CN1284126A - 在分散层状相中的含水洗涤组合物 - Google Patents
在分散层状相中的含水洗涤组合物 Download PDFInfo
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- CN1284126A CN1284126A CN98813322A CN98813322A CN1284126A CN 1284126 A CN1284126 A CN 1284126A CN 98813322 A CN98813322 A CN 98813322A CN 98813322 A CN98813322 A CN 98813322A CN 1284126 A CN1284126 A CN 1284126A
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- composition
- carbon atoms
- water
- solvent
- detergent
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- 238000004140 cleaning Methods 0.000 title abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 131
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- 239000003599 detergent Substances 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 alkylaryl sulphonate Chemical compound 0.000 claims description 40
- 239000004094 surface-active agent Substances 0.000 claims description 34
- 239000013543 active substance Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
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- 238000005406 washing Methods 0.000 claims description 18
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- 230000002209 hydrophobic effect Effects 0.000 claims description 9
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- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
本发明描述的组合物是含水洗涤剂组合物,优选硬表面洗涤组合物,它含有分散在水相中的挠性层状片相。该组合物是粘稠的,提供杰出的皂垢去除和硬水性质,并易于漂洗。该组合物通过使用烷基芳基洗涤剂组分并与醇和/或阳离子表面活性剂结合,和水溶助长溶剂一起在酸性体系中配制,它还选择性地含有过氧化物。
Description
发明领域
本发明涉及用于清洗硬表面，尤其是浴室表面的液体洗涤剂组合物，该组合物通常含有洗涤剂表面活性剂、溶剂、助洗剂等。
发明背景
使用溶剂和有机水溶性合成洗涤剂表面活性剂清洗硬表面是已知的，已知的液体洗涤剂组合物含有有机洗涤溶剂、洗涤剂表面活性剂和选择性的洗涤剂助洗剂和/或磨料。
液体洗涤组合物所具有的显著优点是它们能够以纯净或浓缩形式施用于硬表面，因此直接向污垢提供相对高含量的例如表面活性剂物质和/或有机溶剂。因此，与稀释的洗涤溶液，例如由粉末洗涤组合物制备的溶液相比，液体洗涤组合物能够提供杰出的皂垢、油腻和油质污垢去除力。
通常需要提高液体硬表面洗涤剂的粘度。较高的粘度能够使产品在使用时更特定的分散，此外，较高的粘度能够促进产品在非水平表面，例如厕所、浴室管、喷淋器等上更好地作用。增强表面附着和覆盖使表面活性剂/溶剂体系能改善洗涤作用，具有剪切稀化粘度的产品是尤其优选的，因为它可作为喷洒或液体产品包装和销售，它们易于使用，可在表面上提供良好的附着和覆盖。它们是重要的产品特性，从而限制了在使用过程中由于滴下而浪费的产品的数量。此外，粘稠的、剪切稀化的液体产品在使用中不太刺激，可感觉更温和。粘度和剪切稀化性质可通过现有技术中已知的方法获得，例如使用剪切稀化胶或聚合物。然而，增稠剂，例如胶或聚合物具有提高配方成本、以及仅提供单一效果，增稠的缺点。它们不参与表面的实际洗涤，因此表示为“惰性”物质。在许多情况下，这些聚合物在表面上留下条纹和膜，并且通常不足以剪切稀化以用于喷雾瓶使用。
优选粘度由“自增稠”体系产生，其中在组合物中的表面活性剂/溶剂活性物质用于提供粘度。相对于聚合物增稠剂，该方法有若干优点，首先，表面活性剂/溶剂体系通常比聚合物更经济，其次，表面活性剂/溶剂通过提供粘度和洗涤从而提供双重效果。增稠聚合物趋向于竞争表面位置，会抑制洗涤体系的作用，第三，表面活性剂/溶剂的正确选择能够改善在酸性pH下和/或与选择性添加剂，例如过氧化物的相容性。许多聚合物增稠剂在pH低于4时是无效的，或与选择性添加剂，例如过氧化物不相容。最后，表面活性剂的残余物更容易清洗掉。
