CN1202925A - 杀菌的酸性硬表面清洁组合物 - Google Patents
杀菌的酸性硬表面清洁组合物 Download PDFInfo
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- CN1202925A CN1202925A CN96198430.9A CN96198430A CN1202925A CN 1202925 A CN1202925 A CN 1202925A CN 96198430 A CN96198430 A CN 96198430A CN 1202925 A CN1202925 A CN 1202925A
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Abstract
具有酸性pH的改进的硬表面清洁组合物,具有良好的去除肥皂泡污渍的性能,并对使用者的刺激性较低。该组合物包括:0.1~10%重量的酸性螯合剂组分;0.1~10%重量的疏水和亲水溶剂的混合物;1~8%重量的表面活性剂和/或水溶助长剂组分;0~20%重量的一种或多种任选组分;平衡量的水至100%重量,其中该含水硬表面清洁组合物的pH为7.0或更低,尤其是5.0或更低。这种改进的硬表面清洁组合物尽管呈酸性但对消费者的眼睛和皮肤的刺激低。该组合物还具有消毒作用。另外还说明了该组合物的生产方法及其使用方法。
Description
本发明涉及改进的清洁组合物,该组合物特别适用于硬表面的清洁。
已经开发出清洁剂组合物中的多种配方,并且是本领域公知的。例如,含有强酸(如盐酸)的强酸性清洁剂用于除去硬水污斑,但是,已知强酸是皮肤的刺激物,并具有潜在的中毒危险。并且,极少数为处理过的硬表面提供任何杀菌或卫生作用。
因此,本发明的目的之一是提供改进的清洁组合物,其对提供消毒作用是有效的,并且便于肥皂泡和硬水垢的除去,尤其是从硬表面。本发明的再一个目的是提供改进的清洁组合物,其特别有效于硬水垢的去除和肥皂泡的去除,并且对消费者的眼、皮肤和粘液组织的刺激最小。
本发明提供了一种杀菌含水的硬表面清洁组合物,其含有下列必要组分:
组分(A):酸性螯合剂
组分(B):疏水和亲水溶剂的混合物;
组分(C):表面活性剂和/或水溶助长剂。
本发明的组合物也可以包括一种或多种其它的任选组分,如本领域已知的添加剂。作为非限制性的实例,这类组分包括:其它表面活性剂、特别是适用于除去油脂污渍的表面活性剂,起泡剂和泡沫稳定剂,着色剂(包括染料和颜料组合物),香料(天然或合成的)、香料助剂和/或香料加溶剂,粘度改变剂(包括增稠剂或胶凝剂),pH调节剂,pH缓冲剂,抗氧剂,水软化剂,可用于一种或多种组分溶于水的其它加溶剂,保存剂组合物以及其它已知的添加剂,这里不再特别加以列举。上述这类组分包括本领域已知的组合物,包括那些在McCutcheon′s Detergents and Emulsifiers,北美版本,1991年和Kirk-Othmer,Encyclopedia of Chemical Technology(化工技术百科全书),第三版,第22卷,第346~387页中描述的那些组合物,将其内容引入本文作为参考。
本发明的组合物优选是酸性的,其pH小于7.0,理想的pH范围约为5.0~1.0,更理想的pH范围是约4.0~1.0,最理想的pH范围是3.0~1.0。
本发明的再一个方面还提供了一种改进的清洁和消毒表面(特别是硬表面)的方法,其包括将一种本发明的除污和消毒有效量的组合物应用到这类有污斑的表面上的步骤。组分A
含有组分A(即本发明的酸性螯合剂)的组分实际上可以是从硬表面(特别是上述的厕所表面除去硬水垢是有效的任何一种酸。典型的有用的酸包括:柠檬酸、甲苯基酸、十二烷基苯磺酸、磷酸、水杨酸、山梨酸、氨基磺酸、乙酸、苯甲酸、硼酸、癸酸、己酸、氰尿酸、二氢乙酸、二甲基氨基磺酸、丙酸、聚丙烯酸、2-乙基-己酸、甲酸、富马酸、1-谷氨酸、异丙基氨基磺酸、环烷酸、草酸、磷酸、戊酸、苯磺酸、二甲苯磺酸、以及作为美国环保局注册的农药活性成分而列举的任何酸。其它有用的酸包括:磺酸、马来酸、乙酸、己二酸、乳酸、丁酸、葡糖酸、苹果酸、酒石酸、以及乙醇酸。理想的是使用乙醇酸和柠檬酸,因为它们是有效的且供应充足,并且可以有利地使用。这些酸性螯合剂在清洁组合物中提供了游离酸,这些游离酸与肥皂泡污渍中所含的脂肪酸金属盐反应,释放出金属离子并游离出脂肪酸,便于从硬表面除去这些不需要的污渍。这些酸性螯合剂也螯合肥皂泡污渍中释放出的游离金属离子。同样当选择酸性螯合剂来起消毒作用时,它们同时提供必需的用于消毒清洁过的表面所必须的抗微生物活性。
优选的是,组分A含有柠檬酸和至少一种上述的其它酸,因为本发明人已观察到在本发明组合物中柠檬酸提供了良好的消毒作用,但是在某些配方中可能酸性不足以有效地除去某些污渍。加入至少一种其它的酸提供了在某些只含有柠檬酸的配方中所不能观察到的其它清洁效果。
