CN116964186A - 带气味变化的厕所边缘块 - Google Patents
带气味变化的厕所边缘块 Download PDFInfo
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- CN116964186A CN116964186A CN202180094909.6A CN202180094909A CN116964186A CN 116964186 A CN116964186 A CN 116964186A CN 202180094909 A CN202180094909 A CN 202180094909A CN 116964186 A CN116964186 A CN 116964186A
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- sodium
- acid
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- polyether
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- YRIDFQASBDRMBJ-UHFFFAOYSA-N undec-10-enamide Chemical compound NC(=O)CCCCCCCCC=C YRIDFQASBDRMBJ-UHFFFAOYSA-N 0.000 description 1
- 229940075466 undecylenate Drugs 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 229940078465 vanillyl butyl ether Drugs 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229940084883 wheat amino acids Drugs 0.000 description 1
- 235000021119 whey protein Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- JGPDIWYMBVWJCD-UHFFFAOYSA-L zinc;dodecyl sulfate Chemical compound [Zn+2].CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O JGPDIWYMBVWJCD-UHFFFAOYSA-L 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0056—Lavatory cleansing blocks
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/044—Solid compositions
Abstract
一种固体组合物,其包含以下物质或由以下物质组成:(a)一种固体水溶性载体和(b)至少一种香料,其具有至少4的logP和/或至少250℃的沸点。
Description
发明领域
本发明涉及固体洗涤剂领域,更具体地涉及能够在水冲洗期间改变其气味的马桶边缘块。
背景技术
马桶边缘块是用于冲水马桶的块状物质,其缓慢溶解在水中。它们通常装在一个小支架中,固定在马桶边缘并垂入马桶中,因此当马桶冲水时,水会穿过支架与马桶块接触。
边缘块的工作方式与空气清新剂相同,不断散发出相同的香味。然而,人的鼻子在大约20分钟内就会习惯一种气味,因此无法再对这种气味进行适当的评价。随着时间推移香味印象会发生变化的装置会被认为是新鲜的。在厕所里,这种气味转换可以通过冲厕所来触发。
相关背景技术
多年来,人们在能够实现受控气味释放的装置上投入了大量精力,例如在电影技术中,如US 5,963,302 A(WITTEK)中所证明的那样。
特别地,浴室是强烈需要气味转换的地方。一个相当复杂的选择是通过将来自厕所的气体通过恶臭抑制器通风,然后将气体通风回房间来获得这种气味转换,如US 3,108,289A(SMITH)所示。
EP 0728804 B1(IFF)描述了一种特别适用于制造马桶边缘块的物质组合物,其组成为:(a)挤出的聚乙烯醇或部分水解的聚乙酸乙烯酯;(b)聚乙烯醇或部分水解的聚乙酸乙烯酯中含有的约1重量%至约20重量%的相容香料;(c)聚乙烯醇或部分水解的聚乙酸乙烯酯中含有的0%至约20重量%的“发泡剂”,其是第一表面活性剂并且可以是洗涤剂;(d)聚乙烯醇或部分水解的聚乙酸乙烯酯中含有的0至约20重量%的疏水性二氧化硅;(e)除“发泡剂”外,0至约20重量%的至少一种第二表面活性剂;(f)0%至约5重量%的水溶性染料;(g)0%至约4重量%的“泡沫促进剂”。
EP 1048687 A1(IFF)还涉及一种物质组合物,其包含粉末状、水溶性、水分散性或水溶胀性聚合物、相容香料(作为香料与聚合物的共混物或单独混合)和一种或多种表面活性剂。聚合物可以是挤出的聚乙烯醇或部分水解的聚乙酸乙烯酯。还描述了由该物质组合物模制而成的马桶元件,其可以是用于抽水马桶的马桶边缘块,或者是用于马桶水箱的独立式块,以及用于比较该物质组合物和厕所元素的方法。
EP 1469132 B1(P&G)涉及一种盥洗盆边缘块,其包括:a)容纳液体、含香料组合物的容器;b)用于从盥洗盆边缘下方分配所述组合物的分配装置;c)香料递送组分。
