CN1224454A - Detergent composition containing lipolytic enzyme - Google Patents

Abstract

The present invention relates to detergent compositions comprising a specific lipolytic enzyme and at least second lipolytic enzyme. Such compositions provide improved overall detergency performance: reduced redeposition of greasy/oily substances on fabrics, dishware and hard surfaces thereby improving whiteness maintenance, cleaning, reduced spotting and/or filming and stain removal performances.

Description

Detergent composition containing lipolytic enzyme

technical field

The present invention relates to detergent compositions containing complex lipolytic enzymes.

Background of the invention

It is known to include lipolytic enzymes (eg lipases) in detergent compositions for improved cleaning performance, eg better removal of triglyceride containing soils and stains from fabrics. Examples in this regard are: U.S. Patent 4,769,173, Cornelissen et al., issued August 29, 1989; U.S. Patent 5,069,809, Lagerwaard et al., issued December 3, 1991; PCT Application WO 94/03578 and HAPPI (Household & Personal Products Industry Company) No. No. 28/1991.

US Patent 4,769,173 discloses detergent compositions containing certain types of lipases in combination with strong bleaching agents. The lipase consists of a fungal lipase obtained from Humicola lanuginosa.

An example of a fungal lipase in this patent is the lipase from Humicola lanuginosa, which is commercially available from Amano Corporation under the tradename Amano-CE.

US Patent 5,069,809 discloses a combination of high-strength bleach and a lipase. The lipase can be produced by cloning the gene encoding the lipase produced by Humicola lanuginosa and expressing the gene with Aspergillus oryzae as a host, and used in detergent compositions.

WO 94/03578 discloses an enzyme-containing detergent composition containing 10 to 20000 LU (lipolytic units) lipase per gram of detergent composition, wherein the lipase exhibits significant lipolysis during the main cycle of the washing process active. This lipase was chosen inter alia for its property of not being inactivated by fluorinated diisopropyl phosphate.

Although there have been a large number of literature reports on lipase, it has been found that only lipase derived from Humicola lanuginosa strain DSM 4106 and produced by Aspergillus oryzae as a host can be widely used as an additive for fabric washing products. It is commercially available from Novo Nordisk under the tradename Lipolase(TM). In HAPPI, Gormsen and Malmos state that the enzyme trade name "Lipolase" is the first detergent lipase with commercially viable performance at a price based on the application of recombinant DNA technology on an industrial scale.

In HAPPI, it is disclosed that Lipolase is most effective in the drying process which is not a washing process itself. During the drying of fabrics, some conditions such as moisture content are more favorable for the hydrolysis of lipolytic enzymes than in the actual washing cycle.

To optimize the stain removal performance of Lipolase, Novo Nordisk has produced some variants.

As described in patent WO/92/05249, the variant D96L of the natural Humicola lanuginosa lipase can remove lard stain by 4.4 times compared with the wild-type lipase. (Enzyme activity was compared in the range of 0.075mg-2.5mg protein content per liter.)

Research Publication No. 35944 published by Novo Nordisk Company on March 10, 1994 discloses that this lipase variant (D96L) can be converted into lipase at an amount equivalent to 0.001 to 100 mg (5-500,000 LU/L) of lipase per liter of washing solution. The amount of body added.

However, the overall performance of a detergent is not only judged by its ability to remove soil and stains, such as the ability to remove greasy/greasy soil, but also by preventing redeposition of soil or soil breakdown products or any insoluble salts on the cleaned items related to the ability. The redeposition effect causes items to be covered with an unsuitable film, streaked or covered with visible stains, which remain intact at the end of the washing process.

Accordingly, considerable technical challenges remain in formulating detergent compositions with superior all-around cleaning performance that meet consumer demand.

The above objects have been met by a laundry, dishwashing and hard surface detergent composition comprising a mixture of a specific lipolytic enzyme and at least a second lipolytic enzyme.

Indeed, it has been surprisingly found that a mixture of a specific lipolytic enzyme and a second lipolytic enzyme improves overall wash performance, such as maintenance of fabric whiteness, and reduces greasy/greasy substances on dishes, hard surfaces Spotting, filming and/or redeposition on etc.

This discovery can improve wash performance or reduce the level of detergent actives while maintaining equivalent wash performance.

Summary of the invention

The present invention relates to detergent compositions comprising a mixture of a specific lipolytic enzyme and at least a second lipolytic enzyme to provide improved overall cleaning performance. Detailed description of the invention

The essential components of the detergent compositions according to the present invention are a mixture of lipolytic enzymes: ie a specific lipolytic enzyme as described hereinafter and at least one other lipolytic enzyme. Specific lipolytic enzymes:

Herein, the term "lipolytic enzyme" means an enzyme having the ability to degrade lipids. For example, the ability to degrade triglycerides, phospholipids, wax esters or cutin. The lipolytic enzyme may be, for example, a lipase, a phospholipase, an esterase or a cutinase.

A specific lipolytic enzyme suitable for use in the present invention is a lipolytic enzyme capable of significantly improving whiteness retention performance when compared to Lipolase ^™ enzymes having the same hydrolytic activity (same amount of LU per liter of wash liquor) .

As used herein, "significant whiteness retention performance" can be assessed visually by an expert grader on a 0 to 4 disc scoring unit (PSU) Scheffe scale (0 being no difference and 4 being much difference).

The specific lipolytic enzyme suitable for the present invention is mixed into the detergent composition of the present invention at a concentration of 50-8500 LU per liter of washing liquid. The preferred lipolytic enzyme concentration is 100LU-7500LU per liter of washing solution, and the more preferred concentration is 150LU-5000LU per liter of washing solution.

Suitable specific lipolytic enzymes for use herein include those of bacterial and fungal origin. Also included are lipolytic enzymes from chemically or genetically engineered mutants.

Preferred lipolytic enzymes include variants of the lipolytic enzymes produced by Humicola lanuginosa and Thermomyces lanuginosus, or cloned and expressed in a host organism such as Aspergillus oryzae as described in European Patent Application 0258068 to produce such variants. The lipolytic enzyme variant produced by the gene of the body. This European patent application is hereby incorporated by reference.

Particularly preferred lipolytic enzymes are the natural lipase variants produced by Humicola lanuginosa described in US Patent Serial No. 08/341,826. Preferably used is Humicola lanuginosa strain DSM 4106. An example of such a variant is D96L lipolytic enzyme.

The D96L lipolytic enzyme variant denotes a lipase variant as described in patent application WO 92/05249 viz. Among them, the natural lipase obtained from Humicola lanuginosa changes the aspartic acid (D) at position 96 to leucine (L). According to this nomenclature, the aspartic acid at position 96 is replaced by leucine to represent For: D96L.

The activity of enzyme D96L was determined by standard LU assay (analytical method, internalNovo Nordisk number AF95/6-GB, 1991.02.07). The substrate of D96L was prepared by emulsifying tributyrin (Merck), and the emulsifier was gum arabic. Lipase activity was measured at pH 7 using the pH fixation method.

One unit of lipase activity (LU/mg) is defined as the amount required to liberate 1 millimole of fatty acid per minute. second lipolytic enzyme

The detergent compositions of the present invention comprise at least a second lipolytic enzyme. A suitable group of lipolytic enzymes are detergent useful lipases which include lipases produced by microorganisms of the genus Pseudomonas such as Pseudomonas stutzeri ATCC 19.154 disclosed in British Patent 1,372,034. Suitable lipases include those produced by the microorganism of the genus Pseudomonas fluorescens IAM 1057 which immunologically cross-react positively with lipase antibodies. This lipase is commercially available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", and is referred to herein as "Amano-P" hereinafter. Especially suitable lipases are lipases such as M1 Lipase ^R and Lipomax ^R (Gist Brocades).

A preferred lipase is derived from Humicola lanuginosa strain DSM 4106 and produced using Aspergillus oryzae as a host. It is commercially available from Novo Nordisk under the tradename Lipolase(TM).

Also applicable are cutinases (EC 3.1.1.50), which can be considered as a special type of lipase, ie lipases that do not require interfacial activation. Suitable cutinases are described in patents WO94/14963 and WO94/14964. WO-A-88/09367 (Genencor) describes the incorporation of cutinases in detergent compositions.

Other suitable second lipolytic enzymes are phospholipases and esterases.

Usually, the second lipolytic enzyme is added to the detergent composition according to a certain activity ratio, that is, the ratio of the specific lipolytic enzyme to the second lipolytic enzyme is 1:5 to 5:1, and the preferred ratio is 1: 3～3:1.

The purpose of washing soiled fabrics is to make them clean, that is, to remove dirt and stains from soiled clothes. However, once the removed soils are present in the cleaning solution, they are re-deposited on the washed fabrics. Especially with white laundry, the redeposition of soil has a strong negative effect on the whiteness of the fabric. Such redeposition also reduces the brightness and freshness of colored fabrics.

The maintenance of whiteness is to test the whiteness of washed and worn fabrics after repeated washing cycles. A well-performing detergent has the appearance of good whiteness retention, i.e. it improves the whiteness of washed fabrics during the total wear and wash cycle by preventing, to the greatest extent possible, the redeposition of removed soils on white fabrics. Well maintained over the life cycle.

It has now been surprisingly found that the incorporation of a specific lipolytic enzyme and at least one other lipolytic enzyme into a detergent according to the present invention has a significant benefit in its whiteness retention performance.

In addition, the use of said lipolytic enzymes in hard surface cleaning and dishwashing (washing and rinsing equipment for dishes) reduces the staining of greasy/greasy soiling substances, the formation of films and/or their formation on plates, dishes, hard surfaces Redeposition on and similar articles. detergent ingredients

The detergent compositions of the present invention may also contain other detergent ingredients. The precise nature of these other ingredients and their incorporation will depend upon the physical form of the composition and the type of cleaning operation being used.

The detergent compositions of the present invention may be in liquid, paste, gel, bar, tablet, powder and granular form. Granular compositions may be in "compact" form and liquid compositions may be in "concentrated" form.

For example, the compositions of the present invention can be formulated as hard surface cleaners, hand and dishwasher compositions, hand and washing machine laundry detergent compositions, which include laundry detergent compositions, and suitable For soaking and/or pretreatment compositions for soiled fabrics, rinse added fabric softener compositions.

When formulated for use in manual dishwashing methods, the compositions of the present invention preferably contain a surfactant, and preferably other detergent compounds selected from organic polymers, suds boosters, second group metal ions, solvents, hydrotropes and other enzymes.

