CA2254069A1 - Detergent compositions comprising a combination of .alpha.-amylases for malodor stripping - Google Patents

Abstract

It is an object of the present invention to provide detergent compositions comprising a combination of different .alpha.-amylases delivering improved malodor stripping from soiled items in hard surface cleaning, dishwashing and laundry applications.

Description

CA 022~4069 1998-ll-12 W O 97/43385 PCT~US97/08103 DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF
a-AMYLASES FOR MALODOR STRIPPIN(~

TECHNICAL FIELD

The present invention relates to detergent compositions comprising a combination of different a-amylases delivering improved malodor stripping from soiled items in hard surface cleaning, dishwashing and laundry applications.

BACKGROUND OF THE INVENTION
For a number of years amylase enzymes have been used for a variety of different purposes, the most important of which are starch liquefaction, textile desizing, starch modification in the paper and pulp industry, and for brewing and baking. A further use of amylases which is becoming 25 increasingly important, is the removal of starch containing soils and stains during the washing of fabrics, hard surfaces and dishes.

Indeed, amylase enzymes have long been recognised in dishwashing, hard surface cleaning and laundry compositions to provide the removal of 30 starchy food residues or starchy films from dishware, flatware, glasses and hard surfaces or to provide cleaning performance on starchy soils as well as other soils typically encountered in laundry applications.

W094/02597, Novo Nordisk A/S published February 03, 1994, 35 describes cleaning compositions which incorporate mutant amylases. See also WO94/18314, Genencor, published August 18, 1994 and WO95/10603, Novo Nordisk A/S, published April 20,1995.

CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 Other amylases known for use in cleaning compositions include both a- and ~-amylases. o~-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; W091 /00353; FR

2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo).

Examples of commercial a-amylases products are Termamyl~, Ban~
and Fungamyl~, all available from Novo Nordisk A/S Denmark.

Recently new amylases have been identified and are described in W095/26397, Novo Nordisk A/S, published October 05, 1995, disclosing an a-amylase having a specific activity superior than Termamyl~.

Combinations of an a-amylase with a starch debranching enzyme selected from pullulanase, isopullulanase and iso amylase are described in EP 368 341, J04065494 and J06172796 for enhanced detergency against dirt containing starch, fat, oils and proteins in laundry and automatic dishwashing .
It has now been discovered that odorous materials are entrapped into different types of amylase-susceptible and everyday stains found on fabrics, dishware, hard surfaces and the like and that an uncomplete and unefficient removal of such stains leads to malodor formation.
It has now surprisingly been found that the combined use of different a-amylases improves the removal of malodor coming from different types of amylase-susceptible and everyday stains. Especially good malodor control on everyday stains such as body soils is obtained when the amylases are 30 further combined with a cellulase.

It is therefore an object of the present invention to provide detergent compositions containing a-amylases which exhibit a good malodor control on amylase-susceptible and everyday stains.

CA 022~4069 1998-11-12 W O 97/43385 PCTrUS97/08103 It is another object of the present invention to provide detergent compositions containing a-amylase enzymes which exihibit a good malodor control on body soils.

SUMMARY OF THE INVENTION

The present invention relates to detergent compositions comprising a combination of different a-amylases delivering improved malodor stripping from soiled items in hard surface cleaning, dishwashing and laundry 0 applications.

DETAILED DESCRIPTION OF THE INVENTION

a-AmYlase Enzvmes Essential components of the detergent compositions of the present 20 invention are a-amylase enzymes.

Without wishing to be bound by any theory, it is believed that a combination of several a-amylases provides a more effective activity in solution and/or a broader hydrolytic cleavage pattern than a single amylase 25 type as different amylases show different hydrolytic activity on various substrates. Odorous materials are entrapped into these substrates and a rapid and effective hydrolysis achieved on several different cleavage points allows a more effective suspension and dissolution of the odorous materials therein entrapped.
Suitable a-amylases inc~ude those disclosed in US Pat. no.
5,003,257; EP 252,666; W091 /00353; FR 2,676,456; EP 285,123; EP
525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Examples of commercial a-amylases products are Termamyl~, Ban'~
35 and Fungamyl@', all available from Novo Nordisk A/S Denmark. Other suitable a-amylases are derived from B. Subtilis or B. stearothermophilvs.

CA 022~4069 l998-ll-l2 W 097/43385 PCT~US97/08103 Other a-amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus a-amylases, regardless of whether one, two or multiple amylases strains are the immediate precursors.

a-Amylases of this invention include those amylases having improved stability in detergents, especially improved oxidative stability. In general, the stability-enhanced amylases can be obtained from Novo Nordisk A/S or from Genencor International:

~a) An amylase according the W094/02597, Novo Nordisk A/S published Feb. 3, 1994:
~i) a variant a-amylase wherein one or more of the Met amino residues is exchanged with any amino acid residue except for Cys and Met, (ii) a Bacillus a-amylase acording to ~i), (iii) a variant a-amylase according to (i-ii) wherein one or more Met amino acid residues is exchanged with a Leu, Thr, Ala, Gly, Ser, lle, or Asp amino acid residue, preferably a Leu, Thr, Ala or Gly amino acid residue, (iv) a variant a-amylase according to (i) in which substitution is made, - using preferably Ala or Thr (more preferably Thr), of the Met residue located in position 197 of the B. Iichenformis a-amylase, or the homologous position variation of as similar parent amylase, such as B. amyloliquefaciens, B. Subtilis, or B. ste~rothermophilus;

(b) Stability-enhanced amylases, including Purafact Ox AM(~), as described in W094/18314, published August 18, 1994. Therein it was noted that improved oxidative stability amylases have been made by Genencor from B.
licheniformjs NCIB8061. Met was identified as the most likely residue to be modified. Met was substitued, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particulary important being M 1 97L and M 1 97T with the M 1 97T variant being the most stable expressed variant; corresponding a-amylases will therefore include:
(i) a variant a-amylase that is the expression product of a mutated DNA sequence encoding an a-amylase, the mutated DNA sequence being derived from a precursor a-amylase by the deletion or CA 022~4069 1998-ll-12 substitution of one or more oxidisable acids seiected from the group consiting of Met, Trp, Cys and Tyr amino acid residues, in the precursor a-amylase, (ii) a variant a-amylase according to (i) wherein the oxidisable amino acid residue to be deleted or substitued is a Met in the precursor a-amylase equivalent to ~8, +15, +197, +256, +304, +366 or + 438 in Bacillus licheniformis a-amylase, (iii) a variant a-amylase according to (ii) which is M197T;