在现有技术中已知如何配制自增稠组合物，其中增稠不通过使用聚合增稠剂获得，参见例如EP518401和EP21581，列为本文参考文献。然而，对于许多用途，这些特定的非聚合物增稠方法是不合乎需要的，因为得到粘度的代价是产生显示非常稳定泡沫的组合物，这导致难以漂洗。WO95/33024(列为本文参考文献)通过在酸性介质中结合使用氧化胺和仲或伯单支链烷基硫酸盐或磺酸盐表面活性剂而解决了该问题。该方法的局限是需要特殊选择的表面活性剂，所需的粘度不能获得，除非产品具有大于3的pH，从而限制了硬水去除效力的范围。此外，人们发现本发明的组合物可加入较高含量的疏水溶剂，导致改善了皂垢去除，而仍保留所需的粘度曲线。化学上类似于本发明但不主要显示挠性层状相结构的组合物不能提供相同的洗涤力。尽管不想限制于理论，但我们相信层状结构提供更好的覆盖和/或更多的表面活性剂与污垢接触。
本发明提供了粘稠的酸性硬表面洗涤组合物，它适用于去除通常在浴室中遇到的污垢，所述组合物通过自增稠体系变得粘稠，然而它是易于漂洗的。这些酸性硬表面清洗组合物去除了皂垢和硬水迹。本发明可提供具有剪切稀化性质的粘稠的酸性硬表面洗涤组合物，它适用于从喷雾器或液体包装中喷洒出，在使用时是非刺激的。该组合物通过选择活性物质，包括柠檬酸和阳离子表面活性剂可具有消毒性质，可在含有或不合有添加剂如过氧化氢情况下使用，以提供附加的防霉效果。
发明概述
本发明的硬表面洗涤剂洗涤组合物主要是分散在水相中的挠性层状片形式。该组合物提供杰出的皂垢洗涤力、良好的硬水污垢去除性质、低量的泡沫和杰出的漂洗特性。该产品的粘度通过相化学，尤其是形成分散在水相中的层状表面活性剂片获得的剪切稀化流变学来提供。更具体地说，本发明涉及含水洗涤剂组合物，其含有：
a．约1％-约5％的烷基芳基磺酸盐洗涤剂表面活性剂；
b．约0.3％-约2％的非离子醇和/或阳离子表面活性剂；
c．约1％-约8％的一种或多种水溶助长溶剂(hydro tropicsolvent)；
d．选择性地有效量的，最多到约5％的过氧化氢；和
e．平衡量的含水溶剂体系，和
其中洗涤组合物主要含有分散在水相中的挠性层状片，其pH为约0.5-约6。
含有表面活性剂的挠性层状片提供了粘度和改善的洗涤力。人们相信改善的洗涤是层状片的直接结果，因为层状结构使得更多的表面活性剂与污垢接触。
发明的详细描述
本发明的组合物特别适用于洗涤通常在浴室中遇到的污垢。它们包括灰尘颗粒、硬水污渍、脂肪酸、甘油三酯、脂质体、不溶性的脂肪酸皂等。洗涤剂组合物可用于许多不同的表面类型，例如陶瓷、玻璃纤维、聚氨酯和塑料表面。A．烷基芳基磺酸盐：
烷基芳基磺酸盐是本发明的主要组分。合适的烷基芳基磺酸盐可用任何碱金属，例如锂、钠、钾等中和，或可用铵或C1-C9铵盐衍生物，例如单乙醇铵、二乙胺、三异丙醇胺等中和。它们可用任何合适的方法制备，形成“低级2-苯基”或“高级2-苯基”衍生物，通常优选“低级2-苯基”衍生物。该表面活性剂在商业上可由几个供应商得到，包括Witco Coporation(0ne American Lane，Greenwich，Connecticut 06831)、Stepan Company(Edens ＆ Witnetka Rd，Northfield，Illinois 60093)和BASF Aktiengesellschaft(ESA/1550，D-67056 Ludwigshafen，Germany)。
本发明的洗涤剂组合物用相对低含量的活性物质制备。组合物通常含有足够的如下讨论的表面活性剂和溶剂，以有效地作为硬表面洗涤剂，而仍保持经济，因此，它们通常含有约0.5％-约5％烷基芳基磺酸盐表面活性剂，更优选约1％-约4.5％烷基芳基磺酸盐表面活性剂，甚至更优选约1.2％-约4％烷基芳基磺酸盐表面活性剂。
本发明的烷基芳基磺酸盐具有平均约8个碳原子-约14个碳原子，更优选约9个碳原子-约13个碳原子，最优选约9个碳原子-约13个碳原子的链长。链长分布可从约8个碳原子-约16个碳原子。直链和/或支链烷基芳基苯磺酸盐的混合物是合适的。
C11-C12直链烷基苯磺酸盐的铵和钠盐在本发明中是最优选的，尤其优选的商业可获得的烷基苯磺酸钠的实例包括由Stepan得到的Polystep A-13、由Pilot Chemical Company(11756 Burke Street，Santa Fe Springs，California)获得的Calsoft L-40浆状物和由Witco Corporation(Greenwich，Conneticut)得到的WitconateP1059。此外，所需的烷基芳基磺酸盐表面活性剂可通过中和相应的烷基芳基磺酸就地制备。合适的烷基芳基磺酸的实例包括由StepanCompany得到的Biosoft100、由Pilot Chemical得到的CalsoftLAS-99和由BASF AG(德国)得到的Lutensit A-LABS。B．非离子醇或阳离子表面活性剂：
本发明的洗涤剂组合物还优选含有一种或多种非离子醇和/或阳离子表面活性剂。烷基芳基洗涤剂表面活性剂与醇和/或阳离子表面活性剂的组合对于本发明是必需的。可采用同时含有非离子醇和阳离子表面活性剂的洗涤组合物。用于本文的“非离子醇”是指含有平均约8个碳原子-约16个碳原子，更优选约9个碳原子至约14个碳原子，最优选约10个碳原子-约13个碳原子的直链或单支链非离子醇。合适非离子醇的实例包括2-丁基-1-辛醇、2-甲基-1-十一烷醇和十二烷醇。直链C10-13非离子醇是最优选的。优选的商业上可获得的非离子醇的实例包括Neodol1和Neodol 23，由Shell Chemical(1Shell Palza，Houston，Texas 77252)得到。人们认为当非离子醇的链长最接近匹配于烷基芳基磺酸盐表面活性剂的链长时获得最佳效果。为此，在本发明中含有少于8个碳原子或长于16个碳原子的非离子醇是不优选的。如果存在，非离子醇的有效浓度不超过组合物重量计约2％，更优选1.5％或以下的浓度，最优选1.25％或以下的浓度。
