CN102973430B - 包括微纤维状纤维素的表面活性剂增稠体系及其制备方法 - Google Patents

包括微纤维状纤维素的表面活性剂增稠体系及其制备方法 Download PDF

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CN102973430B
CN102973430B CN201210559309.5A CN201210559309A CN102973430B CN 102973430 B CN102973430 B CN 102973430B CN 201210559309 A CN201210559309 A CN 201210559309A CN 102973430 B CN102973430 B CN 102973430B
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约翰·M·斯韦齐
尼尔·A·莫里森
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Abstract

本发明描述了表面活性剂体系，其使用微纤维状纤维素来使颗粒悬浮于表面活性剂体系中。本发明还描述了制备这些体系的方法。

Description

包括微纤维状纤维素的表面活性剂增稠体系及其制备方法
本申请是申请日为2007年11月2日，申请号为200780041617.6，发明名称为“包括微纤维状纤维素的表面活性剂增稠体系及其制备方法”的申请的分案申请。
技术领域
本发明涉及包括微纤维状纤维素的表面活性剂增稠体系及其制备方法。
发明背景
基于表面活性剂的产品如沐浴露、香波、洗碗剂(dishwashingdetergent)、洗衣剂(laundry detergent)和汽车洗涤剂以及其它洗涤剂常常通过使用高浓度的表面活性剂、通过结合粘度增效表面活性剂、或者通过将表面活性剂与少量的盐例如钠盐结合来增稠。这些制剂获得了似乎富集且平滑的高粘度产品，但它们受限于它们没有提供足够低的剪切粘度来允许颗粒悬浮。这些颗粒可能包括美化剂(aesthetic agent)(装饰珠粒、珠光剂、气泡、香料珠粒等)或者活性成分(固相酶、包封的活性剂如增湿剂、沸石、剥落剂(例如α-羟基酸和/或乙醇酸或聚乙烯珠粒)、维生素(例如维生素E))等，或包括美化剂和活性成分二者。
诸如黄原胶、羧甲基纤维素(CMC)、羟乙基纤维素(HEC)、羟丙基甲基纤维素(HPMC)和许多类型的聚丙烯酸酯的常规增稠剂和悬浮助剂在表面活性剂增稠体系中并没有很好地起作用，并且常常由于浑浊、凝胶化和/或相分离或缺乏足够的悬浮性能而导致透明度损失。例如，黄原胶将优异的悬浮性能赋予了具有低表面活性剂增稠的某些沐浴露制剂，但在具有高表面活性剂增稠的体系中黄原胶常常失去其悬浮能力，通常导致了浑浊、不规则的外观、以及颗粒状或块状的质地(texture)。作为常规增稠剂的另一个实例，纤维素产品(CMC、HEC、HPMC等)提供了不可靠的悬浮并且具有对于表面活性剂相容性的显著局限性。丙烯酸酯体系是常见的，然而，这些体系并不总是获得足够的澄清度水平，需要高浓度的聚合物，并且不被认为是天然的。盐常常能够在表面活性剂增稠体系中增加高剪切粘度，但并没有赋予长期悬浮能力。
目前在消费品工业中期望提供具有悬浮于其中的颗粒的透明的表面活性剂增稠体系，以及用于高表面活性剂体系的悬浮助剂，在所述高表面活性剂体系中许多可选择的增稠剂将不起作用。
发明简述
本发明提供一种表面活性剂体系，其包括浓度为约0.05％到约1.0％(w/w)的微纤维状纤维素、约5％到约50％(w/w活性表面活性剂)的表面活性剂和颗粒。
在本发明的表面活性剂体系中，所述微纤维状纤维素可以约0.06％存在。所述表面活性剂可以约5％到约15％(w/w活性表面活性剂)存在。进一步地，本发明的表面活性剂体系还可包括悬浮于其中的气泡或悬浮于其中的珠粒。
在本发明的表面活性剂体系中，所述微纤维状纤维素可以约0.075％存在。
在本发明的表面活性剂体系中，所述微纤维状纤维素可以约0.09％存在。所述表面活性剂可以约40％(w/w活性表面活性剂)存在。进一步地，本发明的表面活性剂体系还可包括悬浮于其中的珠粒或悬浮于其中的气泡。
本发明提供一种制备表面活性剂体系的方法，其包括：将微纤维状纤维素与水结合并混合，添加表面活性剂，且然后混合，添加颗粒，然后混合，其中所得到的体系是透明的，且所述颗粒悬浮于所述体系中。
在本发明的方法中，所述微纤维状纤维素可以约0.05％到约1.0％(w/w)的浓度存在，且所述表面活性剂可以约5％到约50％(w/w活性表面活性剂)存在。
