CN87100752A - 保护酶体系 - Google Patents

保护酶体系 Download PDF

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CN87100752A
CN87100752A CN198787100752A CN87100752A CN87100752A CN 87100752 A CN87100752 A CN 87100752A CN 198787100752 A CN198787100752 A CN 198787100752A CN 87100752 A CN87100752 A CN 87100752A CN 87100752 A CN87100752 A CN 87100752A
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爱德华德·图恩斯塔尔·麦森格
安东尼·马丁
阿尼·迪特利夫·福格
普尔·法尔霍特
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Novo Nordisk AS
Solvay Solutions UK Ltd
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Novo Industri AS
Albright and Wilson Ltd
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Abstract

一种适用于贮存的保护酶体系，在使用前存于某种介质(例如能引起该未保护的酶降解的液态去污剂)。该体系至少含有一种分散于疏水物质的酶，这种疏水物质在贮存过程中不溶解，在使用条件下为液态。

Description

本发明涉及保护酶体系，其适用于在能引起酶降解的环境下（例如液态洗涤去污剂）贮存或使用。
酶在粉末状去污剂中通常用作去除污迹的试剂，但是，酶掺入液态清洁制剂（包括液态洗涤去污剂，例如GB    2123846和GB    2153380所描述的例子）至今还是一大难题，那些液体的配方特别有效于污迹的去除，但很快导致洗涤酶的失效，常常是，结果只贮存几天便大大降低了去污效能。在去污剂中存在的更为有效的去污配方所具有的相对高的碱性，大部分增加清洁作用的组分的化学反应及表面活性剂拮抗于去污剂酶体系，并且大大阻碍了酶在这些去污剂中的使用，甚至在相对非碱性组合物中观察到了严重变质，而特别是这种非碱性配方是用来允许酶的掺入的。甚至在粉末去污剂中也能观察到一些酶的降解，尤其是当粉末具有高碱性如机器洗盘用粉末去污剂，或含有一氧化漂白剂如过硼酸盐。
我们现已发现，在拮抗环境（例如液体去污剂中）酶的变质可以通过将酶分散于一疏水物质而大大减少，这种疏水物质不溶于该拮抗环境。此外，我们还发现，只要该疏水介质在使用条件下能够充分流动或易于破碎，所保护的酶即可行使其正常功能。
因此根据一具体实例，本发明提供了一保护酶体系，其在使用前可贮存于一能引起未保护酶逐步降解的环境中，该体系基本上包括至少一种酶分散于一疏水物质，其不溶于上述环境，在正常使用条件下可充分流动或易于破碎。
根据一已提出的方面本发明提供一用于液态清洁组合物的保护酶体系，其含有至少一种分散于一疏水物质的去污剂酶成分，该疏水物质不溶于液体去污剂，但能以粒状或滴状分散其中，在洗涤条件下能充分流动或易于破碎。
根据第二个实施例，本发明提供一保护酶体系，它适用于液态清洁组合物，本质上讲该组合物含有一些团粒，其中至少含有一种包囊于疏水物质中的去污剂酶成分，该疏水物质不溶于液态清洁剂，在正常洗涤温度可流动或脆化。
根据第三个实施例，本发明提供一用于液态去污剂组合物的保护酶体系，本质上讲该组合物含有一种去污剂酶成分分散于一疏水液体，该液体不溶于液态去污剂，
根据第四个实施例，本发明提供一种在使用前贮存于能引起未保护酶逐步降解的环境中酶的保护方法，即分散该酶于一疏水介质，该疏水介质不溶于上述环境，但能以粒状或滴状分散其中并在正常使用条件下可流动或脆化。
根据第五个实施例，本发明提供一保护酶的方法，即分散一去污剂酶成分于一疏水物质中，该物质不溶于液态去污剂，并在正常洗涤温度时流动。
根据第六个实施例，本发明提供一液态清洁组合物，其中以粒状或滴状分散有前面叙述过的本发明的保护酶体系。
