的分散剂包括马来酸/丙烯酸/乙烯醇三元共聚物,例如马来酸/丙烯酸/乙烯醇的45/45/10三元共聚物。
可加入的另一聚合物材料是聚乙二醇(PEG)。PEG可以显示分散剂性能,以及可作为粘土污垢去除-抗再沉积剂。为这些目的使用的一般分子量范围为约500至约100,000,优选为约1,000至约50,000,更优选为约1,500至约10,000。
聚天冬氨酸和聚谷氨酸分散剂也可以使用,特别是同沸石助洗剂混合使用。分散剂如聚天冬氨酸的分子量(平均)约10,000。
泡沫抑制剂
尤其是在自动洗涤过程中可以向组合物中有利的加入常规泡沫抑制剂。适当的泡沫抑制剂包括例如天然或合成皂,其含有大量C18-C24脂肪酸。非表面活性类型的泡沫抑制剂是,例如有机多分子硅醚以及其与微细,任选硅烷化二氧化硅的混合物,以及石蜡、蜡、微晶蜡以及其与硅烷化二氧化硅或二硬脂酰二亚乙基二胺的混合物。优选使用各种泡沫抑制剂的混合物,例如硅酮、石蜡或蜡的混合物。优选地,泡沫抑制剂,尤其是含有硅酮和/或石蜡的泡沫抑制剂,负载到颗粒,水溶性或可分散载体材料上。尤其是在这种情况下优选石蜡和二硬脂酰二亚乙基二胺的混合物。
可以将减少或抑制泡沫形成的化合物加入本发明的洗涤剂组合物。在所谓的“高浓度清洗过程”和前置式欧式洗衣机中抑制泡沫特别重要。
各种材料可以用作泡沫抑制剂,并且本领域技术人员已知泡沫抑制剂。参见,例如Kirk Othmer Encyclopedia of Chemical Technology,Third Edition,Volume 7,pages430-447(John Wiley&Sons,Inc.,1979)。特别感兴趣的一类泡沫抑制剂包括一元羧酸脂肪酸和它们的可溶性盐。用做泡沫抑制剂的一元羧酸脂肪酸及它们的盐通常具备有10至约24个碳原子、优选12至18个碳原子的烃链。适当的盐包括碱金属盐如钠、钾、和锂盐,以及铵和烷醇铵盐。
本发明的洗涤剂组合物还可含有非表面活性剂泡沫抑制剂。这些物质包括例如高分子量烃如石腊、脂肪酸酯(例如,脂肪酸三甘油酯)、脂肪酸的一元醇酯,脂肪族C18-C40酮(例如硬脂酮)等。其它泡沫抑制剂包括N-烷基化氨基三嗪例如作为氰尿酰氯与2至3摩尔的含1至24个碳原子的伯或仲胺的产物而生成的三-至六-烷基三聚氰胺(alkylemlamines)或二至四烷基二胺氯代三嗪,氧化丙烯,单十八烷基磷酸酯如单十八烷醇磷酸酯、单十八烷基二碱金属(例如钠、钾、锂)磷酸盐和磷酸酯。烃如石腊和卤代石腊可呈液态使用。液态烃在室温和大气压下呈液态,倾点在约-40℃至约50℃的范围内,最低沸点不低于约110℃(大气压下)。还公知的是利用含腊烃,优选熔点低于约100℃。现有技术已知烃类泡沫抑制剂并且包括脂肪族、脂环族、芳族、及杂环族具有约12至约70个碳原子的饱和或不饱和烃。术语“石腊”在这一泡沫抑制剂讨论部分中使用是指包括真石腊与环烃的混合物。
另一类优选的非表面活性剂泡沫抑制剂包括硅氧烷泡沫抑制剂。在这一类中包括使用聚有机硅氧烷油,如聚二甲基硅氧烷,聚有机硅氧烷油或树脂的分散液或乳液,以及聚有机硅氧烷与硅胶颗粒的组合物,其中聚有机硅氧烷被化学吸附或熔融在硅胶上。硅氧烷泡沫抑制剂在本领域中是公知的。
其它的硅氧烷泡沫抑制剂公开在US 3,455,839中,其在此全文引用,它涉及的是通过添加少量的聚二甲基硅氧烷流体使水溶液消泡的组合物和方法。
硅氧烷与硅烷化硅胶的混合物记载于例如DE-OS 2124526中,其在此全文引用。。在粒状洗涤剂组合物中的硅氧烷消泡剂和泡沫控制剂公开在US 4,652,392,其在此全文引用。
在优选的用于本发明的硅氧烷泡沫抑制剂中,连续相的溶剂是由某些聚乙二醇或聚乙二醇-聚丙二醇共聚物或它们的混合物(优选)、或聚丙二醇组成。主要的硅氧烷泡沫抑制剂是支链的/交联的,优选不是直链的。
本发明的硅氧烷泡沫抑制剂优选含聚乙二醇和聚乙二醇/聚丙二醇的共聚物,这些聚合物的平均分子量小于约1,000,优选为约100-800。本发明所用的聚乙二醇和聚乙二醇/聚丙二醇共聚物在室温下在水中的溶解度大于约2%重量,优选大于约5%重量。