组分A的酸性螯合剂在配方中理想的含量范围基于组合物的总重量是0.1~10%重量,优选1.0~8.0%重量,更优选4.0~6.0%重量。但是在优选的实施方案中,柠檬酸占组分A中的酸总重量的至少0.1%重量,更优选至少占25%重量,最优选占至少50%重量。组分B
组分B的各组分是疏水性和亲水性溶剂的混合物,它用于帮助脂肪酸从已清洁的表面上的溶解。由于组分B的存在,肥皂泡残余物中存在的某些脂肪酸是加溶的和/或可成为至少部分溶于水的,其起到便于从表面上除去污垢的作用。组分B的各溶剂也有利于透过污垢,并用作本发明的其它组分(特别是含有组分A的组分)的载体,从而使组分A这些组分透过污垢层到达污渍存在的表面上,从而有助于有效溶解和除去所述污垢。
组分B的疏水溶剂组分应具有加溶肥皂泡污渍中所含的脂肪酸的脂族部分的作用。典型的有用的疏水溶剂包括:溶剂油(mineral spirits)、三丙二醇正丁醚、丙二醇苯醚、二丙二醇正丙醚、乙二醇苯醚,特别是丙二醇正丁醚和二丙二醇正丁醚。疏水溶剂可以是一种这类溶剂,或者是两种或多种疏水溶剂的混合物。
疏水溶剂在水中理想的溶解度是0.0毫升/100毫升~20.0毫升/100毫升,并占本发明组合物的组分B总重量的50~99%。更优选的是,疏水组分应占本发明的组合物的组分B的60~95%,最优选占80~90%。
组分B的亲水溶剂可用于加溶或改进疏水溶剂在水中的混溶性。组分B的疏水溶剂溶解肥皂脂肪酸,而亲水溶剂用于将疏水溶剂溶解于水,从而提供了与水相的有效溶解性,并便于疏水溶剂和溶解的肥皂脂肪酸从被清洁的表面去除。
作为非限制性的实例,有用的亲水溶剂包括某些醇、二醇、乙酸酯、醚乙酸盐和二醇醚,包括丙二醇甲醚、二丙二醇甲醚、三丙二醇甲醚、丙二醇正丙醚、乙二醇正丁醚、二乙二醇正丁醚、二乙二醇甲醚、丙二醇、乙二醇、异丙醇、乙醇、甲醇、二乙二醇单乙醚乙酸酯,特别有用的是乙二醇单丁醚乙酸酯。可使用单一亲水溶剂或两种或多种亲水溶剂。
本发明组分B的亲水溶剂应表现出在水中的良好的溶解性,即接近或表现出“无限溶解度”并以基于本发明组合物组分B总重量的1~50%、优选1~40%、再更优选5~30%、最优选10~20%的重量百分数包含在组合物中。
就组分B的有效量来说,组分B理想的存在量基于清洁组合物的总重量约为0.1~10%重量、优选为2.0~8.0%重量、最优选为3.0~6.0%重量。组分C
构成组分C的各组分用于降低污渍和本发明的组合之间的界面张力,便于污渍的润湿以及提供水溶助长功能,这样的水溶助长功能有助于污垢中更多量脂肪酸的溶解以及其从表面的去除。
用作组分C的典型的材料包括一个或多个化合物,如烷基苯氧基苯二磺酸酯、线型烷基苯磺酸酯和烷基萘磺酸酯及其盐。这类组合物是本领域公知的,并可作为阴离子表面活性剂买到。这些材料也包括(但不限于):碱金属盐、铵盐、胺盐、氨基醇盐或者一种或多种下列化合物的镁盐:烷基硫酸盐、烷基醚硫酸盐、烷基酰氨基醚硫酸盐、烷基芳基聚醚硫酸盐、硫酸单甘油脂、烷基磺酸盐、烷基芳基磺酸盐、烯属磺酸盐、石蜡磺酸盐、烷基磺基琥珀酸盐、烷基醚磺基琥珀酸盐、烷基酰胺磺基琥珀酸盐、烷基磺基琥珀酰胺酸盐、烷基磺基乙酸盐、烷基磷酸盐、烷基醚磷酸盐、酰基肌氨酸盐、酰基羟乙磺酸盐和N-酰基牛磺酸盐。这些多种化合物中的烷基或酰基通常含有12~20个碳原了的碳链。
典型的烷基苯氧基苯二磺酸盐包括烷基苯氧基苯二磺酸盐的金属盐和有机盐,如十二烷基二苯基氧二磺酸钠、己基二苯基氧二磺酸钠、正十二烷基二苯基氧二磺酸钠和正十六烷基二苯基氧二磺酸钠。其它金属反离子或有机反离子可以取代在上述提到的烷基苯氧基苯二磺酸盐和两种或多种烷基苯氧基苯二磺酸盐的混合物的钠位置上。
典型的线型烷基苯磺酸盐包括线型烷基苯磺酸盐的金属盐和有机盐,如十二烷基苯磺酸钠、壬基苯磺酸钠、线型烷基苯磺酸异丙基胺盐、十二烷基苯磺酸三乙醇胺、十二烷基苯磺酸二乙醇胺、十二烷基苯磺酸钾、十三烷基苯磺酸钠以及十二烷基苯磺酸钠与甲苯磺酸钠、异丙基苯磺酸钠和/或二甲苯磺酸钠的混合物。其它金属反离子或有机反离子可以取代在上述的线型烷基苯磺酸盐和两种或多种线型烷基苯磺酸盐的相反离子的位置上。
典型的烷基萘磺酸盐包括烷基萘磺酸盐的金属盐和有机盐,如二异丙基萘磺酸钠、丁基萘磺酸钠、壬基萘磺酸钠、二丁基萘磺酸钠和二甲基萘磺酸钠。其它金属反离子或有机反离子可以取代在上面提到的烷基萘磺酸盐和两种或多种烷基萘磺酸盐的混合物的相反离子的位置上。
用于组分C中的其它有用的组分包括二甲苯磺酸钠、异丙基苯磺酸钠和萘磺酸盐。
就组分C的有效量来说,组分C的理想存在量基于清洁组合物总重量约为1.0~8.0%重量、优选约2.0~6.0%重量、更优选2.0~4.0%重量。
如上所述,本发明的组合物是水溶性的。将水加入到组分A、B和C中以便提供100%重量的组合物。所述水可以是自来水,但优选是蒸馏水,最优选是去离子水。
本发明的组合物可含有一种或多种下列任选组分,但这类任选组分的总重量不超过组合物总重量的约20%、更优选不超过约10%,最优选小于本发明组合物总重量的10%重量。
