CN102933761A - 清洁产品 - Google Patents
清洁产品 Download PDFInfo
- Publication number
- CN102933761A CN102933761A CN201180028478XA CN201180028478A CN102933761A CN 102933761 A CN102933761 A CN 102933761A CN 201180028478X A CN201180028478X A CN 201180028478XA CN 201180028478 A CN201180028478 A CN 201180028478A CN 102933761 A CN102933761 A CN 102933761A
- Authority
- CN
- China
- Prior art keywords
- dispensing cartridge
- chamber
- agent
- preparation
- rinsing maching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Abstract
本发明涉及一种用于洗涤机中的洗涤剂配送盒,其中,所述洗涤机适于清洁受污底物,并采用包含多种高分子颗粒的制剂进行润湿底物的处理,所述制剂不含有机溶剂。
Description
本发明涉及用于洗涤机的洗涤剂配送盒。
在自动洗涤机中洗涤衣物是众所周知并被广泛实践的。
常常尝试多种方法通过改进所用的洗涤剂、洗涤循环和机器自身的性质来改善洗涤功能。
对于改进洗涤工序使得可以更有效地使用外部资源(特别是水和电)有着日益增长的需要。还有日益增长的环境压力要求减少清洁中过量化学品的使用。并且,消费者对于进行家务所必须消耗的时间要求愈发苛刻。
根据本发明的第一方面,提供了一种用于洗涤机中的洗涤剂配送盒。
洗涤机是指能用于洗涤操作的任何容器/机器(人工操作或全自动/半自动)。洗涤机优选的是自动衣物洗涤机。最优选的是,洗涤机是已经进行改进从而可以采用共同未决的专利申请WO2007/128962、GB 0902619.6、GB 0907943.5、GB 0916249.6、GB0916250.4、GB 0920565.9、GB 1002245.7和GB 1006076.2中的一个或多个的技术运行的洗涤机;这些专利申请的全文通过参考并入本文中。
根据本发明的第二方面,提供了一种用于洗涤机的洗涤剂配送盒,其中所述洗涤机用于清洁受污底物(substrate),包括用包含多种高分子颗粒的制剂处理润湿底物。
根据本发明的第三方面,提供了一种用于洗涤机的洗涤剂配送盒,其中所述洗涤机用于清洁受污底物,其包括用包含多种高分子颗粒的制剂处理润湿底物,其中所述制剂不含有机溶剂。
优选的是,粒珠与底物的比例通常为30:1~0.1:1重量/重量,优选为10:1~1:1重量/重量,使用5:1~1:1重量/重量的比例可以获得特别有利的结果,最特别优选的是约2:1重量/重量。因此,例如,为了清洁5g织物,将使用10g高分子颗粒。
高分子颗粒的形状和尺寸使其能够具有良好的流动性以及能够与纺织纤维紧密接触。可以使用各种形状的颗粒,例如圆柱形、球形或立方形;可以使用适当的截面形状,包括例如孔环形、哑铃形和圆形。颗粒可以具有光滑或不规则的表面结构,并且可以是实心或空心构造。颗粒优选具有的尺寸使其具有的平均质量为5mg~100mg,优选为10mg~30mg。在最优选的粒珠情况中,优选的平均粒径为0.5mm~6.0mm,更优选为1.0mm~5.0mm,最优选为2.5mm~4.5mm,粒珠的长度优选为0.5mm~6.0mm,更优选为1.5mm~4.5mm,最优选为2.0mm~3.0mm。
所述高分子颗粒可以包括任意的多种不同聚合物。具体而言,可以提及如聚乙烯和聚丙烯等聚烯烃、聚酯和聚氨酯,其可以是发泡的或未发泡的。但优选的是,所述高分子颗粒包括聚酰胺或聚酯颗粒,最特别优选的颗粒是尼龙、聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯,最特别优选的是粒珠形式。发现所述聚酰胺或聚酯对于除去水性污渍/污垢特别有效,而聚烯烃特别可用于除去油性污渍。可选的是,可以使用上述高分子材料的共聚物。
可以使用各种尼龙或聚酯均聚物或共聚物,包括但不限于尼龙6、尼龙6.6、聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯。优选的是,尼龙包括分子量为5000~30000道尔顿、优选为10000~20000道尔顿、最优选为15000~16000道尔顿的尼龙6.6均聚物。通常,聚酯的分子量对应于通过如ASTM D-4603等溶液技术所测量的在0.3~1.5dl/g内的特性粘度测量。
通常,高分子颗粒包括尼龙片,例如尼龙6或尼龙6.6。
