CN109072136A - 包含脂肪酸脱羧酶的洗涤剂组合物 - Google Patents
包含脂肪酸脱羧酶的洗涤剂组合物 Download PDFInfo
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- CN109072136A CN109072136A CN201780025267.8A CN201780025267A CN109072136A CN 109072136 A CN109072136 A CN 109072136A CN 201780025267 A CN201780025267 A CN 201780025267A CN 109072136 A CN109072136 A CN 109072136A
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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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
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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
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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
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- C11D3/16—Organic compounds
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- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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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- C11D3/364—Organic compounds containing phosphorus containing nitrogen
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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
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- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
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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
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- C11D3/38681—Chemically modified or immobilised enzymes
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Abstract
本发明公开了一种洗涤剂组合物,优选手动盘碟洗涤剂组合物以及包括表面活性剂体系和脂肪酸脱羧酶的洗涤方法。
Description
序列表的引用
本申请包含计算机可读形式的序列表。所述计算机可读形式以引用方式并入本文。
技术领域
本发明涉及一种包含表面活性剂体系和脂肪酸脱羧酶的洗涤剂组合物。优选地,该组合物用于衣物洗涤或盘碟洗涤过程,并且可特别用于手动洗涤过程,即用于手洗或在非全自动洗衣机中洗涤,例如半自动洗衣机(例如双浴缸等)。优选地,该组合物是盘碟洗涤剂组合物。优选的组合物是液体形式。
背景技术
洗涤剂组合物应具有良好的起泡特征,同时提供良好的污垢和油脂清洁。使用者通常将泡沫视为洗涤剂组合物性能的指标。此外,洗涤剂组合物的使用者还可使用起泡特征和泡沫的外观(密度、白度)作为洗涤溶液仍含有活性洗涤剂成分的指示剂。对于手动洗涤尤其如此,在本文中也称为手洗,其中使用者通常根据剩余的肥皂泡沫按剂量施用洗涤剂组合物并且当肥皂泡沫/泡沫消退时或当泡沫看起来不足够厚时更新洗涤溶液。因此,洗涤剂组合物,特别是产生很少或低密度泡沫的手动洗涤剂组合物往往会被使用者比所需的更频繁地更换。
因此,希望洗涤剂组合物在洗涤剂与水的初始混合期间和整个洗涤操作期间提供良好的清洁以及良好的泡沫高度和密度以及良好的泡沫持续时间。当在手动洗涤过程中使用时,该组合物优选还提供令人愉快的洗涤体验,即在洗涤过程中对使用者的手感觉良好。优选洗涤剂组合物也易于冲洗。此外,该组合物优选为洗涤过的物品提供良好的光洁度。
已经发现,某些类型的污垢,特别是油脂污垢,起到泡沫抑制剂的作用,因为它们从脏污制品中移入洗涤液体中,引发消费者比所需的更频繁地更换产品。因此,需要提供具有所需泡沫和清洁性能的洗涤剂组合物,特别是随着时间的推移,油脂污垢从脏污的制品中除去。典型的油性/油脂污垢包括烹饪油,例如,植物油如棕榈仁油、椰子油和橄榄油,以及动物污垢如动物脂肪和体垢如皮脂。
发明内容
根据本发明,提供了一种包含脂肪酸脱羧酶和表面活性剂体系的洗涤剂组合物。
优选地,洗涤剂组合物是手动洗涤组合物。优选地,洗涤剂组合物用于手动盘碟洗涤。优选地,洗涤剂组合物包含衣物洗涤组合物,其可特别优选用于洗涤精细织物。组合物可为颗粒或液体或它们的组合。优选的组合物是液体形式,可选地以小袋形式的水溶性膜包封,优选多隔室小袋,任选地在至少一个隔室中具有颗粒组合物。
本发明还提供一种洗涤脏污制品的方法,包括形成包含表面活性剂体系和脂肪酸脱羧酶的洗涤液体,使制品与洗涤液体接触,并且任选地漂洗和干燥。
本发明还提供一种洗涤脏污制品的方法,包括使脏污制品直接与组合物接触,任选地使用清洁装置,然后使脏污制品和洗涤剂组合物与水接触以进一步清洁和/或漂洗。
本发明的组合物提供良好的清洁和良好的起泡特征,特别是在油脂污垢存在下。已发现本发明的组合物特别适用于在洗涤液体中积聚的脂肪酸。这些可存在于污垢中或在去除污垢的过程中释放到洗涤液体中,其中污垢分解产生脂肪酸。
根据本发明,提供了一种手动洗涤的方法,包括以下步骤:将洗涤剂组合物递送至一定体积的水中,并且将脏制品浸入水中。当根据该方法使用本发明的组合物时,实现了优异的起泡特征,具有持久的效果。
根据本发明,提供了一种手动洗涤的方法,包括以下步骤:将本发明的洗涤剂组合物直接递送至脏污制品上或者清洁工具上,并且使用清洁工具清洁脏污制品。优选地,清洁工具是海绵,更优选地,海绵是湿的。
优选地,手动洗涤是盘碟洗涤,并且脏污制品包括脏污的盘碟。如本文所用,“盘碟”包括炊具和餐具。
具体实施方式
定义
如本文所用,当用于权利要求中时,冠词“一个”和“一种”被理解为是指受权利要求书保护或描述的一种或多种。
如本文所用,术语“基本上不含”是指按组合物的重量计,所指示的物质以不超过约5重量%,优选不超过约2%,并且更优选不超过约1重量%的量存在。
如本文所用,术语“基本不含”是指按组合物的重量计,所指示的物质以不超过约0.1重量%的量存在,或优选地不以分析上可检测的水平存在于此组合物中。其可包括这样的组合物,其中所指示的物质仅作为有意加入此类组合物中的一种或多种物质的杂质。
如本文所用,短语“清洁组合物”、“洗涤剂组合物”或“洗涤剂或清洁组合物”可在本文互换使用以指被设计用于清洁脏污制品的组合物和制剂。此类组合物包括但不限于盘碟洗涤组合物、衣物洗涤剂组合物、织物软化组合物、织物增强组合物、织物清新组合物、衣物洗涤预洗剂、衣物洗涤预处理剂、衣物洗涤添加剂、喷雾产品、干洗剂或组合物、衣物洗涤冲洗添加剂、洗涤添加剂、后冲洗织物处理剂、熨烫助剂、餐具洗涤组合物、硬质表面清洁组合物、单位剂量制剂、延迟递送制剂、在多孔基底或非织造片材上或之内包含的洗涤剂、以及根据本文的教导内容对本领域技术人员显而易见的其它合适的形式。此类组合物可被用作清洁预处理剂、清洁后处理剂,或也可在清洁过程的漂洗循环或洗涤循环期间添加。清洁组合物可具有选自下列的形式:液体、粉末、单相或多相单位剂量或小袋形式、片剂、凝胶、糊剂、棒或薄片。在本发明的一个优选的实施方案中,本发明的清洁组合物包含衣物洗涤剂或盘碟洗涤剂组合物,其为由单隔室或多隔室的水溶性小袋中包封的单相或多相单位剂型,该小袋例如由水溶性聚合物诸如聚乙烯醇(PVA)或其共聚物形成。优选地,组合物用于手动洗涤。优选地,本发明的清洁组合物为盘碟洗涤剂。优选地,组合物为液体形式。
如本文所用,术语“衣物洗涤剂”是指液体或固体组合物,并且除非另外指明,其包括颗粒或粉末形式的多用途或“重垢型”洗涤剂,尤其是清洁洗涤剂以及清洁辅剂诸如漂白添加剂或预处理类型。在本发明的一个优选实施方案中,衣物洗涤剂为液体衣物洗涤剂组合物。优选地,组合物用于手动洗涤。优选地,清洁组合物为衣物洗涤剂组合物,优选用于清洁纤细的织物。