本发明所用的优选的溶剂为聚乙二醇,其平均分子量低于约1,000,更优选约为100-800,最优选约为200-400,以及聚乙二醇/聚丙二醇共聚物,优选PPG200/PEG300。聚乙二醇与聚乙二醇/聚丙二醇共聚物的重量比优选为约1:1-1:10,最优选为1:3-1:6。
本发明所用的其它的泡沫抑制剂含有仲醇(例如2-烷基链烷醇)和这些醇与硅氧烷油的混合物。仲醇包括具有C1-C16链的C6-C16烷基醇。优选的醇是2-丁基辛醇,它可由Condea公司以商标12购得。仲醇的混合物可以商标123从Enichem公司购得。混合的泡沫抑制剂一般含醇+硅氧烷的1:5至5:1重量比的混合物。
本发明的组合物一般含0%-约5%的泡沫抑制剂。当用作泡沫抑制剂时,一元脂肪酸及其盐一般用量达洗涤剂组合物的约5重量%。优选的使用约0.5%-3%的一元脂肪酸泡沫抑制剂。硅氧烷泡沫抑制剂一般用量可达洗涤剂组合物的约2重量%,当然更大的量也可以用。用量上限可根据实际确定,主要考虑使成本最低以及较低的量能有效控制起泡的效果。优选使用约0.01%至约1%的硅氧烷泡沫抑制剂,更优选为约0.25%至约0.5%。如本发明所用的。这些重量百分数值包括用于聚有机硅氧烷混合的任意二氧化硅,以及可以使用的任何添加剂。单硬脂酰磷酸盐泡沫抑制剂一般用量为组合物重量的约0.1重量%至约2重量%。烃泡沫抑制剂一般用量为约0.01重量%至约5.0重量%,虽然更大的量也可以用。醇泡沫抑制剂一般用量为成品组合物的0.2重量%-3重量%。
螯合剂
多磷酸盐可被认为是螯合剂或稳定剂,特别是用于对重金属离子敏感的过氧化合物和酶。例如1-羟基乙烷-1,1-二磷酸钠盐、二亚乙基三胺五亚甲基膦酸钠或乙二胺四亚甲基膦酸钠的用量为0.1至5重量%。
本发明的洗涤剂组合物还可任选地含有一种或多种铁和/或锰螯合剂。这些螯合剂可选自组包括氨基羧酸盐、氨基膦酸盐、多官能团取代的芳族螯合剂以及它们的混合物,这些都在下文有定义。不受理论限制,可以认为,这些物质的效益,部分是由于通过生成可溶性螯合物从而可从洗涤溶液中除去铁和锰离子的超凡能力。上文记载的一些洗涤剂助洗剂可以用作螯合剂并且如果这类洗涤剂助洗剂以充足含量存在,可以提供两种功能。
用作任选的螯合剂的氨基羧酸盐包括乙二胺四乙酸盐、N-羟乙基乙二胺四乙酸盐、次氮基三乙酸盐、乙二胺四丙酸盐、三亚乙基四胺六乙酸盐、二亚乙基三胺五醋酸盐和乙醇二甘氨酸,它们的碱金属、铵和取代的铵盐以及它们的混合物。
当至少低的总含量磷允许在洗涤剂组合物中存在时,氨基膦酸盐也适于用作本发明组合物的螯合剂,包括乙二胺四(亚甲基膦酸盐)即DEQUEST。优选地,这些氨基膦酸盐不含6个碳原子以上的烷基或链烯基。
多官能团取代的芳族螯合剂也适用于本发明的组合物。这类呈酸形式的优选化合物是二羟基二磺基苯,如1,2-二羟基-3,5-二磺基苯。
用于本发明的优选的生物降解的螯合剂是乙二胺二琥珀酸盐("EDDS")特别是[S,S]异构体。
如果使用,这些螯合剂在洗涤剂组合物中的含量通常为约0.1重量%至约10重量%。更优选地,如果使用,这类组合物含有约0.1重量%至约3.0重量%的螯合剂。
粘土污垢去除剂/抗再沉积剂
本发明的洗涤剂组合物还能任选地含有具有粘土污垢去除和抗再沉积性能的水溶性乙氧化胺。含这些化合物的粒状洗涤剂组合物一般含约0.01重量%至约10.0重量%的水溶性乙氧化胺;液态洗涤剂组合物通常含有约0.01%至约5%。
最优选的粘土污垢去除剂和抗再沉积剂是乙氧化四亚乙基五胺。示例乙氧化胺在US 4,597,898中进一步记载。另一类优选的粘土污垢去除-抗再沉积剂是EP 111,965中公开的阳离子化合物,EP 111,984 A1中公开的乙氧化胺聚合物,EP 112,592 A1中公开的两性离子聚合物,和US 4,548,744中公开的胺氧化物。另一类优选的抗再沉积剂包括羧甲基纤维素(CMC)物质。这些物质在本领域是众所周知的。
变褐抑制剂
