CN108431196A - 使用扩链表面活性剂的组合来增强溶解性 - Google Patents
使用扩链表面活性剂的组合来增强溶解性 Download PDFInfo
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- CN108431196A CN108431196A CN201780005193.1A CN201780005193A CN108431196A CN 108431196 A CN108431196 A CN 108431196A CN 201780005193 A CN201780005193 A CN 201780005193A CN 108431196 A CN108431196 A CN 108431196A
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Classifications
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
- C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
-
- 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
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Abstract
本发明提供一种表面活性剂共混物，其含有(i)扩链阴离子表面活性剂和(ii)扩链中间体表面活性剂。该表面活性剂共混物可以用于制备清洁组合物，或用于油田处理应用、水基金属加工应用和聚氨酯发泡应用的组合物。
Description
相关申请的交叉参考
本申请要求2016年3月31日提交的美国临时专利申请序列号62/326,203的权益，其全部公开内容通过参考引入本文。
关于联邦赞助的研究或开发的声明
不适用。
发明领域
本发明提供一种包含扩链阴离子表面活性剂和扩链中间体表面活性剂的表面活性剂共混物，及其在不同应用中的用途，例如用于家用和工业组织清洁产品、个人护理和金属加工。
发明背景
扩链表面活性剂是这样的表面活性剂，其中中间极性基团，例如聚环氧丙烷或环氧丙烷与环氧乙烷的共聚物，插入烃尾部与亲水性头部基团之间。由于形成的分子结构，该表面活性剂进一步延伸到油与水相二者中，形成两相之间更大的相互作用，和提供界面的亲水与疏水区域之间更光滑的过渡。这提供了更合适的环境来溶解亲水和亲脂分子。
现有技术的扩链表面活性剂和它们在不同应用中的用途包括例如：
美国专利9,034,813，其公开了一种浸泡组合物，该组合物含有带正电的聚乙烯酰亚胺(PEI)聚合物和扩链阴离子表面活性剂；
美国专利8,697,622，其公开了一种清洁组合物，该组合物含有扩链非离子表面活性剂和连接助表面活性剂，该连接助表面活性剂包括单和二甘油酯，和/或脂肪酸和脂肪二酸；
美国专利8,454,709，其公开了一种扩链阴离子表面活性剂，连接剂例如氧化胺或磺化琥珀酸二辛酯，或者连接助表面活性剂例如单甘油酯、二甘油酯、脂肪酸或脂肪二酸和它们在去除油和脂污点的用途；
美国专利8,172,953，其公开了一种乙氧基化的、丙氧基化的扩链表面活性剂，和它与烷基多聚葡萄糖的组合用于清洁组合物的用途；和
美国专利7,467,633，其公开了一种扩链阴离子表面活性剂和高HLB非离子表面活性剂和/或电解质，和它们从硬和软表面除去油脂和油性物质的用途。
虽然有这些现有技术的表面活性剂体系，但是仍然需要开发新的、通用的表面活性剂体系，其在油与水相之间提供超低的界面张力，这提高亲水和亲脂分子的溶解性。
发明内容
在一方面中，提供一种表面活性剂共混物，其包含：(i)扩链阴离子表面活性剂；和(ii)扩链中间体表面活性剂。
在第二方面中，提供一种清洁组合物，其含有本发明的表面活性剂共混物。
在第三方面中，提供一种单相微乳液，其包含本发明的表面活性剂共混物、水和油组分。
在第四方面中，提供清洁组合物或单相微乳液可以用于的应用，其包括但不限于家用清洁剂或个人护理应用例如洗发剂、洗手液和身体洗液、润肤露、体霜、硬表面清洁剂和衣物或餐具清洁剂。
具体实施方式
如果在本文出现，则术语“包含”及其派生词并不意在排除任何另外的组分、步骤或程序的存在，无论其是否公开。为了避免任何疑义，本文通过使用术语“包含”所要求保护的全部组合物可以包括任何另外的添加剂、助剂或化合物，除非有相反指示。相反地，如果在本文出现，则术语“主要由……组成”从任何后续的限定范围中排除任何其他组分、步骤或程序，除了对于操作性来说并非必要的那些之外，和如果使用，术语“由……组成”排除了没有明确描述或列举的任何组分、步骤或程序。除非另有规定，否则术语“或”指的是单个以及任意组合的所列成员。
冠词“一个”和“一种”在本文用于表示一个/种或多于一个/种(即至少一个/种)的该冠词的语法宾语。作为例子，“一种扩链表面活性剂”表示一种扩链表面活性剂或多于一种扩链表面活性剂。短语“在一个实施方案中”、“根据一个实施方案”等通常表示该短语后面的具体特征、结构或特性被包括在本发明的至少一个实施方案中，并且可以包括在本发明的多于一个实施方案中。重要地，这样的短语不必需指相同的实施方案。如果说明书声称组分或特征“会”、“可以”、“能够”或“可能”被包括或具有特性，则该具体组分或特征无需被包括或具有该特性。