EP 1884251 B1(TAKASAGO)涉及香料组合物在任何家庭和个人护理产品中的用途,所述香料组合物包含选自以下的香料化合物:醛、α,β-不饱和醛、醇、酮及其混合物,在含有0.28重量%的每种香料化合物的合适的新鲜人尿的气密容器中,在室温下培养24小时后,每种香料化合物能够将吲哚的形成限制到低于0.01ppm(wt/wt),从而防止基于粪便和尿液的土壤产生基于吲哚的恶臭。
WO 2017 146182A1(TAKASAGO)要求保护包含香料组合物的家用产品。该香料组合物包含选自以下的化学美化剂:香草基乙基醚、香草基正丙基醚、香草基异丙基醚、香草基丁基醚、榄香酚(elemol)、榄香素(elimicin)、氧化石灰、五氧化罗勒烯、2-异丙烯基-5-甲基-5-乙烯基四氢呋喃和异胡薄荷醇。特别地,家用产品优选为空气清新剂分配装置、地板清洁剂、厨房或浴室表面清洁剂、马桶边缘块或马桶水箱块。
WO 2019 025007A1(SYMRISE)涉及边缘块,其能够冲洗触发气味转换,需要复杂的边缘块笼,阻挡部分制剂与水或空气的接触,以机械地停止其气味。
US 4,666,671 A1(GIVAUDAN)公开了小便池块和抽水马桶边缘块,它们是芳香凝胶并且可用于控制杀菌剂、除臭剂、清洁剂、染料和/或其他可释放的“活性成分”释放到马桶系统中,以用于消毒、清洁和/或除臭的目的。
发明目的
加入香料的马桶边缘块是水溶性产品,仅在一个气味方向上提供香味体验效果。因此,本发明的目的是提供具有在使用后转换原始气味方向的能力的香料,以产生“气味分型”,这意味着将原始气味转换为具有不同气味特征的气味。
发明内容
本发明的第一个目的涉及一种固体组合物,其包含以下物质或由以下物质组成:
(a)一种固体水溶性载体和
(b)至少一种香料,其具有至少4的logP和/或至少250℃的沸点。
采用分析动态测量,申请人能够在接近现实的条件下研究干和湿边缘块中单一原材料和香料的香料顶空行为。令人惊讶地发现,具有低极性(以它们的logP值表示)和/或高分子量(以它们的沸点表示)的香料的气味和行为释放能够使干燥边缘块的原始气味在导致气味转换的实际条件冲水后增强原始气味或强调原始气味的特定香调,而该特定香调迄今为止尚未主导香水的整体感知。例如,带有果香基调和主要花香前调的香水油在冲水后会增强果香。
分析气味分型(split)
本发明的目的是鉴定香料和香料组合物,其在使用后,例如在边缘块中与水接触后,能够转换原始气味方向。通过动态顶空分析法研究了各种香精和香水组合物的香味释放。已经发现,通过极性共价键结合在一起的挥发性有机化合物(VOC)以及具有低电常数且与水不混溶或不充分混溶的VOC在转换例如边缘块中应用的香水的原始气味方面发挥着关键作用。经过多次研究,测量并优化了用于确定冲洗之前和之后的固体组合物(例如边缘块)中的顶部空间浓度的方法,以提供高再现性。基于这些发现,计算了干阶段和湿阶段之间顶部空间中分子的面积浓度比。
载体
优选地,形成边缘块底物的载体包括以下成分或由以下成分组成:
(a1)至少一种表面活性剂,
(a2)至少一种溶剂和任选的
(a3)至少一种助洗剂;
(a4)至少一种盐;和
(a5)至少一种助剂。
选定香料
在第一个优选实施方案中,至少一种香料表现出约5至约8的logP(=log KOW)。该值也称为正辛醇-水分配系数,其是由正辛醇和水组成的两相系统的a分配系数(参见:Sangster,J.(1997).Octanol-water partition coefficients:fundamentals andphysical chemis-try.Chichester:Wiley)。P或Kow用作物质的亲脂性(脂溶性)和亲水性(水溶性)之间的关系量度。如果某种物质更易溶于脂肪类溶剂如正辛醇,则该值大于1;如果更易溶于水,则该值小于1。
在第二个优选实施方案中,至少一种香料表现出约270℃至约400℃的沸点。
总的来说,优选选择结合所有三个优选实施例的香料。例如,所述至少一种香料可以选自由以下各项组成的组:
及其混合物。
根据本发明的组合物可以以约0.1至约10重量%、优选约0.5至8重量%、更优选约1至约5重量%的量掺入至少一种香料。。
附加香料
通常,用于本发明的固体组合物和特别是用于马桶边缘块的香料和芳香油通常包含数十种不同的气味材料以产生特定的香味。因此,组合物还可以包含与作为复杂香料混合物的一部分的组分(a)的定义不匹配的其他香料(组分c)。在这种情况下,表现出至少4的logP和/或至少250℃的沸点的香料占约15至约60重量%、优选约20至约50重量%,并且更优选约25至约40重量%就足够了,基于所述组合物中香料的总量计。
形成组分(c)的附加香料包括例如花(百合、薰衣草、玫瑰、茉莉、橙花、依兰)、茎和叶(天竺葵、广藿香、苦橙)、果实(茴香、胡荽、香菜、杜松)、果皮(佛手柑、柠檬、橙)、根(肉豆蔻、当归、芹菜、小豆蔻、木香、鸢尾、菖蒲)、木材(松木、檀香、愈创木、雪松木、花梨木)、草本植物和禾本植物(龙蒿、柠檬草、鼠尾草、百里香)、松针和树枝(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)的提取物。典型的合成芳香剂化合物是酯、醚、醛、酮、醇和烃类产物。酯类芳香剂化合物实例是乙酸苄酯,异丁酸苯氧基乙酯、环己基乙酸p-叔丁酯、乙酸芳樟酯、乙酸二甲基苄基原酯(dimethyl benzyl carbinylacetate)、乙酸苯乙酯、苯甲酸芳樟酯、甲酸苄酯、苯基甘氨酸乙基甲酯、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;而醛类包括,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。适当的酮类的实例是甲基柏木酮。适当的醇类是茴香脑、香茅醇、丁香酚、异丁香酚、香叶醇、芳樟醇、苯乙醇和松油醇。烃类主要包括萜烯类和香脂类。其它适当的芳香油为大多用作芳香成分的挥发性较低的精油。实例是鼠尾草油、甘菊油、丁香油、蜂花油、薄荷油、肉桂叶油、莱姆花油、杜松子油、香根草油、乳香油、白松香油、岩蔷薇油和熏衣草油。