When formulated as compositions suitable for use in washing machines, the compositions of the present invention preferably contain a surfactant and a builder compound and other detergent ingredient(s), preferably from organic polymeric chemicals, bleaches, other enzymes, defoamers, dispersants, lime soap dispersants, soil release polymers, soil suspending and antideposition agents, and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent ingredients.

The compositions of the present invention may also be used as detergent additives which are intended to supplement or enhance the performance of conventional detergent compositions.

If desired, the granular laundry detergent compositions herein may have a density in the range of 400-1200 g/l, preferably 600-950 g/l, measured at 20°C.

The compositional "compact" form of the granular laundry detergent herein is well reflected in density and, in terms of composition, by the amount of inorganic filler salt. Inorganic filler salts are conventional ingredients in detergent compositions in powder form; in conventional detergent compositions, inorganic filler salts are contained in a considerable amount, generally accounting for 17-35% by weight of the total composition.

In compact compositions, the amount of inorganic filler salt is no more than 15%, preferably no more than 10%, most preferably no more than 5% by weight of the composition.

The inorganic filler salt referred to in the present composition is selected from alkali metal and alkaline earth metal sulfates and chlorides.

A preferred filler salt is sodium sulfate.

The liquid detergent compositions of the present invention may also be in "concentrated form", in which case the liquid detergent compositions of the present invention will contain less water than conventional liquid detergents.

Generally, the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the total detergent composition. Surfactant system

The detergent compositions according to the invention may additionally contain a surfactant system, wherein the surfactant may be selected from anionic and/or nonionic and/or cationic and/or amphoteric and/or zwitterionic and/or semi- Polar surfactant.

Typically, surfactants are present in an amount of 0.1% to 60% by weight. The preferred incorporation amount of the detergent composition in the present invention is 1%-35% by weight, most preferably 1%-30% by weight.

Preferred surfactant systems for use in accordance with the invention contain, as surfactants, one or more nonionic and/or anionic surfactants as described herein.

Nonionic surfactants suitable for use in the surfactant system of the present invention are polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols, preferably polyethylene oxide condensates . These compounds include the condensation products of alkylphenols and alkylene oxides, where the alkyl group on the alkylphenol contains about 6 to 14 carbon atoms, preferably about 8 to 14 carbon atoms, which may be in a straight chain configuration Branched configurations are also possible. In a preferred embodiment, the amount of ethylene oxide present is about 2 to 25 moles, more preferably about 3 to 15 moles, per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630 sold by GAF Corporation and Triton ^™ X-45, X-114, X-100 and X-102 sold by Rohm & Haas, which are surface active Agents are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of primary and secondary fatty alcohols with about 1 to 25 moles of ethylene oxide are suitable as nonionic surfactants in the nonionic surfactant systems of the present invention. The alkyl carbon chain of the fatty alcohol may be straight or branched, it may be primary or secondary, and generally contains about 8 to 22 carbon atoms. Preferred are condensation products with about 2-10 moles of ethylene oxide per mole of alcohol, the alkyl group of the alcohol having about 8-20 carbon atoms, more preferably about 10-18 carbon atoms. From about 2 to 7 moles of ethylene oxide, most preferably from about 2 to 5 moles of ethylene oxide, are present in the condensation product per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (a condensation product of a C ₁₁ -C ₁₅ linear alcohol with 9 moles of ethylene oxide) sold by Union Carbide. ), Tergitol ^TM 24-L-6NMW (a condensation product of C ₁₂ -C ₁₄ primary alcohols and 6 moles of ethylene oxide with a narrow molecular weight distribution); Neodol ^TM 45-9 (C ₁₄ -Condensation product of C ₁₅ linear alcohol and 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ linear alcohol and 3.0 moles of ethylene oxide), Neodol ^TM 45-7 ( Condensation product of C ₁₄ -C ₁₅ linear alcohol with 7 moles of ethylene oxide), Neodol ^TM 45-5 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 5 moles of ethylene oxide); available from The Procter & Gamble Company Kyro ^TM EOB (condensation product of C ₁₃ -C ₁₅ alcohol with 9 moles of ethylene oxide) and Genapol LA 030 or 050 (C ₁₂ -C ₁₄ alcohol with 3 or 5 moles of ethylene oxide) sold by Hoechst condensation products). In these products, the preferred range of HLB is 8-11, and the most preferred range is 8-10.

Also useful as the nonionic surfactant in the surfactant system of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647 issued January 21, 1986 to Llenado et al., which contain about 6 to 30 Carbon atoms, preferably a hydrophobic group of about 10-16 carbon atoms, and a polysaccharide, such as a polyglycoside hydrophilic group, containing about 1.3 to 10, preferably about 1.3 to 3, most preferably about 1.3 -2.7 sugar units. Any reducing sugar containing 5-6 carbon atoms can be used, such as glucose, galactose, and the galactose moiety can be used to replace the glycosyl moiety (hydrophobic groups can be attached to 2-, 3-, 4- isoposition, thus giving glucose and galactose as distinct from glucoside and galactoside). The chemical bond between sugar groups can be, for example, between a position of another sugar unit and the 2-, 3-, 4- and/or 6-position of the previous sugar unit.

The structural formula of preferred alkyl polyglycosides is:

R ² O(C _n H _2n O) _t (glycosyl) _x Here, R ² is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl contains 10～ About 18 carbon atoms, preferably about 12-14 carbon atoms; n is 2 or 3, 2 is preferred; t is about 0-10, 0 is preferred; x is about 1.3-10, 1.3-3 is about Preferably, about 1.3 to 2.7 is most preferable. The glycosyl is preferably derived from glucose. To prepare these compounds, alcohols or alkyl polyethoxyl alcohols are first prepared and then reacted with glucose or a source of glucose to form glycosides (attachment at the 1-position). The other glycosyl groups can be attached via their 1-position to the 2-, 3-, 4- and/or 6-position of the preceding glycosyl group, preferably primarily at the 2-position.

Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable as additional nonionic surfactant systems in the present invention. The hydrophobic moiety in these compounds preferably has a molecular weight of about 1500 to 1800 and shows insolubility in water. The purpose of adding polyoxyethylene in this hydrophobic part is to increase the water solubility of the molecule as a whole and to maintain the liquid nature of the product until polyoxyethylene accounts for about 50% of the total weight of the condensation product, which corresponds to up to about 40 molar Condensation of ethylene oxide. Examples of compounds of this type include some of the commercially available Pluronic ^™ surfactants, marketed by BASF Corporation.

The product generated by the reaction of propylene oxide with ethylenediamine is condensed with ethylene oxide, and the resulting condensation product can also be used as the nonionic surfactant in the nonionic surfactant system of the present invention. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess ethylene oxide and generally has a molecular weight in the range of about 2500-3000. This hydrophobic moiety is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of about 5,000-11,000. Examples of nonionic surfactants of this type include some of the commercially available Tetronic ^(TM) compounds, marketed by BASF Corporation.

Nonionic surfactants which are preferably suitable for use in the surfactant system of the present invention are: polyethylene oxide condensates of alkylphenols, primary or secondary fatty alcohols with from about 1 to 25 moles of ethylene oxide Condensation products, alkylpolysaccharides and mixtures thereof. Most preferred are C ₈ -C ₁₄ alkylphenol ethoxylates containing 3 to 15 ethoxy groups and C ₈ -C ₁₈ alcohol ethoxylates containing 2 to 10 ethoxy groups (average C ₁₀ preferred ) and their mixtures.

Particularly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.

Wherein, R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixed structures, R ² is C _5-31 hydrocarbyl, and Z is a polyhydroxy hydrocarbyl Or an alkoxylated derivative thereof, the polyhydroxyl hydrocarbon group has a straight chain hydrocarbon group directly attached to at least 3 hydroxyl groups. Preferably, R ¹ is methyl, R ² is a straight chain C _11-15 alkyl or C _16-18 alkyl or alkenyl, such as coconut alkyl or mixtures thereof, and Z is Reaction derived from reducing sugars such as glucose, fructose, maltose, lactose.

When included in such detergent compositions, the nonionic surfactant systems of the present invention can enhance the greasy/greasy stain removal properties of such detergent compositions over a wide range of cleaning conditions.

Anionic surfactants suitable for use are straight-chain alkylbenzene sulfonates, alkyl ester sulfonate surfactants, which include straight-chain esters of C ₈ -C ₂₀ carboxylic acids (i.e. fatty acids), which are formulated according to the "United States The Journal of the American Oil Chemists Society "("The Journal of the American Oil Chemists Society"), 52(1975), p323-329 uses gaseous SO ₃ to carry out sulfonation. Suitable starting materials include natural fatty materials derived from tallow, palm oil, and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry cleaning, comprise alkyl ester sulfonate surfactants of the formula:

Wherein, R ³ is a C ₈ -C ₂₀ hydrocarbon group, preferably an alkyl group or their mixed group, R ⁴ is a C ₁ -C ₆ hydrocarbon group, preferably an alkyl group or their mixed group, M is a cation, and it and Alkyl ester sulfonates form a water-soluble salt. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine, and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R ³ is C ₁₀ -C ₁₆ alkyl.

Other suitable anionic surfactants include alkyl sulfate surfactants which are water soluble salts or acids having the formula ROSO ₃ M wherein preferably R is a C ₁₀ -C ₂₄ hydrocarbyl group having a C ₁₀ -C ₂₀ alkyl group Alkyl or hydrocarbyl groups of ingredients are preferred, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is hydrogen or a cation, for example an alkali metal cation (such as sodium, potassium, lithium), or ammonium or substituted ammonium (such as methyl, dimethyl, and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and derived from alkylamines, such as ethylamine, diethylamine amines, quaternary ammonium cations of triethylamine and mixtures thereof, and the like.) Generally, C ₁₂ -C ₁₆ alkyl chains are preferred for lower wash temperatures (i.e., below about 50° C.); for higher For wash temperatures (eg, greater than about 50°C), _C16 - _C18 alkyl chains are preferred.

