EP0912685A1

EP0912685A1 - Detergent compositions comprising laccase enzyme

Info

Publication number: EP0912685A1
Application number: EP97924687A
Authority: EP
Inventors: Ivan Maurice Alfons Jan Herbots; Mary Vijayarani Barnabas; Alfred Busch
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-05-13
Filing date: 1997-05-13
Publication date: 1999-05-06
Also published as: EP0906399A1; EG21406A; CA2254932A1; MA24178A1; EP0906398A1; BR9708995A; MA24177A1; BR9709247A; BR9709244A; WO1997043383A1; AU3004797A; CA2254927A1; JPH11511782A; MA24175A1; CA2254940A1; JPH11509270A; AU3004697A; JPH11511781A; WO1997043382A1; AU3004897A

Abstract

The present invention relates to detergent compositions comprising laccase at a level of from 0.003 % to 0.06 % pure enzyme by weight of total composition. Such compositions provide optimum cleaning and stain removal performance and sanitisation of the treated surface.

Description

DETERGENT COMPOSITIONS COMPRISING LACCASE ENZYME

TECHNICAL FIELD

The present invention relates to detergent compositions comprising a specific level of a laccase enzyme. Such compositions provide optimum cleaning and stain removal performance.

BACKGROUND of the INVENTION

The detergency performance of enzymes in detergent products is judged by a number of factors, including the ability to remove stains present in the typical load of the laundry.

In particular, coloured stains are problematic to remove. Coloured stains are based on carotenoids compounds such as α-,β- and γ-carotene and lycopene and xanthophyls, on porphyrins such as chlorophyll and on flavonoid pigments and dye components. This latter group of natural flavonoid based dye components comprises the highly coloured anthocyanins dyes and pigments based on pelargonidin, cγanidin, delphidin and their methyl esters and the antoxanthins. These compounds are the origin of most of the orange, red, violet and blue colours occurring in fruits and are abundant in all berries, cherry, red and black currents, grapefruits, passion fruit, oranges, lemons, apples, pears, pomegranate, red cabbage, red beets and also flowers. Derivatives of cyanidin are present in up to 80% of the pigmented leaves, in up to 70% of fruits and in up to 50% of flowers. These stains typically originate from red wine, fruit such as black currant, cherry, strawberry and tomato (in particular ketchup and spaghetti sauce), vegetables such as carrots and beetroot, tea, coffee, spices such as curry and paprika, grass, or ball pens/ink.

Commercial detergents normally include bleaching agents to solve the above mentioned problem. Traditionally, high levels of bleaching agents, optionally with bleach percursors, are incorporated in detergent compositions. Bleaching agents are compounds which are precursors of hydrogen peroxide; hydrogen peroxide is then formed in the course of the washing procedure. Perborates and percarbonates are the most important examples of such hydrogen peroxide precursors.

Given the foregoing, there is clearly a continuing need to provide detergent compositions which have an excellent stain removal performance.

Accordingly, it is an object of the present invention to formulate detergent compositions which provide effective and efficient cleaning of stains, in particular coloured stains.

It has now been surprisingly found that a selected level of a laccase enzyme provides optimum stain removal performance. This finding allows to formulate detergent compositions which exhibit excellent cleaning and stain removal performance.

Moreover, it has been found that the detergent compositions of the present invention provide sanitisation of the treated surafces.

WO91 /05839 describes enzymes exhibiting a suitable oxidase activity or peroxidase activity for the inhibition of textile dye transfer from a dyed fabric to another fabric during the wash process. In particular, WO95/01426 provides a detergent additive and a detergent composition comprising an enzyme exhibiting laccase activity, oxygen and an enhancing agent, which are capable of inhibiting the transfer of a textile dye from a dyed fabric to another fabric when said fabrics are washed together in a wash liquor. Hospital laundry detergents containing an oxidase and a protease enzymes are disclosed in J64-60693. WO93/131 93 describes detergent compositions comprising a protease derived from Nocardiopsis and enzymes exhibiting a suitable oxidase activity or peroxidase activity, for stain bleaching and/or dye transfer inhibition. The laccase enzyme is generally included at a level corresponding to 0.00001 -5 mg, preferably at a level corresponding to 0.0001 -1 mg (calculated as pure enzyme protein) per litre of wash liquor.

However, the use of the selected level of from 0.003% to 0.06% pure enzyme by weight of total composition of a laccase, for optimum cleaning of coloured stains and soils has not been recognised.

SUMMARY of the INVENTION

The present invention relates to detergent compositions comprising a laccase at a level of from 0.003% to 0.06% pure enzyme by weight of total composition. Such compositions provide optimum cleaning and stain removal performance. In addition, the detergent compositions of the present invention provide sanitisation of the treated surfaces.

DETAILED DESCRIPTION of the INVENTION

Laccase and Laccase related enzymes

Laccase and laccase related enzymes at a level of from 0.003% to 0.06% pure enzyme by weight of total composition, are an essential component of the detergent compositions of the present invention.

It has been found that a specific level of a laccase enzyme is very efficient in stain removal performance. Accordingly, the detergent composition of the present invention provides excellent cleaning and stain removal performance. In addition, the detergent compositions of the present invention provide sanitisation of the treated surfaces.

Sanitisation includes all positive effects obtained by the inhibition or reduction of microbial activity on fabrics and other surfaces, such as the prevention of malodour development and bacterial/fungal growth. For example, it provides prevention of malodour development on stored and weared fabrics, on stored dishware, especially plastic kitchen gear and in toilets. In particular, the composition of the invention will inhibit or at least reduce the bacterial and/or fungal development on moist fabric waiting for further laundry processing and thereby preventing the formation of malodour. In addition, bacterial and/or fungal growth on hard surfaces such as tiles and their silicone joints, sanitary installations, will be prevented.

The sanitisation potential of the detergent compositions of the present invention can be enhanced by the addition of chemical sanitisers such as Triclosan and/or hexemidine. Parfums Cosmέtiques Actualites No 1 25, Nov, 1 995, 51 -4 describes suitable chemical sanitisers. The sanitisation benefits of the detergent compositions of the present invention can be evaluated by the Minimum Inhibitory Concentration (MIC) as described in Tuber. Lung. Dis. 1 994 Aug; 75(4):286-90; J. Clin. Microbiol. 1 994 May; 32(5): 1 261 -7 and J. Clin. Microbiol. 1 992 Oct; 30(10):2692-7.

According to the present invention, laccases and laccase related enzymes comprise any laccase enzyme comprised by the enzyme classification (EC 1 .10.3.2), any catechol oxidase enzyme comprised by the enzyme classification (EC 1 .10.3.1 ), any bilirubin oxidase enzyme comprised by the enzyme classification (EC 1 .3.3.5) or any monophenol monooxygenase enzyme comprised by the enzyme classification (EC 1 .14.99.1 ).