如本文所用,术语“增加的肥皂泡沫寿命”是指与不存在脂肪酸脱羧酶的相同组合物和方法提供的肥皂泡沫寿命相比,在洗涤过程中使用包含脂肪脱羧酶的组合物清洁脏污制品在可见的肥皂泡沫的持续时间的增加。
如本文所用,术语“脏污制品”非特定地指任何类型的由天然纤维或人造纤维的网络构成的柔性材料,包括天然纤维、人造纤维和合成纤维,诸如但不限于棉、亚麻布、羊毛、聚酯、尼龙、丝绸、丙烯酸类等、以及各种共混物和组合。脏污制品还可指任何类型的硬质表面,包括天然表面、人造表面或合成表面,诸如但不限于砖材、花岗石、灰浆、玻璃、复合材料、乙烯树脂、硬木、金属、烹饪表面、塑料等、以及共混物和组合,以及盘碟。
如本文所用,术语“水硬度”或“硬度”是指存在于水中的未络合阳离子(即,Ca2+或Mg2+),这些阳离子在碱性条件下可能发生沉淀,从而削弱表面活性剂的表面活性和清洁能力。另外,术语“高水硬度”或“提升的水硬度”可互换使用,并且出于本发明的目的,是相关术语,并且旨在包括但不限于包含至少12克钙离子每加仑水(gpg,“美国格令硬度”单位)的硬度水平。
脂肪酸脱羧酶
脂肪酸脱羧酶优选以基于活性蛋白质的重量计0.00001重量%至2重量%的量存在于组合物中。更优选地,脂肪酸脱羧酶可以0.0001重量%至1重量%,更优选0.0005重量%至0.5重量%的量存在。
术语“脂肪酸脱羧酶”或“具有脂肪酸脱羧酶活性的多肽”是指能够催化消除脂肪酸的羧基的酶。出于本发明的目的,脂肪酸脱羧酶活性由如方案1所示能够催化任何C10-20饱和的、单不饱和的或多不饱和的脂肪酸转化成其相应的末端烯烃的酶或酶/辅因子/共底物系统定义。
方案1
合适的酶可在细胞色素P450家族中发现,尽管只有非常小的细胞色素P450酶子集显示出这种活性。一个示例是Jeotgalicoccus sp.8456的OleTJE酶内源性的及其变体。OleTJE与一系列长链脂肪酸强烈结合,并使用过氧化氢作为共底物从各种饱和脂肪酸产生末端烯烃。OleTJE的氨基酸序列是SEQ ID NO:1。其性质描述于J.Belcher等人,J.BiolChem.(2014),289,10:6535-6550。具有融合结构域的酶的变体能够在附加辅因子存在下使用分子氧作为共底物,如Y.Liu等人,Biotechnol.Biofuels(2014)7:28中所述。OleTJE是细胞色素P450家族CYP152的成员,被归类为CYP152L1。相关细胞色素P450酶可表现出与野生型形式的OleTJE一致的显着脱羧酶活性,而其它如CYP152A1和CYP152B1被描述为更有效地催化脂肪酸的β羟基化,尽管已经证明蛋白质工程将这些酶转化为更有效的脂肪酸脱羧酶,例如通过在CYP152A1中进行Gln85His取代。用于本文的优选的脂肪酸脱羧酶与SEQ ID NO:1具有至少40%的同一性,优选至少50%、或60%、或65%、或70%、或75%、或80%、或85%、或90%、或95%、或96%、或97%、或98%、或99%、或100%的同一性。
其它合适的酶是非血红素铁氧化酶,例如对于假单胞菌属(Pseudomonas sp.)内源的UndA酶,如Z.Rui等人,PNAS,(2014),111,18237–18242中所述。这是TENA/THI-4蛋白家族的成员。UndA的氨基酸序列在SEQ ID NO:2中给出。用于本文的优选的脂肪酸脱羧酶与SEQ ID NO:2具有至少40%的同一性,优选至少50%、或60%、或65%、或70%、或75%、或80%、或85%、或90%、或95%、或96%、或97%、或98%、或99%、或100%的同一性。
优选的脂肪酸脱羧酶对具有10至20个碳原子的不饱和脂肪酸,特别是油酸具有活性。
脂肪酸脱羧酶可通过添加剂颗粒(例如酶颗粒)或以包封物的形式掺入洗涤剂组合物中,或者可以液体制剂的形式加入。
合适的酶颗粒包括:(i)喷雾干燥的颗粒,(ii)分层颗粒,其中酶作为预先形成的惰性芯周围的层被涂覆,并且流化床装置用于从含有涂层材料的水溶液中粘附涂层材料层;(iii)将酶吸收到芯中的颗粒,(iv)挤出或造粒的酶颗粒,其中将含酶糊状物压成颗粒或在压力下通过孔挤出并在干燥之前切成颗粒;(v)将酶粉悬浮在熔融蜡中并将悬浮液喷入冷却室(例如通过旋转盘式雾化器)的颗粒状产品,(vi)通过将含酶液体加入到包含常规制粒材料的干粉组合物中的方法制备的附聚酶颗粒,所述制粒材料可包括例如任选与长丝如纤维素纤维或聚合长丝如聚乙烯吡咯烷酮或聚乙烯醇长丝混合的填料和粘合剂,以提供额外的强度并减少粉尘。
特别是当清洁组合物包含液体时,优选可通过包封物掺入酶。包封酶促进了酶在组合物中的稳定性,并有助于抵消组合物中存在的任何不利化合物例如漂白剂、蛋白酶、表面活性剂、螯合剂等的影响。
当处于包封物形式时,酶通常被包封在聚合物材料中。包封酶的方法是,例如,通过喷雾干燥含有酶和聚合物的液体组合物,或通过干燥含有酶和聚合物的液体组合物,或通过任选地在酶存在下的乳液聚合、共同消化、沉淀或界面聚合,任选地随后进行干燥和/或尺寸减小过程。用于包封酶的合适聚合物包括任选改性的:聚乙烯醇,聚乙烯吡咯烷酮,羧甲基纤维素,瓜尔胶,多羧酸,甲基纤维素,羟丙基甲基纤维素,蛋白质,多支链多胺如聚乙烯亚胺(PEI),(疏水改性的)多糖,选自由其构成的组的纤维素聚合物,以及它们的混合物和衍生物或共聚物。改性纤维素聚合物的示例包括上述那些和除此之外的邻苯二甲酸羟丙基甲基纤维素、邻苯二甲酸乙酸纤维素,改性树胶的示例包括改性瓜尔胶、苯甲酸胶、黄蓍胶、阿拉伯树胶和阿拉伯树胶。改性的蛋白质的示例是改性的酪蛋白、明胶和白蛋白。改性聚合物的示例可选自至少一种疏水乙烯基单体与至少一种亲水乙烯基单体的共聚物。合适的亲水乙烯基单体是乙烯基吡咯烷酮。合适的疏水乙烯基单体是丙烯酸C1-C18烷基酯、甲基丙烯酸C1-C18烷基酯、丙烯酸C3-C18环烷基酯、甲基丙烯酸C3-C18环烷基酯和链烷酸乙烯基C1-C18以及它们的混合物。聚合物可包含选自具有C-C-主链的均聚物和共聚物的聚合物,其中C-C-主链带有羧基,其可以酸性形式或以中和形式存在,并且其中C-C-主链包含基于聚合物的总重量计(即基于聚合物P中重复单元的总重量计)至少20重量%,例如20重量%至98重量%的疏水性重复单元。聚合物可包括支化,例如由乙烯基吡咯烷酮和乙酸乙烯酯形成的支化共聚物基质颗粒。聚合物可包含共聚物,例如WO2010/003934中所述,基于马来酸或(甲基)丙烯酸。聚合物可以是交联的。
优选的聚合物的分子量为1000道尔顿至500,000道尔顿,或2000道尔顿至200000道尔顿重均。通常,酶与聚合物的重量比为1:50至10:1。
根据方法1,可选择聚合物基本上可溶于离子强度为0mol/kg的水溶液中并且不溶于离子强度大于1mol/kg的水溶液中,例如WO2008/084093中所述,例如,其中聚合物包含基于聚合物的总重量计35%w/w至95%w/w的亲水性单体单元。
疏水改性的聚乙烯醇或疏水改性的聚乙烯吡咯烷酮可以是优选的,任选地具有高水解水平,大于60%,或甚至大于80%或90%。合适的疏水改性基团包括酮-酯和/或丁酰基以及它们的混合物,优选总取代度(DS)为约3%至20%。
当存在于添加剂颗粒中时,脂肪酸脱羧酶可以是添加剂颗粒中的唯一酶,或者可与一种或多种附加酶组合存在于添加剂颗粒中。
合适的附加酶包括蛋白酶,如金属蛋白酶或碱性丝氨酸蛋白酶,如枯草杆菌蛋白酶,淀粉酶,脂肪酶,纤维素酶,甘露聚糖酶,果胶酶,DNA酶,氧化还原酶,过氧化物酶,脂肪酶,磷脂酶,纤维二糖水解酶,纤维二糖脱氢酶,酯酶,角质酶,果胶酶,果胶酸裂解酶,角蛋白酶,还原酶,氧化酶,酚氧化酶,脂氧合酶,木质素酶,支链淀粉酶,鞣酸酶,戊聚糖酶,葡聚糖酶,阿拉伯糖苷酶,透明质酸酶,软骨素酶,漆酶,淀粉酶,油酸水合酶,以及它们的混合物。在一个优选的实施方案中,脂肪酸脱羧酶可与淀粉酶、纤维素酶、蛋白酶和/或脂肪酶,优选脂肪酶或蛋白酶组合掺入添加剂颗粒中。另外掺入油酸水合酶也是优选的。
表面活性剂体系
洗涤剂通常包含按重量计约1%至约60%,优选约5%至约50%,更优选约8%至约45%的表面活性剂体系。表面活性剂体系包含一种或多种选自由下列构成的组的表面活性剂:阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性(amphoteric)表面活性剂、两性离子(zwitterionic)表面活性剂、以及它们的混合物。优选地,表面活性剂包括选自由下列构成的组的阴离子表面活性剂:烷基苯磺酸盐、烷氧基化的烷基硫酸盐、烷基硫酸盐、以及它们的混合物。
用于提供食物清洁和良好起泡特征的优选表面活性剂体系包含i)阴离子表面活性剂;和ii)两性表面活性剂和/或两性离子表面活性剂。优选地,阴离子表面活性剂与两性表面活性剂和/或两性离子表面活性剂的重量比小于9:1,更优选小于5:1至约1:2,更优选约4:1至约1:1,并且尤其为约4:1至约2:1。