可以以有效量加入此类清洁剂中的通常是已知的和常用的各种非离子表面活性剂。典型的非离子表示活性剂包括通常由疏水部分(如C8~C20伯或仲、支链或直链单醇,C8~C18单-或二烷基苯酚、C6~C20脂肪酰胺)和由烯化氧单元构成的亲水部分组成。这些非离子表面活性剂是例如上述疏水部分的烷氧基化的产物,含有2~30摩尔烯化氧。作为烯化氧,使用乙烯化氧、丙烯化氧、丁烯化氧及其混合物。这类非离子表面活性剂的典型例子是C9~C11伯直链醇与5~9摩尔乙烯化氧的缩合产物、C12~C15伯直链醇与6~12摩尔乙烯化氧或与7~9摩尔乙氧化烯和丙烯化氧的混合物的缩合产物,C11~C15仲醇与3~15摩尔乙烯化氧的缩合产物,和C10~C18脂肪酸二乙醇酰胺,以及叔胺氧化物,如高级烷基二(低级烷基或低级取代的烷基)氧化胺。这类非离子表面活性剂是本领域公知的,并特别描述于上述的McCutcheon′s Detergents and Emulsifiers中。
可以加入起泡剂和泡沫稳定剂,包括烷基硫酸盐、烷基磺酸盐、氧化胺和链烷醇酰胺。当组合物包装在加压装置,即气溶胶罐或手持可泵出的容器(如手持触发喷雾容器)中时,这些是尤其理想的。
其它任选的但理想的组分包括香料,天然或合成的。也可以使用帮助香料组分分散、溶解或混合于含水基质中的香料加溶剂。以较少的量加入该香料加溶剂组分。也可以使用一种或多种本领域已知的着色剂。
可以使用一种或多种pH调节剂,包括少量矿物酸、碱性组合物及有机酸。典型的组合物包括柠檬酸,如可以碱金属柠檬酸的无水盐的形式买到。有效量的这类pH调节剂的加入有利于为本发明的组合物确定一目标pH范围。
也可以加入有效量的用于保持本发明组合物pH的pH缓冲剂。尽管本发明的组合物通常不需要pH缓冲成分,但使用这类pH缓冲成分可提供硬水离子螯合的好处。这类有用的pH缓冲化合物和/或pH缓冲体系或组合物的实例包括碱金属磷酸盐、多磷酸盐、焦磷酸盐、三磷酸盐、四磷酸盐、硅酸盐、偏硅酸盐、多硅酸盐、碳酸盐、氢氧化物、及其混合物。某些盐类,如碱土金属的磷酸盐、碳酸盐和氢氧化物也可以用作缓冲剂。使用这类材料如硅铝酸盐(沸石)、硼酸盐、铝酸盐和某些有机材料如葡糖酸盐、琥珀酸盐、马来酸盐和它们的碱金属盐作为缓冲剂也是适合的。这类缓冲剂将本发明的pH范围保持在可接受的限度内。也可以使用其它的缓冲剂,这些不再特别列举。优选的是,加入柠檬酸,如可买到的碱金属柠檬酸的无水盐的形式,因为它们容易从市场上买到的且是有效的。在某些情况(其中预期组合物有长期即延长的贮存期以及确保所述含水组合物的安全处理)下,加入这类缓冲剂是理想的。
也可以向本发明的组合物中加入少量保存剂,其中保存剂组合物不含有消毒组分。可以使用本领域已知的组合物。这类保存剂化合物的实例包括那些现在可以商标名KathonCG/ICP(Rohm & Haas,费城,美国)、SuttocideA(Sutton Labs,Chatham,新泽西州,美国)以及MidtectTFP(Tri-KCo.,Emerson,新泽西州,美国)买到的那些。
可以向本发明的硬表面清洁组合物中加入增稠和/或胶凝剂以便改变其粘性和/或触变性。例如,在某些用途中,认为无论是美学或功能原因,提供一个比水更粘,即更大粘度是理想的。例如,加入合适量的胶凝剂是理想的,不仅是因为美学原因,而且应用于表面上是为限制组合物的扩散。该功能对于提供一种将组合物施用到一受限的区域上的方法是理想的,如直接施用到污垢上,而不需将多余量应用到表面的周围区域。该功能也有助于在非水平的表面上停留时间,保证清洁组合物与受污的表面接触,而又不会太快地流过。类似地,在某些情况下,触变性能也是需要的。为了给组合物提供这类功能特征,可以加入已知的增稠剂和胶凝剂,包括(但不限于)纤维素化合物、黄原胶、聚合物和/或粘土。
本说明书中描述的组合物的好处尤其包括:消毒、硬水垢的良好去除、肥皂泡污垢的良好去除、相当低的毒性、以及由于其易倾倒性或泵出性使组合物容易处理。另外,当加入一种或多种任选组分时,即香料、起泡剂、着色剂,可有利于改进产品的美学和对消费者的吸引力。
虽然本发明的组合物的优选实施方案的pH小于3.0,但已令人惊奇地发现这些组合物对消费者的眼、皮肤或粘液组织并非特别有刺激。这是令人惊奇的效果,因为组合物中对除去硬水垢有益的酸的存在以及组合物较低的pH预期对消费者的眼、皮肤或粘液组织有严重的刺激性。
本发明的组合物有利于清洁和/或消毒上面沉积有污渍的硬表面。在这样的方法中,清洁和消毒这类表面包括将本文所述的除垢和消毒有效量的组合物应用到这类有污渍的表面上的步骤。随后,任选但理想的是将组合物擦去、擦洗或其它与硬表面接触的方式,随后还任选可从这类清洁和消毒的硬表面上漂洗掉。
本发明提供的硬表面清洁组合物可以理想地以容易使用的方式提供并预期使用在下列情况下:消费者将有效量的组合物应用到将要清洁的表面上,稍过一会儿后用擦布、毛巾或海绵擦拭所处理的表面,通常是用一次性纸或海绵。在某些用途中,其中不需要的污垢沉积物较多,清洁组合物可以留在受污的区域上直到它已有效地疏松污垢沉积物,随后可以擦去污垢。也可以多次使用。
在另一个实施方案中,可以将本发明的组合物配制成可以与“气溶胶”型产品结合使用,其中它从加压的气溶胶容器中排出。可以使用现有技术已知的推进剂,如液体推进剂和非液态的推进剂,即加压气体,包括二氧化碳、空气、氮气、烃以及其它物质。