10 (c) Preferred herein are amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S. These amylases are disclosed in W095/10603, published April 1995:
(i) A variant of a parent a-amylase enzyme having an improved washing and/or dishwashing performance as compared to the parent enzyme, wherein one or more amino acid of the parent enzyme has been replaced by a different amino acid and/or wherein one or more amino acid have been deleted and/or wherein one or more amino acid have been added to the parent a-amylase enzyme, provided that the variant is different from one in which the Met in position 197 of parent B. Iicheniformis a-amylase has been replaced by Ala or Thr amino acid residue, as the only modification being made, (ii) A variant according to (i) comprising a C-terminal part of an a-amylase derived from B. Iicheniformis and a N-terminal part of an a-amylase derived from B. amyloliquefaciens or from B.
stearothermophilus, (iii) A variant known as Duramyl(~) according to (ii) wherein the Met amino acid residue at position 197 has been substitued preferably by a Leu, Thr, Ala, Gly, Ser, lle or Asp amino acid residue;

(d) W095/26397 Novo Nordisk, published October 05, 1995 describes other suitable amylases: a-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl~ at a temperature range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Phadebas~ a-amylase activity assay. Such Phadebas~
a-amylase activity assay is described at pages 9-10, W095/26397.
Variants of these new amylases demonstrating at least one of the following properties relative to the parent enzymes: 1) improved thermal stability, 2) CA 022~4069 1998-11-12 W O 97/43385 PCTrUS97/08103 -oxidation stability and 3) reduced calcium ion dependency properties.
Examples of other desirable improvements or modifications of properties (relative to the parent-a-amylase) which may be achieved with a variant according to the present invention are: increased stability and/or a-amylolytic activity at neutral to relatively high pH values, increased a-amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pl) so as to better match the pl value for a-amylase variant to the pH of the medium, have been described in the co-pending application by Novo Nordisk W096/23873.

(e) Amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382. These improved properties render the a -amylases more suitable for more acidic or alkaline conditions and allow the reduction of the calcium concentration withoùt a loss of performance of the enzyme:
(i) Said a-amylase is derived from an a-amylase of B~cillus licheniformis or an enzyme having at least 70~/0 amino acid identity therewith which comprises one or more amino acid changes at positions 20 selected from the group consisting of positions 104, 128, 187 and 188 of the amino acid sequence of the a-amylase of Bacillus licheniformis, (ii) A variant according to (i) wherein at least one additional amino acid change selected from the group consisting of His at position 133 to Tyr, and Thr at position 149 to lle.
~f) An amylase according to W096/23874, Novo Nordisk A/S published August 08, 1996 describing variants of a parent Termamyl-like a-amylase, in which variant at least one amino acid residue of the parent a-amylase, which is/are present in a fragment corresponding to the amino acid 30 fragments 44-57 of the amino acid sequence of SEQ. ID No. 4, has been deleted or replaced with one or more amino acid residues which is/are present in a fragment corresponding to the amino acid fragment 66-84 of the amino acid sequence shown in SEQ. ID No.10, or in which one or more additional amino acid residues has been added using the relevant part of 35 SEQ. ID No. 10 or a corresponding part of another Fungamyl-like a-amylase as a template. Preferred is the parent hybrid a-amylase comprising at least 430 amino acid residues of the C-terminal part of the B. Iicheniformis a-CA 022~4069 1998-ll-12 amylase and an amino acid segment corresponding to the 37 N-terminal amino acid residues of the B. ~myloliquefaciens a-amylase having the amino acid sequence shown in SEQ. ID No. 4 and the amino acid segment corresponding to the 445 C-terminal amino acid residues of the B.
Licheniformis a-amylase having the amino acid sequence shown in SEQ ID
No. 2.

Preferred combinations of a-amylases are combinations of a non-modified ~-amylase derived from B. Iicheniformis, B. amyloliquefaciens, B.
10 Subtilis or B. stearothermophilus with a a-amylase as described herein above under (a)-(c) and/or W095/26397 and/or W095/35382. More preferred combination are the combination of an a-amylase as described in W095/10603, known as Duramyl(~ and the a-amylase derived from B.
Iicheniformis, known as Termamyl(~) or with a variant of W095/26397 a-amylases, preferably a variant demonstrating improved thermal stability, as described in W096t23873. Other more preferred combinations are the combination of the a-amylase derived from B. Iicheniformis, known as Termamyl(~) with a variant of W095/26397 a-amylases, preferably demonstrating improved thermal stability, as described in W096/23873;
20 with a Purafact OX AM~ ~W094/18314) andtor with the parent hybrid a-amylase described in W096t23874. The detergent compositions of the present invention can comprise a combination of more than two a-amylases .

A cellulase can be added to such combinations.

These enzymes are incorporated into detergent compositions at a level from 0.0001% to 0.1% total pure a-enzymes by weight of the total composition, preferably from 0.0002% to 0.06%, more preferably from 30 0.0003% to 0.05% total pure a-amylase enzymes by weight of total composition. The a-amylases are preferably incorporated into the detergent compositions of the present invention in the range of from 1:3 to 3:1, more preferred ratios are 1:1, 3:7 or 7:3.

Cellulase Enzvme CA 022~4069 1998-11-12 W O 97/43385 PCTnUS97/08103 The cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between ~ and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and W096/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.

Examples of cellulase components which may be usable in the present invention are:
The complexe of cellulases commercailly available under the tradename Celluzyme(g), or 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 antibody 20 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. WO91/17244, or 25 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 30 activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. W091/17244, or any of the cellulases 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
35 not less than 7 or whose relative activity at a pH of not less than 8 is 50%
or over of the activity under optimum conditions when carboxy methyl cellulose (CMC) is used as a substrate, or . .

CA 022~4069 1998-ll-12 W O 97/43385 PCT~US97/08103 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. W0 91/17243, or an endoglucanase component which is immunoreactive with an antibody raised against a highly purified -60kD endoglucanase derived from Bacillus lautus, NCIMB 40250, or which is a homologue or derivative of the -60kD
0 endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. W0 91/10732.

Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).

According to the present invention, preferred cellulases are those as described in Danish Patent Application 1159/90 or PCT patent application W091/17243 which is also known as carezyme(TMl available from Novo Nordisk A/S in Bagsvaerd, in Denmark. The cellulase preparation described in these publications and the Carezyme~TM) consistent with this description, can consist essentially of a homogeneous endoglucanase component, which is immunoreactive with an anti-body raised against a highly purified 43 kD cellulase derived from Humicola Insulens, DSM 1800, or which is homologous to said 43 kD endoglucanase. An alternative screening for appropriate cellulases for use in the laundry detergent composition according to the present invention is the method specified in EP-A-495 258 or more specifically in EP-A-350 098.
For industrial production of the cellulase preparation herein, however, it is preferred to employ recombinant DNA techniques or other techniques involving adjustments of fermentations or mutation of the microorganisms involved to ensure overproduction of the desired enzymatic activities. Such methods and techniques are known in the art and may readily be carried out by persons skilled in the art.

