CN111218349A - 液体衣物洗涤剂 - Google Patents

液体衣物洗涤剂 Download PDF

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CN111218349A
CN111218349A CN201911113687.9A CN201911113687A CN111218349A CN 111218349 A CN111218349 A CN 111218349A CN 201911113687 A CN201911113687 A CN 201911113687A CN 111218349 A CN111218349 A CN 111218349A
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detergent
water
soluble
sodium
bicarbonate
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彼得曼·迪特尔
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Global Cosmed Group SA
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Abstract

本发明涉及适用于清洁纺织品的液体衣物洗涤剂组合物。除至少一种表面活性剂外，根据本发明的洗涤剂在水性介质中包含至少一种水溶性偏硅酸盐、至少一种水溶性碳酸氢盐、至少一种水溶性谷氨酸盐和至少一种聚合物流变改性剂。这些组分形成洗涤剂框架，与常规的液体洗涤剂相比，可以减少表面活性剂的量，这在经济、安全和环境方面是有利的，因为用以实现类似的洗涤/清洁性能所消耗的并随后丢弃到废水中的表面活性剂较少。

Description

液体衣物洗涤剂
技术领域
本发明涉及适用于清洁纺织品的液体衣物洗涤剂组合物。特别地，本发明涉及液体衣物洗涤剂的基本框架，其可转移至一系列液体衣物洗涤剂。与常规液体洗涤剂相比，通过配制这种基本框架，可以减少表面活性剂的量，以实现类似的洗涤/清洁性能，这在经济和环境方面都是有利的，因为减少了表面活性剂的消耗，随后将其丢弃到废水中。
背景技术
液体衣物洗涤剂通常含有一定量的表面活性剂组分，其与各种添加剂例如酶、荧光增白剂、膦酸盐/酯等结合使用，可实现良好的洗涤效果。下面的表1显示了不同类型的常规液体家用洗涤剂的示例性组成以及各个成分的参考。
表1：所选的常规液体家用洗涤剂的组成
Figure BDA0002273466180000011
上表中提供的所有信息仅应视为参考。各个市场产品的成分可能有所不同。
表1显示了各种洗涤剂配方的复杂性。除了表1中提到的成分外，例如阴离子表面活性剂、非离子表面活性剂和皂，根据洗涤剂的定位和用途，还可以使用以下物质：
·两性表面活性剂
·膦酸盐/酯、羧酸盐/酯
·去污聚合物
·荧光增白剂
·染料转移抑制剂
·酶–蛋白酶、淀粉酶、脂肪酶、甘露聚糖酶、果胶裂解酶、纤维素酶
·防腐剂
·其他染料、乳浊剂、香料等。
所用原材料的比例越高，其在废水中所占的比例越高，这与水污染直接相关。另外，总表面活性剂含量越高，皮肤和/或眼睛刺激或损害的风险越高和/或与液体洗涤剂接触的过敏反应的可能性越高。
使用脂肪酸或直链烷基苯磺酸作为酸对于许多洗涤剂来说是必不可少的，该脂肪酸或直链烷基苯磺酸通过浸出将其转化为皂或烷基苯磺酸盐，这是由于这些物质的性能非常好。皂有助于碱土离子的结合，而直链烷基苯磺酸盐显示出极好的去污力。根据洗涤剂的具体类型，这两种物质的含量会有所不同。皂以及直链烷基苯磺酸盐本身可以直接使用，或可以通过上述各种酸与碱性介质的反应而原位制备。由于这是放热反应，因此使用即用型表面活性剂进行的洗涤过程更安全，但也更昂贵。
US7304023公开了一种包含水溶性小袋和织物护理组合物的制品，其中第一隔室包括第一组分，第二隔室包括第二组分。第一组分包含阳离子织物柔软剂和非水性液体基质。第二组分包含去污表面活性剂。第一组分还可以包含选自以下至少一种的增稠剂：刺梧桐胶、黄蓍胶、瓜尔豆胶、刺槐豆胶、藻酸盐角叉菜胶、黄原胶或其组合。
US20180216038又公开了包含聚合物和表面活性剂的洗涤剂，其中所述洗涤剂包含10重量％至80重量％的烷氧基化烷基硫酸盐阴离子去污表面活性剂和0.5重量％至20重量％的流变改性剂，该流变改性剂选自非季铵化的烷氧基化聚乙烯亚胺(其中所述烷氧基化的聚亚烷基亚胺具有聚亚烷基亚胺核心，该亚烷基亚胺核心具有一个或多于一个烷氧基侧链，该侧链键合到该聚亚烷基亚胺核心中的至少一个氮原子上)、环氧乙烷-环氧丙烷-环氧乙烷(EOx1POyEOx2)三嵌段共聚物(其中x1和x2分别为约2至约140，并且y为约15至约70)、N,N,N′,N′-四(2-羟乙基)乙二胺、及其混合物。该洗涤剂的优点是高度浓缩。