组合物
优选地,根据本发明的组合物代表马桶边缘块或固体洗涤剂组合物,例如粉末洗衣洗涤剂或洗衣片。这些产品可以掺入其他添加剂,其典型用于洗涤剂应用,并且还用作所选香料的载体或边缘块底物,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、酶和附加助剂例如不同于组分(a)的驱污剂、增稠剂、着色剂、香料及其混合物。
阴离子和两性离子表面活性剂
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、椰油酰两性基二丙酸、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、癸基葡糖苷、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钠、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、羟基月桂基/羟基肉豆蔻基甜菜碱、羟基硬脂酸、羟基琥珀酰亚胺C10-40异烷酸乙基己酯、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大豆油胺氧化物共聚物、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、异月桂醇聚醚-4磷酸酯、异聚甘油-3聚二甲基硅氧烷、异聚甘油-3聚二甲基硅氧烷醇、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、月桂醇聚醚硫酸酯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酰胺酸酯、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甘油牛油酸酯、PEG-80甘油牛油酸酯、PEG-82甘油牛油酸酯、PEG-130甘油牛油酸酯、PEG-200甘油牛油酸酯、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-66三羟基硬脂精、PEG-200三羟基硬脂精、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、聚甘油-20八异壬酸酯、聚甘油-6五辛酸酯、聚甘油-10五辛酸酯、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、异硬脂酸钾、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(SAPONARIAOFFICINALIS)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、椰油酰谷氨酸钠、椰油酰谷氨酰胺钠、椰油酰甘氨酸钠、椰油酰/氢化牛脂谷氨酸钠、椰油酰水解胶原钠、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、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、二聚亚油酰胺丙基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、月桂亚氨基二丙酸钠、月桂酰两性基乙酸钠,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、棕榈仁油酰羟乙磺酸钠、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 Rose Hipsamphoacetate、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、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、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、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。
非离子(辅助)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。
阳离子辅助表面活性剂
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 91/01295 A1,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
液态轻役型或重役型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、根据US 5,204,015和US 5,244,791由Genencor International,Inc.生产的蛋白酶B和蛋白酶。