变褐抑制剂的任务是,使由纤维脱离的污物保持悬浮在清洗液体中,并从而避免污物的再次吸附。为此大部分有机天然的水溶性溶胶,例如(共)聚羧酸、胶料、明胶的盐、淀粉或纤维素的醚羧酸或醚磺酸盐、或纤维素或淀粉的酸性硫酸酯的盐是适合的。同样适用于此目的的是含有酸性基团的水溶性聚酰胺。此外可溶解的淀粉制剂等,例如水解淀粉、醛淀粉等可以用作上述淀粉产品。同样可以使用的是聚乙烯吡咯酮。然而优选纤维素醚是如羧甲基纤维素(钠盐)、甲基纤维素、羟烷基纤维素和混合醚如甲基羟乙基纤维素、甲基羟丙基纤维素、甲基羧甲基纤维素及其混合物,以及聚乙烯吡咯烷酮,使用量为0.1至5重量%,基于组合物计。
荧光增白剂和UV-吸收剂
现有技术已知的任何荧光增白剂或其他提亮或增白制剂通常可以约0.05重量%至约1.2重量%的量加入本发明的洗涤剂组合物。可在本发明中使用的市售荧光增白剂可以分为亚组,包括但不限于二苯乙烯、吡唑啉、香豆素、羧酸、甲烷青色素、二苯并噻吩-5,5-二氧化物、唑类、5-和6-元杂环的衍生物和其他各种制剂。
优选的增白剂包括Verona的系列增白剂。其他公开的增白剂包括:UNPA,Tinopal CBS和Tinopal 5BM,购自Ciba-Geigy;ArticCC和ArticWhite CWD,购自Hilton-Davis;2-(4-苯乙烯基-苯基)-2H-萘酚[1,2-d]三唑类;4,4'-二-(1,2,3-三唑-2-基)-二苯乙烯类;4,4'二(苯乙烯基)联苯类;和氨基香豆素。这些增白剂的具体实例包括4-甲基-7-二乙基-氨基香豆素、1,2-二(苯并咪唑-2-基)乙烯、1,3-二苯基-吡唑啉类、2,5-二(苯并噁唑-2-基)噻吩、2-苯乙烯基-萘并[1,2-d]噁唑和2-(二苯乙烯-4-基)-2H-萘并[1,2-d]三唑。阴离子增白剂可优选用于本发明组合物中。
组合物可以含有例如二氨芪二磺酸衍生物及其碱金属盐作为荧光增白剂。适当的荧光增白剂是例如4,4'-双(2-苯胺基-4-吗啉基-1,3,5-三嗪基-6-氨基)芪-2,2'-二磺酸或类似结构的化合物,该化合物携带有二乙醇氨基、甲基氨基、苯氨基或2-甲氧基乙基氨基以代替吗啉基。此外可以存在取代的联苯苯乙烯基类增白剂,例如4,4'-双(2-磺基苯乙烯基)-联苯、4,4'-双(4-氯-3-磺基苯乙烯基)-联苯或4-(4-氯苯乙烯基)-4'-(2-磺基苯乙烯基)-联苯的碱金属盐。也可以使用上述荧光增白剂的混合物。
此外可以加入UV吸收剂。UV吸收剂是对紫外线辐射具备出色吸附性能的化合物,其作为UV稳定剂还可以改善用于纺织纤维的颜料和染料的光稳定性以及通过防止UV辐射渗透过纤维波保护纤维产品穿戴者的皮肤。通常高效的无辐射惰化化合物是由羟基和/或烷氧基取代,特别是2位和/或4位的二苯酮的衍生物。同样适当的是取代的苯并三唑,3位苯基取代并任选2位氰基取代的丙烯酸酯(肉桂酸衍生物)、水杨酸酯、有机Ni配合物、以及天然物质如伞形酮以及本体尿刊酸。在优选实施方案中UV吸收剂吸收UV-A和UV-B辐射以及可能的UV-C辐射并再次放射蓝光波长的光,使其额外地具有光学增亮效果。优选的UV吸收剂含有三嗪衍生物,例如羟基芳基-1,3,5-三嗪、磺化1,3,5-三嗪、o-羟苯基苯并三唑和2-芳基-2H-苯并三唑以及双(苯胺基三嗪基-氨基)芪二磺酸及其衍生物。也可以使用紫外吸收染料如二氧化钛作为UV吸附剂。
染料转移抑制剂
本发明的洗涤剂组合物也可以含有一种或多种有效用于防止染料在洗涤过程中由一种织物转移至另一种织物的物质。通常该染料转移抑制剂包括聚乙烯基吡咯烷酮聚合物、聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、酞菁锰、过氧化物酶和它们的混合物。如果使用这些制剂,其含量通常为组合物的约0.01重量%至约10重量%,优选约0.01重量%至约5重量%,并且更优选约0.05重量%至约2重量%。
更具体地,在本发明中优选使用的聚胺N-氧化物聚合物记载于US 6,491,728,在此全文引用。