术语“表面活性剂”表示含有亲脂片段和亲水片段的化合物，当添加到水和油或溶剂时，其降低体系的表面张力。
术语“扩链表面活性剂”是这样的表面活性剂，其具有插入表面活性剂的常规亲脂片段和亲水片段之间的中间极性连接链，例如聚环氧丙烷嵌段或聚环氧乙烷嵌段或其混合物。
术语“电解质”指当溶解在水中或者当与之接触时将提供离子传导性的物质；这样的化合物可以是固体或液体。
术语“硬表面”指固体的、基本上非柔性的表面，例如柜台表面、瓦、地板、墙壁、面板、窗、管道夹具、厨房和浴室家具、器具、发动机、电路板和餐具。
术语“软表面”指更柔软的、高柔性材料，例如织物、毯、头发和皮肤。
“污物”或“污点”指非极性油性物质，其可以或可以不含有颗粒物质，例如矿物粘土、沙、天然矿物质、炭黑、石墨、高岭土、环境灰尘等。
术语“微乳液”指透明胶体分散体，其是当它的组分与含水介质接触时自发或基本上自发形成的。微乳液是热力学稳定的，并且含有平均直径小于约300nm，例如小于约250nm，小于150nm，小于100nm的分散颗粒，和可以大于约2-4nm，其通过标准光散射技术来测量。
当就材料基本上不存在来使用时，术语“基本上不含”表示这样的材料作为偶然的杂质或副产物存在，如果有的话。例如，在一些实施方案中，该材料可以在组合物中以不大于100ppm的量存在，在一些情况中小于20ppm，在另外的情况中小于1ppm。
根据一方面，本发明提供一种表面活性剂共混物，其包含：(i)扩链阴离子表面活性剂；和(ii)扩链中间体表面活性剂。如本领域技术人员已知的，扩链表面活性剂允许在最佳的盐度时油与水相之间超低的界面张力。该盐用于降低水溶解度，和驱使一些表面活性剂进入油相。随着盐浓度增加，扩链表面活性剂变得不太溶于水，并在油与水相之间分隔。当界面两侧的相互作用变得相同时，实现界面张力最小化。已经令人惊讶地发现，本发明的表面活性剂共混物能够提供油与水相之间超低的界面张力，因此允许溶解大量的水不溶性油(包括但不限于矿物油、植物油、动物油、硅油、芳香油、醚、酯等)，而无需使用电解质(和/或醇)。
根据一方面，表面活性剂共混物包含：(i)式(I)的扩链阴离子表面活性剂
R-(L)x-(O-CH2-CH2)y-O-SO3-A (I)
和(ii)式(II)的扩链中间体表面活性剂
R-(L)x-(O-CH2-CH2)y-OH (II)
其中R是线性或支化的、饱和或不饱和的、取代或未取代的具有约6-约36个碳原子的芳族或芳族烃基；L是连接基团，例如聚环氧丙烷嵌段或聚环氧乙烷嵌段或其混合物；A是存在用于电中性的任何阳离子物类，例如氢或一价或二价金属阳离子，例如碱金属阳离子或碱土金属阳离子、铵阳离子或有机基团取代的铵阳离子；x是连接基团L的平均烷氧基化度，其为约2-约20；和y是平均乙氧基化度，其为0-约5。
在一个实施方案中，R是线性的C8-C20烷基链或支化的C8-C20烷基链。在另一实施方案中，R是线性和支化的C8-C20烷基链的混合物。在另外的实施方案中，R的烷基分支的数目可以是0-7，在其他的实施方案中是0-4，在另外的实施方案中是0-3。支化可以发生在从第二个碳原子到(B-1)个碳原子的任何碳原子中，其中B是烷基链中的碳原子数。在一个具体实施方案中，支化发生在第二个碳原子中。如果存在，则支化长度可以是1-8个碳原子。
根据另一实施方案，A选自钠、钾、镁和铵。在另一实施方案中，A是取代的铵，例如N+(CH3)4或N+(C2H5)4或N+(C2H4OH)4或N+H3CH3或N+H2(CH3)2或NH+(CH3)3或N+H(C2H4OH)3或N+H2(C2H4OH)2或N+H3(C2H4OH)或N+H(CH3)(C2H4OH)2。在另一实施方案中，A是钠。
在又一实施方案中，平均烷氧基化度x可以是约2-约18，或约3-约18，或约4-约18，或约5-约18，或约6-约18，或约7-约18，或约8-约18，或约9-约18，或甚至约10-约18。
在又一实施方案中，平均乙氧基化度y可以是约1-约5，或约2-约5，或约3-约5。
在又一实施方案中，平均烷氧基化度x+平均乙氧基化度y可以是约6-约24，或约8-22，或甚至约10-20。
式(I)的扩链阴离子表面活性剂可以例如源自适当的醇例如Ziegler、Oxo、Guerbet或天然醇的丙氧基化、乙氧基化和硫酸化，该天然醇具有约6-约36个碳原子的不同链长和烷基链分布，在一些实施方案中约8-约20个碳原子。适当的醇的例子包括但不限于商购醇例如(Vista Chem.Co.)、(Sasol Ltd.)、(Shell)和(BASF)醇。
制备式(I)的扩链阴离子表面活性剂的合适的化学方法包括适当的醇与环氧丙烷和环氧乙烷在碱催化剂例如氢氧化钠、氢氧化钾、甲氧化钠、甲氧化钾或G2催化剂存在下反应来产生烷氧基化醇。烷氧基化醇然后与氨基磺酸、氯磺酸、空气/SO3、发烟硫酸、硫酸等反应来产生酸性酯(sour ester)，该酸性酯可以用不同的碱包括氢氧化钠、氢氧化钾、单乙醇胺、二乙醇胺或三乙醇胺中和，来产生扩链阴离子表面活性剂。
类似地，式(II)的扩链中间体表面活性剂可以源自适当的醇例如Ziegler、Oxo或天然醇的例如丙氧基化和乙氧基化，该天然醇具有约6-约36个碳原子的链长和烷基链分布，在一些实施方案中约8-约20个碳原子。同样，适当的醇的例子包括但不限于商购醇例如(Vista Chem.Co.)、(Sasol Ltd.)、(Shell)和(BASF)醇。
