EP0912681A1 - Detergent compositions comprising specific lipolytic enzyme and lime soap dispersant - Google Patents

Abstract

The present invention relates to detergent compositions comprising a specific lipolytic enzyme and a lime soap dispersant. 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, filming and stain removal performances.

Description

DETERGENT COMPOSITIONS COMPRISING SPECIFIC LIPOLYTIC ENZYME AND LIME SOAP DISPERSANT

TECHNICAL FIELD

The present invention relates to detergent compositions comprising a specific lipolytic enzyme and a lime soap dispersant.

BACKGROUND OF THE INVENTION

The inclusion of lipolytic enzyme (e.g. lipase) in detergent compositions for improved cleaning performance is known, e.g. enhancement of removal of triglycerides containing soils and stains from fabrics. Examples are US Patent 4,769,173, Cornelissen et al. issued August 29, 1989; US Patent 5,069,809, Lagerwaard et al., issued December 3, 1991; PCT application WO94/03578 and HAPPI (Household & Personal Products Industry) No. 28/1991.

In USP 4,769,173 is disclosed a certain class of lipases consisting of fungal lipases ex Humicola lanuginosa together with strong bleaching agents in detergent compositions.

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

In USP 5,069,809 is disclosed the combination of strong bleaching agents with a lipase enzyme produced by cloning the gene encoding the lipase produced by Humicola lanuginosa and expressing the gene in Aspergillus oryzae as host for use in detergent compositions.

In WO 94/03578 is disclosed an enzymatic detergent composition containing 10 to 20 000 LU (Lipolytic units) per gram of detergent composition of a lipase showing a substantial lipolytic activity during the main cycle of a wash process. This lipase is selected in particular on its inactivation behaviour with Diisopropyl Fluoro Phosphate (DFP) .

In spite of the large number of publications on lipase enzymes only the lipase derived from Humicola lanuginosa strain DSM 4106 and produced in Aspergillus oryzae as host has so far found wide-spread application as additive for fabric washing products. It is available from Novo Nordisk under the tradename Lipolase (TM) . Gormsen and Malmos describe in HAPPI this enzyme with trademark "Lipolase" as being the first detergent lipase with a commercially relevant cost performance based on the use of recombinant DNA technology on an industrial scale.

In HAPPI is disclosed that Lipolase is the most effective during the drying step rather than the washing process itself. During the drying of the fabric, the conditions like water level are more favourable for lipolytic hydrolysis than during the actual wash cycle.

In order to optimize the stain removal performance of Lipolase, Novo Nordisk have made a number of variants.

As described in WO 92/05249 D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per litre) .

In Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk is disclosed that the lipase variant (D96L) may be added in an amount corresponding to 0.001-100 mg (5-500.000 LU/1) lipase variant per litre of wash liquor.

A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. Some but not all, lime soap dispersants also demonstrate surfactant capabilities. Conversely, not all surfactants may act as effective lime soap dispersants. It is however, desirable in the detergent compositions that the lime soap dispersant also has surface active capability

The overall performance of a detergent is judged by not only its ability to remove soils and stains, e.g. greasy/oily soils, but also its ability to prevent redeposition of the soils, or the breakdown products of the soils or of any insoluble salt, on the article washed. Redeposition effects results in the articles being coated in an unseemly film, appearing streaked or being covered in visible spots which remain intact at the end of the wash process.

Therefore, there remains a substantial technical challenge in formulating detergent compositions in such a manner to meet the consumer's need for superior overall detergency performance.

The above need has been met by detergent compositions including laundry, dishwashing and hard surface cleaner, containing specific lipolytic enzyme and lime soap dispersant.

It has indeed been surprisingly found that the combination of specific lipolytic enzyme with a lime soap dispersant improves the overall detergency performance e.g. whiteness maintenance on fabrics and reduced spotting, filming and/or redeposition of greasy/oily substances on dishware, hard surfaces and the like.

This finding allows either improved performance or a reduction of the lime soap dispersant/lipolytic enzyme levels while keeping the same detergency performance.

SUMMARY OF THE INVENTION

The present invention relates to detergent compositions comprising a specific lipolytic enzyme and a lime soap dispersant providing improved overall detergency performance.

DETAILED DESCRIPTION OF THE INVENTION

Specific lipolytic enzyme

An essential component of the detergent composition according to the invention is a specific lipolytic enzyme.

In the present context, the term "lipolytic enzyme" is intended to indicate an enzyme exhibiting a lipid degrading capability, such as a capability of degrading a triglyceride, a phospholipid, a wax-ester or cutin. The lipolytic enzyme may, e.g., be a lipase, a phospholipase, an esterase or a cutinase. The specific lipolytic enzymes suitable for the present invention are those lipolytic enzymes which provide a significantly improved whiteness maintenance performance when compared to an identical hydrolytic activity (same amount of LU per litre of wash solution) of the Lipolase™ enzyme. The significant whiteness maintenance performance as used herein can be visually evaluated by expert graders using the 0→4 panel score units (PSU) Scheffe scale (0 stands for no difference and 4 represents a very large difference) .

The specific lipolytic enzyme suitable for the present invention is incorporated into the detergent composition in accordance with the invention at a level of from 50 LU to 8500 LU per litre wash solution. Preferably said lipolytic enzyme is present at a level of from 100 LU to 7500 LU per litre of wash solution. More preferably at a level of from 150 LU to 5000 LU per litre of wash solution.

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

Preferred lipolytic enzymes include variants of lipolytic enzymes producible by Humicola lanuginosa and Thermomyces lanuginosus, or by cloning and expressing the gene responsible for producing said variants into a host organism, e.g. Aspergillus oryzae as described in European Patent Application 0 258 068, incorporated herein by reference.

Highly preferred lipolytic enzymes are variants of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826. Preferably the Humicola lanuginosa strain DSM 4106 is used. An example of said variants is D96L lipolytic enzyme.

By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa the aspartic acid (D) residue at position 96 is changed to Leucine (L) . According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.

To determine the activity of the enzyme D96L the standard LU assay was used (Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07) . A substrate for D96L was prepared by emulsifying glycerine tributyrate

(Merck) using gum-arabic as emulsifier. Lipase activity was assayed at pH 7 using pH stat. method.

One unit of lipase activity (LU/mg) is defined as the amount needed to liberate one micromole fatty acid per minute.

Lime soap dispersant

An essential component of the detergent compositions of the invention is a lime soap dispersant compound, which has a lime soap dispersing power (LSDP) , as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap dispersant compound is present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.