在本发明的方法中，所述微纤维状纤维素可以约0.06％存在。
在本发明的方法中，所述微纤维状纤维素可以约0.075％存在。
在本发明的方法中，所述微纤维状纤维素可以约0.09％存在。
在本发明的方法中，所述表面活性剂可以约5％到约15％(w/w活性表面活性剂)存在。
在本发明的方法中，所述表面活性剂可以约40％(w/w活性表面活性剂)存在。
已经发现，细菌来源或其他来源的微纤维状纤维素(MFC)能够在表面活性剂增稠体系中以及在具有高表面活性剂浓度的制剂中用于提供颗粒的悬浮。还发现，MFC可以与或不与活性助剂(co-agent)一起用于该目的。当使用细菌来源的微纤维状纤维素时，可以消除细胞碎片，这获得了典型使用水平的透明溶液。
微纤维状纤维素似乎不受表面活性剂胶束形成的影响，并且在这些体系中保持良好的悬浮。微纤维状纤维素在这些体系中发挥作用的能力是独特的，很大程度地因为它是被分散而非溶解，从而在制剂中获得所需的悬浮性能，该制剂否则会显示使用可选择的可溶性聚合物所常见的浑浊和/或沉淀。
描述了包括微纤维状纤维素的表面活性剂体系。“表面活性剂体系”意指包括但不限于表面活性剂增稠体系和高表面活性剂体系。微纤维状纤维素(MFC)包括通过微生物发酵制备的MFC或通过机械碎裂/改变基于谷物、木材或棉花的纤维素纤维制备的MFC。当使用细菌来源的微纤维状纤维素时，可以消除细胞碎片，这产生了典型使用水平的透明溶液。本发明通过使用微纤维状纤维素，利用表面活性剂来获得具有悬浮于其中的颗粒的、在高剪切速率下非常稠的(高粘性的)体系。
这些体系的表面活性剂浓度的范围从约5％到约50％(w/w活性表面活性剂)，其中具体浓度取决于产物。沐浴露通常含有约5％到约15％(w/w)表面活性剂，洗碗液(dishwashing liquid)通常含有约20％到约40％(w/w)表面活性剂(对于40％，是“超”浓缩产品)，以及洗衣剂通常含有约15％到约50％(w/w)表面活性剂。
MFC以约0.05％到约1.0％的浓度存在，但该浓度将取决于所需的产品。例如，尽管优选约0.06％(w/w)MFC用于使小的藻酸盐珠粒悬浮在沐浴露中，但优选约0.075％用于使气泡悬浮在沐浴露中，以及优选约0.150％(w/w)用于使气泡或珠粒悬浮在含有约40％(w/w)表面活性剂的体系中。此外，如果需要高度透明的体系，则将相应地调节MFC的浓度。具体地说，用约0.055％到约0.25％(w/w活性表面活性剂)的MFC水平能够获得在约5％到约15％(w/w活性表面活性剂)下非常透明的沐浴露。
待被悬浮的颗粒能够包括美化剂(装饰珠粒、珠光剂、气泡、香料珠粒等)或者活性成分(固相酶、包封的活性剂如增湿剂、沸石、剥落剂(例如α-羟基酸和/或乙醇酸或聚乙烯珠粒)、维生素(例如维生素E))等，或包括美化剂和活性成分二者。其他适合的颗粒是本领域技术人员所清楚的。
本发明还涉及活性助剂和/或共处理剂(co-processing agents)如CMC、黄原胶和/或瓜尔胶与微纤维状纤维素在本文所述的表面活性剂体系中的用途。微纤维状纤维素共混物是含有活性助剂的微纤维状纤维素产品。描述了两种共混物，比率为6∶3∶1的MFC、黄原胶和CMC，以及比率为3∶1∶1的MFC、瓜尔胶和CMC。这些共混物允许MFC被制备为干燥产物，该干燥产物可以在高剪切或高度扩展混合(extensional mixing)到水或其他水基溶液中的情况下“活化”。当将MFC共混物加入到水中且活性助剂/共处理剂被水合时发生了“活化”。在活性助剂/共处理剂水合之后，然后一般需要高剪切来有效地分散微纤维状纤维素纤维，以便产生显示真屈服点的三维功能网络。出乎意料的是，存在于这些微纤维状纤维素共混物中的活性助剂和/或共处理剂CMC、黄原胶和/或瓜尔胶似乎在许多高表面活性剂制剂中保持被溶解(在水中活化后)，尽管它们在高表面活性剂体系中通常缺乏相容性，最大可能是由于这些聚合物在这些具有MFC的制剂中的低使用水平。
本发明进一步涉及用或不用活性助剂和/或共处理剂制备所述表面活性剂体系的方法。
附图的一些视图的简述
在结合发明详述和图1-5阅读时，将更好地理解以上概述。
图1：在具有悬浮于其中的气泡的表面活性剂增稠的沐浴露中的0.125％微纤维状纤维素共混物(MFC/黄原胶/CMC 6∶3∶1共混物)
图2：在具有悬浮于其中的藻酸盐珠粒的表面活性剂增稠的沐浴露中的0.125％微纤维状纤维素共混物(MFC/黄原胶/CMC 6∶3∶1共混物)
图3：在Ultra浓缩洗碗皂中的0.125％微纤维状纤维素共混物(用水∶MFC/黄原胶/CMC 6∶3∶1共混物以1∶1稀释)