不含非离子醇的本发明洗涤剂组合物通常将含有一种或多种阳离子表面活性剂。用于本文时，阳离子表面活性剂是在酸性pH情况下主要作为阳离子物质的那些。阳离子表面活性剂通过与上述烷基芳基磺酸盐表面活性剂形成离子对产生粘度。阳离子表面活性剂还提供消毒性质，可选择以增加该效果。优选的阳离子物质具有约8个碳原子-约16个碳原子，更优选约10个碳原子-约16个碳原子，最优选约12个碳原子-约14个碳原子的疏水链长。合适的阳离子表面活性剂包括烷基和烷基苄基季铵盐(例如由Lonza Incorporated，1717Route 208，Fairlawn，New Jersey 07410得到的Bardac)、乙氧基化季铵盐(例如由Akzo Nobel Chemicals，300 South RiversideP1aza，Chicago，Illinois得到的Ethoquad)、乙氧基化胺(例如由Akzo Nobel Chemical得到的Ethomeen表面活性剂)、烷基二甲基甜菜碱(例如由Witco Corporation得到的Rewoteric AM DML-35)或酰氨基丙基甜菜碱(例如由Witco Corporation得到的Rewoteric AMB 15U)和氧化胺(例如由Lonza Incorporated得到的Barlox 10S)。对于需要提供杀菌、抑霉、杀真菌性质的组合物加入季铵表面活性剂是尤其优选的。季铵表面活性剂在现有技术中是已知的，包括C10-16烷基三甲基铵、C8-14二烷基二甲基铵和C10-16烷基二甲基苄基铵衍生物和它们的混合物。合适和商业上可得到的C10-16烷基三甲基铵和C8-14二烷基二甲基季铵盐由Witco Corporation以商品名Aogen得到；合适的C10-16烷基二甲基苄基铵表面活性剂由LonzaIncorporated以商品名Bardac购买。
本发明组合物中阳离子表面活性剂的含量优选不超过按组合物重量计约2％，更优选不超过约1.5％，最优选不超过约1.25％。为达到粘度，阳离子表面活性剂可单独使用或与非离子醇结合使用。阳离子表面活性剂加上非离子醇的含量按组合物重量计为至少约0.3％，更优选至少0.4％，最优选至少约0.5％，更优选约0.5％-约2.0％。C．水溶助长溶剂：
组合物还可含有有效量的，通常不少于按组合物重量计约2％，优选约2％-约8％，更优选约2％-约6％，最优选约3％-约6％的一种或多种水溶助长溶剂。
实验发现粘度的产生需要使用水溶助长溶剂。水溶助长溶剂是指帮助增溶组合物中的疏水组分的试剂。水溶助长溶剂参与粘度的产生并增加组合物的稳定性。该溶剂通常含有连接于1-3个乙二醇或丙二醇部分的端C3-C6烃基。基于乙二醇化学的商业可得到的水溶助长溶剂的实例包括乙二醇单丁基醚(Butyl Cellosolye，由UnionCarbide，39 Old Ridgebury road，Danbury，Connecticut得到)，二乙二醇单丁基醚(Butyl Carbito1，由Union Carbide得到)和单乙二醇正丁基醚(Hexyl Cellosolve，由Union Carbide得到)。商业可得到的合适的基于丙二醇化学的水溶助长溶剂的实例包括丙基和丁基醇的单-、二-和三-丙二醇衍生物，它们由Arco Chemical(3801West Chester Pike，Newtown Square，PA 19073)和DowChemical(1691N.Sweede Road，Midland，Michigan)以商品名Arcosolv和Dowanol得到。最优选的水溶助长溶剂是二丙二醇正丁基醚，以商品名Arcosolv DPnB和Dowanol DPnB出售。水溶助长溶剂的数量可根据组合物中存在的其它组分的数量变化，但应以按总组合物重量计约2％-约8％，更优选约2％-约6％，最优选约3％-约5％的浓度存在。
在不存在水溶助长溶剂的情况下，本发明的组合物通常呈现乳状、低粘度混合物，它在室温条件下通常是无期限稳定的。加入水溶助长溶剂用于增加产品粘度以产生更加半透明的溶液。人们相信溶剂稀释了最初形成的相并将其主要转变为分散在含水溶剂体系中的挠性层状片。低温学隧道电子显微镜(下文称为Cryo-TEM)测量显示相化学由小的同心囊泡组成，在加入水溶助长溶剂时，它的挠性增加和成为更开放的层状片。D.pH：
为达到去除硬水污渍的目的，组合物是pH为约0.5-约6，更优选约1.5-约5，还更优选约2.0-约4的酸性。为除去硬水污渍，PH通常为约3或以下。酸性优选通过使用一种或多种pKa小于约6，优选小于约4的有机酸达到。该有机酸有助于相形成，并提供硬水污渍去除性质。在本发明组合物的框架中有机酸被发现在促进良好的硬水去除性质方面是非常有效的。发现较低pH和使用一种或多种合适的酸还有利于消毒效果。合适的有机酸的实例包括柠檬酸、苯甲酸、乳酸、酒石酸，乙醇酸、琥珀酸、戊二酸、己二酸、葡糖酸和它们的混合物。该酸在商业上是容易得到的。更优选的酸的实例包括柠檬酸(由Aldrich Corporation，1001 West Saint Paul Avenue，Milwaukee，Wisconsin得到)、苯甲酸(由Aldrich Chemical得到)和由DuPont(Wilmington，Delaware)作为“精制AGS二元酸”出售的琥珀酸、戊二酸和己二酸的混合物。柠檬酸是最优选的。在本组合物中有机酸的数量为按组合物重量计约1％-约10％，更优选约2％-约8％，最优选约3％-约6％。E．选择性的过氧化物源：