CA 022~4069 1998-11-12 Preferred cellulases to be used in the present invention are 50 kD
endoglucanase and 43kD endoglucanase.

5 Detergent comPonents The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical 0 form of the composition, and the nature of the cleaning operation for which it is to be used.

The cleaning compositions according to the invention can be liquid, paste, gels, bars, tablets, powder or granular forms. Granular compositions 15 can also be in "compact" form, the liquid compositions can also be in a "concentrated" form.

The compositions of the invention may for example, be formulated as hard surface cleaner, hand and machine dishwashing compositions, hand 20 and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions.

When formulated as compositions for use in manual dishwashing 25 methods the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group 11 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.

.

CA 022~4069 1998-11-12 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.

0 The "compact" form of the granular laundry detergent compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition.
In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
The inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides .
A preferred filler salt is sodium sulphate.

Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
Typically the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

Surfactant svstem The detergent compositions according to the present invention comprise a surfactant system wherein the surfactant can be selected from CA 022~4069 1998-11-12 W O 97/43385 PCTrUS97/08103-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 detergent compositions in accord with the invention.

The surfactant is preferably formulated to be compatible with enzyme 10 components present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.

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

Polyethylene, polypropylene, and polybytylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the 20 surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene 25 oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
Commercially available nonionic surfactants of this type include IgepalTM
C0-630, marketed by the GAF Corporation; and TritonTM X-4~, X-114, X-30 100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable 35 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 ... .

CA 022~4069 1998-ll-12 W O 97/43385 13 PCTrUS97/08103 about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alky! 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 TergitolTM 1 5-S-9 ~the condensation product of C1 1-C1 5 linear alcohol with 9 moles ethylene oxide), TergitolTM
0 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribytion), both marketed by Union Carbide Corporation; NeodolTM 45-9 ~the condensation product of C 1 4-C 1 5 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 C 1 4-C 1 5 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C 1 4-C 1 5 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the condensation product of C 1 3-C 1 5 alcohol with 9 moles ethylene oxide), 20 marketed by The Procter & Gamble Company, and Genapol LA 030 or 050 (the condensation product of C 1 2-C 1 4 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-1 1 and most preferred from 8-10.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued danuary 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, 30 hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties ~optionally the hydrophobic group is 35 attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactoseas opposed to a glucoside or galactoside). The intersaccharide bonds can CA 022~4069 1998-ll-12 W O 97143385 PCTrUS97/08103 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(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to 0 about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available 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 CA 022~4069 1998-ll-12 W O 97143385 15 PCTrUS97/08103-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 5 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available 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-C 14 15 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C1g alcohol ethoxylates (preferably C1 0 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.

Highly preferred nonionic surfactants are polyhydroxy fatty acid 20 amide surfactants of the formula.

R2 - C - N - z Il I
O Rl wherein R 1 is H, or R 1 is C 1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative 30 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.

Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S03 CA 022~4069 1998-11-12 W O 97/43385 PCTrUS97/08103 -according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry 5 applications, comprise alkyl ester sulfonate surfactants of the structural formula:

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 ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C 1 o-C 1 6 alkyl.

Other suitable anionic surfactants include the linear alkyl benzene sulfonate, alkyl sulfate surfactants which are water soluble salts or acids of the formula ROS03M wherein R preferably is a C 1 0-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 1 0-c20 alkyl component, more preferably a C12-C1g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Typically, alkyl chains of 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) .

CA 022~4069 1998-11-12 W O 97/43385 17 PCTrUS97/08103 Other anionic surfactants useful for detersive purposes can also be included in the detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and 5 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 citrates, e.g., as described in British patent specification No. 1,082,179, Cg-C24 0 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, alkylphosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates snd sulfosuccinates, monoesters of sulfosuccinates 5 (especially saturated and unsaturated C12-C1g monoesters~ and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates 20 such as those of the formula RO(CH2CH20)k-CH2COO-M + wherein R is a Cg-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.
25 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).
30 When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate 35 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 o-C24 alkyl component, preferably a C 1 2-C20 alkyl or CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 hydroxyalkyl, more preferably C1 2-C1 8 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H
or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific ex~mples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and 0 dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, rnixtures thereof, and the like.
Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-C1gE(1.0)M~, C12-C1g alkyl polyethoxylate (2.25) sulfate (C12-C18E(2 25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-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 selected from sodium and potassium.

The detergent compositions of the present invention may also contain 20 cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described hereln.

Cationic detersive surfactants suitable for use in the detergent 25 compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula:

IR2(0R3)yllR4(0R3)yl2R5N + 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-, 35 and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any CA 022~4069 1998-ll-12 W 097/43385 PCTrUS97/08103 -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; each y is from 0 to about 10 and the sum of the y values is from 5 0 to about 15; and X is any compatible anion.

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

R1~o J~ 'R~
Formula I
whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (Il):
o Formula ll y is 2-4, preferably 3.
whereby R2 is H or a C1-C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, 20 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~ is a counterion, preferably a halide, e.g. chloride or methylsulf ate.

2~ ~o7zH
Formula lll R6 is C1-C4 and z is 1 or 2.

Preferred quat ammonium surfactants are those as defined in formula 30 I whereby R1 is Cg, C10 or mixtures thereof, x=o, CA 022~4069 1998-11-12 R3, R4 = CH3 and Rs = CH2CH20H.

Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having 5 the formula:
R1 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 o 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-C1s particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin byild up or OXO alcohols 5 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:
20 coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C1 2-1 5 dimethyl hydroxyethyl ammonium chloride or bromide;
25 coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is CH2-CH2-O-C-C12_14 alkyl and R2R3R4 are methyl).

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

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

CA 022~4069 1998-11-12 W O 97/43385 21 PCTrUS97/08103 -When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about I % to about 8% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which o the aliphatic radical can be straight- or branched-chain. One of the aliphaticsubstituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, 5 lines 18-35, for examples of ampholytic surfactants.