图4：在Ultra浓缩液体洗衣剂中的0.125％微纤维状纤维素共混物(用水∶MFC/黄原胶/CMC 6∶3∶1共混物以1∶1稀释)
图5：在Ultra浓缩液体洗衣剂中的0.125％微纤维状纤维素(以湿饼形式添加)(用水∶MFC溶液以1∶1稀释)。不使用活性助剂。图显示了气泡悬浮。
发明详述
在实施例1和实施例2中描述了使用0.125％MFC/黄原胶/CMC(6∶3∶1)共混物来表明表面活性剂增稠和悬浮性能的沐浴露制剂。所述沐浴露显示了非常良好的澄清度和悬浮气泡和珠粒的能力。
还描述了具有比在沐浴露中所发现的更高的表面活性剂水平的手工洗碗液和液体洗衣剂。在实施例3中描述了具有悬浮于其中的藻酸盐的手工洗碗液。
实施例4中描述了具有悬浮于其中的香料珠粒的液体洗衣剂。
在实施例5中使用湿饼形式的微纤维状纤维素来制备包括具有悬浮于其中的气泡的浓缩的液体洗衣皂的高表面活性剂体系。
实施例1
制备具有气泡的液体沐浴露。图1显示了该体系的澄清度和悬浮性质。所得到的沐浴露表现出基于目测的非常稠的表面活性剂流变性(rheology)、具有悬浮气泡的能力和约3.4Pa的屈服值(用屈服流变仪测定)。
步骤A：将去离子水、10％NaCl溶液和CG加入到小型混合广口瓶内。将微纤维状纤维素(MFC/黄原胶/CMC 6∶3∶1共混物)加入到水的上部，且然后装配混合叶片，并将混合物在最高速度(“液化”速度)下混合5分钟。
步骤B：将内容物转移到具有涂漆的混合叶片的400mL高型烧杯内。将聚氧乙烯十二烷基醚硫酸钠(sodium laureth sulfate，ES-3)加入到步骤A中所述的溶液中，并在约1000rpm下混合5分钟。然后将椰油酰胺丙基甜菜碱钠(sodium cocamidopropylbetaine，CAB-LC)加入到该混合物中，并且在1000rpm下混合另外5分钟。然后添加香料。
步骤C：将椰油酰胺DEA加入到步骤B中所述的溶液中。当添加更多的DEA时，发生了增稠。然后以50％的溶液添加柠檬酸，以便将pH减小到所需的水平(在该情况下pH为5.5)。从混合器中排出内容物。在混合过程中夹带的空气由于MFC/黄原胶/CMC 6∶3∶1共混物的存在而被稳定。
表1：沐浴露沐浴乳
实施例2
如实施例1所述制备沐浴露，但引入珠粒的悬浮液代替气泡。在步骤C结束时添加藻酸盐珠粒。该实施方案的直观表示可以在图2中见到。
实施例3
使用手工洗碗液和洗衣剂制备高表面活性剂体系。将藻酸盐珠粒或空气悬浮于溶液中。将Palmolive洗碗皂(dish soap)稀释至一半浓度(diluted in half)，以制备“标准”浓度洗碗皂。首先制备含有去离子水中的0.25％微纤维状纤维素共混物(MFC/黄原胶/CMC 6∶3∶1共混物)的浓缩物。该浓缩物通过将溶液在混合器上在“液化”速度(最高速度)下混合5分钟来制备。然后，使用涂漆的混合叶片或螺旋桨叶片将微纤维状纤维素共混物用Palmolive洗涤剂或Dawn洗涤剂(含有0.1％三氯生的)进行1∶1稀释。在混合的同时将洗碗皂加入到微纤维状纤维素溶液中。Palmolive洗涤剂和Dawn先涤剂两种样品均获得了优异的澄清度和空气和/或藻酸盐珠粒的悬浮。虽然涂漆混合叶片或螺旋桨混合叶片的剪切力是相对低的，但微纤维状纤维素良好地稀释。这些溶液的屈服点是约2.5Pa。直观表示可以在图3中发现。
实施例4
制备使用浓缩的液体洗衣皂的高表面活性剂体系。使用“All Small and三倍浓缩(three times concentrated)”洗涤剂。0.25％微纤维状纤维素共混物(MFC/黄原胶/CMC 6∶3∶1共混物)浓缩物在蒸馏水中采用设定在最高速度(液化)下的混合器来活化。混合时间为5分钟。微纤维状纤维素溶液用All Small and三倍浓缩洗涤剂进行1∶1稀释。稀释物获得了非常好的澄清度和悬浮，得到0.62Pa的屈服点。将洗涤剂放入45℃烘箱内以评价热稳定性，并显示了优异的稳定性，且在老化4周后没有澄清度或悬浮的损失。直观表示可以在图4中见到。
实施例5
使用湿饼型的微纤维状纤维素来制备使用浓缩的液体洗衣皂的高表面活性剂体系。使用“All Small and三倍浓缩”洗涤剂。1.56％湿饼状的微纤维状纤维素浓缩物在蒸馏水中采用设定在最高速度(液化)下的混合器来活化。混合时间为5分钟。该湿饼形式的MFC的活性(％固体)是约16％，所以活性MFC水平在浓缩物中是约0.25％。该微纤维状纤维素溶液用All Small and三倍浓缩洗涤剂进行1∶1稀释。稀释物获得了非常好的悬浮，得到13Pa的屈服点。直观表示可以在图5中见到。

