CN1062374A - Liquid detergent composition containing lipase and protease - Google Patents

Liquid detergent composition containing lipase and protease Download PDF

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Publication number
CN1062374A
CN1062374A CN 91111550 CN91111550A CN1062374A CN 1062374 A CN1062374 A CN 1062374A CN 91111550 CN91111550 CN 91111550 CN 91111550 A CN91111550 A CN 91111550A CN 1062374 A CN1062374 A CN 1062374A
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detergent composition
protease
composition according
lipase
mixtures
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CN 91111550
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P·J·约翰斯顿
P·M·A·勒努瓦
C·A·J·K·特恩
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普罗格特-甘布尔公司
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Priority to EP19910200149 priority patent/EP0486073B1/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease, amylase
    • C11D3/38663Stabilised liquid enzyme compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease, amylase
    • C11D3/38618Protease or amylase in liquid compositions only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease, amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease, amylase containing lipase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Abstract

本发明公开了液体洗涤剂组合物,该洗涤剂组合物含有常用的洗涤成分和酶体系,其中酶体系含有脂肪酶或其混合物,和改性的细菌丝氨酸蛋白酶或所说的蛋白酶的混合物。 The present invention discloses a liquid detergent composition, the detergent composition comprising conventional detergent ingredients and an enzyme system, wherein the enzyme system comprising a lipase or mixtures thereof, and modified bacterial serine protease or mixtures of said proteases.

Description

本发明涉及含有酶体系的液体洗涤剂组合物。 The present invention relates to liquid detergent compositions containing enzyme system. 该酶体系是改性的蛋白酶和脂肪酶的混合物。 The enzyme system is a mixture of a modified protease and a lipase.

众所周知,在本技术领域中,洗涤剂组合物可便利地含有酶体系。 It is well known in the art, the detergent compositions may conveniently contain an enzyme system. 这类酶体系包括纤维素酶、蛋白酶、脂肪酶和淀粉酶。 Such enzyme systems include cellulase, protease, amylase and lipase. 本发明的目的特别是在于提供液体洗涤剂组合物,在该液体洗涤剂组合物中的酶体系含有蛋白酶和脂肪酶的混合物。 Object of the present invention is in particular to provide a liquid detergent composition, the enzyme system in the liquid detergent composition containing a mixture of protease and lipase.

配制这类颗粒洗涤剂组合物不会引起特殊的问题,因为这两种酶在物理上能够分离。 Such granular detergent compositions formulated without causing a particular problem, since both enzymes can be physically separated. 反之,配制这类液体洗涤剂混合物引起的特殊技术问题在于,蛋白酶很可能被看作是一种存在于该洗涤剂组合物中的任何蛋白质的作用物。 Conversely, specific technical problems formulated liquid detergent mixture caused such that the protease is likely to be seen as any kind of action of a protein present in the detergent composition.

特别是,可以看出,也可以存在于洗涤剂组合物中的脂肪酶更易于发生这类蛋白水解的降解作用。 In particular, it can be seen, may be present in detergent compositions lipases easier to proteolytic degradation of such occurrence. 结果,在洗涤剂组合物中的脂肪酶的残余活性将随着该洗涤剂组合物的存储时间而很快减少,以致于到现在为止,配制同时含有脂肪酶和蛋白酶的液体洗涤剂组合物是不可能的,而对于商品利用来说,上述的洗涤剂组合物却是足够的稳定。 As a result, the residual activity of the lipase in the detergent composition will vary with the storage time of the detergent composition being rapidly reduced, so that up to now, while formulating liquid detergent compositions containing lipase and protease are impossible, and for using the product, the above detergent composition is sufficiently stable.

因此,本发明的目的是提供一种含有包括脂肪酶和蛋白酶的酶体系的液体洗涤剂组合物,其中所说的酶体系是稳定的。 Accordingly, an object of the present invention is to provide a liquid detergent composition comprising a lipase and a protease enzyme system, wherein said enzyme system is stable. 稳定的意思是指基本上减小了该脂肪酶的蛋白水解的降解作用。 Stability is meant that substantially reduces proteolytic degradation of the lipase.

现在已发现,这一目的能够被实现是通过使用任何脂肪酶、或其混合物、以及细菌丝氨酸蛋白酶或这类蛋白酶的混合物,在该蛋白酶中,与活性部位的丝氨酸相邻的蛋氨酸已被另外的氨基酸代替。 It has now been found that this object can be achieved by using any lipase, or mixtures thereof, and mixtures of such bacterial protease or a serine protease, the protease, adjacent to the active site serine has been additional methionine amino acids instead. 实际上,已经发现,这种特殊的组合物将会提供含有蛋白酶和脂肪酶的酶体系,而脂肪酶在液体洗涤剂组合物中将是稳定的。 Indeed, it has been found that such compositions will provide specific enzyme systems containing protease and lipase, and the lipase in the liquid detergent compositions are stable.

这种溶液具有的优点是简单,因为它只需要市场上可买到的成分。 This solution has the advantage that simple, because it only requires ingredients available on the market. 确实,不但适合于在洗涤剂组合物中使用的各种脂肪酶是在市场上可买到的,而且适合于本发明的目的的各种改性的细菌丝氨酸蛋白酶也是在市场上可买到的。 Indeed, not only used for a variety of lipase in detergent compositions are commercially available and are suitable for purposes of the present invention, various modified bacterial serine proteases are also available on the market . 此外,本发明的洗涤剂组合物不需要添加特殊的脂肪酶稳定剂,因此,就产品的价格和对环境的适应性来说,本发明的洗涤剂组合物是特别具有吸引力的。 Further, the detergent composition of the present invention does not need to add special lipase stabilizers, thus, on the price of the product and adaptability to the environment, the detergent compositions of the present invention are particularly attractive.