发现使用配送盒可以在容易使用方面为消费者提供重大益处。使用配送盒能够在下述情况下将洗涤剂组合物排放入洗涤机中(在多个洗涤循环中):消费者无需称量洗涤剂组合物或与其接触就可以得到保障,知道已将正确的洗涤剂组成施用于洗涤机的洗涤负载物(wash load)。
优选的是,配送盒具有多个腔室。通常,各腔室可以分别进行激活以使各腔室的内容物可以单独/顺次释放。可将各腔室设计为容纳预定的完整的洗涤剂制剂或主要为(focus on)洗涤剂制剂的单一活性成分的制剂。优选的是各腔室可分别进行激活;即完全单独激活的方式或者在洗涤循环的预定部分激活一个或多个腔室使其能够释放一部分腔室内容物的“程序”方式。以此种方式,发现可以根据洗涤负载物的大小、组成和其上存在的污渍类型来定制洗涤剂的释放从而适合特定的洗涤负载物。清楚的是,可设想,特定的腔室可以在洗涤循环中激活一次,不激活或激活多次。
发现单独容纳和释放是有益的,原因很多,包括腔室成分的储存稳定性,特别是对于对抗性成分的储存稳定性。例如,可以避免漂白剂和酶之间的对抗相互作用。进一步的实例是具有相反离子电荷的成分的还原/抵消。在此方面,大多数固色剂/染料转移抑制剂(例如,如PVP、PVP-VI、PVNO类化合物及其衍生物)(下文称为DTI)具有正电荷。该正电荷的存在会引起经常在洗涤剂中使用(特别是衣物洗涤剂,以提供清洁功能)的阴离子型表面活性剂之间的有害相互作用。固色剂/DTI和阴离子型表面活性剂因其相反电荷而“结合”在一起,削弱了它们各自的功能。避免该问题的一种方式是将阴离子型表面活性剂替换为非离子型表面活性剂,这虽然避免了结合效应,但非离子型表面活性剂通常比阴离子型表面活性剂的清洁功能差。通过将固色剂/DTI放入腔室中与任何阴离子型表面活性剂隔开,可以避免此类结合问题。
除了在单独的腔室中容纳/释放外,还可以定制洗涤液的温度/加热从而使其能够得到优化,在该结合点时与释放的腔室内容物相作用。例如,当释放漂白剂/漂白活化剂组合物时,对洗涤液进行加热(例如约40℃~60℃)可能适合于确保漂白剂/漂白活化剂组合物出现最佳功能。相反,许多其他洗涤剂成分无需进行洗涤液加热就能实现其最佳功能。在这个方面,应当理解,可以对全部洗涤液或其一部分进行加热。当仅加热洗涤液的一部分时,所述部分可以是穿过或邻近配送盒的洗涤液部分,或者是穿过或邻近任何洗涤液循环系统的洗涤液部分。
并且,在单独的腔室中进行容纳/释放能够定制洗涤液的pH使得其能够得到优化,在该结合点时与释放的腔室内容物相作用。例如,当释放漂白剂/漂白活化剂组合物时,升高洗涤液的pH(例如,通过释放适当的pH改性剂将pH升高至碱性pH)可能适合于确保漂白剂/漂白活化剂组合物出现最佳功能。相反,许多其他洗涤剂成分无需进行pH调节就能实现其最佳功能。
除了在单独的腔室中进行容纳/释放,可以定制单独洗涤剂活性物的释放以使能够得到优化,与WO2007/128962的系统相作用。
就这一点而言,发现一种优选的释放模式(profile)是以下述顺序释放:
a)含酶制剂的释放;
b)氧化性制剂的释放;
c)含助洗剂/织物柔顺剂的制剂的释放。
另一种优选的释放模式是以下述顺序释放:
a)含固色剂/DTI的制剂的释放;
b)含酶制剂的释放;
c)氧化性制剂的释放;
d)含助洗剂/织物柔顺剂的制剂的释放。
组合物(a)和/或(b)和/或(c)还可包含表面活性剂。氧化性制剂可以包含漂白剂和/或漂白活化剂/催化剂。
根据WO2007/128962的方法,所用的高分子颗粒可以存在于整个衣物洗涤循环,或仅存在于部分衣物洗涤循环中。如果高分子颗粒仅存在于部分洗涤循环中,则优选的是高分子颗粒在洗涤机操作的漂洗循环(优选最终的漂洗循环)中从洗涤机的洗涤区除去。
配送盒可包括用于在洗涤机操作的预洗循环(可在粒珠添加至洗涤机中之前)中释放部分洗涤剂成分的腔室。发现这对某些洗涤剂成分(其活性会因吸附在高分子颗粒上而削弱)是有利的。
除此之外或作为选择,配送盒可包含用于在洗涤机操作的漂洗循环(优选最终的漂洗循环)中释放部分洗涤剂成分的腔室。发现这对某些洗涤剂成分(其活性会因吸附在高分子颗粒上而削弱)是有利的。在该阶段释放的洗涤剂成分(优选的是在配送盒中存在此成分的腔室)的优选实例是增白剂和芳香剂。配送盒腔室可以是模块化的,例如,可以更换配送盒的一个或多个腔室而不更换整个配送盒。同样,优选的是消费者可以选择最适合其常规洗涤类型的腔室,从而可以采用他们的洗涤中最可能需要的腔室来组装整个配送盒。
各腔室的体积可以是1cc~5000cc,更优选为10cc~900cc,更优选为20cc~600cc,更优选为20cc~400cc,更优选为20cc~300cc,更优选为20cc~200cc,最优选为20cc~100cc。
洗涤机中的配送盒可灵活放置。清楚的是,优选放置配送盒以使配送盒内容物能够配送入洗涤机的洗涤区。可存在导管来连接配送盒输出端与洗涤区。作为选择和/或除此之外,可放置配送盒以使其输出端邻近或连接至新进洗涤流体(例如水)。可放置配送盒/可设计洗涤机以使新进洗涤流体/洗涤液流经所述设备的上方/周围。