适用于本文的示例性可用的表面活性剂体系包括包含阴离子表面活性剂并且还包含除此之外的氧化胺和/或甜菜碱表面活性剂的那些。氧化胺表面活性剂是尤其优选的。优选地,表面活性剂体系包含选自烷基硫酸盐、烷基烷氧基硫酸盐,尤其是烷基乙氧基硫酸盐以及它们的混合物的阴离子表面活性剂,与氧化胺组合,最优选重量%比率为小于9:1,更优选小于5:1至约1:2,更优选约4:1至约1:1,尤其是约4:1至约2:1。
用于本文的另一种优选的表面活性剂体系包括阴离子和两性/两性离子体系,其中两性与两性离子的重量比优选为约2:1至约1:2。特别是其中两性表面活性剂包括氧化胺表面活性剂且两性离子表面活性剂包括甜菜碱的体系。氧化胺与甜菜碱的优选比例为1.5:1至1:1.5,优选1.2:1至1:1.2,最优选约1:1。
还优选用于本文的是包含非离子表面活性剂的表面活性剂体系。用于本发明组合物的特别优选的表面活性剂体系包括阴离子表面活性剂,优选选自由下列构成的组:烷基硫酸盐、烷基烷氧基硫酸盐以及它们的混合物,更优选烷氧基化硫酸盐。优选的表面活性剂体系另外包含两性表面活性剂,优选氧化胺表面活性剂。优选的表面活性剂体系包括非离子表面活性剂。总之,用于本文的最优选的表面活性剂体系包括烷氧基化硫酸盐表面活性剂、氧化胺和非离子表面活性剂。最优选地,非离子表面活性剂是烷氧基化醇表面活性剂,尤其是乙氧基化醇表面活性剂。
阴离子表面活性剂
阴离子表面活性剂包括但不限于那些含有在其分子结构中通常含有8至22个碳原子或通常含有8至18个碳原子的有机疏水基团和至少一个优选选自磺酸盐、硫酸盐的水溶性基团以形成水溶性化合物的表面活性化合物。通常,疏水基团包含C8-C22烷基和/或酰基。这些表面活性剂以水溶性盐的形式使用,并且成盐阳离子通常选自钠、钾、铵、镁和单-、二-或三-C2-C3链烷醇铵,其中钠阳离子是通常选择的。
优选表面活性剂体系包含阴离子表面活性剂或其混合物。阴离子表面活性剂包括任何阴离子清洁表面活性剂,优选选自阴离子硫酸盐或磺酸盐表面活性剂或它们的混合物。
优选地,阴离子表面活性剂是烷氧基化的烷基硫酸盐表面活性剂,优选乙氧基化的烷基硫酸盐表面活性剂,优选具有约0.2至约3,更优选约0.3至约2,甚至更优选约0.4至约1.5,尤其是约0.4至约1的平均乙氧基化度。当阴离子表面活性剂是表面活性剂的混合物时,烷氧基化度是混合物的所有组分的重均烷氧基化度(重均烷氧基化度)。在重均烷氧基化度计算中,还应包括不具有烷氧基化基团的阴离子表面活性剂组分的重量。
重均烷氧基化度=(x1*表面活性剂1的烷氧基化度+x2*表面活性剂2的烷氧基化度+……)/(x1+x2+……)其中x1、x2、……是混合物中每种阴离子表面活性剂的重量(以克为单位),并且烷氧基化度是每种阴离子表面活性剂中烷氧基的数目。
还优选的是通常具有2重量%至60重量%的重均支化度的支化阴离子表面活性剂,特别是具有约5重量%至40重量%的重均支化度的那些。
优选地,用于本发明的洗涤剂中的阴离子表面活性剂包括支化阴离子表面活性剂,其支化度为约5%至约40%,优选约10%至约35%,并且更优选约20%至约30%。优选地,支化基团是烷基。通常,烷基选自甲基、乙基、丙基、丁基、戊基、环状烷基以及它们的混合物。在用于制备本发明洗涤剂中使用的阴离子表面活性剂的起始醇的主烃基链上可存在单个或多个烷基支链。最优选地,支化阴离子表面活性剂选自烷基硫酸盐、烷基乙氧基硫酸盐、以及它们的混合物。
支化阴离子表面活性剂可以是单一阴离子表面活性剂或阴离子表面活性剂的混合物。在单一表面活性剂的情况下,支化百分比是指在衍生表面活性剂的原始醇中支化的烃基链的重量百分比。
在表面活性剂混合物的情况下,支化百分比是重均分子量,并且根据下式定义:
支化的重均分子量(%)=[(x1*在醇1中的支链醇1的重量%+x2*在醇2中的支链醇2的重量%+……)/(x1+x2+……)]*100
其中x1、x2、……是在用作本发明洗涤剂的阴离子表面活性剂的原料的醇的总醇混合物中每种醇的重量(以克为单位)。在重均支化度计算中,还应包括不具有支链基团的阴离子表面活性剂组分的重量。
表面活性剂体系优选包含按表面活性剂体系重量计至少50%,更优选至少60%,并且优选至少70%的支化阴离子表面活性剂。在特别优选的表面活性剂体系中,支化阴离子表面活性剂包含大于50%重量的具有约0.1至5或0.2至约3的乙氧基化度并且优选约5%至约40%的支化度的烷基乙氧基化硫酸盐。
优选地,支化阴离子表面活性剂包含按支化阴离子表面活性剂的重量计至少50%,更优选至少60%,并且尤其至少70%硫酸盐表面活性剂。从清洁观点来看特别优选的洗涤剂是其中支化阴离子表面活性剂包含按重量计大于50%,更优选至少60%,并且特别是至少70%的硫酸盐表面活性剂并且硫酸盐表面活性剂选自由烷基硫酸盐、烷基乙氧基硫酸盐以及它们的混合物构成的组的那些。甚至更优选的是其中当阴离子表面活性剂具有约10%至约35%,更优选约20%至30%的支化度时支化阴离子表面活性剂具有约0.2至约3,更优选约0.3至约2,甚至更优选约0.4至约1.5,并且尤其是约0.4至约1,甚至更优选的乙氧基化度的那些。
硫酸盐表面活性剂
表面活性剂优选包含阴离子硫酸盐表面活性剂。选自由硫酸烷基酯、烷基烷氧基硫酸盐和它们的混合物构成的组的阴离子硫酸盐表面活性剂可以是特别优选的,特别是用于盘碟组合物。
尤其优选的是烷氧基化阴离子表面活性剂,更优选烷基烷氧基硫酸盐表面活性剂。用于本文的优选烷基烷氧基磺酸盐为烷基乙氧基硫酸盐。适用于本文的合适的硫酸盐表面活性剂包括C8-C18烷基或羟烷基硫酸盐和/或醚硫酸盐的水溶性盐。合适的抗衡离子包括碱金属阳离子或铵或取代的铵,但优选钠。
硫酸盐表面活性剂可选自C8-C18伯支链和无规烷基硫酸盐(AS);C8-C18仲(2,3)烷基硫酸盐;C8-C18烷基烷氧基硫酸盐(AExS),其中优选x为1-30,其中烷氧基可选自乙氧基、丙氧基、丁氧基或甚至更高级的烷氧基以及它们的混合物。烷氧基化阴离子表面活性剂通常具有约0.1至11,或者0.1至7,优选约0.2至约4,甚至更优选约0.3至约3,甚至更优选约0.4至约1.5,并且尤其是约0.4或0.2至约1的平均烷氧基化度。优选地,烷氧基是乙氧基。
烷基硫酸盐和烷基烷氧基硫酸盐可商购获得,具有各种链长、乙氧基化和支化度。可商购的硫酸盐包括那些基于Shell公司的Neodol醇,来自Sasol公司的Lial-Isalchem和Safol,以及Procter&Gamble Chemicals公司的天然醇。
优选地,表面活性剂体系包含烷基硫酸盐和/或烷基乙氧基硫酸盐;更优选烷基硫酸盐和/或烷基乙氧基硫酸盐的组合,其总组合平均乙氧基化度小于5,优选小于3,更优选小于2且大于0.5。优选地,阴离子表面活性剂具有约5%至约40%的平均支化水平。
磺酸盐表面活性剂
适用于本文的磺酸盐表面活性剂包括C8-C18烷基或羟烷基磺酸盐的水溶性盐;C11-C18烷基苯磺酸盐(LAS),改性烷基苯磺酸盐(MLAS);甲酯磺酸盐(MES);和α-烯烃磺酸盐(AOS)。那些还包括链烷磺酸盐,可以是单磺酸盐和/或二磺酸盐,其通过磺化10至20个碳原子的链烷烃得到。磺酸盐表面活性剂还包括烷基甘油基磺酸盐表面活性剂。具体地,对于衣物洗涤剂,阴离子表面活性剂优选包含至少40%或更优选至少50%或至少60%或甚至至少80%或90%的磺酸盐表面活性剂。
脂肪酸
高级脂肪酸的水溶性盐,即“皂”,也可以是本发明清洁组合物中有用的阴离子表面活性剂,特别是用于衣物洗涤剂。然而,优选地本发明的清洁组合物包含相对低含量的皂,例如不大于约3重量%,更优选地不大于约2重量%或1重量%,并且最优选地所述清洁组合物基本上不含皂。在加入脂肪酸时,它们优选包含非常低含量的油酸。组合物中的油酸含量优选低于0.5重量%,更优选低于0.3重量%,更优选低于0.2重量%或甚至低于0.1重量%的组合物,最优选基本上不含油酸。然而,可容纳更高含量,可能需要存在附加酶以抵消由其存在引起的竞争。当掺入油酸时,也可优选掺入酶稳定剂。诸如通过包封的物理稳定可能是特别优选的。
非离子表面活性剂
当存在时,非离子表面活性剂通常以按组合物的重量计0.05%至30%,优选0.1%至20%,最优选0.5%至10%,或者0.5%至7%,或者甚至0.5%至3%的量存在。非离子表面活性剂优选以表面活性剂体系的1重量%至60重量%的量存在于表面活性剂体系中,特别是对于衣物洗涤剂,优选为基于表面活性剂体系计2重量%至60重量%,或5重量%至55重量%。合适的非离子表面活性剂包括脂族醇与1摩尔至25摩尔环氧乙烷的缩合产物。脂族醇的烷基链可为直链或支链、伯烷基或仲烷基,并通常含有8至22个碳原子。尤其优选的是具有具有10至18个碳原子,优选地10至15个碳原子的烷基的醇与每摩尔醇2摩尔至18摩尔,优选地2摩尔至15摩尔,更优选5摩尔至12摩尔的环氧乙烷的缩合产物。高度优选的非离子表面活性剂是Guerbet醇与2摩尔至18摩尔,优选2摩尔至15摩尔,更优选5摩尔至12摩尔环氧乙烷/摩尔醇的缩合产物。
然而,在本发明的某些优选的实施方案中,尤其对于盘碟洗涤,清洁组合物包含相对低含量的非离子表面活性剂,例如不大于约3重量%,更优选地不大于约2重量%或1重量%,并且最优选地所述清洁组合物基本上不含非离子表面活性剂。