制备式(II)的扩链中间体表面活性剂的化学方法包括适当的醇与环氧丙烷和环氧乙烷在碱催化剂例如氢氧化钠、氢氧化钾或甲氧化钠存在下的反应。
在一个具体实施方案中，适当的醇可以首先与环氧丙烷和/或环氧乙烷在碱催化剂存在下反应来生成式(II)的扩链中间体表面活性剂，其然后分离成第一和第二部分，第一部分用作式(II)的扩链表面活性剂，而第二部分与氯磺酸或HSO3Cl反应，然后中和来生成式(I)的扩链阴离子表面活性剂。因此，式(I)的扩链阴离子表面活性剂和式(II)的扩链中间体表面活性剂将具有相同的分子结构，除了用-SO3-A基团取代端羟基上的氢之外。
根据另一实施方案，式(I)的扩链阴离子表面活性剂和式(II)的扩链中间体表面活性剂以一定的摩尔比合并来形成表面活性剂共混物，当与水和水不溶性油或溶剂合并时该摩尔比足以提供单相微乳液。在一些实施方案中，式(I)的扩链阴离子表面活性剂与式(II)的扩链中间体表面活性剂的摩尔比是约15:1-约1:15，或约12:1-1:12，或约9:1-约1:9，或甚至约约7:1-约1:7。
在另一实施方案中，表面活性剂共混物由式(I)的扩链阴离子表面活性剂和式(II)的扩链中间体表面活性剂组成。在一个实施方案中，表面活性剂共混物包括式(I)的扩链阴离子表面活性剂与式(II)的扩链中间体表面活性剂的重量％之比大于1:1，或大于1.1:1。在又一实施方案中，表面活性剂共混物包括式(II)的扩链中间体表面活性剂与式(I)的扩链阴离子表面活性剂的重量％之比大于1:1，或大于1.1:1。
在另一方面中，表面活性剂共混物作为含水清洁组合物提供，其可以直接施用到有污物或有污点的软或硬表面。经过接触，在表面上形成单相微乳液，这使得油性或油脂性物质溶解并从该表面上除去。清洁组合物可以包含约1重量％-约60重量％的表面活性剂共混物和约5％-约99.5重量％的水，基于清洁组合物的总重量计。在其他实施方案中，清洁组合物可以包含约20重量％-约55重量％，或约30重量％-约50重量％的表面活性剂共混物，重量％基于清洁组合物的总重量计。在其他的实施方案中，清洁组合物包含至少约5重量％，或至少约10重量％，或甚至至少约15重量％，或甚至仍然至少约20重量％的水，重量％基于清洁组合物的总重量计。
在另一实施方案中，表面活性剂共混物以例如浓缩的清洁组合物的形式提供，其可以随后由使用者用水稀释来形成待用的清洁组合物。浓缩的清洁组合物通常包含约5重量％-约90重量％的表面活性剂共混物和小于约50重量％，或小于约40重量％，或甚至小于约30重量％的水。因此，清洁组合物还可以作为待用的清洁组合物提供给使用者，其中浓缩的清洁组合物已经用至多约95-99重量％的水稀释，基于备用清洁组合物的总重量计。
除了表面活性剂共混物和水之外，清洁组合物还可以包含一种或多种水不溶性溶剂或油或其混合物(本文称作油组分)，由此形成单相微乳液。油组分帮助形成单相微乳液和同时可以充当溶剂或软化剂来除去表面的污物或污点。油组分可以以约0.5重量％-约75重量％的量提供，基于单相微乳液的总重量计，或者在其他实施方案中约1重量％-约50重量％的量，基于单相微乳液的总重量计，在又一实施方案中约2重量％-约35重量％的量，在又一实施方案中约3重量％-约25重量％，基于单相微乳液的总重量计。
在一个实施方案中，油组分可以包括：醚，例如二醇醚或PPG丁基醚；烃或溶剂，例如角鲨烷、柠檬烯、液体链烷烃、液体异链烷烃、α-烯烃低聚物、十六烷、己烷、二戊烯、辛基苯、矿油精、矿物油等；液体酯，例如肉豆蔻酸异丙酯、肉豆蔻酸辛基十二烷基酯、油酸油烯基酯、油酸癸基酯、异硬脂酸2-己基癸基酯、辛酸己基癸基二甲酯、棕榈酸异丙酯、棕榈酸乙基己基酯、甲氧基肉桂酸辛基酯(OMC)、月桂酸己基酯、硬脂酸丁酯、己二酸二异丙酯等；车用机油；植物油，例如鳄梨油、芥花油、杏仁油、希蒙得木油、橄榄油、芝麻油、油茶油(sasanqua oil)、红花油、大豆油、蓖麻油、山茶油、玉米油、菜籽油、米糠油、par chic油、棕榈仁油、棕榈油、茶树油、葵花籽油、葡萄籽油、棉籽油、大麻籽油、薰衣草油等；动物油、例如鳌油、貂油、蛋黄脂肪油、藻类油等；和硅油，例如二甲基聚硅氧烷、甲基苯基聚硅氧烷、甲基氢聚硅氧烷、八甲基环四硅氧烷等；及其混合物。
在一个具体实施方案中，单相微乳液基本上不含醇。在另一实施方案中，单相微乳液基本上不含电解质。在又一实施方案中，单相微乳液基本上不含醇和电解质。
在又一实施方案中，本文的清洁组合物是中性组合物，因此在25℃测量的pH是约6-8，或约6.5-7.5，或甚至约7。在其他实施方案中，本文的清洁组合物的pH高于4，可选地pH低于10。
因此，本文的清洁组合物可以包含合适的碱和酸来调节它的pH。可以使用的碱包括有机和/或无机碱。这样的碱的例子是苛性碱例如氢氧化钠、氢氧化钾和/或氢氧化锂，和/或碱金属氧化物例如钠和/或钾氧化物或其混合物，氨，碳酸铵，全部可利用的碳酸盐例如K2CO3、Na2CO3、CaCO3、MgCO3等，烷醇胺(例如单乙醇胺)，尿素和尿素衍生物和多胺。当存在时，这样的碱典型的水平是约0.01重量％-约5.0重量％，或约0.05重量％-约3.0重量％，甚至约0.1重量％-约0.6重量％，基于清洁组合物的总重量计。