可使用任何聚合物骨架只要形成的氧化胺聚合物是水溶性的和具有染料转移抑制性质。适当的聚合骨架的实例是聚乙烯、聚亚烷基、聚酯、聚醚、聚酰胺、聚酰亚胺、聚丙烯酸酯和它们的混合物。这些聚合物包括无规或嵌段共聚物,其中一种单体类型是胺N-氧化物,而另一种单体类型是N-氧化物。胺N-氧化物聚合物通常具有胺与胺N-氧化物的比例为10:1至1:1,000,000。然而,在聚胺氧化物聚合物中存在的氧化胺基团的数目可通过合适的共聚或合适程度的N-氧化改变。聚胺氧化物几乎可以任何聚合程度得到。平均分子量通常为500-1000000;更优选为1000-500000;最优选为5000-100000。优选类的物质可称为“PVNO”。
用于本发明洗涤剂组合物中的最优选聚胺N-氧化物是聚(4-乙烯基吡啶-N-氧化物),它的平均分子量为约50000,胺与胺N-氧化物比例为约1:4。
N-乙烯基吡咯烷酮和N-乙烯基咪唑聚合物的共聚物(称为“PVPVI”)也优选用于本发明中。PVPVI的平均分子量优选为5000-1000000,更优选5000-200000,最优选10000-20000。PVPVI共聚物通常具有N-乙烯基咪唑与N-乙烯基吡咯烷酮的摩尔比为1:1-0.2:1,更优选0.8:1-0.3:1,最优选0.6:1-0.4:1。这些共聚物可以是直链或支链的。
本发明的组合物也可以使用平均分子量为约5000-约400000,优选约5000-约200000,更优选约5000-约50000的聚乙烯基吡咯烷酮("PVP"),PVP是洗涤剂领域的技术人员已知的。含有PVP的组合物还可含有平均分子量为约500-约100000,优选约1000-约10000的聚乙二醇("PEG")。在洗涤溶液中提供的PEG与PVP的比例为约2:1至约50:1,更优选为约3:1至约10:1。
本发明的洗涤剂组合物也可以任选含有约0.005重量%至5重量%的某些亲水光学增白剂,其可以提供染料转移抑制作用。如果使用,本发明的组合物优选含有约0.01重量%至1重量%的这类荧光增白剂。
一种优选的增白剂是4,4'-二[(4-苯胺基-6-(N-2-二-羟乙基)-s-三嗪-2-基)氨基]-2,2'-芪二磺酸和二钠盐。这种特定的增白剂种类以商品名由Ciba-Geigy公司出售。Tinopal-UNPA-GX是在本发明的洗涤剂组合物中优选使用的亲水荧光增白剂。
另一种优选的增白剂是4,4'-二[(4-苯胺基-6-(N-2-羟乙基-N-甲氨基)-s-三嗪-2-基)氨基]2,2'-芪二磺酸二钠盐。这种特定的增白剂种类以商品名Tinopal由Ciba-Geigy公司出售。
当与上述选择的聚合染料转移抑制剂结合使用时,选择用于本发明的特定荧光增白剂提供特别有效的染料转移抑制性能。这类选择的聚合物材料(例如PVNO和/或PVPVI)与这类选择的荧光增白剂(例如Tinopal UNPA-GX、Tinopal 5BM-GX和/或Tinopal AMS-GX)的结合在水性洗涤溶液中提供了比单独使用的这两种洗涤剂组合物组分的任一种显著好的对染料转移的抑制。不受理论限制,相信这种增白剂的作用方式是:由于它们对洗涤溶液中的织物有高亲合力,因此相对快速地沉积在这些织物上。增白剂沉积在洗涤溶液中织物上的程度被用称为“消耗系数”的参数来定义。该消耗系数一般指a)沉积在织物上的增白剂物质与b)在洗涤水溶液中的初始增白剂浓度的比例。具有相对高消耗系数的增白剂在本发明的这类技术内容中最适合用于抑制染料转移。
当然,也会意识到这些化合物其它类型常规荧光增白剂可任选地用于本发明组合物中以提供常规的织物“增白”益处,但实际上没有抑制染料转移的效果。这种应用是常规的并且是洗涤剂配制中公知的。
增稠剂
组合物也可以含有常规增稠剂和抗沉积组合物以及粘度调节剂如聚丙烯酸酯、聚羧酸、多糖及其衍生物、聚氨酯、聚乙烯吡咯烷酮、蓖麻油衍生物、多胺衍生物如季铵化和/或乙氧基化六亚甲基二胺及其混合物。优选的组合物粘度小于10,000mPa*s,使用Brookfield粘度计在20℃的温度和50min-1剪切速率下测定。
无机盐
组合物的其他适当成分是水溶性无机盐如碳酸氢盐、碳酸盐、无定型硅酸盐或其混合物;特别使用碱金属碳酸盐和无定型硅酸盐,主要是Na2O:SiO2摩尔比为1:1至1:4.5,优选1:2至1:3.5的硅酸钠。优选的组合物含有碱金属盐、助洗剂和/或辅助助洗剂,优选碳酸钠、沸石、晶体层状硅酸钠和/或柠檬酸三钠,含量为0.5至70重量%,优选0.5至50重量%,特别是0.5至30重量%的无水物质。