淀粉酶包括例如α-淀粉酶如International Bio-Synthetics,Inc.,和/>Novo Industries。
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 19.154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)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。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WO 1989099813 A1。
酶稳定剂。本文中使用的酶可被在成品洗涤剂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,其在此全文引用。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%,按组合物中硼酸或能够形成硼酸的其他硼酸盐化合物的重量计(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那些通过,例如国际专利申请WO 91/08171A1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受到限制。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,其能使糖环的至少一个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EP0232202A1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 95/20029A1。
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。
也可以使用过氧漂白剂。适宜的过氧漂白化合物包括碳酸钠过氧水合物和其等同物“过碳酸盐”漂白剂,焦磷酸钠过氧水合物,脲过氧水合物,和过氧化钠。也可以使用过硫酸盐漂白剂(例如,由DuPont商业生产)。
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。
非氧漂白剂的那些漂白剂也是本领域公知的,并且可以用于本发明中。一类特别好的非氧漂白剂包括光敏化的漂白剂如磺化的酞菁锌和/或铝。如果使用,洗涤剂组合物一般含有约0.025%至约1.25重量%的该类漂白剂,尤其是酞菁磺酸锌。
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烯基或氧化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%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)优选约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-OS2124526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。
本发明所用的优选的硅氧烷泡沫抑制剂不含聚丙二醇,特别是分子量4000的聚丙二醇。它们还优选不含环氧乙烷和环氧丙烷的嵌段共聚物,如L101。
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-羟乙基乙二胺三乙酸盐、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 111,984A1中公开的乙氧化胺聚合物,EP 112,592A1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烷酮。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;Artic/>CC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。
另一种优选的增白剂是4,4'-二[(4-苯胺基-6-吗啉代-s-三嗪-2-基)氨基]-2,2'-芪二磺酸,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。
着色剂
组合物可以包含其他典型洗涤剂和清洁组合物成分,例如着色剂,其中优选这样的着色剂,其在被洗涤的织物上不留下或留下可忽略不计的着色。添加的着色剂总量的优选量低于1重量%,优选低于0.1重量%,基于组合物计。该组合物还可以包含白色颜料,例如TiO2。
工业应用
本发明的另一个目的涉及用于转换香料气味的第一方法,包括以下步骤或由以下步骤组成:
(a)提供至少一种香料,其具有至少4的logP和/或至少250℃的沸点,和
(b)使所述的步骤(a)的至少香料与水接触。
还要求保护一种用于在使用期间转换马桶边缘块气味的第二种方法,包括以下步骤或由以下步骤组成:
(a)提供根据权利要求1所述的固体边缘块组合物;
(b)将步骤(a)的所述组合物放入分配器中;
(c)将包含边缘块的分配器放入抽水马桶中;和
(d)通过冲洗马桶使包含边缘块的分配器与水接触。
本发明的另一个目的涉及至少一种香料,其具有至少4的logP和/或至少250℃的沸点,用于制备当与水接触时具有气味转换能力的固体组合物的用途。优选地,所述固体组合物代表马桶边缘块或固体洗涤剂组合物。
实施例