Other anionic surfactants useful for detersive purposes are also included in the detergent compositions of the present invention. These may include salts of soaps (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₈ -C ₂₄ Olefin sulfonates, sulfonated polycarboxylic acids obtained by sulfonating the pyrolysis products of alkaline earth metal citrates, e.g. as described in British Patent Specification 1,082,179, C ₈ -C ₂₄ alkyl polycarboxylic acids Glycol ether sulfonates (contains up to 10 moles of alkylene oxide); Alkyl glycerol sulfonates, Fatty acyl glycerol sulfonates, Fatty oleoyl glycerol sulfates, Alkylphenol oxirane ether sulfates, Paraffin Hydrocarbon sulfonates, alkyl phosphate salts, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinate mono Esters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, alkyl Based polysaccharide sulfates such as alkyl polyglucoside sulfates (nonionic, nonsulfated compounds are described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of formula such as RO( A compound of CH ₂ CH ₂ O) _k -CH ₂ COO-M+, wherein R is a C ₈ -C ₂₂ alkyl group, k is an integer ranging from 1 to 10, and M is a cation that forms a soluble salt. Resin acids and hydrogenated resin acids are also suitable for use, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Other examples are described in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch), and a list of such surfactants is also generally found in U.S. Patent 3,929,678, published December 30, 1975, Laughlin et al., column 23, line 58 to column 29, line 23 (herein incorporated by reference).

Particularly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants which are water soluble salts or acids having the formula RO(A) _m SO ₃ M where R is an unsubstituted C ₁₀ -C ₂₄ Alkyl or hydroxyalkyl with C ₁₀ -C ₂₄ alkyl moiety, C ₁₂ -C ₂₀ alkyl or hydroxyalkyl is preferred, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is ethyl Oxygen or propoxy units, m greater than zero, usually around 0.5 to 6, more preferably around 0.5 to 3, M is H or a cation, which can be, for example, a metal cation (e.g., sodium, potassium , lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are also included herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as Ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are: C ₁₂ -C ₁₈ alkyl polyethoxylated (1.0) sulfate (C ₁₂ -C ₁₈ E(1.0)M), C ₁₂ -C ₁₈ alkyl polyethoxylated (2.25) Sulfate (C ₁₂ -C ₁₈ E(2.25)M), C ₁₂ -C ₁₈ Alkyl Polyethoxylated (3.0) Sulfate (C ₁₂ -C ₁₈ E(3.0)M), and C ₁₂ -C ₁₈ alkyl polyethoxylated (4.0) sulfate (C ₁₂ -C ₁₈ E(4.0)M), wherein M may conveniently be selected from sodium and potassium.

Cationic detersive surfactants suitable for use in the detergent compositions herein are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants, such as alkyltrimethylammonium halides, and surfactants having the formula:

[R ² (OR ³ ) _y ][R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ^{+ X} -wherein, R ² is an alkyl group or an alkyl benzyl group, and there are about 8 to 18 Carbon atom, each R ³ is selected from -CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -CH ₂ CH(CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ -, and mixtures thereof ; Each R ⁴ is selected from: C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl ring structure formed by connecting two R ⁴ groups, -CH ₂ CHOHCHHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is any hexose or a hexose polymer having a molecular weight of less than about 1000, and ^R4 can be H when y is not 0; ^R5 is the same as ^R4 , or an alkyl chain wherein ^R2 and ^R5 The total number of carbon atoms in is not more than about 18; each y is about 0-10, and the sum of the y values is about 0-15; X is any compatible anion.

Particularly preferred cationic surfactants for use in the present compositions are water-soluble quaternary ammonium compounds having the structure:

R ₁ R ₂ R ₃ R ₄ N ⁺ X ^- (i) wherein R ₁ is C ₈ -C ₁₆ alkyl, each R ₂ , R ₃ and R ₄ are independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl, and -(C ₂ H ₄₀ ) _x H, where x has a value of 2 to 5, and X is an anion. Not more than one of R ₂ , R ₃ or R ₄ should be benzyl. For R ₁ , the preferred alkyl chain length is C ₁₂ -C ₁₅ , especially when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fats, or through olefins or carbonyl Synthetic alcohol can be synthesized.

Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl, and the anion X may be selected from halogen, methosulfate, acetate and phosphate ions.

Examples of quaternary ammonium compounds of formula (i) suitable for use herein are:

Cocotrimethylammonium Chloride or Bromide;

Cocomethyldihydroxyethylammonium chloride or bromide;

Decyltriethylammonium chloride;

Decyldimethylhydroxyethylammonium chloride or bromide;

Chloride or Bromide C _12-15 Dimethyl Hydroxyethylammonium;

Cocodimethylhydroxyethylammonium chloride or bromide;

Myristyltrimethylammonium methylsulfate;

Lauryldimethylbenzylammonium chloride or bromide;

烷基且R₂R₃R₄是甲基)。Lauryl dimethyl (ethoxy) ₄ ammonium chloride or bromide; choline esters (compounds of formula (i), wherein _R is

alkyl and R ₂ R ₃ R ₄ is methyl).

Dialkylimidazolines [compounds of formula (i)].

Other cationic surfactants useful herein are also described in US Patent 4,228,044, Cambre, issued October 14, 1980, and European Patent Application EP 000,224.

式ⅠThe quaternary ammonium surfactant applicable to the present invention has the structural formula as (I):

Formula Ⅰ

式Ⅱy为2～4,3为优选。其中R₂是H或C₁-C₃烷基，其中x为0～4,0～2为优选，0为最优选，其中R₃,R₄和R₅可以是相同或不同的基团，且可以是一个短链烷基(C₁-C₃)或如式(Ⅲ)所示的烷氧基化烷基，其中X^-是一种相反离子，优选为卤离子，例如氯或甲基硫酸根。

式ⅢR₆是C₁-C₄且z为1或2。Wherein R ₁ is a short chain length alkyl group (C ₆ -C ₁₀ ) or an alkylamidoalkyl group as shown in formula (II)

Formula IIy is 2 to 4, and 3 is preferred. Wherein R ₂ is H or C ₁ -C ₃ alkyl, wherein x is 0-4, 0-2 is preferred, 0 is the most preferred, wherein R ₃ , R ₄ and R ₅ can be the same or different groups, And it can be a short chain alkyl group (C ₁ -C ₃ ) or an alkoxylated alkyl group as shown in formula (III), wherein X ^- is a counter ion, preferably a halide ion, such as chlorine or methyl Sulfate.

Formula III R ₆ is C ₁ -C ₄ and z is 1 or 2.

Preferred quaternary ammonium surfactants are defined by formula (I), wherein R ₁ is C ₈ , C ₁₀ or mixtures thereof, x=0, R ₃ , R ₄ =CH ₃ and R ₅ =CH ₂ CH ₂ OH .

When included herein, the detergent compositions of the present invention will generally contain from 0.2% to about 25% by weight of such cationic surfactants, preferably at levels from 1% to about 8% by weight.

Amphoteric surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group may be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, usually about 8-18 carbon atoms, and at least one of them contains an anionic water-soluble group, such as carboxyl, sulfonic acid, or sulfuric acid. Examples of amphoteric surfactants are found in US Patent 3,929,678 (Laughlin et al., issued December 30, 1975, column 19, lines 18-35.).

When included herein, the detergent compositions of the present invention will generally contain from 0.2% to about 15% by weight of such amphoteric surfactants, preferably from about 1% to about 10%.

Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammoniums. Quaternary phosphonium salt or tertiary sulfonium salt compound. Examples of zwitterionic surfactants are found in US Patent 3,929,678 (Laughlin et al., issued December 30, 1975, column 19, line 38 through column 22, line 48).

When included herein, the detergent compositions of the present invention will generally contain from 0.2 to about 15% by weight of such zwitterionic surfactants, preferably from 1% to about 10%.

Semi-polar nonionic surfactants are a special class of nonionic surfactants that include water-soluble amine oxides containing an alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from Alkyl and hydroxyalkyl groups containing about 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two other moieties selected from the group consisting of about 1 to 3 carbon atoms Alkyl and hydroxyalkyl groups of atoms; and water-soluble sulfoxides containing an alkyl moiety of about 10 to 18 carbon atoms and another moiety selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to 3 carbon atoms group.

Semi-polar nonionic detergent surfactants include amine oxide surfactants of the formula: Wherein, R ³ is an alkyl group, a hydroxyalkyl group, or an alkylphenyl group or a mixture thereof, which contains about 8 to 22 carbon atoms; R ⁴ is an alkylene or hydroxyalkylene group containing about 2 to 3 carbon atoms Alkyl or a mixture thereof; x is about 0 to 3; each ^R5 is an alkyl or hydroxyalkyl group containing about 1 to 3 carbon atoms, or a polycyclic ring containing about 1 to 3 oxirane groups Oxyethane. The R ⁵ groups can be linked to each other, for example, through an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants include in particular C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides.

When included herein, the detergent compositions of the present invention generally contain from about 0.2% to 15% by weight of such semi-polar nonionic surfactants, preferably from about 1% to about 10%.

The detergent compositions of the present invention may preferably further contain a cosurfactant selected from primary or tertiary amines.

Primary amines suitable for use herein include amines of the formula R ₁ NH ₂ , wherein R ₁ is a C ₆ -C ₁₂ alkyl chain, preferably a C ₆ -C ₁₀ alkyl chain, or R ₄ X(CH ₂ ) _n , X is -O-, -C(O)NH- or -NH-, R ₄ is a C ₆ -C ₁₂ alkyl chain, n is 1-5, 3 is preferred. The R ₁ alkyl chain may be straight or branched and may be interrupted by up to 12 oxirane moieties, but less than 5 oxirane moieties are preferred.

Preferred amines of the above formula are n-alkylamines. Amines suitable for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine, and laurylamine. Other preferred primary amines include C ₈ -C ₁₀ oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

Tertiary amines suitable for use herein include tertiary amines having the formula R ₁ R ₂ R ₃ N, wherein R ₁ and R ₂ are C ₁ -C ₈ alkyl chains or R ₃ is a C ₆ -C ₁₂ alkyl chain, preferably a C ₆ -C ₁₀ alkyl chain, or R ₃ is R ₄ X(CH ₂ ) _n , where X is -O-, -C(O)NH -or-NH-, R ₄ is C ₄ -C ₁₂ , n is 1-5, preferably 2-3. R ₅ is H or C ₁ -C ₂ alkyl and x is 1-6. _R3 and _R4 may be linear or branched and the _R3 alkyl chain may be interrupted by up to 12 oxirane moieties, but preferably less than 5 oxirane moieties.

R₅是H或甲基且x=1～2。Preferred tertiary amines are R ₁ R ₂ R ₃ , wherein R ₁ is C ₆ -C ₁₂ alkyl, R ₂ and R ₃ are C ₁ -C ₃ alkyl or

R ₅ is H or methyl and x=1-2.

其中R₁是C₆-C₁₂烷基；n为2～4，3为优选；R₂和R₃是C₁-C₄。Also preferred are amidoamines of the formula

Wherein R ₁ is C ₆ -C ₁₂ alkyl; n is 2-4, preferably 3; R ₂ and R ₃ are C ₁ -C ₄ .