本发明的组合物可含有过氧化物，例如过氧化氢或过氧化氢源以获得进一步的消毒、抑霉和杀菌效果。过氧化物被认为提高了效果的耐久性，这是由于它已知的残留能力和缓慢分解以产生游离基物质。本发明组合物的组分基本上与过氧化物的使用相容。优选的过氧化物包括苯甲酰基过氧化物和过氧化氢。它们可以约0.05％-约5％，更优选约0.1％-约3％，最优选约0.2％-约1．5％的含量选择性地存在于本发明组合物中。
当过氧化物存在时，需要提供稳定体系。合适的稳定体系是已知的。优选的稳定体系由游离基清除剂和/或金属螯合剂组成，以按组合物重量计约0.01％-约0.5％，更优选约0.01％-约0.25％，最优选约0.01％-约0.10％的含量存在。游离基清除剂的实例包括抗氧化剂，例如没食子酸丙酯、丁基化羟基甲苯(BHT)、丁基化羟基苯甲醚(BHA)等。合适的金属螯合剂的实例包括二亚乙基三胺五乙酸盐、二亚乙基三胺五亚甲基膦酸盐、羟基乙基二膦酸盐等。选择性的表面活性剂和溶剂：
除了烷基芳基磺酸盐和水溶助长溶剂外，本发明的组合物优选含有其它附加阴离子表面活性剂。该表面活性剂通常含有约8个碳原子-约18个，优选约10-约16个碳原子的疏水链，并包括硫酸盐、磺酸盐或羧酸盐亲水首基。合适的阴离子表面活性剂的实例包括直链或支链烷基硫酸盐洗涤剂表面活性剂(例如由Stepan得到的StepanolAM)、石蜡磺酸盐(由Hoechst，Aktiengesell schaft，D-6230Frankfurt，Germany得到的Hostapur SAS)、烷基乙氧基羧酸盐洗涤剂表面活性剂(由Shell Chemical Corporation得到的Neodex)等。人们发现烷基硫酸盐表面活性剂是尤其优选的，因为它们提供改善的皂垢洗涤效果。通常，在本发明组合物中选择性阴离子表面活性剂的含量为按组合物重量计约0.5％-约2％，优选约0.6％-约1％。
也可以存在非离子洗涤剂表面活性剂。用于本发明的合适的非离子洗涤剂表面活性剂是乙氧基化醇，在醇的疏水烷基链中通常含有约6-约16个碳原子。典型的烷氧基化基团是乙氧基和/或丙氧基。该化合物在商业上由Shell以Neodol系列或由BASF AG以Lutensol得到，具有各种链长和烷氧基化程度。用于本发明的优选非离子洗涤剂表面活性剂具有式R(X)nH，其中R是含有约6-约16个碳原子，优选约6-约10的烷基链，X是烷氧基，优选乙氧基，或乙氧基和丙氧基的混合物，n是约4-约30的整数，优选约5-约8。其它可使用的非离子表面活性剂包括由天然源，例如蔗糖得到的物质，包括烷基聚葡糖苷(例如由Seppic Corporation，75 Quai d’Orsay，75321 Paris，Cedex 7，France得到的Simusol表面活性剂)和N-烷基葡糖酰胺表面活性剂。如果存在，非离子表面活性剂的浓度为按组合物重量计约0.1％-约3％，更优选约0.1％-约2％。
本发明的组合物还可包括两性离子表面活性剂，例如磺基甜菜碱和羟基磺基甜菜碱，有效浓度优选不超过按组合物重量计约2％。
该表面活性剂的其它商业来源可在McCutcheon’s EMULSIFIERSAND DETERGENTS，North American Edition，1997，McCutcheonDivision，MC Publishing Company中找到，列为本文参考文献。含水溶剂体系和其它溶剂。
组合物是含水形式，含有按组合物重量计至少约60％的含水溶剂，更优选按组合物重量计约60％-约90％。含水溶剂体系可含有在洗涤剂组合物中通常存在的低分子量溶剂，如乙醇、异丙醇等。
发明的组合物还可含有其它溶剂，尤其是石蜡烃，它们被发现明显降低组合物产生的泡沫。
选择性的组分，例如香料和其它常规辅助组分也可存在。选择性香料和附加辅助组分：
选择性的，但十分优选的组分是香料，通常是香料组分的混合物。事实上，也许是通过支持产品的相结构以及改善产品的总体稳定性，通常是疏水物质的香料组分被发现有助于粘度的产生。用于本发明的香料包括主要是由于其嗅觉贡献而加入的香料的组分。
大多数硬表面洗涤剂产品含有一些香料以提供嗅觉美感效果和遮盖产物可能有的任何“化学”气味。在这些香料组分中少量高挥发性、低沸点(有低的沸点)香料组分的主要作用是改善产物本身的芳香气味，而不是影响被洗涤表面随后的气味。然而，某些低挥发性，高沸点的香料组分提供表面新鲜和清洁的印象，这些组分沉积和存在于干表面上有时是合乎需要的。香料优选是更水溶性和/或挥发性的物质以减少斑点和膜。用于本文的香料在1992年4月28日颁布的Michael的US5108660的第8栏48行-68行和第9栏第1-68行和第10栏1-24行中详细描述，所述专利，尤其是所述具体部分列为本文参考文献。