包括不但用于洗涤剂组合物中而且也适合于在本发明的组合物中使用的蛋白酶的改性的细菌丝氨酸蛋白酶公开在例如EP-A-0328229中。 Includes not only a modified detergent compositions but also suitable for use in the compositions of the present invention, the protease bacterial serine proteases disclosed, for example in EP-A-0328229. 该专利申请尤其描述了改性的细菌丝氨酸蛋白酶,该种蛋白酶是市场上可买到的(来自GISTBROCADES),其商标名为MAXAPEM15R。 In particular, this patent application describes a modified bacterial serine protease, the protease is a commercially available (from GISTBROCADES), the trade name MAXAPEM15R.

在1988年3月公开的Biotechnology Newswatch(第6页)和EP-A-0258 268描述了一种脂肪酶,该脂肪酶是市场上可买到的(来自NOVO NORDISKA/S),其商标名为LIPOLASER。 In March 1988 disclosed Biotechnology Newswatch (p. 6), and EP-A-0258 268 describes a lipase, the lipases are commercially available (from NOVO NORDISKA / S), under the trade name LIPOLASER. 该欧洲专利申请提到了LIPOLASER能够与蛋白酶结合以形成颗粒酶类洗涤剂添加剂。 The European Patent Application mentioned LIPOLASER capable of binding with a protease enzyme to form a particulate detergent additive.

EP-A-0 381262描述了含有蛋白酶和脂肪酶(最好为LIPOLASER)同时具有稳定体系的洗涤剂组合物。 EP-A-0 381262 describes a detergent composition comprising a protease and a lipase (preferably LipolaseR) while having a stabilizing system. 在该参考文献中公开的蛋白酶包括细菌蛋白酶。 Disclosed in this reference include bacterial proteases are proteases.

因此,本发明是含有酶体系的液体洗涤剂组合物,其特征在于该酶体系含有改性的细菌丝氨酸蛋白酶或其混合物,以及脂肪酶或其混合物。 Accordingly, the present invention is a liquid detergent composition comprising an enzyme system, characterized in that the enzyme system comprises a modified bacterial serine protease or mixtures thereof and a lipase or mixtures thereof. 该细菌丝氨酸蛋白酶的改性在于相邻于活性位点的丝氨酸的蛋氨酸被其他氨基酸代替。 The modified bacterial serine proteases in that adjacent to the active site serine is replaced by another amino acid methionine.

本发明的酶体系含有脂肪酶和蛋白酶。 The enzymatic system of the present invention comprises a lipase and a protease. 正如在EP0381262或EP271152中描述的那样,任何适合于在洗涤剂组合物中使用的脂肪酶都能在本发明的组合物中使用。 As described in EP271152 or EP0381262 any lipase suitable for use in detergent compositions can be used in the compositions of the present invention. 正如在授予NOVO INDUSTRIA/S的EP-A-0258068中所描述的那样,在本发明组合物中使用的优选的脂肪酶是由Humicolalanuginosa得到的脂肪酶。 As granting NOVO INDUSTRIA / S of EP-A-0258068 described, preferred lipase for use in the compositions of the present invention are obtained by the Humicolalanuginosa lipase. 该专利申请描述如何得到所说的特殊的脂肪酶,但是所说的特殊的脂肪酶也是市场上可买到的(来自NOVO NORDISKA/S,商标名称为LIPOLASER)。 This patent application describes how to get special said lipase, but said specific lipase is also commercially available on the market (from NOVO NORDISKA / S, trade name LIPOLASER). 适用于本发明的其他市场上可买到的脂肪酶是Amono-P LipaseR、Amono-B LipaseR、Amono CES LipaseR、Amono AKG LipaseR,这些脂肪酶都来自Amono pharma-ceuticals(日本);Toyo Jozo Co(日本)和US biochemical Corp.(USA)以及Diosynth Co.(NL)也已成为用于本发明组合物中的适合的脂肪酶商品。 Applicable to other markets of the present invention is commercially available lipases Amono-P LipaseR, Amono-B LipaseR, Amono CES LipaseR, Amono AKG LipaseR, all these lipases from Amono pharma-ceuticals (Japan); Toyo Jozo Co ( Japan) and US biochemical Corp. (USA) and Diosynth Co. (NL) has become suitable lipases commercial compositions used for the present invention.

本发明的组合物一般每克成品含有0.1至10000脂解单位,最好是每克成品含有10至2500脂解单位。 The composition of the present invention generally contain from 0.1 to 10,000 finished Lipolytic Units per gram, per gram of finished product preferably contains from 10 to 2500 Lipolytic Units. 脂解单位被定义例如在EP0258268(第5页38行)中。 Lipolytic units are defined for example in EP0258268 (page 5, line 38) in the.

本发明所使用的蛋白酶是改性的细菌丝氨酸蛋白酶。 Protease used in the present invention is a modified bacterial serine proteases. 所有的天然细菌丝氨酸蛋白酶的特征在于其活性位点总是含有三种氨基酸,这三种氨基酸为丝氨酸、组氨酸和天冬氨酸。 All native bacterial serine proteases characterized in that it always contains three active site amino acids, three amino acid is serine, histidine and aspartic acid. 这些氨基酸以酶的天然形式并以这样一种方法定位,以致它们催化分裂蛋白质的内肽键。 These amino acids are positioned in such a way and the natural form of the enzyme, such that they catalyze the cleavage of peptide bonds of proteins. 在这些细菌丝氨酸蛋白酶之间的另一个共同点在于总是有以天然顺序存在的相邻于活性位点的丝氨酸的蛋氨酸。 Another common point between these bacterial serine proteases is that there is always methionine adjacent to the serine of the active site present in the native sequence. 适用于本发明的那些细菌丝氨酸蛋白酶是其中相邻于活性位点的丝氨酸的蛋氨酸已被另外的氨基酸所代替。 Useful in the present invention are those wherein the bacterial serine proteases is adjacent to the active site serine has been replaced by methionine another amino acid. 活性位点的丝氨酸也能定义为这样的丝氨酸,即它是同源于在由枯草杆菌(Bacillus Subtilis)产生的细菌枯草杆菌蛋白酶的氨基酸顺序中的221位上的丝氨酸。 Serine active site can also be defined as a serine, i.e., it is the same amino acid sequence from serine in Bacillus subtilis by bacteria (Bacillus Subtilis) protease produced 221 bits. 所说的顺序列入下文的图1中。 Included in said sequence below FIG.