可用于本文的其它表面活性剂包括两性表面活性剂、两性离子表面活性剂和阳离子表面活性剂。此类表面活性剂通常以约0.2重量%、0.5重量%或1重量%至约10重量%、20重量%或30重量%的含量存在。优选地,本发明的组合物还将包含两性表面活性剂和/或两性离子表面活性剂,更优选氧化胺和/或甜菜碱表面活性剂,最优选氧化胺。
在本发明的一个优选但并非必须的实施方案中,清洁组合物为液体餐具洗涤剂组合物,其包含约0.5重量%至约20重量%的一种或多种两性表面活性剂和/或两性离子表面活性剂,优选地氧化胺。
两性表面活性剂
优选的两性表面活性剂选自由下列构成的组:例如氧化胺表面活性剂,诸如烷基二甲基氧化胺或烷基酰胺基丙基二甲基氧化胺,更优选地烷基二甲基氧化胺并且特别为椰油二甲基氧化胺。氧化胺可具有直链的或中间支化的烷基部分。典型的直链氧化胺包括水溶性氧化胺,水溶性氧化胺包含一个R1C8-18烷基部分和选自由C1-3烷基和C1-3羟烷基构成的组的两个R2和R3部分。优选氧化胺的特征在于式R1–N(R2)(R3)O,其中R1是C8-18烷基,并且R2和R3选自由甲基、乙基、丙基、异丙基、2-羟基乙基、2-羟丙基和3-羟丙基构成的组。具体地,直链氧化胺表面活性剂可包括直链的C10-C18烷基二甲基氧化胺和直链的C8-C12烷氧基乙基二羟基乙基氧化胺。优选的氧化胺包括直链的C10、直链的C10-C12和直链的C12-C14烷基二甲基氧化胺。本文所使用的“中间支化的”是指氧化胺具有一个含n1个碳原子的烷基部分,在该烷基部分上具有一个含n2个碳原子的烷基支链。该烷基支链位于烷基部分上氮原子的α碳原子。这种类型分枝的氧化胺在本领域作为内氧化胺也是已知的。n1和n2的总和为10至24个,优选12至20个,并且更优选10至16个碳原子。一个烷基部分的碳原子数(n1)应近似为相同的一个烷基支链的碳原子数(n2),使得一个烷基部分和一个烷基支链是对称的。本文所用的“对称的”是指在至少50重量%,更优选至少75重量%至100重量%的可用于本文的中度支化的氧化胺中|n1–n2|小于或等于5,优选4,更优选0至4个碳原子。氧化胺还包含两个部分,其独立地选自C1-3烷基、C1-3羟烷基或聚环氧乙烷基团(平均包含约1至约3个环氧乙烷基团)。优选地两个部分选自C1-3烷基,更优选两者选自C1烷基。最优选地,氧化胺为烷基二甲基氧化胺,尤其是C10-C18烷基二甲基氧化胺。
两性离子表面活性剂
其它合适的表面活性剂包括甜菜碱,诸如烷基甜菜碱、烷基酰胺基甜菜碱、咪唑啉盐甜菜碱、磺基甜菜碱(也称为INCI磺基甜菜碱)以及磷酸甜菜碱。优选的甜菜碱符合化学式I:
R1-[CO-X(CH2)n]x-N+(R2)(R3)-(CH2)m-[CH(OH)-CH2]y-Y-(I),其中
R1为饱和或不饱和的C6-22烷基残基,优选地C8-18烷基残基,具体地为饱和的C10-16烷基残基,例如饱和的C12-14烷基残基;
X为NH、具有C1-4烷基残基R4的NR4、O或S,
n为1至10,优选为2至5,具体地3的数,
x为0或1,优选1,
R2、R3独立地为C1-4烷基残基,可能是羟基取代的,如羟乙基,优选甲基。
m为1至4,具体地1、2或3的数,
y为0或1,并且
Y为COO、SO3、OPO(OR5)O或P(O)(OR5)O,其中R5为氢原子H或C1-4烷基残基。
优选的甜菜碱为式(Ia)的烷基甜菜碱、式(Ib)的烷基酰胺丙基甜菜碱、式(Ic)的磺基甜菜碱和式(Id)的酰胺基磺基甜菜碱;
R1-N+(CH3)2-CH2COO-(Ia)
R1-CO-NH(CH2)3-N+(CH3)2-CH2COO-(Ib)
R1-N+(CH3)2-CH2CH(OH)CH2SO3-(Ic)
R1-CO-NH-(CH2)3-N+(CH3)2-CH2CH(OH)CH2SO3-(Id),其中R11与式I中的含义相同。特别优选的甜菜碱是碳酰甜菜碱[其中Y-=COO-],特别是式(Ia)和(Ib)的碳酰甜菜碱,更优选的是式(Ib)的烷基酰胺基甜菜碱。
合适的甜菜碱和磺基甜菜碱的示例是以下的[根据INCI命名的]:杏仁酰胺基丙基甜菜碱、杏酰胺基丙基甜菜碱、鳄梨酰胺基丙基甜菜碱、巴巴苏酰胺丙基甜菜碱的、山嵛甜菜碱、山嵛基甜菜碱、甜菜碱、中间酰胺丙基甜菜碱、辛醇/辛基酰胺丙基甜菜碱、肉碱、鲸蜡醇甜菜碱、椰油酰胺乙基甜菜碱、椰油酰胺丙基甜菜碱、椰油酰胺丙基羟基磺、椰油甜菜碱、椰油羟基磺、椰油/油酸酰胺丙基甜菜碱、椰油磺基甜菜碱、癸基甜菜碱、二羟基乙基油基甘氨酸、二羟基乙基大豆甘氨酸盐、二羟基乙基硬脂基甘氨酸盐、二羟基乙基牛油脂甘氨酸盐、PG-甜菜碱的聚二甲基硅氧烷丙基、芥酸酰胺丙基羟基磺甜菜碱、氢化牛油甜菜碱、异硬脂酸酰胺丙基甜菜碱、月桂酰胺丙基甜菜碱、月桂基甜菜碱、月桂基羟基磺基、月桂基磺基甜菜碱、乳酰胺丙基甜菜碱、水貂酰胺基丙基甜菜碱、肉豆蔻酰胺丙基甜菜碱、肉豆蔻基甜菜碱、油酸酰胺丙基甜菜碱、油酸酰胺丙基羟基磺、油基甜菜碱、橄榄酰胺丙基甜菜碱、棕榈酰胺丙基甜菜碱、棕榈酰胺基丙基甜菜碱、棕榈酰肉碱、棕榈仁异丙基甜菜碱、聚四氟乙烯乙酰氧基甜菜碱、蓖麻油酰胺丙基甜菜碱、芝麻油酰胺丙基甜菜碱,大豆酰胺丙基甜菜碱、硬脂酰胺丙基甜菜碱、硬脂基甜菜碱、牛油酰胺丙基甜菜碱、牛油酰胺丙基羟基磺基甜菜碱、牛油甜菜碱、牛油二羟乙基甜菜碱、十一烯酸酯酰胺丙基甜菜碱和小麦胚芽酰胺丙基甜菜碱。优选的甜菜碱为例如椰油酰胺基丙基甜菜碱。
尤其用于本发明的盘碟洗涤剂组合物的最优选的表面活性剂体系包含:(i)按组合物的总重量计1重量%至40重量%,优选地6重量%至32重量%,更优选8重量%至25重量%的阴离子表面活性剂,优选地包含烷氧基化硫酸盐表面活性剂;(ii)按组合物的重量计0.01重量%至20重量%,优选0.2重量%至15重量%,更优选0.5重量%至10重量%的两性和/或两性离子和/或非离子表面活性剂。优选的组合物包含按组合物的重量计0.01重量%至20重量%的两性表面活性剂和非离子表面活性剂,最优选其中两性表面活性剂包括氧化胺表面活性剂。已经发现,这种表面活性剂体系与脂肪酸脱羧酶组合将提供洗涤洗涤剂所需的优异清洁,同时具有非常好的起泡特征,特别是在油脂污垢和油脂污垢分解产物的存在下,并且提供洗涤物品的良好表面。
酶稳定剂
优选地,本发明的组合物包含酶稳定剂。合适的酶稳定剂可选自由下列构成的组:(a)优选选自由下列构成的组的单价、二价和/或三价阳离子:碱土金属、碱金属、铝、铁、铜和锌的无机或有机盐,优选碱金属和碱土金属,优选碱金属和碱土金属盐与卤化物、硫酸盐、亚硫酸盐、碳酸盐、碳酸氢盐、硝酸盐、亚硝酸盐、磷酸盐、甲酸盐、乙酸盐、丙酸盐、柠檬酸盐、马来酸盐、酒石酸盐、琥珀酸盐、草酸盐、乳酸盐、以及它们的混合物。在优选的实施方案中,盐选自由下列构成的组:氯化钠、氯化钙、氯化钾、硫酸钠、硫酸钾、乙酸钠、乙酸钾、甲酸钠、甲酸钾、乳酸钙、硝酸钙以及它们的混合物。最优选的是选自由下列构成的组的盐:氯化钙、氯化钾、硫酸钾、乙酸钠、乙酸钾、甲酸钠、甲酸钾、乳酸钙、硝酸钙以及它们的混合物,特别是选自由下列构成的组的钾盐:氯化钾、硫酸钾、乙酸钾、甲酸钾、丙酸钾、乳酸钾以及它们的混合物。最优选的是乙酸钾和氯化钾。优选的钙盐是甲酸钙、乳酸钙和硝酸钙,包括硝酸钙四水合物。可优选甲酸钙和甲酸钠盐。这些阳离子以按组合物的总重量计至少约0.01重量%,优选至少约0.03重量%,更优选至少约0.05重量%,最优选至少约0.25重量%,至多约2重量%或甚至至多约1重量%的量存在。这些盐配制为相对于组合物的总重量的约0.1重量%至约5重量%,优选约0.2重量%至约4重量%,更优选约0.3重量%至约3重量%,最优选约0.5重量%至约2重量%。其它酶稳定剂可选自由下列构成的组:(b)选自由低聚糖、多糖以及它们的混合物构成的组的碳水化合物,诸如单糖甘油酸酯;(c)高效可逆蛋白酶抑制剂,高效可逆蛋白酶抑制剂选自由下列构成的组:苯基硼酸以及它们的衍生物,优选4-甲酰基苯基硼酸;(d)醇类,如1,2-丙烷二醇、丙二醇;(e)肽醛稳定剂,如三肽醛,如Cbz-Gly-Ala-Tyr-H,或二取代的丙氨酰胺;(f)羧酸,苯基烷基二羧酸或在苄基的至少两个碳原子上包含羧基的多取代苄基羧酸,邻苯二甲酰谷氨酰胺酸,邻苯二甲酰基天冬酰胺酸,氨基邻苯二甲酸和/或低聚氨基-联苯-低聚羧酸;以及;(g)它们的混合物。合适的混合物的示例包括:(1)可逆蛋白酶抑制剂,如含硼化合物;(2)1-2丙二醇;(3)甲酸钙和/或甲酸钠;以及(4)它们的任意组合。
如果本发明的清洁组合物以粉末形式提供,则其还可特别优选包含低含量助洗剂或甚至基本上不含助洗剂的粉末。术语“基本上不含”是指组合物“不含刻意加入的”量的该种成分。在一个优选的实施方案中,本发明的清洁组合物不含助洗剂。
过氧化氢源
组合物优选包含过氧化氢源。过氧化氢源包括例如无机过氧化氢合物盐,包括碱金属盐诸如过硼酸钠盐(通常为一水合物或四水合物)、过碳酸钠盐、过硫酸钠盐、过磷酸钠盐、过硅酸钠盐以及它们的混合物。在本发明的一个方面,无机过氧化氢合物盐选自由下列构成的组:过硼酸钠盐、过碳酸钠盐以及它们的混合物。过碳酸盐是优选的。当使用无机过氧化氢合物盐时,无机过氧化氢合物盐通常以总的织物和家居护理产品的0.05重量%至40重量%、或1重量%至30重量%的量存在,并且通常以可被包覆的结晶固体形式被掺入到此类织物和家居护理产品中。合适的涂层包括:无机盐诸如碱金属硅酸盐、碳酸盐或硼酸盐或它们的混合物,或有机材料诸如水溶性或水分散性聚合物、蜡、油或脂肪皂。这些可与漂白活化剂和/或漂白催化剂组合存在。