所谓介质中的溶解性指：在介质的水相或其它连续溶剂相中的溶解作用以及在分散于介质的表面活性微团或任何其它不连续相中的增溶作用。
疏水物质可以是一有机聚硅氧烷油，例如一种聚二烷基硅氧烷，其中烷基最好有1-4个碳原子，尤其是聚二甲基硅氧烷。特别建议采用一种疏水液体，其中悬浮有疏水性固体颗粒以便稳定体系。例子包括硅酮组合物，在液态去污剂中作为消沫成分，含有疏水性硅油和疏水性硅石，例如，细碎的硅石，硅酮至少部分键合于硅石颗粒的表面。例如具有羟基功能的有机硅氧烷可以与硅石表面的羟基缩合。这种组合物的例子包括以下列注册商标出售的产品：“WACKER”Antifoam    S132，“BEVALOID”4237，“UNION    CARBIDE”Y1206，或DIAMOND    SHAMROCK′S“NOPCO”8315。硅酮消沫成分可以用一未修饰硅油如聚二甲基硅氧烷稀释。此外，可通过加入细碎的硅石使硅酮的粘性增大，例如熏制的硅石（如DEGUSSA′S    AEROSIL200）。
另外，疏水物质可以是高分子量烃，例如石油光亮油或一种所谓矿脂，高分子量醇例如多于28个碳原子的醇或高分子量氟代烃或疏水性磷酸酯例如单和/或双-脂肪烷基磷酸酯或其盐类，特别是钠盐或钙盐，或者三烷基磷酸酯或三芳基磷酸酯，通过加入疏水固体粒子，例如通过使硅石与如上所述的硅酮或脂肪醇缩合而形成的疏水固体粒子可使疏水流体物质更为稳定。根据一具体实例，疏水物质在室温下可以是固体或蜡状物质，其具有一低于正常洗涤温度的软化点或合适的熔点，例如，低于60℃，最好低于50℃，通常为40℃，常为低于30℃。这种固体物质提供的产品除了应用于液态去污剂外特别适用于粉末去污剂。更为独特的是，我们采用的疏水物质具有在正常贮存温度（例如室温下）大于0.05帕斯卡秒的粘性，大于0.2帕斯卡秒较好，大于0.5帕斯卡秒更好，大于0.8帕斯卡秒最好。特别建议粘性应大于1.0帕斯卡秒，例如大于2帕斯卡秒，特别是大于10帕斯卡秒。
除了特别声明者外，本文中粘性均在25℃，24秒剪应变下测得。
酶可以是例如-去污酶，如蛋白酶，脂酶，淀粉酶，脱羧酶或纤维素酶，如，Novo    Industri    AS以下列注册商标出售的酶：SAVINASE”，“TERMAMYL”，“ESPERASE”及“ALCALASE”，或其它能去除或改善污渍迹的酶，或是这些酶的混合物。
酶可以酶溶液的分散液滴形式存在于疏水物质，例如，酶的水溶液或能与水混溶的低级一元醇，二元醇或多元醇溶液，如丙烯乙二醇，并可任意选择含有文献已知的酶的稳定剂。可能出现的酶稳定剂包括低级醇（如丙三醇），低级一元或二元羧酸及其盐，尤其是甲酸盐，草酸盐，硼酸盐和钙盐。
此外，酶还可以含酶固体的悬浮颗粒形式存在，固态酶建议从酶溶液中干燥或沉淀得到，可任意选择含有前述的稳定剂，例如US3，723，250中所述，特别在Colunm    12;EP0006    638，实施例2a和b;GB1.296.839;US.4，435，307;EP0130064或比利时专利889336。
酶还可存在于水溶性颗粒或圆柱形挤压颗粒中。更为特别的是这是商品酶出售的形式。因此，一水溶性结晶糖如蔗糖，或盐如氯化钠，碳酸钠或硫酸钠可与酶一起粒化或制成圆柱形挤压颗粒，可任意选择带有酶稳定剂，例如U.S.4，106，991或GB1，362，365，第9页所述的稳定剂，产品分散于或包被于硅酮或烃类，例如矿脂。
酶可通过简单搅拌分散掺入惰性油。如果室温下疏水物质是固体，在分散酶之前要先熔化，然后冷却至室温。可任意选择将分散液喷雾冷却以得到颗粒状产品。
当保护酶体系需要在液态处理和贮存时，酶的比例由体系所需的粘性决定。比例升高粘性增大，但不易使所分散酶沉降。然而，我们并不排除沉降体系的使用，规定在该体系加入去污剂组合物之前酶可以通过搅拌很容易地再分散。
建议选择微粒大小和酶的比例以提供保护酶体系总粘性在贮存条件下大于0.1帕斯卡秒，典型的是大于0.5帕斯卡秒，特别是大于1帕斯卡秒，大于2帕斯卡秒更好，大于3帕斯卡秒最好，可任意选择大于10.0帕斯卡秒。
