CA2254941A1 - Detergents with protease enzyme and laccase enzyme - Google Patents

Abstract

The present invention relates to detergent compositions comprising a serine protease and a laccase. Such compositions provide improved cleaning and stain removal performance.

Description

CA 022~4941 1998-11-12 W 097/43384 PCTrUS97/08048 DETERGENTS WITH PROTEASE ENZYME
AND LACCASE ENZYME

TECHNICAL FIELD

The present invention relates to detergent compositions comprising a serine protease and a laccase. Such compositions provide improved 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 soils and stains present in the typical load of the laundry.

The complex nature of everyday 'skin' soils typically found on pillowcases, T-shirts, collars and socks, provides a thorough cleaning - challenge for detergents. These soils are difficult to remove completely and often residues build up on fabric leading to dinginess and yellowing.
In addition, these soils or their breakdown products tend to redeposit on the articles in the wash.
Proteases have been used in detergent compositions to provide removal of soils. Indeed, their ability to hydrolyse proteins has been taken advantage of by incorporating naturally occurring and protein engineered proteases as an additive to hard surface cleaners, dishwashing compositions, laundry compositions and the like. Many soils are proteinaceous and wide-specifity proteases can substantially improve the removal of such stains.

CA 022~4941 1998-11-12 W 097/43384 PCTrUS97/08048 Stains, in particular coloured stains, are problematic to remove. These stains typically originate from red wine, fruit such as black currant, cherry, strawberry and tomato (in particular ketchup and spaghetti sauce), 5 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 10 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 overall detergency performance. Accordingly, it is an object of the present invention to formulate detergent compositions which provide effective and efficient 20 cleaning of coloured and everyday "skin" stains and soils.

It has now been surprisingly found that the overall detergency performance of serine proteases is synergistically enhanced by a laccase. In addition, it has been found that the bleaching performance of the laccase is 25 synergistically enhanced by the presence of a serine protease.

This finding allows either improved cleaning and stain removal performance or a reduction of the enzyme levels while keeping the same cleaning and stain removal performance.
It has also been found that the detergent composition of the present invention provide sanitisation of the treated surfaces.

W091/05839 describes enzymes exhibiting a suitable oxidase activity 35 or peroxidase activity for the inhibition of textile dye transfer from a dyedfabric to another fabric during the wash process. In particular, W095/01426 CA 022~4941 1998-11-12 provides a detergent additive and a detergent composition comprising an enzyme exhibiting laccase activity, oxygen and an enhancing agent, which are capabie 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.
5 Hospital laundry detergents containing an oxidase and a protease enzymes ~ are disclosed in J64-60693. WO93tl3193 describes detergent compositions comprising a protease derived from Nocardiopsis and enzymes exhibiting a suitable oxidase activity or peroxidase activity, for stain bleaching and/or dyetransfer inhibition.

However, the use of a laccase and a serine protease for effective and efficient cleaning of colou-ed and everyday "skin" stains and soils, has not been recognised.

SUMMARY of the INVENTION

The present invention relates to detergent compositions comprising a serine protease and a laccase. Such compositions provide improved cleaning and stain removal performance.

DETAILE~ DESCRIPTION of the INVENTION

Serine Protease Serine protease enzymes are an essential component of the detergent compositions of the present invention. It has been surprisingly found that the bleaching performance of the serine protease is enhanced by the presence of a laccase. Accordingly, the detergent compositions of the present invention provide effective and efficient cleaning of coloured and everyday "skin"
stains and soils.

The detergent compositions of the present invention comprise a protease at a level from 0.0001% to 2%, preferably from 0.001% to 0.5%, more preferably from 0.002% to 0.085% pure enzyme by weight of total composition, in addition to the laccase.

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 The serine proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or non-purified forms of an enzyme may be used.
5Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Particularly preferred by way of proteolytic enzyme is bacterial serine proteolytic enzyme obtained from Bacillus, Bacil/~Js subtilis and/or Bacillus licheniformis. Suitable commercial proteolytic enzymes which may be considered for inclusion in the 0present invention compositions include Alcalase(~), Esperase~', Durazym(~, Savinase(~', Maxatase~', Maxacal@), Maxapem~' 15 ~protein engineered Maxacal~; Purafect(~) and Substilin BPN and BPN'.

Serine proteolytic enzymes also encompass modified bacterial serine 15proteases, such as those described in European Patent Application No.
87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98~, and which is called herein "Protease B", and in European Patent Application EP
199 404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protease which is called "Protease A" herein. More preferred 20is what is called herein "Protease C" being a variant of an alkaline serine protease from Bacillus in which the Iysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123 and alanine replaced threonine at position 274. Protease C is described in EP 909159~8.4, corresponding to WO 91/06637, published 25May 16, 1991. Genetically modified variants, particularly of Protease C, are also included therein.

~efer,e~ proteolytic enzymes are selected from the group consisting of Savinase~), Esperase~, Maxacal@~, Purafect~), BPN', Protase A and Protease 30B and mixtures thereof. Bacterial serine protease enzymes obtained from Bacillus subtilis and/or Bacillus /icheniformis are preferred.

An especially preferred protease herein referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in 35nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in said carbonyl CA 022~4941 1998-11-12 W 097143384 PCT~US97/08048 hydrolase equivalent to + 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, + 123, + 27, + 105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or + 274 according to the numbering of B~cillus ~myloliq~lefaciens substilisin, as described in thepatent application of A. Baeck et al. entitled "Protease-containing cleaning compositions" having US serial No. 08/322,676, filed October 13, 1994.