尽管打算以上述的液态形式使用本发明,但应理解本说明书不限制本发明的组合物与更多量的水一起使用以形成清洁溶液。在这类建议的稀释的清洁溶液中,用于形成所述清洁稀释液所加入的水的比例越大,由此形成的清洁溶液对硬表面的清洁速率和/或功效以及消毒功效的降低越大。因此,在污垢上较长的停留时间使它们分散和/或使用更大量的组合物是必要的。相反地,也应理解本说明书对于上述组合物决非限制其形成一种“超浓缩的”清洁组合物。
尽管以那种形式(即上述形式)使用的清洁组合物是最有益的,但它们也可以稀释。消费者或其它最终用户可以容易地制备这类清洁组合物,即通过将已称量的组合物以组合物/水的某一重量比稀释在较多的水中,并可以搅拌以保证组合物均匀分布在水中。可以不进行进一步稀释而使用本发明的含水的组合物,但也可以进一步用水稀释而使用,即组合物/水的浓度为1∶0到极稀的稀释液如1∶10,000,但优选以1∶10~1∶100的重量或体积比使用。预期在较低的组合物和水的稀释液时通常有更好和更快的去污效果。
下列实施例示出本发明组合物的典型的配方和优选的配方。在整个说明书和所附的权利要求书中,任何组分的重量百分数应理解成所涉及到的组分的活性部分,除非特别指明。
实施例组合物实施例组合物的制备
例举本发明组合物的某些特定的优选实施方案和下表I所详细描述的典型组合物均根据下列方法配制。
将已称量的水加入合适大小的容器中,随后以下列顺序加入各组分:增稠剂、表面活性剂、溶剂、酸,最后加入着色和香料组分。搅拌,通常持续5分钟到120分钟,直到该组合物呈现出均相。典型的组合物是容易倾倒的,在放置较长时期(即使超过120天)后保持良好的混合特性(即稳定的混合物)。应注意的是,也许可以以任何顺序加入各组分,但优选是水首先加入到混合容器或容器中,因为水是主要组分,向其中加入其它组分是很方便的。
下表I列出了实施例组合物的准确成分。
表1: 实施例组合物 | ||||||||||
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 | 实施例10 | |
组分 | ||||||||||
Poly-TergertSL-62 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
RhodaponLCP | 4.17 | 4.17 | 4.17 | 4.17 | 4.17 | 4.17 | 4.17 | 3.00 | 4.17 | 4.17 |
Ninol11-CM | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | - | 0.20 | 0.20 |
StepanaleSCS | - | 6.67 | - | - | 6.67 | - | - | - | - | - |
Poly-Tergert2A1 | - | - | 3.00 | - | - | 3.00 | 3.00 | 3.00 | 3.00 | - |
Petro LBA | 3.00 | - | - | 3.00 | - | - | - | - | - | 3.00 |
DcwanolDPn B | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | - | 4.00 | 4.00 |
DcwanolPnP | 2.00 | 2.00 | - | - | - | 2.00 | - | 0.90 | 2.00 | 2.00 |
DcwanolPnB | - | - | - | - | - | - | - | 3.90 | - | - |
Butyl Cellosolve乙酸盐 | - | - | 2.00 | 2.00 | 2.00 | - | 2.00 | - | - | - |
柠檬酸 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
乳酸 | - | - | - | - | 2.84 | 2.84 | 2.84 | - | - | - |
乙醇酸 | - | 3.57 | - | 3.57 | - | - | - | 3.57 | 3.57 | 3.57 |
香料 | - | - | - | - | - | - | - | 0.20 | - | - |
KelzanT | - | - | - | - | - | - | - | - | - | - |
酒石酸 | 2.50 | - | 2.50 | - | - | - | - | - | - | - |
去离子水 | 80.63 | 75.89 | 80.63 | 79.56 | 76.62 | 80.29 | 80.29 | 81.93 | 79.56 | 79.56 |
表1:实施例组合物(续) | |||||||||||
实施例11 | 实施例12 | 实施例13 | 实施例14 | 实施例15 | 实施例16 | 实施例17 | 实施例18 | 实施例19 | 实施例20 | 实施例21 | |