Suitable enzymes are laccase enzymes obtainable from Coprinaceae disclosed in WO96/06930.

The above mentioned enzymes may be derived from plants, bacteria or fungi (including filamentous fungi and yeasts) and suitable examples include a laccase derivable from a strain of Apergillus, Neurospora, e.g. N. crassa, Podospora, Botrytis, Collybia, Fomes, Lentinus, Pleurotus, Trametes, e.g. T. villosa and T. versicolor, Rhizoctonia, e.g. R. solani, Coprinus, e.g. C. plicatilis and C. cinereus, Psatyrella, Myceliophthora, e.g. M. thermophila, Schytalidium, Polyporus, e.g. P. pinsitus, Phlebia, e.g. P. radita (WO 92/01046) or Coriolus, e.g. C. hirsutus (JP 2-238885).

The laccase or the laccase related enzyme may furthermore be one which is producible by a method comprising cultivating a host cell transformed with a recombinant DNA vector which carries a DNA sequence encoding said laccase as well as DNA sequences encoding functions permitting the expression of the DNA sequence encoding the laccase, in a culture medium under conditions permitting the expression of the laccase enzyme, and recovering the laccase from the culture.

Especially suitable laccases that function at a pH above 7 are obtainable from a strain of Coprinus, Myceliophtora. Most preferred are laccases active at solution pH above 7 from Coprinus cinereus or Myceliophtora thermophila.

According to the invention laccases displaying immunochemical cross- reactivity with an antibody raised against above described laccases are also included.

Determination of Laccase Activity (LACU)

Laccase activity is determined from the oxidation of syringaldazin under aerobic conditions. The violet colour produced is photometered at 530nm. The analytical conditions are 1 9μM syringaldazin, 23.2mM acetate buffer, pH 5.5, 30°C, 1 min. reaction time.

1 laccase unit (LACU) is the amount of enzyme that catalyses the conversion of 1 .0 μmole syringaldazin per minute at these conditions.

Enhancing agents

The detergent compositions according to the present invention may contain an enhancing agent.

According to the invention an enhancing agent is any compound that enhances the oxidation of the target soil or stain. The enhancing agent will typically be an oxidizable compound, e.g. a metal ion or a phenolic compound such as 7-hydroxycoumarin, vanillin, or p-hydroxybenzenesulfonate, (for reference see WO 92/18683, WO 92/18687 and Kato M and Shimizu S, Plant Cell Physiol. 1 985 26 (7), pp. 1 291 -1 301 (cf. Table 1 in particular). Particularly useful enhancing agents may be described by the following formula :

where R-| is H, OH, C_nH2_n + 1 # in which n is an integer of from 1 to 10; and R2 and R3 are the same or different and selected from C_mH2m + 1 _> 'ⁿ which m is an integer of from 1 to 10. R-| , R2 and R3 may also contain double bonds or cyclic groups.

In preferred embodiments, the enhancing agent is alkylsyringate in particular methyl, ethyl, propyl, butyl, hexyl syringate. Other suitable enhancing agents for the present invention are the new group of organic chemical substances performing excellently as enhancers of phenol oxidising enzymes, such as acetosyringone; described in WO96/10079.

Other particularly useful enhancing agents may be described by the following formula :

in which formula X represents (-O-) or (-S-), and the substituent groups RΪ -R9, which may be identical or different, independently represents any of the following radicals : hydrogen, halogen, hydroxy, formyl, carboxy and esters and salts hereof, carbamoyl, sulfo, and esters and salts hereof, sulfamoyl, nitro, amino, phenyl, C-j -C^-alkyl, Cq -Cs-alkoxy, carbonyl-C-| - Cs-alkyl, aryl-Cι -C5-alkyl; which carbamoyl, sulfamoyl, and amino groups may furthermore be unstubstituted or substituted once or twice with a substituent group R^'O; and which phenyl may furthermore be unsubstituted or substituted with one or more substituent groups R^'O; and which C-| -Ci 4-alkyl, C-| -C5-alkoxy, carbonyl-C-| -C5-alkyl, and aryl-C i -Cs-alkyl groups may be saturated or unsaturated, branched or unbranched, and may furthermore be unsubstitued or substituted with one or more substituent groups R^ ⁰; which substituent groups R10 represents any of the following radicals : halogen, hydroxy, formyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and salts hereof, sulfamoyl, nitro, amino, phenyl, aminoalkyl, piperidino, piperazinyl, pyrrolidin-1 -yl, C-| -C5-alkyl, C-| -C5-alkoxy; which carbamoyl, sulfamoyl and amino groups may furthermore be unsubstituted or substituted once or twice with hydroxy, C-| -C5-alkyl, C-| -C5-alkoxy; and which phenyl may furthermore be substituted with one or more of the following radicals : halogen, hydroxy, amino, formyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and salts hereof, and sulfamoyl; and which Cι -C5-alkyl, and C-| -C5-alkoxy groups may furthermore be saturated or unsaturated, branched or unbranched and may furthermore be substituted once or twice with any of the following radicals : halogen, hydroxy, amino formyl, carboxy and esters and salts hereof, carbamoyl, sulfo and esters and salts hereof, and sulfamoyl; or in which general formula two of the substituent groups R^ -R^ may together form a group -B-, in which B represents any of the following groups : (-CHR^{1 0}-N = N-),

(-CH = CH-)_n, (-CH = N-)_n or (-N-CR^{1 0}-NR^{1 1} -), in which groups n represents an integer of from 1 to 3, R10 is a substituent group as defined above and R 1 1 is defined in the same way as R^ (jt is to be understood that if the above mentioned formula comprises two or more R^ O-substituent groups, these R O-substituent groups may be the same or different).

In particular embodiments, the enhancing agent is 1 0- methylphenothiazine, phenothiazine- 10-propionic acid, N-hydroxysuccinimide phenothiazine-10-propionate, 10-ethyl-phenothiazine-4-carboxylic acid, 10- ethylphenothiazine, 10-propylphenothiazine, 10-isopropylphenothiazine, methyl-phenothiazine-10-propionate, 10-phenylphenothiazine, 1 0- allylphenothiazine, 1 0-(3-(4-methylpiperazin-1 -yl)propyl) phenothiazine, 10-(2- pyrrolidin-1 -yl-ethyl)phenothiazine, 2-methoxy-10-methylphenothiazine, 1 - methoxy- 10-methyl-phenothiazing, 3-methoxy-1 0-methylphenothiazine, 3, 10- dimethylphenothiazine, 3,7, 10-trimethylphenothiazine, 10-(2- hydroxyethyDphenothiazine, 10-(3-hydroxypropyl) phenothiazine, 3-(2- hydroxyethyl)-10-methylphenothiazine, 3-hydroxymethyl-10- methylphenothiazine, 3,7-dibromopheno-thiazine-10-propionic acid, phenothiazine- 10-propionamide, chlorpromazine, 2-chloro-10- methylphenothiazine, 2-acetyl- 10-methylphenothiazine, 10- methylphenoxazine, 10-ethyl-phenoxazine, phenoxazine- 10-propionic acid, 10-(2-hydroxyethyl)phenoxazine or 4-carboxyphenoxazine- 10-propionic acid.