当酶以溶液形式掺入体系时，溶液最好含有1～90%（重量）的酶浓缩物，例如2～80%，典型的是5～60%，并且其在油中的分散物常含1-80%，更为常用5～70%，10-60%较好，15-50%更好，例如20-40%或30～50%（重量）酶溶液，百分比用总的保护酶体系重量表示。固态酶浓缩物在疏水物质中的悬浮液典型含量为1-90%，更常用5-80%，建议用20-60%，即30-50%或20～30%（固体重量）基于悬浮液的总重量。
保护酶体系中酶的比例可取决于是否需要疏水物质执行任何其自身有用的功能，例如作为消沫剂。当需要一种低泡沫组合物时，酶与消沫剂的比例可以很方便地与最后组合物中所需比例一致。另外，制备更浓的酶悬浮液并在使用之前用更多消沫剂稀释，或者与额外的消沫剂同时或分别加入到组合物中。
如果不需要疏水物质执行除了保护酶以外的功能，那么酶浓度可以是与一易处理的产品相一致的最大值。
在保护酶体系中分散的酶的微粒大小可在广泛范围内变动。典型的是，分散酶微粒在1μ到2mm范围，最好5μ～1mm，例如10μ～700μ。固态酶浓缩物趋于上述范围较低部分，液态溶液正常分散微粒大小在该范围中间，例如100μ～800μ。微团酶常有该范围上限的微粒大小，例如300μ～1mm。
保护酶体系通常以简单搅拌方式很容易分散于液体去污剂中。该体系可作为直径2μ～2.5mm的微粒或液滴而分散，更常用为5μ～500μ，建议用10μ～100μ，一分散溶液或酶浓缩物用作保护体系。当酶以微团存在时，建议液态去污剂中体系的微粒大小为500μ～1mm。
如果需要的话可使用分散剂和乳化剂，但通常不需要。
建议该组合物加入一液体去污剂，其含有水相，表面活性剂，足够的溶于水相的电解质，后者与表面活性剂形成一能支持悬浮微粒的结构，本发明的保护酶体系悬浮于去污剂组合物中。
建议该组合物中含有一有效量的去污增效剂。合适的增效剂包括缩聚磷酸盐，特别是三聚磷酸钠，较少取的是焦磷酸钾或四磷酸钠，碳酸钠，硅酸钠，正磷酸钠，柠檬酸钠，次氮基三乙酸钠，膦酸盐如乙二胺四甲撑膦 酸钠，乙酰二膦酸钠或甲叉膦酸盐，乙二胺四乙酸钠或沸石。其次可采用上述钠盐或钾或锂的类似物。
去污增效剂的典型比例从约5%到大约40%液体去污剂组合物的重量，通常10%～35%，15%～30%较好，18%～28%更好，20～27%最好，常采用两种或多种去污增效剂的混合物，例如三聚磷酸钠与硅酸钠和/或碳酸钠，或与沸石混合;或次氮基三乙酸钠与柠檬酸钠混合。
建议去污增效剂至少有一部分是以悬浮于组合物中的固体颗粒存在的。
特别建议采用根据前面提到的GB2，123，846或G132，153，380液体去污剂组合物。
本发明还可应用于制备未加去污增效剂的清洁组合物或所有这种增效剂处于溶液状态的组合物。
表面活性剂可以是阴离子型，非离子型，阳离子型，两性的，两性离子的和/或半极性的表面活性剂，其典型存在浓度为2～35%组合物重量，建议5～30%，更常用的是7～25%，例如10～20%。
通常组合物含有烷基苯磺酸盐与一种或多种其它表面活性剂例如烷基聚氧烷撑硫酸盐和/或非离子型表面活性剂，后者通常为链烷醇酰胺或聚氧烷基化的醇。
其它阴离子型表面活性剂包括烷基硫酸盐，烷烃磺酸盐，烯烃磺酸盐，脂肪酸盐，磺酸盐，肥皂，烷基硫酸琥珀酸盐，烷基磺基琥珀酰胺酸盐，N-酰氨基乙磺酸盐，羟乙基磺酸盐，以及前面列出的阴离子型表面活性剂的聚氧烷撑衍生物。在每种情形下，这里采用的表面活性剂具有平均8～22个碳原子的烷基，建议10～20个，例如12～18个碳原子。烷基最好为一级直链，然而并不排除支链或二级烷基。在非离子型表面活性剂如醇的情形下，有时需要含有支链。
表面活性剂可以全部或多数是非离子型，例如，只用聚氧烷基化的醇或与聚氧烷撑乙二醇混合。可以采用的其它的非离子型表面活性剂包括羧酸，丙三醇，山梨聚糖，烷基苯酚，链烷醇酰胺或胺氧化物的聚氧烷基化衍生物。
这里所提到的聚氧烷撑基最好取聚氧乙烯基，较少取聚氧丙烯基或混合的氧乙烯氧丙烯共聚物或嵌段共聚物基团或是这些基团与一个或多个丙三醇基团共聚物。建议聚氧烷撑基具有1～30个烯烃氧基单位，通常为2～20个，例如5～15个。
根据本发明所用的阳离子型表面活性剂包括四级烷基胺，酰胺基胺和咪唑类。两性表面活性剂包括甜菜碱和硫酸甜菜碱。
通常可采用GB1，123，846或在Schwartz的“表面活性剂和去污剂”中所述的任何一种表面活性剂。
建议液体去污剂组合物PH值为碱性，例如约7.5，特别是7.5～12，典型的是8～11，如9～10.5。