When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1 % to about 10% by weight of such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary 25 phosphonium or tertiary sulfonium compounds. See U.S. Patent No.
3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.
When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from 30 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 35 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 CA 022~4069 1998-11-12 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 5 of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-poiar nonionic detergent surfactants include the amine oxide surfactants having the formula R3 (oR4)xN(Rs)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R4 is an alkylene 15 or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an 20 oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C1o-C18 alkyl dimethyl amine oxides and Cg-C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.

The detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.
Suitable primary amines for use herein include amines according to the formula R1NH2 wherein R1 is a C6-C12 preferably C6-C10 alkyl chain or R4X(CH2)n, X is -0-,-C(O)NH- or -NH-, R4 is a C6-C1 2 alkyl chain n is between 1 to 5, preferably 3. R1 alkyl chains may be straight or branched CA 022~4069 1998-11-12 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, 1-5 octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido propylamine and amido propylamine.

Suitable tertiary amines for use herein include tertiary amines havin~
0 the formula R1 R2R3N wherein R1 and R2 are C1-Cg alkylchains or - (CH2 - CH - O ~H
R3 is either a C6-C12 preferably C6-C1o 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 .
5 R3 and R4 may be linear or branched; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or - (CH2 - CH - O ~H

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

Also preferred are the amidoamines of the formula:

R1--C--NH--~ CH2 )--N--( R2 )2 wherein R1 is C6-C1 2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1-C4 Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine,C8-lOoxypropylamine, N coco CA 022~4069 1998-ll-12 W O 97/43385 PCTrUS97/08103 -1-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis~hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10 5 amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and 0 cocoamido propylamine.

OPtional deterqent ingredients:

Other detergent enzymes The detergent compositions can in addition to the combination of a-amylase enzymes and eventually cellulases further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.

Said enzymes include enzymes selected from hemicellulases, peroxidases, proteases, gluco-amylases, other amylases, xylanases, lipases, esterases, cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, 13-glucanases, arabinosidases chondroitinase, laccase or mixtures thereof.
A preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.

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 CA 022~4069 l998-ll-l2 W O 97/43385 PCTrUS97/08103 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 peroxidases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.

0 Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S ~Denmark), those sold under the tradename Maxatase, Maxacal, Maxapem and Properase by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Also proteases described in patent applications EP 251 446, WO91/06637, W094/10591 and US serial number 08/322676 can be included in the detergent composition of the invention. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 2% active 20 enzyme by weight of the composition.

It has been found that the addition of proteases to the combination of a-amylases according to the present- invention, enhance the malodor stripping from soiled items.
Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as 30 disclosed in British Patent 1,372,034. Suitable lipases inciude 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, ~apan, under the trade name Lipase P "Amano," hereinafter referred to as 35 "Amano-P". Especially suitable lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UltraR(Novo) which CA 022~4069 1998-ll-12 W O 97t43385 PCT~US97/08103 have found to be very effective when used in combination with the compositions of the present invention.

It has been found that the addition of lipases to the combination of a-amylases according to the present invention, enhance the malodor stripping from soiled items.

Also suitable are cutinases [EC 3.1.1.50~ which can be considered as a special kind of lipase, namely lipases which do not require interfacial 0 activation. Suitable cutinases are described in WO 94/14963 and WO
94/14964. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

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 %
20 to 2% of active enzyme by weight of the detergent composition. They can be added as separate ingredients ( prills, granulates,...) or as cogranulate of two or more enzymes.

Other suitable detergent ingredients that can be added are enzyme 25 oxidation scavengers which are described in the copending European patent application 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

Color care benefits Technologies which provide a type of color care benefit can also be included. 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.
35 94870206.3.
Bleaching agenf CA 022~4069 1998-11-12 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, - 5 depending upon the bleaching agent chosen, one or more bleach activators.When present oxygen bleaching compounds will typically be present at levels of from about 1 % to about 25%.

The bleaching agent component for use herein can be any of the 0 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 20 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.
25 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 30 product, preferably 1 -5 % by weight.

The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591), Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in W094/28106) or pentaacetylglucose (PAG), which are CA 022~4069 1998-11-12 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, 0 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 20 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 25 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.

30 Bvilder 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 CA 022~4069 l998-ll-l2 W O 97/43385 PCT~US97/08103 pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
Phosphate builders as sodium tripolyphosphate can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g.
0 SKS-6 (Hoechst) . SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si20s).
Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.

CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 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, 1,2,3,4,5,6-5 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 disciosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates 0 containing up to three carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, 5 zeolite MAP 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 accordance with the invention is ethylenediamine-N,N'-disuccinic acid 20 ~EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS.
Examples of such preferred magnesium salts of EDDS include MgEDDS and 25 Mg2EDDS. 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 aluminosilicate builder such as zeolite MAP, zeolite A, and a watersoluble 30 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 phosphonates, amino polyalkylene phosphonates and amino 35 polycarboxylates.

CA 022~4069 1998-11-12 W 097/43385 31 PCTrUS97/08103 Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.

0 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.

Suds suppressor Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic 20 silicas of various types. These materials can be incorporated as particulatesin which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or 2s more of the other components.
A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2-bytyl-octanol which are commercially available under the trade name Isofol 12 R.
Such suds suppressor system are described in Copending European Patent application N 92870174.7 filed 10 November, 1992.

CA 022~4069 1998-11-12 Especially preferred silicone suds controlling agents are described in Copending European Patent application N~92201649.8. Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.

The suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
to Others Other components used in detergent compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.

Especially suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds 20 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 25 dextrins are,preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as 30 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 35 their salts. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or CA 022~4069 1998-ll-12 W O 97/43385 PCTrUS97/08103 methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5%
to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis-0 (2,4-dianilino-s-triazin-6-ylamino~stilbene-2:2' - disulphonate, monosodium 4',4" -bis-(2,4-dianilino-s-tri-azin-6 ylamino)stilbene-2-sulphonate, disodium 4,4 ' -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino~stilbene-2,2' - disutphonate, di-sodium 4,4' -bis-(4-phenyl-2, 1,3-triazol-2-yl)-stilbene-2,2 ' disulphonate, di-so-dium 4,4'bis(2-anilino-4-( 1-methyl-2-hydroxyethylamino)-s-triazin-6- ylami-no)stilbene-2,2'disulphonate, sodium 2(stilbyl-4"-(naphtho-1',2':4,5)-1,2,3 - triazole-2"-sulphonate and 4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred brighteners are the specific brighteners of copending European Patent application No.
95201 943.8.
Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These 25 polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities, Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos.
4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula CA 022~4069 1998-11-12 W O 97/43385 PCTAUSg7/08103 3(pEG)43)o.75(poH)o.25[T-po)2.8(T-pEG)o.4]T( H~0.25((pEG)43cH3)o.7!~

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 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, 0 "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.
The selected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13 % by weight of dimethyl sulfobenzoic acid and about 15 % by weight of sulfoisophthalic acid, and 20 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, 25 using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the a-amylase enzymes. Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 30 filed January 31, 1992.