The enhancing agents may be obtained from Sigma-Aldrich, Janssen Chimica, Kodak, Tokyo Kasai Organic Chemicals, Daiichi Pure Chemicals Co. or Boehringer Mannheim; N-methylated derivatives of phenothiazine and phenoxazine may be prepared by methylation with methyliodide as described by Cornel Bodea and loan Silberg in "Recent Advances in the Chemistry of Phenothiazines" (Advances in heterocyclic chemistry, 1 968, Vol.9, pp.321 - 460); B. Cardillo & G. Casnati in Tetrahedron, 1 967, Vol. 23, p.3771 . Phenothiazine and phenoxazine propionic acids may be prepared as described in J.Org. Chem. 15, 1950, pp. 1 125-1 130. Hydroxyethyl and hydroxypropyl derivatives of phenothiazine and phenoxazine may be prepared as described by G.Cauquil in Bulletin de la Society Chemique de France, 1 960, p.1049.

The enhancing agent may be present in concentrations of from 0.01 to 500μM, preferably in concentrations of from 0.1 to 250μM in the wash solution.

The enhancing agent is present in the detergent compositions at a level of 0.1 % to 5 % by weight of the total detergent composition.

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

In a preferred embodiment, the present invention relates to a laundry and/or fabric care composition comprising a specific level of a laccase enzyme (Examples 1 -1 1 ). It has been found that the incorporation of a specific level of a laccase enzyme in a softener matrix does also deliver effective and efficient cleaning of coloured stains and soils during the rinse cycle, with colour safety. In a second embodiment, the present invention relates to dishwashing or household detergent compositions (Examples 12- 20).

The compositions of the invention may for example, be formulated as 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, and compositions for use in general household hard surface cleaning operations. Compositions comprising a laccase enzyme at a level of from 0.003% to 0.06% pure enzyme by weight of total composition, can also be formulated as a sanitisation product.

Such compositions containing a specific level of laccase, can provide fabric cleaning, stain removal, whiteness maintenance, softening, color appearance and dye transfer inhibition when formulated as laundry detergent 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, dispersants, lime- soap dispersants, 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 laundry detergent compositions herein ranges from 400 to 1 200 g/litre, preferably 600 to 950 g/litre of composition measured at 20°C.

The "compact" form of the 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 1 5% 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 comprise a surfactant system wherein the surfactant can be selected from nonionic and/or anionic 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 accord with the invention.

The surfactant is preferably formulated to be compatible with enzyme components present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.

Preferred surfactant 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 polybutylene 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 1 4 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 1 5 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-1 14, 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 1 0 to about 1 8 carbon atoms, with from about 2 to about 1 0 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 TergitolTM 1 5-S-9 (the condensation product of C1 1 -C1 5 linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the condensation product of C1 2-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol™ 45-9 (the condensation product of C14-C1 5 linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3 (the condensation product of C1 2- C-| 3 linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45.7 (the condensation product of C14-C1 5 linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-5 (the condensation product of C^ 4-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM £OB (the condensation product of C1 3-C1 5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA O3O or O5O (the condensation product of C1 2-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-1 1 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 1 6 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1 .3 to about 1 0, 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

R²O(C_nH2nO)_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 1 500 to about 1 800 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 Plurafac^M |_F404 and Pluronic^M 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 1 1 ,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 C3-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cs-Ci s alcohol ethoxylates (preferably C -J O 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

O R¹ wherein Rl is H, or R^ is C1.4 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 C-| ι _.-j 5 alkyl or Ci β-18 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.

Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1 975), 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: O

I I

R3 - CH - C - OR*

I SO3M

wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R^- is a C-| -C6 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,

R3 is ^c10"Ci 6 ^alky'/ and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R^ is C-| 0"Ci 6 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 C-| Q-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C -| 0"C20 a'kyl component, more preferably a C-| 2"Cl 8 ^a'M 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 C1 2-C1 6 are preferred for lower wash temperatures (e.g. below about 50 °C) and C-| 6-18 ^a,M 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 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, C8-C22 primary of secondary alkanesulfonates, C8-C24 oiefinsulfonates, 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, 1 79, C8-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 i 2"Cl 8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C1 2 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(CH2CH2θ)|_c-CH2COO-M + wherein R is a C8-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,

1 975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).

When included therein, the laundry detergent compositions of the present invention typically comprise from about 1 % to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mSO3M wherein R is an unsubstituted C-) 0"C24 ^a'M ^or hydroxyalkyl group having a C-| 0"C24 ^a"^<V' component, preferably a C-| 2~C20 ^a'^kv' ^or hydroxyalkyl, more preferably C-| 2~Cl 8 ^a'M ^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 C-J 2* C-| 8 alkyl polyethoxylate (1.0) sulfate (Ci 2-Ci 8^EH .0)M), C12-C18 ^alM polyethoxylate (2.25) sulfate (Ci 2-^c18^E(²-²⁵)^Mh ^c12^_c18 ^a,kV' polyethoxylate (3.0) sulfate (C-| 2-Cl 8^E(³-°)^M)' ^{and c}1 2"^c18 ^alkY' polyethoxylate (4.0) sulfate (C-| 2-Ci 8^E(4.0)M), wherein M is conveniently selected from sodium and potassium.

The detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described herein.

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 1 8 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 C1 -C4 alkyl, C1 -C4 hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, -CH₂CHOH-CHOHCOR6CHOHCH₂OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R§ js 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 1 8; each y is from 0 to about 10 and the sum of the y values is from 0 to about 1 5; and X is any compatible anion.

Quaternary ammonium surfactant suitable for the present invention has the formula (I):

Formula whereby R 1 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 III R6 is C 1 -C4 and z is 1 or 2.

Preferred quat ammonium surfactants are those as defined in formula I whereby

Rl is Cs, C10 ^or mixtures thereof, x = o, R3, R4 = CH3 and R5 = CH2CH2OH.

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

Rl R2^R3R4N + X^" (i)

wherein R-| is Cβ-C-j g alkyl, each of R2. R3 and R4 is independently C 1 -C4 alkyl, C1 -C4 hydroxy alkyl, benzyl, and -(C2H4Q)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 Ri is Ci 2^_Ci 5 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO 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; C-| 2-1 5 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 R-j is CH2-CH2-O-C-C1 2-I 4 ^alkYl ^and R2^R3^R4 ^are methyl).