通过动态顶空分析进行香味分型
加权部分
·干法测量:20mg碎边缘块置于20ml顶空GC瓶中
·湿法测量:20mg碎边缘块和20mg水置于20ml顶空GC瓶中。
动态顶空设置
·30℃孵育30分钟
·以100ml/分钟捕获200ml;载气:氮气
·GC/MS系统上的Gerstel TDU设备
计算
湿/干变化百分比(%)=湿面积(%)/干面积(%)-100
实施例1
8-环十六酮(Globanone)
将市售香料油组合物POWER PLATIN配制成马桶边缘块组合物,并如上文所解释地测定干和湿阶段顶空的浓度。在各种成分中,8-环十六酮经鉴定显示出146%的变化值。
实施例2
水杨酸己酯
将市售香料油组合物MARINA配制成马桶边缘块组合物,并如上文所解释地测定干和湿阶段期间顶空的浓度。在各种成分中,水杨酸己酯经鉴定显示出250%的变化值。
使用根据组分(a)的香料的根据本发明的气味转换的概念在图1和2中进一步说明。图1显示了包含石榴/玉兰香精油的马桶边缘块的嗅觉特征。干边缘块显示出主要的果香前调和花香次要香调。冲水后,花香占主导地位,而果香的强度则减弱。这同样适用于图2,显示了柠檬草/绿茶香精油的类似特征:干成分显示出主要的新鲜香调,但冲洗后柑橘香调成为主要的前调。
下表1至7包含能够显著气味转换的香料组合物。所有数量均以克为单位。
表1
“MARINA”
/>
表2“桃”
/>
表3“POWER PLATIN”
/>
表4
“覆盆子&椰子水”
/>
表5
“石榴&玉兰”
/>
表6
“椰子&酸橙”
/>
表7
“柠檬草&绿茶”
/>
/>
Claims (14)
1.一种固体组合物,其包含以下物质或由以下物质组成:
(a)一种固体水溶性载体和
(b)至少一种香料,其具有至少4的logP和/或至少250℃的沸点。
2.根据权利要求1所述的组合物,其中载体包括以下成分或由以下成分组成(a1)至少一种表面活性剂,
(a2)至少一种溶剂和任选的(a3)至少一种助洗剂;
(a4)至少一种盐;和
(a5)至少一种助剂。
3.根据权利要求1所述的组合物,其中至少一种香料具有约5至约8的logP。
4.根据权利要求1所述的组合物,其中至少一种香料具有约270至约400℃的沸点。
5.根据权利要求1所述的组合物,其中至少一种香料选自由以下各项组成的组:
及其混合物。
6.根据权利要求1所述的组合物,进一步含有阴离子、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、酶和附加助剂例如不同于组分(a)的驱污剂、增稠剂、着色剂、香料。
7.根据权利要求1所述的组合物含有约0.1至约10重量%的至少一种香料。
8.根据权利要求1所述的组合物含有不同于成分(a)的附加香料。
9.根据权利要求8所述的组合物,其中成分(a)在组合物中所有香料的总量(a+c)中占有约15至约60重量%。
10.根据权利要求1所述的组合物是马桶边缘块或固体洗涤剂组合物。
11.一种转化气味的方法,包括以下步骤或由以下步骤组成:
(a)提供至少一种香料,其具有至少4的logP和/或至少250℃的沸点,和
(b)使所述的步骤(a)的至少香料与水接触。
12.一种用于在使用期间转换马桶边缘块气味的方法,包括以下步骤或由以下步骤组成:
(a)提供根据权利要求1所述的固体边缘块组合物;
(b)将步骤(a)的所述组合物放入分配器中;
(c)将包含边缘块的分配器放入抽水马桶中;和
(d)通过冲洗马桶使包含边缘块的分配器与水接触。
13.至少一种香料,其具有至少4的logP和/或至少250℃的沸点,用于制备当与水接触时具有气味转换能力的固体组合物的用途。
14.根据权利要求14所述的用途,其中固体组合物是马桶边缘块或固体洗涤剂组合物。
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PCT/EP2021/055285 WO2022184247A1 (en) | 2021-03-03 | 2021-03-03 | Toilet rim blocks with scent change |
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CN116964186A true CN116964186A (zh) | 2023-10-27 |
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EP (1) | EP4301833A1 (zh) |
JP (1) | JP2024510569A (zh) |
KR (1) | KR20230152114A (zh) |
CN (1) | CN116964186A (zh) |
WO (1) | WO2022184247A1 (zh) |
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- 2021-03-03 KR KR1020237033205A patent/KR20230152114A/ko unknown
- 2021-03-03 WO PCT/EP2021/055285 patent/WO2022184247A1/en active Application Filing
- 2021-03-03 CN CN202180094909.6A patent/CN116964186A/zh active Pending
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