The most preferred amines in the present invention include: 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C ₈ -C ₁₀ oxypropylamine, N coconut base 1～3 diaminopropane, Cocoalkyl Dimethylamine, Lauryl Dimethylamine, Lauryl Bis(Hydroxyethyl)amine, Cocoyl Bis(Hydroxyethyl)amine, Laurylamine 2 Mole Propoxylate, Octylamine 2 Mole Propoxylate amide, lauryl amidopropyl dimethylamine, C ₈ -C ₁₀ amidopropyl dimethylamine and C ₁₀ amidopropyl dimethylamine. The most preferred amines for use in the compositions herein are: 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly suitable are: n-dodecyldimethylamine and bishydroxyethylcocoalkylamine and oleylamine 7 times ethoxylate, laurylamidopropylamine and cocoamidopropylamine. Optional Detergent Ingredients: Other Detergent Enzymes

Detergent compositions may contain, in addition to specific lipolytic enzymes, one or more enzymes which provide cleaning performance and/or fabric care benefits.

The enzyme may be selected from: cellulase, hemicellulase, peroxidase, protease, glucose-amylase, amylase, xylanase, pectinase, reductase, oxidase, phenol oxidase , lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, beta-glucanase, arabinosidase, chondroitinase, laccase or their mixture.

Preferred compositions are cleaning compositions having a mixture of commonly used enzymes such as proteases, amylases, lipases, pectinases and/or cellulases in combination with one or more plant cell wall degrading enzyme.

Cellulases useful in the present invention include bacterial or fungal cellulases. Preferably, they should have an optimum pH range of 5-9.5. Suitable cellulases are disclosed in US Patent 4,435,307, (Barbesgoard et al.), which discloses fungal cellulase from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2.247,832.

Examples of such cellulases are cellulases produced by strains of Humicola insolens (Humicola griseus var. thermoidea), especially Humicola insolens strain DSM1800. Another suitable cellulase is a cellulase derived from Humicola insolens having a molecular weight of about 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids. Particularly suitable cellulases are cellulases with color care benefits. Examples of such cellulases are described in European Patent Application No. 91202879.2, [filing date November 6, 1991 (Novo)].

Peroxidase is used in combination with an oxygen source, such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used as "solution bleaching", that is, to prevent the transfer of dyes or pigments removed from wash items during washing to other wash items in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidases.

Detergent compositions containing peroxidase are disclosed, for example, in PCT International Application WO 89/099813 and European Patent Application EP 91202882.6, filed November 6, 1991.

The cellulase and/or peroxidase is usually added to the detergent composition at a concentration of 0.0001% to 2% active enzyme by weight of the detergent composition.

Preferred commercially available proteases include those sold by Novo Nordisk A/S (Denmark) under the trade names Alcalase, Savinase, Primase, Durazym, and Esperase, those sold by Gist-Brocades under the trade names Maxatase, Maxacal, Maxapem and Proteases are sold by Properase, those sold by Genencor International, and those sold by Solvay Enzymes under the tradenames Opticlean and Optimase. The protease described in patent application EP 251 446, WO 91/06637, WO94/10591 and U.S. Patent Serial No. 08/322676 can also be included in the detergent composition of the present invention at a concentration of 0.0001% to 2% by weight of the composition. % active enzyme.

Alpha and/or beta amylases may be included to remove carbohydrate based stains. WO/94/02597 Novo Nordisk A/S, published February 3, 1994, describes cleaning compositions containing amylase mutants. See also WO/94/18314 Genencor, published August 18, 1994 and WO/95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in detergent compositions include alpha and beta amylases. Alpha-amylases are known in the art, including those disclosed in US Patent 5,003,257; EP252,666; WO/91/00353; FR2,676,456; EP285,123; Those in specification 1,296,839 (Novo). The remaining suitable amylases are stability-enhanced amylases including Purafact Ox Am ^R described in WO 94/18314, published August 18, 1994 and available from Novo Nordisk A/S with other Additional modified amylase variants disclosed in WO 95/10603, published April 1995. Examples of commercial alpha-amylase products are ^Termamyl® , ^Ban® , ^Fungamyl® and ^Duramyl® , all available from Novo Nordisk A/S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases, characterized in that the α-amylases, as determined by the ^Phadebas® α-amylase activity test, at 25°C to 55°C and at a pH range of 8-10, The enzyme has a specific activity at least 25% higher than that of Termamyl ^(R) . Other amylolytic enzymes with improved activity levels and the combined properties of thermostability and higher activity levels are described in WO95/35382.

The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The enzyme is usually added to the detergent composition with an active enzyme content of 0.0001% to 2% by weight of the detergent composition, and the enzyme can be added as an independent single component (a pellet containing an enzyme, a granule, a stable liquid, etc...) or as a mixture of two or more enzymes (e.g. composite granules).

Other suitable detergent ingredients which may be added are enzyme oxidation scavengers, which are described in European Patent Application 92870018.6, filed January 31,1992. An example of such an enzyme oxidation scavenger is ethoxylated tetraethylenepolyamine. Color care

Technologies that can provide color care benefits can be included. Examples of these technologies are metal catalysts with color maintenance which are described in European patent EP 0 596 184 and co-pending European patent application 94870206.3. bleach

Bleaching systems which may be included in the detergent compositions of the present invention comprise bleaching agents such as PB1, PB4 and percarbonate having a particle size of 400-800 microns. These bleach compositions may contain one or more oxygen bleaches and, depending on the bleaching agent chosen, one or more bleach activators. When present, oxygen bleaching compounds are typically added at levels of from about 1% to about 25%.

The bleaching agent component used herein can be any bleaching agent useful in detergent compositions, including oxygen bleaching agents as well as others known in the art.

Bleaching agents suitable for use in the present invention can be activated and non-activated bleaching agents.

One class of useful oxygen bleaches includes percarboxylic acid bleaches and their salts. Suitable examples of such materials include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid . Such bleaches are disclosed in US Patent 4,483,781, US Patent Application 740,446; European Patent Application 0,133,354 and US Patent 4,412,934. Particularly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Patent 4,634,551.

Another class of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, sodium and potassium trichloroisocyanurates and dichloroisocyanurates and N-chloro and N-bromo alkane sulfonamides. These substances are usually added at 0.5% to 10% by weight of the finished product, preferably 1% to 5%.

Hydrogen peroxide release agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (described in NOBS, US4,412,934), 3,5-trimethylhexanol Oxybenzenesulfonate (described in ISONOBS, EP120,591), phenolsulfonate of penta-acetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid (described in NACA-OBS, WO94/28106), They are perhydrolyzed to form peracids as active bleaching substances, resulting in improved bleaching results. The acylated citrates disclosed in co-pending European Patent Application 91870207.7 are also suitable activators.

It has been found that the combination of specific lipolytic enzymes with a bleaching agent, particularly nonanoyloxybenzenesulfonate (NOBS) and phenolsulfonate of N-nonanoyl-6-aminocaproic acid (NACA-OBS) When used as a bleach activator, it reduces staining, filming and/or redeposition, thereby increasing whiteness maintenance and removal of greasy/greasy soils.

Useful bleaching agents are described in our co-pending applications USSN 08/136,626, PCT/US 95/07823, WO 95/27772, WO 95/27773, WO 95/27774 and WO 95/27775, which include The peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds of the detergent compositions of the present invention.

Hydrogen peroxide can also be provided by adding an enzyme system (ie an enzyme and corresponding substrate) which generates hydrogen peroxide at the beginning or during washing and/or rinsing. Such enzyme systems are disclosed in European Patent Application 91202655.6, filed October 9,1991.

Bleaching agents other than non-oxygen bleaching agents are also known in the art and can be used herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. These substances can adhere to the laundry during the washing process. After light, in the presence of oxygen, such as hanging clothes in sunlight, the sulfonated zinc phthalocyanine is activated, and the washed clothes are bleached. A preferred zinc phthalocyanine and photoactivated bleaching process is described in US Patent 4,033,718. Typically, detergent compositions will contain from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine. Builder system

The compositions of the present invention may contain a builder system.

Any conventional builder system is suitable for use here including aluminum silicate materials, silicates, polycarboxylates and fatty acids such as ethylenediaminetetraacetate, diethylenetriaminepentamethylene Acetate materials, such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid are metal ion sequestrants. Phosphate builders such as sodium tripolyphosphate are also useful here.

A suitable builder may be an inorganic ion exchange material, usually an inorganic hydrated aluminosilicate material, especially a hydrated synthetic zeolite such as hydrated zeolites A, X, B, HS and MAP.

Another suitable inorganic builder material is layered silicate, such as SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate composed of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates containing one carboxyl group include lactic acid, glycolic acid, and ether derivatives thereof, as disclosed in Belgian Patents 831,368, 821,369, and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, hydroxymalonic acid and fumaric acid, and ether carboxylates, as described in German Patents 2,446,686 and 2,446,687 and US Patent 3,935,257, and also thionyl carboxylates as described in Belgian Patent 840,623. Polycarboxylates containing three carboxy groups include, inter alia, the water-soluble citrate, aconitate, and citraconic acid salts, and succinate derivatives such as carboxymethyloxyl as described in British Patent 1,379,241 Succinates, lactate oxysuccinates as described in Dutch application 7205873 and oxopolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates in British Patent 1,387,447.

Polycarboxylates containing 4 carboxyl groups include oxydisuccinates disclosed in British Patent 1,261,829, 1,1,2,2-ethane tetracarboxylate, 1,1,3,3-propane tetracarboxylate salt, and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421, 1,398,422 and U.S. Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent No. 1,082,179, and Polycarboxylates containing phosphone substituents are disclosed in British Patent 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadiene pentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis- Tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran tetracarboxylate, 1,2,3,4,5,6-hexanehexacarboxylate , and carboxymethyl derivatives of polyhydric alcohols, such as sorbitol, mannitol, and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and phthalic acid derivatives disclosed in British Patent 1,425,343.

As stated above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per mole, especially citrates.

A preferred builder system for use in the present compositions comprises a water insoluble aluminum silicate builder such as layered silicate (SKS-6) and a water soluble carboxylate chelating agent such as citric acid mixture.

A chelating agent suitable for incorporation into the detergent compositions of the present invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or their mixture. Preferred EDDS compounds are their free acid forms and their sodium and magnesium salts. Examples of preferred sodium salts of EDDS include _Na2EDDS and _Na4EDDS . Examples of preferred magnesium salts of EDDS include MgEDDS and _Mg2EDDS , most preferred for inclusion in the composition according to the present invention are magnesium salts.