I I O di-alkyl imidazolines [compounds of formula (i)J.

Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1 980 and in European Patent Application EP 000,224.

Typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives or thei corresponding amine precursor, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.

Preferred cationic softeners among these include the following:

1 ) ditallow dimethylammonium chloride (DTDMAC);

2) dihydrogenated tallow dimethylammonium chloride;

3) dihydrogenated tallow dimethylammonium methylsulfate; 4) distearyl dimethylammonium chloride;

5) dioleyl dimethylammonium chloride;

6) dipalmityl hydroxyethyl methylammonium chloride;

7) stearyl benzyl dimethylammonium chloride;

8) tallow trimethylammonium chloride; 9) hydrogenated tallow trimethylammonium chloride;

10) C i 2^_14 alky' hydroxyethyl dimethylammonium chloride;

1 1 ) C1 2-I 8 ^a'^kY' dihydroxyethyl methylammonium chloride;

12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);

13) di(tallow-oxy-ethyl) dimethylammonium chloride; 14) ditallow imidazolinium methylsulfate;

1 5) 1 -(2-tallowylamidoethyl)-2-tallowyl imidazolinium methylsulfate.

Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups. Said materials and fabric softening compositions containing them are disclosed in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.

The quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below :

(I) (ID

wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR⁴-C(O)-,

C(O)-NR⁴-; R² is (CH2)_m-Q-T⁴ or T& or R3;

R³ is C1-C4 alkyl or C1 -C4 hydroxyalkyl or H;

R⁴ is H or C1 -C4 alkyl or C1 -C4 hydroxyalkyl;

T¹ , T², T³, T⁴, T^ are independently Ci 1 -C22 ^a'M or alkenyl; n and m are integers from 1 to 4; and X^" is a softener-compatible anion.

Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.

The alkyl, or alkenyl, chain T , T², τ3, T⁴, T must contain at least 1 1 carbon atoms, preferably at least 1 6 carbon atoms. The chain may be straight or branched.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein T¹ , T², T³, T⁴, T^ represents the mixture of long chain materials typical for tallow are particularly preferred. Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :

1 ) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; 2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;

3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;

4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; 5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;

6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;

7) N-(2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-ammonium chloride; and

8) 1 ,2-ditallowyl-oxy-3-trimethylammoniopropane chloride; and mixtures of any of the above materials.

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 1 8 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, 1 975 at column 1 9, 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 1 5%, 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, 1 975 at column 1 9, 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 1 5%, 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 1 8 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 1 0 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 R§ 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 R5 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 Cι o^_Ci 8 alkyl dimethyl amine oxides and C8-C1 2 alkoxy ethyl dihydroxy ethyl amine oxides.

When included therein, the cleaning compositions of the present invention typically comprise from 0.2% to about 1 5%, preferably from about 1 % to about 1 0% by weight of such semi-polar nonionic surfactants.

The detergent composition of the present invention may 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 R1 NH2 wherein R-j is a Cβ-Ci 2, preferably Cβ-Ci o alkyl chain or R4X(CH2)rv ^x »s -O-,-C(O)NH- or -NH-, R4 is a C6-C-| ₂ alkyl chain n is between 1 to 5, preferably 3. Ri alkyl chains may be straight or branched and may be interrupted with up to 1 2, 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 R1 R2R3N wherein R1 and R2 are C-| -C8 alkylchains or

T'

— ( CH₂ — CH θ )χH

R3 is either a C6-C1 2, preferably CQ-C ^ Q alkyl chain, or R3 is R4X(CH2)rv whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-C1 2, ⁿ is between 1 to 5, preferably 2-3. R5 is H or C 1 -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 1 2, preferably less than 5, ethylene oxide moieties. Preferred tertiary amines are R1 R2R3N where R1 is a C6-C1 2 alkyl chain, R2 and R3 are C1 -C3 alkyl or

— ( C H₂ — CH θ )χH where R5 is H or CH3 and x = 1 -2.

Also preferred are the amidoamines of the formula:

0 II Ri — C-NH— ( CH₂ )— N— (R₂ )

wherein R -| is C6-C1 2 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 1 -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 C10 amidopropyldimethylamine. The most preferred amines for use in the compositions herein are 1 - hexylamine, 1 -octylamine, 1 -decylamine, 1 -dodecylamine. Especially desirable are n-dodecyidimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

Conventional detergent enzymes

The detergent compositions can in addition to a laccase 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, lipases, phosphofipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.

A preferred combination is a detergent composition having cocktail df 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 cellulases. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A- 2.095.275; DE-OS-2.247.832 and WO95/26398.

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 41 5 amino acids; and a ^"43kD endoglucanase derived from Humicola insolens, DSM 1 800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91 /1 7243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801 , Genencor, published September 29, 1 994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91 202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91 /1 7244 and WO91 /21 801 . Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/1 7994 and WO95/24471 .

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

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with use of phenolic substrate as bleach enhancing molecule. 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 89/09981 3, WO89/0981 3 and in European Patent application EP No. 91 202882.6, filed on November 6, 1 991 and EP No. 9687001 3.8, filed February 20, 1 996. Enhancers are generally comprised at a level of from 0.1 % to 5% by weight of total composition. Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine- 4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10- methylphenoxazine (described in WO 94/12621 ) and substitued syringates (C3-C5 substitued alkyl sγringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

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

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 1 9.1 54, 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 fluorescent 1AM 1 057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano- P" . Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipo/yticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as M 1 Lipase^{R and} Lipomax^R (Gist-Brocades) and Lipolase^R and Lipolase Ultra^R(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitables are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/2261 5 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever. 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. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The 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.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN').

One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-1 2, developed and sold as ESPERASE^® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo. Other suitable proteases include ALCALASE^®, DURAZYM^® and SAVINASE^® from Novo and MAXATASE^®, MAXACAL®, PROPERASE^® and MAXAPEM®

(protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in

European Patent Application Serial Number 87 303761 .8, filed April 28, 1 987 (particularly pages 1 7, 24 and 98), and which is called herein "Protease

B", and in European Patent Application 1 99,404, Venegas, published October 29, 1 986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A" herein. Suitable is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 1 23, and alanine replaced threonine at position 274. Protease C is described in EP 9091 5958:4, corresponding to WO 91 /06637, Published May 1 6, 1 991 . Genetically modified variants, particularly of Protease C, are also included herein. A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position + 76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of + 99, + 101 , + 103, + 104, + 107, + 1 23, + 27, + 105, + 1 09, + 1 26, + 128, + 135, + 1 56, + 166, + 1 95, + 1 97, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265, and/or + 274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, filed October 1 3, 1 994.

Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91 /06637, protease BLAP^® described in WO91 /02792 and their variants described in WO 95/23221 . See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

The proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.001 % to 0.2%, more preferably from 0.005% to 0.1 % pure enzyme by weight of the composition. Amylases (α and/or β) can be included for removal of carbohydrate- based stains. WO94/02597, Novo Nordisk A/S published February 03, 1994, describes detergent compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1 995. Other amylases known for use in detergent 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 amylases are stability-enhanced amylases described in WO94/1 8314, published August 1 8, 1 994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 21 6, WO95/26397 and WO96/23873 (all by Novo Nordisk).

Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl" , all available from Novo Nordisk A/S Denmark. WO95/26397 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. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). 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 WO95/35382.

The amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.

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 separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 9287001 8.6 filed on January 31 , 1 992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and

WO 9307260 A to Genencor International, WO 8908694 A to Novo, and

U.S. 3,553, 1 39, January 5, 1 971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S.

4,507,21 9, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261 ,868, Hora et al, April 14, 1981 . Enzymes for use in detergents can be stabilised by various' techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 1 7,

1 971 , Gedge et al, EP 1 99,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in

U.S. 3,51 9,570. A useful Bacillus, sp. AC1 3 giving proteases, xylanases and cellulases, is described in WO 9401 532 A to Novo.

Color care and fabric care benefits Technologies which provide a type of color care benefit can also be included. Examples of these technologies are metallo catalysts for color maintenance. Such metallo catalysts are described in copending European Patent Application No. 92870181 .2. Dye fixing agents, polyolefin dispersion for anti-wrinkles and improved water absorbancy, perfume and amino- functional polymer for color care treatment and perfume substantivity are further examples of color care / fabric care technologies and are described in the co-pending Patent Application No. 96870140.9, filed November 07, 1 996.

Fabric softening agents can also be incorporated into 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 5,01 9,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-BO 01 1 340 and their combination with mono C1 2-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 91 9. 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 1 5% by weight, with the material being added as a dry mixed component to the remainder of the formulation. 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 0.1 5% 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.

Bleaching agent Additional optional detergent ingredients that can be included in the detergent compositions of the present invention include bleaching agents such as hydrogen peroxide, 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- oxoperoxybutyric 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 0,1 33,354 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 4,41 2,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 1 20,591 ) or 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. 91 870207.7.

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 08/1 36,626, PCT/US95/07823, WO95/27772,

WO95/27773, WO95/27774 and WO95/27775.

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 91 202655.6 filed October 9, 1 991 .

Metal-containing catalysts for use in bleach compositions, include cobalt-containing catalysts such as Pentaamine acetate cobalt(lll) salts and manganese-containing catalysts such as those described in EPA 549 271 ; EPA 549 272; EPA 458 397; US 5,246,621 ; EPA 458 398; US 5, 1 94,41 6 and US 5,1 14,61 1 . Bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3.

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 further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid 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 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, HS or MAP.

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- 1 ,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, 1 79, 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 as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.

Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid. Preferred builder systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.

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 5% to 80% by weight of the composition preferably from 10% to 70% and most usually from 30% to 60% by weight.

Chelating Agents

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine- hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,81 2,044, issued May 21 , 1 974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1 987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.

If utilized, these chelating agents will generally comprise from about

0.1 % to about 1 5% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions.

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 1 26 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-butyl-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, 1 992.

Especially preferred silicone suds controlling agents are described in Copending European Patent application N °92201 649.8. Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.

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-(1 - 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. 95201 943.8.

Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1 000-10000, 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. 41 1 6885 and 471 1 730 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)o.25[T-PO)2.8(T-PEG)o.4]T(PO- H>0.25..P^EG)43CH₃)o.75

where PEG is -(OC2H4)O-,PO is (OC3H6O) 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 1 6% by weight of propane -1 .2 diol, about 10% by weight ethylene glycol about 1 3% by weight of dimethyl sulfobenzoic acid and about 1 5% 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 31 1 342.

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 detergent enzymes. Compositions comprising chlorine scavenger are described in the European patent application 9287001 8.6 filed January 31 , 1 992.

Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91 /08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula

-(CH2CH2O)_m(CH2)_nCH3 wherein m is 2-3 and n is 6-1 2. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.

Dispersants

The detergent composition of the present invention can aiso contain dispersants : 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 1 ,000 to 100,000.

Especially, copolymer of acrylate and methylacrylate such as the 480N having a molecular weight of 4000, at a level from 0.5-20% by weight of composition can be added in the detergent compositions of the present invention.

The compositions of the invention may contain a lime soap peptiser compound, which has preferably 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 peptiser compound is preferably present at a level from 0% to 20% by weight.

A numerical measure of the effectiveness of a lime soap peptiser is given by the lime soap dispersant power (LSDP) which is determined using the lime soap dispersant test as described in an article by H.C. Borghetty and CA. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1 950). 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, page 3; W.N. Linfield, Tenside surf, det., volume 27, pages 1 59-163, (1990); and M.K. Nagarajan, W.F. Master, 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.

Surfactants having good lime soap peptiser 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 present invention include Ci β-C-j s dimethyl amine oxide, C-] 2-C-| 8 ^a'^ky' ethoxysulfates with an average degree of ethoxylation of from 1 -5, particularly C-| 2"C l 5 alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3 (LSDP = 4), and the C14-C1 5 ethoxylated alcohols with an average degree of ethoxylation of either 1 2 (LSDP = 6) or 30, sold under the tradenames Lutensol A012 and Lutensol A030 respectively, by BASF GmbH. Polymeric lime soap peptisers suitable for use herein are described in the article by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume 1 04, pages 71 -73, (1 989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-{N-nonanoyl-6-aminohexanoyl]benzeπe sulfonate, 4-[N-decanoyl- 6-aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds.

Dye transfer inhibition

The detergent compositions 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 inhibiting 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-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both.

A is NC, CO, C, -O-,-S-, -N- ; x is O or 1 ;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.

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

0 0

I I (R1 )x -N- (R2)y = N- (R1 )x

I

(R3)z

wherein R1 , 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-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.

The N-O 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-O 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-O 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-O group is attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O 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-O 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-O 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 : 1 000000. 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 < 1 0, 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 1 1 3, "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 Q.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 1 5,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-1 5 (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) Polyvinyloxazolidone :

The detergent compositions of the present invention may also utilize polyvinyloxazolidone 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 1 5,000.

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 1 5,000.