胶囊和包封
组合物通常通过固体封装材料封装,该固体封装材料优选选自淀粉、降解的或化学或物理改性的淀粉(特别是糊精和麦芽糖糊精)、明胶、阿拉伯树胶、琼脂、加蒂胶、结冷胶、改性和非改性纤维素、支链淀粉、凝胶多糖、角叉菜聚糖、海藻酸、海藻酸盐、果胶、菊粉、黄原胶和两种或更多种所述物质的混合物。
固体封装材料优选地选自明胶(优选猪肉、牛肉、鸡肉和/或鱼明胶及其混合物,优选包含至少一种bloom值大于或等于200的明胶,优选具有bloom值大于或等于240)、麦芽糊精(优选从玉米、小麦、木薯或马铃薯中获得,优选麦芽糊精的DE值为10-20)、改性纤维素(例如纤维素醚)、海藻酸盐(例如海藻酸钠)、角叉菜胶(β-、r-、λ-和/或κ角叉菜胶)、阿拉伯树胶、卡德兰胶和/或琼脂。特别优选使用明胶,因为它在不同bloom值下具有良好的可用性。特别优选,特别是对于口服使用的是无缝明胶或海藻酸盐胶囊,其封装在口中非常迅速地溶解或在咀嚼时爆裂。制备,可以根据例如EP 0389700 A1、US 4,251,195、US 6,214,376、WO 2003 055587或WO 2004 050069 A1所述进行。
胶囊也可以是微胶囊。术语“微胶囊”被本领域技术人员理解为直径为约0.0001至约5mm的球形聚合体,其含有至少一种固体或液体核,该核被至少一个连续的膜包围。更确切地,是指由成膜聚合物所包裹的细分散的液相或固相,制备时,在乳化和凝聚或界面聚合后聚合物沉积在待包裹的材料上。在另一种方法中,液态活性物质被吸收在基质(“微海绵”)中,其作为微颗粒额外用成膜聚合物包裹。极微小的胶囊,也被称为纳米胶囊,可以如粉末般干燥。除单核微胶囊外,多核聚合体,也称为微球,含有在连续包膜材料中分布的两个或多个核。单核或多核微胶囊可以被额外的第二、第三层膜包围。该膜可以由天然材料、半合成材料或合成材料构成。天然的膜材料是例如阿拉伯树胶、琼脂、琼脂糖、麦芽糊精、海藻酸及其盐,例如海藻酸钠或海藻酸钙、脂肪和脂肪酸、鲸蜡醇、胶原质、壳聚糖、卵磷脂、明胶、白蛋白、虫胶、多糖,如淀粉或葡聚糖、多肽、蛋白质水解物、蔗糖和蜡。半合成的膜材料包括化学改性的纤维素,特别是纤维素酯和纤维素醚,例如乙酸纤维素、乙基纤维素、羟丙基纤维素、羟丙基甲基纤维素和羧甲基纤维素,以及淀粉衍生物,特别是淀粉醚和淀粉酯。合成膜材料是例如聚合物,如聚丙烯酸酯、聚酰胺、聚乙烯醇或聚乙烯吡咯烷酮。
已知的微胶囊的实例是以下市售商品(括号里是膜材料):Hallcrest微胶囊(明胶、阿拉伯树胶)、Coletica Thalaspheres(海洋胶原)、Lipotec Millicapseln(海藻酸、琼脂)、Induchem Unispheres(乳糖、微晶纤维素、羟丙基甲基纤维素)、Unicerin C30(乳糖、微晶纤维素、羟丙基甲基纤维素)、Kobo Glycospheres(改性淀粉、脂肪酸酯、磷脂)、Softspheres(改性琼脂)和Kuhs Probiol Nanospheres(磷脂)。
已知的微胶囊的实例是以下市售商品(括号里是膜材料):Hallcrest微胶囊(明胶、阿拉伯树胶)、Coletica Thalaspheres(海洋胶原)、Lipotec Millicapseln(海藻酸、琼脂)、Induchem Unispheres(乳糖、微晶纤维素、羟丙基甲基纤维素)、Unicerin C30(乳糖、微晶纤维素、羟丙基甲基纤维素)、Kobo Glycospheres(改性淀粉、脂肪酸酯、磷脂)、Softspheres(改性琼脂)和Kuhs Probiol Nanospheres(磷脂)。
·由凝胶形成剂、阳离子聚合物和活性成分制备基质;
·任选地将所述基质分散在油相中;和
·用阴离子聚合物的水溶液处理所述分散的基质,并在该过程中任选地去除同相。
当然,步骤(a)和(c)中的阴离子和阳离子聚合物可以互换。
凝胶形成剂