Softening agents Fabric softening agents can also be incorporated into laundry 35 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

CA 022~4069 l998-ll-l2 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 51 4 276 and EP-B0 011 340 and their combination with mono C1 2-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.

Levels of smectite clay are normally in the range from 2% to 20%, 0 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 20 solid components of the composition.

Dye transfer inhibition The detergent composition of the present invention can also include 25 compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.

Polymeric dye transfer inhibiting agents The detergent compositions according to the present invention also comprise from 0.001% to 10 %, preferably from 0.01 % to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally 35 incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed CA 022~4069 1998-11-12 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, 5 polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

Addition of such polymers also enhances the performance of the enzymes according the invention.

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

p I

(I) 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 ~1 A is NC, co, c, -o-,-s-, -N-; x is 0 or li R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.

The N-0 group can be represented by the following general structures O o CA 022~4069 l998-ll-l2 (Rl)x -N- (R2)y =N- (Rl)x I

(R3)Z

wherein R 1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is O
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 o groups.

The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula ~I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of 30 said R group.
Examples o,f these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or 35 alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R groups.

CA 022~4069 1998-ll-12 W O 97/43385 38 PCTrUS97/08103 Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.

Any polymer backbone can be used as long as the amine oxide 5 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.

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

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 5,000-200,000.
Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-3~ 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.

CA 022~4069 1998-11-12 W O 97/43385 PCTrUS97/08103 The average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern - Methods of Polymer Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an - 5 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 0 inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone The detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinylpyrrolidones which are commercially available from BASF
Cooperation include Sokalan HP 165 and Sokalan HP 12;
polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).

d) 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 CA 022~4069 1998-11-12 W O 97143385 PCTrUS97108103 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.

5 e) Polyvinylimidazole:

to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
f) Cross-linked polymers:

Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or ~5 physical nature, possibly with active groups n the backbone or on branches;
cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.

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

Such cross-linked polymers are described in the co-pending patent application 94870213.9 Method of washing The compositions of the invention may be used in essentially any 30 washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.

The process described herein comprises contacting fabrics with a 35 laundering solution in the usual manner and exemplified hereunder.

CA 022~4069 l998-ll-l2 W O 97/43385 41 PCTrUS97/08103 The process of the invention is conveniently carried out in the course of the cleaning process. The method of cleaning is preferably carried oùt at 5 ~C to 95 ~C, especially between 1 0~C and 60~C. However, specific amylase enzymes within the specified enzymatic concentration, have 5 demonstrated superior starch cleaning even for wash cycles occuring at very low temperatures (between 10~C and 25~C). The pH of the treatment solution is preferably from 7 to 11.

A preferred machine dishwashing method comprises treating soiled 0 articles with an aqueous solution of the machine diswashing or rinsing composition. A conventional effective amount of the machine dishwashing composition means from 8-60 9 of product dissolved or dispersed in a wash volume from 3-10 litres.

15 According to a manual dishwashing method, soiled dishes are contacted with an effective amount of the diswashing composition, typically from 0.5-209 (per 25 dishes being treated). Preferred manual dishwashing methods include the application of a concentrated solution to the surfaces of the dishes or the soaking in large volume of dilute solution of the detergent 20 composition.

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

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

In the detergent compositions, the enzymes levels are expressed in pure enzyme by weight of the total composition and the abbreviated component identifications have the following meanings:

LAS : Sodium linear C12 alkyl benzene sulphonate.

TAS : Sodium tallow alkyl sulphate.

.

CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 XYAS : Sodium c1x - C1y alkyl sulfate.

SAS : C12-C14 secondary (2,3) alkyl sulfate in the form of the sodium salt.

AEC : Alkyl ethoxycarboxylate surfactant of formula C12 ethoxy (2) carboxylate.

SS : Secondary soap surfactant of formula 2-bytyl octanoic acid.

25EY : A C 1 2-C 1 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 : C 1 2-C 1 5 mixed ethoxylated and/or propoxylated fatty alcohol with an average degree of ethoxylation of 3 to 7 and an average degree of propoxylation of 4.5.

CFAA : C 1 2-C 1 4 alkyl N-methyl glucamide TFAA : C16-C18 alkyl N-methyl glucamide.

Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio =
2.0) CA 022~4069 1998-11-12 W O 97/43385 PCT~US97108103 NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si205 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.

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(A1~2SiO2)12- 27H20 having a primary particle size in the range from 1 to 10 micrometers Citrate : Tri-sodium citrate dihydrate Citric : Citric Acid CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 Perborate : Anhydrous sodium perborate monohydrate bleach, empirical formula NaBO2.H202 PB4 : Anhydrous sodium perborate tetrahydrate Percarbonate : Anhydrous sodium percarbonate bleach of empirical formula 2Na2C03.3H2O2 TAED : Tetraacetyl ethylene diamine Paraffin : Paraffin oil sold under the tradename Winog 70 by Wintershall.

Pectinase : Pectolytic enzyme sold under the tradename Pectinex AR by Novo Nordisk A/S.

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

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

Lipase : Lipolytic enzyme sold under the tradename Lipolase and Lipolase Ultra by Novo Nordisk A/S.

Peroxidase : Peroxidase enzyme.

Cellulase 1, ll : Endoglucanase 50 kD, endoglucanase 43 kD.

CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 Amylase 1, ll : a-amylase enzyme derived from B.
Licheniformis, known as Termamyl~, o~-amylase enzyme known as Duramyl(~ and a-amylase enzyme described in W095/10603, W096/23873 and W096/23874.

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.

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

Granular Suds : t2% Silicone/silica, 18% stearyl alcohol,70%
Suppressor starch in granular form SCS : Sodium cumene sulphonate Sulphate : Anhydrous sodium sulphate.

HMWPE0 : High molecular weight polyethylene oxide.

PGMS : Polyglycerol monostearate having a tradename of Radiasurf 248.

TAE 25 : Tallow alcohol ethoxylate (25).

CA 022~4069 l998-ll-l2 W O 97/43385 46 PCT~US97/08103 BTA : Benzotriazole.

Bismuth nitrate : Bismuth nitrate salt.

NaDCC : Sodium dichloroisocyanurate.