配送盒腔室的激活可以通过多种机制中的一种或多种来执行。对于不同的配送盒腔室,可以使用不同的激活机制。
优选的运行机制可以是人工机制或非人工机制。优选的非人工运行机制包括与洗涤循环中的变化相关的物理和化学激活触发。优选的实例包括时间、温度/温度变化、气味/味道、湿度/水存在(或清洁液的一些其他相关性质,例如,如离子强度或pH)、转筒转动/离心力或其他力。其他运行机制可源于由配送盒到洗涤机的导管(特别是洗涤机运行程序(schematics)),使得由洗涤机程序触发的洗涤机运行在洗涤循环内的一个或多个时间点影响或引发配送盒或一个或多个腔室的运行。以此方式,不同的洗涤循环会触发其配送盒/腔室的不同的激活/运行。此外,不同的洗涤负载物/条件会引发一个或多个腔室不同程度的运行。
配送盒还可具有可由消费者操作的人工超控(manual override)。该人工超控可超越配送盒的任何常规配送行为并影响配送,以增加/减少一个或多个腔室的释放和/或影响释放时机。
腔室的全部内容物可在一个洗涤循环中释放,或者在一个洗涤循环的一部分中释放,或者在其多个部分中释放。更优选的是,为了增加消费者的便利性,腔室的内容物可在多个洗涤循环中释放,例如,在10~30个洗涤循环(如约20个洗涤循环)中释放。在这种情况下,配送盒内容物仍可在多个循环的多个点释放。优选的是,配送盒和/或其一个或各个腔室可具有“耗尽”指示器以使消费者明确注意到一个或多个腔室的内容物已经耗尽并需要补充。“耗尽”指示器可以通过与洗涤机程序关联而触发或产生。
同样,在设备的一个实施方式中,配送盒预定用于一个洗涤循环。
腔室释放操作可以通过多种机制中的一种或多种来进行。优选的腔室释放机制包括人工释放(例如,开启或挤压)、重力释放、主动释放(例如,通过电机/泵,如驱动电机、蜡电机、压电、注入或喷洒)和被动释放(通过穿过或邻近腔室的洗涤液/高分子颗粒的流动从中吸出腔室内容物(或其一部分)而驱动)。释放可以是主动机制和被动机制的组合,例如,腔室的通路单元(access means)可以在一定条件下开启以使活性物能够从腔室中释放出。这种激活机制的优选实例是双金属驱动开启单元,使得该开启单元能够在某一预定温度进行激活,从而发生释放(通过任何机制)。
对于构成整个洗涤剂制剂的较小部分的洗涤剂成分(和相关腔室)(例如,芳香剂、增白剂),优选的是较主动的配送方法,例如喷洒。对于构成整个洗涤剂制剂的较大部分的洗涤剂成分(和相关腔室)(例如,表面活性剂、助洗剂),优选的是较被动的配送方法。
腔室内容物可以是任何适当的物理形式。优选的形式包括液体(分散液、悬浮液、糊剂、溶液、乳剂和凝胶)和固体(固化凝胶、粉末和片剂)。在配送盒中,不同腔室的内容物可以是不同的物理形式。
腔室内容物可以容纳在二级包装物中,例如,如封装单元、袋或小袋。
腔室内容物可以是能够再填充(refillable)的。根据所述/各个腔室的组合物性质的化学/物理性质,再填充内容物可以是颗粒、粉末或液体/凝胶的形式。再填充组合物可以是“单元剂量”组合物的形式,例如压缩/固化/模压片剂,或者再填充物可以是膜袋中的包装物,其中膜可以是整体水溶性/分散性的,或者具有水溶性部分或可刺穿区以使袋的内容物能够释放。膜袋可包含金属箔或塑料材料,例如,聚丙烯、聚乙烯、聚乙烯醇、ABS、PET、聚酰胺、PMMA或PC。清楚的是,单元剂量组合物的大小应与各自的腔室匹配并能够容易进行再填充而无需消费者接触任何有害化学品。一个腔室中可匹配多个单元剂量个体;这样的设置可具有彼此关联的分离型支撑框架。
除了常规的洗涤剂活性物(见下文)外,配送盒还可包含一种或多种用于增加高分子颗粒活性的活性物。就此点而言,一种优选的活性物是高分子颗粒用增塑剂。据推测,使用这样的增塑剂,高分子颗粒的Tg将降低,使得高分子颗粒能够在低温具有更高活性。制剂可包含吸附到高分子颗粒位点上的牺牲剂,其中,这些位点原本会引起一种或多种洗涤剂活性物的有害吸附。
配送盒可包含含(补充的)高分子颗粒的腔室。这些颗粒可以是纯粹的聚合物,或者可以经过物理或化学改变以影响其活性。化学改变的优选方式包括这样一种高分子颗粒:其中洗涤剂活性物(例如,酶或漂白催化剂)已经可逆/不可逆地吸附于其中或洗涤剂活性物已涂布于其上。
通过使用本发明的配送盒,发现因高分子颗粒的存在而可以改变整个洗涤剂制剂。改变的一个实例是每个洗涤循环所需的洗涤剂的总量显著减少。实际上就此而言,发现所需洗涤剂的量可低至自动衣物洗涤机中洗衣操作通常预期量的50%、40%、30%、20%甚至10%。例如,发现通过使用本发明的配送盒,对于自动衣物洗涤机中的5kg衣物负载,可使用少至15g的液体洗涤剂制剂即可达到同等的洗涤标准(而在自动衣物洗涤机中的常规洗涤过程中,将需要150g同样的液体制剂)。