建议液体去污剂组合物含有溶解的电解质。这可能包括去污增效剂的溶解部分和/或任何其它盐，无机或有机物，其本身不是表面活性剂，从溶液中（包括胶状溶液）盐析出表面活性剂。例如包括氯化钠，硝酸钠，溴化钠，碘化钠，硼酸钠，甲酸钠或乙酸钠，或相应的钾盐。然而，建议采用在清洗液中能执行有用功能的盐类作为电解质。
电解质可能含有低浓度硫酸钠，但电解质混合物含有约3%或更高的硫酸钠浓度，基于去污剂剂组合物的总重量，这种混合物不宜使用，因为它们在放置过程中导致发生不必要的结晶。
去污剂组合物可含有任何常见的少量混合物成分，例如污物悬浮剂（例如羧甲基纤维素），光学发光剂，香料，颜料，可任意选择漂白剂。
最佳的液体去污剂含有长链如C10-14链状烷基苯磺酸酯，含量5～12%;长链烷基醚硫酸盐，如1～5乙烯氧单位，含量0～3%;脂肪酸链烷醇酰胺，如二乙醇酰胺，含量1～5%;单和双长链烷基磷酸盐混合物，含量0-3%，例如0.1～1%;三聚磷酸钠（最好预先用0.5～5%（重量）的水进行水合）含量14-30%，例如14～18%或20～30%;可任意选择碳酸钠含量直到10%，例如5-10%，使三聚磷酸钠和碳酸钠总浓度为20～30%，抗再沉积试剂例如羧甲基纤维素钠盐含量0.05～0.5%，光学发光剂0.05～0.5%，螯合剂如氨基膦酸盐，例如二胺或聚胺的甲叉膦酸盐，特别是乙二胺四[甲叉膦酸]钠或二乙烯基三氨基六[甲叉膦酸]盐，可任意选择含量0.1～1%，以及常规添加物如香料，其余为水，上述百分比基于总液体去污剂的重量。液态去污剂可具有PH6～13，建议7～12，通常8～11，例如9～10.5。
本发明的组合物典型含量为0.01～10%，如0.05～0.5%重量的保护酶体系。
本发明的保护酶体系可用作粉末清洁组合物的添加剂。例如，分散于硅酮消沫剂或粘性烃类的酶可掺入粉末洗涤去污剂。按惯例这些粉末可含有表面活性剂（总量通常为5～30%（重量）），去污增效剂，一种固态填料和可任意选择一漂白剂。通常表面活性剂含有一烷基苯磺酸钠（烷基最好为C12-14线型），含量2～20%，建议5～15%（组合物的总重量），以及可任选一种烷基（如C12-18）聚氧乙烯（如2～10%摩尔）硫酸钠和/或一非离子型表面活性剂如链烷醇酰胺;例如椰子，单或双-乙醇酰胺和/或聚乙氧基化的脂肪醇。
典型的去污增效剂为三聚磷酸钠，尽管还有沸石，碳酸钠，硅酸钠，柠檬酸钠，次氮基三乙酸钠及其混合物或用它们代替三聚磷酸钠。增效剂的总含量通常介于10和40%总粉末重量，如20～30%。
典型的填料是硫酸钠，典型含量0～60%，通常为20～50%组合物总重量，以保证自由流动粉末。
漂白粉常为过氧化物，特别是过硼酸盐或过碳酸盐。
粉末通常还含有常见少量混合物例如污物悬浮剂（典型为羧甲基纤维素钠），光学发光剂，香料和任选颜料。
根据本发明，保护酶体系可加入机器洗盘粉末，擦洗乳剂和其它硬表面清洗剂，地毯清洗剂，去油污剂，炉灶清洗剂，洗盘液，肥皂粉末，洗涤前浸渍剂和其它清洁剂。
根据本发明，典型的洗盘粉末含有20～60%的实际比例，建议30～50%的碱例如碳酸钠，及小比例，如1～5%的表面活性剂，最好是非离子型表面活性剂如烷氧基化的醇，任选但最好是与一去污增效剂如三聚磷酸钠按比例直到约45%组合物重量，例如20～35%，一种碱性硅酸盐如硅酸钠及一碱性缓冲液如硼砂一起加入。该组合物可任意含有一漂白剂例如氯化的磷酸三钠盐以及0.1～2%保护酶体系重量。
本发明的典型液体洗盘剂含有高溶解性的去污增效剂，例如焦磷酸钾，和/或硅酸钾，总浓度为10～30%（重量），表面活性剂建议用非离子型，浓度0.2～5%（重量），助水溶物如二甲苯磺酸钠，甲苯磺酸钠或苯磺酸钠，浓度为1～10%（重量）。
本发明的典型硬表面清洗剂含有1～10%表面活性剂，尤其是非离子型或阴离子型/非离子型混合物，1～10%助水溶物和2～10%水溶性去污增效剂如焦磷酸钾，硬表面清洗剂还可任意选择含有研磨料如硅石或碳酸钙作为霰石或方解石悬浮于结构液中。
本发明的地毯清洗剂可根据本发明含有较高浓度例如5～20%（重量）的高泡表面活性剂如阴离子表面活性剂（如烷基硫酸盐）与发泡剂（如链烷醇酰胺）混合物。
本发明的炉灶清洗剂可能具有腐蚀性，如含4～12%碱（如氢氧化钠），典型高泡阴离子型表面活性剂（例如烷基醚硫酸钠），或含10～30%水互溶有机溶剂（例如低级一元醇，二元醇或多元醇或其它醇），例如丙烯二醇，典型非离子型表面活性剂，以及与去污增效剂（如三聚磷酸钠）一起使用的磷化型溶剂。