本文的清洁组合物还可以包含酸来将它的pH调节到所需水平，虽然存在酸，但是本文的清洁组合物将保持它们如上所述的pH。使用的酸包括有机和/或无机酸。有机酸的pKa可以小于6，可以选自柠檬酸、乳酸、乙醇酸、琥珀酸、戊二酸、己二酸及其混合物。无机酸可以选自盐酸、硫酸、磷酸及其混合物。当存在时，这样的酸典型的水平是约0.01重量％-约5.0重量％，或约0.04重量％-约3.0重量％，甚至约0.05重量％-约1.5重量％，基于清洁组合物的总重量计。
根据本发明的清洁组合物还可以包含多种辅助组分，这取决于目标的技术益处和待处理的表面。
辅助组分的例子包括抗氧化剂、悬浮助剂、螯合剂、助表面活性剂、自由基清除剂、香料、清洁和表面改性聚合物、增洁剂(builder)、抗菌剂、杀菌剂、水溶助剂、着色剂、稳定剂、漂白剂、漂白活化剂、促进泡沫和抑制泡沫的泡沫控制剂如脂肪酸、酶、污物悬浮剂、抗腐蚀抑制剂、增白剂、除尘剂、分散剂、颜料、染料、珠光剂、流变改性剂和皮肤护理活性成分例如润肤剂、湿润剂和/或调节聚合物。这些辅助组分的水平可以是约0.00001重量％直至约90重量％，基于清洁组合物的总重量计。
任选地将抗氧化剂或防腐剂添加到清洁组合物中，其包括化合物例如福尔马林、5-氯-2-甲基-4-异噻唑啉酮、和2,6-二叔丁基对甲酚。还可以包括用于清洁组合物的任何其他常规抗氧化剂例如2,6-二叔丁基-4-甲酚(BHT)、氨基甲酸盐/酯、抗坏血酸盐/酯、硫代硫酸盐/酯、单乙醇胺(MEA)、二乙醇胺和三乙醇胺。当存在时，这些组分可以以约0.001重量％-约5重量％的量被包含，基于清洁组合物的总重量计。
当存在时，腐蚀抑制剂和/或防锈助剂也以低水平引入，例如约0.01重量％-约5重量％，基于清洁组合物的重量计，并且包括偏硅酸钠、碱金属硅酸盐例如硅酸钠或硅酸镁、铋盐、锰盐、苯并三唑、吡唑、硫羟、硫醇、脂肪酸铝盐及其混合物。
任何荧光增白剂或增白剂或漂白剂可以用于本发明的清洁组合物中。典型地，当引入清洁组合物时，增白剂的水平是约0.01重量％-约1.2重量％，基于清洁组合物的总重量计。增白剂可以包括计以下的衍生物：芪、吡唑啉、香豆素、羧酸、次甲基花青、二苯并噻吩-5,5-二氧化物、唑类、5和6元环杂环物，和其他各类试剂。另外，可以通常以约1重量％-约30重量％的水平使用过氧酸、过硼酸盐、过碳酸盐和氯漂白剂，基于清洁组合物总重量计。漂白剂还可以与漂白活化剂，例如酰胺、酰亚胺、酯和酸酐和/或漂白剂稳定剂一起使用。
可以存在于清洁组合物中的抗菌剂包括消毒剂例如氯化苯甲烃铵、聚六亚甲基双胍、酚消毒剂、两性消毒剂、阴离子消毒剂和金属消毒剂(例如银)。其他抗菌剂包括过氧化氢、过酸、臭氧、次氯酸盐和二氧化氯。可以引入清洁组合物的抗菌剂的量是约0.1重量％-约10重量％，基于清洁组合物的总重量计。
可以包括的杀菌剂是化合物例如硫酸铜。如果存在，杀菌剂可以是约0.01重量％-约5重量％，基于清洁组合物的总重量计。
本文可以使用任何合适的有机和无机悬浮助剂，其典型地作为凝胶化剂、增稠剂或悬浮剂用于清洁组合物中。有机悬浮助剂包括多糖聚合物、聚羧酸酯聚合物增稠剂、层状硅酸盐小片例如锂蒙脱石、膨润土或蒙脱石、含羟基的结晶结构化剂例如含羟基脂肪酸、脂肪酸酯、或脂肪皂蜡状材料例如12-羟基硬脂酸、9,10-二羟基硬脂酸、三-9,10-二羟基硬脂酸甘油酯和三-12-羟基硬脂酸甘油酯、蓖麻蜡或氢化蓖麻油。用于本文的具体多糖聚合物包括取代的纤维素材料如羧甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基纤维素、羟甲基纤维素；微原纤纤维素(MFC)、琥珀酰聚糖和天然存在的多糖聚合物如黄原胶、结冷胶、瓜尔胶及其衍生物、槐树豆胶、黄蓍胶、琥珀酰聚糖胶或其衍生物。当存在时，悬浮助剂的用量可以是约0.01重量％-约10重量％，基于清洁组合物的总重量计。
如果存在，螯合剂在本文的组合物中的引入量可以是约0.01重量％-约10.0重量％，基于清洁组合物的总重量计。用于本文的螯合剂的例子可以包括碱金属乙烷1-羟基二膦酸酯(HEDP)、亚烷基聚(亚烷基膦酸酯)以及氨基膦酸酯化合物包括氨基氨基三(亚甲基膦酸)(ATMP)、次氮基三亚甲基膦酸酯(NTP)、亚乙基二胺四亚甲基膦酸酯和二亚乙基三胺五亚甲基膦酸酯(DTPMP)、二羟基二磺基苯例如1,2-二羟基-3,5-二磺基苯、亚乙基二胺N,N’-二琥珀酸或其碱金属或碱土金属、铵或其取代的铵盐或其混合物、亚乙基二胺四乙酸酯、二亚乙基三胺五乙酸酯、二亚乙基三胺五乙酸酯(DTPA)、N-羟乙基亚乙基二胺三乙酸酯、次氮基三乙酸酯、亚乙基二胺四丙酸酯、三亚乙基四胺六乙酸酯、乙醇-二甘氨酸、亚丙基二胺四乙酸(PDTA)和甲基甘氨酸二乙酸(MGDA)，都为它们的酸形式，或者为它们的碱金属、铵和取代的铵盐形式、水杨酸、天冬氨酸、谷氨酸、甘氨酸、丙二酸或其混合物。
可以使用的助表面活性剂包括非离子、阴离子、两性离子、两性、阳离子表面活性剂或其混合物。合适的表面活性剂的例子描述在McCutcheon的第1卷：Emulsifiers andDetergents，North American Ed.，McCutcheon Division，MC Publishing Co.，2002中。本文的组合物可以包含约0.01％-约50重量％，或约0.5％-约40重量％，或甚至约1％-约36重量％的助表面活性剂或其混合物，基于清洁组合物的总重量计。
非离子表面活性剂的非限定性例子包括烷基多糖、胺氧化物、脂肪酸酰胺、环氧乙烷和环氧丙烷的嵌段共聚物、氟表面活性剂和硅基表面活性剂或其混合物。