当使用较小量的洗涤剂时,发现可以减少家用衣物洗涤剂中通常所含的某些成分的量。特别是,已发现可以降低所需助洗剂的量。另一种改变是发现可以改变洗涤剂表面活性剂(在其量和/或性质方面),这是因为高分子颗粒可形成改性洗涤剂胶束,其中高分子颗粒在胶束的中心。再一种改变是,由于洗涤液的量较少,因而会因由过量漂洗水提取而浪费的某些活性物(例如,如芳香剂或增白剂)的量会显著减少。
由于需要较小量的洗涤剂(与常规衣物洗涤相比),已发现配送盒及其各腔室的总尺寸可以较小,提高了消费者的便利性。
通过使用本发明的配送盒,已发现可以改变总洗涤循环。改变的一个实例是可以使用较高的温度(对于至少部分洗涤液),通常在短时间内使用(由于洗涤机中洗涤液的量较少,因此不会对所用的能量产生不利)。已发现此点由于可提高某些洗涤剂成分(例如漂白剂)的作用而是有利的,这种效果通常在活性物浓度较低且可能没有任何辅助活性物(对于漂白剂,辅助活性物可以是漂白催化剂/漂白活化剂)的情况下取得。
应理解,通常而言,洗涤循环温度为0℃~90℃,更优选为5℃~90℃,更优选为5℃~70℃,更优选为15℃~40℃,例如,约30℃。
洗涤循环时间优选为15分钟~150分钟,更优选为15分钟~120分钟,最优选为20分钟~40分钟。循环的漂洗比例优选为总循环时间的至多50%,更优选为至多40%,更优选为至多20%,更优选为至多10%。最终甩干可以是总循环时间的约5%。中间甩干(例如,部分循环之间)可以(单独或总共)为总循环时间的约1%~2%。
洗涤循环中所用的洗涤水的量优选为约6升/千克洗涤负载物;对于洗涤阶段是约3升,对于漂洗阶段是3升。水量可以减少,例如,优选为2.5:1~0.1:1升/千克洗涤负载物;更优选的是,该比例为2.0:1~0.8:1升/千克洗涤负载物,在1.5:1升/千克洗涤负载物、1.2:1升/千克洗涤负载物和1.1:1升/千克洗涤负载物的比例下,已获得特别优选的结果。
与此相比较,常规洗涤机为约13升/千克洗涤负载物;其中洗涤阶段为约4升,漂洗阶段为9升。
可将配送盒设计为置于洗涤机中(或上)的适当位置,例如转筒/抽屉中。
配送盒可由洗涤机内或与洗涤机相关联的适当的配送盒接收单元来操作。配送盒接收单元可以是完全机械的。作为选择,配送盒接收单元可包括与部分配送盒相关联的电子元件(并可选地驱动部分配送盒的运行)。配送盒接收单元可包括识别配送盒(和/或其各腔室)存在的机构,例如,如射频识别(RFID)机构,例如,通过如配送盒上的条形码。
配送盒优选包含塑料材料,例如,聚丙烯、聚乙烯、ABS、PET、聚酰胺、PMMA或PC。配送盒/腔室材料可以涂布有例如障壁层。此类层可用于承受腐蚀性更强的化学内含物(例如,有助于预防聚合物应力开裂)。
在本发明的一个实施方式中,优选的是在洗涤机/洗涤机循环中可同时使用多个单独的配送盒。各配送盒可配置在洗涤机的不同部分或者洗涤机的相同部分。各配送盒可包含相同或互补的洗涤剂组合物(例如,在多个腔室中)。
粒珠清洁过程通常可在每5~6次洗涤后进行,使得粒珠表面在洗涤过程中能够保持高活性。优选的是,粒珠清洁如下进行:将各剂量的表面活性剂(非离子型和/或阴离子型和/或阳离子型表面活性剂)、和可选的其他更具腐蚀性的化学品(选自例如氢氧化钠/氢氧化钾、次亚氯酸盐、次氯酸盐或其他漂白剂和前述活化剂)添加到一定量的水中,以使水与粒珠的比例优选为0.5~3升水/kg粒珠。可以通过由配送盒释放适当的清洁组合物来促进粒珠清洁过程。
表面活性剂的优选实例包括阴离子型表面活性剂、非离子型表面活性剂、阳离子型表面活性剂、两性或两性离子型表面活性剂或其混合物。
阴离子型表面活性剂的实例是直链或支化的烷基硫酸盐和烷基聚烷氧基化硫酸盐,也称为烷基醚硫酸盐。此类表面活性剂可以通过C8~C20高级脂肪醇的硫酸盐化来制备。
伯烷基硫酸盐表面活性剂的实例是下式所示的那些:
ROSO3 -M+
其中,R是线型C8~C20烃基,M是水溶性阳离子。
优选的是,R是C10~C16烷基,例如C12~C14,M是如锂、钠或钾等碱金属。
仲烷基硫酸盐表面活性剂的实例是在分子的“骨架”上具有硫酸盐部分的那些,例如下式所示的那些:
CH2(CH2)n(CHOSO3 -M+)(CH2)mCH3
其中m和n独立地是2以上,m+n的和通常为6~20,例如9~15,M是水溶性阳离子,例如锂、钠或钾。
特别优选的仲烷基硫酸盐是下式所示的(2,3)烷基硫酸盐表面活性剂:
CH2(CH2)x(CHOSO3 -M+)CH3和
CH3(CH2)x(CHOSO3 -M+)CH2CH3
上式分别是2-硫酸盐和3-硫酸盐。在这些式中,x至少为4,例如6~20,优选为10~16。M是阳离子,如碱金属,例如锂、钠或钾。
烷氧基化烷基硫酸盐的实例是下式所示的乙氧基化烷基硫酸盐:
RO(C2H4O)nSO3 -M+
其中,R是C8~C20烷基,优选为C10~C18,例如C12~C16,n至少为1,例如1~20,优选为1~15,特别是1~6,M是成盐阳离子,例如锂、钠、钾、铵、烷基铵或烷醇铵。当与烷基硫酸盐组合使用时,这些化合物可以提供特别合意的织物清洁性能益处。