合适的漂白活化剂是具有R-(C=O)-L的那些,其中R为烷基,任选支化的烷基,当漂白活化剂疏水时,其具有6至14个碳原子,或8至12个碳原子,并且当漂白活化剂亲水时,其具有小于6个碳原子,或甚至小于4个碳原子;并且L为离去基团。合适的离去基团的示例为苯甲酸及其衍生物-尤其是苯磺酸盐。合适的漂白活性剂包括十二烷酰基羟基苯磺酸盐、癸酰基羟基苯磺酸盐、癸酰基羟苯甲酸或其盐、3,5,5-三甲基己酰基羟基苯磺酸盐、四乙酰基乙二胺(TAED)和壬酰羟苯磺酸盐(NOBS)。虽然可采用任何合适的漂白活性剂,但如果主题组合物包含NOBS、TAED或它们的混合物,则可能是优选的。
合适的漂白催化剂包括一种或多种能够接纳来自过氧酸和/或其盐的氧原子,并且将氧原子传递至可氧化基质。合适的漂白催化剂包括但不限于:亚胺鎓阳离子和聚离子;亚胺鎓两性离子;改性的胺;改性的氧化胺;N-磺酰基亚胺;N-膦酰基亚胺;N-酰基亚胺;噻二唑二氧化物;全氟亚胺;环状糖酮和α-氨基酮、以及它们的混合物。
合适的漂白催化剂包括过氧亚胺正离子的漂白催化剂、过渡金属漂白催化剂,尤其是锰和铁离子漂白催化剂。合适的漂白催化剂具有符合下列通式的结构:
其中R13选自由下列构成的组:2-乙基己基、2-丙基庚基、2-丁基辛基、2-戊基壬基、2-己基癸基、正十二烷基、正十四烷基、正十六烷基、正十八烷基、异壬基、异癸基、异十三烷基和异十五烷基。
另一种合适的过氧化氢源包括预先形成的过酸。合适的预成型过酸包括但不限于选自由下列构成的组的化合物:预成型过氧酸或其盐,通常为过羧酸及其盐、过碳酸及其盐、过亚胺酸及其盐、过一硫酸及其盐(例如),以及它们的混合物。合适的示例包括过氧羧酸或其盐,或过氧磺酸或其盐。适用于本文的典型过氧羧酸盐具有对应于下列化学式的化学结构:
其中:R14选自烷基、芳烷基、环烷基、芳基或杂环基;R14基团可以是直链或支化的,取代或未取代的;当过酸为疏水性时,具有6至14个碳原子,或8至12个碳原子,并且当过酸为亲水性时,具有小于6个碳原子,或甚至小于4个碳原子,并且Y为获得电中性的任何适宜的抗衡离子,Y优选选自氢、钠或钾。R14优选为直链或支化的,取代或未取代的C6-9烷基。优选地,过氧酸或其盐选自过氧己酸、过氧庚酸、过氧辛酸、过氧壬酸、过氧癸酸、它们的任何盐,或它们的任意组合。尤其优选的过氧酸为苯二甲酰亚氨基过氧链烷酸,特别是ε-苯二甲酰亚氨基过氧己酸(PAP)。过氧酸或其盐优选具有30℃至60℃范围内的熔点。
预成形的过氧酸或其盐也可为过氧磺酸或其盐,通常具有对应于下列化学式的化学结构:
其中:R15选自烷基、芳烷基、环烷基、芳基或杂环基;R15基团可以是直链或支化的,取代或未取代的;并且Z为获得电中性的任何合适的抗衡离子,优选地,Z选自氢、钠或钾。R15优选为直链或支化的,取代或未取代的C4-14,优选C6-14烷基。优选地,此类漂白剂组分可以0.01至50%,最优选0.1%至20%的量存在于本发明的组合物中。
也可通过掺入碳水化合物氧化酶来提供过氧化氢。这将在洗涤过程中与来自污垢或也存在于组合物中的基质的碳水化合物原位反应,以产生过氧化氢。由于这将倾向于产生低含量的过氧化氢,因此这可能是优选的。
附加酶
合适的附加酶包括蛋白酶,如金属蛋白酶或碱性丝氨酸蛋白酶,如枯草杆菌蛋白酶,淀粉酶,脂肪酶,纤维素酶,甘露聚糖酶,果胶酶,DNA酶,氧化还原酶,过氧化物酶,脂肪酶,磷脂酶,纤维二糖水解酶,纤维二糖脱氢酶,酯酶,角质酶,果胶酶,果胶酸裂解酶,角蛋白酶,还原酶,氧化酶,酚氧化酶,脂氧合酶,木质素酶,支链淀粉酶,鞣酸酶,戊聚糖酶,葡聚糖酶,阿拉伯糖苷酶,透明质酸酶,软骨素酶,漆酶,淀粉酶,油酸水合酶,以及它们的混合物。
本发明的优选组合物包含一种或多种选自脂肪酶、蛋白酶、纤维素酶、淀粉酶以及它们的任意组合的酶。
每种附加酶通常以0.0001重量%至1重量%(活性蛋白质的重量),更优选0.0005重量%至0.5重量%,最优选0.005重量%至0.1重量%的量存在。特别优选的是,本发明的组合物另外包含脂肪酶。脂肪酶将脂肪酯污垢分解成脂肪酸,然后脂肪酸被脂肪酸脱羧酶作用于泡沫中性或泡沫促进剂。合适的脂肪酶包括细菌、真菌或合成来源、以及它们的变体的那些。化学改性的或蛋白质工程化的突变体也是适宜的。适宜的脂肪酶的示例包括来自腐质霉属(Humicola)(同义词嗜热霉属(Thermomyces)),如来自柔毛腐质霉(H.lanuginosa)(疏棉状嗜热丝孢菌(T.lanuginosus))的脂肪酶。
所述脂肪酶可为“第一循环脂肪酶”,如,诸如描述于WO06/090335和WO13/116261中的那些。在一个方面,所述脂肪酶为第一洗涤脂肪酶,优选为来自包含T231R和/或N233R突变的疏棉状嗜热丝孢菌的野生型脂肪酶的变体。优选的脂肪酶包括以商品名和由Novozymes(Bagsvaerd,Denmark)出售的那些。
其它合适的脂肪酶包括:Lipr1 139和TfuLip2。
特别优选的是,本发明的组合物另外包含蛋白酶。由于油酸和其它泡沫抑制脂肪酸存在于体垢甚至人体皮肤中,因为蛋白酶用作皮肤护理剂或分解蛋白质污垢,释放的脂肪酸因此被脂肪酸脱羧酶分解,从而防止泡沫相应地抑制。适宜的蛋白酶包括金属蛋白酶和丝氨酸蛋白酶。合适的中性或碱性蛋白酶的示例包括:枯草杆菌蛋白酶(EC 3.4.21.62);胰蛋白酶型或胰凝乳蛋白酶型蛋白酶;和金属蛋白酶。合适的蛋白酶包括前述合适蛋白酶的经化学修饰或基因修饰的突变体。
合适的可商购获得的蛋白酶包括以商品名 LiquanaseSavinase和由Novozymes A/S(Denmark)出售的那些;以商品名 Preferenz系列蛋白酶,包括P280、P281、P2018-C、P2081-WE、P2082-EE和P2083-A/J、PurafectPurafect和Purafect由DuPont出售的那些;以商品名和由Solvay Enzymes出售的那些;得自Henkel/Kemira的那些即BLAP(序列示于US 5,352,604的图29中,具有下列突变S99D+S101R+S103A+V104I+G159S,下文称为BLAP);均得自Henkel/Kemira的BLAP R(具有S3T+V4I+V199M+V205I+L217D的BLAP)、BLAP X(具有S3T+V4I+V205I的BLAP)和BLAP F49(具有S3T+V4I+A194P+V199M+V205I+L217D的BLAP);以及得自Kao的KAP(具有突变A230V+S256G+S259N的嗜碱芽孢杆菌枯草杆菌蛋白酶)。
特别优选的是,本发明的组合物另外包含淀粉酶。由于油性污垢通常被捕获在淀粉质污垢中,淀粉酶和脂肪酸脱羧酶协同作用:通过用淀粉酶分解淀粉质酶来释放脂肪酸污垢,因此,脂肪酸脱羧酶特别有效地确保不会对洗涤液体中的肥皂泡沫产生负面影响。优选的淀粉酶衍生自内源于芽孢杆菌属DSM 12649的AA560α淀粉酶,优选具有下列突变:R118K、D183*、G184*、N195F、R320K和/或R458K。适宜的可商购获得的淀粉酶包括Plus、Natalase、Ultra、SZ、(均得自Novozymes)和AA,Preferenz系列淀粉酶,和Ox Am,HT Plus(均得自Du Pont)。合适的淀粉酶描述于WO06/002643中。
特别优选的是,本发明的组合物另外包含纤维素酶。合适的纤维素酶包括细菌源或真菌源的那些。化学改性的或蛋白质工程化的突变型也是适宜的。适宜的纤维素酶包括来自芽孢杆菌属(Bacillus)、假单胞菌属(Pseudomonas)、腐质霉属(Humicola)、镰孢属(Fusarium)、草根霉属(Thielavia)、枝顶孢霉属(Acremonium)的纤维素酶,例如由特异腐质霉(Humicola insolens)、嗜热毁丝菌(Myceliophthora thermophila)和尖孢镰孢菌(Fusarium oxysporum)产生的真菌纤维素酶。
可商购获得的纤维素酶包括和Premium,和(Novozymes A/S)、系列酶(Du Pont),和系列酶(AB Enzymes)。适宜的可商购获得的纤维素酶包括Premium、Classic。
特别优选的是,本发明的组合物另外包含油酸水合酶。合适的油酸水合酶可选自EC分类号1.11.2.3(植物种子过氧化酶),1.13.11.77(油酸10S脂氧合酶),3.1.2.14(油酰基-[酰基-载体-蛋白质]水解酶,3.5.1.99(脂肪酸酰胺水解酶),4.2.1.53(油酸水合酶)以及它们的混合物。必要时,该组合物包含,提供进入或原位形成酶的有效功能所必需的任何附加基底:用于植物种子过氧化酶的氢过氧化物;油酸10S脂氧合酶;油酰[酰基载体蛋白质]水解酶的硫醇;用于脂肪酸水解酶的氨或胺;用于油酸水合酶的水。优选地,油酸转化酶是来自EC 4.2.1.53的油酸水合酶。合适的油酸水合酶包括表1中列出的野生型油酸水合酶以及它们的表现出油酸水合酶活性的变体。
表1
螯合剂
本文洗涤剂组合物通常包含按组合物的总重量计0.1%至20%,优选0.2%至5%,更优选0.2%至3%的螯合剂。