0 Laccase and Laccase related enzvmes Laccase and laccase related enzymes are an essential component of the detergent compositions of the present invention. It has been surprisingly found that the bleaching performance of the laccase is enhanced by the presence of a serine protease. Accordingly, the detergent compositions of the present invention provide effective and efficient cleaning of coloured and everyday "skin" stains and soils.

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 Cosmétiques Actualités No 125, Nov, 1995, 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 . ., .. ~, .. . ~

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 described in Tuber. Lung. Dis. 1994 Aug; 75(4):286-90; J. Clin. Microbiol.
1994 May; 32(5):1261-7 and J. Clin. Microbiol. 1992 Oct; 30(10):2692-7.

According to the present invention, laccases and laccase related 5 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).
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 (W0 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 fucnctions 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 l~ccases that function at a pH above 7 are obtainable from a strain of Coprinus and/or Myceliophtora.
According to the invention laccases displaying immunochemical cross-reactivity with an antibody raised against above described laccases are also included .

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97108048 The detergent composition of the present invention comprise a laccase at a level from 0.0001% to 2%, preferably from 0.003% to 0.06% pure enzyme by weight of the total composition.
The ratio of active laccase to active protease varies from 1:1000 to 1000:1, preferably from 1:100 to 100:1, more preferably from 1:10 to 20:1.

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 19~1M syringaldazin, 23.2mM acetate buffer, pH 5.5, 30~C, 1 min. reaction time.
1 iaccase unit (LACU~ is the amount of enzyme that catalyses the conversion of 1.0 llmole syringaldazin per minute at these conditions.
Enhancin~ 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. 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.
1985 26 (7), pp. 1291-1301 (cf. Table 1 in particular).
Particularly useful enhancing agents may be described by the following formula:

OH
R2~ ~ ~OR3 f=o Rl where R1 is H, OH, CnH2n+ 1, in which n is an integer of from 1 to 10; and R2 and R3 are the same or different and selected from CmH2m+ 1, in which . .

CA 022~4941 1998-11-12 W 097143384 PCT~US97/08048 m is an integer of from 1 to 10. R1, 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 5 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 W096/10079.

Other particularly useful enhancing agents may be described by the 0 following formula:

Rl R9 R2~X~R8 E~4 Rs E~6 in which formula X represents (-O-) or (-S-), and the substituent groups 15 R1-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, C1 -C1 4-alkyl, C1 -Cs-alkoxy, carbonyl-C1-Cs-alkyl, aryl-C1-Cs-alkyl; which carbamoyl, sulfamoyl, and amino groups 20 may furthermore be unstubstituted or substituted once or twice with a substituent group R10; and which phenyl may furthermore be unsubstituted or substituted with one or more substituent groups R10; and which C1-C14-alkyl, C1-Cs-alkoxy, carbonyl-C1-Cs-alkyl, and aryl-C1-Cs-alkyl groups may be saturated or 25 unsaturated, branched or unbranched, and may furthermore be unsubstitued or substituted with one or more substituent groups R1 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, 30 piperidino, piperazinyl, pyrrolidin-1-yl, C1-Cs-alkyl, C1-Cs-alkoxy; which carbamoyl, sulfamoyl and amino groups may furthermore be unsubstituted or . , . _ . _ CA 022~4941 1998-11-12 W097/43384 PCTrUS97/08048 substituted once or twice with hydroxy, C 1 -Cs-alkyl, C 1 -Cs-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 C1-Cs-alkyl, and C1-Cs-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;
0 or in which general formula two of the substituent groups R1-R9 may together form a group -B-, in which B represents any of the following groups : (-CHR 10-N = N-), (-CH=CH-)n, (-CH=N-)n or (-N-CR10-NR11-), in which groups n represents an integer of from 1 to 3, R10 is a substituent group as defined above and R11 is defined in the same way as R10 (it is to be.understood that if the above mentioned formula comprises two or more R 1 ~-substituent groups, these R10-substituent groups may be the same or different).

In particular embodiments, the enhancing agent is 10-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, 10-allylphenothiazine, 10-(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- 10-methylphenothiazine, 3,10-dimethylphenothiazine, 3,7,10-trimethylphenothiazine, 10-~2-hydroxyethyl)phenothiazine, 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.

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 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, 1968, Vol.9, pp.321-460); B. Cardillo & G. Casnati in Tetrahedron, 1967, Vol. 23, p.3771.
Phenothiazine and phenoxazine propionic acids may be prepared as described in J.Org. Chem. 15, 1950, pp. 1125-1130. Hydroxyethyl and hydroxypropyl 10 derivatives of phenothiazine and phenoxazine may be prepared as described by G.Cauquil in Bulletin de la Society Chemique de France, 1960, p.1049.
The enhancing agent may be present in concentrations of from 0.01 to 500~1M, preferably in concentrations of from 0.1 to 25011M 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.

Deterqent 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.
In a preferred embodiment, the present invention relates to a laundry and/or fabric care composition comprising a laccase and a serine protease (Examples 1-11). It has been found that the incorporation of a laccase enzyme and a serine protease in a softener matrix does also deliver effective 30 and efficient cleaning of coloured and everyday "skin" stains and soils during the rinse cycle, with colour safety. In a second embodiment, the present invention relates to dishwashing or household cleaning compositions (Examples 12-20).