烷基硫酸盐和烷基醚硫酸盐通常以包含不同的烷基链长度、和不同的烷氧基化程度(如果存在)的混合物形式使用。
可使用的其他阴离子型表面活性剂是脂肪酸的盐,例如C8~C18脂肪酸,特别是钠盐、钾盐或烷醇铵盐,和烷基(例如C8~C18)苯磺酸盐。
非离子型表面活性剂的实例是脂肪酸烷氧基化物。优选的是乙氧基化和丙氧基化非离子型表面活性剂。优选的烷氧基化表面活性剂可以选自以下类别:烷基酚的非离子型缩合物、非离子型乙氧基化醇、非离子型乙氧基化/丙氧基化脂肪醇、与丙二醇的非离子型乙氧基化/丙氧基化缩合物、以及与氧化丙烯/乙二胺加合物的非离子型乙氧基化缩合产物。优选的脂肪酸乙氧基化物特别是下式所示的那些:
R(C2H4O)nOH
其中,R是直链或支化C8~C16烷基,优选为C9~C15,例如C10~C14或C12~C14烷基,并且n至少为1,例如1~16,优选为2~12,更优选为3~10。
烷氧基化脂肪醇非离子型表面活性剂的亲水亲油平衡值(HLB)通常为3~17,更优选为6~15,最优选为10~15。
脂肪醇乙氧基化物的实例是由12~15个碳原子的醇制成且含约7摩尔氧化乙烯的那些化合物。此类材料以Shell Chemical Company的商标Neodol 25-7和Neodol 23-6.5市售。其他可用的Neodol包括Neodol 1-5,其为烷基链平均含11个碳原子且含约5摩尔氧化乙烯的乙氧基化脂肪醇;Neodol 23-9,其为具有约9摩尔氧化乙烯的乙氧基化伯C12~C13醇;和Neodol 91-10,其为具有约10摩尔氧化乙烯的乙氧基化C9~C11伯醇。
此种类型的醇乙氧基化物已经以Shell Chemical Company的Dobanol商标销售。Dobanol 91-5是平均每分子脂肪醇含5摩尔氧化乙烯的乙氧基化C9~C11脂肪醇,Dobanol 25-7是平均每分子脂肪醇含7摩尔氧化乙烯的乙氧基化C12~C15脂肪醇。
适合的乙氧基化醇非离子型表面活性剂的其他实例包括Tergitol 15-S-7和Tergitol 15-S-9,均为可由Union Carbide Corporation获得的线型仲醇乙氧基化物。Tergitol 15-S-7是具有7摩尔氧化乙烯的C11~C15线型仲烷醇的混合乙氧基化产物,Tergitol 15-S-9是同样的混合乙氧基化产物,但具有9摩尔氧化乙烯。
其他适合的乙氧基化醇非离子型表面活性剂是Neodol 45-11,其为具有14~15个碳原子的脂肪醇的类似的氧化乙烯缩合产物,每摩尔中氧化乙烯基团的数量为约11。此类产物也可由Shell Chemical Company获得。
其他非离子型表面活性剂是,例如C10~C18烷基糖苷,如C12~C16烷基糖苷,特别是糖苷。当需要高度起泡时,这些表面活性剂特别有效。其他表面活性剂是多羟基脂肪酸酰胺,如C10~C18N-(3-甲氧基丙基)咪唑双酰胺和Pluronic类型的氧化乙烯-氧化丙烯嵌段聚合物。
阳离子型表面活性剂的实例是季铵盐类型的那些化合物。
优选的季铵盐化合物具有式(I)或(Ia),或者包括其混合物:
[R’-(CO)-O-R-N+(-R”)(-(RO)nH)(-R-O-(CO)-R’)]X- (I)
[R’-(CO)-NH-R-N+(-R1)(-(RO)nH)(-R-NH-(CO)-R’)]X-(Ia)
其中:
R是具有2~4个碳原子的亚烷基或亚烯基;
R’是具有8~22个碳原子的烷基或烯基;
n是1~4的整数值;
R”是具有1~4个碳原子的烷基;R1是具有1~4个碳原子的烷基或氢;并且
X-是软化剂相容性阴离子。
软化剂相容性阴离子(X-)的非限制性实例包括氯离子、甲酸根、硝酸根、硫酸根或C1-4烷基硫酸根,优选甲基硫酸根。
烷基或烯基R’理想地必须含至少10个碳原子,优选为至少14个碳原子,更优选为至少16个碳原子。该基团必须是直链或支化的。
季铵化合物的一个具体实例是二-(牛脂基羧乙基)羟基乙基甲基铵X-。
可以存在阳离子型织物助软化剂。
两性表面活性剂的实例是C10~C18氧化胺、C12~C18甜菜碱和磺基甜菜碱。
适合的助洗剂是碱金属或铵的磷酸盐、聚磷酸盐、膦酸盐、聚膦酸盐、碳酸盐、碳酸氢盐、硼酸盐、多羟基磺酸盐、聚乙酸盐、羧酸盐(如柠檬酸盐)和其他聚羧酸盐/聚乙酰基羧酸盐(如琥珀酸盐、丙二酸盐、羧甲基琥珀酸盐)。
水软化剂有下述三种主要类型的作用方式:
1)离子交换剂——此类试剂包括碱金属(优选为钠)的铝硅酸盐,其为结晶型、非晶型或两者的混合物。此类铝硅酸盐的钙离子交换容量通常为至少50mg CaO/克铝硅酸盐,符合下述通式:
0.8-1.5Na2O.Al2O3.0.8-6SiO2
并且含有一些水。上式范围内的优选铝硅酸钠含1.5~3.0个SiO2单元。非晶型和结晶型铝硅酸盐均可通过硅酸钠和铝酸钠之间的反应制备,如文献中详细描述的那样。