用于本文的阴离子表面活性剂的非限定性例子包括烷基磺酸酯、烷基芳基磺酸酯、烷基硫酸酯、烷基烷氧基化的硫酸酯表面活性剂、C6-C20烷基烷氧基化的线性或支化的二苯基氧化二磺酸酯或其混合物。
两性和两性离子表面活性剂的非限定性例子包括烷基甜菜碱、胺氧化物、聚羧酸酯、烷基氨基丙酸、烷基亚氨基丙酸、咪唑啉羧酸酯、磺化甜菜碱和磺基甜菜碱。
阳离子表面活性剂的非限定性例子包括伯胺盐、二胺盐、季铵盐、乙氧基化的胺及其混合物。
如果存在，水溶助剂包括但不限于二甲苯磺酸钠、枯烯磺酸钠、甲苯磺酸钠、丙二醇、甘油、山梨醇丙二醇、乙醇和尿素。当存在时，水溶助剂的存在量通常是约0.5重量％-约40重量％，基于清洁组合物的总重量计。
用于本文的自由基清除剂包括公知的取代的单和二羟基苯和它们的类似物、烷基和芳基羧酸酯及其混合物。用于本文的优选的自由基清除剂包括二叔丁基羟基甲苯(BHT)、对苯二酚、二叔丁基对苯二酚、单叔丁基对苯二酚、叔丁基羟基苯甲醚(anysole)、苯甲酸、甲苯酸、儿茶酚、叔丁基儿茶酚、苄胺、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、没食子酸正丙酯或其混合物，非常优选二叔丁基羟基甲苯。当使用时，自由基清除剂在本文的组合物中的存在量可以至多约10重量％，基于清洁组合物的总重量计。
合适的增洁剂可以选自磷酸酯和多磷酸酯，特别是钠盐；碳酸酯、碳酸氢酯、倍半碳酸酯和碳酸酯矿物，除了碳酸钠或倍半碳酸钠；有机单、二、三和四羧酸酯，特别是酸、钠、钾或烷醇铵盐形式的水溶性非表面活性剂羧酸酯，以及低聚物或水溶性低分子量聚合物羧酸酯，包括脂族和芳族类型；和无机增洁剂例如硫酸酯、柠檬酸酯、沸石、铝硅酸盐和植酸。这些可以通过硼酸盐补偿，例如用于pH缓冲目的，或者通过硫酸盐补偿，特别是硫酸钠和任何其他填料或载体，其会对于稳定的表面活性剂和/或含增洁剂的清洁剂组合物的工程化是重要的。还可以使用增洁剂混合物(有时称作“增洁剂体系”)，典型地包含两种或更多种常规的增洁剂，任选地通过螯合剂、pH缓冲剂或填料来补偿，不过当描述本文的材料量时，对这些后者的材料通常分别说明。当存在时，增洁剂占约1重量％-约90重量％，基于清洁组合物的总重量计。
合适的着色剂和香料是本领域技术人员公知的。着色剂包括直接蓝86(Miles)、Fastusol蓝(Mobay Chemical Corp.)、酸性橙7(American Cyanamid)、碱性紫10(Sandoz)、酸性黄23(GAF)、酸性黄17(Sigma Chemical)、暗绿(Keyston Analine and Chemical)、酸性间胺黄(Keystone Analine and Chemical)、酸性蓝9(Hilton Davis)、Sandolan蓝/酸性蓝182(Sandoz)、Hisol坚牢红(Capitol Color and Chemical)、荧光素(Capitol Colorand Chemical)和酸性绿25(Ciba-Geigy)。香料的例子包括天然产品例如龙涎香、苯偶因、海狸香、麝猫香、丁香油、白松香(galbanum)、茉莉、迷迭香油、檀香、橙油、柠檬油、玫瑰提取物、薰衣草、麝香、松油、雪松等。芳香化学品的例子包括但不限于乙酸异戊基酯(香蕉)；丙酸异丁酯(朗姆酒)；氨基苯甲酸甲酯(葡萄)；乙酸苄酯(桃)；丁酸甲酯(苹果)；丁酸乙酯(菠萝)；乙酸辛酯(橙)；乙酸正丙酯(梨)；和乙酸乙基苯酯(蜂蜜)。根据本发明的清洁组合物可以含有上述类型的化合物以产生气味遮盖效应或将不想要的气味降低到可接受水平所必需的有效量的任意组合，在一些实施方案中，上面列举的油和酯可以用作油组分。用量可以由本领域技术人员容易地确定，可以是约0.01重量％-约5重量％，基于清洁组合物的总重量计。
聚合物泡沫稳定剂可以选自(N,N-二烷基氨基)烷基酯和(N,N-二烷基氨基)烷基丙烯酸酯的均聚物和疏水改性纤维素聚合物，包括甲基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素及其混合物。聚合物泡沫稳定剂的量可以是约0.01重量％-约15重量％，基于清洁组合物的总重量计。
如果需要，清洁组合物中可以包含酶来提供清洁性能益处。当存在时，酶是约0.0001重量％-约5重量％的活性酶，基于清洁组合物的总重量计，包括以下的一种或共混物：纤维素酶、半纤维素酶、过氧化物酶、蛋白酶、葡萄糖淀粉酶、淀粉酶、脂肪酶、角质酶、果胶酶、木聚糖酶、还原酶、氧化酶、酚氧化酶、脂肪氧合酶、木质素酶、支链淀粉酶、丹宁酶、戊聚糖酶、苹果酸酶(malanase)、β-葡聚糖酶和阿拉伯糖苷酶。
当酶存在时，酶稳定剂也可以以清洁组合物总重量约0.001重量％-约10重量％的量包含在清洁组合物中。酶稳定剂是与酶相容的化合物，包括钙离子、硼酸、丙二醇、短链羧酸、硼酸及其混合物。例如，硼酸盐例如碱金属硼酸盐或硼酸胺(例如烷醇胺)或碱金属硼酸盐如硼酸钾、氯化钙、氢氧化钙、甲酸钙、苹果酸钙、马来酸钙、氢氧化钙和乙酸钙是可以用于本发明的清洁组合物的酶稳定剂。
为了制造本发明的组合物，将上述组分依靠本领域公知的手段合并在一起。选择组分的相对量，来产生组合物在硬表面或软表面清洁应用中所需的性能，并且一方面要关注确保组分以足够有效的水平存在，但是另一方面通过限定组分的上限范围来避免过量成本。