Other builder materials that can be used in granular compositions as part of the builder system include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as organic phosphonates, amino Polyalkylene phosphonates and amino polycarboxylates.

Other suitable water-soluble organic salts are homo- or co-polymeric acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by not more than two carbon atoms. Such polymers are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates having a molecular weight of 2000-5000 and their copolymers with maleic anhydride, such as copolymers having a molecular weight of 20,000-70,000, especially copolymers having a molecular weight of about 40,000.

The builder salt of the cleaning agent generally comprises 10% to 80% by weight of the composition, preferably 20% to 70%, most preferably usually 30% to 60% by weight. In granular compositions, the total amount of builders is preferably from 15% to 60% by weight, preferably from 10 to 45% by weight. Defoamer

Another optional ingredient is an antifoam agent, examples being polysiloxanes and silica-polysiloxane mixtures. Polysiloxanes can generally be represented by alkylated polysiloxane materials, while silica is usually applied in the form of a fine powder, examples being silica gels and xerogels and various types of hydrophobic silica. These materials can be incorporated in the form of granules wherein the antifoam is advantageously released from a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier. Antifoams can also be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more other ingredients.

A preferred silicone suds control agent is disclosed in US Patent 3,933,672 to Bartollota et al. Other particularly useful suds eliminators are the self-emulsifiable silicone suds eliminators described in German Patent Application DTOS 2,646,126, published April 28,1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a copolymer of silicone and ethylene glycol. Particularly preferred suds control agents are suds suppressor systems comprising mixtures of silicone oils and 2-alkyl-alkanols. A suitable 2-alkyl-alkanol is 2-butyl-octanol, which is commercially available under the trade name lsofol 12R.

Such a defoamer system is described in co-pending European patent application N92870174.7, filed November 10, 1992.

Copending European Patent Application N92201649.8 describes particularly preferred silicone suds control agents. The composition may contain a polysiloxane/silica mixture in combination with a fumed non-porous silica, such as Aerosil ^R.

The above-mentioned antifoaming agent is generally applied at 0.001%-2% by weight of the composition, preferably 0.01%-1% by weight. other

Other ingredients capable of being used in detergent compositions, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, colorants, and/or encapsulated or non-encapsulated flavoring agent.

A particularly suitable encapsulating material is a water soluble capsule consisting of a matrix of polysaccharides and polyols, GB 1,464,616 describes such compounds.

Other suitable water-soluble encapsulating materials include dextrins, which are derived from non-gelatinizing starch esters of substituted dicarboxylic acids, as described in US 3,455,838. These acid-ester dextrins are preferably prepared from the following starches: waxy maize, waxy sorghum, sago, tapioca and potato. A suitable example of said encapsulating material includes N-Lok produced by National Starch. This N-Lok encapsulant consists of modified starch and glucose. Modification of starch is carried out by adding monofunctional substituent groups such as octylsuccinic anhydride.

Anti-redeposition and soil suspension agents suitable herein include cellulose derivatives, such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, and homo- or copolymers of polycarboxylic acids or their salts . Polymers of this type include the aforementioned polyacrylates and maleic anhydride-acrylic acid copolymers as builders, as well as polymers of maleic anhydride with ethylene, methyl vinyl ether, or methacrylic acid, Maleic anhydride constitutes at least 20 mole percent of the copolymer. These materials are typically used in amounts of 0.5% to 10% by weight, more preferably 0.75% to 8%, most preferably 1% to 6% by weight of the composition.

Preferred optical brighteners are anionic, an example of which is 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'- Disodium Disulfonate, 4,4′-Bis-(2-morpholino-4-anilino-s-triazin6-ylamino-stilbene-2:2′-Disodium Disulfonate, 4,4 '-Bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disodium disulfonate, 4,4"bis-(2,4-dianilino -s-triazin-6-ylamino)stilbene-2 sulfonate monosodium, 4,4′-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s -Triazin-6-ylamino)stilbene-2,2′-disodium sulfonate, 4,4′-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene -2,2′-Disodium disulfonate, 4,4′-bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene -2,2′-Disodium sulfonate, 2(stilbene 4″-(naphthalene-1′,2′:4,5)-1,2,3-triazole-2″-sodium sulfonate and 4 , 4'-bis(2-sulfostyryl)biphenyl. Particularly preferred brighteners are the specific brighteners of co-pending European Patent Application 95201943.8.

Other useful polymers are polyethylene glycols, especially those having a molecular weight of 1,000-10,000, especially 2,000-8,000, most preferably around 4,000. They are used in an amount of 0.20% to 5% by weight, more preferably 0.25% to 2.5% by weight. Homo- or copolymers of these polymers and the aforementioned polycarboxylates will help improve whiteness retention, fiber ash deposition, and resistance to soil stains, proteins and oxidizable Dirt cleaning ability.

Soil release agents useful herein are conventional copolymers or terpolymers of terephthalic acid and ethylene glycol and/or propylene glycol units in various arrangements. Examples of such copolymers are disclosed in commonly assigned US Patents 4,116,885 and 4,711,730 and European Patent Application 0,272,033. According to EP-A-0272033, a particularly preferred polymer has the formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 (T-PO) _2.8 (T-PEG) _0.4 ]T(PO-H) _0.25 ((PEG) ₄₃ CH ₃ ) _0.75 where PEG is -(OC ₂ H ₄ )O-, PO is (OC ₃ H ₆ O) and T is (PCOC ₆ H ₄ CO).

Modified polyesters are also very useful, which are random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol, and 1,2-propanediol, the end groups of which are mainly composed of sulfo benzoate, with ethylene glycol and/or propylene glycol monoester as a minor component of the end group. The goal is to have polymers capped at both ends with sulfobenzoate, and "predominantly" in this context means that the majority of said copolymer is capped with sulfobenzoate. However, some copolymers are not completely capped, so that their end groups may consist of monoesters of ethylene glycol and/or 1,2-propanediol, and then "secondarily" consist of such groups.

The polyester selected here contains about 46% by weight dimethyl terephthalate, about 16% by weight 1,2-propanediol, about 10% by weight ethylene glycol, about 13% dimethyl sulfobenzoate and about 15% by weight sulfoisophthalic acid, and has a molecular weight of about 3000. Such polyesters and their preparation are described in detail in EPA311342.

It is well known in the art that free chlorine in tap water can quickly inactivate enzymes included in detergent compositions. Thus the use of chlorine scavengers such as perborate, ammonium sulfate, sodium sulfite, and polyethyleneimine in excess of about 0.1% by weight of the composition in the formulation will increase the stability of the amylase throughout the wash cycle . Compositions containing chlorine scavengers are described in European Patent Application 92870018.6, filed 31 January 1992. softener

Fabric softening agents may also be included in laundry detergent compositions according to the present invention, and they may be of the inorganic or organic type. Inorganic softening agent is with GB-A-1400 898 and USP5,019, the earth clay disclosed in 292 as example, and organic softening agent then comprises the water-insoluble tertiary amine disclosed in GB-A1 514 276 and EP-B0 011 340, EP-B- 0 026 527 and EP-B-0 026 528 their mixtures with mono-C12-C14 quaternary ammonium salts, and the dilong-chain amides disclosed in EP-B-0 242 919. Other useful organic ingredients for fabric softener systems include the high molecular weight polyethylene oxide materials disclosed in EP-A-0 299 575 and 0 313 146.

Regardless of whether the material is spray-dried or mixed-dried, the content of smectite clay is generally 2% to 20% by weight, more preferably 5 to 15%. The addition amount of organic fabric softener such as water-insoluble tertiary amine or two long-chain amide materials is 0.5～5% by weight, usually 1%～3% by weight, and high molecular weight polyethylene oxide material and water-soluble cationic materials are added in an amount of 0.1% to 2%, usually 0.15% to 1.5% by weight. These materials are generally added to the spray-dried portion of the composition, although in some cases it may be more convenient to add them as dry mixed particles or as a molten liquid sprayed onto the other solid ingredients of the composition. dye transfer inhibition

The detergent compositions of the present invention may also contain dye transfer inhibiting compounds for inhibiting the transfer of dissolved and suspended dyes from one fabric to another encountered in fabric laundering operations involving colored fabrics. polymeric dye transfer inhibitor

According to the invention, the detergent compositions may also contain from 0.0001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1%, by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are added to detergent compositions for the purpose of preventing the transfer of dyes from colored fabrics to fabrics which are washed at the same time. These polymers have the ability to complex and adsorb these fugitive dyes that are washed from dyed fabrics before the dye has an opportunity to combine with other items during laundering.

Particularly suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinyl imidazoles or their mixtures.

Incorporation of such polymers also enhances enzyme performance according to the present invention. a) Polyamine N-oxide polymers

Suitable polyamine N-oxide polymers contain units of the formula:

Wherein, P is a polymerizable unit to which the R-N-O group may be attached, or the R-N-O group forms part of the polymerizable unit, or a combination of the above two cases.

x是0或1；R是脂肪族的，乙氧基化的脂肪族的，芳香族的，杂环的或脂环基团，或它们的任何组合，并且N-O基团中的N可连接于其上或者其中N-O基团的氮是这些基团的一部分。A is NC,

x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or any combination thereof, and the N in the NO group may be attached to The nitrogen on or in the NO group is part of these groups.

其中，R₁,R₂和R₃是脂肪族基团，芳族的，杂环或脂环基团或它们的组合，x或/和y或/和z是0或1，且N-O基团中的N可连接于其上或N-O基团中的N形成这些基团的一部分。The NO group can be represented by the following general formula:

wherein, R ₁ , R ₂ and R ₃ are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z are 0 or 1, and the NO group The N in may be attached thereto or the N in the NO group forms part of these groups.

The N-O group may be part of the polymerisable unit (P) or be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides, wherein the N-O group forms part of the polymerisable unit, include polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the N of the N-O group forms part of the R group. In preferred polyamine N-oxides, R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and their derivatives.

Another class of said polyamine N-oxides includes the group of polyamine N-oxides wherein N of the N-O group is attached to the R group.

Other suitable polyamine N-oxides are polyamine oxides in which N-O groups are attached to the polymerisable unit.

Preferred such polyamine N-oxides are polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein N in the N-O functional group is said R part of the base.

Examples of these classes of compounds are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives.

Another preferred class of polyamine N-oxides are polyamine oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein N in the N-O functional group is attached to said R group superior.