如洗涤剂领域中通常理解的,本文的螯合是指双齿或多齿配体的结合或络合。这些配体通常是有机化合物,称为螯合剂、螯合物、螯合试剂和/或多价螯合剂。螯合剂与单一金属离子形成多个键。螯合剂是与某些金属离子形成可溶性络合分子的化学物质,使离子失活,使得它们不能与其它元素或离子发生正常反应,产生沉淀物或结垢,或在污垢上形成结壳,使其更难被除去。配体与底物形成螯合络合物。该术语保留用于其中金属离子与螯合剂的两个或更多个原子结合的络合物。
合适的螯合剂可选自由下列构成的组:氨基羧酸盐、氨基膦酸盐、多羧酸盐螯合剂以及它们的混合物。
用于本文的优选螯合剂是基于氨基酸的螯合剂,优选谷氨酸-N,N-二乙酸(GLDA)、甲基甘氨酸-N,N-二乙酸(MGDA)和衍生物,和/或基于膦酸盐的螯合剂,并且优选二亚乙基三胺五甲基膦酸或羟乙基二膦酸。根据本发明,GLDA(其盐和衍生物)是特别优选的,其中特别优选其四钠盐。
其它螯合剂包括多元羧酸的均聚物和共聚物以及它们的部分或完全中和的盐、单体多元羧酸和羟基羧酸以及它们的盐。合适的多元羧酸是无环、脂环、杂环和芳族羧酸,在这种情况下它们含有至少两个羧基,它们在每种情况下通过优选不多于两个碳原子彼此分开。合适的羟基羧酸是例如柠檬酸。另一种合适的多元羧酸是丙烯酸的均聚物。优选的是用磺酸盐封端的聚羧酸盐。
溶剂
当清洁组合物为液体洗涤剂组合物特别是衣物洗涤剂或液体盘碟洗涤剂形式时,还可包含一种或多种有机溶剂,其可以按组合物的总重量计约1重量%至约80重量%,优选5重量%至约70重量%,更优选约10重量%至约60重量%,甚至更优选约15重量%至约50重量%,并且最优选约20重量%至约45重量%的量存在。优选地,组合物包含清洁溶剂,尤其是当组合物是盘碟洗涤组合物时。
清洁溶剂
本发明的液体组合物可包含油脂清洁溶剂或它们的混合物作为高度优选的任选成分。合适的溶剂选自由下列构成的组:具有4至14个碳原子,优选6至12个碳原子,并且更优选8至10个碳原子的醚和二醚;二醇或烷氧基化二醇;烷氧基化芳族醇;芳族醇;烷氧基化脂族醇;脂族醇;C8-C14烷基和环烷基烃和卤代烃;C6-C16乙二醇醚;链烷醇胺;萜烯以及它们的混合物。通常,本文的液体组合物可包含按组合物的总重量计至多30%,优选1%至25%,更优选1%至20%,并且最优选2%至10%的所述溶剂或它们的混合物。
因为相分离对于液体洗涤剂组合物是一个持续的挑战,特别是当此类组合物中的盐含量高时,本发明的溶剂体系被特别设计成使相分离的风险最小化。具体地,本发明的溶剂体系主要由二醇构成,诸如乙二醇、二乙二醇、丙二醇、二丙二醇、丁二醇、戊二醇以及它们的组合。二醇以约2重量%至约50重量%范围内的总量存在于本发明的液体洗涤剂组合物中。优选地,组合物包含总量在约5重量%至约40重量%范围内的乙二醇、二乙二醇和/或丙二醇。更优选地,组合物包含约15重量%至约35重量%范围内的丙二醇。也可存在其他有机溶剂,其包括但不限于:甲醇、乙醇、甘油、异丙基苯磺酸钠、异丙基苯磺酸钾、异丙基苯磺酸铵、甲苯磺酸钠、甲苯磺酸钾、二甲苯磺酸钠、二甲苯磺酸钾、二甲苯磺酸铵或它们的混合物。还可使用其它低级醇,诸如C1-C4链烷醇胺例如单乙醇胺和/或三乙醇胺。在本发明的一个特别优选的实施方案中,除二醇之外,本发明的液体洗涤剂组合物还包含约5重量%至约20重量%,优选6重量%至18重量%,更优选8重量%至16重量%的甘油。
本发明的液体洗涤剂组合物优选地包含水,水作为载体与上述有机溶剂组合。在一些实施方案中,水以约20重量%至约90重量%,优选地约25重量%至80重量%,并且更优选地约30重量%至约70重量%范围内的量存在于本发明的液体洗涤剂组合物中。在其它实施方案中,组合物不含水并且是无水的。本发明提供的高度优选的组合物是澄清的各向同性液体。
如本文所述的液体洗涤剂组合物还可包含外部结构剂,外部结构剂可以按组合物的总重量计在约0.001%至约1.0%、优选地约0.05%至约0.5%、更优选地约0.1%至约0.3%的范围内的量存在。用于实施本发明的特别优选的外部结构剂选自氢化蓖麻油,其也称为三羟基硬脂酸甘油酯,并且可以商品名商购获得,和任选改性的天然纤维如柑橘纤维。
本发明的清洁组合物的余量通常包含约5重量%至约70重量%,或约10重量%至约60重量%的助剂成分。
适用于衣物洗涤剂产品的助剂成分包括:助洗剂、螯合剂、染料转移抑制剂、分散剂、流变改性剂、催化物质、漂白活性剂、过氧化氢、过氧化氢源、预成形的过酸、聚合物分散剂、粘土污垢去除/抗再沉积剂、增白剂、抑泡剂、染料、光漂白剂、结构增弹剂、织物软化剂、载体、水溶助长剂、加工助剂、溶剂、调色剂、抗菌剂、游离香料油、辛辣剂、厌恶剂、催吐剂、苦味剂和/或颜料。这些助剂成分的明确性质以及它们在液体衣物洗涤剂组合物中的含量将取决于因素如组合物的具体类型以及它将被使用的清洁操作的性质。
用于餐具洗涤剂产品的合适助剂成分包括:助洗剂、螯合剂、调理聚合物、清洁聚合物、表面改性聚合物、污垢絮凝聚合物、结构剂、润肤剂、湿润剂、皮肤更新活性物质、羧酸、擦洗粒子、漂白剂和漂白活性剂、香料、恶臭控制剂、颜料、染料、遮光剂、小珠、珠光颗粒、微胶囊、有机和无机阳离子诸如碱土金属诸如Ca/Mg-离子和二胺、抗菌剂、防腐剂和pH调节剂以及缓冲装置。
当组合物包含固体自由流动的颗粒洗涤剂组合物时,优选包含完全配制的衣物洗涤剂组合物,而不是其一部分,例如仅形成衣物洗涤剂组合物的一部分的喷雾干燥的、挤出的或附聚颗粒。通常,固体组合物包含多个化学上不同的颗粒,如喷雾干燥的基础洗涤剂颗粒和/或附聚物的基础洗涤剂颗粒和/或基础的基础洗涤剂颗粒;组合了一个或多个、通常两个或更多个、或五个或更多个、或甚至十个或更多个颗粒,颗粒选自:表面活性剂颗粒,包括表面活性剂附聚物、表面活性剂挤出物、表面活性剂针状物、表面活性剂面状物、表面活性剂片状物;磷酸盐颗粒;沸石颗粒;硅酸盐颗粒,尤其是硅酸钠颗粒;碳酸盐颗粒,尤其是碳酸钠颗粒;聚合物颗粒,如羧酸盐聚合物颗粒、纤维素聚合物颗粒、淀粉颗粒、聚酯颗粒、聚胺颗粒、对苯二甲酸聚合物颗粒、聚乙二醇颗粒;美观颗粒,如有色面条粒、针状物、层状颗粒和环颗粒;酶颗粒,如蛋白酶颗粒、淀粉酶颗粒、脂肪酶颗粒、纤维素酶颗粒、甘露聚糖酶颗粒、果胶酸裂解酶颗粒、木葡聚糖酶颗粒、漂白酶颗粒和任何这些酶的共颗粒,优选这些酶颗粒包含硫酸钠;漂白剂颗粒,如过碳酸盐颗粒,尤其是涂覆的过碳酸盐颗粒,如涂覆有碳酸盐、硫酸盐、硅酸盐、硼硅酸盐或任意组合的过碳酸盐,过硼酸盐颗粒,漂白活化剂颗粒如四乙酰基乙二胺颗粒和/或烷基氧基苯磺酸盐颗粒,漂白催化剂颗粒如过渡金属催化剂颗粒,和/或异喹啉鎓漂白催化剂颗粒,预成形过酸颗粒,尤其是涂覆的预成形过酸颗粒;填料颗粒,如硫酸盐颗粒和氯化物颗粒;粘土颗粒,如蒙脱石颗粒和粘土与有机硅颗粒;絮凝剂颗粒,如聚环氧乙烷颗粒;蜡颗粒,如蜡质附聚物;有机硅颗粒,增白剂颗粒;染料转移抑制剂颗粒;染料固定剂颗粒;香料颗粒,如香料微胶囊和淀粉包封的香料谐香剂颗粒,以及前香料颗粒,如席夫碱反应产物颗粒;调色染料颗粒;螯合剂颗粒,如附聚螯合剂;以及它们的任意组合。
聚合物
羧酸盐聚合物:组合物可包含羧酸酯聚合物,诸如马来酸酯/丙烯酸酯无规共聚物或聚丙烯酸酯均聚物。合适的羧酸盐聚合物包括:分子量为4,000Da至9,000Da的聚丙烯酸酯均聚物;分子量为50,000Da至100,000Da,或60,000Da至80,000Da的马来酸酯/丙烯酸酯无规共聚物。
另一种合适的羧酸盐聚合物是共聚物,其包含:(i)50重量%至少于98重量%的衍生自一种或多种包含羧基的单体的结构单元;(ii)1重量%至小于49重量%的衍生自一种或多种包含磺酸根部分的单体的结构单元;和(iii)1至49重量%的结构单元,所述结构单元衍生自一类或多类单体,所述单体选自由式(I)和(II)表示的包含醚键的单体:
式(I):
其中在式(I)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0-5,前提条件是当R为单键时X表示数字1-5,并且R1为氢原子或C1至C20有机基团;
式(II)
其中在式(II)中,R0表示氢原子或CH3基团,R表示CH2基团、CH2CH2基团或单键,X表示数字0-5,并且R1为氢原子或C1至C20有机基团。
可以优选的是,聚合物具有至少50kDa或甚至至少70kDa的重均分子量。
去垢性聚合物:
所述组合物可包含去垢性聚合物。合适的去垢性聚合物具有如由下列结构(I)、(II)、或(III)之一定义的结构:
(I)-[(OCHR1-CHR2)a-O-OC-Ar-CO-]d
(II)-[(OCHR3-CHR4)b-O-OC-sAr-CO-]e
(III)-[(OCHR5-CHR6)c-OR7]f
其中:
a、b和c为1至200;
d、e和f为1至50;
Ar为1,4-取代的亚苯基;
sAr为在5位被SO3Me取代的1,3-取代的亚苯基;
Me为Li、K、Mg/2、Ca/2、Al/3、铵、单烷基铵、二烷基铵、三烷基铵或四烷基铵,其中烷基基团为C1-C18烷基或C2-C10羟烷基、或它们的混合物;
R1、R2、R3、R4、R5和R6独立地选自H或C1-C18正烷基或异烷基;并且