The compositions of the invention may for example, be formulated as hard surface cleaner, hand and machine dishwashing compositions, hand and CA 022~4941 1998-11-12 WO 97/43384 PCT~US97/08048 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.
Compositions comprising a laccase and a serine protease enzymes can also be formulated as sanitisation products.

The present invention also relates to a process for contacting fabrics with a laundering solution as hereinbefore described. The washing process is preferably carried out at 5~C to 75~C, especially 20 to 60~ The pH of the 0 treatment solution is preferably from 7 to 11, especially from 7.5 to 10.5.The process and 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.

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 l l 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 granular laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 600 to 950 g/litre of composition measured at 20~C.

. . .

CA 022~4941 1998-11-12 The "compact" form of the granular laundry detergent compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional 5 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%, 10 most preferably not exceeding 5% by weight of the composition.
The inorganic filler salts are typically 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 20 preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

Surfactant svstem The detergGnt 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 20% by weight of laundry and rinse added fabric softener compositions in accordance with the invention.
The surfactant is preferably formulated to be compatible with enzyme components present in the composition. In liquid or gel compositions the CA 022~494l l998-ll-l2 W O 97/43384 PCTrUS97/08048 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 5 invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein. Preferred surfactant systems comprise an anionic to nonionic weight ratio of 1:1 to 10:1, preferably 1:1 to 3:1. It has been found that said ratios of anionic to nonionic provide optimized stain removal performance.

Polyethylene, polypropylene, and polybytylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl 5 phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodi,.,e..t, 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~
moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylatesi.
The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products.
Examples of commercially available nonionic surfactants of this type include .. ~ , ., . .. . ~ .... ....

CA 022~494l l998-ll-l2 W O 97/43384 PCTrUS97/08048 TergitolTM 1 5-S-9 (the condensation product of C1 1-C1 5 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 1 2-C 1 4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribytion), both marketed by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 ~the condensation product of C14-C1s linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C14-C1s linear alcohol 0 with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most ,,~referably 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 asopposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula R20(CnH2nO)t(9lycosyl)x wherein R2 js selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl CA 022~494l l998-ll-l2 W 097/43384 PCT~US97/08048 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 aikylpolyethoxy 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 0 predominately the 2-position.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the 20 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 PluronicTM 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 30 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 35 5,000 to about 11,000. Examples of this type of nonionic surfactant include CA 022~494l l998-ll-l2 certain of the commercially available TetronicTM compounds, marketed by BASF .

Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are Cg-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C1g alcohol ethoxylates (preferably C1o 0 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, O Rl wherein Rl is H, or R1 is C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs 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 C11 15 alkyl or C16 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.

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

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mS03M wherein R is an unsubstituted C1o-C24 alkyl or hydroxyalkyl group having a C 1 0-C24 alkyl component, preferably a C 1 2-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy CA 022~4941 1998-11-12 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 5 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, 0 triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-C18 alkyl polyethoxylate ~1.0) sulfate IC1 2-C1 gE(1 .O)M), C1 2-C1 8 alkyl polyethoxylate ~2.25) sulfate (Cl 2-C1 gE(2.25)M), C1 2-C1 8 alkyl polyethoxylate (3.0) sulfate (C1 2-C1 gE(3.0)M), and C1 2-C1 8 alkyl polyethoxylate (4.0) sulfate (C1 2-C1 gE(4.0)M), wherein M is conveniently 5 selected from sodium and potassium.

Suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S03 according to "The Journal of 20 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 25 formula:
o R3 - CH - C - oR4 I

wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C 1 -C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl 35 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, .

CA 022~494l l998-ll-l2 W O 97/43384 PCTrUS97/08048 R3 is C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C1 0-C1 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 C1 o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C1 0-c20 alkyl component, more preferably a C1 2-C1 8 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium,potassium, lithium), or ammonium or substituted ammonium ~e.g. methyl-, 0 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 C16 18 alkyl chains are preferred for higher wash temperatures ~e.g. above about 50~C).

Other anionic surfactants useful for detersive purposes can also be included in the laundry deter~ent compositions of the present invention.
20 These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal 25 citrates, e.g., as described in British patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates ~containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-30 acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C1g 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 35 described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH20)k-CH2COO-M +

CA 022~4941 1998-11-12 W O 97/43384 PCT~US97/08048 wherein R is a Cg-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.
5 Further examples are described in "Surface Active Agents and Detergents"
(Vol. I and ll by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
10 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.

The detergent composition of the present invention may further 5 comprise a cosurfactant selected from the group of primary or tertiary amines.
Suitable primary amines for use herein include amines according to the formula RlNH2 wherein R1 is a C6-C12, preferably C6-C10 alkyl chain or R4X(CH2)n, X is -O-,-C(O)NH- or -NH-, R4 is a C6-C1 2 alkyl chain n is 20 between 1 to 5, preferably 3. R1 alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
Preferred amines according to the formula herein above are n-alkyl amines.
Suitable amines for use herein may be selected from 1-hexylamine, 1-25 octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C 10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido propylamine and amido propylamine.

Suitable tertiary amines for use herein include tertiary amines having 30 the formula R1 R2R3N wherein R1 and R2 are C1 -C8 alkylchains or --( CH2--CH--O )xH
R3 is either a C6-C12, preferably C6-C10 alkyl chain, or R3 is R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-,R4 is a C4-C12, n is between 1 to 5, preferably 2-3. Rs is H or C1-C2 alkyl and x is between 1 to 6 .