US20030050218描述了用于处理纺织纤维制品的组合物的预配制的添加剂，该添加剂包括分散在基质中的呈纳米颗粒形式的颗粒状固体有机聚合物和在基质/聚合物界面处的表面活性剂。水溶性或水分散性碱金属或碱土金属硅酸盐、黄原胶和谷氨酸钠是可用于形成基质的化合物。根据US20030050218的添加剂可用于保护纺织品免于物理或化学降解和/或赋予它们诸如软化和抗皱性的优点。预配制的添加剂可用作洗涤剂配方、漂洗/软化配方、滚筒干燥机添加剂和纺织纤维制品洗涤添加剂中的护理剂。
发明内容
与当前市场上可获得的液体衣物洗涤剂相关的问题之一是由于表面活性剂的高含量而对环境产生不利影响，特别是产生水污染。与常规洗涤剂中相对较高的表面活性剂含量有关的另一个问题是对皮肤或眼睛的刺激以及潜在的过敏活性。因此，本发明的一个目的是开发一种在保持高质量和良好性能的同时显示出改善的生态特性的洗涤剂。本发明的另一个目的是提供一种对皮肤和眼睛刺激性较小并且具有较低过敏潜力的洗涤剂。
本发明基于在水性介质中的以下物质的组合：
(a)至少有一种表面活性剂，
(b)至少一种水溶性偏硅酸盐，至少一种水溶性碳酸氢盐和至少一种水溶性谷氨酸盐；和
(c)至少一种聚合物流变改性剂
其形成一种液体框架配方，该液体框架配方能够在液体衣物洗涤剂中提供比基于单独使用的每种起始原料的特性所预期的更好的洗涤效果。组分(b)和(c)的主要作用是在实现相同的清洁/洗涤性能的情况下所需的表面活性剂(a)少得多，从而可以减少由于在液体洗涤剂中使用表面活性剂而导致的所有上述负面影响。
因此，本发明涉及独立权利要求1中限定的组合物。优选的实施方案在从属权利要求中定义。
表面活性剂，例如阴离子表面活性剂，优选为式CH3(CH2)m(OCH2CH2)nOSO3Na，其中m＝11至14并且n＝2，更优选月桂基乙醚硫酸钠(SLES)负责初级清洁性能并且是洗涤剂的必需成分。然而，由于经济、安全和环境原因，通常在不显著降低洗涤剂的洗涤能力的情况下，尽可能地减少表面活性剂的含量。
水溶性碳酸氢盐，例如碳酸氢钠、碳酸氢钾和/或碳酸氢铵，有助于掩盖水的硬度，并且还有助于络合、脱脂和去除污渍。
在适当的pH条件下(优选弱碱性，例如7.5至8.8)，水溶性偏硅酸盐例如偏硅酸钠或偏硅酸钾有助于形成网状结构，从而积极影响污垢颗粒的分散，并为纤维提供保护，以防止彩色颜料脱离(易去污性)。
水溶性谷氨酸盐，如谷氨酸钠或谷氨酸钾，可提高清洁性能，并且由于其极性结构在离子络合中显示出协同作用。
聚合物流变改性剂，优选碳水化合物聚合物例如黄原胶、羧甲基纤维素或果胶，具有黏度调节性能并用于稳定体系。其还显示出分散效果，因此可以防止再次污染。
如果根据本发明的洗涤剂包含至少一种酶，则其通常还应当包含至少一种酶稳定剂，优选选自甲酸、水溶性甲酸盐、氯化钙、甘油和1,2-丙二醇。
如果根据本发明的洗涤剂被设计用于洗涤白色衣物，则其应优选包含荧光增白剂。反过来，如果打算将洗涤剂用于洗涤有色织物，则其应优选包含染料转移抑制剂。
优选地，根据本发明的洗涤剂含有柠檬酸三钠，因为其具有良好的乳化作用。
根据本发明的洗涤剂优选以包括以下步骤的方法制备：
(i)将至少一种聚合物流变改性剂添加至水中，优选添加至软化水中，并混合直至将其溶解；
(ii)加入至少一种水溶性偏硅酸盐、至少一种水溶性谷氨酸盐和至少一种水溶性碳酸氢盐，然后混合直至将它们溶解；
(iii)使混合物溶胀；
(iv)加入至少一种表面活性剂；
(v)将洗涤剂的pH调节到7.5至8.8。
尽管上述步骤(i)至步骤(v)的顺序被认为是最佳的，但是根据本发明的洗涤剂也可以以上述步骤的不同顺序来制备。
优选地，在步骤(ii)中，依次添加至少一种水溶性偏硅酸盐、至少一种水溶性谷氨酸盐和至少一种水溶性碳酸氢盐。
优选地，如果要使用酶，则在步骤(ii)中，在至少一种水溶性谷氨酸盐之后且在至少一种水溶性碳酸氢盐之前添加酶稳定剂，在步骤(v)之后在附加步骤(vi)中将酶加入洗涤剂中。
优选在步骤(iv)和(v)之间将另外的成分例如另外的表面活性剂和/或香料和/或乳浊剂和/或染料和/或螯合剂和/或防腐剂和/或稳定剂和/或荧光增白剂或染料转移抑制剂加入到混合物中。
在根据本发明的洗涤剂中，至少一种聚合物流变改性剂(例如黄原胶)、至少一种水溶性偏硅酸盐(例如偏硅酸钠)和至少一种水溶性谷氨酸盐(例如谷氨酸钠)形成复杂的大分子网状结构。不受任何具体理论的束缚，假定该大分子结构显示出表面活性。大分子结构是水溶性的，并且还结合钙离子和镁离子，从而降低了水的硬度。所得的网状结构对表面活性剂体系具有稳定作用，并在清洁过程中同时黏合灰尘和油脂颗粒。由于偏硅酸盐和谷氨酸盐的电荷性质，在网状结构内形成了伪分子离子活性复合物。