R7为直链或支链的C1-C18烷基,或者直链或支链的C2-C30烯基,或者具有5至9个碳原子的环烷基基团,或者C8-C30芳基基团,或者C6-C30芳烷基基团。
适宜的去垢性聚合物由Clariant以系列聚合物出售,如,SRN240和SRA300。其它适宜的去垢性聚合物由Solvay以Repel-o-系列聚合物出售,如Repel-o-SF2和Repel-o-Crystal。
抗再沉积聚合物:合适的抗再沉积聚合物包括聚乙二醇聚合物和/或聚乙烯亚胺聚合物。
合适的聚乙二醇聚合物包括无规接枝共聚物,无规接枝共聚物包含:(i)包含聚乙二醇的亲水性主链;以及(ii)选自由下列构成的组的疏水侧链:C4-C25烷基基团、聚亚丙基、聚亚丁基、饱和C1-C6一元羧酸的乙烯基酯、丙烯酸或甲基丙烯酸的C1-C6烷基酯,以及它们的混合物。合适的聚乙二醇聚合物具有聚乙二醇主链,该聚乙二醇主链带有无规接枝的聚乙酸乙烯酯侧链。聚乙二醇主链的平均分子量可在2,000Da至20,000Da,或4,000Da至8,000Da的范围内。聚乙二醇主链与聚乙酸乙烯酯侧链的分子量比率可为1:1至1:5,或1:1.2至1:2。每个亚乙基氧单元的平均接枝位点数可小于1,或小于0.8,每个亚乙基氧单元的平均接枝位点数可在0.5至0.9的范围内,或者每个亚乙基氧单元的平均接枝位点数可在0.1至0.5、或0.2至0.4的范围内。合适的聚乙二醇聚合物为Sokalan HP22。
纤维素聚合物:合适的纤维素聚合物选自烷基纤维素、烷基烷氧基烷基纤维素、羧基烷基纤维素、烷基羧基烷基纤维素、磺酸基烷基纤维素,更优选选自羧甲基纤维素、甲基纤维素、甲基羟乙基纤维素、甲基羧甲基纤维素以及它们的混合物。
适宜的羧甲基纤维素具有0.5至0.9的羧甲基取代度和100,000Da至300,000Da的分子量。
合适的羧甲基纤维素具有大于0.65的取代度和大于0.45的嵌段度。
护理聚合物:合适的护理聚合物包括阳离子改性或疏水改性的纤维素聚合物。此类改性的纤维素聚合物在洗涤循环期间可向织物提供抗磨蚀有益效果和染料锁定有益效果。适宜的纤维素聚合物包括阳离子改性的羟乙基纤维素。
其它合适的护理聚合物包括染料锁定聚合物,例如通过咪唑和表氯醇,优选以1:4:1比率缩合产生的缩合低聚物。适宜的可商购获得的染料锁定聚合物为FDI(Cognis)。
其它合适的护理聚合物包括氨基硅氧烷,其可提供织物触感有益效果和织物成形保持有益效果。
漂白剂:合适的漂白剂包括过氧化氢源、漂白活化剂、漂白催化剂、预形成的过酸以及它们的任意组合。尤其适宜的漂白剂包括过氧化氢源与漂白活化剂和/或漂白催化剂的组合。
增白剂:合适的荧光增白剂包括:二苯乙烯基联苯化合物,例如CBS-X,二氨基均二苯代乙烯二磺酸化合物,例如DMS pure Xtra和HRH,以及吡唑啉化合物,例如SN和香豆素化合物,例如SWN。
优选的增白剂为:2(4-苯乙烯基-3-磺苯基)-2H-萘酚[1,2-d]三唑钠、4,4'-双{[(4-苯氨基-6-(N甲基-N-2羟乙基)氨基1,3,5-三嗪-2-基)];氨基}二苯乙烯-2-2’二磺酸二钠、4,4'-双{[(4-苯氨基-6-吗啉代-1,3,5-三嗪-2-基)]氨基}均二苯代乙烯-2-2'二磺酸二钠、和4,4'-双(2-磺基苯乙烯基)联苯二钠。合适的荧光增白剂为C.I.荧光增白剂260,该增白剂可以其β或α晶形或这些晶形的混合物形式使用。
调色剂:合适的调色剂包括小分子染料,通常属于酸性、直接、碱性、活性(包括它们水解的形式)或溶剂或分散染料的颜色索引(C.I.)分类,例如被分类为蓝、紫、红、绿或黑的染料,并且单独地或组合地提供所期望的色调。优选的,此类调色剂包括酸性紫50,直接紫9、66和99,溶剂紫13和它们的任意组合。
可适用于本发明的许多调色剂是已知的并且描述于本领域。合适的调色剂包括酞菁和偶氮染料缀合物。
合适的调色剂可为烷氧基化的。此类烷氧基化化合物可通过有机合成制备,这可产生具有不同烷氧基化度的分子的混合物。此类混合物可直接用于提供调色剂,或可经历纯化步骤,以增加目标分子的比例。合适的调色剂包括烷氧基化双偶氮染料。
调色剂可作为反应混合物的一部分被掺入洗涤剂组合物中,反应混合物是通过一个或多个任选纯化步骤有机合成染料分子的结果。此类反应混合物一般包含染料分子自身,并且此外还可包含未反应的原料和/或有机合成途径的副产物。可将合适的调色剂掺入调色染料颗粒中。
染料转移抑制剂:合适的染料转移抑制剂包括聚胺N-氧化物聚合物、N-乙烯基吡咯烷酮和N-乙烯基咪唑的共聚物、聚乙烯吡咯烷酮、聚乙烯基噁唑烷酮、聚乙烯基咪唑以及它们的混合物。优选的是聚(乙烯基吡咯烷酮)、聚(乙烯基吡啶甜菜碱)、聚(乙烯基吡啶N-氧化物)、聚(乙烯基吡咯烷酮-乙烯基咪唑)以及它们的混合物。适宜的可商购获得的染料转移抑制剂包括PVP-K15和K30(Ashland),HP165、HP50、HP53、HP59、HP56K、HP56、HP66(BASF),S-400、S403E和S-100(Ashland)。
香料:合适的香料包括选自下列的组的香料材料:(a)具有小于3.0的ClogP和小于250℃的沸点香料材料(第1象限香料材料);(b)具有小于3.0的ClogP和250℃或更大的沸点的香料材料(第2象限香料材料);(c)具有3.0或更大的ClogP和小于250℃沸点的香料材料(第3象限香料材料);(d)具有3.0或更大的ClogP和250℃或更大的沸点的香料材料(第4象限香料材料);以及(e)它们的混合物。
对于香料可以优选的是为香料递送技术的形式。此类递送技术还稳定并且增强沉积和香料材料从洗涤过的织物上的释放。此类香料递送技术也可用于进一步增加从洗涤过的织物上释放香料的持久性。适宜的香料递送技术包括:香料微胶囊、前香料、聚合物辅助递送、分子辅助递送、纤维辅助递送、胺辅助递送、环糊精、淀粉包封的谐香剂、沸石和其它无机载体以及它们的任意混合物。
优选的洗涤剂组合物优选是手动盘碟洗涤剂,优选液体形式。其通常包含30重量%至95重量%,优选40重量%至90重量%,更优选50重量%至85重量%的液体载体,其中其它基本组分和任选组分溶解、分散或悬浮。液体载体的一个优选组分是水。
优选地,洗涤剂的pH调节至在3至14之间,更优选在4至13之间,更优选在6至12之间,并且最优选在8至10之间。可使用本领域已知的pH调节成分来调节洗涤剂的pH。
洗涤方法
本发明的其它方面涉及用本发明的组合物洗涤器皿,尤其是餐具的方法。所述方法包括将组合物,优选液体形式,以稀释或纯态形式施用到脏污表面,尤其是餐具表面上的步骤,以及冲洗或使组合物在表面上干燥而不冲洗表面的步骤。
所谓的“纯态形式”在本文中是指所述组合物直接施用到待处理的表面上和/或施用到清洁装置或器具上,如预处理装置、洗碗布、海绵或洗碗刷,而在施用之前(立即)不进行任何稀释。在将组合物递送至清洁装置或器具之前或之后,清洁装置或器具优选是湿的。所谓的“稀释形式”在本文中是指组合物被使用者用大量适当的溶剂典型地用水稀释。所谓的“冲洗”在本文中是指在将本文的液体组合物施用到所述盘碟的步骤之后,用显著量的适宜溶剂(通常为水)接触用根据本发明所述的方法清洁表面如盘碟。所谓的“显著量”是指通常约1升至约10升。
本文的组合物可以其稀释形式施用。用有效量通常约0.5ml至约20ml(每约25个待处理的盘碟),优选约3ml至约10ml的用水稀释的本发明的洗涤剂组合物,优选液体形式接触脏污的如盘碟。洗涤剂组合物的实际用量将基于使用者的判断,并且将典型地根据以下因素:如,具体的组合物产品制剂,包括组合物中活性成分的浓度、待清洁的脏盘碟数量、盘碟脏的程度等。通常,将约0.01ml至约150ml,优选约3ml至约40ml的本发明的液体洗涤剂组合物与约2000ml至约20000ml,更通常约5000ml至约15000ml的水混合在容积为约1000ml至约20000ml,更通常为约5000ml至约15000ml范围内的洗碗池中。可将脏污盘碟浸入包含稀释组合物的洗碗池,然后用洗碗布、海绵或类似制品接触盘碟的脏污表面来实现清洁它们。可将洗碗布、海绵或类似制品在与盘碟表面接触之前浸入洗涤剂组合物和水的混合物中,然后典型地与盘碟表面接触约1秒至约10秒的时间,虽然实际时间将随每个应用和使用者的不同而不同。织物、海绵或类似制品与表面的接触优选伴随着表面的同时洗擦。
本发明的另一种方法包括将诸如盘碟的脏污制品浸入水浴中或保持在流水下而没有任何洗涤剂组合物。将用于吸收洗涤剂组合物的装置如海绵或预处理装置直接放入单独量的未稀释的洗涤剂组合物中,优选以液体形式放置,通常为约1秒至约5秒范围内的时间段。接着将该吸收装置和因此未稀释的洗涤剂组合物独立地接触每个脏盘碟的表面以移除所述的污垢。吸收装置典型与每个表面接触的时间为约1秒至约10秒,虽然施用的实际时间将取决于如表面脏污程度这样的因素。优选吸收装置接触脏污表面的同时伴随着洗擦。
另选地,可在装置与脏污表面接触之前将该装置浸入洗涤剂组合物和水的混合物中,通过在小容器中用水稀释洗涤剂组合物来制备浓缩溶液,该容器可容纳重量比分别为约95:5至约5:95,优选约80:20至约20:80,并且更优选约70:30至约30:70范围内的洗涤剂组合物的清洁装置,优选液体形式的洗涤剂组合物:水的比例分别取决于使用者习惯和清洁任务。这些方法特别适用于作为盘碟的脏污制品。