香料组分可以是天然产物，例如香精油、净油、香树脂、树脂、凝香体等和/或合成香料组分，例如烃、醇、醛、酮、醚、酸、缩醛、酮缩醇、腈等，包括饱和和不饱和化合物、脂族、碳环和杂环化合物。该香料组分的实例是香叶醇、乙酸香叶酯、里哪醇、乙酸里哪醇酯、四氢里哪醇、香茅醇、乙酸香茅醇酯、二氢月桂烯醇、乙酸二氢月桂烯酯、萜品醇、乙酸萜品酯、乙酸酯、2-苯基乙醇、乙酸2-苯基乙酯、苄醇、乙酸苄酯、水杨酸苄酯、苯甲酸苄酯、乙酸甲基苯基原酯、水杨酸戊酯、二基苄甲醇、乙酸三氯甲基苯基甲醇酯、乙酸对叔丁基-环己酯、乙酸异壬酯、α-正戊基肉桂醛、α-己基肉桂醛、2-甲基-3-(对叔丁基苯基)-丙醛、2-甲基-3-(对异丙基苯基)-丙醛、3-(对叔丁基苯基)-丙醛、乙酸三环癸烯酯、丙酸三环癸烯酯、4-(4-羟基-4-甲基戊基)-3-环己烯甲醛、4-(4-甲基-3-戊烯基)-3-环己烯甲醛、4-乙酰氧基-3-戊基四氢吡喃、二氢茉莉酮酸甲酯、2-正庚基环戊酮、3-甲基-2-戊基-环戊酮、正-癸醛、正十二醛、9-癸烯醇-1、异丁酸苯氧基乙酯、苯基乙醛二基缩醛、苯基乙醛二鲸蜡基缩醛、香叶腈、香茅腈、乙酸雪松酯、3-异莰基环己醇、雪松基醚、异长叶酮、茴香腈、茴香酸、胡椒醛、香豆素、丁子香酸、香兰素、二苯基氧化物、羟基香茅醛、紫罗兰酮、甲基紫罗兰酮、异甲基紫罗兰酮、甲基芷香酮、顺-3-己烯醇和它们的酯、1，2-二氢化茚麝香香料、1，2，3，4，-四氢化萘麝香香料、异色满麝香香料、大环酮、大内酯麝香香料、亚乙基巴西基酸酯、芳香硝基麝香。本发明的组合物通常含有按总组合物重量计0.1％-2％的香料组分或其混合物，优选0.1％-1.0％。在含有过氧化物的优选实施方案的情况下，必须选择香料以与氧化剂相容。在优选实施过程中，香料组分是疏水和高挥发的，即组分具有低于约260℃，优选低于约255℃，更优选低于约250℃的沸点，ClogP为至少约3，优选超过约3.1，甚至更优选超过约3.2。
许多香料组分的logP已在例如Pomona 92数据库中报导，由Daylight Chemical Information Systems，Inc.(Daylight CIS)，Irvine，California得到，包括许多引用的原始文献。然而，logP值最方便由“CLOGP”程序计算，也可由Daylight CIS得到。当可由Pomona 92数据库得到时，该程序还列出了实验logP值。“计算的logP”(ClogP)由Hansch和Leo的片断法测定(参见，ComprehensiveMedicinal Chemistry，第4卷，C.Hansch，P.G.Sammens，J.B.Taylor和C.A.Ramsden，Eds.，295页，Pergamon Press，1990，列为本文参考文献)。片断法基于每个香料组分的化学结构并考虑原子的数目和类型、原子连通性和化学键。用于确定物化性质的最可靠和广泛使用的ClogP值在选择用于本发明的主溶剂组分时优选用于代替实验logP。可用于计算ClogP的其它方法包括，例如在J.Chem，Inf.comput.Sci.，27，21(1987)中公开的Crippen’s片断方法；在J.Chem，Inf.comput.Sci.，29，163(1989)中公开的Viswanadhan’s片断方法；和在Eur.J.Med.Chem.Chim.Theor.，19，71(1984)中公开的Broto’s方法。
本发明的组合物还可以含有各种其它选择性组分，包括其它的活性物质和洗涤剂助洗剂以及仅仅有美学效果的组分。组合物的流变性尤其适合于在组合物中悬浮颗粒，例如磨料的颗粒。
临界含量的对于硬表面洗涤剂有效的和具有降低成膜/条纹特性的洗涤剂助洗剂是另一种选择性组分。优选的洗涤剂助洗剂是上述公开的作为羧酸部分的羧酸洗涤剂助洗剂，包括柠檬酸和酒石酸。酒石酸改善了洗涤和能够减少在洗涤剂助洗剂加入硬表面洗涤剂中时通常出现的成膜/条纹问题。
洗涤剂助洗剂以提供洗涤剂助洗的含量存在，并且如果不是上述酸pH调节部分，通常以约0.1％-约0.3％，更优选约0.2％-约2％，最优选约0.5-约1.0％的含量存在。
通常关于可接受的成膜/条纹结果的改善大多数是在助洗剂与两性和/或两性离子洗涤剂表面活性剂组合物结合时发生，尽管对于不太优选的阴离子或阴离子/非离子洗涤剂表面活性剂组合物也可看到改善。
本发明的组合物还可含有其它洗涤剂组合物领域中已知的各种辅助组分。优选它们不以产生不可接受的膜/条纹的含量使用。
其它辅助组分的非限制实例是：酶，例如蛋白酶；增溶剂，例如甲苯磺酸钠、枯烯磺酸钠和二甲苯磺酸钾；增稠剂，例如黄原胶，例如Keltrol或Keltrol RD，通常含量为约0.01％-约2％，优选约0.05％-约0.5％；和提高美观的组分，例如着色剂，前提是它们不会不利地影响成膜/条纹。
可存在杀菌剂，但优选仅以避免成膜/条纹问题的低含量存在。避免更疏水的杀菌/杀菌剂，如邻苄基-对-氯苯酚。如果存在，该物质应保持在低于约0.1％的含量。组合物制备：
本发明的组合物可通过将所有的组分混合在一起制备。通常，添加的优选顺序是首先加入水、烷基芳基磺酸盐表面活性剂和有机酸，随后是选择性的阴离子、非离子和/或两性离子表面活性剂。混合物最初是混浊的，随着水溶助长溶剂的加入不透明性减小；加入水溶助长溶剂还由于形成更挠性和更开放的囊泡和/或层状片而导致产品粘度的明显增加。在大多数情况下，加入水溶助长溶剂导致溶液变得半透明或透明。一旦加入溶剂，配制者根据需要调节pH至最佳值。选择性的过氧化物、香料和染料则可加入。本发明的组合物最终达到用Brookfield粘度计以60RPM剪切速率和锭子#2测定的50cP-200cP粘度。
本文中使用的所有数值是基于正常变化的近似值，所有份数、百分数和比率为按重量计，除非另有说明，所有专利和其它出版物列为本文参考文献。实验：
Crvo-TEM的相化学：在J.ElectronMicrosc.Tech.，1988，10，87-11l中所述的控制环境的玻璃固化体系(CEVS)中制备样品，所述文章列为本文参考文献。将5μl液滴的样品溶液放置在在薄膜中带有孔的碳涂覆的聚合物载体薄膜上，所述薄膜固定在标准300目TEM栅格表面(Ted Pella，Inc.，Catalog#01883)。液滴用滤纸吸干直至降低至样品的薄膜(10-200nm)，跨越载体薄膜的孔(2-8μm)。然后样品通过CEVS底部的同步闸门迅速投入冰点的液体乙烷中被玻璃化。玻璃状样品在液氮中被转移到带有联合生物滤池的Philips CMl2显微镜或CM120显微镜中成像。在实验过程中样品的温度保持在-170℃以下。图像用Kodak SO-163胶片或带有Digital Micrograph软件的Gatan缓慢扫描CCD照相机记录。