KOH : 100% Active solution of Potassium Hydroxide.

pH : Measured as a 1 % solution in distilled water at 20~C.

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

11 111 lV V
LAS 22.0 22.0 22.0 22.0 22.0 Phosphate 23.0 23.0 23.0 23.0 23.0 Carbonate 23.0 23.0 23.0 23.0 23.0 Silicate 14.0 14.0 14.0 14.0 14.0 Zeolite A 8.2 8.2 8.2 8.2 8.2 DETPM P 0.4 0.4 0.4 0.4 0.4 Sodium sulfate 5.5 5.5 5.5 5.5 5.5 Amylase 1 0.0035 0.01 0.005 0.003 0.014 Amylase ll 0.0025 0.01 0.005 0.007 0.006 Cellulase 1 0.001 - - 0.00i Cellulase ll - - 0.001 0.001 Protease 0.01 0.02 0.01 0.005 -Pectinase 0.02 - - - -Xylanase - - 0.01 0.02 Lipase 0.005 0.01 Water & minors Up to 100%

CA 022~4069 1998-11-12 Example 2 Granular fabric cleaning compositions in accord with the invention were prepared as follows:
11 111 lV V
LAS 12.0 12.0 12.0 12.0 12.0 Zeolite A 26.0 26.0 26.0 26.0 26.0 SS 4.0 4.0 4.0 4.0 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 - 16.0 TAED 5.0 5.0 5.0 - 5.0 Protease 0.06 0.03 0.02 0.08 Lipase 0.005 0.01 Cellulase I - 0.001 - - 0.001 Cellulase ll - - - 0.001 0.001 11 111 lV V
Amylase 1 0.01 0.0045 0.05 0.014 0.005 Amylase ll 0.01 0.0105 0.05 0.006 0.005 Water & minors Up to 100%

ExamPle 3 Granular fabric cleaning compositions in accord with the invention 10 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 45E7 4.0 4.0 25E3S - - 3.0 68E11 1.8 1.8 CA 022~4069 1998-11-12 W O 97/43385 48 PCT~US97/08103-25E5 - - 8.0 Citrate 14.0 1 5.0 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 Ceilulase I - - 0.001 Cellulase ll 0.002 - 0.001 Amylase 1 0.015 0.020.0025 Amylase ll 0.015 0.010.0035 Silicate 2.0 2.5 Sulphate 3.5 5.2 3.0 PVP 0.3 0.5 Poly (4-vinylpyridine~-N-oxide/copolymer - - 0.2 of vinyl-imidazole and vinyl-pyrrolidone ll lll Perborate 0. 5 1 .0 Peroxidase 0.01 0.01 Phenol sulfonate 0.1 0.2 Water/Minors Up to 1 00%

- ExamDle 4 Granular fabric cleaning compositions in accord with the invention were prepared as follows:

ll LAS 6.5 8.0 Sulfate 15.0 18.0 Zeolite A 26.0 22.0 Sodium nitrilotriacetate 5.0 5.0 PVP 0.5 0.7 CA 022~4069 1998-ll-12 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 Silicate 5.0 5.0 Carbonate 15.0 15.0 Peroxidase 0.1 0.1 Pectinase 0.02 Cellulase 1 0.005 0.002 Cellulase ll - 0.001 Amylase 1 0.005 0.01 Lipase 0.01 Amylase ll 0.005 0.003 Water/minors Up to 100%

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

45AS 8.0 25E3S 2.0 25E5 ~ 3 0 25E3 3.0 TFAA 2.5 Zeolite A 17.0 NaSKS-6 12.0 Citric acid 3.0 Carbonate 7.0 MA/AA 5.0 Poly (4-vinylpyridine)-N-oxide/ 0.2 copolymer of vinylimidazole and vinylpyrrolidone Protease 0 05 CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 Lipase 0.001 Celiulase 1 0.01 Cellulase ll Amylase 1 0.005 Amylase ll 0.005 TAED 6.0 Percarbonate 22.0 EDDS 0.3 Granular suds suppressor 3.5 water/minors Up to 100%

Exam~le 6 A granular fabric cleaning compositions in accord with the invention which provide "softening through the wash" capability were prepared as follows:

ll 45AS - 10.0 LAS 7.6 45E7 4.0 Coco-alkyl-dimethyl hydroxy- 1.4 1.0 ethyl ammonium chloride Citrate 5.0 3.0 Na-SKS-6 - 1 1 .0 Zeolite A 15.0 15.0 MA/AA 4.0 4.0 DETPMP 0.4 0.4 Perborate 1 5.0 Percarbonate - 15.0 TAED 5.0 5.0 Smectite clay l O . 0 10 0 CA 022~4069 l998-ll-l2 W O 97/43385 5l PCTrUS97/08103 -HMWPE0 - 0.1 Protease 0.02 0.01 Lipase 0.02 0.01 Amylase 1 0.015 0.0035 Amylase ll 0.015 0.0025 Cellulase 1 0.001 Cellulase ll 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 Liquid fabric cleaning compositions in accord with the invention were prepared as follows:

11 111 lV V Vl AS 12.0 18.0 15.0 15.0 10.0 15.0 AE3S 8.0 4.0 5.0 4.0 5.0 4.0 Polyhydroxy fatty 3.0 3.0 4.0 4.0 4.0 6.0 acid amide Nonionic 2.5 3.0 5.0 6.0 2.0 4.0 Amido propyl 1.5 1.5 1.5 1.0 2.5 2.5 amine Tallow palm 5.0 9.0 7.0 7.0 5.0 7.0 kernel FA
Rapeseed FA 2.0 3.0 4.0 3.0 3.0 3.0 Citric acid 2.0 1.0 1.0 2.0 3.0 1.0 Protease 0.03 0.03 0.03 0.03 0.03 0 03 Lipase 0.003 0.003 0.003 0.003 0 003 0 003 Amylase 1 0.006 0.007 0.008 0.009 0.006 0.006 Amylase ll 0.006 0.003 0.005 0.004 0.009 0.007 Cellulase 1 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 Cellulase ll 0.008 0.008 0.008 0.008 0.008 0.008 CA 022~4069 1998-11-12 W O 97/43385 52 rCTAUS97/08103 Ethoxylated 0. 7 O. 7 O. 7 0.7 0.7 0.7 tetraethylene pentaimine 1,2 Propylene 0.1 0.1 0.1 0.1 0.1 0.1 glycol, methyl capped PEG
Ethanol 2.0 3.0 2.0 2.2 3.0 2.2 Propanediol 9.0 8.0 9.0 9.0 10.0 9.0 MeA 4.5 3.5 4 5 5 5 4 5 4 5 NaOH 2.5 3.5 2.5 1.5 2.5 2.5 Borax-Ca Format 2.0 3.0 2.0 1.5 2.0 2.0 Brightener 36 0.1 0.1 0.1 0.1 0.1 0.1 DETPMP 0.7 0.9 1.3 0.9 0.9 0.9 Water and minors Balance to 100%