Claims (8)

1.一种高表面活性剂体系或表面活性剂增稠体系，其基本上由水、微纤维状纤维素共混物、5％至50％w/w浓度的表面活性剂以及悬浮的颗粒组成，其中所述微纤维状纤维素共混物由比率为6:3:1的微纤维状纤维素、黄原胶和羧甲基纤维素的共混物组成且所述微纤维状纤维素共混物中的所述微纤维状纤维素以所述高表面活性剂体系或表面活性剂增稠体系的0.05％至0.15％w/w的浓度存在。
2.如权利要求1所述的高表面活性剂体系或表面活性剂增稠体系，其中所述微纤维状纤维素共混物以0.125％w/w的浓度存在。
3.如权利要求2所述的高表面活性剂体系或表面活性剂增稠体系，其中所述高表面活性剂体系或表面活性剂增稠体系为沐浴露、洗碗液或洗衣剂。
4.一种高表面活性剂体系或表面活性剂增稠体系，其基本上由水、微纤维状纤维素共混物、5％至50％w/w浓度的表面活性剂以及悬浮的颗粒组成，其中所述微纤维状纤维素共混物由比率为3:1:1的微纤维状纤维素、瓜尔胶和羧甲基纤维素的共混物组成且所述微纤维状纤维素共混物中的所述微纤维状纤维素以所述高表面活性剂体系或表面活性剂增稠体系的0.05％至0.15％w/w的浓度存在。
5.一种高表面活性剂体系，所述高表面活性剂体系基本上由水、以从0.05％到0.09％w/w的浓度存在的微纤维状纤维素、以从20％到50％w/w的浓度作为活性表面活性剂存在的表面活性剂、悬浮的颗粒以及活性助剂组成；其中所述微纤维状纤维素是细菌来源的且所述表面活性剂体系是透明的；并且其中所述微纤维状纤维素和活性助剂由比率为3:1:1的微纤维状纤维素、瓜尔胶和羧甲基纤维素的共混物组成，或由比率为6:3:1的微纤维状纤维素、黄原胶和羧甲基纤维素的共混物组成。
6.如权利要求5所述的高表面活性剂体系，其中所述微纤维状纤维素以从0.06％到0.09％w/w的浓度存在。
7.如权利要求5所述的高表面活性剂体系，其中所述表面活性剂以从20％到40％w/w的浓度作为活性表面活性剂存在。
8.如权利要求5所述的高表面活性剂体系，其中所述高表面活性剂体系为沐浴露、洗碗液或洗衣剂。
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