皂垢洗涤：用于提供可重现的标准染污表面的标准染污盘子用每个产品处理，表面随后用加德纳直线式耐洗刷性试验机用海棉擦洗。测定和记录完全洗涤所需的冲程数。皂垢洗涤指数用如下公式计算：(#用于对照产品的冲程数/#用于实验产品的冲程数)*100，其中对照产品是Mastro Lindo(意大利)，实验原型是本文公开的组合物1-8。指数超过100暗示产品具有杰出的皂垢去除性质。
硬水洗涤：用于每个试验产品的尺寸为约3/4”x3/4”x1/4”的四块大理石碎片用分析天平称重至4位小数。随后将碎片放置在含有20克产品的100ml烧杯中共10分钟。随后取出大理石碎片，漂洗和干燥。随后重新称重，计算重量损失。对于每个产品使用四个试验的平均值，硬水去除指数计算如下：(浸在对照产品中的大理石碎片的平均重量损失/浸在实验组合物中的大理石碎片的平均重量损失)*100。
实施例-实验数据
本发明进一步用如下实施例和数据说明。如下组合物通过以所列出的比例、以所列出的添加次序混合所列出的组分制备。皂垢去除比较用在意大利出售的商业得到的产品，Mastro Lindo进行，其是一种在pH3.7下配制的产品。
组合物
*LAS：C12直链烷基苯磺酸盐(Calsoft L-40，来自Pilot)。**Bardac 208M是由Lonza，Incorporated出售的季铵表面活性剂混合物。***n-BPP：二丙二醇正丁基醚(Dowanol DPnB，由Dow Chemical出售)。+组合物不能完全除去皂垢数据分析：
| 组分 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| C12LAS* | 4.00 | 3.50 | 3.50 | 1.60 | 1.60 | 1.60 | 1.85 | 2.25 |
| C12-14烷基硫酸盐 | - | - | - | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| C12-13醇 | - | - | - | 1. 15 | 1.15 | 1.15 | 1.15 | 1.15 |
| C12氧化胺 | 0.70 | 0.70 | 0.70 | - | - | - | - | - |
| Bardac 208M** | - | - | - | - | - | - | - | 0.20 |
| n-BPP*** | - | 2.0 | 5.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 |
| 柠檬酸 | 4.0 | 4.0 | 4.0 | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 |
| 氨 | 0.43 | 0.43 | 0.43 | 0.29 | 0.29 | 0.29 | 0.29 | 0.23 |
| C12石蜡烃 | - | - | - | 0.75 | 0.75 | - | 0.75 | - |
| 过氧化氢 | - | - | - | - | 1.5 | - | - | 0.25 |
| 香料 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| pH | 3.7 | 3.7 | 3.7 | 3.1 | 3.1 | 3.0 | 3.0 | 3.0 |
| 粘度，cP | 20 | 50 | 120 | 90 | 80 | 80 | 100 | 140 |
| 层状片相? | 否 | 否 | 是 | 是 | 是 | 否 | 否 | 是 |
| 皂垢除去指数 | + | - | 110 | 125 | 125 | 60 | 60 | 125 |
| 硬水去除 | - | - | - | 400 | 400 | - | - | 200 |
所有组合物含有C12烷基苯磺酸盐作为选择的阴离子表面活性剂，除了组合物1外，全都包括所需的水溶助长溶剂。组合物1、2和3说明水溶助长溶剂对相化学和产品粘度的影响。不同于常规产品，水溶助长溶剂(n-BPP)通过将同心囊泡结构转变为挠性层状片增加了产品粘度。其结果是改善了皂垢洗涤。
使用长链醇代替阳离子表面活性剂，构成了组合物4-8的相化学和粘度。组合物4和5显示挠性层状相结构，而化学上非常接近于组合物5的组合物6和7的相结构由同心囊泡组成。组合物6和7与组合物4和5之间的洗涤性能的差异是相化学之间的差异引起的。
组合物8使用长链醇和季铵表面活性剂的组合以产生由挠性层状片组成的高粘度产品。注意该组合物还含有过氧化物，具有高粘度和显示杰出的皂垢洗涤性能。
硬水试验限制于在皂垢试验中显示最强结果的产品。注意到所有三个优选的组合物具有杰出的硬水除去性质。
Claims (10)
1．一种含有挠性层状片相的含水粘性硬表面洗涤剂。
2．根据权利要求1的组合物，其含有：
a．约1％-约5％，优选约4.5％的烷基芳基磺酸盐洗涤剂表面活性剂；
b．约0.3％-约2％，优选约0.4％-约1.5％的非离子醇和/或阳离子表面活性剂；
c．约1％-约8％，优选约2％-约6％的一种或多种水溶助长溶剂；
d．选择性地有效量的，最多到约5％的过氧化物，优选过氧化氢；和
e．平衡量的含水溶剂体系，
其中所述组合物具有约0.5-约6，优选约1．5-约5的pH。