ExamPle 8 Liquid fabric cleaning compositions in accord with the invention were prepared as follows:

11 111 lV V
AS 12.0 15.0 15.0 10.0 15.0 AE3S 2.0 2.0 2.0 2.0 2.0 Polyhydroxy fatty acid 4.0 5.0 5.0 4.0 5.0 amide Nonionic 5.0 5.0 6.0 4.0 5.0 Tallow palm kernel FA 6.0 7.0 4.5 7.0 7.0 Rapeseed FA 3.0 2.0 5.0 3.0 3.0 Citric acid 1.0 2.0 3.0 1.0 2.0 Protease 0.03 0.03 0.03 0.03 0.03 Lipase 0 003 0 003 0 003 0 003 0 003 Amylase 1 0.006 0.007 0.008 0.009 0.006 Amylase ll 0.006 0.003 0.005 0.004 0.009 Cellulase 1 0.0003 0.0003 0.0003 0.0003 0.0003 Cellulase ll 0.008 0.008 0.008 0.008 0.008 Ethoxylated tetraethylene 0.7 0.7 0.7 0.7 0.7 pentaimine CA 022~4069 1998-ll-12 W O 97143385 PCTrUS97/08103 1,2 Propylene glycol, 0.1 0.1 0.1 0.1 0.1 methyl capped PEG
Ethanol 2.0 3.0 2.0 2.2 3.0 Propanediol 9.0 8.0 9.0 9.0 10.0 MeA 4-5 3 5 4-5 5 5 4 5 NaOH 2.5 3.5 2.5 1.5 2.5 Borax-Ca Format 2.0 3.0 2.0 1.5 2.0 Brightener 36 0.1 0.1 0.1 0.1 0.1 Silicone 0.2 0.2 0.2 0.2 0.2 DETPMP 0.7 0.9 1.3 0.9 0.9 Water and minors Balance to 100%

ExamPle 9 Liquid fabric cleaning compositions in accord with the invention were prepared as follows:

11 111 lV V
AS 12.0 12.0 12.0 15.0 14.0 AE3S 7-5 7-5 7 5 5.0 4.0 Polyhydroxy fatty acid 4.0 6.0 3.0 5.0 4.0 amide Nonionic 2.5 2.5 2.5 4.0 4.5 Amido propyl amine 1.0 1.0 1.0 1.5 1.0 Tallow palm kernel FA 4.5 4.5 4.5 8.0 7.5 Rapeseed FA 3.0 3.0 3.0 3.0 3.0 Citric acid 2.0 3.5 2.0 1.0 1.0 Protease 0.03 0.03 0.03 0.03 0.03 Lipase 0.003 0.003 0.003 0.003 0.003 Amylase 1 0.015 0.006 0.007 0.008 0.009 Amylase ll 0.014 0.006 0.003 0.005 0.004 Cellulase 1 0.0005 0.0003 0.0003 0.0003 0.0003 Cellulase ll 0.008 0.008 0.008 0.008 0.008 CA 022~4069 1998-ll-12 Ethoxylated tetraethylene 0.7 0.7 0.7 0.7 0.7 pentaimine 1,2 Propylene glycol, 0.1 0.1 0.1 0.1 0.1 methyl capped PEG
Ethanol 2.0 3.0 2.0 2.2 3.0 Propanediol 9.0 8.0 9.0 9.0 10.0 MeA 4-5 3-5 4-5 5-5 4 5 NaOH 2.5 3.5 2.5 1.5 2.5 Borax-Ca Format 2.0 3.0 2.0 1.5 2.0 Brightener 36 0.1 0.1 0.1 0.1 0.1 Silicone 0.2 0.2 0.2 0.2 0.2 DETPMP 0.7 0.9 1.3 0.9 0.9 Water and minors Balance to 100%

ExamPle 10 Heavy duty liquid fabric cleaning compositions suitable for use in the pretreatment of stained fabrics, and for use in a machine laundering method, in accord with the invention were prepared as follows:

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 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 Protease 0.005 0.03 0.02 0.04 0.01 Lipase 0.002 0.01 0.02 - 0.004 Amylase 1 0.005 0.005 0.001 0.01 0.002 Amylase ll 0.0025 0.002 0.001 0.007 0.002 Cellulase 1 0.04 - 0.01 Cellulase ll - 0.02 0.01 - 0.001 Pectinase 0.02 0.02 - - -Water/propylene glycol/ethanol 1100:1 :1 ) CA 022~4069 1998-11-12 W O 97/43385 PCTrUS97108103 Example 11 Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:

11 111 lV
LAS acid form - - 25.0 C12 14 alkenyl succinic 3.0 8.0 10.0 acid Citric acid 10.0 15.0 2.0 2.0 25AS acid form 8.0 8.0 - 15.0 25AE2S acid form - 3.0 - 4.0 25AE7 - 8.0 - 6.0 25AE3 8.0 - - -CFAA - - - 6.0 DETPMP 0.2 - 1.0 1.0 Fatty acid - - - 10.0 Oleic acid 1.8 - 1.0 Ethanol 4.0 4.0 6.0 2.0 Propanediol 2.0 2.0 6.0 10.0 1. Il 111 lV
Protease 0.02 0.02 0.02 0.01 Cellulase 1 0.04 - - 0.01 Cellulase ll - 0.001 0.0010.001 Amylase 1 0.002 0.007 0.0030.005 Amylase ll 0.002 0.003 0.0020.005 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 NaOH Up to pH 7.5 Waters/minors Up to 100%

CA 022~4069 1998-11-12 Exampie 1 2 The following rinse added fabric softener composition, in accord with the invention, was prepared (parts by weight).