在以上任何液体配方中分散该保护酶体系所遇到的任何困难通常可按下法加以避免：加入少量常用分散剂或悬浮剂（如水溶性树胶或聚电解质）。
洗涤剂的正常洗涤条件包括，温度50℃～60℃，洗涤液含2～15gm/l洗涤剂，强力搅拌。然而，某些洗涤剂建议在冷或中间清洗温度时配制和使用（分别是20～30，或30～40℃），或者是因为纤维敏感，或者是为了节约能量。
用下列实施例说明本发明：
例1
一蛋白酶溶液，以注册商标“Esperase”8.OL出售，分散于下述等重量物质混合物，消泡沫硅油，在25℃，24秒时粘性为22.57帕斯卡秒，其含有羟基末端聚硅氧烷，与固体熏制硅石缩合的，以注册商标“Wacker”Antifoam S132出售;及一中性聚硅氧烷油，以注册商标“Wacker”AK50出售。硅酮混合物的粘性为3.4帕斯卡秒。所产生的分散液含有38%（重量）的酶溶液，基于分散液总重量，在25℃24秒-1下粘性为11.9帕斯卡秒。
该分散液通过搅拌掺入到液体复配洗涤剂中，得到下列配方：
重量%
线型C12烷基苯磺酸钠 9.3
线型C12-18烷基醚硫酸钠（每分
子平均含3个乙氧烯基单位）    1.85
椰子二乙醇酰胺    1.85
三聚磷酸钠    16.7
碳酸钠    6.7
羧甲基纤维素钠    0.9
光学发光剂    0.1
酶分散液    3
pH    10.5～11.0
这个配方与没有酶的对照配方比较对一实验样品的去污能力，样品为血液，奶迹和碳（EMPA116）污染的棉花，在清洗液中浓度为591，清洗液含有200ppm碳酸钙，洗涤温度60℃，洗30分钟。
观察到下列去污百分比：
对照    36%
新鲜配方    57%
30℃存放22天后的配方    52%
例2和例3
25%（重量）的悬浮液的制备：搅拌固态“ESPERASE”蛋白酶浓缩物（制备如U.S.Patent    No.3，723，250at    Col.12所述）加入粘性为1.83帕斯卡秒的硅油中，后者由Diamond-shamrock以商标“NOPCO    8315”硅酮消泡剂出售。
该悬浮液具有粘性7.32帕斯卡秒，掺入到复配液态去污剂中，得到下列配方：
例2    例3
十二烷基苯磺酸钠    6%    7%
线型C12-18烷基醚硫酸钠（每分
子平均含有3个乙烯氧基单位）    2%    -
椰子二乙醇酰胺    1.5%    3%
单和双C16-18烷基硫酸酯混合物 0.5% 0.5%
三聚磷酸钠    24%    24%
羧甲基纤维素钠    0.1%    0.1%
酶硅油悬浮液    1.25%    1.25%
光学发光剂    0.2%    0.2%
二乙烯基三氨基五
（甲叉磷酸）钠盐    0.5%    0.5%
香料    0.3%    0.3%
水    至100%    至100%
pH    约9.0%    约9.0%
例2配方的蛋白酶活力为每克15.4千NOVO蛋白酶单位（KNPU）。
例4和例5
以例2和3中同样方式，“ESPERASE”（注册商标）蛋白酶固态浓缩物在另一消泡沫硅油，具有粘性1.22帕斯卡秒（“BEVALOID”4237）中悬浮得到25%（重量）的悬浮液，并按例2和3方法掺入复配液体中分别得到例4和5的相应配方。悬浮液粘性为3.66帕斯卡秒。
蛋白酶活性（例4配方）为14.8KNPU/每克。
贮存稳定性试验
例2和4的配方保存在37℃5星期的稳定性被确定并与相应于例2的参考配方（等量酶但没加硅油）比较。
每种配方的残余蛋白水解活性用Novo    Publication    AF101/4-GB描述的二甲基酪蛋白（DMC）方法确定。结果列于下表，活性用该配方的起始活性的百分比表示：
数周后残余活性
配方    2    4    5
例2    80%    70%    70%
例4    85%    65%    63%
参考    33%    9%    无活性
例6至例13
一系列其它保护酶体系每个均通过搅拌25%固态酶浓缩物至该疏水物，试验结果如下表所示：
例号    酶    疏水物    疏水物    疏水物    体系粘性
商品名    化学类型    粘性P.S    P.S.