3．根据权利要求2的组合物，其含有约1．2％-约4％的烷基芳基磺酸盐表面活性剂；(b)按组合物重量计约0.5％-约1．25％的所述非离子醇和/或阳离子表面活性剂；按组合物重量计约3％-约6％的一种或多种水溶助长溶剂；按组合物重量计约0.05％-约3％的所述氧化氢；和按组合物重量计约60％-约90％的所述含水溶剂体系，所述组合物具有约2.0-约4的pH。
4．根据权利要求1-3的任何之一的组合物，其中所述烷基芳基磺酸盐洗涤剂表面活性剂是烷基苯磺酸盐，其中所述烷基含有约8-约14个碳原子和/或其中所述非离子醇是直链或单支链醇，其含有约8-约16个碳原子和/或其中所述阳离子表面活性剂含有含约8-约16个碳原子的疏水链。
5．根据权利要求1-4的任何之一的组合物，其中所述阳离子表面活性剂选自C8-C14二烷基二甲基铵表面活性剂、C10-C16烷基三甲基铵表面活性剂、C10-C16烷基二甲基苄基铵表面活性剂和它们的混合物。
6．根据权利要求1-5的任何之一的组合物，其中过氧化氢以约0.05％-约3％的含量存在。
7．根据权利要求1-6的任何之一的组合物，其中所述水溶助长溶剂含有连接于约1-约3个环氧乙烷和/或环氧丙烷部分的含有约3-约6个碳原子的烃基部分。
8．根据权利要求1-7的任何之一的组合物，其含有柠檬酸作为pH调节剂，并具有约3或以下的pH。
9．洗涤表面的方法，其包括将有效量的权利要求1-8的任何之一的组合物施用于所述表面和漂洗所述表面。
10．权利要求9的方法，其中所述表面被霉污染，所述组合物含有有效量的过氧化氢。
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| US6444707B1 (en) * | 2000-08-22 | 2002-09-03 | West Agro | Topically applied hoof treatment composition and concentrate |
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| GB2379223A (en) * | 2001-08-31 | 2003-03-05 | Reckitt Benckiser Inc | Cleaning composition comprising citric acid |
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| US20040077519A1 (en) * | 2002-06-28 | 2004-04-22 | The Procter & Gamble Co. | Ionic liquid based products and method of using the same |
| US20080305182A1 (en) | 2002-11-15 | 2008-12-11 | Ramirez Jose A | Hydrogen peroxide disinfectant containing a cyclic carboxylic acid and/or aromatic alcohol |
| WO2005009385A2 (en) * | 2003-07-22 | 2005-02-03 | Rhodia Inc. | New branched sulfates for use in personal care formulations |
| US7226899B2 (en) | 2003-12-23 | 2007-06-05 | Kimberly - Clark Worldwide, Inc. | Fibrous matrix of synthetic detergents |
| US6969698B2 (en) * | 2004-04-13 | 2005-11-29 | S. C. Johnson & Son, Inc. | Aerosol cleaner |
| JP2007532765A (ja) * | 2004-04-15 | 2007-11-15 | ローディア インコーポレイティド | 組織化界面活性剤組成物 |
| WO2005113735A1 (en) * | 2004-04-21 | 2005-12-01 | Stepan Company | Acidic hard surface cleaner with alkoxylated quaternary compound |
| US20060135627A1 (en) * | 2004-08-17 | 2006-06-22 | Seren Frantz | Structured surfactant compositions |
| JP5154931B2 (ja) * | 2004-08-17 | 2013-02-27 | ローディア インコーポレイティド | 低ｐＨ構造化界面活性剤組成物 |
| CA2582414C (en) * | 2004-10-04 | 2013-01-08 | W.R. Grace & Co.-Conn. | Integrally waterproofed concrete |
| US20060094621A1 (en) * | 2004-11-01 | 2006-05-04 | Jordan Glenn T Iv | Process for improving processability of a concentrate and compositions made by the same |