在由枯草杆菌产生的这种细菌枯草杆菌蛋白酶的顺序中,蛋氨酸紧接在221位上的丝氨酸之后,因此它是在需要由另外的氨基酸代替的222位上的蛋氨酸。 In order produced by the bacteria Bacillus subtilisin, the methionine is immediately after the serine at 221, so it is required in the 222 methionine replaced by another amino acid. 可能的是,在其他的细菌丝氨酸蛋白酶的顺序中,这种蛋氨酸不总是紧接在活性位点的丝氨酸的后面。 It is possible that in the sequence of other bacterial serine proteases, this methionine is not always immediately following the serine of the active site. 在这样的情况下,它是同源于在由枯草杆菌产生的这种细菌枯草杆菌蛋白酶的顺序中的222位上的蛋氨酸,该种蛋氨酸需要由另外氨基酸代替。 In such a case, it is the same from the methionine in the sequence 222 generated by the bacterium Bacillus subtilisins in this kind requires methionine amino acid replaced by another.

当然,本发明不在于这些改性的蛋白酶本身、相反,应在于将这些改性的蛋白酶特别应用于还含有脂肪酶的液体洗涤剂组合物中。 Of course, the present invention is not in these modified proteases per se and, instead, that the particular application of these modified proteases to liquid detergent compositions also comprising a lipase. 因此。 therefore. 详细说明如何能够得到这些改性蛋白酶不是本发明的目的。 Detail how these modified proteases can be obtained are not object of the present invention. 这种改性是能够通过定向位点致突变或通过在本技术领域中为此目的的已知的任何其他遗传工程技术来完成。 Such modifications are capable of mutagens or by site-directed be accomplished by any other genetic engineering techniques known in the art for this purpose. 例如,EP-A-0328229(授予GIST-BROCADES NV)描述了如何得到这类蛋白酶。 For example, EP-A-0328229 (granted GIST-BROCADES NV) describes how to obtain such proteases. 另外适合的方法描述在EP130756中,该文献也描述了适用于本发明的组合物中的改性的细菌丝氨酸蛋白酶。 Additional suitable methods are described in EP130756, which also describes a composition suitable for use in the present invention is a modified bacterial serine proteases.

此外,适用于本发明组合物中的某些改性的细菌丝氨酸蛋白酶是市场上可买到的,例如DURAZYMR(来自NOVO),它是SAVINASER的改性形式的蛋氨酸。 Further, the present invention is useful in the compositions of some modified bacterial serine proteases are commercially available, e.g. DURAZYMR (from NOVO), which is a modified form of SAVINASER methionine. 另一种可得到的改性的蛋白酶的例子是MAXAPEM15(来自GIST-BROCADES),它是MAXACALR的改性形式,其中在216位上的蛋氨酸已被代替。 Another example of available modified protease is MAXAPEM 15 (from GIST-BROCADES), which is a modified form of MAXACALR, wherein the methionine at position 216 has been replaced. 改性的OPTICLEANR和OPTIMASER(来自SOLVAY酶)的试验样品也是可得到的,两者的改性在于在222位上的蛋氨酸被胱氨酸代替。 And OPTIMASER OPTICLEANR modified test sample (from SOLVAY enzymes) are also available, both modified methionine that is at position 222 in place of cystine. 本发明优选的改性的细菌丝氨酸蛋白酶是MAXAPEM15R(来自GIST BROCADES)和DURAZYMR(来自NOVO)。 Preferably the present invention is a modified bacterial serine proteases MAXAPEM15R (from GIST BROCADES) and DURAZYMR (from NOVO).

本发明的组合物一般每克成品含有0.005至10mg活性蛋白酶,最好每克成品含有0.01至5.0mg活性蛋白酶。 The composition of the present invention generally contain from 0.005 to 10mg finished active protease per gram of finished preferably contain from 0.01 to 5.0mg of active protease per gram. 本文上述的改性的细菌丝氨酸蛋白酶的混合物也适用于本发明组合物。 The mixture is bacterial serine proteases modified herein can also useful in the compositions of the present invention.

本发明的液体洗涤剂组合物的剩余部分是由常用的洗涤成分,即水、表面活性剂、助洗涤和其他物质所组成。 The remaining portion of the liquid detergent compositions of the present invention is a conventional detergency ingredients, i.e. water, surfactants, detergency and other substances composed. 对于这些成分的下列叙述是为了使叙述具有完整性,而不能认为是将本发明的组合物限制到所述的那些常用的成分上。 For the following description of these ingredients it is to make the narrative with integrity, but not to be considered to limit the composition of the present invention to those conventional ingredients described.

本发明的液体洗涤剂组合物含有液体洗涤剂组合物总重量的5%至60%,优选10%至40%重量的有机表面活性剂,该有机表面活性剂选自非离子的、阴离子的、阳离子的和两性离子的表面活性剂和其混合物。 The liquid detergent compositions of the invention contain 5-60% by weight of the total liquid detergent composition, preferably 10% to 40% by weight of organic surfactant, the organic surfactant is selected from nonionic, anionic, cationic surfactants and zwitterionic and mixtures thereof.

适合的阴离子表面活性盐选自磺酸盐和硫酸盐。 Suitable anionic surface-active salt selected from sulfonates and sulfates. 类似的阴离子表面活性剂在洗涤剂技术领域中是熟知的,并已被发现广泛应用于商品洗涤剂中。 The like anionic surfactants are well known in the detergent art and have been found widely used in commercial detergents. 优选的阴离子水溶性磺酸盐或硫酸盐在它们的分子结构中具有含约8至约22个碳原子的烷基。 Preferred anionic water-soluble sulfonate or sulfate salts having an alkyl group containing from about 8 to about 22 carbon atoms in their molecular structure.