组分 | |||||||||||
Poly-TergertSL-62 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
RhodaponLCP | 4.17 | 4.17 | 4.17 | 3.00 | 3.00 | 4.17 | 4.17 | 4.17 | 3.00 | 3.00 | 4.17 |
Ninol11-CM | 0.20 | 0.20 | 0.20 | - | - | 0.20 | 0.20 | 0.20 | - | - | - |
StepanaleSCS | 6.67 | 6.67 | - | - | - | - | - | 6.67 | - | - | - |
Poly-Tergert2A1 | - | - | - | 3.00 | 3.00 | 3.00 | - | - | 3.00 | 3.00 | 3.00 |
Petro LBA | - | - | 3.00 | - | - | - | 3.00 | - | - | - | - |
DcwanolDPnB | 4.00 | 4.00 | 4.00 | 3.90 | - | - | - | - | 4.50 | 4.00 | - |
DcwanolPnP | 2.00 | - | - | 0.90 | 0.90 | - | - | - | - | 1.00 | - |
DcwanolPnB | - | - | - | - | 3.90 | 2.50 | 2.50 | 2.50 | - | - | 4.00 |
Butyl Cellosolve乙酸盐 | - | 2.00 | 2.00 | - | - | 2.50 | 2.50 | 2.50 | 0.50 | - | 1.00 |
柠檬酸 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
乳酸 | - | - | - | - | - | - | 2.84 | 2.84 | - | - | - |
乙醇酸 | - | 3.57 | - | 3.57 | 2.57 | 3.57 | - | - | - | 3.57 | - |
香料 | - | - | - | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | - | - | - |
KelzanT | - | - | - | - | 0.60 | - | - | - | 1.00 | 0.75 | 0.60 |
酒石酸 | 2.50 | - | 2.50 | - | - | - | - | - | 2.50 | - | 2.50 |
去离子水 | 76.96 | 75.89 | 80.63 | 81.33 | 81.33 | 80.36 | 81.09 | 77.42 | 82.00 | 81.18 | 81.23 |
也制备了几种比较组合物,这些组合物以与表I的实施例组合物相同的方式制备,在下面的表2中进行详细描述
表2:比较组合物 | |||
组分 | 比较例1 | 比较例2 | 比较例3 |
Poly-TergentSL-62 | 1.00 | 1.00 | 1.00 |
RhodaponLCP(30%) | 3.00 | 3.00 | 3.00 |
Ninol11-CM | - | - | - |
StepanateSCS | - | - | - |
Polytergent2Al(45%) | 3.00 | 3.00 | - |
Petro LBA | - | - | - |
DowanolPnB | 3.90 | - | 3.90 |
DowanolPnP | 0.90 | - | 0.90 |
Butyl Cellosolve乙酸盐 | - | - | - |
香料 | 0.20 | 0.20 | 0.20 |
柠檬酸 | - | 2.50 | 2.50 |
乳酸(88%) | - | - | - |
乙醇酸(70%) | - | 3.57 | 3.57 |
酒石酸 | - | - | - |
去离子水 | 88.00 | 86.73 | 84.93 |
用于制备表1和2的各组分将下表3进行详细描述。表3:组分表组分PolytergentSL-62 描述为非离子烷氧基化的线性醇表面活
性剂,每分子约8摩尔乙氧基(Olin Chem.Co.,
Stamford CT)RhodaponLCP 月桂基硫酸钠(30%活性成分)(Rhone-
Poulenc,Princeton NJ)Ninol11-CM 作为泡沫稳定剂组分的椰油二乙醇酰胺(Stepan
Chem.Co.,Chicago IL)StepanateSCS 作为阴离子水溶助长剂的异丙基苯磺酸钠(45
%活性成分)Poly-Tergernt2A1 作为阴离子表面活性剂/水溶助长剂的十二烷基
二苯基氧二磺酸钠(45%活性成分)(Olin Chem.