Examples of these classes of compounds are polyamine oxides, where the R group may be an aromatic group such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyethylenes, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the present invention generally have a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the amount of amine oxide groups in the polyamine oxide polymer can be varied by appropriate copolymerization and appropriate degree of N-oxidation. The preferred ratio of amine to amine N-oxide is 2:3 to 1:1000000. More preferably 1:4 to 1:1000000, most preferably 1:7 to 1:1000000. The polymers of the present invention actually include random or block copolymers in which one monomer is an amine N-oxide and the other monomer may or may not be an amine N-oxide. The amine oxide units of the polyamine N-oxides have a PKa<10, preferably a PKa<7, more preferably a PKa<6. Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical so long as the material has the desired water solubility and dye-suspending power.

Usually, the average molecular weight is in the range of 500-1,000,000, preferably 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole and N-vinylpyrrolidone polymers used in the present invention have an average molecular weight of 5,000-1,000,000, preferably 5,000-200,000.

According to the present invention, particularly preferred polymers for use in detergent compositions include polymers selected from N-vinylimidazole N-vinylpyrrolidone copolymers, wherein said polymers have an average molecular weight in the range of 5,000 to 50,000, More preferably, it is 8,000 to 30,000, and most preferably, it is 10,000 to 20,000.

The average molecular weight range is determined by light scattering, a method described by Barth H.G and Mays J.W in Chemical Analysis, Volume 113 "Modern Methods for Characterization of Polymers".

Particularly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight ranging from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.

N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties without negatively affecting the cleaning power of detergent compositions formulated with them.

The molar ratio of N-vinylimidazole and N-vinylpyrrolidone in the N-vinylimidazole and N-vinylpyrrolidone copolymer of the present invention is 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6～0.4. c) Polyvinylpyrrolidone

The detergent compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of about 2,500 to 400,000, preferably about 5,000 to 200,000, more preferably about 5,000 to 50,000, and most preferably about 5,000 to 15,000. . Suitable polyvinylpyrrolidones are available from ISP Corporation, New York, NY and Montreal, Canada, under the tradenames PVP-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average Molecular weight is 160,000), and PVP K-90 (average molecular weight is 360,000). Other polyvinylpyrrolidones commercially available from the company BASF include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones are known to those skilled in the detergent art (see examples in EP-A-262,897 and EP-A-256,696). d) Polyvinyloxazolidinone

The detergent compositions of the present invention may also employ polyvinyloxazolidinones having an average molecular weight of from about 2,500 to 400,000, preferably from about 5,000 to 200,000, as polymeric dye transfer inhibiting agents. , more preferably about 5,000-50,000, and most preferably about 5,000-15,000. e) Polyvinylimidazole

The detergent compositions of the present invention may also employ polyvinylimidazoles as polymeric dye transfer inhibiting agents. The polyvinylimidazole has an average molecular weight of about 2,500-400,000, preferably about 5,000-200,000, more preferably about 5,000-50,000, most preferably about 5,000-15,000. f) Cross-linked polymers

Cross-linked polymers are polymers in which the backbone is interconnected to some extent. These linkages may be physical or chemical in nature, possibly through reactive groups on the backbone or branches; in Journal of Polymer Science, 22 Cross-linked polymers have been described in Vol. 1035-1039.

In one embodiment, the fabricated cross-linked polymer forms a rigid three-dimensional structure that traps the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer entraps the dye by swelling.

Such crosslinked polymers are described in co-pending patent application 94870213.9. cleaning method

The compositions of the present invention can be used in essentially any washing or cleaning method, including immersion methods, pretreatment methods and methods with a rinse step, the latter of which may incorporate a separate rinse aid composition.

The method described herein involves contacting the fabric with a laundry solution in the usual manner and as indicated hereinafter.

The process of the present invention can be conveniently carried out during the washing process. The washing method is preferably carried out at 5°C to 95°C, especially at 10 to 60°C. The preferred pH value of the treatment solution is 7-11. Typically, the amount of detergent composition to be added per liter is 4-10 g and 1-2 g, respectively, under European and American washing conditions.

A preferred machine dishwashing method comprises treating soiled items with an aqueous solution of a machine dishwashing or rinsing composition. A typical effective amount for machine dishwashing compositions is to dissolve or disperse 8 to 60 g of product in a wash volume of 3 to 10 liters.

For manual dishwashing, the soiled dishes are contacted with an effective amount of the dishwashing composition, typically 0.5 to 20 g (25 dishes per treatment). A preferred manual dishwashing method involves applying a concentrated solution to the surface of the dishes or soaking the dishes in a bulky dilute solution of the detergent composition.

The compositions of the present invention may also be formulated as hard surface cleaner compositions.

The following examples are illustrative of compositions of the invention and are not meant to limit or otherwise define the scope of the invention.

In the detergent composition, except the lipolytic enzyme among the present invention, the content of enzyme is represented by pure enzyme accounting for total composition weight, and the abbreviated component name has following meaning: LAS: straight chain C ₁₂ alkylbenzene sulfonate Sodium Acid TAS: Sodium Tallow Alkyl Sulfate XYAS: Sodium C _1X -C _1Y Alkyl Sulfate SAS: C ₁₂ -C ₁₄ Secondary (2,3) Alkyl Sulfate in Sodium Salt Form AEC: Alkyl Ethoxy Carboxylate surfactant, formula C ₁₂ ethoxy (2) carboxylate SS: secondary soap surfactant of formula 2-butyloctanoic acid 25EY: mainly C ₁₂ -C ₁₅ linear primary alcohols with an average of Y moles of ethylene oxide condensation 45EY: predominantly C ₁₂ -C ₁₅ linear primary alcohols with an average of Y moles of ethylene oxide condensation XYEZS: per mole of C _1X -C _1Y sodium alkyl sulfate with an average of Z moles of ethylene oxide Condensed nonionic: C ₁₃ -C ₁₅ mixed ethoxylated/propoxylated fatty alcohols, ethoxylated flat

The average degree of propoxylation is 3.8, the average degree of propoxylation is 4.5, the trade name is Plurafac LF404,

BASF Gmbh sells CFAA: C ₁₂ -C ₁₄ Alkyl N-methyl Glucamide TFAA: C ₁₆ -C ₁₈ Alkyl N-Methyl Glucamide Silicate: Amorphous Sodium Silicate (SiO ₂ : Na ₂ O ratio = 2.0) NaSKS-6: crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅ Carbonate: anhydrous sodium carbonate metasilicate: sodium metasilicate (SiO ₂ : Na ₂ O Ratio = 2.0) Phosphate or STPP: sodium tripolyphosphate MA/AA: 1:4 copolymer of maleic acid/acrylic acid, the average molecular weight is about 80,000 PA30: polyacrylic acid terpolymer with an average molecular weight of about 8,000: average Terpolymer of molecular weight about 7,000, including acrylic acid:maleic acid:

The weight ratio of ethacrylic acid monomer units is 60:20:20480N:3:7 random copolymer of acrylic acid/methacrylic acid, with an average molecular weight of about 3,500 polyacrylate: polyacrylate homopolymer with an average molecular weight of 8,000, commercial Name PA30,

BASF GmbH sells Zeolite A: Sodium aluminosilicate hydrate, formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ -27H ₂ O, main particle size

1 to 10 microns Citrate: trisodium citrate dihydrate Citric acid: citric acid Perborate: dehydrated sodium perborate monohydrate bleaching agent, the empirical formula is NaBO ₂ ·H ₂ O ₂ PB4: dehydrated perboric acid Sodium tetrahydrate percarbonate: Anhydrous sodium percarbonate bleach with the empirical formula _{2Na2CO3 3H2O2 TAED} : Tetraacetylethylenediamine NOBS: _{Nonanoyloxybenzene} -sulfonate NACA-OBS : N-nonanoyl-6-aminocaproic acid phenolsulfonate Paraffin: paraffin oil, trade name Winog70, sold by Wintershall Pectinase: Pectinase, trade name Pectinex, xylanase sold by Novo Nordisk A/S : Xylanase, trade name Pulpzyme HB or SP431, by Novo

Sold by Nordisk A/S; or trade name Lyxasan by Gist-Brocades

marketed; or trade names Optipulp or Xylanase, sold by Solvay Protease: proteolytic enzymes, trade names Savinase, Alcalase, Durazym, sold by Novo

Sold by Nordisk A/S; trade name Maxacal, Maxapem, Gist-Brocades

Sales and Patents WO91/06637 and/or WO95/10591 and/or EP251446

Protease Amylase described in: Amylolytic enzyme, trade name Purafact Ox Am ^R , described in WO94/18314,

Genencor sells; trade names Termamyl ^® , Fungamyl ^® and Duramyl ^® ,

Both are commercially available from Novo Nordisk A/S and those described in WO95/26397. Specific lipolytic enzyme: Lipolase Ultra, Novo Nordisk A/S

Sells a second lipolytic enzyme: Lipolase under the trade name Lipolase, Novo Nordisk A/S sells Peroxidase: Peroxidase Cellulase: Cellulase under the trade name Garezyme or Celluzyme, Novo Nordisk

A/S Sales CMC: Carboxymethylcellulose Sodium HEDP: 1,1-Hydroxyethane Diphosphonic Acid DETPMP: Diethylene Triamine Penta (Methylene Phosphonic Acid), trade name Dequest 2060,

Monsanto sells PAAC: cobalt(III) pentaamine acetate BzP: benzoyl peroxide PVP: polyvinylpyrrolidone polymer PVNO: poly(4-vinylpyridine)-N-oxide LSD: C ₁₆ -C ₁₈ di Methylamine Oxide, C ₁₂ -C ₁₈ Alkyl Ethoxy Sulfate, B

Oxylation degree 1-5; and C ₁₃ -C ₁₅ ethoxylated alcohol 12 or 30, trade name

For Lutensol A012 and Lutensol A030, the company BASF GmbH sells SRP: sulfonated poly-ethoxy/propoxy-terminated ester oligomers and/or short block copolymers,

Dimethyl terephthalate, 1,2-propanediol, methyl blocked PEG or sulfoethyl

Oxygenate Synthesis EDDS: Ethylenediamine-N,N'-Disuccinic Acid, [S,S] Isomer in Sodium Salt Form Granular Foam Suppressor: 12% Polysiloxane/Silicon Dioxide, 18% Stearyl Alcohol, 70% Granules

Starch SCS: Sodium cumene sulfonate Sulfate: Anhydrous sodium sulfate HMWPEO: High molecular weight polyethylene oxide PGMS: Polyglyceryl monostearate with trade name Radiasurf 248 TAE25: Tallow alcohol ethoxylate (25) PEG (-6): polyethylene glycol (molecular weight 600) BTA: benzotriazole bismuth nitrate: bismuth nitrate salt NaDCC: sodium dichloroisocyanurate KOH: 100% active solution of potassium hydroxide pH: 20 ° C, Determination of Example I in 1% distilled water

According to the present invention, granular fabric cleaning compositions can be prepared as follows.