这类优选的阴离子表面活性剂盐的例子是由硫酸化的C6-C16脂肪族醇(来自例如动物脂油、棕榈油、棕榈仁油和椰子油)得到的反应产物;烷基苯磺酸盐(其中的烷基含有约9至约15个碳原子);烷基甘油醚磺酸钠;由动物脂油和椰子油得到的脂肪族醇的醚硫酸盐;椰子脂肪酸单酸甘油酯硫酸盐和磺酸盐;和在烷基链中具有约8至约22个碳原子的链烷磺酸盐的水溶性盐。 Examples of such preferred anionic surfactant salts are the sulfated C6-C16 aliphatic alcohol (e.g. derived from tallow, palm oil, palm kernel oil and coconut oil) the reaction product obtained; alkyl benzene sulfonates ( wherein the alkyl group contains from about 9 to about 15 carbon atoms); an alkyl glyceryl ether sulfonates; ether sulfates derived from tallow and coconut oil fatty alcohol; coconut fatty acid monoglyceride sulfates and salt; and a chain alkoxy having from about 8 to about 22 carbon atoms in the alkyl chain sulfonates water-soluble salts. 正象在如US3,332,880的专利说明书中更全面地描述的那样,磺化的烯烃表面活性剂也是可使用的。 Just as in patent specifications, such as in US3,332,880 described more fully sulfonated olefin surfactants are also usable. 用于阴离子合成的磺酸盐和/或硫酸盐的中和阳离子可通过广泛使用在洗涤剂技术中的常用阳离子例如钠、钾或链烷醇铵来提供。 For the anionic synthetic sulfonates and / or sulfates and cationically sodium, potassium or alkanolammonium provided by widely used in detergent technology common cation such.

本发明中适合的阴离子合成表面活性剂成分是由烷基苯磺酸的水溶性盐优选烷基苯磺酸钠来提供的,优选是在烷基中具有约10至13个碳原子的烷基苯磺酸钠。 In the present invention, suitable anionic synthetic surfactant component is preferably a water soluble salt of alkylbenzene sulfonic acid to provide sodium alkylbenzene sulfonate, an alkyl group preferably having from about 10 to 13 carbon atoms in the alkyl group benzenesulfonate. 本发明中另一种优选的阴离子表面活性剂成分是在烷基中具有约10至15个碳原子的烷基硫酸钠。 The present invention Another preferred anionic surfactant component is alkyl sulfate having from about 10 to 15 carbon atoms in the alkyl group.

适用于本发明的非离子表面活性剂包括,通过在酸性或碱性催化剂存在下,环氧乙烷与具有活性氢原子,例如羟基、羧基或酰氨基的烃进行缩合而产生的那些物质,并包括具有通式为RA(CH2CH2O)nH的化合物,在该通式中,R代表疏水部分,A代表带有活性氢原子的基团,n代表环氧乙烷部分的平均数,R通常含有约8至22个碳原子,它们也可通过1,2-环氧丙烷与低分子量化合物进行缩合来形成,n通常在约2至约24间变化。 Nonionic surfactants useful in the present invention include those substances produced in the presence of an acidic or basic catalyst, ethylene oxide and having an active hydrogen atom such as hydroxyl, carboxyl, or amido group of condensed hydrocarbons, and nH comprising a compound of the general formula RA (CH2CH2O), in the formula, R represents the hydrophobic moiety, a representative of the group carrying the reactive hydrogen atom, n is representative of the average number of ethylene oxide moieties, R generally contains from about 8 to 22 carbon atoms, which may be formed by condensation of propylene oxide with low molecular weight compounds, n-typically from about 2 to about 24 vary.

优选类的非离子乙氧基化物可通过具有12至15个碳原子的脂肪族醇和约4至10摩尔的环氧乙烷(每摩尔脂肪族醇)的缩合产物来提供。 A preferred class of nonionic ethoxylates can be provided by an aliphatic alcohol having 12 to 15 carbon atoms, from about 4 to 10 moles of ethylene oxide (per mole of aliphatic alcohol) condensation products. 这类适合的乙氧基化物包括C12-C15的羰基合成醇和3至9摩尔的环氧乙烷(每摩尔醇)的缩合产生;窄馏分C14-C15的羰基合成醇和3至9摩尔的环氧乙烷(每摩尔脂肪族(羰基合成)醇)的缩合产物;窄馏分C12-C13的脂肪族(羰基合成)醇和6.5摩尔环氧乙烷(每摩尔脂肪族醇)的缩合产物;具有在4至8范围内的乙氧基化度(摩尔环氧乙烷/摩尔脂肪醇)的C10-C14椰子脂肪醇的缩合产物。 Such suitable ethoxylates include C12-C15 carbonyl Synthesis of alcohols and 3 to 9 moles of ethylene oxide (per mole of alcohol) to produce condensation; oxo narrow cut C14-C15 alcohols and 3 to 9 moles of ethylene ethane (per mole of fatty (oxo) alcohol) condensation products; narrow cut C12-C13 fatty (oxo) alcohol and 6.5 moles of ethylene oxide (per mole of aliphatic alcohol) condensation products; has 4 condensation products of the range 8 to the degree of ethoxylation (moles EO / mole fatty alcohol) of C10-C14 coconut fatty alcohols. 脂肪族羰基合成醇尽管主要为直链的,也有一定程度的支化,特别是短链如甲基支化,这取决于工艺条件和原料烯烃。 Aliphatic oxo alcohol although predominantly linear, but also a certain degree of branching, particularly short chain such as methyl branching, depending upon the processing conditions and raw material olefins. 在商品羰基合成醇中常见的支化度在15%至50%(重量%)的范围内。 Common in commercial oxo alcohols degree of branching in the range of 15-50% (wt%).

适合的阳离子表面活性剂包括式R1R2R3R4N+的季铵化合物,在该式中,R1、R2和R3是甲基,R4是C12-15的烷基,或R1是乙基或羟乙基,R2和R3是甲基,R4是C12-15的烷基。 Suitable quaternary ammonium compounds include cationic surfactants of the formula R1R2R3R4N +, in the formula, R1, R2 and R3 are methyl, R4 is C12-15 alkyl, or R1 is ethyl or hydroxyethyl, R2 and R3 is methyl, R4 is C12-15 alkyl.