由于对表面活性剂体系的稳定作用以及网状结构结合污垢和脂肪颗粒的固有能力，与可商购获得的产品相比，达到足够/相似的性能的洗涤剂整体上所需的表面活性剂要少得多。由于显著的二次洗涤能力，取决于特定的应用，还可以减少或甚至完全省去所用的其他常规添加剂例如膦酸盐/酯或羧酸盐/酯的量。因此，根据本发明的洗涤剂显示出与常规洗涤剂相当的洗涤/清洁性能，而同时，由于降低了表面活性剂的含量，其更便宜并且对环境的危害较小。另外，使用相对低含量的表面活性剂使本发明的洗涤剂与市场上可买到的其他环保产品不同，后者含有大量的植物基表面活性剂，而其中某些产品表现出较差的性能。
由于洗涤剂的性能，它可以完全免用皂。在这种情况下，在制备过程中排除了与浓氢氧化钠或氢氧化钾溶液进行脂肪酸反应的放热反应步骤。
具体实施方式
实施例1a：通用衣物洗涤剂的制备(每一个洗涤周期的用量为75ml)
以下混合说明是指产品体积为1000ml。将2.87g的黄原胶添加到667.26g的软化水中，并剧烈混合约45分钟，直到其完全溶解。接下来，依次添加10.64g的五水合偏硅酸钠、2.66g的谷氨酸钠和31.91g的碳酸氢钠，并且在添加每种成分之后将混合物混合直至其完全溶解。接下来加入5.53g柠檬酸和0.085g甲酸并混合。将混合物静置15分钟而不进行混合以使其溶胀。接下来加入48.4g月桂基(聚氧乙烯)醚硫酸钠，并将混合物混合。此外，在该步骤中还可以将以下材料添加到混合物中：带支链和直链的乙氧基化的醇C13-15；甘油；二亚乙基三胺五亚甲基膦酸钠。产品变得黏稠。接下来，加入香料油、着色剂、防腐剂和荧光增白剂并混合，直到产品变得不黏为止。混合物的pH保持在7.5至8.8。接下来，添加酶并将混合物混合。最后，加入氯化钙和剩余的水，并将衣物洗涤剂混合20分钟。通用衣物洗涤剂中的成分含量及其功能列于表2。
表2：实施例1a的通用衣物洗涤剂的组成。
Figure BDA0002273466180000061
Figure BDA0002273466180000071
通用衣物洗涤剂(用量为75ml)的特点：
pH：7.5至8.8
干物质：15.5重量％至18重量％
实施例1b：通用衣物洗涤剂(用量为55ml)的制备
以下混合说明是指产品体积为1000ml。将3.23g的黄原胶添加到466g的软化水中，并剧烈混合约45分钟，直到其完全溶解。接下来，依次添加12.92g的五水合偏硅酸钠、2.69g的谷氨酸钠和16.15g的碳酸氢钠，并且在添加每种成分之后将混合物混合直至其完全溶解。接下来加入5.6g柠檬酸和0.085g甲酸并混合。将混合物静置15分钟而不进行混合以使其溶胀。接下来加入121.3g月桂基(聚氧乙烯)醚硫酸钠，并将混合物混合。此外，在该步骤中还可以将以下材料添加到混合物中：带支链和直链的乙氧基化的醇C13-15；甘油；二亚乙基三胺五亚甲基膦酸钠。产品变得黏稠。接下来，加入香料油、着色剂、柠檬酸钠、防腐剂和荧光增白剂并混合，直到产品变得不黏为止。混合物的pH保持在7.5至8.8。接下来，添加酶并将混合物混合。最后，加入氯化钙和剩余的水，并将衣物洗涤剂混合20分钟。通用衣物洗涤剂中的成分含量及其功能列于表2。
表3：实施例1b的通用衣物洗涤剂的组成。
Figure BDA0002273466180000081
通用衣物洗涤剂(用量为55ml)的特点：
pH：7.5至8.8
干物质：24.0重量％至27.0重量％
密度：1.050g/cm3至1.060g/cm3
实施例2：根据本发明的洗涤剂的生物降解性
将根据本发明(A)(根据实施例1b获得)的衣物洗涤剂的生物降解性与市售的四种商业衣物洗涤剂(B)-(E)的生物降解性进行了比较，以BOD5/COD(5天后的生化需氧量/化学需氧量)比进行测量(参见表4)。该比表示例如在废水处理装置中可以通过生物手段降解的组分的百分比。高BOD5/COD表示良好的生物降解性。
表4：生物降解性比较
Figure BDA0002273466180000091
*(根据DIN ISO 15705：2003-01(H45)
**(根据DIN EN 1899-1 H51(1998-05))
与现有技术的洗涤剂相比，BOD5和COD的商显示出根据本发明的洗涤剂的生态足迹显著降低。该商明显高于市场上其他产品的商。根据本发明的洗涤剂的改善的生态友好性能的另一个良好指示是洗涤周期的化学需氧量(根据标签上指示的用量)。表4表明，单次洗涤周期的化学需氧量约为市场上现有技术洗涤剂的该参数各自值的一半。因此，相对于每个单洗涤周期的剂量，在所计算的根据本发明的液体洗涤剂的情况下，显著减少了释放到废水中的可生物降解物质的量。总而言之，应当注意的是，与市售的其他测试产品(B)-(E)相比，本发明的洗涤剂(样品A)显示出最佳的生物降解性。