A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. A numerical measure of the effectiveness of a lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by H.C. Borghetty and CA. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950) . This lime soap dispersion test method is widely used by practitioners in this art field being referred to , for example, in the following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3; W.N. Linfield, Tenside Surf. Det. , Volume 27, pages 159-161, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Volume 104, pages 71-73, (1989) . The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in

30ml of water of 333ppm

CaCθ₃ (Ca:Mg=3:2) equivalent hardness.

In the Borghetty/Bergman lime soap dispersion test 5ml of a 0.5% by weight solution of sodium oleate is added to a test tube, followed by 10ml of a hard water solution containing 600ppm Ca²⁺ and 400ppm Mg²+ (lOOOppm as CaC0₃ equivalent, 70° Clark Hardness) which will cause formation of a lime soap deposit (or curd) . An arbitrary amount (less than 15ml) of dispersing agent as a 0.25% by weight solution is then added to the test tube. The total volume of solution in the test tube is then made up to 30ml and the test tube is stoppered, inverted 20 times and then allowed to stand for 30 seconds. The contents of the test tube are then visually inspected to check if the lime soap deposits are still intact or whether they have been dispersed into the solution. The test procedure is repeated using different amounts of dispersing agent solution until the minimum amount of dispersing agent solution which will cause dispersion of the lime soap deposits is obtained.

The lime soap dispersing power is then obtained as:

LSDP = (weight of lime soap dispersing agent) x 100 (weight of sodium oleate)

Thus in accord with the test method described above a material with a lower LSDP is a more effective lime soap dispersant than one with a higher LSDP.

A listing of suitable lime soap dispersants for use in accord with the invention is given in the above mentioned review by M. Linfield to be found in Tenside. Sust. Det., Volume 27, pages 159-161 (1990) . Polymeric lime soap dispersants suitable for use herein are described in the above mentioned article by M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989) . Examples of such polymeric lime soap dispersants include certain water- soluble salts of copolymers of acrylic acid, methacrylic acid or mixtures thereof, and an acrylamide or substituted acrylamide, where such polymers typically have a molecular weight of from 5,000 to 20,000.

Surfactants having good lime soap dispersant capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.

Exemplary surfactants having a LSDP of no more than 8 for use in accord with the invention include C^g-C^g dimethyl amine oxide, Ci2-Ci8 alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly Cl2~^c15 alkyl ethoxysulfate surfactant with a degree of ethoxylation of about 3 (LSDP=4), and the C13-C15 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

The objective of the washing process of soiled fabrics is to clean these, i.e. to remove soils and stains from the soiled clothes. However, as soon as the removed soils appear in the wash solution, they can redeposit onto the fabrics being washed. Especially for white garments the redeposition of soil has a strong negative impact on the whiteness of the fabric. But also the brightness and freshness of colored fabrics is reduced by such redeposition.

Whiteness maintenance is the monitoring of the whiteness of wash & wear fabrics over a number of washing cycles. A good performing detergent has a good whiteness maintenance profile, i.e. it ensures that the whiteness of washed fabrics is maintained at a high level during the complete life cycle of wearing & washing by preventing as much as possible the redeposition onto white fabrics of removed soils.

It has now been surprisingly found that the incorporation into detergents of the specific lipolytic enzymes according to the present invention together with a lime soap dispersant delivers a significant benefit in whiteness maintenance performance.

In addition, under hard surfaces cleaning and dishcare (dishwashing and rinse aid) conditions the use of said specific lipolytic enzymes with a lime soap dispersant, shows a reduced spotting, filming and/or redeposition of greasy/oily soil substances on dishes, plates, hard surfaces and the like.

Detergent components

The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.

The cleaning compositions according to the invention can be liquid, paste, gels, bars, tablets, powder or granular forms. Granular compositions can also be in "compact " form, the liquid compositions can also be in a "concentrated" form.

The compositions of the invention may for example, be formulated as hard surface cleaner, hand and machine dishwashing compositions, hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions.

When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.

When formulated as compositions suitable for use in a laundry machine washing method, the compositions of the invention preferably contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, soil release polymer, dispersant, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional detergent components.

The compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.

If needed the density of the granular laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 600 to 950 g/litre of composition measured at 20°C.

The "compact" form of the granular laundry detergent compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition.

In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition. The inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides. A preferred filler salt is sodium sulphate.

Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents. Typically 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 detergent composition.

Surfactant system

The detergent compositions according to the present invention can additionally comprise a surfactant system wherein the surfactant can be selected from anionic and/or nonionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.

The surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation are 1% to 35% by weight, most preferably from 1% to 30% by weight of detergent compositions in accordance with the present invention.

Preferred systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.

Polyethylene, polypropylene, and polybytylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight- chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal™ CO-630, marketed by the GAF Corporation; and Triton™ X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates) .

The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol™ 15-S-9 (the condensation product of linear alcohol with 9 moles ethylene oxide) , Tergitol™ 24- L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribytion) , both marketed by Union Carbide Corporation; Neodol™ 45-9 (the condensation product of ^c14~^c15 linear alcohol with 9 moles of ethylene oxide) , Neodol™ 23-3 (the condensation product of Ci2~^c13 linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide) , Neodol™ 45-5 (the condensation product of C14-CX5 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro™ EOB (the condensation product of C1₃-C15 alcohol with 9 moles ethylene oxide) , marketed by The Procter & Gamble Company, and Genapol LA 030 or 050 (the condensation product of C_]_2- C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside) . The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units. The preferred alkylpolyglycosides have the formula

R²0(C_nH_2n0)_t(glycosyl)_x

wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position) . The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially- available Pluronic™ surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic™ compounds, marketed by BASF.

Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are Cg-Ci4 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C g alcohol ethoxylates (preferably C^Q avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.

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

R² - c - N - Z, I I I 0 R¹

wherein Rl is H, or Rl is Cι_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R² is C5.-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl, R² is a straight Cχχ_i5 alkyl or Cig-ig alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

When included in such detergent compositions, the nonionic surfactant systems of the present invention act to improve the greasy/oily stain removal properties of such detergent compositions across a broad range of cleaning conditions.

Suitable anionic surfactants to be used are linear alkyl benzene solfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc. The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :

0

R 3 _ CH - C - OR'

SO3M wherein R³ is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a Ci_^-Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. 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^ is Cιo~^c16 alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ is Cιo~^c16 alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a Cχo^-c24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cl0~C20 alkyl component, more preferably a C^-Cig alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) . Typically, alkyl chains of Ci2~Ci6 are preferred for lower wash temperatures (e.g. below about 50°C) and C g-ig alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C) .

Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22 primary of secondary alkanesulfonates, C8~^c24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide) ; alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C^-C^g monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated ^c6~^c12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)]_c-CH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt- forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference) .

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mS03M wherein R is an unsubstituted Cιo~^c24 alkyl or hydroxyalkyl group having a ^c10~^c24 alkyl component, preferably a Ci2^_c20 alkyl or hydroxyalkyl, more preferably Ci2-Cιg alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and 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 cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are Ci2~^cιg alkyl polyethoxylate (1.0) sulfate (Ci2-Ci8E (1.0)M) , C^-C^g alkyl polyethoxylate (2.25) sulfate (C₁2~C₁gE (2.25)M) , C₁₂- Ciβ alkyl polyethoxylate (3.0) sulfate (C₁₂-C₁gE (3.0)M) , and Ci2^-C18 alkyl polyethoxylate (4.0) sulfate (C]_2~ CιgE(4.0)M), wherein M is conveniently selected from sodium and potassium.

Cationic detersive surfactants suitable for use in the detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula :

[R²(OR³)_y] [R⁴ (OR³) _y]₂R⁵N+X-

wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH2CH2-/ CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected from the group consisting of ^cl^_c4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, -CH2CHOH- CHOHCOR⁶CHOHCH2θH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R⁵ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R^ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Highly preferred cationic surfactants are the water- soluble quaternary ammonium compounds useful in the present composition having the formula :

R₁R₂R3R4N⁺X^" (i)

wherein R^ is Cg-C^g alkyl, each of R2, R₃ and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4o)χH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R₃ or R4 should be benzyl. The preferred alkyl chain length for R^ is C]_2~^C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin byild up or 0X0 alcohols synthesis.

Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; ^c12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy) 4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein Rι_ is CH2-CH2-O-C-C12-I4 alkyl and R2R3R4 are methyl) . I I

0 di-alkyl imidazolines [compounds of formula (i) ] .

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

Quaternary ammonium surfactants suitable for the present invention have the formula (I) :

Formula I whereby Rl is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :

Formula II

y is 2-4, preferably 3. whereby R2 is H or a C1-C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, whereby R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,

whereby X~ is a counterion, preferably a halide, e.g. chloride or methylsulfate.

Formula I cII R6 is C1-C4 and z is 1 or 2.

Preferred quat ammonium surfactants are those as defined in formula I whereby Rl is Cg, C10 ^or mixtures thereof, x=o, R₃, R₄ = CH₃ and R₅ = CH₂CH₂OH.

When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.

Ampholytic 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 in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.

When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.

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 ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.

When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water- soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula

0

R³(OR⁴)xN(R⁵)2 wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R^ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include ^c10"^c18 alkyl dimethyl amine oxides and Cg-C^ alkoxy ethyl dihydroxy ethyl amine oxides.

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

The detergent composition of the present invention may preferably further comprise a cosurfactant selected from the group of primary or tertiary amines. Suitable primary amines for use herein include amines according to the formula R1NH2 wherein R^ is a C5-C12 preferably Cg-Cio alkyl chain or R₄X(CH2_)n, X is -O-,- C(0)NH- or -NH-_/ R4 is a Cg-C]^ alkyl chain n is between 1 to 5, preferably 3. R^ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.

Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl- oxypropylamine, lauryl amido propylamine and amido propylamine.

Suitable tertiary amines for use herein include tertiary amines having the formula R^R2^R3^N wherein Rl and R2 are Cχ-C_β alkylchains or Ψ

— ( CH₂ — CH θ )_xH

R3 is either a Cg-Cχ2 preferably Cg-Cio alkyl chain, or R3 is R4X(CH2₎n' whereby X is -0-, -C(0)NH- or -NH-^4 is a C4-C12, ⁿ is between 1 to 5, preferably 2-3. R5 is H or Cτ_- C2 alkyl and x is between 1 to 6 .

R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary amines are R1R2R3N where Rl is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or

—(CH₂—CH θ)_xH where R5 is H or CH3 and x = 1-2. Also preferred are the amidoamines of the formula:

0 Ri—C—NH—(CH₂)—N—(R₂)

wherein R^ is Cg-C]^ alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1-C4

Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1- dodecylamine,C8-10oxypropylamine, N coco l-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis (hydroxyethyl) amine, coco bis (hydroxyehtyl) amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and CIO amidopropyldimethylamine. The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1- dodecylamine. Especially desirable are n- dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

Optional detergent ingredients :

Other detergent enzymes

The detergent compositions can in addition to specific lipolase enzymes further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.

Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, other lipases, other esterases, other cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, chondroitinase, laccase or mixtures thereof.

A preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced 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 a strain of Humicola insolens (Humicola grisea var. thermoidea) , particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo) .

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo- peroxidase.

Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.

Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Preferred commercially available protease enzymes include those sold under the tradenames Alealase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S (Denmark) , those sold under the tradename Maxatase, Maxacal, Maxapem and Properase by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Also proteases described in patent applications EP 251 446, WO91/06637 and WO94/10591 and USSN 08/332 676 can be included in the detergent composition of the invention. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.

The detergent compositions of the present invention can include other lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fl uorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano, " hereinafter referred to as "Amano-P". Especially suitable lipases are lipases such as Ml Lipase** ^anc* Lipomax^R (Gist- Brocades) and Lipolase^R(Novo) which have found to be very effective when used in combination with the compositions of the present invention.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Suitable cutinases are described in WO 94/14963 and WO 94/14964.

Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor) . The other lipases and/or cutinases are normally incorporated in the detergent composition at levels from

0.0001% to 2% of active enzyme by weight of the detergent composition.

Amylases (α and/or β) can be included for removal of carbohydrate-based stains. WO/94/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. 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 cleaning compositions include both α- and β-amylases. α-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylase are stability-enhanced amylases including Purafact Ox Am^R described in WO 94/18314, published August 18, 1994 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Examples of commercial α-amylases products are Termamyl^®, Ban^® ,Fungamyl^e and Duramyl^®, all available from Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases : α-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl^® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas^® α-amylase activity assay. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition. The enzymes can be added as single ingredients (prills, granulates, stabilised liquids...) or as mixture of two or more enzymes (e.g. cogranulates) .

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in the copending European patent application 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

Color care benefits

Technologies which provide a type of color care benefit can be also included. Examples of these technologies are metallo catalysts for color maintenance. Such metallo catalysts are described in the European patent EP 0 596 184 and in the copending European Patent Application No. 94870206.3.