两性离子表面活性剂包括脂族的季铵、鏻和铳化合物的衍生物,在该衍生物中,脂族部分可以是直链的或支链的,其中一个脂族取代基含有约8至约24个碳原子,另一个取代基至少含有阴离子水溶性基团。 Zwitterionic surfactants include aliphatic quaternary ammonium, phosphonium, and gun compound, the derivative, the aliphatic moiety can be straight chain or branched, wherein a substituted aliphatic groups contain from about 8 to about 24 carbon atoms, at least another substituent contains an anionic water-solubilizing group. 特别优选的两性离子物质是乙氧基化的磺酸铵和硫酸铵[公开在U,S专利3,925,262(Laughlin等人,1975年12月9日出版)和3,929,678(Laughlin等人,1975年12月30日出版)中]。 Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates [disclosed in U, S Patent No. 3,925,262 (Laughlin et al., December 9, 1975 publication) and 3,929,678 ( Laughlin et al., December 30, 1975 publication) in].

半极性的非离子表面活性剂包括水溶性氧化胺,该水溶性氧化胺含有一个烷基或羟烷基(含有约8至约28个碳原子)部分和选自烷基和羟烷基(含有1至约3个碳原子)的两部分(可任意被连接成环状结构)。 Semi-polar nonionic surfactants include water-soluble amine oxides, water-soluble amine oxides containing one alkyl or hydroxyalkyl group (containing from about 8 to about 28 carbon atoms) moiety and selected from alkyl and hydroxyalkyl ( part 1 contains two to about 3 carbon atoms) (which may optionally be connected in a cyclic structure).

具有式 Having the formula

的多羟基脂肪酸酰胺的表面活性剂也是适合的,在上式中,R1是H、C1-4烃基、2-羟乙基、2-羟丙基或其混合体,R2是C5-31烃基,Z是具有线性烃基链且至少有3个羟基直接连在该链上的多羟基烃基或其烷氧基化衍生物。 Polyhydroxy fatty acid amide surfactants are also suitable in the above formula, R1 is H, C1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-31 hydrocarbyl, Z is a linear hydrocarbon chain with at least 3 hydroxyls directly connected to the polyhydroxy hydrocarbon or an alkoxylated derivative thereof in the chain. 优选R1是甲基,R2是直链的C11-15烷基链或链烯基链,或其混合体,且Z是在还原胺化反应中由还原糖,如葡萄糖、果糖、麦芽糖、内脂衍生得到的。 Preferably, R1 is methyl, R2 is C11-15 alkyl or alkenyl chain, or a mixture of straight-chain, and Z is in a reductive amination reaction from a reducing sugar such as glucose, fructose, maltose, lactone derived.

本发明的组合物可进一步含有助洗剂体系。 The compositions of the invention may further comprise a builder system. 任何常用的助洗剂体系都是适合的,但最好是柠檬酸和取代的琥珀酸的混合物。 Any conventional builder system is suitable, but preferably a mixture of citric acid and a substituted succinic acid.

在本发明的实施中所使用的柠檬酸助洗剂将以柠檬酸的任何水溶性盐的形式存在于成品中。 Form of any water soluble salt of citric acid builders in the embodiment of the present invention will be used in the citric acid is present in the finished product. 这类盐包括,例如钠、钾、铵或链烷醇铵盐。 Such salts include, for example, sodium, potassium, ammonium or alkanolammonium salts. 实际上,使用柠檬酸一水化合物浆作为起始原料是很方便的,它将就地被中和,以便形成上述的盐。 Indeed, citric acid monohydrate slurry as a starting material is convenient, it will be neutralized in situ, to form the salt.

本发明的取代的琥珀酸助洗剂具有通式为R-CH(COOH)CH2(COOH),即琥珀酸的衍生物,在上式中,R是C10-C16烷基或链烯基,最好是C12-C14链烯基。 The substituted succinic acid builders of the present invention have the general formula R-CH (COOH) CH2 (COOH), i.e. derivatives of succinic acid, in the formulas, R is C10-C16 alkyl or alkenyl, most preferably from C12-C14 alkenyl.

这些取代的琥珀酸助洗剂最好是以它们的水溶性盐包括钠、钾、铵和链烷醇铵盐(例如一、二、或三乙醇铵)的形式存在于成品中。 These substituted succinic acid builders are preferably in their water-soluble salts include sodium, potassium, ammonium and alkanolammonium salts (e.g., mono-, di-, or triethanolammonium) form in the finished product.

作为原料,最好是以这些琥珀酸的二酸或酐的形式使用它们的衍生物。 As a starting material, preferably in the form of diacid or anhydride, succinic acid using these derivatives thereof. 二酸可被就地中和,而酐则经过水解/中和过程。 Acid may be neutralized in situ, while the anhydride is subjected to a hydrolysis / neutralization process.

取代的琥珀酸助洗剂的具体实例包括月桂基琥珀酸、肉豆蔻基琥珀酸、棕榈基琥珀酸、2-十二碳烯基琥珀酸(优选的)、2-十四碳烯基琥珀酸,等等。 Specific examples of substituted succinic acid builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-tetradecenyl succinic acid ,and many more.

优选的助洗剂体系包含有组合物总重量的4至12%的上述取代的琥珀酸助洗剂和组合物总重量的4至12%的柠檬酸。 The preferred builder system comprises from 4 to 12% of the total weight of the composition 4-12% of the total weight of the substituted succinic acid builders, and citric acid composition. 作为另一种助洗剂,本发明的组合物也可含有脂肪酸,优选的是油酸和棕榈油酸。 As an alternative builder, the compositions of the present invention may also contain a fatty acid, preferably oleic acid and palmitoleic acid.

本技术领域中技术熟练的人员所熟知的是组合物的PH值可极大地影响酶体系的性能。 The art skilled person in the art that the PH value of the composition can greatly affect the performance of the enzyme system. 因此,本发明的组合物最好具有被调节在6至10范围内的PH值,优选为7.5至8.0。 Thus, the compositions of the present invention preferably has to be adjusted in the range of PH value of 6 to 10, preferably 7.5 to 8.0.