Co.,Stamford CT)Petro LBA 作为阴离子表面活性剂/水溶助长剂的烷基萘
磺酸盐(Witco Corp.,New York,NY)DowanolDPnB 作为疏水溶剂的二丙二醇正丙醚(Dow
Chemical Co.,Midland MI)DowamolPnP 作为亲水溶剂的丙二醇正丙醚(Dow Chemical
Co.,Midland MI)DowanolPnB 作为疏水溶剂的丙二醇正丁醚(Dow Chemical
Co.,Midland MI)Butyl Cellosolve乙酸盐 作为亲水溶剂的乙二醇单丁醚乙酸盐(Union
Carbide Corp.,Danbury CT)柠檬酸 柠檬酸,无水USP级,作为酸性螯合剂,乳酸 乳酸,USP级,(88%活性成分),热稳定性,
作为酸性螯合剂甘醇酸 羟乙酸,作为酸性螯合剂(70%活性成分),
(DuPont Specialty Chemicals,Wilmington DE)香料 市售的香料(国际调味品和香料公司,Teterboro
NJ)KelzanT 黄原胶(Kelco Co.,San Diego,CA)酒石酸 USP级,作为酸生螯合剂去离子水 去离子水清洁功效的评估
使用下列规则评估上面所列的各种组合物在瓷砖表面上的清洁功效。清洁功效的视觉评估
由一组二十人的专家组通过视觉检查来评估上述各种配方的清洁功效,这些专家被要求根据下列规则对瓷砖表面的污渍去除进行观察和定级。
制备试验中用的“标准弄脏的瓷砖”。首先,制备污渍试验用的组合物,它含下列组分:3.90%重量的硬脂酸基条皂、0.35%重量的含有烷基乙氧基硫酸盐而不含有调理或处理添加剂的中等清洁香波、0.06%重量球状或黑带状粘土、0.15%重量人造皮脂以及95.54%重量去离子水,以2∶1的比例加入钙/镁以得到20,000ppm CaCO3的总硬度。如下制备污渍试验用的组合物:首先将条皂削进一个合适的容器中,接着按下列顺序加入其余组分:香波、粘土、皮脂和水。用三翼螺旋桨式混合器搅拌试验组合物并加热到45~50℃,搅拌直到得到光滑的无块状的悬浮液。随后通过配有Whatman#1滤纸或等价物的Buchner漏斗过滤悬浮液,然后将滤液再悬浮在干净的去离子水中,使用与制备试验污渍组合物等量的水,并以相同的方式再次过滤,将滤饼从滤纸上取下,在45℃将滤饼干燥过夜。干燥后,将滤饼压成粉末并储存在干燥的密闭容器中。
接着,按照下列步骤制备作为试验底物的4.5英寸方的标准黑瓷砖。首先用工业轻负载液体洗盘产品来清洗瓷砖,尽可能避免与瓷砖的多孔背面的接触。接着,用干净的水完全漂洗瓷砖,然后在45℃的炉中干燥过夜,每个瓷砖的表面朝向炉架;将瓷砖放在纸巾上以避免刮擦。
在制备试验污渍组合物和试验底物后,制备试验受脏的表面样品。如下重新配制试验污渍组合物:将4.5%重量的试验组合物、9.00%重量的上述硬水、0.77%重量的盐酸(0.1N)和85.73%重量的丙酮加入合适的烧杯中。然后,通过搅拌将这些组分均化并形成悬浮液,直到颜色由白变灰,这大约在20~30分钟内发生。在搅拌过程中,烧杯尽可能多地覆盖以避免过多的溶剂即丙酮的损失。随后,将合适量的如此重配制的试验污渍组合物装入工匠的喷枪中以在40psi的空气压力下操作。
将重新组合的试验污渍组合物施用到如上述制备的已清洁和干燥的瓷砖表面上,这些瓷砖纵横排列,在上面均匀喷洒污渍。每片大约施用0.10~0.26克组合物。然后空气干燥30分钟,随后将每片放在加热到约320℃的实验热板上直到观察到污渍开始熔化并开始聚结成大滴。然后移走每个加热的瓷砖并使之冷却约30分钟,每个处理过的瓷砖表面摸上去很粘。
接着,使用Gardner Washability装置,在标准压力和海绵冲程设置下进行清洁模拟实验以确定或定量组合物的清洁效率。首先,对于每个新的组合物,用水漂洗海绵,在后挤压直到仅剩有17.5±0.5克水。然后,约抽12次(约1克)试验产品喷到一片瓦的受脏的区域上,随后将产品在瓷砖的受脏表面上停留30秒,接着起动Garder装置使海绵在瓷砖的一侧上通过瓷砖12次,相当于该装置的六次擦洗循环。移走试验的瓷砖,用自来水冲洗并使之干燥。
该标准弄脏瓷砖的制备和清洁规则不仅用于每个实施例组合物,而且用于类似数目的比较例组合物中,该比较例组合物是以商品名“CometBathroon Celaner”销售的市售的硬表面清洁组合物,它是根据标签指示直接从触发喷雾器中作为泡沫而使用。
二十人担任检查专家组通过比较实施例组合物的清洁面积和比较例组合物的清洁面积以相同时间的弄脏的/未干净的面积比来以百分数(0%~100%)对清洁的级别定级。专家组的每人对所有瓷砖定级,专家组决不允许有大于10%(即10,20,30...100%)的差别。对每个评估瓷砖的专家测定的记录进行平均,每个瓷砖的平均记录值列于下面的表4-清洁的视觉评估。
表4-清洁的视觉评估
实施例组合物 | 实施例组合物的评估结果 | 比较例组合物的评估结果 |
实施例1 | 44 | 36 |
实施例2 | 49 | 45 |
实施例4 | 46 | 41 |
实施例5 | 53 | 29 |
实施例6 | 48 | 34 |
实施例7 | 73 | 51 |
实施例9 | 55 | 39 |
实施例11 | 53 | 47 |
实施例12 | 46 | 39 |
如表4的结果和图1所示,测定出各种组合物至少与已知的工业组合物的清洁效率可比,在某些情况下,发现其清洁效率比现有技术的工业清洁组合物显著的改进。清洁评估