因为本文的组合物通常制备为液体配制物，并且由于无需特别的混合来形成单相微乳液，所以组合物可以容易地在任何合适的器皿或容器中制备。组分的混合顺序不是特别重要，通常不同的组分可以依次添加或以水溶液形式一次性添加。
令人惊讶地，上述组分形成微乳液是自发进行的，这是由于组分混合在一起时形成有利的自由能。虽然微乳液是热力学有利的，但是动力学屏障在一些情况中会阻碍它们的形成。因此，如果在微乳液形成中必须克服这样的动力学屏障，则可以适度增加应用混合能或温度。
一旦经配制，本发明的组合物可以在多种容器中包装，例如钢、锡或铝罐、塑料瓶或玻璃瓶和纸或纸板容器。
除了通过将所需组分混合在一起来生产的上述清洁组合物之外，本发明的清洁组合物还可以作为棒来配制，使用粘结剂将该棒以粘合、可溶的形式保持在一起。粘结剂可以是天然或合成淀粉、树胶、增稠剂或其任意共混物。此外，清洁组合物可以通过添加增稠剂或凝胶化剂例如气相法二氧化硅、有机树胶、聚合物、链烷烃蜡、膨润土粘土和纤维素醚而配制为糊剂或凝胶。
在另一实施方案中，本发明的清洁组合物作为低至适度堆密度粉末来提供。可以通过喷雾干燥包含本发明的清洁组合物的液体浆料和任选地干混另外的成分来制备低至适度堆密度粉末。在另一实施方案中，通过使用高速混合器/造粒机，或其他非塔式干燥方法混合和粒化粉末组合物来浓缩或压实低至适度堆密度粉末。在又一实施方案，可以通过压实包含本发明的清洁组合物的浓缩粉末来制备片剂。
本发明的清洁组合物可以用于多种应用，在一个具体实施方案中特别适于清洁硬表面或软表面。
因此，在另一方面中，本发明提供一种从硬表面或软表面除去污物或污点的方法。一种常规处理手段是以多种施用手段使根据本发明的清洁组合物接触或施用到或对着硬表面或软表面，施用手段例如喷雾，例如以气溶胶形式或使用标准喷雾喷嘴，摩擦，刮擦，涂刷，浸入，涂覆，凝胶形式施用，或将清洁组合物倾倒到或对着硬表面或软表面。然后可以通过用水冲洗和/或擦拭来从硬表面或软表面除去清洁组合物，直到肉眼不再能够看见清洁组合物。硬或软表面还可以空气干燥来从表面上除去清洁组合物或剩余的水。
虽然表面活性剂共混物在清洁组合物中特别有用，但是它们也已经被发现非常通用，可以包含在含水组合物或微乳液中用于油田应用，水基金属加工应用，聚氨酯发泡应用，或化妆品和皮肤病学应用。
因此，在另一实施方案中，提供一种包含本发明的表面活性剂共混物和水的个人护理组合物。“个人护理”涉及局部施用到人的毛发或皮肤的组合物，但是不口服摄入。优选地，个人护理组合物在冲洗应用中局部施用到人的皮肤。预期包含表面活性剂共混物的个人护理组合物包括身体洗液、沐浴液、除表皮组合物、洗发剂、冲洗调节剂、剃须泡沫、洗面液、清洁剂、洗手液、清洁霜/奶、收敛洗液、皮肤调色剂或清凉剂、泡沫浴、可溶洗浴油和条皂。
根据一些实施方案，个人护理组合物包含0.05重量％或更大，任选地0.1重量％或更大的表面活性剂共混物，其中重量％基于个人护理组合物的总重量计。在另一实施方案中，个人护理组合物包含10重量％或更少，或者5重量％或更少的表面活性剂共混物，其中重量％基于个人护理组合物的总重量计。
可以包含在个人护理组合物中的其他组分(和它们的量)是本领域技术人员公知的，可以包括上面所列的那些。例如，可以包含的其他组分是湿润剂、防腐剂、pH调节剂、保湿剂和/或抗刺激剂例如真芦荟、PEG-7椰酸甘油酯、黄春菊、鳄梨油或甜杏仁油、染料或香料。
在又一实施方案中，提供一种可用于金属形成或切割应用的润滑油浓缩物，其包含本发明的表面活性剂共混物和基础油，例如石油基油、植物油、动物来源的油或合成油。润滑油配制物和它们的组分/量描述在US20150051132中，其全部公开内容通过参考引入本文。
在一个具体实施方案中，润滑油浓缩物可以分散在含水介质，并用于切割方法。润滑油浓缩物配制物可以以约5重量份-20重量份油浓缩物/100重量份含水介质(例如水)的浓度分散在含水介质中，可以包含以下：
| 油浓缩物组分 | wt％，基于油浓缩物总重量计 |
| 基础油 | 60-75 |
| 本发明的表面活性剂共混物 | 10-18 |
| 二甘醇胺 | 3-6 |
| 无机酸 | 1-4 |
| 有机酸 | 1-2 |
| 稳定剂 | 2-4 |
| 妥尔油脂肪酸 | 6-10 |
| 去离子水 | 0.5-3 |
在另一实施方案中，润滑油浓缩物可以分散在含水介质中，并用于铝切割或研磨方法。用于铝切割或研磨方法的润滑油浓缩物配制物可以以约5重量份-约20重量份油浓缩物/100份含水介质(例如水)分散在含水介质中，可以包含以下：
| 油浓缩物组分 | wt％，基于油浓缩物总重量计 |
| 基础油 | 5-20 |
| 本发明的表面活性剂共混物 | 10-20 |
| 非离子表面活性剂 | 0-15 |
| 妥尔油 | 6-10 |
| 稳定剂 | 1-3 |
| 二甘醇胺 | 5-10 |
| 无机酸 | 3-5 |
| 有机酸 | 1-3 |
| 胺 | 0.2-0.6 |
| 去离子水 | 余量至100 |
实施例
实施例1.使用不同的油制备微乳液。
下表确认了组分，其使用不同的油合并来形成单相微乳液：
表1(鳄梨油/用于个人护理的保湿剂配制物的实施例)
| 组分 | 1A | 1B |
| 扩链表面活性剂1 | 32g | 37g |
| 扩链中间体表面活性剂 | 14g | 16.9g |
| 二甲苯磺酸钠(40％) | 10g | 17g |
| 鳄梨油 | 20g | 21.6g |