Bleaching agent

Bleach systems that can be included in the detergent compositions of the present invention include bleaching agents such as PB1, PB4 and percarbonate with a particle size of 400-800 microns. These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. When present oxygen bleaching compounds will typically be present at levels of from about 1% to about 25%.

The bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.

The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4- nonylamino-4-oxoperoxybytyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551. Another category of bleaching agents that can be used encompasses the halogen bleaching agents. Examples of hypohalite bleaching agents, for example, include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.

The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED) , nonanoyloxybenzene- sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591), pentaacetylglucose (PAG) or Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters such as disclosed in Copending European Patent Application No. 91870207.7.

It has been found that combination of specific lipolytic enzyme with a bleaching agent and especially with nonanoyloxybenzene-sulfonate (NOBS) and Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS) as bleach activator, reduce the spotting, filming and/or redeposition thereby enhancing the whiteness maintenance and the greasy/oily stain removal performance. Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co-pending applications USSN 08/136,626, PCT/US95/07823, W095/27772, W095/27773, W095/27774 and W095/27775.

The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically, detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.

Builder system

The compositions according to the present invention may comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Phosphate builders as sodium tripolyphosphate can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS. Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst) . SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2θ5) .

Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 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, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,1,3-propane tricarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1,2,2-ethane tetracarboxylates, 1,1,3,3- propane tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2, 3, 4, 5-tetrahydro- furan - cis, cis, cis-tetracarboxylates, 2, 5-tetrahydro- furan -cis - dicarboxylates, 2, 2, 5, 5-tetrahydrofuran tetracarboxylates, 1,2, 3, 4,5, 6-hexane -hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic poly¬ carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such a layered silicate (SKS-6) , and a water-soluble carboxylate chelating agent such as citric acid.

A suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.

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

Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight. The total amount of detergency builder in the granular composition ranges preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.

Suds suppressor Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non- surface-active detergent impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, 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 siloxane-glycol copolymer. Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2- bytyl-octanol which are commercially available under the trade name Isofol 12 R.

Such suds suppressor system are described in Copending European Patent application N 92870174.7 filed 10 November, 1992.

Especially preferred silicone suds controlling agents are described in Copending European Patent application

N°92201649.8. Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil^R.

The suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight. Others

Other components used in detergent compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.

Especially suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464, 616.

Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid- esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.

Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.

Preferred optical brighteners are anionic in character, examples of which are disodium 4, 4'-bis- (2- diethanolamino-4-anilino -s- triazin-6-ylamino) stilbene- 2:2' disulphonate, disodium 4, - 4'-bis- (2-morpholino-4- anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis- (2, 4-dianilino-s-triazin-6- ylamino) stilbene-2:2' - disulphonate, monosodium 4',4'' - bis- (2, 4-dianilino-s-tri-azin-6 ylamino) stilbene-2- sulphonate, disodium 4,4' -bis- (2-anilino-4- (N-methyl-N-2- hydroxyethylamino)-s-triazin-6-ylamino) stilbene-2,2' disulphonate, di-sodium 4,4' -bis- (4-phenyl-2, 1, 3-triazol- 2-yl)-stilbene-2,2' disulphonate, di-so-dium 4, 4'bis (2- anilino-4- (l-methyl-2-hydroxyethylamino)-s-triazin-6- ylami-no) stilbene-2,2'disulphonate, sodium 2 (stilbyl-4' '- (naphtho-1',2' :4,5)-1,2,3 - triazole-2''-sulphonate and 4,4'-bis (2-sulphostyryl)biphenyl. Highly preferred brighteners are the specific brighteners of copending European Patent application No. 95201943.8.

Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.

Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula

(CH₃ (PEG) 43) o.75 (POH) ₀.25fT-PO) 2.8 (T-PEG) 0.4]T(PO-

H⁾ ₀.25^{( (}PEG⁾43CH₃ ⁾0.75 where PEG is - (OC2H4) 0-,PO is (OC₃H₆0) and T is (PCOC6H4CO) . Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end- capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 342.

Is is well known in the art that free chlorine in tap water rapidly deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the amylase enzymes. Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31, 1992.

Softening agents

Fabric softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their combination with mono C12- C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.

Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added either spray-dried or as a dry mixed component. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight. These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.

Dye transfer inhibition

The detergent composition of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.

Polymeric dye transfer inhibi ting agents

The detergent compositions according to the present invention also comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash. Especially suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N- vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Addition of such polymers also enhances the performance of the enzymes according the invention.

a) Polyamine N-oxide polymers

The polyamine N-oxide polymers suitable for use contain units having the following structure formula : P

I

( I ) A_x I R

wherein P is a polymerisable unit, whereto the R-N-0 group can be attached to or wherein the R-N-0 group forms part of the polymerisable unit or a combination of both.

0 0 0 I I II I I A is NC, CO, C, -0-,-S-, -N- ; x is 0 or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.

The N-0 group can be represented by the following general structures :

0 0 I I

(Rl)x -N- (R2)y =N- (Rl)x

(R3)z

wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups. The N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein 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 nitrogen of the N-0 group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group is attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.

Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.

Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.

Examples of these classes are polyamine oxides wherein R groups can be aromatic 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 polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N- oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N- oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferred PKa < 6.

The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water- solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 5,000-200,000. Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000. The average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization".

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

The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith. The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .

c) Polyvinylpyrrolidone

The detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90

(average molecular weight of 360,000). Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A- 256,696) .

d) Polyvmyloxazolidone :

The detergent compositions of the present invention may also utilize polyvmyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.

e) Polyvinylimidazole :

The detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.

f) Cross-linked polymers

Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039. In one embodiment, the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymers entrap the dyes by swelling.

Such cross-linked polymers are described in the co- pending patent application 94870213.9

Method of washing

The compositions of the invention may be used in essentially any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.

The process described herein comprises contacting fabrics with a laundering solution in the usual manner and exemplified hereunder.

The process of the invention is conveniently carried out in the course of the cleaning process. The method of cleaning is preferably carried out at 5 °C to 95 °C, especially between 10°C and 60°C. The pH of the treatment solution is preferably from 7 to 11. Typically, the following dosing quantities under european and american washing conditions are respectively : 4-10 g and 1-2 g of detergent composition per litre.