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 9487021 3.9

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 1 2. A preferred machine dishwashing method comprises treating soiled articles with an aqueous liquid having dissolved or dispensed therein an effective amount 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 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 enzymes levels are expressed by pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions. The abbreviated component identifications therein have the following meanings:

LAS : Sodium linear C-J 2 alkyl benzene sulphonate.

TAS : Sodium tallow alkyl sulphate.

XYAS : Sodium C ι χ - Cι γ alkyl sulfate.

SAS : C1 2-C14 secondary (2,3) alkyl sulfate in the form of the sodium salt. AEC : Alkyl ethoxycarboxylate surfactant of formula

C1 2 ethoxy (2) carboxylate. SS : Secondary soap surfactant of formula 2-bytyl octanoic acid. 25EY A C-| 2-Ci 5 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide.

45EY A C14 - C-| 5 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide.

XYEZS C -J X - C-| γ sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole.

Nonionic C1 3-C1 5 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 Plurafax LF404 by BASF Gmbh.

AAPA C8-C 10 amidopropyldimethylamine.

CFAA Ci 2"Ci 4 alkyl N-methyl glucamide.

TFAA C1 5-C1 8 ^a'^kyl N-methyl glucamide.

DEQA Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.

DEQA d ) Di-(oleyloxyethyl) dimethyl ammonium methylsulfate.

DEQA (2) Di-(soft-tallowyloxyethγl) hydroxyethyl methyl ammonium methylsulfate.

DTDMAMS Ditalllow dimethyl ammonium methylsulfate.

SDASA 1 :2 ratio of stearyldimethyl amine:triple-pressed stearic acid.

Neodol 45-1 3 C14-C1 5 linear primary alcohol ethoxylate, sold by Shell Chemical CO.

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

Nai 2(A1 O2SiO2> i 2- 27H2O having a primary particle size in the range from 1 to 10 micrometers

Zeolite MAP Alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1 .33

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 2Na2CO3-3H2O2

TAED Tetraacetyl ethylene diamine.

Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.

Peroxidase Peroxidase enzyme sold under the tradename Guardzyme by Novo Nordisk A/S.

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 (Gist-Brocades) or Optipulp or Xylanase (Solvay).

Protease Protease B.

Lipase Lipolytic enzyme sold under the tradename

Lipolase. Cellulase I Cellulolytic enzyme sold under the tradename

Carezyme or Celluzyme by Novo Nordisk A/S

43kD.

Cellulase II Endoglucanase 50kD sold under the tradename

"Endolase" by Novo Nordisk A/S.

Laccase Laccase from Myceliophtora thermophila.

Enhancer Butyl syringate.

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) salt.

BzP Benzoyl peroxide.

PVP Polyvinyl pyrrolidone polymer.

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

Soil Release Polymer Sulfonated poly-ethoxy/propoxy end capped ester oligomer.

EDDS Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer in the form of the sodium salt. Suds Suppressor 25% paraffin wax Mpt 50°C, 1 7% hydrophobic silica, 58% paraffin oil.

Granular Suds 1 2% Silicone/silica, 1 8% stearyl alcohol, 70%

Suppressor 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 detergent compositions in accord with the invention were prepared as follows:

II III IV

LAS 22.0 22.0 22.0 22.0 22.0 AE5 9.0 9.0 9.0 9.0 9.0 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 5.5 5.5 5.5 5.5 5.5

Amylase 0.005 0.02 0.01 0.01 0.02

I II III IV V

Protease 0.01 0.02 0.01 0.005 0.005 Laccase 0.005 0.01 0.01 0.06 0.003 Enhancer 0.5 0.5 0.5 0.5 0.5 Pectinase 0.02 - - - - Xylanase - - 0.01 0.02 - Lipase 0.005 0.01 - - - Cellulase I 0.001 - - 0.001 - Water & minors Up to 100%

Example 2

III IV

AE 6.0 6.0 6.0 6.0 6.0

LAS 12.0 12.0 12.0 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 17.0 17.0 17.0 28.0 17.0

Perborate 16.0 16.0 16.0 - -

TAED 5.0 5.0 5.0 . - Protease 0.06 0.03 0.02 0.08 0.01

Laccase 0.06 0.003 0.04 0.04 0.02

Enhancer 0.5 0.5 0.5 0.5 0.5

Lipase 0.005 0.01 - - -

Amylase 0.01 0.015 0.01 0.02 0.00

Water & minors Up to 100%

Example 3

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

I II III

LAS 1 1.4 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

68E1 1 1 .8 1 .8

25E5 - - 8.0

Citrate 14.0 15.0 7.0

Carbonate - - 10

Citric 3.0 2.5 3.0

Zeolite A 32.5 32.1 25.0

Na-SKS-6 - - 9.0

MA/AA 5.0 5.0 5.0

DETPMP 1 .0 0.2 0.8

Protease 0.02 0.02 0.01

Amylase 0.03 0.03 0.005

Silicate 2.0 2.5 -

Sulphate 3.5 5.2 3.0

PVP 0.3 0.5 . PVNO/copolymer of vinyl¬ - - 0.2 imidazole and vinyl- pyrrolidone

Perborate 0.5 1 .0 -

Peroxidase 0.01 0.01 -

Laccase 0.01 0.01 0.005

Enhancer 0.5 1 .0 0.5

Phenol sulfonate 0.1 0.2 -

Water/Minors Up to 1 00%

Example 4

II

LAS 6.5 8.0

AE 8.0 8.0

Alkyl Sulfate 1 5.0 1 8.0

Zeolite A 26.0 22.0

Sodium nitrilotriacetate 5.0 5.0

PVP 0.5 0.7

TAED 3.0 3.0

Boric acid 4.0 -

Perborate 0.5 1 .0

Protease 0.06 0.02

Laccase 0.01 0.003

Enhancer 0.5 0.8

Silicate 5.0 5.0

Carbonate 1 5.0 1 5.0

Peroxidase - 0.1

Pectinase 0.02 -

Cellulase I 0.005 0.002

Lipase 0.01 -

Amylase 0.01 0.01

Water/minors Up to 100% Example 5

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

45AS 8.0

25E3S 2.0

25E5 3.0

25E3 3.0

TFAA 2.5

Zeolite A 1 7.0

NaSKS-6 1 2.0

Citric acid 3.0

Carbonate 7.0

MA/AA 5.0

CMC 0.4

PVNO/copolymer of vinylimidazole and 0.2 vinylpyrrolidone

Protease 0.05

Laccase 0.06

Enhancer 0.8

Lipase 0.005

Cellulase 1 0.001

Amylase 0.01

TAED 6.0

Percarbonate 22.0

EDDS 0.3

Granular suds suppressor 3.5 water/minors Up to 100%

Example 6

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

1 II

Na-SKS-6 _ 11.0

Zeolite A 15.0 15.0

MA/AA 4.0 4.0

DETPMP 0.4 0.4

Perborate 15.0 -

Percarbonate - 15.0

TAED 5.0 5.0

Smectite clay 10.0 10.0

HMWPEO - 0.1

Protease 0.02 0.01

Laccase 0.02 0.02

Enhancer 1.0 1.0

Lipase 0.02 0.01

Amylase 0.03 0.005

Cellulase 1 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 Upto 100%

Example 7 Heavy duty liquid fabric detergent 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