根据本发明的洗涤剂组合物还可用作衣物洗涤剂组合物,用于在将脏污物品暴露于自动的,特别是半自动的洗衣机中或之前使用。在任选地预处理之后,脏污表面可在洗衣机中洗涤或以其它方式洗涤。在机器方法中,脏污制品可用含水洗涤液体处理,其中有效量的本发明的清洁组合物溶解或分配到其中。清洁组合物的“有效量”通常是指约10g至约300g的产品溶解或分散于约5L至约65L体积的洗涤溶液中。水温可在约5℃至约100℃范围内。水与脏污材料(例如织物)的比率可在约1:1至约30:1的范围内。组合物可以溶液中约500ppm至约15,000ppm的浓度使用。在织物衣物洗涤组合物的情况下,用量还可不仅取决于污垢和污渍的类型和严重度,而且取决于洗涤水温度、洗涤水的体积和洗衣机的类型(例如顶部加载式、前加载式、顶部加载式、垂直轴日式自动洗衣机)而变化。
本发明特别涉及手动洗涤方法或手洗/浸泡方法,并且还包括与半自动洗衣机的组合手动洗涤。温度通常较低,低于50℃、45℃、40℃、35℃、30℃或25℃。
实施例
下文中,根据实施例更详细地描述了本发明。除非另外指明,所有百分比均按重量计。
实施例1:示例性手动盘碟洗涤剂组合物
实施例2
示例性液体衣物洗涤剂组合物
经由本领域普通技术人员已知的传统装置,通过将以下成分混合来制备以下液体衣物洗涤剂组合物。
实施例3
用于单位剂量(UD)产品的示例性液体洗涤剂组合物
制备以下液体洗涤剂组合物,并将其包封在由聚乙烯醇膜形成的多隔室小袋中。
表6
*可包括但不限于丙二醇、甘油、乙醇、二丙二醇、聚乙二醇、聚丙二醇。
实施例4:用于手洗或洗衣机(通常为顶部加载式洗衣机)的颗粒状衣物洗涤剂组合物。
1 AES可为量在0%至20%范围内的AE1.5S、AE2S和/或AE3S。
2 AES可在0%至20%范围内的量提供。
3 AE是C12-14醇乙氧基化物,其平均乙氧基化度为7至9,由Huntsman(Salt LakeCity,Utah,USA)供应。其可以在0%-10%范围内的量提供。
4 蛋白酶可由Genencor International(Palo Alto,California,USA)供应(例如,Purafect),或由Novozymes(Bagsvaerd,Denmark)供应(例如,
5购自Novozymes(Bagsvaerd,Denmark)(例如,
6购自Novozyme(例如
7无规接枝共聚物为聚乙酸乙烯酯接枝的聚环氧乙烷共聚物,其具有聚环氧乙烷主链和多个聚乙酸乙烯酯侧链。聚氧化乙烯主链的分子量为约6000,并且聚氧化乙烯与聚乙酸乙烯酯的重量比为约40:60,并且每50个氧化乙烯单元具有不超过1个接枝点,以Sokalan购自BASF。
8具有以下通式结构的化合物:双((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-双((C2H5O)(C2H4O)n),其中n=20至30,并且x=3至8,或其硫酸化或磺酸化变体,以Lutenzit Z购自BASF
9DTPA为二亚乙基三胺五乙酸,由Dow Chemical(Midland,Michigan,USA)供应。
10合适的荧光增白剂为例如AMS、CBS-X、磺化酞菁锌(CibaSpecialty Chemicals(Basel,Switzerland))。其可以在0%-5%范围内的量提供。
11合适的防腐剂包括甲基异噻唑啉酮(MIT)或苯并异噻唑啉酮(BIT),其可以0%至1%范围内的量提供。
12 DTI为聚(4-乙烯基吡啶-1-氧化物)(如Chromabond S-)和/聚(1-乙烯基吡咯烷酮-共-1-乙烯基咪唑)(如Sokalan
13螯合剂为二亚乙基三胺五乙酸、1-羟基乙烷1,1-二膦酸和/或乙二胺-N,N'-二琥珀酸,(S,S)异构体(EDDS)的钠盐
14 S-ACMC为由Megazyme提供的活性蓝19偶氮-CM-纤维素
15光学增白剂为4,4'-双{[4-苯胺-6-吗啉代-均三嗪-2-基]氨基}-2,2'-芪二磺酸二钠、4,4'-双-(2-磺基苯乙烯基)联苯二钠(钠盐)和/或来自3V Sigma的Optiblanc
针对酶给出的所有百分比和比率均基于活性蛋白质。除非另外指明,本文所有的百分比和比率都按重量计算。除非另外指明,否则所有百分比和比率均基于总组合物计算。
应当理解,贯穿本说明书给出的每一最大数值限度包括每一较低数值限度,如同该较低数值限度在本文中明确写出。贯穿本说明书给出的每一最小数值限度将包括每一较高数值限度,如同该较高数值限度在本文中明确写出。贯穿本说明书给出的每一数值范围将包括落在该较大数值范围内的每一更窄的数值范围,如同该更窄的数值范围全部在本文中明确写出。
本文所公开的量纲和值不应理解为严格限于所引用的精确数值。相反,除非另外指明,否则每个此类量纲旨在表示所述值以及围绕该值的功能上等同的范围。例如,公开为“40mm”的量纲旨在表示“约40mm”。
Claims (15)
1.一种洗涤剂组合物,包含脂肪酸脱羧酶和表面活性剂体系。
2.根据权利要求1所述的洗涤剂组合物,其中所述脂肪酸脱羧酶选自细胞色素P450及其混合物的组,优选选自CYPBSβ和CYPSPα家族。
3.根据前述权利要求中任一项所述的洗涤剂组合物,其中所述脂肪酸脱羧酶与SEQ IDNO:1具有至少40%的同一性。
4.根据前述权利要求中任一项所述的洗涤剂组合物,还包含过氧化氢源。
5.根据前述权利要求中任一项所述的洗涤剂组合物,包含一种或多种附加酶,优选选自蛋白酶、淀粉酶、脂肪酶、纤维素酶、脂氧合酶、碳水化合物氧化酶和油酸水合酶、以及它们的混合物。
6.根据权利要求5中任一项所述的洗涤剂组合物,其中所述附加酶包括脂肪酶、脂氧合酶、碳水化合物氧化酶和/或油酸水合酶。
7.根据前述权利要求中任一项所述的洗涤剂组合物,其中所述脂肪酸脱羧酶以基于活性蛋白质计0.0001重量%至1重量%,优选0.001重量%至0.8重量%的量存在。
8.根据前述权利要求中任一项所述的洗涤剂组合物,其中所述表面活性剂体系包含一种表面活性剂或者多于一种表面活性剂的混合物,并且以所述组合物的5重量%至80重量%的量存在,优选包含阴离子表面活性剂和/或非离子表面活性剂,优选阴离子表面活性剂和非离子表面活性剂两者。
9.根据前述权利要求中任一项所述的组合物,其中所述表面活性剂体系优选除阴离子表面活性剂之外还包含两性表面活性剂和/或两性离子表面活性剂,并且优选地,其中所述阴离子表面活性剂和所述两性表面活性剂和/或所述两性离子表面活性剂的重量比小于约9:1,更优选约5:1至约1:1,更优选约4:1至约2:1。
10.根据权利要求11所述的组合物,其中所述两性表面活性剂包括氧化胺表面活性剂,并且所述两性离子表面活性剂包括甜菜碱表面活性剂。
11.根据前述权利要求中任一项所述的洗涤剂组合物,其中所述组合物为手动盘碟洗涤组合物。
12.根据前述权利要求中任一项所述的组合物,还包含选自化学稳定剂和/或物理稳定剂的组的酶稳定剂,其中所述物理稳定剂可包含包封的酶。
13.根据前述权利要求中任一项所述的组合物,还包含螯合剂,优选选自氨基羧酸盐螯合剂或氨基膦酸盐螯合剂,诸如MGDA、GLDA以及它们的混合物。
14.一种手动洗涤脏污制品优选盘碟或织物的方法,包括以下步骤:将根据前述权利要求中任一项所述的组合物递送至一定体积的水中以形成洗涤液体,并且将所述脏污制品浸入所述洗涤液体中,或者:任选地在水存在下,将根据前述权利要求中任一项所述的组合物直接递送至所述脏污制品上或者清洁工具上,并且使用所述清洁工具清洁所述脏污制品。
15.脂肪酸脱羧酶在含水洗涤液体中提供增加的泡沫寿命和/或增强脂肪/油脂污渍去除的用途。
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CA3020606C (en) | 2021-03-30 |
JP2019513878A (ja) | 2019-05-30 |
PL3243896T3 (pl) | 2020-03-31 |
EP3556834B1 (en) | 2020-10-14 |
EP3243896A1 (en) | 2017-11-15 |
CA3020606A1 (en) | 2017-11-16 |
CN109072136B (zh) | 2021-08-24 |
ES2835648T3 (es) | 2021-06-22 |
US10526565B2 (en) | 2020-01-07 |
EP3243896B1 (en) | 2019-07-03 |
PL3556834T3 (pl) | 2021-02-08 |
EP3556835A1 (en) | 2019-10-23 |
ES2746120T3 (es) | 2020-03-04 |
MX2018013706A (es) | 2019-05-02 |
US20170321162A1 (en) | 2017-11-09 |
EP3556834A1 (en) | 2019-10-23 |
WO2017196786A1 (en) | 2017-11-16 |
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