测量表1中详细描述的实施例8的组合物以及上表2所示的三种比较实施例组合物清洁功效。使用Gardner Washability装置,并采用根据上述规则制备的标准弄脏的瓷砖在标准压力和海绵冲程设置下进行评估以测定或定量组合物的清洁效率。原样使用这些组合物并且不进一步稀释成清洁组合物。在测定每个组合物的清洁效率,使用Gardner Micro-Tri-Gloss测量仪测定反射值,该测量仪测试每片瓦至少五次,其平均反射值记录在下表5中。对下列每一种瓷砖进行测试:干净的未弄脏的瓷砖、弄脏的瓷砖和GardnerWashability装置擦洗后的弄脏的瓷砖。然后用这类反射值根据下式计算清洁效率(%):其中:
Lt=擦洗固体瓷砖后的反射平均值(%);
Ls=清洗弄脏的瓷砖前的反射平均值(%);
Lo=弄脏前原始的反射平均值(%)。
下表5示出了清洁效率结果:
表5-清洁效率
组合物 清洁效率%
实施例8 63.1
比较例1 2.1
比较例2 29.8
比较例3 19.1
如所示的那样,试验样品的清洁效率的测量值显示本发明的清洁组合物具有很强的从试验底物上除去试验污渍的能力。考察表5所述的组合物,比较例1不含有组分A的酸性螯合剂,比较例2不含有组分B,比较例3不含有本发明的组分C。正如从表5所示的结果可以看出,含有本发明人所定义的组分A、B和C的本发明的组合物提供了协同的清洁效率,该协同效应用其它方式是不能提供的。该效应从图2可以更清楚地看出,图2示出了由本发明的组合物提供的令人惊奇的改进的清洁效率。对眼部刺激的评估:
采用已知的Draize眼部试验规则评估本发明的组合物的眼部刺激特性。对上表1的实施例8的组合物进行评估,测定该组合物的pH为2.0。
本领域普通技术人员周知,Draize眼部试验测量眼部刺激以为眼部伤害的严重性定级。在进行Draize试验期间,试验第1天的Draize试验值为11.33,进一步观察到至第7天,所有6个试验者的所有结膜刺激症状消失。Draize试验结果表明EPA分类III是合适的,在7天或更短的时间内角膜刺激消失。在USA环保局(EPA),40C.F.R.第1章,第162.10节(1986)的指南中,根据Draize眼部试验结果,所试验的组合物测定为属于EPA分类表III,其中角膜刺激在7天或更短的时间内消除。这样的结果是用一种具有良好清洁功效的产品在很强的酸性pH下得到的,这尤其令人惊奇。
再次重复前面的评估,但使用表1所述的实施例13的组合物。在每次试验前评估该组合物的pH,并测定为2.0。在进行Draize试验期间,试验第1天的Draize试验值为16.5,并观察到6个试验者中仅3个有角膜混浊,但是到第三天消失。在6个试验者中4人有虹膜炎,但是第二天消失。所有6个试验者的结膜刺激的所有症状到第7天消失。Draize试验结果表明EPA分类III是合适的,其中角膜刺激在7天或更短的时间内消失。用一种具有良好的清洁功效的产品在2.0的酸性pH下得到这些结果也是特别令人惊奇的。皮肤刺激评估
评估表1的实施例8的组合物的对皮肤刺激的影响:在进行试验前,测定组合物的pH为2.0。原样使用表1的实施例8的组合物,即不进一步稀释在水中。
根据下列规则进行皮肤刺激评估收集一组6个年青的成年新西兰白兔(重2.0~3.5千克,性别无区别)作为试验动物。在用于试验前,剪去每个动物背部和侧面的毛。选择两个位置,脊柱的每一侧各一个并保持不接触。每试验动物在给药前都装有Elizabethan型限制环。接着,将试验组合物加到2.5cm2的纱布片上。将纱布片敷于动物的两个未接触的位置,并用胶带固定,试验位置不封闭。将试验组合物与皮肤接触4小时后,除去覆盖物,用100毫升自来水清洗该部位。此时移去限制环。
在应用试验用品后在4、24和72小时观察皮肤反应由此进行兔的体内评估,包括溃汤和坏死。基于下列标准进行评分:红斑
无红斑 0
极少量红斑(几乎观察不到) 1
清晰的红斑 2
中等到严重的红斑 3
严重的红斑(甜菜红)到
少量焦痂形成(深度伤害) 4水肿
无水肿 0
极少量水肿(几乎观察不到) 1
少量水肿(由确切的突起明确限定区域的边缘) 2
中等水肿(突起约1毫米) 3
严重水肿(突起大于1毫米并伸出暴露区) 4
有腐馈的症状 >4
将两个位置红斑/焦痂的分数相加,再加上两个位置水肿的分数,得出平均值。将得到的4个和的每一个除以6(动物数)得到每个单一时间段的4个平均值。通过下列步骤得出基本刺激指数(Primary Irritation Index)的测量值:将24和72小时的4个平均值(总共8个值)相加并将该和除以4(2位置×2时间段)以得到基本刺激指数。根据联邦规则(Federal Regulations)1500.3(C)(1)的16号规定,基本刺激物定义为不腐蚀但得到经验值为5或更多的物质。作为试验规则的结果,发现表1的实施例8的组合物尽管具有酸性pH,但对试验者观察72小时未引起刺激。抗微生物功效的评估
评估上表1详细描述的几种典型的组合物以便评估其抗金黄色葡萄球菌(革兰氏阳性病原细菌)(ATCC6538)、猪霍乱沙门菌(革兰氏阴性病原细菌)(ATCC10708)和铜绿假单胞菌(ATCC15442)的抗微生物功效。根据下列规程中概述的方法进行测试:“使用-稀释法”(“Use-Dilution Method”),在“官方分析方法”(“Official Methods of Analysis”)的第6章所述的规则955.14、955.15和964.02,官方分析化学家协会,第16版;“消毒剂的杀菌和洗涤卫生作用”(“Germicidal and Detergent Sanitizing Action ofDisinfectants”),“官方分析方法”的第6章描述的960.09规则,官方分析化学家协会,第15版;或美国材料试验学会(ASTM)E1054-91;将这些内容引入本文作为参考。该试验通常也称为“AOAC使用-稀释试验法”(“AOAC Use-Dilution Test Method”)。