6“TERMAMYL”＊“BEVALOID”＊硅油+    1.22    2.44
4237    疏水硅石
7“SAVINASE”＊    〃    硅油+疏水硅石1.22    2.74
8“ALKALASE”＊    〃    硅油+疏水硅石1.22    2.13
9    〃    “WACKER”＊    硅油+疏水硅石
S132+（用硅油稀释）    9.76
“WACKER”＊
AK50
10“TERMAMYL”＊    〃    硅油+疏水硅石
（用硅油稀释）    10.06
11“ESPERASE”＊“CATANEX”＊石油光亮油    1.62    4.09
79
12“ESPERASE”＊“VASELINE”＊矿脂
13“ESPERASE”＊“EMPICOL”＊混合单/双
7062P C16-18烷
基硫酸盐
13A“ESPERASE”＊“WACKER”＊S132硅油+疏水硅石22.7
＊：注册商标
根据例3，例6到13每一例均可用作液体去污剂酶体系。在室温下贮存两星期后发现与未保护酶的体系相比酶活性和去污能力都有提高。
例14
洗盘粉末状去污剂具有下列配方
脂肪醇12摩尔乙氧基化物
（以注册商标“EMPILAN”KCMP0705/F）    2%
三聚磷酸钠    30%
氯化磷酸三钠    9%
硼砂    2%
硅酸钠    8%
例10    0.5%
碳酸钠    平衡
例15
洗盘液体去污剂具有下列配方
30%二甲苯磺酸钠活性水溶液
（注册商标“ELTESOL”SX30）    10%
80%合成醇8摩尔乙氧基化物活性水溶液
（注册商标“EMPILAN”KA880）    0.5%
氢氧化钾    1%
焦磷酸四钾    15%
硅酸钾    10%
例9    0.5%
水    平衡
例16
硬表面清洗剂具有下列配方
30%二甲苯磺酸钠
（注册商标“ELTESOL”SX30）    10%
80%合成醇8摩尔乙氧基化物
（注册商标“EMPILAN”KA880）    2%
30%十二烷基硫酸钠
（注册商标“EMPILAN”SL30）    5%
焦磷酸四钾    5%
例12    0.5%
水    平衡
例17
地毯清洗剂具有下列配方
14%十二烷基硫酸钠+14%十二
烷基单乙醇酰胺磺基琥珀酸
（注册商标“EMPIMIN”3119）    25.0%
例8    0.5%
水    平衡
例18
地毯清洗剂具有下列配方
28%合成十二烷基硫酸钠
（注册商标“EMPICOL”LX288/5）    36%
十二烷基异丙醇酰胺    2%
例13    0.5%
水    平衡
例19
炉灶清洗剂具有下列配方
壬基苯基9摩尔乙氧基化物
（注册商标“EMPILAN”NP9）    15%
丙烯乙二醇    20%
三聚磷酸钠    10%
例7    0.5%
水    平衡
例20
炉灶清洗剂具有下列配方
27%十二烷基硫酸醚
（注册商标“EMPIMIN”27/T）    20%
氢氧化钠（固体）    8%
例12    0.5%
水    平衡

Claims (79)

1、一种适于贮存的保护酶体系，其在使用前作为不连续相分散于能引起来保护酶逐步降解的环境中，该体系包含有至少一种酶分散于疏水物质的分散液，该疏水物质在该环境中基本不溶，在正常使用条件下能充分流动或易于破碎。
2、一种用于液体清洁剂的保护酶体系，该体系至少含有一种分散于一疏水物质的去污剂酶，该疏水物质在液体洗涤剂中基本不溶，但以粒状或滴状分散其中，在洗涤条件下可充分流动或易于破碎。
3、权项2的体系，该体系含有一亲水溶液，其中至少有一种分散于疏水液体中的去污剂酶。
4、权项2的体系，该体系含有固体组合物颗粒，该组合物至少含有一种分散于一疏水液体中的去污剂酶。
5、一种用于液体清洁制剂的保护酶体系，该体系含有大量微团，其中至少有一种包被于一种疏水物质，这种疏水物质在液体清洁制剂中基本不溶，在正常洗涤温度时流动或易碎。
6、一种保护酶体系，该体系含有至少一种分散于-疏水物质的去污剂酶，该疏水物质在水基液体洗涤剂中基本不溶并具有低于60℃的软化点。
7、一种用于水基的液体去污剂的保护酶体系，该体系含有至少一种分散于一种疏水物质的去污剂酶，该疏水物质基本上不溶于所述的液体去污剂并具有低于60℃熔点。
8、一种权项7的保护酶体系，其中，所述的疏水物质熔点低于50℃。
9、一种权项8的保护酶体系，其中，所述的疏水物质熔点低于40℃。
10、一种保护酶体系，该体系基本上由分散于一种疏水液体中的一种去污剂酶组成，该疏水液体基本上不溶于水基的液体洗涤剂。
11、据前述任一权项的一种体系，其中，疏水物质具有在25℃，24秒-1剪应变下大于0.05帕斯卡秒的粘性。
12、一种权项11的体系，其中，疏水物质具有在25℃，24秒-1剪应变下大于10帕斯卡秒的粘性。