Claims (14)

1.一种在水性介质中包含至少一种表面活性剂的液体衣物洗涤剂，其特征在于它还包含至少一种水溶性偏硅酸盐、至少一种水溶性碳酸氢盐、至少一种水溶性谷氨酸盐和至少一种聚合物流变改性剂。
2.根据权利要求1所述的洗涤剂，其中所述表面活性剂是阴离子表面活性剂，优选式CH3(CH2)m(OCH2CH2)nOSO3Na的化合物，其中m＝11至14且n＝2，最优选月桂基乙醚硫酸钠(SLES)。
3.根据权利要求1或2所述的洗涤剂，其中所述水溶性偏硅酸盐是偏硅酸钠和/或偏硅酸钾。
4.根据权利要求1至3中任一项所述的洗涤剂，其中所述水溶性碳酸氢盐是碳酸氢钠、碳酸氢钾和/或碳酸氢铵。
5.根据权利要求1至4中任一项所述的洗涤剂，其中所述聚合物流变改性剂是碳水化合物聚合物，优选选自黄原胶、羧甲基纤维素和果胶。
6.根据权利要求1至5中任一项所述的洗涤剂，包含1重量％至25重量％的月桂基乙醚硫酸钠、0.1重量％至5.0重量％的偏硅酸钠、0.1重量％至10重量％的碳酸氢钠、0.01重量％至1重量％的谷氨酸钠和0.1重量％至0.8重量％的黄原胶。
7.根据权利要求6所述的洗涤剂，其中谷氨酸钠与碳酸氢钠的重量比为1:12至12:1。
8.根据权利要求6或7所述的洗涤剂，其中黄原胶与椰子脂肪醇的乙醚硫酸盐的重量比为1:15至1:40。
9.根据权利要求1至8中任一项所述的洗涤剂，其中所述洗涤剂的pH为7.5至8.8。
10.根据权利要求1至9中任一项所述的洗涤剂，还包含选自其他阴离子表面活性剂、非离子表面活性剂、两性表面活性剂、膦酸盐/酯、酶、乳化剂、乳浊剂、染料、络合剂、防腐剂、香料和稳定剂的至少一种添加剂。
11.根据权利要求1至10中任一项所述的洗涤剂，还包含荧光增白剂。
12.根据权利要求1至10中任一项所述的洗涤剂，还包含染料转移抑制剂。
13.根据权利要求10至12中任一项所述的洗涤剂，包含柠檬酸三钠。
14.根据权利要求10所述的洗涤剂，包含至少一种酶和至少一种酶稳定剂，优选选自甲酸、水溶性甲酸盐、氯化钙、甘油和1,2-丙二醇。
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