正如本领域熟练人员所理解的那样,AOAC使用-稀释试验法的结果表示,根据AOAC使用-稀释试验评估的其中受测试的微生物与试验的消毒组合物接触10分钟后保持存活的试验底物数与接受试验的底物(柱状体)的总数的比例。因此,“0/60”结果表示60个带有试验微生物的试验底物在试验消毒组合物中接触10分钟,0个试验底物在试验结束时具有存活的试验微生物体。这样的结果是极好的,表示受试验的组合物的良好的消毒效果。
抗微生物试验结果列于下表6中。所记录的结果表示带有活的试验微生物的试验柱状体的数目与每个实施例组合物所用的试验柱状体和试验微生物数目的比例
表6-抗微生物功效
实施例组合物 | 金黄色葡萄球菌 | 猪霍乱沙门氏菌 | 铜绿假单胞菌 |
实施例15 | 0/60 | 0/60 | 0/60 |
实施例17 | 0/60 | - | 0/60 |
实施例18 | 0/60 | - | 0/60 |
“-”表示未测试
从上述结果可以看出,本发明的组合物提供了对硬表面包括那些很难除去污垢的表面的良好的清洁效果,同时它们对使用者的皮肤和粘液组织具有惊人的温和性,这表明该清洁组合物不含有任何显著比例的酸性成分。其优点还包括这些组合物对浴室、厨房和其它环境中通常发现的已知细菌具有杰出的抗微生物功效,以及这些组合物还具有抗脊髓灰质炎病毒的功效。这些优点清楚说明了本发明组合物的优越特性,它的清洁和抗微生物优点使其具有本领域以前所未知的应用。
Claims (8)
1.一种杀菌含水的用于硬表面的清洁组合物,其包括:
0.1~10%重量的酸性螯合剂组分;
0.1~10%重量的疏水和亲水溶剂的混合物;
1~8%重量的表面活性剂和/或水溶助长剂组分;
0~20%重量的一种或多种任选组分;
平衡量的水至100%重量,
其中该含水的硬表面清洁组合物的pH为7.0或更低。
2.权利要求1的含水的硬表面清洁组合物,其中酸性螯合剂组分选自:柠檬酸、甲苯基酸、十二烷基苯磺酸、磷酸、水杨酸、山梨酸、氨基磺酸、乙酸、苯甲酸、硼酸、癸酸、己酸、氰尿酸、二氢乙酸、二甲基氨基磺酸、丙酸、聚丙烯酸、2-乙基-己酸、甲酸、富马酸、1-谷氨酸、异丙基氨基磺酸、环烷酸、草酸、磷酸、戊酸、苯磺酸、二甲苯磺酸、磺酸、马来酸、己酸、己二酸、乳酸、丁酸、萄糖酸、苹果酸、酒石酸、以及乙醇酸。
3.根据权利要求1或2的含水硬表面清洁组合物,其中酸性螯合剂组分含至少50%重量的柠檬酸。
4.权利要求1的含水硬表面清洁组合物,其中酸性螯合剂组分的存在量为4.0~6.0%重量。
5.权利要求1的含水硬表面清洁组合物,其中疏水和亲水溶剂的混合物包括有机的疏水溶剂和亲水溶剂,所述疏水溶剂选自:溶剂油、三丙二醇正丁醚、丙二醇苯醚、二丙二醇正丙醚、乙二醇苯醚、丙二醇正丁醚和二丙二醇正丁醚,所述亲水溶剂选自:二醇甲醚、二丙二醇甲醚、三丙二醇甲醚、丙二醇正丙醚、乙二醇正丁醚、二乙二醇正丁醚、二乙二醇甲醚、丙二醇、乙二醇、异丙醇、乙醇、甲醇、二乙二醇单乙醚、乙二醇单丁醚乙酸酯和二乙二醇单乙醚乙酸酯。
6.权利要求1的含水硬表面清洁组合物,其中疏水和亲水溶剂混合物的存在量为3.0~6.0%重量。
7.权利要求1-6任一项的含水硬表面清洁组合物,其中组合物的pH为5.0~1.0。
8.权利要求1-6任一项的含水硬表面清洁组合物,其包括胶凝剂,且所述组合物呈凝胶状。
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GB9521829A GB2306499A (en) | 1995-10-25 | 1995-10-25 | Hard surface cleaning compositions |
GB9521829.3 | 1995-10-25 | ||
GB9612645.3 | 1996-06-17 | ||
GB9612645A GB2306500B (en) | 1995-10-25 | 1996-06-17 | Acidic hard surface cleaners |
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- 1996-09-27 CN CN96198430A patent/CN1088748C/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
EP0904343A1 (en) | 1999-03-31 |
DE69631549T2 (de) | 2004-12-30 |
CN1088748C (zh) | 2002-08-07 |
AU718194B2 (en) | 2000-04-06 |
BR9611215A (pt) | 1999-06-01 |
IN191414B (zh) | 2003-11-29 |
US6221823B1 (en) | 2001-04-24 |
ES2211989T5 (es) | 2009-10-09 |
CA2235484C (en) | 2008-11-25 |
AU7374196A (en) | 1997-05-15 |
EP0904343A4 (zh) | 1999-03-31 |
ES2211989T3 (es) | 2004-07-16 |
DE69631549T3 (de) | 2010-02-18 |
CA2235484A1 (en) | 1997-05-01 |
DE69631549D1 (de) | 2004-03-18 |
EP0904343B1 (en) | 2004-02-11 |
NZ320903A (en) | 1999-10-28 |
EP0904343B2 (en) | 2009-07-08 |
WO1997015649A1 (en) | 1997-05-01 |
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