在本发明的上下文中,优选的凝胶形成剂是能够在高于40℃的温度下在水溶液中形成凝胶的物质。这种凝胶形成剂的典型实例是杂多糖和蛋白质。优选的热凝胶杂多糖是琼脂糖,其可以可从红藻获得的琼脂形式存在,甚至与高达30重量%的非凝胶形成琼脂胶一起存在。琼脂糖的主要成分是半乳糖和3,6-脱水-L-半乳糖的线性多糖,具有交替的1,3-和1,4-糖苷键。杂多糖优选具有110000至160000的分子量并且无臭无味。合适的替代品是果胶、黄原胶(包括黄原胶)及其混合物。其他优选的类型是那些在1重量%的水溶液中仍形成凝胶,在80℃以下不熔化并且在40℃以上再次凝固。来自热凝胶蛋白组的实例是各种明胶。
阴离子聚合物
为此目的优选海藻酸盐。海藻酸是含羧基多糖与以下理想化单体单元的混合物:
海藻酸或海藻酸盐的平均分子量在150000至250000的范围内。海藻酸盐及其完全和部分中和产物被理解为特别是碱金属盐,优选藻酸钠(“algin”)以及铵盐和碱土金属盐。特别优选混合的海藻酸盐,例如海藻酸钠/镁或海藻酸钠/钙。然而,在本发明的一个替代实施方案中,羧甲基纤维素和阴离子壳聚糖衍生物,例如羧基化和尤其是琥珀酰化产物也适用于该目的。
阳离子聚合物
壳聚糖是属于水胶体组的生物聚合物。在化学上,它们是部分去乙酰化的几丁质,区别在于分子量,包含以下-理想化的-单体单元。
与在生物pH值下带负电荷的大多数水胶体相反,壳聚糖在这些条件下是阳离子生物聚合物。带正电荷的壳聚糖能够与带相反电荷的表面相互作用,因此可用于美容护发和身体护理产品以及药物制剂。
在本发明的一个优选实施方案中,通常制备1至10,优选2至5重量%的凝胶形成剂,优选琼脂水溶液,并在回流下加热。将含有0.1至2重量%,优选0.25至0.5重量%的阳离子聚合物,优选壳聚糖,和0.1至25重量%,优选0.25至10重量%的活性成分的第二水溶液加入到反应器中,优选在80至100℃下加热至沸腾,这种混合物被称为基质。因此,微胶囊中的活性成分也可以占胶囊重量的0.1-25重量%。如果需要,水不溶性成分,例如无机颜料,也可以在这个阶段加入以调节粘度,通常以水或水/醇分散体的形式。此外,为了乳化或分散活性成分,向基质中添加乳化剂和/或增溶剂可能是有用的。在由凝胶形成剂、阳离子聚合物和活性成分制备后,任选地使用强烈剪切使基质非常精细地分散在油相中,以便在随后的包封过程中产生小颗粒。已证明在这方面特别有利的是,将基质加热到40至60℃的温度范围内,同时将油相冷却至10至20℃。实际的封装,即通过使基质中的阳离子聚合物与阴离子聚合物接触来形成膜,发生在第三步中。为此,建议用0.1至3且优选0.25至0.5重量%的阴离子聚合物水溶液,优选海藻酸盐水溶液,在40至100和优选50至60℃的温度范围内清洗分散在油相中的基质,同时除去—如果存在—油相。所得水性制剂通常具有1至10重量%的微胶囊含量。在某些情况下,聚合物溶液中含有其他成分是有利的,例如乳化剂或防腐剂。过滤后,获得平均直径优选为1至3mm的微胶囊。建议过筛胶囊以确保均匀的尺寸分布。如此获得的微胶囊可具有生产相关限制内的任何形状,但优选基本上为球形。
工业应用
本发明的另一个目的涉及一种获得具有改进的抗变色稳定性的化妆品、个人护理或洗涤剂组合物的方法,包括或由以下步骤组成:
(i)提供化妆品、个人护理或洗涤剂组合物;和
(ii)添加权利要求1的香料组合物或权利要求10的香料制剂。
如上所述,根据本发明选择的腈包括组(i)至(iv)。
组(i)代表式(I)的腈,其中R代表取代的苯基,这意味着基团(i)代表选择的五种苄腈,即
·2,3-二甲基苄腈
·2,4,5-三甲基苄腈
·4-乙基苄腈
·4-丙基苄腈
·4-苯基苄腈。
当添加到其他香料或香料油中时,显示出特别高的促进效果。在根据本发明的一个优选实施方案中,式(I)的组(i)选自2,3-二甲基苄腈。
组(ii)是指腈基连接至降冰片烷基的结构,其可带有其它取代基,优选C1-C5烷基、烷氧基或烷氧基烷基。该组的优选代表是3,3-二甲基降冰片烷-2-甲腈,包括所有相关的立体异构体,例如(1R)(2S)(4S)和(1R)(2R)(4S)产物。
组(iii)是指腈基连接到环戊基或环戊烯基的结构,其还可以带有其他取代基,优选C1-C5烷基、烷氧基或烷氧基烷基。该组的优选代表是2-[3-(甲氧基-甲基)-2-2-二甲基-环戊-3-烯-1-基]乙腈。