| 甘油 | 10g | 12.5g |
| 丙二醇 | - | 5g |
| 水 | 20g | 23g |
1PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠
2L24-16PO-2EO中间体
表2(硅油/头发调节或皮革处理配制物的实施例)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表3(植物油/保湿剂配制物的实施例)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表4(貂油/皮革处理配制物的实施例)
| 组分 | 4A |
| 扩链表面活性剂1 | 20g |
| 扩链中间体表面活性剂2 | 19g |
| 二甲苯磺酸钠(40％) | 15.5g |
| 貂油 | 15.5g |
| 丙二醇 | 8.6g |
| 甘油 | 8.6g |
| 水 | 10.3g |
| 聚山梨醇酯20 | 1.7g |
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表5(米糠油，蓖麻油/抗氧化剂喷剂的实施例)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表6(葵花油/金属加工配制物的实施例)
| 组分 | 6A |
| 扩链表面活性剂1 | 18g |
| 扩链中间体表面活性剂2 | 18.9g |
| 二甲苯磺酸钠(40％) | 16.2g |
| 葵花油 | 18g |
| 丙二醇 | 7.2g |
| 甘油 | 8g |
| 水 | 13.5g |
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表7(醚，酯/润肤剂的实施例)
1 PES101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表8(醚，酯/润肤剂和保湿剂配制物的实施例)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表9(芥花油，酯)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表10(植物油，硅油)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表11(植物油)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表12(海藻油)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表13(貂油/皮革处理配制物的实施例)
| 组分 | 13A |
| 扩链表面活性剂1 | 80g |
| 扩链中间体表面活性剂2 | 134g |
| 二甲苯磺酸钠(40％) | 102g |
| 貂油 | 34g |
| Albrite皮革 | 4g |
| SLES(ESB70) | 4g |
| 水 | 76g |
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
表14(茶树油/消毒剂配制物的实施例)
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)
2L24-16PO-2EO中间体
实施例2.去污力效果
表面活性剂共混物对于聚酯和聚酯/棉花样品的去污力显示在下面表15和16中：
表15.预处理
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠):L24-16PO-2EO中间体。
表16.清洗
1 PES 101表面活性剂(PPG-16/PEG-2月桂基聚氧乙烯醚硫酸钠)：L24-16PO-2EO中间体。
虽然前面涉及本发明的实施方案，但是可以设计本发明的其他和另外的实施方案而不脱离其基本范围，并且其范围由所附权利要求书来限定。
Claims (14)
1.表面活性剂共混物，其包含：
(i)式(I)的扩链阴离子表面活性剂：
R-(L)x-(O-CH2-CH2)y-O-SO3-A (I)
和(ii)式(II)的扩链中间体表面活性剂：
R-(L)x-(O-CH2-CH2)y-OH (II)
其中R是线性或支化的、饱和或不饱和的、取代或未取代的具有约6-约36个碳原子的脂族或芳族烃基；
L是连接基团，其包含聚环氧丙烷嵌段或聚环氧乙烷嵌段或其混合物；
A选自氢、一价金属阳离子、二价金属阳离子、铵阳离子和有机基团取代的铵阳离子；
x是连接基团L的平均烷氧基化度，其为约2-约20；和
y是平均乙氧基化度，其为0-约5。
2.根据权利要求1所述的表面活性剂共混物，其中R是线性C8-C20烷基链或支化的C8-C20烷基链或其混合物。
3.根据权利要求1所述的表面活性剂共混物，其中A选自钠、钾、镁和铵。
4.根据权利要求1所述的表面活性剂共混物，其中式(I)的扩链阴离子表面活性剂与式(II)的扩链中间体表面活性剂的摩尔比是约9:1-约1:9。
5.单相微乳液，其包含根据权利要求1所述的表面活性剂共混物、水和油组分。
6.根据权利要求5所述的单相微乳液，其中该表面活性剂共混物的存在量是约1重量％-约60重量％，基于该单相微乳液的总重量计。