Ⅰ     Ⅱ     Ⅲ       Ⅳ      VLAS             22.0   22.0   22.0     22.0    22.0磷酸盐          23.0   23.0   23.0     23.0    23.0碳酸盐          23.0   23.0   23.0     23.0    23.0硅酸盐          14.0   14.0   14.0     14.0    14.0沸石A            8.2    8.2    8.2      8.2     8.2DETPMP           0.4    0.4    0.4      0.4     0.4硫酸钠           5.5    5.5 5.5 5.5 5.5 5.005-0.01 — 0.02 Proteinase 0.01 0.02 0.005-Pornase 0.---0.01 0.02-Specific Lipidase 0.005 0.005 0.003 Second Decoase 0.004 0.004 0.004 0.01 0.002 0.008 0.005 Cellulase 0.001 - - - 0.001 - Water and minor ingredients up to 100% Example 2

A granular fabric cleaning composition according to the invention is prepared as follows.

Ⅰ Ⅱ III a VLAS 12.0 12.0 12.0 12.0 12.0 Burle A 26.0 26.0 26.0 26.0SS 4.0 4.0 4.0 4.0 5.0 5.0 5.0 5.0 5.0 5.0 Sulfate 17.0 17.0 17.0 17.0 overlap. 16.0-16.0TAed 5.0--5.0Nobs-3.0---NACA-OBS-4.0-2.5 protease 0.06 0.03 0.02 0.08 0.05 Specific lipidase 0.004 0.008 0.010 0.002 The second lipidase 0.03 0.006 0.006 0.00404 Amylase 0.01 - 0.01 - 0.005 water and minor ingredients up to 100% Example 3

A granular fabric cleaning composition, especially for colored fabric washing, according to the invention is prepared as follows.

Ⅰ Ⅱ ⅢLAS 11.4 10.7 -TAS 1.8 2.4 -TFAA-4.045as 3.1 10.045E7 4.0-25E3S-3.068E1 1.8 -25E5-8.0 citrate 15.0 7.0 carbonate 3.0 2.5 3.0 Burrastone A 32.5 32.1 25.0NA-SKS-6-9.0MA/AA 5.0 5.0 5.0detpmp 1.0 0.2 0.8 protease 0.02 0.02 0.01 Specific lipidase 0.002 0.008 0.002 Second lipidase 0.003 0.006 0.003 amylase 0.01-- Silicate 2.0 2.5-Sulfate 3.5 5.2 3.0pvp 0.3 0.5-Pacity (4-ethylene pyridine) -n-oxide/ethylene-based-0.2 imidazole and ethylene nepopylkine is boron salt 0.5 1.0-passing Oxidase 0.01 0.01 -Phenol Sulfonate 0.1 0.2 -Water/Minor Component up to 100% Example 4

The granular fabric cleaning compositions of the present invention are prepared as follows.

Ⅰ Ⅱ Ⅲ slas 6.5 8.0 9.0 8.025Ae3s-1.0 1.0AS 15.0 7.07.023e6.5-2.0 3.0 Burle A 26.0 22.0 28.0 sodium nitrogen azine 5.0 -PVP 0.7 -Nobs-3..0-3.0- DTPA             -       -     0.3     -过硼酸盐        0.5     1.0    2.0    1.0硼酸            4.0      -      -      -苯酚磺酸盐      0.1     0.2     -      -PEG              -       -     1.0    1.0聚丙烯酸盐       -       -     3.0    3.0蛋白酶          0.06    0.02   0.02   0.01硅酸盐          5.0     5.0    1.0    1.0 Carbonate 15.0 15.0 15.0 30.0 peroxidase 0.1 0.1-0.02--cellulose enzyme 0.0052 0.0005 0.002 Specific lipidase 0.001 0.001 0.001 The second lipidase 0.001 0.001 0.0005 amylase enzyme enzymes 0.01 0.01 0.01 -SRP - - - - 0.2 0.2 Sulphate - - 19.5 6.5 water/minor ingredient up to 100% Example 5

The granular fabric cleaning compositions of the present invention are prepared as follows. LAS-8.0TAS-2.045as 8.0 -25E3S 2.0 0.525E5 3.0 5.025E3 3.0-TFAA 2.5-Coconut alkyl dihydroxyl hydroxylceamium chloride-1.0 amporor A 17.0nasks-6 12.0 citrate 3.0 2.0 carbonic acid Salt 7.0 8.0mA/AA 5.0 1.0cmc 0.4 0.4 polymer (4-ethylene pyridine) -n-oxide/ethylene-based 0.2-imazole and ethylenechecopylpylpylene aluminylinase 0.05 0.03 specific lipidase 0.002 0.004 second lipid Solutase 0.002 0.003 Astronase 0.001 0.001 amylase 0.01 0.006taed 6.0 3.0 over carbonate 22.0 20.0naca-OBS-3.0edds 0.3 0.2 granular foaming agent 3.5 3.0 water/time (sulfate) is as high as 100 %. Examples 6

The "in-wash softening performance" granular fabric cleaning composition of the present invention was prepared as follows.

Ⅰ Ⅱ45as-10.0las 7.6 -68as 1.3 -45E7 4.0-25E3-5.0 Coconut alkyl dihydroxyl hydroxylchloride 1.4 1.0 citrate 5.0Na-SKS-6-6-6-10.0 Biite A 15.0ma/AA 4.0 4.0DetPMP 0.4 0.4 overlavate 15.0-Passive carbonate-14.0TAed 5.0 5.0NACA-OBS-2.0 green soil clay 10.0hmwpeo-0.1 protease 0.02 0.01 Specific lipidase 0.01 second lipidase 0.001001 0.01 0.01 0.01 Ayrase 0.03 0.005 cellulose enzyme 0.001-silicate 3.0 5.0 carbonate 10.0 10.0 granular foaming agent 1.0 4.0cmc 0.2 0.1 water/submissive component (sulfate) of 100 % implement example 7

A heavy duty liquid fabric cleaning composition according to the invention suitable for pretreatment of soiled fabrics and for use in a washing machine washing process is prepared as follows.

Ⅰ Ⅱ Ⅲ ⅴ 4 24AS 20.0 20.0 20.0 20.0SS 5.0 5.0 5.0 5.0 Citrate 1.0 1.0 1.0 1.0 1.012e ₃ 13.0 13.0 13.0 13.0 Monatolamine 2.5 2.5 2.5 2.5 0.03 0.02 0.04 0.01 Special 0.01 0.007 0.0005 0.004 second lipolytic enzyme 0.006 0.01 0.005 0.0010 0.010 amylase 0.005 0.005 0.001 0.01 0.004 cellulase 0.04 - 0.01 - - pectinase 0.02 0.02 - - - water/propylene glycol/ethanol (1:1) Up to 100% Example 8

The heavy duty liquid fabric cleaning compositions of the present invention were prepared as follows.

Ⅰ Ⅱ Ⅲ IV Acid form of LAS - - 25.0 -C _12-14 alkenylsuccinic acid 3.0 8.0 10.0 - Citric acid 10.0 15.0 2.0 2.025AS acid form 8.0 8.0 - 15.025AE3S acid form - 3.0 - 4.025AE7 - 8.0 - 6.025AE3 8.0 - 4.0 -CFAA - - 4.0 6.0 DETPMP 0.2 - 1.0 1.0 Fatty Acid - - - 10.0 Oleic Acid 1.8 - 1.0 - Ethanol 4.0 4.0 6.0 2.0 Propylene Glycol 2.0 2.0 6.0 10.0 Protease 0.02 0.02 0.02 0.01 Specific Lipolytic Enzyme 0.0105 0.000 0.0 Two lipolytic enzymes 0.005 0.01 0.005 0.002 Amylase 0.005 0.01 - - Coconut alkyl dimethyl hydroxyethyl ammonium chloride - - 3.0 -SRP - - 0.2 0.2 Smectite clay - - 5.0 -PVP 1.0 2.0 - - Perboron Acid Acid - 1.0 - - Phenol Sulfonate - 0.2 - - Peroxidase - 0.01 - - NaOH up to pH 7.5 Water / minor ingredients up to 100% Example 9

The heavy duty liquid fabric cleaning compositions of the present invention were prepared as follows.

Ⅰ Ⅱ Ⅲ MSI. Ethanlamine 1.0 1.1 0.7C12HLAS-9.6C25AE2.5S 19.0 19.0 13.8 propylene glycol 6.3 4.923E9 2.0 2.2 Sodium toluene Sulfate 2.8 1.5NAOH 3.4 3.1 6.6 Mumroxyl fatty acid amine 3.0 3.0 7.1 fatty acid 3.0 7.1 fatty acids 3.0 7.1 fatty acids 3.0 7.1 fat acid. 2.0 2.0-Specific lipidase 0.004 0.01 0.01 The second type of lipidase 0.010 0.01 0.005 borax 2.5 2.5 2.2 ethanol 3.4 1.9sRP 0.2 0.3E15-18 Batobaine Bidramine 1.2 1.3 1.2 Glycerin- - 3.0 water and minor ingredients up to 100% Example 10

A nonaqueous bleach-containing fabric cleaning composition of the present invention was prepared as follows. C _12-15 Alkyl Ether (EO=3) Sodium Sulfate 14.0 CFAA _{8.0 C} 12-14 Ethoxylated Alcohol (EO=5) 14.0 N-Butoxy Propoxy Propanol 20.0 Fragrance 0.7 Topped Palm Kernel Fatty Acid Sodium salt 5.7 Trisodium citrate 1.9 Sodium percarbonate 9.4 Sodium carbonate 7.5 Sodium hydroxyethyl diphosphonate 1.7 Calcium [4-[N-nonanoyl-6-aminocaproyloxy]benzenesulfonate 4.7 Brightener 0.2 Silicone oil DB -10 0.5 specific lipolytic enzyme 0.005 second lipolytic enzyme 0.005 amylase 0.05 protease 0.01 cellulase 0.001 minor components up to 100% Example 11

The rinse-added fabric softener compositions of the present invention (by parts by weight) were prepared as follows. Active softener 24.5 PGMS 1.5 Alkyl Sulfate 3.5 TAE25 1.5 Specific lipolytic enzyme 0.001 Second lipolytic enzyme 0.001 Cellulase 0.001 HCL 0.12 Antifoam agent 0.019 Blue dye 80 ppm CaCl ₂ 0.35 Perfume 0.90 Example 12

Syndet bar fabric cleaning compositions of the present invention were prepared as follows.