本发明的组合物也可包含酶稳定体系。 The composition of the present invention may also comprise an enzyme stabilizing system. 实际上,本发明提供了一个其中蛋白酶不明显破坏天然脂肪酶的体系,但是由于其他洗涤成分的存在,该酶体系或其组分仍然可能容易发生不稳定的问题。 Indeed, the present invention provides a protease obvious problem wherein the native lipase breaking system, due to the presence of other detergent ingredients, the enzyme system or components thereof may still be prone to instability. 因此,稳定剂可能是需要的,这些稳定剂是常用的并且是本技术领域所熟知的。 Accordingly, the stabilizer may be required, these stabilizers are commonly used and are well known in the art. 优选的酶稳定体系选自硼酸、1,2-丙二醇、羧酸和其混合物。 A preferred enzyme stabilizing system is selected from boric acid, 1,2-propanediol, carboxylic acids, and mixtures thereof. 这些酶稳定体系一般存在的量为组合物总重量的0.01%至5%。 These enzyme stabilizing systems are typically present in an amount of from 0.01 to 5% of the total weight of the composition.

本发明的组合物也可含有其他酶,例如纤维素酶或淀粉酶。 The composition of the present invention may also contain other enzymes, such as cellulases or amylases. 特别是,在蛋白酶存在的情况下,淀粉酶似乎是稳定的,因此,本发明的组合物最好含有淀粉酶。 In particular, in the presence of protease, amylase appeared to be stabilized, and therefore, the composition of the present invention preferably contains amylase.

本发明的组合物可含有一系列另外可选择的成分。 The composition of the present invention may contain a series of further optional ingredients. 这类的添加剂的例子包括:泡沫调节剂、遮光剂、为改善对于搪瓷涂层表面的机器相容性的添加剂、杀菌剂、染料、香料、包括过硼酸盐和过碳酸盐的漂白剂、增白剂、污垢除去剂、柔软剂等。 Examples of such additives include: suds regulants, opacifiers, agents to improve the machine for the surface coating of enamel compatible additives, bactericides, dyes, perfumes, include perborate and percarbonate bleaches , brighteners, soil release agents, softening agents and the like.

本发明的液体组合物可含有另外添加剂的量一般为0.05至5%。 The amount of the liquid compositions of the invention may contain additional additives is generally 0.05 to 5%. 这些添加剂包括多氨基羧化物,例如亚乙基二氨基四乙酸、二亚乙基三氨基五乙酸、亚乙基二氨基二琥珀酸或其水溶性碱金属盐。 These additives include polyaminocarboxylates thereof, such as ethylene diamino tetra acetic acid, diethylene triamino pentacetic acid, ethylenediamine disuccinic acid or the water-soluble alkali metal salt. 其他的添加剂包括有机膦酸,特别优选的是亚乙基二氨基四亚甲基膦酸、六亚甲基二氨基四亚甲基膦酸、二亚乙基三氨基五亚甲基膦酸和氨基三亚甲基膦酸。 Other additives include organic phosphonic acids, particularly preferred are ethylene diamino tetramethylene phosphonic acid, hexamethylene diamino tetramethylene phosphonic acid, diethylene triamino pentamethylene phosphonic acid, and amino trimethylene phosphonic acid.

实施例本发明的下述组合物是按表中的比例将列出的成分混合制得的。 The following compositions of Examples of the present invention is a composition proportion of the table lists the obtained mixture.

1 2 3 4 5直链烷基苯磺酸盐 12 7 6 7 8C12-15烷基硫酸钠2 2 3 3 2C14-15烷基2.5 乙氧基化的硫酸盐0 0 2 2 0 12,345 linear alkyl benzene sulfonate 12 7 6 7 8C12-15 alkyl sulfate 2 2 3 3 2C14-15 alkyl ethoxylated sulfates 2.5 00,220

C12萄葡糖酰胺0 0 6 6 07 乙氧基化的C12-15醇8 0 0 0 05 乙氧基化的12-15醇0 8 0 0 8油酸 2 0 0 0 0柠檬酸 3 9 9 13 15C12-14链烯基取代的琥珀酸10 5 5 7 6乙醇 4 4 3 4 51,2-丙二醇 2 3 3 1 2NaOH 6 8 8 11 11二亚乙基三胺五(亚甲基膦酸) 0.5 0.7 0.7 1 1淀粉酶(143KNU/g) 0.1 0.1 0.05 0.2 0.1LipolaseR(100KLU/g商品溶液) 0.4 0.2 0.3 0.3 0.3PEM15R(50mg/g商品溶液) 0.3 0 0 0 0.4DurazymR(39mg/g商品溶液) 0 0.2 0 0 0Opticlean M222CR(试验样品) 0 0.1 0 0.4 0Optimase M222CR(试验样品) 0 0 0.3 0 0CaCl2 0.01 0 0.01 0.01 0.02偏硼酸钠 2.2 2 2 4 3三乙醇胺 0 0 0 0 0甲酸钠 0 0 0 0 0脂肪酸 0 0 0 0 0水和辅助物 -平衡至100%-实施例本发明的下述组合物是按表中的比例将列出的成分混合制得的。 C12 glucamides grapes 006607 C12-15 ethoxylated alcohol 800 005 12-15 ethoxylated alcohol 08,008 oleic citrate 20 000 399 13 15C12-14 alkenyl substituted succinic acid ethanol 105 576 4434 51,2- propanediol 2 3 3 1 2NaOH 6 8 8 11 11 diethylene triamine penta (methylene phosphonic acid) 11 0.5 0.7 0.7 amylase (143KNU / g) 0.1 0.1 0.05 0.2 0.1LipolaseR (100KLU / g product solution) 0.4 0.2 0.3 0.3 0.3PEM15R (50mg / g product solution) 0.3 0 0 0 0.4DurazymR (39mg / g solution trade ) 0 0.2 0 0 0Opticlean M222CR (test sample) 0 0.1 0 0.4 0Optimase M222CR (test sample) 0 0 0.3 0 0CaCl2 0.01 0 0.01 0.01 0.02 Na metaborate 2.2 2 243 triethanolamine 00 000 sodium 000 fatty acid 00 00 000 water and adjuncts - balance to 100% - the following ingredient composition of embodiment of the present invention is the proportion of the table prepared by mixing the listed.