Monethanolamine 2.5 2.5 2.5 2.5 2.5

Boric acid 2.75 5.75 1.5 1.5 1.5

1 II III IV V

Formic acid - - 1.0 1.0 1.0

Protease 0.005 0.03 0.02 0.04 0.01

Laccase 0.005 0.01 0.02 0.02 0.06

Enhancer 0.5 0.5 0.5 1.0 1.0

Lipase 0.002 0.01 0.02 - 0.004

Amylase 0.005 0.005 0.001 0.01 0.004

Cellulase I 0.04 - 0.01 - -

Pectinase 0.02 0.02 - - -

Water/propylene glycol/ethanol (100:1 :1 )

Example 8

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

I II III IV V

LAS acid form - - 25.0

Cl2-14 alkenyl succinic 3.0 8.0 10.0 acid

Citric acid 10.0 15.0 2.0 2.0 2

23AS acid form 8 25AS acid form 8.0 8.0 - 15.0 4

25AE3S acid form - 3.0 - 4.0 -

35AE35 acid form - - - - 8

25AE7 - 8.0 - 6.0 -

45AE7 - - - - 2.5

25AE3 8.0 - 4.0 - -

CFAA - - - 6.0 4

A A PA 1.5

N-Cocoyl N-methyl glucamine - - 4.0 - -

DETPMP 0.2 - 1.0 1.0 1.0

Fatty acid - - - 10.0 5.0

Oleic acid 1.8 - 1.0 - 3.0

Ethanol 4.0 4.0 6.0 2.0 1.0

1 II III IV V

Propanediol 2.0 2.0 6.0 10.0 12.0

Boric acid 2.75 2.75 1.5 1.5 3.0

Formic acid - - 1.0 1.0 -

Protease 0.02 0.02 0.02 0.01 0.02

Laccase 0.003 0.01 0.02 0.06 0.003

Enhancer 0.3 0.4 0.8 1.0 0.3

Amylase 0.005 0.01 0.005 0.01 0.05

Cellulase 1 - - - - 0.03

Cellulase II - - - - 0.09

Coco-alkyl dimethyl hydroxy - - 3.0 - - ethyl ammonium chloride

Smectite clay - - 5.0 - -

PVP 1.0 2.0 - - -

Perborate - 1.0 - - -

Phenol sulphonate - 0.2 - - -

Peroxidase - 0.01 - - -

Monoethanol amine 6.2

NaOH UptopH 7.5

Waters / minors Upto 100%

Example 9 The following rinse added fabric softener composition, in accord with the invention, was prepared (parts by weight).

DEQA 24.5

PGMS 1 .5

Alkyl sulfate 3.5

TAE 25 1 .5

Protease 0.005

Laccase 0.01

Enhancer 0.8

Amylase 0.001

Cellulase I 0.001

Boric acid 2.00

HCL 0.12

Antifoam agent 0.01 9

Blue dye 80ppm

CaCl2 0.35

Perfume 0.90

Example 10

The following fabric softener and dryer added fabric conditioner compositions were prepared in accord with the present invention :

I II III IV V

DEQA 2.6 19.0

DEQA(2) - - - - 51 .8

DTMAMS - - - 26.0

SDASA - - 70.0 42.0 40.2

Stearic acid of IV = 0 0.3

Neodol 45-1 3 - - 1 3.0 -

Hydrochloride acid 0.02 0.02

Ethanol - - 1 .0

Laccase 0.003 0.005 0.01 0.01 0.06 Enhancer 0.05 0.01 0.2 0.5 0.9

Perfume 1.0 1.0 0.75 1.0 1.5

Glycoperse S-20 - - - - 15.4

Glycerol monostearate - - - 26.0 -

Digeranyl Succinate - - 0.38 - -

Silicone antifoam 0.01 0.01 - - -

Electrolyte - 0.1 - - -

Clay - - - 3.0 -

Dye 10ppm 25ppm 0.01 - -

Water and minors 100% 100% - - -

Example 11

Syndet bar fabric detergent 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

C12-14 N-methyl glucamide 5.0 5.0 5.0 5.0

C11-13 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

Amylase 0.01 0.02 0.01 0.01

Protease 0.3 0.4 0.5 0.05

Laccase 0.06 0.05 0.06 0.05

Enhancer 1.0 0.5 0.5 0.3

Brightener, perfume 0.2 0.2 0.2 0.2

CaSO4 1.0 1.0 1.0 1.0

MgSO4 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 CaCO3, talc, clay (Kaolinite, Smectite), silicates, and the like.

Example 1 2

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 - - 48.80 37.39 - -

Citrate 32.95 17.05 - - 17.05 25.40

Carbonate - 17.50 - 20.00 20.00 25.40

1 II Ill IV V VI

Silicate 33.00 14.81 20.36 14.81 14.81 -

Metasilicate - 2.50 2.50 - - -

PB1 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 2.39 - - 4.00

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

Protease 0.075 0.05 0.10 0.10 0.08 0.01

Laccase 0.01 0.01 0.04 0.04 0.06 0.005

Enhancer 0.5 0.5 0.8 1 .0 1.5 0.3

Lipase - 0.001 - 0.005 - -

Amylase 0.01 0.005 0.01 5 0.015 0.005 0.002. 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 7.1 1 20.77 8.44 - 26.24 1 .00 pH ( 1 % solution) 10.80 1 1 .00 10.90 1 0.80 10.90 9.60

Example 1 3

The following granular dishwashing detergent compositions examples 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 34.50 26.70

Carbonate 30.50 30.50 30.50 23.00 30.50 2.80

I II III IV V VI

Silicate 7.40 7.40 7.40 12.00 8.00 20.34

PB1 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 - - -

Protease 0.05 0.05 0.05 0.1 0.1 0.2

Laccase 0.005 0.0075 0.01 0.02 0.04 0.04

Enhancer 0.2 0.3 0.4 0.4 0.4 0.8

Lipase 0.005 - 0.001 - - -

Amylase 0.003 0.001 0.01 0.02 0.01 0.01 E

BTA 0.1 5 - 0.15 - - -

Sulphate 23.90 23.90 23.90 31 .40 17.40 - pH (1 % solution) 10.80 1 0.80 10.80 10.70 10.70 1 2.30 Example 14

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 1 3KN/cm² using a standard 1 2 head rotary press:

I II III

STPP - 48.80 47.50

Citrate 26.40

Carbonate - 5.00 -

Silicate 26.40 14.80 25.00

Protease 0.03 0.075 0.01

Laccase 0.0075 0.0075 0.01

Enhancer 0.3 0.6 1

Lipase 0.005 - -

I II Ill

Amylase 0.01 0.005 0.001

PB1 1.56 7.79 -

PB4 6.92 - 1 1.40

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 25.05 14.70 3.20 pH (1 % solution) 10.60 10.60 1 1.00

Example 1 5 The following liquid dishwashing detergent compositions in accord with the present invention, of density 1 .40Kg/L were prepared:

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 -

Boric acid 1 .0 2.0

Formic acid 1 .0 -

Protease 0.03 0.02

Laccase 0.01 0.01

Enhancer 0.2 0.5

Amylase 0.005 0.0025

480N 0.50 4.00

1 II

KOH - 6.00

Sulphate 1 .60 - pH (1 % solution) 9.10 10.00

Example 1 6

The following liquid dishwashing compositions were prepared in accord with the present invention :

I II III IV V

Alkyl (1 -7) ethoxy sulfate 28.5 27.4 19.2 34.1 34.1

Amine oxide 2.6 5.0 2.0 3.0 3.0

C12 glucose amide - - 6.0 - -

Betaine 0.9 - - 2.0 2.0 Xylene sulfonate 2.0 4.0 - 2.0 -

Neodol C1 1 E9 - 5.0 - -

Polyhydroxy fatty acid amide - - 6.5 6.5

Sodium diethylene penta acetate - 0.03 - -

(40%)

Diethylenetriamine penta acetate - - 0.06 0.06

Sucrose - - 1.5 1.5

Ethanol 4.0 5.5 5.5 9.1 9.1

Alkyl diphenyl oxide disulfonate - - - 2.3

Calcium formate - - 0.5 1 .1

Ammonium citrate 0.06 0.1

Sodium chloride 1 .0

Magnesium chloride 3.3 0.7

Calcium chloride 0.4

Sodium sulfate 0.06

Magnesium sulfate 0.08

Magnesium hydroxide 2.2 2.2

Sodium hydroxide 1 .1 1 .1

Hydrogen peroxide 200pp 0.1 6 0.006 m

Laccase 0.01 0.02 0.03 0.06 0.06 I II III IV V

Enhancer 0.5 0.5 0.5 1.0 1.5 Protease 0.017 0.005 .0035 0.003 0.00

2

Perfume 0.18 0.09 0.09 0.2 0.2

Water and minors Up to 100%

Example 1 7

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

I II III IV VI Amylase 0.01 0.002 0.005 0.02 0.001 0.005

Protease 0.05 0.01 0.02 0.03 0.005 0.005

Laccase 0.005 0.01 0.04 0.06 0.005 0.06

Enhancer 0.5 0.5 0.5 0.5 1 .0 1 .0

Boric acid 2.75 2.75 2.75 2.75 2.75 2.75

EDTA* - - 2.90 2.90 - -

Na Citrate - - - - 2.90 2.90

NaC12 Alkyl benzene 1 .95 - 1 .95 - 1 .95 - sulfonate

NiEO9 1 .50 2.00 1 .50 2.00 1 .50 2.00

NaC 1 2 Alkyl sulfate - 2.20 - 2.20 - 2.20

NaC1 2(ethoxy) - 2.20 - 2.20 - 2.20

* * sulfate

C1 2 Dimethylamine - 0.50 - 0.50 - 0.50 oxide

Na Cumene sulfonate 1 .30 - 1 .30 - 1 .30 -

Hexyl Carbitol* * 6.30 6.30 6.30 6.30 6.30 6.30

Water Balance to 100%

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

Example 1 8

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

Amylase 0.01 Protease 0.01 Laccase 0.01 Enhancer 0.5 Boric acid 2.00 Sodium octyl sulfate 2.00

Sodium dodecyl sulfate 4.00

NiEO9 2.00

Sodium hydroxide 0.80

Silicate (Na) 0.04

Perfume 0.35 Water/minors up to 100%

Example 1 9

The following lavatory cleansing block compositions were prepared in accord with the present invention.

I II III

C1 6-18 fatty alcohol/50EO 80.0

LAS - - 80.0

Nonionic - 1 .0

Oleoamide surfactant - 26.0

Partially esterified copolymer of vinylmethyl 5.0 ether and maleic anhydride, viscosity 0.1 -

0.5

Polyethylene glycol MW 8000 - 39.0

Water-soluble K-polyacrylate MW 4000- - 1 2.0

8000

Water-soluble Na-copolymer of acrylamide - 19.0

(70%) and acryclic acid (30%) low MW

Na triphosphate 10.0

Carbonate - - 8.0

Laccase 0.06 0.05 0.06

Enhancer 1.0 1 .5 1 .5

Dye 2.5 1 .0 1 .0

Perfume 3.0 - 7.0

KOH / HCL solution pH 6-1 1 Example 20

The following toilet bowl cleaning composition was prepared in accord with the present invention.

I II

C14-15 linear alcohol 7EO 2.0 10.0

Citric acid 10.0 5.0

Laccase 0.05 0.06

Enhancer 1.0 1.5

DETPMP - 1.0

Dye 2.0 1.0

Perfume 3.0 3.0

NaOH PH 6-11

Water and minors Upi to 100%

Claims

1 . A detergent composition comprising a laccase at a level of from 0.003% to 0.06% pure enzyme by weight of total composition.

2. A detergent composition according to claim 1 wherein said laccase is derivable from a strain of Myceliophtora and/or Coprinus.

3. A detergent composition according to claims 1 -2, further comprising an enhancing agent.

4. A detergent composition according to claim 3, wherein the enhancing agent is phenothiazine or phenoxazine or a derivative one of these.

5. A detergent composition according to claim 4, wherein the enhancing agent is selected from phenothiazine-1 0-propionic acid, 10- methylphenothiazine.

6. A detergent composition according to claim 3, wherein the enhancing agent is alkylsyringate, preferably butylsγringate.

7. A softening composition comprising a laccase at a level of from 0.003% to 0.06% pure enzyme by weight of total composition and a cationic surfactant comprising two long chain length.

8. Use of a composition according to any of the preceding claims for fabric cleaning and/or fabric stain removal and/or fabric whiteness maintenance and/or fabric softening and/or fabric color appearance and/or fabric dye transfer inhibition.

9. Use of a detergent composition according to claims 1 -6 for hard surface cleaning.

10. Use of a detergent composition according to claims 1 -6 for hand and machine dishwashing.

11. Use of a composition according to claims 1-7 for sanitisation of the treated surface.