Ⅰ Ⅱ Ⅱ Ⅳ C _12-16 sodium alkyl sulfate 10.0 10.0 10.0 10.0 CFAA 5.0 5.0 5.0 5.0C _11-13 sodium alkylbenzene sulfonate 10.0 10.0 10.0 10.0 sodium carbonate 25.0 25.0 25.0 25.0 sodium pyrophosphate 7.0 7.0 7.0 7.0 triphosphate Sodium 7.0 7.0 7.0 7.0 Zeolite A 5.0 5.0 5.0 5.0 Carboxymethylcellulose 0.2 0.2 0.2 0.2 Polyacrylate (MW1400) 0.2 0.2 0.2 0.2 Coconut monoethanolamide 5.0 5.0 5.0 5.0 Specific lipolytic enzyme 0.010 0.01 0.005 0.001 Second Lipolytic Enzyme 0.008 0.01 0.008 0.003 Protease 0.3 - 0.5 0.05 Brightener, Fragrance 0.2 0.2 0.2 0.2CaSO ₄ 1.0 1.0 1.0 1.0MgSO ₄ 1.0 1.0 1.0 1.0 Water 4.0 4.0 4.0 4.0

Filler ^* : balanced to 100% ^* can be selected from convenient raw materials such as CaCO ₃ , talc, clay (kaolin, smectite), sodium silicate, etc. Example 13

Compact high density (0.96 kg/liter) dishwashing compositions I to VI of the present invention were prepared.

Ⅰ Ⅱ III ⅴ ⅵ ⅵStpp-46.0 35.00-citrate 32.95 17.05-17.05 25.00 carbonate-17.50-18.0 15.00 25.00 Silicate 33.00 14.81 20.36 14.81 14.81-2.50 2.50-- Carbonate 1.94 9.74 7.79 14.28 9.74 6.70pb4 8.56-------alkyl sulfate 3.00 3.00 3.00 3.00 3.00 Non-ion type 1.50 1.50 1.50 2.0.60TAed 4.78-2.39-2.00Nobs-4.00-4.00NACAACA -OBS-2.50- -HHDP 0.83 1.00 0.46-0.83 -DetpMP 0.65 0.65--PAAC--0.20 -BZP--4.44-Paraffin 0.50 0.50 0.50 0.20 protease 0.075 0.10 0.08 0.01 0.01 0.01 0.01 0.01 0.01 Specific lipidase 0.0005 0.001 0.001 0.005 0.0004 0.001 The second type of lipidase 0.001 0.001 0.004 0.0010 0.002 amylase 0.005-0.015 00.0025bta 0.30 0.30 0.30------------------------are use ---Three yuan co-vector--4.00 -480N-6.00 2.77-6.67-Sulfate 5.00 17.00 3.00-23.00 1.00LSD-2.50-10.0PH (1 % solution) 10.80 11.00 10.80 10.90 9.60 and water up to 100% Example 14

Prepare the following bulk density (1.02kg/l) granular dishwashing agent composition example Ⅰ～Ⅳ

Ⅰ Ⅱ III ⅴ ⅵ ⅵStpp 30.00 30.00 30.00 27.90 30.0 26.70 carbonate 30.50 30.50 25.0 23.00 25.0 2.80 silicate 7.40 7.40 12.00 8.00 20.34 Volumes of Boron 4.40 4.40-4.40 -NADCC--2.00-15100-15 Salt 1.0 1.0 1.0 2.0 2.0 1.5 non-ion type 0.75 0.75 0.75 1.90 1.20 0.50TAed 1.00-1.00-PAAC-0.004- -BZP-1.40--paraffin 0.25 0.25--protease 0.05 0.05-0.11 -Depators with specific lipidase 0.005 0.001 0.001 0.0005 0.0008 0.001 The second type of lipidase 0.01 0.002 0.002 0.0008 0.002 amylase 0.003-0.01 0.015bta 0.15-0.15--sulfate 18.0 20.0 12.0 -LSD -LSD -LSD -LSD -LSD -LSD -LSD -LSD 5.0 - 10.0 -pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30 Minor ingredients and water up to 100% Example 15

Preparation of the following 25 g heavy cleaning agent composition tablets of the present invention was prepared by extruding the granular dishwashing agent composition with a standard 12 head rotary press under a pressure of 13 KN/cm ² .

Ⅰ Ⅱ IIISTPP-48.80 47.50 citrate 26.40-carbonate-carbonate-5.00-silicate 26.40 15.00 protease 0.03 0.075 0.01 Specific lipidase 0.005 0.001 0.0005 0.0002 0.0005 amylase 0.005.0011过硼酸盐        1.56    7.79      -PB4             6.92     -       11.40烷基硫酸盐      2.00    3.00     2.00非离子型        1.20    2.00     1.10TAED            4.33    2.39     0.80HEDP            0.67     -        -DETPMP          0.65     -        -石蜡            0.42    0.50      -BTA             0.24    0.30      -PA30            3.2      -        -LSD             10.0 - - Sulfate 10.0 10.5 3.20pH (1% solution) 10.60 10.60 11.00 Minor ingredients and water to 100% Example 16

Prepare the following liquid dishwashing composition I-II of the present invention with a density of 1.40 kg/liter.

Ⅰ Ⅱstpp 33.30 20.00 carbonate 2.70 2.00 silicate-4.40NADCC 1.10 1.15 alkyl sulfate 3.00 1.50 non-ionic 2.50 1.00 Packs 2.20-protease 0.03 0.02 Specific lipidase 0.00525 The second lipidase 0.00518480N 0.50 4.00KOH - 6.00LSD 2.0 - Sulfate 1.60 -pH (1% solution) 9.10 10.00 Minor ingredients and water to 100% Example 17

In accordance with the present invention, the following liquid hard surface cleaning compositions are prepared.

^Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ specific lipolytic enzyme 0.01 0.002 0.005 0.02 0.001 0.005 second lipolytic enzyme 0.008 0.005 0.005 0.025 0.001 0.010 protease 0.05 0.01 0.02 0.03 0.005 0.005 protease 0.05 0.01 0.02 0.03 0.005 0.005 EDTA - 2.90 2.90C12 Sodium Alkylbenzene Sulfonate 1.95 - 1.95 - 1.95 -NiEO9 1.50 2.00 1.50 2.00 1.50 2.00C12 Sodium Alkyl Sulfate - 2.20 - 2.20 - 2.20C12 Sodium (Ethoxy) Sulfate ^** - 2.20 - 2.20 - 2.20 C12 Dimethylamine Oxide - 0.50 - 0.50 - 0.50SCS 1.30 - 1.30 - 1.30 - Hexyl Carbitol ^** 6.30 6.30 6.30 6.30 6.30 6.30 Water and Minor Components to 100% ^* Tetrasodium EDTA ^** Diethylene glycol monohexyl ether ^*** All formulations adjusted to pH are 7 Example 18

In accordance with the present invention, the following spray-on compositions are prepared for hard surface cleaning and household mildew removal.

Ⅰ amylase 0.01 Specific lipidase 0.01 The second lipidase 0.015 protease 0.01 sodium cindic sulfate 2.00 sodium dulate sodium sodium 4.00Nieo9 2.00 sodium sodium sodium silicate 0.04 spice/sub -component is as high as 100 up to 100 %

Claims (13)

1. A detergent composition comprising one specific lipolytic enzyme and at least a second lipolytic enzyme, when compared under conditions of equal hydrolytic activity, i.e. the same amount of LU per liter of wash solution, the former Specific lipolytic enzymes provide significantly improved whiteness retention properties over Lipolase( ^R) enzymes. 2. A detergent composition according to claim 1, wherein said second lipolytic enzyme is selected from the group consisting of lipase, cutinase, esterase, and/or phospholipase. 3. A detergent composition as claimed in claims 1-2, wherein said second lipolytic enzyme is a lipase, which is selected from the positive immunology with lipase antibody produced by microorganism Pseudomonas fluorescens IAM 1057 Cross-reactive lipase, wild-type lipase produced by Pseudomonas pseudoalcaligenes and its variants M21X and M21L, native lipase produced by Humicola lanuginosa strain DSM 4106 or cutinase or cutinase variants. 4. A detergent composition as claimed in claim 3, wherein said second lipolytic enzyme is a lipase, preferably a natural lipase obtained from Humicola lanuginosa strain DSM 4106. 5. A detergent composition according to any preceding claim, wherein said specific lipolytic enzyme is present in an amount of 50 LU to 8500 LU per liter of cleaning solution. 6. A detergent composition according to any preceding claim, wherein the specific lipolytic enzyme is a variant of the natural lipolytic enzyme produced by Humicola lanuginosa and Thermomyces lanuginosus, or by cloning and in a host organism The natural lipolytic enzyme variant produced by expressing the gene encoding the variant in . 7. A detergent composition as claimed in claim 6, wherein said specific lipolytic enzyme is a variant of the native lipase from Humicola lanuginosa strain DSM 4106. 8. 10. A detergent composition according to claim 7, which contains the lipolytic enzyme variant D96L of the natural lipase from Humicola lanuginosa. 9. A detergent composition as claimed in any preceding claim, wherein the lipolytic activity ratio of the second lipolytic enzyme contained is: the lipolytic activity ratio of specific lipolytic enzyme to the second lipolytic enzyme is 1:5-5:1, preferably 1:3-3:1. 10. A detergent composition according to any one of the preceding claims, further comprising one or more ingredients selected from the group consisting of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, bleaching systems, builder compounds, Defoamers, Soil Suspending and Anti-redeposition Agents, Smectite Clays, Soil Release Polymers, Lime Soap Dispersants, etc. 11. 3. A detergent composition according to any preceding claim which additionally contains other enzymes which provide cleaning performance and/or fabric care benefits. 12. A detergent additive comprising one specific lipolytic enzyme and at least a second lipolytic enzyme, the former specific when compared under conditions of equal hydrolytic activity, i.e. same amount of LU per liter of wash solution Lipolytic lipolytic enzymes provide significantly improved whiteness maintenance performance over Lipolase( ^R) enzymes. 13. Detergent compositions according to claims 1-11 for hard surface cleaning and/or hand and machine dishwashing and/or hand and machine laundry.