13、据前述任一权项的一种体系，其中，疏水物质具有在60℃，24秒-1剪应变下低于200帕斯卡秒的粘性。
14、一种权项13的体系，其中，疏水物质具有在60℃24秒-1剪应变下低于60帕斯卡秒的粘性。
15、一种权项14的体系，其中，疏水物质在室温下具有1～50帕斯卡秒之间的粘性。
16、据前述任一权项的一种体系，其粘性在25℃，24秒-1剪应变下大于0.1帕斯卡秒。
17、一种权项16的体系，该体系在25℃24秒-1剪应变下粘性大于10帕斯卡秒。
18、据前述任一权项的一种体系，其粘性在60℃，24秒-1剪应变下低于200帕斯卡秒。
19、据权项16～18任一项的一种体系，其具有在25℃，24秒-1剪应变下从2到60帕斯卡秒的粘性。
20、一种保护酶体系，该体系基本上由水溶性微团组成，其含有一种去污剂酶并为矿脂所包被。
21、据权项1～19任何一项的一种体系，其中疏水物质为烃类。
22、一种权项21的体系，其中，疏水物质为矿脂。
23、据权项1～19任何一项的一种体系，其中，疏水物质为有机硅氧烷聚合物。
24、一种权项23的体系，其中，疏水物质为硅酮消沫剂。
25、一种权项23或24的体系，该体系包括细碎的疏水硅微粒和硅油。
26、据权项1～19任何一项的一种体系，其中，疏水物质为疏水磷酸酯。
27、据前述任一权项中所述的一种体系，其中，酶包括一种或多种蛋白酶，脂酶，淀粉酶和纤维素酶。
28、一种保护适于贮存酶的方法，该酶在使用前作为不连续相分散在能降解未保护酶的环境中，该方法包括将该酶分散于一种疏水物质中，该疏水物质不溶于所述环境，而且在正常使用条件下为液态，并使所述疏水物质分散在所述环境中。
29、一种用于在液体去污剂中保护至少一种去污剂酶的方法，该方法包括将该酶分散于一疏水物质中，该疏水物质在液体去污剂中基本不溶，但以粒状或滴状分散于其中，而且在正常洗涤条件下为液态。
30、一种液体洗涤组合物，据权项1～27任一项的保护酶体系以粒状或滴状分散于其中。
31、一种权项30的组合物，该组合物含有表面活性剂和水。
32、一种权项31的液体清洁组合物，该组合物含有水，表面活性剂，溶于该组合物的足够的电解质与表面活性剂一起构成支持分散的固体或液体颗粒或液滴的结构，据权项1～27任一项的保护酶体系分散于该组合物中。
33、一种权项32的组合物，该组合物含有去污增效剂。
34、一种权项33的组合物，其中，所述的去污增效剂至少有一部分以悬浮固体颗粒存在。
35、一种权项30～34任一项的组合物，该组合物具有碱性pH值。
36、一种权项35的组合物，该组合物具有pH7.5～12。
37、一种权项36的组合物，该组合物具有pH8～11。
38、一种权项30～37任一项的组合物，其中表面活性剂包括一阴离子型和/或一非离子型的表面活性剂。
39、一种权项38的组合物，该组合物包括（ⅰ）烷基苯磺酸盐，（ⅱ）烷基硫酸醚和/或一非离子型表面活性剂。
40、一种权项33～39任一项的组合物，其中，去污增效剂包括一缩聚磷酸盐、正磷酸盐、膦酸酯、沸石、碱金属碳酸盐、碱金属硅酸盐、次氮基三乙酸盐、柠檬酸盐和/或乙二胺四乙酸盐。
41、一种权项40的组合物，其中，去污增效剂包括三聚磷酸钠。
42、据权项31～41任意一项的组合物，其中，电解质包括去污增效剂溶解的部分和/或加入的水溶性非表面活性盐类，后者能将表面活性剂盐析出来。
43、据权项30～42任一项的组合物，该组合物含有5～30%（重量）的表面活性剂和0.01～10%（重量）的保护酶体系。
44、据权项33～43任一项的组合物，该组合物含有10～40%（重量）的去污增效剂。
45、据权项30～44任一项的组合物，该组合物还额外含有至少一种污物悬浮剂，光学发光剂，香料，漂白粉和颜料。
46、一种权项45的组合物，该组合物含有羧甲基纤维素钠。
47、一种粉末清洗剂组合物，该组合物含有据权项1～4和6～27任一项的保护酶体系。
48、一种权项47的去污剂粉剂，该粉剂至少含有一种表面活性剂，一种去污增效剂及一种固体填料。
49、一种权项48的去污剂粉剂，该粉剂含有一种漂白粉。
50、据权项47～49任一项的去污剂粉剂，其中，表面活性剂含有烷基苯磺酸钠和至少一种硫酸烷基醚以及一种非离子型表面活性剂。
51、据权项48～50任一项的组合物，其中，去污增效剂含有三聚磷酸钠。
52、据权项48～51任一项的组合物，其中，填料为硫酸钠。
53、据权项49～52任一项的组合物，其中，漂白剂为过硼酸钠。
54、一种机器洗盘粉剂，该粉剂含有权项1～27任一项中的保护酶体系。
55、一种权项54的洗盘粉剂，该粉剂含有30～60%碱。
56、一种权项55的洗盘粉剂，其中所述的碱包括碳酸钠。
57、一种权项54～56任一项的洗盘粉剂，该粉剂含有10～40%（重量）的三聚磷酸钠。
58、据权项54～57任一项的洗盘粉剂，该粉剂含有1～5%非离子型表面活性剂。
59、据权项54～58任一项的洗盘粉剂，该粉剂含有硅酸盐。