CA 022~4941 1998-11-12 R3 and R4 may be linear or branched; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary amines are R1 R2R3N where R1 is a C6-C12 alkyl 5 chain, R2 and R3 are C1-C3 alkyl or --( CH2--CH--O )xH

where R5 is H or CH3 and x = 1-2.

Also preferred are the amidoamines of the formula:

Rl--C--NH--( cH2 )--N--( R2 )2 wherein R 1 is C6-C 1 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,C8-1 Ooxypropylsmine, N coco 1-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl 20 bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyidimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyldimethylamine .
The most preferred amines for use in the compositions herein are 1-25 hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

The laundry 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 hereln .

CA 022~4941 1998-11-12 According to the present invention, it has been found that cationic surfactants enchance the overall cleaning performance of the laccase.
Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain 5 hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula:

[R2(oR3)y] [R4(oR3)y]2R5N + X-wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 5 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18;
20 each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

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

~0~ N~Rs Formula I
whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (Il~:
C6~N~ ~

Formula ll y is 2-4, preferably 3.

CA 022~4941 1998-11-12 W O 97/43384 rCT~US97/08048 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 lll, whereby X~ is5 a counterion, preferably a halide, e.g. chloride or methylsulfate.

H
Formula lll R6 is C1-C4 and z is 1 or 2.

Preferred quat ammonium surfactants are those as defined in formula I
whereby R 1 is Cg, C 10 or mixtures thereof, x = o, R3, R4 = CH3 and Rs = CH2CH20H.
Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula:
R 1 R2R3R4N + X~ (i) wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H40)XH 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 R1 is C12-C1~ particularly where the aJkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin byild up or OX0 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;

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 C12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
5 lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula ~i) wherein R1 is CH2-Ctl2-0-C-C12 14 alkyl and R2R3R4 are methyl).
Il O
di-alkyl imidazolines [compounds of formula ~i)].

Other cationic surfactants useful herein are also described in lJ.S.
Patent 4,228,044, Cambre, issued October 14, 1980 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 20 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) C12-14 alkyl hydroxyethyl dimethylammonium chloride;
1 1 ) C 1 2-1 8 alkyl dihydroxyethyl methylammonium chloride;
1 2) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallow-oxy-ethyl) dimethylammonium chloride;
1 4) ditallow imidazolinium methylsulf ate;
15) 1-(2-tallowylamidoethyl~-2-tallowyl imidazolinium methylsulfate.

,, . ~ . . ....

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 24 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 5 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-0,239,91 0.

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

R3~ R3 \ / + N -(CH2)n~CIH -CH2 X
+ N -(C ~ -Q--T 1 X- R3 Q
Rl Tl T2 -- Or 1 5 (I) (Il) wherein Q is selected from -0-C(0)-, -C(0)-0-, -0-C(0)-0-, -NR4-C(o)-, -C(o)-NR4-;
R 1 is (CH2) n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 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, T5 are independently C1 1-C22 alkyl 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 T1, T2, T3, T4, T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched.

W O 97/43384 PCTnUS97/08048 Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein T1, T2, ~3, T4, T5 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 0 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-l 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 laundry 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 laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyciic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column l 9, lines 18-3~, for examples of ampholytic surfactants.

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 When included therein, the laundry detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry 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.
0 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, iine 48, for examples of zwitterionic surfactants.

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

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

Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula o R3(oR4)xN(R5)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof 35 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 W 097143384 PCTrUS97/08048 mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or hydroxya!kyl 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 C1 o-C1 8 alkyl dimethyl amine oxides and Cg-C 12 alkoxy ethyl dihydroxy ethyl amine oxides.

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

Ootional deterqent inqredients:

Dispersant 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. Exarnples of such salts are polyacrylates of MW 2000-~000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 1,000 to 1 00,000.

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.

Other detergent enzymes . .

CA 022~4941 1998-11-12 W O 97/43384 PCT~US97108048 The detergent compositions can in addition to a laccase and serine protease enzymes further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.

Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, gluco-amylases, amylases, xylanases, lipases, esterases, cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, 13-glucanases, arabinosidases chondroitinase, or mixtures thereof.

A preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes like amylase, lipase, cutinase and/or cellulase.
The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of cellulase components which may be usable are:
A cellobiohydrolase component which is immunoreactive with an antibody raised against a highly purified -70kD cellobiohydrolase ~EC 3.2.1.91) derived from Humicola insolens, DSM 1800, or which is a homologue or derivative of the -70kD cellobiohydrolase exhibiting cellulase activity, or an endoglucanase component which is immunoreactive with an anitbody raised against a highly purified -50kD endoglucanase derived from Humicola insolens, DSM 1800, or which is a homologue or derivative of the -50kD
endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. W091/17244, or an endoglucanase component which is immunoreactive with an antibody raised against a highly purified -50kD (apparent molecular weight, the amino acid composition corresponds to 45kD with 2n glycosylation sites) endoglucanase derived from Fusarium oxysporum, DSM
2672, or which is a homologue or derivative of the -50kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the .