A preferred machine dishwashing method comprises treating soiled articles with an aqueous solution of the machine diswashing or rinsing composition. A conventional effective amount of the machine dishwashing composition means from 8-60 g of product dissolved or dispersed in a wash volume from 3-10 litres. According to a manual dishwashing method, soiled dishes are contacted with an effective amount of the diswashing composition, typically from 0.5-20g (per 25 dishes being treated) . Preferred manual dishwashing methods include the application of a concentrated solution to the surfaces of the dishes or the soaking in large volume of dilute solution of the detergent composition.

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

The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.

In the detergent compositions, the level of the enzymes other than the specific lipolytic enzyme of the present invention, are expressed in pure enzyme by weight of total composition and the abbreviated component identifications have the following meanings :

LAS : Sodium linear Cχ2 alkyl benzene sulphonate

TAS : Sodium tallow alkyl sulphate

XYAS : Sodium Cχ_X - C^y alkyl sulfate

SAS : Ci2^-C14 secondary (2,3) alkyl sulfate in the form of the sodium salt.

AEC : Alkyl ethoxycarboxylate surfactant of formula C^2 ethoxy (2) carboxylate. SS Secondary soap surfactant of formula 2-bytyl octanoic acid

25EY A Ci2-^C15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide

45EY A C14 - C15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide

XYEZS ^C1X ~ ^C1Y sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole

Nonionic ^c13^_c15 ^mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh

CFAA ^c12~^c14 alkyl N-methyl glucamide

TFAA ^c16^-c18 alkyl N-methyl glucamide.

LSD ^c16^-c18 dimethyl amine oxide, Cχ2^~ Cig alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, Ci2"^c15 alkyl ethoxysulfate surfactant with a degree of ethoxylation of about 3 (LSDP=4), and the Ci3~Cι_5 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

Silicate Amorphous Sodium Silicate (Siθ2:Na2θ ratio = 2.0)

NaSKS-6 Crystalline layered silicate of formula δ-Na2Si2θ5

Carbonate Anhydrous sodium carbonate

Metasilicate Sodium metasilicate (Si0₂:Na₂0 ratio =

2.0) Phosphate or STPP Sodium tripolyphosphate

MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000

PA30 Polyacrylic acid of average molecular weight of approximately 8,000.

Terpolymer Terpolymer of average molecular weight approx. 7,000, comprising acrylic.maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20 480N Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500.

Polyacrylate Polyacrylate homopolymer with an average molecular weight of 8,000 sold under the tradename PA30 by BASF GmbH

Zeolite A Hydrated Sodium Aluminosilicate of formula Naχ2 ⁽Alθ2Siθ2) 12- 27H20 having a primary particle size in the range from 1 to 10 micrometers.

Citrate Tri-sodium citrate dihydrate,

Citric Citric Acid

Perborate Anhydrous sodium perborate monohydrate bleach, empirical formula NaBθ2-H2θ2

PB4 Anhydrous sodium perborate tetrahydrate.

Percarbonate Anhydrous sodium percarbonate bleach of empirical formula 2Na2Cθ₃.3H2O2

TAED Tetraacetyl ethylene diamine.

NOBS Nonanoyloxybenzene-sulfonate.

NACA-OBS Phenolsulfonate ester of N-nonanoyl- 6-aminocaproic acid.

Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall. Pectinase Pectolytic enzyme sold under the tradename Pectinex AR by Novo Nordisk A/S.

Xylanase Xylanolytic enzyme sold under the tradenames Pulpzyme HB or SP431 by Novo Nordisk A/S or Lyxasan by Gist- Brocades or Optipulp or Xylanase by Solvay.

Protease Proteolytic enzyme sold under the tradename Savinase, Alealase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem sold by Gist Brocades and proteases described in patents WO91/06637 and/or WO95/10591 and/or EP 251 446.

Amylase Amylolytic enzyme sold under the tradename Purafact Ox Am^R described in WO 94/18314, sold by Genencor; Termamyl^®, Fungamyl^® and Duramyl^®, all available from Novo Nordisk A/S and those described in W095/26397.

Specific Lipolytic Lipolytic enzyme sold under the enzyme tradename Lipolase Ultra by Novo Nordisk A/S.

Peroxidase Peroxidase enzyme.

Cellulase Cellulosic enzyme sold under the tradename Carezyme or Celluzyme by Novo Nordisk A/S.

CMC Sodium carboxymethyl cellulose HEDP 1, 1-hydroxyethane diphosphonic acid

DETPMP Diethylene triamine penta (methylene phosphonic acid) , marketed by Monsanto under the Trade name Dequest 2060.

PAAC pentaamine acetate cobalt (III) sal

BzP Benzoyl peroxide.

PVP Polyvinyl pyrrolidone polymer.

PVNO Poly(4-vinylpyridine)-N-Oxide,

SRP Sulfonated poly-ethoxy/propoxy end capped ester oligomer and/or short block polymer synthetised from Dimethyl-terephtalate, 1,2 propylene Glycol, methyl capped PEG or sulfoethoxylate.

EDDS Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer in the form of the sodium salt.

Granular Suds 12% Silicone/silica, 18% stearyl Suppressor alcohol,70% starch in granular form

SCS Sodium cumene sulphonate

Sulphate Anhydrous sodium sulphate.

HMWPEO High molecular weight polyethylene oxide PGMS Polyglycerol monostearate having a tradename of Radiasurf 248

TAE 25 Tallow alcohol ethoxylate (25)

PEG(-6) Polyethylene glycol (having a molecular weight of 600) .

BTA Benzotriazole

Bismuth nitrate Bismuth nitrate salt

NaDCC Sodium dichloroisocyanurate

KOH 100% Active solution of Potassium

Hydroxide

PH Measured as a 1% solution in distilled water at 20°C.

Example 1

Granular fabric cleaning compositions in accord with the invention were prepared as follows:

I II Ill IV V

LAS 22.0 22.0 22.0 22.0 22.0

Phosphate 23.0 23.0 23.0 23.0 23.0

Carbonate 23.0 23.0 23.0 23.0 23.0

Silicate 14.0 14.0 14.0 14.0 14.0

Zeolite A 8.2 8.2 8.2 8.2 8.2

DETPMP 0.4 0.4 0.4 0.4 0.4

Sodium sulfate 3.0 3.0 3.0 3.0 3.0

LSD 2.5 2.5 2.5 2.5 2.5

Amylase 0.005 - 0.01 - 0.02

Protease 0.01 0.02 0.01 0.005 -

Pectinase 0.02 - - - -

Xylanase 0.01 0.02 Specific lipolytic enzyme 0.005 0.01 0 . 002 0.005 0.003 Cellulase 0.001 - 0.001 -

Water & minors Up to 100^!