6 7 8 9 10直链的烷基苯磺酸盐 5 7 9 8 10C12-15烷基硫酸钠5 2 1.75 0 3C14-15烷基2.5乙氧基化的硫酸盐2 0 2 0 0C12萄葡糖酰胺6 0 7 0 07 乙氧基化的C12-15醇0 0 0.5 0 11.65 乙氧基化的C12-15醇0 8 0 8油酸 0 0 0 3.5 2.5柠檬酸 10 9 9.5 4 1C12-14链烯基取代的琥珀酸11 0 11.5 0 0三聚磷酸钠 0 20 0 0 0沸石 0 0 0 26 0乙醇 6 4 4 3 61,2-丙二醇 3 2 2 2 1.5NaOH 9 9 9.8 9 3.5二亚乙基三胺五(亚甲基膦酸) 1.0 1.0 1.0 0.5 0.8淀粉酶(143KNU/g) 0.2 0.1 0.2 0.05 1LipolaseR(100KLU/g商品溶液) 0.5 0.5 0.3 0.2 0.3PEM15R(50mg/g商品溶液) 0.4 0 0 0 0.2DurazymR(39mg/g商品溶液) 0 0 0.5 0 0.2Opticlean M222CR(试验样品) 0 0 0 0.3 0Optimase M222CR(试验样品) 0 0.5 0 0 0 678,910 linear alkylbenzene sulfonate 5 7 9 8 10C12-15 alkyl sulfate 5 2 1.75 0 3C14-15 alkyl ethoxylated sulfates 2.5 2 0 2 0 0C12 where glucose amide 607 007 C12-15 alcohols ethoxylated 0 0 0.5 0 11.65 C12-15 alcohol ethoxylated oleic acid 0808 0 0 0 3.5 2.5 citric Acid 10 9 9.5 4 1C12-14 chain alkenyl substituted succinic acid 11 0 11.5 0 0 sodium tripolyphosphate zeolite 020 000 000 260 6443 61,2- ethanol propanediol 3 2 2 2 1.5NaOH 9 9 9.8 9 3.5 diethylenetriamine triamine penta (methylene phosphonic acid) 1.0 1.0 1.0 0.5 0.8 amylase (143KNU / g) 0.2 0.1 0.2 0.05 1LipolaseR (100KLU / g product solution) 0.5 0.5 0.3 0.2 0.3PEM15R (50mg / g product solution) 0.4 0 0 0 0.2DurazymR (39mg / g product solution) 0 0 0.5 0 0.2Opticlean M222CR (test sample) 0 0 0 0.3 0Optimase M222CR (test sample) 0 0.5 0 0 0

CaCl2 0.01 0.01 0.02 0.02 0.01偏硼酸钠 4 2 4 3 0三乙醇胺 0 0 0 0 6甲酸钠 0 0 0 0 1脂肪酸 0 0 0 0 12水和辅助物 -平衡至100%-实施例本发明的下述组合物是按表中的比例将列出的成分混合制得的。 CaCl2 0.01 0.01 0.02 0.02 0.01 Sodium metaborate 42430 triethanolamine sodium 00,006 00,001 000,012 fatty acid and water aids - balance to 100% - of the embodiment of the present invention the following examples the composition according to the component ratio is listed in the table prepared mixture.

11 12 13 14 15直链的烷基苯磺酸盐 5 7 9 8 10C12-15烷基硫酸钠5 2 1.75 0 3C14-15烷基2.5 乙氧基化的硫酸盐2 0 2 0 0C12萄葡糖酰胺6 0 7 0 07 乙氧基化的C12-15醇0 0 0.5 0 11.65 乙氧基化的C12-15醇0 8 0 8油酸 0 0 0 3.5 2.5柠檬酸 10 9 9.5 4 1C12-14链烯基取代的琥珀酸11 0 11.5 0 0酒石酸单琥珀酸盐 0 15 0 17 20二乙氧基化聚(1,2-亚丙基对苯二甲酸盐)1.0 0.5 0.7 0 0.5 1112131415 linear alkylbenzene sulfonate 5 7 9 8 10C12-15 alkyl sulfate 5 2 1.75 0 3C14-15 alkyl ethoxylated sulfates 2.5 2 0 2 0 0C12 where glucose amide 607 007 C12-15 alcohols ethoxylated 0 0 0.5 0 11.65 C12-15 alcohol ethoxylated oleic acid 0808 0 0 0 3.5 2.5 citric Acid 10 9 9.5 4 1C12-14 chain alkenyl substituted succinic acid 11 0 11.5 0 0 tartrate monosuccinate 01501720 diethoxy poly (1,2-propylene terephthalate) 0 1.0 0.5 0.7 0.5

乙醇 6 4 4 3 61,2-丙二醇 3 2 2 2 1.5NaOH 9 9 9.8 9 3.5二亚乙基三胺五(亚甲基膦酸) 1.0 1.0 1.0 0.5 0.8淀粉酶(143KNU/g) 0.2 0.1 0.2 0.05 1LipolaseR(100KLU/g商品溶液) 0.5 0.5 0.3 0.2 0.3PEM15R(50mg/g商品溶液) 0.4 0 0 0 0.2DurazymR(39mg/g商品溶液) 0 0 0.5 0 0.2Opticlean M222CR(试验样品) 0 0 0 0.3 0Optimase M222CR(试验样品) 0 0.5 0 0 0CaCl2 0.01 0.01 0.02 0.02 0.01偏硼酸钠 4 2 4 3 0三乙醇胺 0 0 0 0 6甲酸钠 0 0 0 0 1脂肪酸 0 0 0 0 12水和辅助物 -平衡至100%- Ethanol 6443 61,2- propanediol 3 2 2 2 1.5NaOH 9 9 9.8 9 3.5 Diethylene triamine penta (methylene phosphonic acid) 1.0 1.0 1.0 0.5 0.8 Amylase (143KNU / g) 0.2 0.1 0.2 0.05 1LipolaseR (100KLU / g product solution) 0.5 0.5 0.3 0.2 0.3PEM15R (50mg / g product solution) 0.4 0 0 0 0.2DurazymR (39mg / g product solution) 0 0 0.5 0 0.2Opticlean M222CR (test sample) 0 0 0 0.3 0Optimase M222CR (test sample) 0 0.5 0 0 0CaCl2 0.01 0.01 0.02 0.02 0.01 sodium metaborate 42430 triethanolamine 00006 sodium 00001 fatty 000012 water and aids - balance to 100% -