60、一种硬表面清洗剂，该清洗剂含有权项1～27任一项所述的保护酶体系。
61、一种权项60的硬表面清洗剂，该清洗剂含有1～10%（重量）的阴离子型和/或非离子型表面活性剂，2～15%（重量）的溶解的去污增效剂和1～10%（重量）的助水溶物。
62、一种权项61的硬表面清洗剂，其中，去污增效剂为焦磷酸钾。
63、据权项61或62任一项的硬表面清洗剂，其中，水溶助长剂为碱金属苯，或烷基苯，达4个脂肪族碳原子的磺酸盐。
64、据权项60～63任一项的一种清洗乳剂。
65、一种权项64的清洗乳剂，该乳剂含高达70%（重量）的研磨料悬浮其中。
66、一种权项65的清洗乳剂，其中研磨料为硅石或碳酸钙。
67、一种炉灶清洁剂，该清洁剂含有权项1～27任一项的保护酶体系。
68、一种权项67的炉灶清洁剂，该清洁剂含有2～15%（重量）的氢氧化钠或氢氧化钾和2～15%（重量）的阴离子型和/或非离子型表面活性剂。
69、一种权项67的炉灶清洗剂，该清洗剂含有5～20%（重量）的非离子型和/或阴离子型表面活性剂，5～40%（重量）的水互溶性液态低级一元醇，二元醇或多元醇或醇醚，以及5～15%（重量）的去污增效剂。
70、一种地毯清洗剂，该清洗剂含有根据权项1～27任一项所述的保护酶体系。
71、一种权项70的地毯清洗剂，该清洗剂含有2～20%（重量）的阴离子型和/或非离子型表面活性剂。
72、一种权项71的地毯清洗剂，其中所述的表面活性剂是烷基硫酸盐和链烷醇酰胺混合物。
73、据权项70～72任一项的地毯清洗剂，该清洗剂含高达10%（重量）的水互溶低级一元醇，二元醇或多元醇，或醇醚。
74、权项1～27任一项的保护酶体系，本质上讲这里所叙述的保护酶体系可参见任一实施例。
75、权项30～47任一项的组合物，本质上讲这里所叙述的组合物可参见任一实施例。
76、一种基本上由分散在疏水液体中的去污剂酶组成的组合物，该疏水液体具有0.05～200帕斯卡秒的粘性。
77、据权项1～27任一项和权项76的一种组合物，其中，所述的疏水液体具有0.8～200帕斯卡秒的粘性。
78、一种权项77的组合物，其中，所述的疏水液体具有1～100帕斯卡秒的粘性。
79、一种权项78的组合物，其中，所述的疏水液体具有2～50帕斯卡秒的粘性。
CN198787100752A 1986-02-20 1987-02-20 保护酶体系 Pending CN87100752A (zh)

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GB868604164A GB8604164D0 (en) 1986-02-20 1986-02-20 Enzymatic liquid detergent compositions
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CN111742041A (zh) * 2017-12-21 2020-10-02 丹尼斯科美国公司 包含耐热干燥剂的含酶的热熔细粒

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US4906396A (en) 1990-03-06
NO870679D0 (no) 1987-02-20
NO870679L (no) 1987-08-21
PL264223A1 (en) 1988-03-31
TR23421A (tr) 1989-12-29
AU594120B2 (en) 1990-03-01
DE3762629D1 (de) 1990-06-13
PT84338B (pt) 1989-09-14
GR3000585T3 (en) 1991-07-31
EP0238216A1 (en) 1987-09-23
HUT44286A (en) 1988-02-29
DK86187D0 (da) 1987-02-20
GB8704038D0 (en) 1987-03-25
FI870726A (fi) 1987-08-21
DK86187A (da) 1987-08-21
EG18543A (en) 1993-07-30
DK160886B (da) 1991-04-29
FI870726A0 (fi) 1987-02-20
GB2186884A (en) 1987-08-26
NZ219353A (en) 1990-04-26
DK160886C (da) 1991-10-21
ES2015572B3 (es) 1990-09-01
AU6911187A (en) 1987-08-27
EP0238216B1 (en) 1990-05-09
PT84338A (en) 1987-03-01
PL154945B1 (en) 1991-10-31

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