W O 97/43384 PCTnUS97/08048 amino acid sequence disclosed in PCT Patent Application No. WO91/17244, or any of the cellulase disclosed in the published European Patent Application No. EP-A2-271 004, the cellulases having a non-degrading index (NDI) of not less than 500 and being alkalophilic cellulases having an optimum pH not less than 7 or whose relative activity at a pH of not less than 8 is 50% or over the activity under opitmum conditions when carboxy methyl cellulose ~CMC) is used as a substrate, or an endoglucanase component which is immunoreactive with an antibody raised against a highly purified -43kD
endoglucanase derived from Humicola insolens, DSM 1800, or which is a homologue or derivative of the -43kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 90/17243, or an endoglucanase component which is immunoreactive with an antibody raised against a highly purified -60k~ endoglucanase derived from Bacillus lautus, NCIMB 40250, or which is a homologue or derivative of the -60kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/10732.

Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase .
Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase . . .

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, lapan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Especially suitable lipases are lipases such as M1 LipaseR and LipomaxR
(Gist-Brocades) and LipolaseR- Also suitable are cutinases [EC 3.1.1.50]
0 which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Suitable cutinases are described in WO
94/14963 and WO 94114964. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
The lipases andlor cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Amylases (a and/or 13) can be included for removal of carbohydrate-based stains. Suitable amylases are TermamylR~ (Novo Nordisk), FungamylR
20 and BANR (Novo Nordisk). Highly preferred amylases are amylase variants disclosed in W095/10603.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.

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

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in the copending European patent application 92870018.6 filed on January 31, 1992. Examples of such 35 enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

CA 022~494l l998-ll-l2 W O 97/43384 PCTrUS97/08048 Color care benefits Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are metallo catalysts for color maintenance. Such metallo catalysts are described in the European patent EP O 596 184 and in the copending European Patent Application No. 94870206.3.

0 Ble~ching agent Bleach systems that can be included in the detergent compositions of the present invention include bleaching agents such as PB 1, 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%. Bleaching agents are preferred detergent ingredients since the combination with laccase results in enhanced cleaning and whiteness performance.

The bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybytyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S.
Patent 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.

. . .

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 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), 0 nonanoyloxybenzene-sulfonate tNOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters such as disclosed in Copending European Patent Application No. 91870207.7.

Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co-pending applications USSN 08/136,626, PCT/US95/07823, W095/27772, W095/27773, W095/27774 and W095/27775.

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

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

5 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 and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequeslrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.

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 (Na2si2o5) Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereo~ as disclosed in Belgian PatentNos. 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.

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 Po!ycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No.
0 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 25 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.

A suitable chelant for inclusion in the detergent compositions in 30 accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples 35 of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS.

CA 022~4941 1998-11-12 W O 97143384 PCTrUS97108048 The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.

- Preferred builder systems include a mixture of a water-insoluble 5 aluminosilicate byilder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
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 10 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 15 carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 10%
to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.

25 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 30 divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates inwhich 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 35 dispersed in a liquid carrier and applied by spraying on to one or more of the other components.

~ . . .

CA 022~4941 1998-11-12 W O 97/43384 PCT~US97/08048 A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2-bytyl-octanol which are commercially available under the trade name Isofol 12 R.
0 Such suds suppressor system are described in Copending European Patent application N 92870174.7 filed 10 November, 1992.
Especially preferred silicone suds controlling agents are described in Copending European Patent application N~92201649.8. Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous 15 silica such as AerosilR.

The suds suppressors described above are normally employed at ievels 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, 25 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 30 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 35 and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists CA 022~4941 1998-11-12 WO 97/43384 PCTrUS97/08048 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 byilders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent 0 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-6-20 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 25 brighteners of copending European Patent application No. 95201943.8.

Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 30 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.
~5 ., . =

CA 022~4941 1998-11-12 Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos.
4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH3(PEG)43)0.75(PoH)o.25[T-po)2.8(T-pEG)o-4]T( H~0.25~(PEG)43CH3)0.75 where PEG is -(OC2H4)0-,P0 is (OC3H60) and T is (pcOC6H4C0).
Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 5 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 20 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 25 dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 342.
Is is well known in the art that free chlorine in tap water rapidly deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1 % by weight of total 35 composition, in the formulas will provide improved through the wash stability of the specific amylase enzymes. Compositions comprising chlorine CA 022~4941 l99X-11-12 W O 97/43384 PCTrUS97/08048 scavenger are described in the European patent application 92870018.6 filed January 31, 1992.

Softening agents Fabric softening agents are very suitable for incorporation into laundry detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in USP
0 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-~-O 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 57~ and 0 313 146.

Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added 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 0.15% to 1.5% by weight. These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.
Dye transfer inhibition The detergent composition of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.

, CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 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 0 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, 15 polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

a) Polyamine N-oxide polymers The polyamine N-oxide polymers suitable for use contain units having 20 the following structure formula:
p I

(I) Ax I

R

wherein P is a polymerisable unit, whereto the R-N-0 group can be attached to or wherein the R-N-0 group forms part of the polymerisable unit or a combination of both.
O O O
Il 11 11 A is NC, C0, C, -0-,-S-, -N-; x is 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen CA 022~4941 1998-11-12 WO 97/43384 PCTrUS97/08048 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:

O O
(R1)x-N- (R2)y =N- (R1~x (R3)z wherein R 1, R2, and R3 are aiiphatic 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.
20 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.
25 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 35 alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.

. ~, . . . . . .

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97108048 Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazoie 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 alicyclic5 groups wherein the nitrogen of the N-0 functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.