适合的结晶型铝硅酸钠离子交换型洗涤助洗剂例如GB 1429143(Procter&Gamble)中所述。这种类型的优选铝硅酸钠是公知的市售沸石A和X及其混合物。感兴趣的还有EP 384070(Unilever)中所述的沸石P。
另一类化合物是层状硅酸钠助洗剂,如US-A-4464839和US-A-4820439中所公开,并在EP-A-551375中引用的那些。
这些材料在US-A-4820439中被定义为具有下述通式的、结晶型层状硅酸钠:
NaMSixO2x+1.YH2O
其中:
M表示钠或氢;
x是1.9~4,y是0~20。
描述这些材料的制备的引用参考文献包括Glastechn.Ber.37,194-200(1964),Zeitschrift für Kristallogr.129,396~404(1969),Bull.Soc.Franc.Min.Crist.,95,371~382(1972)和Amer.Mineral,62,763~771(1977)。这些材料还用于从水中除去钙离子和镁离子,还包括也显示为有效的水软化剂的锌盐。
2)离子捕获剂——防止金属离子形成不溶性盐或与表面活性剂反应的试剂,例如聚磷酸盐、单分子多羧酸盐(monomeric polycarboxylate)如柠檬酸或其盐,多羧酸盐聚合物如聚丙烯酸盐、丙烯酸/马来酸共聚物和丙烯酸膦酸盐、EDTA、藻酸、藻酸盐。
3)抗螯合剂——防止晶种生长的试剂,例如多羧酸盐聚合物如聚丙烯酸盐、丙烯酸/马来酸共聚物和丙烯酸膦酸盐,以及磺酸盐。此类聚合物也可用作离子捕获剂。
优选的可用有机水溶性水软化剂包括多羧酸盐聚合物,如聚丙烯酸盐、丙烯酸/马来酸共聚物和丙烯酸膦酸盐;单分子多羧酸盐,如柠檬酸盐、葡糖酸盐、氧基二琥珀酸盐、甘油单琥珀酸盐、甘油双琥珀酸盐和甘油三琥珀酸盐、羧甲基氧基琥珀酸盐、羧甲基氧基丙二酸盐、吡啶二羧酸盐、羟乙基亚氨基二乙酸盐、膦酸盐、亚氨基二琥珀酸盐、聚天冬氨酸、BHT;膦酸盐稳定剂,如二亚乙基三胺五(亚甲基膦酸)及其相应的五钠盐,可以以商标名Dequest 2060和Dequest 2066(Monsanto Chemical Co.)、DTPMP和DTPMA (Dequest 2010)获得,以及HEDP。
优选的是,水溶性水软化剂是经中和或部分中和的羧酸,如柠檬酸、琥珀酸或马来酸,和/或经中和或部分中和的聚羧酸,如Mw为4000~8000的聚丙烯酸盐(如Acusol 445N(Rohm&Haas),CAS注册号66019-18-9或来自BASF的Sokalan)。
此类适合的聚合物的其他实例包括基于不饱和磺酸单体的聚合物。不饱和磺酸单体优选为下述化合物中的一种:2-丙烯酰胺基甲基-1-丙烷磺酸、2-甲基丙烯酰胺基-2-甲基-1-丙烷磺酸、3-甲基丙烯酰胺基-2-羟基丙烷磺酸、烯丙基磺酸、甲基烯丙基磺酸、烯丙氧基苯磺酸、甲基烯丙氧基苯磺酸、2-羟基-3-(2-丙烯氧基)丙烷磺酸、2-甲基-2-丙烯-1-磺酸、苯乙烯磺酸、乙烯基磺酸、丙烯酸3-磺基丙基酯、甲基丙烯酸3-磺基丙基酯、磺基甲基丙烯酰胺、磺基甲基甲基丙烯酰胺,以及它们的水溶性盐。
不饱和磺酸单体最优选为2-丙烯酰胺基-2-丙烷磺酸(AMPS)。
适合的酶包括过氧化物酶、蛋白酶、脂酶、淀粉酶和纤维素酶。这些酶是市售的,例如以Nova Nordisk A/S的注册商标Esperase、Alcalase、Savinase、Termamyl、Lipolase和Celluzyme销售。如果存在,则理想的是酶的存在量(相对于配送盒内容物的比例)为0.5重量%~3重量%,特别是1重量%~2重量%。
可以使用增稠剂或胶凝剂。适合的增稠剂是聚丙烯酸酯聚合物,如以商标CARBOPOL或商标ACUSOL(Rohm&Hass Company)销售的那些试剂。其他适合的增稠剂是黄原胶。
如果存在增稠剂,则其存在量通常为0.2重量%~4重量%,特别是0.2重量%~2重量%。
可选的是,可以包含一种或多种额外的组分。这些额外组分包括常规洗涤剂成分,例如另外的表面活性剂、漂白剂、漂白增强剂、助洗剂、增泡剂或消泡剂、防锈剂和防蚀剂、有机溶剂、助溶剂、相稳定剂、乳化剂、防腐剂、污渍悬浮剂、污渍释放剂、杀菌剂、抗微生物剂/抗细菌剂、磷酸盐(如三聚磷酸钠或三聚磷酸钾)、pH调节剂或缓冲剂、非助洗剂碱性源、螯合剂、粘土(如蒙脱石)、酶稳定剂、阻垢剂、着色剂、染料、助水溶物、染料转移抑制剂、增白剂和增香剂。如果使用,则这些可选的组分通常占配送盒内容物总重量的不高于10重量%,例如1重量%~6重量%。
如果存在酶,则可选的是,可以存在用于保持酶稳定性的材料。此类酶稳定剂包括例如多元醇(如丙二醇)、硼酸和硼砂。也可以使用这些酶稳定剂的组合。如果使用,则酶稳定剂通常占配送盒内容物总重量的0.1重量%~1重量%。