7.根据权利要求5所述的单相微乳液，其中该油组分的存在量是约0.5重量％-约75重量％，基于该单相微乳液的总重量计。
8.根据权利要求7所述的单相微乳液，其中该油组分选自醚、液体酯、矿物油、植物油、动物油及其混合物。
9.根据权利要求5的单相微乳液，其进一步包含包括以下至少一种的辅助组分：抗氧化剂、悬浮助剂、螯合剂、助表面活性剂、自由基清除剂、香料、清洁和表面改性聚合物、增洁剂、抗菌剂、杀菌剂、水溶助剂、着色剂、稳定剂、漂白剂、漂白活化剂、泡沫控制剂、酶、污物悬浮剂、抗腐蚀抑制剂、增白剂、除尘剂、分散剂、颜料、染料、珠光剂、流变改性剂和皮肤护理活性成分。
10.根据权利要求5所述的单相微乳液，其中该单相微乳液基本上不含电解质。
11.生产单相微乳液的方法，其包括将根据权利要求1所述的表面活性剂共混物与水和油组分进行混合。
12.含水清洁组合物，其包含表面活性剂共混物，其中该表面活性剂共混物包含：(i)式(I)的扩链阴离子表面活性剂
R-(L)x-(O-CH2-CH2)y-O-SO3-A (I)
和(ii)式(II)的扩链中间体表面活性剂：
R-(L)x-(O-CH2-CH2)y-OH (II)
其中R是线性或支化的、饱和或不饱和的、取代或未取代的具有约6-约36个碳原子的脂族或芳族烃基；
L是连接基团，其包含聚环氧丙烷嵌段或聚环氧乙烷嵌段或其混合物；
A选自氢、一价金属阳离子、二价金属阳离子、铵阳离子和有机基团取代的铵阳离子；
x是连接基团L的平均烷氧基化度，其为约2-约20；和
y是平均乙氧基化度，其为0-约5。
13.根据权利要求12所述的含水清洁组合物，其进一步包含包括以下至少一种的辅助组分：抗氧化剂、悬浮助剂、螯合剂、助表面活性剂、自由基清除剂、香料、清洁和表面改性聚合物、增洁剂、抗菌剂、杀菌剂、水溶助剂、着色剂、稳定剂、漂白剂、漂白活化剂、泡沫控制剂、酶、污物悬浮剂、抗腐蚀抑制剂、增白剂、除尘剂、分散剂、颜料、染料、珠光剂、流变改性剂和皮肤护理活性成分。
14.从硬表面或软表面除去污物或污点的方法，其包括使根据权利要求12所述的含水清洁组合物与该硬表面或软表面接触。
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- 2017-03-09 EP EP17776275.4A patent/EP3436561B1/en active Active
- 2017-03-09 CA CA3006623A patent/CA3006623C/en active Active
- 2017-03-09 US US15/778,669 patent/US11629311B2/en active Active
- 2017-03-09 MX MX2018008044A patent/MX2018008044A/es unknown
- 2017-03-09 CN CN201780005193.1A patent/CN108431196A/zh active Pending
- 2017-03-09 JP JP2018529565A patent/JP6883583B2/ja active Active
- 2017-03-09 WO PCT/US2017/021585 patent/WO2017172320A1/en active Application Filing
- 2017-03-28 AR ARP170100754A patent/AR107986A1/es active IP Right Grant
- 2017-03-31 TW TW106111288A patent/TWI713724B/zh active
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| Publication number | Publication date |
|---|---|
| AU2017240417A1 (en) | 2018-08-09 |
| AU2017240417B2 (en) | 2020-09-17 |
| US20190010422A1 (en) | 2019-01-10 |
| JP2019511584A (ja) | 2019-04-25 |
| US11629311B2 (en) | 2023-04-18 |
| TW201809246A (zh) | 2018-03-16 |
| AR107986A1 (es) | 2018-07-04 |
| EP3436561A4 (en) | 2019-10-30 |
| EP3436561A1 (en) | 2019-02-06 |
| WO2017172320A1 (en) | 2017-10-05 |
| TWI713724B (zh) | 2020-12-21 |
| CA3006623A1 (en) | 2017-10-05 |
| MX2018008044A (es) | 2018-08-23 |
| EP3436561B1 (en) | 2023-05-10 |
| CA3006623C (en) | 2023-08-15 |
| JP6883583B2 (ja) | 2021-06-09 |
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