0 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 presel-t invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1 :1000000. More preferably from 1 :4 to 1 :1000000, most preferably from 1:7 to 1: 1 000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 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 10 described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern Methods of Polymer Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
20 The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar rstio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .

c) Polyvinylpyrrolidone The detergent compositions of the present invention may also utilize polyvinvlpyrrolidone ("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 30 preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 laverage molecular weight of 160,000), and PVP K-90 ~average molecular 35 weight of 360,000). Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and CA 022~494l l998-ll-l2 Sokalan tlP 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 15,000.
e) Polyvinylimidazole:

The detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 20 15,000.
f) Cross-linked polymers:

Cross-linked polymers are polymers whose backbone are 25 interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymers entrap the dyes by swelling.

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

CA 022~4941 1998-11-12 The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define 5 the scope of the invention. In the detergent compositions, the level of the enzymes are expressed in pure enzyme by weight of total composition and the abbreviated component identifications have the following meanings:

LAS : Sodium linear C1 2 alkyl benzene sulphonate.

TAS : Sodium tallow alkyl sulphate.

XYAS : Sodium c1x - C1y alkyl sulfate.

SAS : C12-C14 secondary 12,3) 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 C1 2 C1 5 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide.
45EY : A C14 - C1s predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide.
XYEZS : c1x - C1y sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole.
Nonionic : C13-C1s 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-C10 amidopropyldimethylamine.

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 CFAA : C 1 2-C 14 alkyl N-methyl glucamide.

TFAA : C 1 6-C 1 8 alkyl N-methyl glucamide.

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

DEQA (1) : Di-(oleyloxyethyl) dimethyl ammonium methylsulfate.
DEQA (2) : Di-(soft-tallowyloxyethyl) hydroxyethyl methyl ammonium methylsulfate.
DTDMAMS : Ditalllow dimethyl ammonium methylsulfate.

SDASA : 1:2 ratio of stearyldimethyl amine:triple-pressed stearic acid.
Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by Shell Chemical C0.
Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio =
2.0~.
NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si20s.

Carbonate : Anhydrous sodium carbonate.

Metasilicate : Sodium metasilicate (SiO2:Na20 ratio = 2.0~.

Phosphate or STPP : Sodium tripolyphosphate.

MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
PA30 : Polyacrylic acid of average molecular weight of approximately 8,000.
Terpolymer : Terpolymer of average molecular weight approx.
7,000, comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20.
480N : Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500.

W 097/43384 PCT~US97/0804B

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 Na12(A1~2Si~2)12- 27H20 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 NaB02.H202 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.

CA 022~4941 1998-11-12 W O 97/43384 PCT~US97/08048 Cellulase I : Cellulolytic enzyme sold under the tradename Carezyme or Celluzyme by Novo Nordisk A/S
43kD.
Cellulase ll : Endoglucanase 50kD, cellulolytic enzyme sold under the tradename "Endolase" by Novo Nordisk.
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 (Ill) 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, 17% hydrophobic siiica, 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.

CA 022~4941 1998-11-12 W 097/43384 PCT~US97108048 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.

ExamDle 1 Granular fabric cleaning compositions in accord with the invention were 5 prepared as follows:

11 111 lV V

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 Protease 0.01 0.02 0.01 0.005 0.005 .

CA 022~4941 1998-11-12 W O 97/43384 PCTrUS97/08048 Laccase 0.005 0.01 0.01 0.01 0.005 Enhancer 0. 5 0. 5 0. 5 0. 5 0. 5 11 111 lV V

Pectinase 0.02 Xylanase - - 0.01 0.02 Lipase 0.005 0.01 Cellulase 1 0.001 - - 0.001 Water & minors Up to 100%

Exam~le 2 Granular fabric cleaning compositions in accord with the invention were 5 prepared as follows:

11 111 lV V

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 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 0.005 0.01 0.04 0.04 0.01 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 0.005 Water & minors Up to 100%

Exam~le 3 CA 022~494l l998-ll-l2 W O 97/43384 PCT~US97/08048 Granular fabric cleaning compositions in accord with the invention which are especially useful in the laundering of coloured fabrics were prepared as follows:

LAS 11.4 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 68E11 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 PVN0/copolymer of vinyl- - - 0. 2 imidazole and vinvl-pyrrolidone Perborate 0.5 1.0 Peroxidase 0.01 0.01 Laccase 0.01 0.01 0.02 Enhancer 0.5 1.0 0.5 Phenol sulfonate 0.1 0.2 Water/Minors Up to 100%
Exam~le 4 .

CA 022~4941 1998-11-12 W 097/43384 52 PCT~US97/08048 Granular fabric cleaning compositions in accord with the invention were prepared as follows:

ll LAS 6. 5 8 .0 AE 8.0 8.0 Alkyl Sulfate 15.0 18.0 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 Phenol sulphonate 0.1 0.2 Protease 0.06 0.02 Laccase 0.01 0.1 Enhancer 0. 5 0. 8 Silicate 5.0 5-0 Carbonate 15.0 15.0 Peroxidase - 0.1 Pectinase 0.02 Cellulase 1 0.005 0.002 Lipase 0.0 1 Amylase 0.01 0.01 Water/minors Up to 100%

ExamPle 5 A compact granular fabric cleaning composition in accord with the 0 invention was prepared as follows:

45AS 8.0 25E3S 2.0 W O 97/43384 PCTrUS97/08048 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 o CMC 0.4 PVN0/copolymer of vinylimidazole and 0.2 vinylpyrrolidone Protease 0.05 Laccase 0.02 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 cleaning compositions in accord with the invention 5 which provide "softening through the wash" capability were prepared as follows:

ll 45AS - 10.0 LAS 7.6 68AS 1 . 3 45E7 4.0 25E3 - 5.0 CA 022~4941 1998-11-12 Coco-alkyl-dimethyl hydroxy- 1.4 1.0 ethyl ammonium chloride Citrate 5.0 3.0 Na-SKS-6 - 1 1 .0 Zeolite A 1 5 .0 1 5.0 MAIAA 4.0 4.0 DETPMP 0.4 0 4 Perborate 1 5.0 ll Percarbonate - 15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPE0 - 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 Up to 100%