最后,组(iv)是指腈符合式(I)的结构
NC–(CH2)n-CH=CH2 (II)
其中n代表1至20的整数,优选10至15。优选的物质是十三-12-烯腈。
在根据本发明的最优选实施方案中,香料组合物包含或由至少一种式(I)的腈组成
R-CN(I),其中式(I)的腈选自2,3-二甲基苄腈。换言之,在根据本发明的最优选实施方案中,香料组合物包含2,3-二甲基苄腈或由其组成。
最后,本发明还涵盖香料组合物或香料制剂制备化妆品、个人护理或洗涤剂组合物的用途。上述针对本发明方法的优选实施例在这里同样适用。为了清楚起见,上面公开的所有优选实施例、组合和范围也适用于根据本发明的方法和用途;因此没有必要重复。
实施例
实施例M1
2,3–二甲基苄腈(化合物A)
实施例M2
4–乙基苄腈(化合物B)
实施例M3
4–苯基苄腈(化合物3)
实施例M4
2,4,5–三甲基苄腈(化合物4)
实施例M5
4–丙基苄腈(化合物5)
实施例M6
(1R,2S,4S)–3,3–二甲基降冰片烷–2–甲腈和(1R,2R,4S)–3,3–二甲基降冰片烷–2–甲腈(化合物6)
实施例M7
2-[3-(甲氧基甲基)-2,2-二甲基-环戊-3-烯-1-基]乙腈(化合物7)
实施例M8
十三-12-烯腈(化合物8)
稳定性实施例
将20重量%的表面活性剂溶液与0.5重量%的本发明化合物1、3、6和7中的每一种以及三种对比产品混合。将7种溶液装入透明瓶中,并在20或40℃下储存2周。由3位调香师在从(10)=强烈到(0)=不存在的范围内评估与新鲜生产的样品相比的气味强度和黄色颜色。实施例1至4是根据本发明的,实施例C1至C3用于比较。结果总结在表1中。
重新为实施例编号,因为前四个实施例为根据本发明,后三个实施例为对比实施例。请检查是否正确。
表1
香料强度和变色
在对比实施例的情况下,储存期间的香味强度严重降低,变色迅速增加,特别是在较高温度下。相比之下,根据本发明的产品显示出明显更好的稳定性,因为香味强度在储存两周后仍然保持并且仅观察到变色。
制剂实施例
以下实施例F1至F55显示了用于化妆品、个人护理和洗涤剂组合物的各种配方。
表F1
液体皂;透明(用量为重量%)
表F2
合成皂,液态(用量为重量%)
表F3
用于沐浴的化妆乳液(用量为重量%)
表F4
用于沐浴的含有三氯生的化妆乳液(用量为重量%)
表F5
敏感部位清洁液(用量为重量%)
表F6
液体皂(用量为重量%)
表F7
洗发香波(用量为重量%)
表F8
2合1香波(用量为重量%)
表F9
抗头皮屑香波(用量为重量%)
表F10
含有Crinipan的护发素,洗除(用量为重量%)
表F11
含有吡硫鎓锌的可喷护发素,免洗(用量为重量%)
表F12
含有UV防晒因子的护发素(用量为重量%)
表13
沐浴露(用量为重量%)
表F14
剃须膏(用量为重量%)
表F15
脱毛霜(用量为重量%)
表F16
须后水(用量为重量%)
表F17
滚珠凝胶形式的除臭制剂(用量为重量%)
表F18
除臭止汗滚珠(用量为重量%)
表F19
除臭棒(用量为重量%)
表F20
锆悬浮胶体止汗棒(用量为重量%)
表F21
含有SymClariol的除臭喷剂(用量为重量%)
表F22
止汗制剂(用量为重量%)
表F23
含有三氯生的除臭喷雾(用量为重量%)
表F24
O/W乳液(用量为重量%)
表F25
身体乳液(用量为重量%)
表F26
油膏(用量为重量%)
表F27
油膏(用量为重量%)
表F28
护手霜和护体霜(用量为重量%)
表F29
面霜(用量为重量%)
表F30
滋润护体霜(用量为重量%)
表F31
抗皱霜(用量为重量%)
表F32
功能性皮肤用消毒油(用量为重量%)
表F33
感染伤口用膏(用量为重量%)
表F34
保湿和消毒面膜(用量为重量%)
表F35
可喷消毒凝胶(用量为重量%)
表F36
矿物清洗和清洁凝胶(用量为重量%)
表F37
抗痤疮洗剂(用量为重量%)
表F38
化妆品防晒组合物(用量为重量%)
表F39
防晒喷雾(用量为重量%)