Claims (11)

1.一种液体洗涤剂组合物,该洗涤剂组合物含有常用的洗涤成分,其特征在于含有脂肪酶或其混合物和蛋白酶,其中蛋白酶是细菌丝氨酸蛋白酶或所说的蛋白酶的混合物,在蛋白酶中,相邻于活性位点的丝氨酸的蛋氨酸已被另外的氨基酸代替。 1. A liquid detergent composition, the detergent composition comprising conventional detergent ingredients, characterized in that it contains a protease and a lipase or mixtures thereof, wherein said protease is a serine protease or a mixture of bacterial protease, the protease adjacent to the active site serine has been replaced by methionine another amino acid.
2.根据权利要求1的洗涤剂组合物,其中脂是肪酶是LIPOLASER。 2. The detergent composition according to claim 1, wherein the lipid is a lipase LIPOLASER.
3.根据权利要求1的洗涤剂组合物,该洗涤剂组合物含有脂肪酶,其含量使之每克成品具有0.1至10000脂解单位。 3. A detergent composition according to claim 1 wherein the detergent composition contains a lipase in an amount so that per gram of finished with 0.1 to 10000 Lipolytic Units.
4.根据权利要求1的洗涤剂组合物,该洗涤剂组合物含有权利要求1所述的蛋白酶或其混合物,其含量使之每克成品具有0.005至10mg活性蛋白酶。 4. A detergent composition according to claim 1, comprising the detergent composition according to claim 1 protease or mixtures thereof, in an amount so that per gram of finished 0.005 to 10mg active protease.
5.根据权利要求1的洗涤剂组合物,其中改性的细菌丝氨酸蛋白酶选自MAXAPEM15R、DURAZYMR、M222C OPTICLEANR和M222C OPTIMASER,或其混合物。 5. A detergent composition according to claim 1, wherein the modified bacterial serine protease is selected from MAXAPEM15R, DURAZYMR, M222C OPTICLEANR and M222C OPTIMASER, or mixtures thereof.
6.根据权利要求1的洗涤剂组合物,该洗涤剂组合物另外含有淀粉酶。 6. A detergent composition according to claim 1, the detergent composition additionally comprises an amylase.
7.根据权利要求1的洗涤剂组合物,该洗涤剂组合物另外含有酶稳定体系。 The detergent composition of claim 1 wherein the detergent composition further comprises an enzyme stabilizing system.
8.根据权利要求7的洗涤剂组合物,其中酶稳定体系是由为组合物总重量的0.01至5%的硼酸组成。 A detergent composition according to claim 7 wherein the enzyme stabilization system is 0.01 to 5% by weight of the total composition of boric acid.
9.根据权利要求7的洗涤剂组合物,其中酶稳定体系含有1,2-丙二醇和/或羧酸和其混合物。 A detergent composition according to claim 7 wherein the enzyme stabilization system comprises 1,2-propanediol and / or carboxylic acids and mixtures thereof.
10.根据权利要求1的洗涤剂组合物,该洗涤剂组合物具有PH值在6至10的范围内。 10. A detergent composition according to claim 1, the detergent composition having a PH value in the range 6 to 10.
11.根据权利要求10的洗涤剂组合物,该洗涤剂组合物具有PH值为7.0至8.5。 A detergent composition according to claim 10, wherein the detergent composition having a PH of 7.0 to 8.5.
CN 91111550 1990-11-14 1991-11-14 Liquid detergent composition containing lipase and protease CN1062374A (en)

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CN102604754A (en) * 2012-02-03 2012-07-25 深圳市绿微康生物工程有限公司 Biological enzyme cleaning agent and method for preparing same
CN101925669B (en) 2008-01-28 2013-08-14 埃科莱布有限公司 Multiple enzyme cleaner for surgical instruments and endoscopes
CN107810260A (en) * 2015-06-26 2018-03-16 荷兰联合利华有限公司 Laundry detergent composition

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CN101925669B (en) 2008-01-28 2013-08-14 埃科莱布有限公司 Multiple enzyme cleaner for surgical instruments and endoscopes
CN102444018A (en) * 2011-10-26 2012-05-09 芜湖南翔羽绒有限公司 Biochemical combination precision washing technology for eiderdown
CN102604754A (en) * 2012-02-03 2012-07-25 深圳市绿微康生物工程有限公司 Biological enzyme cleaning agent and method for preparing same
CN102604754B (en) 2012-02-03 2013-07-03 深圳市绿微康生物工程有限公司 Biological enzyme cleaning agent and method for preparing same
CN107810260A (en) * 2015-06-26 2018-03-16 荷兰联合利华有限公司 Laundry detergent composition

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WO1992008779A1 (en) 1992-05-29
MX9102022A (en) 1992-07-08
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EP0486073B1 (en) 1996-07-24
EP0486073A2 (en) 1992-05-20
ES2091280T3 (en) 1996-11-01
EP0486073A3 (en) 1993-06-23
TW215108B (en) 1993-10-21
JPH06504555A (en) 1994-05-26
DE69121059D1 (en) 1996-08-29
CA2096256A1 (en) 1992-05-15
DE69121059T2 (en) 1997-03-06
DK0486073T3 (en) 1996-12-09
NZ240571A (en) 1994-11-25
CA2096256C (en) 1999-05-11
AU9041691A (en) 1992-06-11

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