ExamPle 7 Heavy duty liquid fabric cleaning compositions suitable for use in the 5 pretreatment of stained fabrics, and for use in a machine laundering method, in accord with the invention were prepared as follows:

11 111 lV V

24AS 20.0 20.0 20.0 20.0 20.0 SS 5.0 5.0 5.0 5.0 5.0 CA 022~4941 1998-11-12 W O 97/43384 PCT~US97/08048 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 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 0.04 Enhancer 0.5 0.5 0.5 1.0 1.0 Lipase 0.002 0.01 0.02 - 0.004 11 111 lV V

Amylase 0.005 0.005 0.001 0.01 0.004 Cellulase 1 0.04 - 0.01 Pectinase 0.02 0.02 Water/propylene glycol/ethanol (100 ExamDle 8 Heavy duty liquid fabric cleaning compositions in accord with the 5 invention were prepared as follows:

11 111 lV V

LAS acid form - - 25.0 C 12- 14 alkenyl succinic 3 0 8.010.0 acid Citric acid 10.0 16.0 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 AAPA - - - - 1.5 . .. . . . . . . . ....

CA 022~4941 1998-11-12 W 097/43384 rcTrusg7/o8048 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 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 0.010.02 Laccase 0.00 0.01 0.02 0.040.008 11 111 lV V

Enhancer 0.3 0.4 0.8 1.0 0.3 Amylase 0.00 0.01 0.00 0.010.05 Cellulase I - - - - 0.03 Cellulass 11 - - - - O.Og 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 Up to pH 7.5 Water / minors Up to 100%

ExamDle 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 10.001 Boric acid 2.00 HCL 0.12 Antifoam agent 0.01 9 Blue dye 80ppm CaCI2 0.35 Perfume 0.90 .

CA 022~4941 1998-11-12 W 097/43384 PCTnUS97/08048 ExamPle 1 0 The following fabric softener and dryer added fabric conditioner compositions were prepared in accord with the present invention:

11 111 lV V

DEQA 2.6 19.0 - - -DEQA(2) - - 51.8 DTMAMS - - - 26.0 SDASA - - 70.0 42.0 40.2 Stearic acid of IV=O 0.3 - - - -Neodol 45- 13 13 o Hydrochloride acid 0.02 0.02 Ethanol - - 1.0 Protease 0.02 0.005 0.008 0.05 0.005 Laccase 0.002 0.005 0.01 0.01 0.1 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 1 Oppm 25ppm 0.01 Water and minors 100% 100%

ExamDle 1 1 Syndet bar fabric cleaning compositions in accord with the invention 10 were prepared as follows:

11 111 lV

C12-16 alkyl sulfate, Na 10.0 10.0 10.0 10.0 CA 022~4941 1998-11-12 W 097/43384 PCT~US97/08048 C12-14 N-methyl glucamide 5.0 5.0 5.0 5.0 11 111 lV

C11-13 alkyl benzene 10.0 10.0 10.010.0 sulphonate, Na Sodium carbonate 25.0 25.0 25.025.0 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 0.010.01 Protease 0.3 0.4 0.5 0.05 Laccase 0.3 0.05 0.1 0.05 Enhancer 1.0 0.5 0.5 0.3 Brightener, perfume 0.2 0.2 0.2 0.2 CaS04 1.0 1.0 1.0 1.0 MgS04 1.0 1.0 1.0 1.0 Water 4.0 4.0 4.0 4.0 Filler*: balance to 100%

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

Exam~le 1 2 The following compact high density (0.96Kg/l) dishwashing detergent compositions I to Vl were prepared in accord with the invention:
11 111 lV V Vl STPP - - 48.80 37.39 Citrate 32.95 17.05 - - 17.05 25.40 Carbonate - 17. 50 - 20.00 20.00 25.40 Silicate 33.00 14.81 20.36 14.81 14.81 .

CA 022~4941 1998-11-12 W O g7/43384 PCTrUS97/08048 Metasilicate - 2.50 2.50 PB1 1.94 9.74 7.79 14.28 9.74 11 111 lV V Vl 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 0.08 0.005 Enhancer 0.5 0.5 0.5 1.0 1.5 0.3 Lipase - 0.001 - 0.005 Amylase 0.01 0.005 0.015 0.015 0.005 0.0025 BTA 0.30 0.30 0.30 0.30 Bismuth Nitrate - 0.30 PA30 4.02 Terpolymer - - - 4.00 480N - 6.00 2.77 - 6.67 Sulphate 7.11 20.77 8.44 - 26.24 1.00 pH ~1% solution)10.80 11.00 10.90 10.80 10.90 9.60 Example 13 The following granular dishwashing detergent compositions examples I
5 to IV of bulk density 1.02Kg/L were prepared in accord with the invention:

11 111 lV V Vl 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 CA 022~494l l998-ll-l2 W O 97/43384 PCTrUS97/08048 Silicate7.40 7.40 7.40 12.00 8.00 20.34 PB1 4.40 4.40 4.40 - 4.40 NaDCC - - - 2.00 - 1.50 11 111 lV V Vl 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 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 0.015 BTA 0.15 - 0.15 Sulphate 23.90 23.90 23.90 31.40 17.40 pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30 Exam~le 14 The following detergent composition tablets of 25g weight were 5 prepared in accord with the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:

ll lll 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 1.0 CA 022~4941 1998-11-12 W O 97/43384 PCTnUS97/08048 Lipase 0.005 Amylase 0.01 0.005 0.001 PB1 1.56 7.79 PB4 6.92 - 11.40 Alkyl sulfate 2.00 3.00 2.00 Nonionic 1.20 2.00 1.10 TAED 4.33 2.39 0.80 HEDP 0.67 DETPMP 0.65 Paraffin 0.42 0.50 BTA 0.24 0.30 PA30 3.2 Sulphate 25.05 14.70 3.20 pH (1% solution) 10.60 10.60 11.00 Exam~le 15 The following liquid dishwashing detergent compositions in accord 5 with the present invention, of density 1.40Kg/L were prepared:

ll 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 W 097/43384 63 PCTrUS97/08048 Amylase 0.005 0.0025 480N 0. 50 4.00 KOH - 6.00 Sulphate 1.60 pH (1% solution) 9.10 10.00 . .

CA 022~494l l998-ll-l2 W O 97/43384 PCT~US97108048 ExamPIe 16 The following liquid dishwashing compositions were prepared in accord with the present invention:

11 111 lV 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 C 11 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 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 0.16 0.006 m Laccase 0.01 0.02 0.03 0.06 0.08 Enhancer 0.5 0.5 0.5 1.0 1.5 Protease 0.017 0.005 .0035 0.003 0.00 Perfume 0.18 0.09 0.09 0.2 0.2 W O 97/43384 PCT~US97108048 Water and minors Up to 100%

ExamPle 17 The following liquid hard surface cleaning compositions were prepared in accord with the present invention:

11 111 lV V Vl 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 0.1 0.005 0.1 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 NiE09 1.50 2.00 1.50 2.00 1.50 2.00 NaC12 Alkyl sulfate - 2.20 - 2.20 - 2.20 NaC12(ethoxy) - 2.20 - 2.20 - 2.20 * *sulfate C 12 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%

0 *Na4 ethylenediamine diacetic acid **Diethylene glycol monohexyl ether ***AII formulas adjusted to pH 7 ExamPle 18 CA 022~4941 1998-11-12 W O 97/43384 PCT~US97/08048 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 NiE09 2.00 Sodium hydroxide 0.80 Silicate (Na) 0.04 Perfume 0.35 Watertminors up to 100%

ExamDle 1 9 The following lavatory cleansing block compositions were prepared in 10 accord with the present invention.

C16-18 fatty alcohol/50E0 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 CA 022~4941 1998-11-12 W 097/43384 67 PCTrUS97/08048 Water-soluble K-polyacrylate MW 4000- - 12.0 Water-soluble Na-copolymer of acrylamide - 1 9.0 ~70%) and acryclic acid (30%) low MW
Na triphosphate 10.0 Carbonate - - 8.0 Protease 0.8 0.005 0.01 Laccase 0.08 0.1 0.1 Enhancer 1.0 1 5 1 5 ll lll Dye 2.5 1.0 1.0 Perfume 3.0 - 7.0 KOH / HCL solution pH 6-11 Example 20 The following toilet bowl cleaning composition was prepared in accord with 5 the present invention.

ll C14-15 linear alcohol 7EO 2.0 10.0 Citric acid 10.0 5.0 Protease 0.8 0.005 Laccase 0.08 0.1 Enhancer 1.0 1.0 DETPMP - 1.0 Dye 2.0 1.0 Perfume 3.0 3.0 NaOH pH 6-1 1 Water and minors Up to 100%

Claims (16)

1. A detergent composition comprising a serine protease and a laccase.

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 any of the preceding claims wherein said protease is a bacterial serine protease obtained from Bacillus, preferably Bacillus subtilis and/or Bacillus licheniformis.

4. A detergent composition according to claims 1-3, additionally comprising an enhancing agent.

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

6. A method according to claim 5, wherein the enhancing agent is selected from phenothiazine-10-propionic acid, 10-methylphenothiazine.

7. A detergent composition according to claim 4, wherein the enhancing agent is alkylsyringate, preferably butylsyringate.

8. A detergent composition according to any of the preceding claims wherein said serine protease is comprised at a level of from 0.0001% to 2%, preferably from 0.001% to 0.5%, more preferably from 0.002% to 0.085% pure enzyme by weight of total composition.

9. A detergent composition according to any of the preceding claims wherein said laccase is comprised at a level of from 0.0001% to 2%, preferably from 0.003% to 0.06% pure enzyme by weight of the total composition .

10. A detergent composition according to any of the preceding claims wherein the ratio of active laccase to active serine protease varies from 1:10 to 20:1.

11. A detergent composition according to any of the preceding claims, further comprising one or more components selected from anionic, nonionic, cationic, amphoteric and zwitterionic surfactants.

12. A softening composition comprising a serine protease, a laccase and a cationic surfactant comprising two long chain length.

13. A detergent composition according to claims 1-11 characterized in that the composition is a granular detergent composition containing no more than 15% by weight of inorganic filler salt.

14. A detergent composition according to claims 1-11 characterized in that the composition is a heavy duty liquid composition.

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

16. Use of a composition according to claims 1-14 for the sanitisation of the treated surface.