表F40
防晒喷雾O/W.SPF 15-20(用量为重量%)
表F41
防晒软膏(W/O),SPF 40(用量为重量%)
表F42
防晒乳(W/O)(用量为重量%)
表F43
晒后凝胶(用量为重量%)
表F44
晒后乳液(用量为重量%)
表F45
头发定型发胶(用量为重量%)
表F46
硅油乳液(用量为重量%)
表F47
微乳凝胶(用量为重量%)
表F48
凝胶形式的空气清新剂(用量为重量%)
表F49
清洁剂.APC液体.碱性pH 8-10(用量为重量%)
表F50
织物柔软剂(用量为重量%)
表F51
液体洗涤剂(用量为重量%)
表F52
液体洗涤剂浓缩物(用量为重量%)
表F53
厕所清洁剂(用量为重量%)
表F54
餐具洗涤浓缩液(用量为重量%)
表F55
餐具洗涤浓缩液(用量为重量%)
表F56
湿纸巾溶液(用量为重量%)
Claims (15)
1.一种香料组合物,其包含或由至少一种式(I)的腈组成
R-CN(I)
其中R代表
(i)取代的苯基;
(ii)任选取代的降冰片基;
(iii)任选取代的环戊(烯)基;和/或
(iv)-(CH2)n-CH=CH2基团,其中n表示1至20的整数;
条件是形成组(i)的腈选自下组包括:
·2,3-二甲基苄腈
·2,4,5-三甲基苄腈
·4-乙基苄腈
·4-丙基苄腈
·4-苯基苄腈。
2.根据权利要求1所述的组合物,其中式(I)的腈是3,3-二甲基降冰片烷-2-甲腈。
3.根据权利要求1所述的组合物,其中式(I)的腈是2-[3-(甲氧基-甲基)-2-2-二甲基-环戊-3-烯-1-基]乙腈。
4.根据权利要求1所述的组合物,其中式(I)的腈是十三-12-烯腈。
5.根据权利要求1所述的组合物,进一步含有至少一种与式(I)的香料不同的次要香料。
6.根据权利要求6所述的组合物,其中所述的至少一种次要香料选在组包括具有木质、琥珀、水果或麝香气味的香料组。
7.根据权利要求6所述的组合物是含有约0.01至约0.1重量%的式(I)的腈类的香料油。
8.根据权利要求1至6任一项所述的组合物进一步含有一种溶剂。
9.根据权利要求8所述的组合物,其中所述溶剂选自组包括苯甲醇、苯甲酸苄酯、邻苯二甲酸二乙酯、二丙二醇、乙醇、肉豆蔻酸异丙酯、柠檬酸三乙酯、downolDPM、IsoPar L、三醋精及其混合物。
10.一种香料制剂,含有
(a)至少一种权利要求1所述的香料和
(b)乙醇和/或柠檬酸三乙酯。
11.一种化妆或个人护理组合物,含有根据权利要求1所述的香料组合物或根据权利要求10所述的香料制剂。
12.一种洗涤剂组合物,含有根据权利要求1所述的香料组合物或根据权利要求10所述的香料制剂。
13.一种胶囊,含有根据权利要求1所述的香料组合物或根据权利要求10所述的香料制剂。
14.一种获得具有改进的抗变色稳定性的化妆品、个人护理或洗涤剂组合物的方法,包括或由以下步骤组成:
(i)提供化妆品、个人护理或洗涤剂组合物;和
(ii)添加根据权利要求1所述的香料组合物或根据权利要求10所述的香料制剂。
15.根据权利要求1所述的香料组合物或根据权利要求10所述的香料制剂制备化妆品、个人护理或洗涤剂组合物的用途。
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CN115353932A (zh) * | 2022-09-07 | 2022-11-18 | 江门市和馨香精技术有限公司 | 用于控制皂化速度的香精组合物及其应用、冷制皂 |
CN115353932B (zh) * | 2022-09-07 | 2023-10-20 | 江门市和馨香精技术有限公司 | 用于控制皂化速度的香精组合物及其应用、冷制皂 |
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US20230159854A1 (en) | 2023-05-25 |
WO2021228352A1 (en) | 2021-11-18 |
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