| US7939485B2 (en) * | 2004-11-01 | 2011-05-10 | The Procter & Gamble Company | Benefit agent delivery system comprising ionic liquid |
| US20060090271A1 (en) * | 2004-11-01 | 2006-05-04 | Price Kenneth N | Processes for modifying textiles using ionic liquids |
| US20060094616A1 (en) * | 2004-11-01 | 2006-05-04 | Hecht Stacie E | Ionic liquids derived from surfactants |
| US20060090777A1 (en) * | 2004-11-01 | 2006-05-04 | Hecht Stacie E | Multiphase cleaning compositions having ionic liquid phase |
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| US7776810B2 (en) * | 2004-11-01 | 2010-08-17 | The Procter & Gamble Company | Compositions containing ionic liquid actives |
| US7786065B2 (en) * | 2005-02-18 | 2010-08-31 | The Procter & Gamble Company | Ionic liquids derived from peracid anions |
| US7737106B2 (en) * | 2005-11-29 | 2010-06-15 | The Procter & Gamble Company | Process for making an ionic liquid comprising ion actives |
| WO2008118381A1 (en) * | 2007-03-23 | 2008-10-02 | Rhodia Inc. | Structured surfactant compositions |
| EP2225354A1 (en) * | 2007-12-10 | 2010-09-08 | Reckitt Benckiser Inc. | Improved hob cleaning composition |
| US9499662B2 (en) * | 2010-04-02 | 2016-11-22 | Chemtreat, Inc. | Foam control compositions |
| JP5819685B2 (ja) * | 2010-11-24 | 2015-11-24 | 花王株式会社 | 硬質表面用液体洗浄剤組成物 |
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| GB8919254D0 (en) | 1989-08-24 | 1989-10-11 | Albright & Wilson | Liquid cleaning compositions and suspending media |
| US5861367A (en) * | 1993-08-04 | 1999-01-19 | Colgate Palmolive Company | Cleaning and disinfecting composition in microemulsion/liquid crystal form comprising aldehyde and mixture of partially esterified, fully esterified and non-esterified polyhydric alcohols |
| EP0763083B1 (en) | 1994-05-31 | 2001-07-18 | The Procter & Gamble Company | Cleaning compositions |
| US5707952A (en) * | 1996-04-24 | 1998-01-13 | Colgate-Palmolive Company | Thickened acid composition |
| GB2319179A (en) * | 1996-11-12 | 1998-05-20 | Reckitt & Colman Inc | Cleaning and disinfecting compositions |
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| JP2001524592A (ja) | 2001-12-04 |
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| DE69810965D1 (de) | 2003-02-27 |
| EP1047765A1 (en) | 2000-11-02 |
| DE69810965T2 (de) | 2004-01-08 |
| US6479446B1 (en) | 2002-11-12 |
| EP1047765B1 (en) | 2003-01-22 |
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