可以使用用作相稳定剂和/或助溶剂的材料。实例是C1~C3醇或二醇,如甲醇、乙醇、丙醇和1,2-丙二醇。也可以使用C1~C3烷醇胺,如单乙醇胺、双乙醇胺和三乙醇胺以及单异丙醇胺,这些烷醇胺可以自身单独使用或与上述醇组合使用。
洗涤剂成分如果是液态,则可以是无水的,或者例如含至多5重量%的水。理想的是,水性物质包含多于10重量%、15重量%、20重量%、25重量%或30重量%的水,但理想的是少于80重量%的水、更理想的是少于70重量%、60重量%、50重量%或40重量%的水。例如,其可以包含30重量%~65重量%的水。
可选的是,可以使用调节或保持pH水平的成分。pH调节剂的实例是NaOH和柠檬酸。配送盒内容物/洗涤液的pH可以是例如1~13。
参考下述实施例对本发明进行说明。
实施例
实施例1
采用一组试验条件和对照条件(参见表1)进行清洁试验。因此,试验涉及使用PCT申请GB2011/050243中所述的优选清洁装置、根据本发明的方法(“Xeros Plus”多剂量)运行,而对照则在相同的装置中进行但采用单次洗涤剂剂量方式(“Xeros Plus”单剂量)在主洗涤开始时添加。在两种情况中,洗涤负载物在两种情况中均为总重12kg的组成相同的混合服装。洗涤剂成分为:表面活性剂——Christeyns提供的Mulan200S;过氧化氢——氧化性成分—Procter&Gamble提供的ACE B;四乙酰基乙二胺(TAED)——氧化性成分活化剂——由Warwick Chemicals提供;增白剂—Clariant提供的Leucophor BMB;和增香剂——AG提供的Amour Japonais。将污渍加在洗涤负载物上,从而使洗涤剂发生作用——6off WFK PCMS-5505-05×05标准工业/商业衣物污渍监测器、以及12off WFK SBL2004模拟皮脂油斑片。后者用于产生约8g/kg洗涤负载物的皮脂水平,从而使所用的洗涤剂发生作用。
表1.清洁试验
Xeros Plus多剂量循环和Xeros Plus单剂量循环均在28℃的相同洗涤温度进行。不过在Xeros Plus多剂量循环中,利用该方法能够与主洗涤分开在混合槽中于60℃加热氧化性成分及其活化剂的能力,由此使其在添加前变得更具化学活性。然而,如上所述,该循环过程中的洗涤温度仅达到28℃,这是因为虽然添加了少量60℃的水,但其他洗涤成分的环境温度使得总温度下降。注意,在Xeros Plus单剂量循环的洗涤循环过程中同时添加同样量的60℃热水,但不添加任何氧化性成分或活化剂(如表1所示,其在主洗涤开始时已经添加)。因而,在Xeros Plus单剂量循环中添加热水的目的是:确保全程的温度曲线与Xeros Plus多剂量情况的相同,达到相同的最终洗涤温度28℃。因此,这两种循环之间仅有的区别是添加洗涤剂的方式(即,在整个循环中多次供给成分VS在主洗涤开始时一次供给所有成分)。两种循环的总循环时间(包括主洗涤、粒珠分离和漂洗)相同,均为90分钟。二者均采用三次漂洗程序,并如表1所示,在Xeros Plus多剂量循环中,在最终漂洗时添加增白剂和增香剂。
采用颜色测试评价清洁水平。采用接口至个人电脑的Datacolor SpectraflashSF600分光光度计来测量WFK污渍监测器的反射率值:采用10°标准观测器,光源D65,包含UV分量且排除镜面反射分量;采用3cm观察孔。通过污渍监测器获得各处污渍的CIE L*色坐标,然后对各污渍类型取这些值的平均值。注意,较高的L*值表示清洁性更好。结果示于表2中。
表2.清洁结果
从表2中可以看出,Xeros Plus多剂量循环的清洁性大多优于Xeros Plus单剂量循环。在所测试的13种污渍类型中,Xeros Plus多剂量对10种污渍类型显示优异的清洁性,两种循环对1种污渍类型显示相等的清洁性,Xeros Plus单剂量仅对2种污渍类型显示优异的清洁性。
然后对污渍监测器基底材料的背景白度进行分析,也对污渍10D和20D的皮脂油去除进行分析以检查在整个可见光谱(400nm~700nm)中这些值的波长依赖性。低洗涤温度下的油脂去除是用高分子粒珠清洁的主要优势,特别是当其与这种多次成分供给方法组合进行洗涤时。采用上述同样的分光光度计设置,测量相对于可见光波长的反射率,从而确定色度值(K/S),并示于图1~3中。注意,在任何指定波长,较低的K/S值表示背景白度和清洁性较好。
从图1可以看出,使用Xeros Plus多剂量循环,污渍监测器的基底材料的背景白度得到改善。这是在最终漂洗中较晚添加增白剂的效果(参见表1)。关键的是,420nm~480nm范围的K/S值得以改善,因此使材料具有更蓝的色调(是可见光谱的蓝色端),并且使用者通常将此视为显著的性能改进。显然,这表明与单剂量相比,通过使用多次成分供给方式进行洗涤,还有降低增白剂水平的空间。还进行了目视评价测试,6个志愿者评价了该效果。为了避免偏差,覆盖了测试污渍监测器的所有编码,所有6个志愿者均指出当采用Xeros Plus多剂量循环洗涤时,污渍监测器的基底材料的背景白度更优异。