Example 2

Granular fabric cleaning compositions in accord with the invention were prepared as follows:

I II III IV V

LAS 12.0 10.0 10.0 12.0 12.0

Zeolite A 26.0 26.0 26.0 26.0 26.0

SS 4.0 4.0 4.0 4.0 4.0

SAS 5.0 5.0 5.0 5.0 5.0

Citrate 5.0 5.0 5.0 5.0 5.0

Sodium Sulfate 14.0 14.0 14.0 25.0 14.0

Perborate 16.0 16.0 16.0 - 16.0

TAED 5.0 - - - 5.0

NOBS - 3.0 - - -

NACA-OBS - - 4.0 - 2.5

LSD 2.5 4.0 4.0 2.5 2.5

Protease 0.06 0.03 0.02 0.08 0.05

Specific lipolytic 0.004 0.005 0.008 0.010 0.002 enzyme

Amylase 0.01 - 0.01 - 0.005

Water & minors Up to 100%

Example 3

Granular fabric cleaning compositions in accord with the invention which are especially useful in the laundering of coloured fabrics were prepared as follows :

I II III

LAS 10.0 10.7 TAS 1.8 2.4 TFAA - - 4.0

45AS 3.0 3.1 10.0

45E7 4.0 4.0 -

25E3S - - 3.0

68E11 1.8 1.8 -

25E5 - - 8.0

Citrate 12.0 12.0 7.0

Carbonate - - 10

Citric 3.0 2.5 3.0

Zeolite A 32.5 32.1 22.0

Na-SKS-6 - - 9.0

MA/AA 5.0 5.0 5.0

DETPMP 1.0 0.2 0.8

LSD 3.0 3.0 3.0

Protease 0.02 0.02 0.01

Specific lipolytic enzyme 0.002 0.008 0.002

Amylase 0.01 - -

Silicate 2.0 2.5 -

Sulphate 3.5 5.2 3.0

PVP 0.3 0.5 -

Poly (4-vinylpyridine)- -N- - - 0.2 oxide/copolymer of vinyl- imidazole and vinyl pyrrolidone

Perborate 0.5 1.0 -

Peroxidase 0.01 0.01 -

Phenol sulfonate 0.1 0.2 -

Water/Minors Up to 100%

Example 4

Granular fabric cleaning compositions in accord with the invention were prepared as follows:

I II Ill IV

LAS 6.5 8.0 9.0 8.0 25AE3S - - 1.0 1.0 AS 15.0 18.0 7.5 7.0

23E6.5 - - 2.0 3.0

Zeolite A 26.0 22.0 24.0 28.0

Sodium nitriloacetate 5.0 5.0 - -

PVP 0.5 0.7 - -

NOBS - - 3.0 -

DTPA - - 0.3 -

Perborate 0.5 1.0 2.0 1.0

Boric acid 4.0 - - -

Phenol sulfonate 0.1 0.2 - -

PEG - - 1.0 1.0

Polyacrylate - - 3.0 3.0

LSD 4.0 2.5 1.5 2.5

Protease 0.06 0.02 0.02 0.01

Silicate 5.0 5.0 1.0 1.0

Carbonate 15.0 15.0 15.0 30.0

Peroxidase 0.1 0.1 - -

Pectinase 0.02 - - -

Cellulase 0.005 0.002 0.0005 0.002

Specific lipolytic enzyme 0.001 0.0005 0.001 0.001

Amylase 0.01 0.01 0.01 -

SRP - - 1.35 0.5

Sulfate - - 18.5 5.0

Water/minors Up to 100%

Example 5

A compact granular fabric cleaning composition in accord with the invention was prepared as follows:

I II

LAS 0.0 8.0

TAS 0.0 2.0

45AS 8.0 0.0

25E3S 2.0 0.5

25E5 3.0 5.0

25E3 3.0 0.0 TFAA 2.5 0.0

Coco-alkyl-dimethyl hydroxy¬ 0.0 1.0 ethyl ammonium chloride Zeolite A 16.0 15.0 NaSKS-6 12.0 10.0 Citric acid 3.0 2.0 Carbonate 7.0 8.0 MA/AA 5.0 1.0 CMC 0.4 0.4

Poly (4-vinylpyridine)-N-oxide/ 0.2 0.0 copolymer of vinylimidazole and vinylpyrrolidone LSD 3.5 1.5

Protease 0.05 0.03

Specific lipolytic enzyme 0.002 0.004 Cellulase 0.001 0.001 Amylase 0.01 0.006 TAED 6.0 3.0

Percarbonate 20.0 20.0 NACA-OBS 0.0 3.0 EDDS 0.3 0.2

Granular suds suppressor 3.5 3.0 water/minors (sulfate) Up to 100%

Example 6

A granular fabric cleaning compositions in accord with the invention which provide "softening through the wash" capability were prepared as follows:

I II 45AS - 10.0

LAS 7.6

68AS 1.3

45E7 4.0

25E3 - 5.0 Coco-alkyl-dimethyl hydroxy- 1.4 1.0 ethyl ammonium chloride

Citrate 5.0 3.0

Na-SKS-6 - 10.0

Zeolite A 15.0 12.0

MA/AA 4.0 4.0

DETPMP 0.4 0.4

Perborate 15.0 -

Percarbonate - 14.0

TAED 5.0 5.0

NACA-OBS - 2.0

Smectite clay 10.0 10.0

HMWPEO - 0.1

LSD 2.5 1.5

Protease 0.02 0.01

Specific lipo÷ Lytic enzyme 0.0005 0.01

Amylase 0.03 0.005

Cellulase 0.001 -

Silicate 3.0 5.0

Carbonate 10.0 10.0

Granular suds suppressor 1.0 4.0

CMC 0.2 0.1

Water/minors (sulfate) Up to 100%

Example 7

Heavy duty liquid fabric cleaning compositions suitable for use in the pretreatment of stained fabrics, and for use in a machine laundering method, in accord with the invention were prepared as follows:

I II III IV V

24AS 20.0 20.0 20.0 20.0 20.0

SS 5.0 5.0 5.0 5.0 5.0

Citrate 1.0 1.0 1.0 1.0 1.0

12E₃ 13.0 13.0 13.0 13.0 13.0 Monoethanolamine 2.5 2.5 2.5 2.5 2.5

LSD 1.5 1.5 1.5 1.5 2.5

Protease 0.005 0.03 0.02 0.04 0.01

Specific lipolytic 0.008 0.01 0.007 0.0005 0.004 enzyme

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 (100:1:1) Up to 100%

Example 8

Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:

I II Ill IV

LAS acid form - - 25.0 - ^c12-14 alkenyl succinic 3.0 8.0 10.0 - acid

Citric acid 10.0 15.0 2.0 2.0

25AS acid form 8.0 8.0 - 15.0

25AE3S acid form - 3.0 - 4.0

25AE7 - 8.0 - 6.0

25AE3 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

Propanediol 2.0 2.0 6.0 10.0

LSD 2.0 2.0 3.5 3.5

Protease 0.02 0.02 0.02 0.01

Specific Lipolytic enzyme 0.005 0.01 0.005 0.02

Amylase 0.005 0.01 - -

Coco-alkyl dimethyl - - 3.0 - hydroxy ethyl ammonium chloride Smectite clay 5.0

PVP 1.0 2. .0 -

Perborate 1. .0 -

Phenol sulphonate 0. .2 -

SRP - 0. ,2 0.1

Peroxidase 0. .01 -

NaOH Up to pH 7, .5

Waters/minors Up to 100^! i

Example 9

Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:

I II III

Mono ethanol amine 1.0 1.1 0.7

C12HLAS - - 9.6

C25AE2.5S 19.0 19.0 13.8

Propane diol 6.2 6.3 4.9

23E9 2.0 2.0 2.2

Sodium toluene sulfonate 2.5 2.8 1.5

NaOH 3.4 3.1 6.6

Polyhydroxy fatty acid 3.5 3.5 - amide

Citric acid 3.0 3.0 7.1

Fatty acid 2.0 2.0 -

Specific lipolytic enzyme 0.004 0.01 0.01

LSD 1.5 2.5 3.5

Borax 2.5 2.5 2.2

Ethanol 3.4 3.4 1.9

SRP 0.2 0.1 0.3

E15-18 ethoxylated 1.2 1.3 1.2 tetraethylene pentaimine

Glycerine - - 3.0

Water & Minors Up to 100%

Example 10 Bleach-containing non-aqueous fabric cleaning composition in accord with the invention was prepared as follows :

C12-15 alkyl ether (EO=3) sulfate Na Salt 14.0

CFAA 8.0

C12-14, Eo=5 alcohol ethoxylate 14.0

N-butoxy propoxy propanol 20.0

Perfume 0.7

Topped palm kernel fatty acid Na salt 5.7

Trisodium citrate 1.9

Sodium percarbonate 9.4

Sodium carbonate 7.5

Sodium hydroxyethyl diphosphonate Na salt 1.7

[4- [N-nonanoyl-6-aminohexanoyloxy]benzene 4.7 sulfonate] 2 Ca salt

Brightener 0.2

Silicone oil DB-10 0.5

LSD 2.0

Specific lipolytic enzyme 0.005

Amylase 0.05

Protease 0.01

Cellulase 0.001

Minors Up to 100%

Example 11

The following rinse added fabric softener composition, in accord with the invention, was prepared (parts by weight) .

Softener active 24.5

PGMS 1.5

Alkyl sulfate 3.5

TAE 25 1.5 Specific lipolytic enzyme 0.001

LSD 1.5

Cellulase 0.001

HCL 0.12

Antifoam agent 0.019

Blue dye 80ppm

CaCl2 0.35

Perfume 0.90

Example 12

Syndet bar fabric cleaning compositions in accord with the invention were prepared as follows:

I II III IV

C12-16 alkyl sulfate, Na 10.0 10.0 10.0 10.0

CFAA 5.0 5.0 5.0 5.0

Cll-13 alkyl benzene 10.0 10.0 10.0 10.0 sulphonate, Na

Sodium carbonate 25.0 25.0 25.0 25.0

Sodium pyrophosphate 7.0 7.0 7.0 7.0

Sodium tripolyphosphate 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 (MW 1400) 0.2 0.2 0.2 0.2

Coconut monethanolamide 5.0 5.0 5.0 5.0

LSD 2.0 2.0 2.0 2.0

Specific lipolytic enzyme 0.01 0.01 0.005 0.001

Protease 0.3 - 0.5 0.05

Brightener, perfume 0.2 0.2 0.2 0.2

CaS04 1.0 1.0 1.0 1.0

MgS04 1.0 1.0 1.0 1.0

Water 4.0 4.0 4.0 4.0

Filler* : balance to 100%

*Can be selected from convenient materials such as CaC03, talc, clay (Kaolinite, Smectite), silicates, and the like. Example 13

The following compact high density (0.96Kg/l) dishwashing detergent compositions I to VI were prepared in accord with the invention:

I II III IV V VI

STPP - - 46.0 30.0 - -

Citrate 32.95 17.05 - - 17.05 25.0

Carbonate - 17.50 - 18.0 15.00 25.0

Silicate 33.00 14.81 20.36 14.81 14.81 -

Metasilicate - 2.50 2.50 - - -

Perborate 1.94 9.74 7.79 14.28 9.74 -

PB4 8.56 - - - - -

Percarbonate - - - - - 6.70

Alkyl sulfate 3.00 3.00 3.00 3.00 3.00 3.00

Nonionic 1.50 2.00 1.50 1.50 2.00 2.60

TAED 4.78 - 2.39 - 2.00 4.00

NOBS - 4.00 - - - 4.00

NACA-OBS - - 2.50 - -

HEDP 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 0.50 - 0.20

LSD 3.0 5.0 2.5 2.5 7.0 10.0

Protease 0.075 0.05 0.10 0.10 0.08 0.01

Specific 0.0005 0.001 0.001 0.005 0.0004 0.001 lipolytic enzyme

Amylase 0.01 0.005 - 0.015 - 0.0025

BTA 0.30 0.30 0.30 0.30 - -

Bismuth Nitrate - 0.30 - - - -

PA30 4.02 - - - - -

Terpolymer - - - 4.00 - -

480N - 6.00 2.77 - 6.67 -

Sulphate 5.0 17.0 3.0 - 23.0 1.00 pH (1% solution) 10.80 11.00 10.90 10.80 10.90 9.60 Water and Minors Up to 100%

Example 14

The following granular dishwashing detergent compositions examples I to IV of bulk density 1.02Kg/L were prepared in accord with the invention:

I II III IV V VI

STPP 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 7.40 12.00 8.00 20.34

Perborate 4.40 4.40 4.40 - 4.40 -

NaDCC - - - 2.00 - 1.50

Alkyl sulfate 1.0 1.0 1.0 2.0 2.0 1.5

Nonionic 0.75 0.75 0.75 1.90 1.20 0.50

TAED 1.00 1.00 - - 1.00 -

PAAC - - 0.004 - - -

BzP - 1.40 - - - -

Paraffin 0.25 0.25 0.25 - - -

LSD 3.0 3.0 3.0 5.0 2.0 10.0

Protease 0.05 0.05 0.05 - 0.1 -

Specific 0.005 0.001 0.001 0.0005 0.0008 0.001 lipolytic enzyme

Amylase 0.003 - 0.01 - 0.01 0.015

BTA 0.15 - 0.15 - - -

Sulphate 15.0 15.0 17.0 21.0 10.0 - pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30

Water and minors Up to 100%

Example 15

The following detergent composition tablets of 25g weight were prepared in accord with the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm² using a standard 12 head rotary press: I II III

STPP - 48.80 44.50

Citrate 26.40 - -

Carbonate - 5.00 -

Silicate 26.40 14.80 25.00

LSD 10.0 2.5 5.0

Protease 0.03 0.075 0.01

Specific lipolytic enzyme 0.005 0.001 0.0005

Amylase 0.01 0.005 0.001

Perborate 1.56 7.79 -

PB4 6.92 - 11.40

Alkyl sulfate 2.00 3.00 2.00

Nonionic 1.20 2.00 1.10

TAED 4.33 2.39 0.80

HEDP 0.67 - -

DETPMP 0.65 - -

Paraffin 0.42 0.50 -

BTA 0.24 0.30 -

PA30 3.2 - -

Sulphate 10.0 8.0 3.20 pH (1% solution) 10.60 10.60 11.00

Water and Minors Up to 100%

Example 16

The following liquid dishwashing detergent compositions in accord with the present invention I to II, of density 1.40Kg/L were prepared:

I II

STPP 33.30 20.00

Carbonate 2.70 2.00

Silicate - 4.40

NaDCC 1.10 1.15

Alkyl sulfate 3.00 1.50

Nonionic 2.50 1.00 Paraffin 2.20 -

LSD 2.0 3.0

Protease 0.03 0.02

Specific Lipolytic Enzyme 0.005 0.0025

48ON 0.50 4.00

KOH - 6.00

Sulphate 1.60 - pH (1% solution) 9.10 10.00

Water and Minors Up to 100%

Example 17

The following liquid hard surface cleaning compositions were prepared in accord with the present invention :

I II III IV VI

Specific lipolytic 0.01 0.002 0.005 0.02 0.001 0.005 enzyme

Protease 0.05 0.01 0.02 0.03 0.005 0.005

LSD 5.0 5.0 5.0 2.0 3.5 3.5

EDTA* 2.90 2.90

Na Citrate 2.90 2.90

NaCl2 Alkyl 1.95 1.95 1.95 benzene sulfonate

NiE09 1.50 2.00 1.50 2.00 1.50 2.00

NaC12 Alkyl 2.20 2.20 2.20 sulfate

NaC12 (ethoxy) 2.20 2.20 2.20

**sulfate

C12 Dimethylamine 0.50 0.50 0.50 oxide

SCS 1.30 1.30 1.30

Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30

Water and minors Balance to 100%

*Na4 ethylenediamine diacetic acid **Diethylene glycol monohexyl ether ***A11 formulas adjusted to pH 7

Example 18

The following spray composition for cleaning of hard surfaces and removing household mildew was prepared in accord with the present invention :

I

Amylase 0.01

Specific lipolytic enzyme 0.01

Protease 0.01

LSD 3.00

Sodium octyl sulfate 2.00

Sodium dodecyl sulfate 4.00

NiE09 2.00

Sodium hydroxide 0.80

Silicate (Na) 0.04

Perfume 0.35

Water/minors up to 100%

Claims

What is claimed is:

1. A detergent composition comprising a specific lipolytic enzyme which provides a significantly improved whiteness maintenance performance over the Lipolase® enzyme when compared at an equal hydrolytic activity (same amount of LU per liter of wash solution) and a lime soap dispersant having a lime soap dispersing power (LSDP) of no more than 8.

2. A detergent composition according to claim 1 wherein said lipolytic enzyme is present at a level of from 50LU to 8500LU per liter wash solution.

3. A detergent composition according to claims 1-2 wherein said lipolytic enzymes are variants of the native lipolytic enzymes producible by Humicola lanuginosa and Thermomyces lanuginosus, or by cloning and expressing the gene responsible for producing said variants into a host organism.

4. A detergent composition according to claim 3 wherein the lipolytic enzyme is a variant of the native lipase derived from Humicola lanuginosa strain DSM 4106.

5. A detergent composition according to claim 4 comprising the lipolytic enzyme variant D96L of the native lipase derived from Humicola lanuginosa.

6. A detergent composition according to any of the preceding claims wherein said lime soap dispersant is comprised at a level from 0.1% to 40%, preferably from 1% to 20%, more preferably from 2% to 10% by weight of total composition.

7. A detergent composition according to any of the preceding claims wherein the lime soap dispersant has a lime soap dispersant power (LSDP) of no more than 7.

8. A detergent composition according to any of the preceding claims further comprising from 1% to 80% by weight of a detergent builder compound.

9. A detergent composition according to claim 8 wherein said detergent builder compound is water-soluble.

10. A detergent composition according to claims 8-9 wherein said detergent builder compound is sodium tripolyphosphate.

11. A detergent composition according to any of the preceding claims further comprising a bleach system.

12. A detergent composition according to any of the preceding claims further comprising one or more components selected from anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, suds suppressors, soil suspension and anti-redeposition agents, smectite clays, soil release polymer and the like.

13. A detergent composition according to any of the preceding claims further comprising other enzymes providing cleaning performance and/or fabric care benefits.

14. A detergent composition according to claims 1-13 characterised in that said composition is a dishwashing composition.

15. A detergent composition according to claims 1-13 characterised in that the composition is a granular detergent composition containing no more than 15% by weight of inorganic filler salt.

16. A detergent composition according claims 1-13 characterised in that the composition is a heavy duty liquid composition.

17. A detergent additive comprising a specific lipolytic enzyme which provides a significantly improved whiteness maintenance performance over the Lipolase® enzyme when compared at an equal hydrolytic activity

(same amount of LU per liter of wash solution) and a lime soap dispersant having a lime soap dispersing power (LSDP) of no more than 8.

18. Use of a detergent composition according to any of the preceding claims for hard surface cleaning and/or hand and machine dishwashing and/or hand and machine laundry cleaning.