对于棉布(污渍10D)和聚酯/棉布底物(污渍20D),Xeros Plus多剂量循环对于皮脂/颜料的清洁性能(参见图2和图3)也均显示优异。该污渍特别令人感兴趣,因为此污渍的低温去除是洗衣应用的关键驱动因素,在低洗涤温度(如本文所用)去除污渍极为重要但非常困难。因此,这样的性能改进再次清楚地显示多次成分供给进行洗涤的益处。
最后,上述同一批6个志愿者进行感官测试以评价两种循环中所用的污渍监测器的清新度/香味。再次覆盖测试污渍监测器的所有编码以避免偏差,4个志愿者认为Xeros Plus多剂量循环在这些监测器中产生了更清新的气味;1个志愿者辨别不出任何差异;1个志愿者认为Xeros Plus单剂量产生更清新的气味。因此,在这里证据还是有力地支持了多次成分供给方式进行洗涤。
实施例2
使用与实施例1相同的洗涤条件来测试不同粒珠对于不同染料的性能。采用分光仪(如上)对结果进行评价。
实施例3
使用与实施例1相同的洗涤条件来测试不同粒珠对于不同染料的性能。还通过6个志愿者评价该效果来进行目视评价测试。
染料类别 | 染料编号 | 染料类型 | 织物 |
磺化染料 | 1 | 硫化黑 | 棉布 |
还原染料 | 3 | 还原绿 | 棉布 |
5 | 还原蓝 | 棉布 | |
直接染料 | 8 | 直接黄 | 棉布 |
反应性染料 | 16 | 反应性红A1 | 棉布 |
20 | 反应性黑,浅色 | 棉布 | |
21 | 反应性黑,深色 | 棉布 | |
22 | 反应性橙 | 棉布 | |
24 | 反应性蓝B2 | 棉布 | |
26 | 反应性紫 | 棉布 | |
27 | 普施安H-EXL三色混合物1 | 棉布 | |
29 | 雷马素三色混合物3 | 棉布 | |
分散性染料 | 33 | 分散深蓝混合物 | 聚酯 |
酸性染料 | 39 | 酸性红E | 聚酰胺 |
WM 40°C | Xeros Active 40 | |
染料1 | 3.9 | 4.4 |
染料8 | 2.4 | 2.6 |
染料39 | 1.5 | 1.6 |
Claims (10)
1.一种用于洗涤机的洗涤剂配送盒,其中,所述洗涤机用于清洁受污底物,包括用包含多种高分子颗粒的制剂处理润湿底物,其中所述制剂不含有机溶剂。
2.如权利要求1所述的配送盒,其中,所述高分子颗粒包括尼龙片,例如尼龙6或尼龙6.6。
3.如权利要求1或2所述的配送盒,其中,所述配送盒具有多个腔室。
4.如权利要求3所述的配送盒,其中,各个腔室均容纳预定的完整的洗涤剂制剂或者主要为洗涤剂制剂的单一活性成分的制剂。
5.如权利要求3或4所述的配送盒,其中,所述配送盒腔室是模块化的。
6.如权利要求3、4或5所述的配送盒,其中,各个腔室均可具有5cc~5000cc的体积。
7.如权利要求3~6中任一项所述的配送盒,其中,所述腔室内容物容纳在二级包装物中。
8.如权利要求3~6中任一项所述的配送盒,其中,所述腔室内容物能够再填充。
9.如权利要求1~8中任一项所述的配送盒,其中,所述配送盒包含塑料材料,例如聚丙烯、聚乙烯。
10.权利要求1~9中任一项所述的配送盒在用于清洁受污底物的自动洗涤机的洗涤操作中的应用,包括用包含多种高分子颗粒的制剂处理润湿底物,其中所述制剂不含有机溶剂。
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GBGB1006076.2A GB201006076D0 (en) | 2010-04-12 | 2010-04-12 | Novel cleaning apparatus and method |
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GBGB1010595.5A GB201010595D0 (en) | 2010-04-12 | 2010-06-24 | Product |
PCT/GB2011/050718 WO2011128676A1 (en) | 2010-04-12 | 2011-04-12 | Cleaning product |
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CN201180028478.XA Expired - Fee Related CN102933761B (zh) | 2010-04-12 | 2011-04-12 | 清洁产品 |
CN201180028781.XA Expired - Fee Related CN103003485B (zh) | 2010-04-12 | 2011-04-12 | 用聚合物颗粒清洁湿润的固体底物的方法 |
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