Softener active 24. 6 PGMS 2.0 TAE 25 1.5 Amylase 1 0.0005 Amylase 1 0.0005 Cellulase 1 0.001 Cellulase ll HCL 0. 12 Antifoam agent 0.01 9 Blue dye 80ppm CaC12 0.35 Perfume 0 90 Example 1 3 Syndet bar fabric cleaning compositions in accord with the invention were prepared as follows:
11 111 lV
C12-16 alkyl sulfate, Na 20.0020.00 20.00 20.00 CFAA 5.0 5.0 5.0 5 0 C1 1-13 alkyl benzene 10.0 10.0 10.0 10.0 sulphonate, Na Sodium carbonate 25.0 25.0 25.0 25.0 Sodium pyrophosphate 7.0 7.0 7.0 7.0 Sodium tripolyphosphate 7.0 7.0 7.0 7.0 Zeolite A 5.0 5.0 5.0 5.0 CMC 0.2 0.2 0.2 0.2 CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103 Polyacryiate ~MW 1400) 0.2 0.2 0.2 0.2 Coconut monethanolamide 5.0 5.0 5.0 5.0 Amylase 1 0.01 0.006 0.007 0.01 Amylase 11 0.005 0.014 0.003 0.005 Cellulase I - 0.004 - 0.01 Cellulase ll 0.001 - - 0.001 Protease 0.3 - 0.5 0.05 Brightener, perfume 0.2 0.2 0.2 0.2 CaS04 1.0 1.0 1.0 1.0 MgS04 1.0 1.0 1.0 1.0 Water 4.0 4.0 4.0 4.0 Filler*: balance to 100%

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

Example 14 The following compact high density (0.96Kg/l) dishwashing detergent 0 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 Metasilicate - 2.50 2.50 Perborate 1.94 9.74 7.79 14.28 9.74 PB4 8.56 Percarbonate - - - - - 6.70 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 CA 022~4069 1998-ll-12 W O 97t43385 PCTAUS97/08103 -Paraffin 0.50 0.50 0.50 0.50 - 0.20 Protease 0.0750.05 0.10 0.10 0.08 0.01 Lipase - 0.001 - 0.005 Amylase 1 0.0050.003 0.0050.01 0.005 0.0007 Amylase ll 0.0050.002 0.01 0.005 0.005 0.0018 Cellulase 1 0.001 - 0.005 - - 0.001 Cellulase ll0.001 - - - 0.001 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 11.0010.90 10.80 10.90 9.60 Example 15 5The following granular dishwashing detergent compositions examples I 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 Silicate 7.40 7.40 7.40 12.00 8.00 20.34 Perborate 4.40 4.40 4.40 - 4.40 NaDCC - - - 2.00 - 1.50 Nonionic 0.75 0.75 0.75 1.90 1.20 0.50 TAED 1.00 1.00 - - 1.00 PAAC - ~ 0 004 BzP - 1.40 Paraffin 0.25 0.25 0.25 Protease 0.05 0.05 0.05 - 0.1 Lipase 0.005 - 0.001 Amylase 1 0.002 0.001 0.005 0.006 0.007 0.01 Amylase ll 0.001 0.001 0.005 0.014 0.003 0.005 CA 022~4069 l998-ll-l2 W 097/43385 PCT~US97/08103 -Cellulase I 0.0010 005 0 001 Cellulase ll - - - 0.001 - 0.001 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 Example 16 The following detergent composition tablets of 25g weight were prepared in accord with the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:

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 Lipase 0.005 - -Amylase 1 0.005 0.002 0.001 ll lll Amylase ll 0.005 0.003 0.001 cellulase I - 0.01 0.01 Cellulase ll 0.004 0.01 Perborate 1.56 7.79 PB4 6.92 - 11.40 Nonionic 1.Z0 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 CA 022~4069 1998-11-12 W O 97/43385 PCT~US97/08103-Example 17 The following liquid dishwashing detergent compositions in accord 5 with the present invention I to ll, 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 Nonionic 2.50 1.00 Paraffin 2.20 Protease 0.03 0.02 Amylase 1 0.0025 0.0018 Amylase ll 0.00025 0.0007 Cellulase 1 0.04 0.01 cellulase ll - 0.005 480N 0.50 4.00 KOH - 6.00 Sulphate 1.60 pH (1% solution) 9.10 10.00 Examcle 18 0 The following liquid hard surface cleaning compositions were prepared in accord with the present invention:

11 111 lV V Vl Amylase 1 0.01 0.002 0.005 0.006 0.0007 0.003 Amylase ll 0.01 0.003 0.005 0.014 0.0003 0.002 Cellulase 1 0.01 - - 0.01 Cellulase ll 0.005 0.01 Protease 0.05 0.01 0.02 0.03 0.005 0.005 EDTA* - - 2.90 2.90 Na Citrate - - - - 2.90 2.90 , CA 022~4069 l998-ll-l2 W O 97/43385 PCTrUS97/08103 -NaC12 Alkyl benzene 1.95 - 1.95 - 1.95 sulfonate NaC12 Alkyl sulfate - 2.20 - 2.20 - 2.20 NaC1 2~ethoxy) - 2.20 - 2.20 - 2.20 * *sulfate C12 Dimethylamine - 0.50 - 0.50 - 0.50 oxide SCS 1.30 - 1.30 - 1.30 Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30 Water Balance to 100%

*Na4 ethylenediamine diacetic acid **Diethylene glycol monohexyl ether ***AII formulas adjusted to pH 7 ExamPle 1 9 The following spray composition for cleaning of hard surfaces and removing household mildew was prepared in accord with the present invention:

Amylase 1 0.005 Amylase ll 0 005 Cellulase I
Cellulase ll 0.01 Protease 0.01 Sodium octyl sulfate 2.00 Sodium dodecyl sulfate 4.00 Sodium hydroxide 0.80 Silicate (Na) 0.04 Perf ume 0 3 5 Water/minors up to 100%

Claims (11)

1. A detergent composition characterised in that said detergent composition comprises at least two .alpha.-amylases.

2. A detergent composition according to claim 1 wherein said .alpha.-amylases are comprised at a level of from 0.0001% to 0.1%, preferably from 0.0002% to 0.06%, more preferably from 0.0003% to 0.05% total pure .alpha.-amylase enzymes by weight of total composition.

3. A detergent composition according to any of the preceding claims wherein said .alpha.-amylases are an .alpha.-amylase derived from Bacillus licheniformis and an .alpha.-amylase variant comprising a C-terminal part of an .alpha.-amylase derived from B. licheniformis and a N-terminal part of an .alpha.-amylase derived from B. amyloliquefaciens or from B.
stearothermophilus wherein the Met amino acid residue at position 197 has been substituted preferably by a Leu, Thr, Ala, Gly, Ser, Ile or Asp amino acid residue.

4. A detergent composition according to any of the preceding claims further comprising a cellulase.

5. A detergent composition according to claim 4 wherein said cellulase is a 50kD endoglucanase or 43kD endoglucanase.

6. 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, builder, bleach system, suds suppressors, soil suspension and anti-redeposition agents, smectite clays and the like.

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

8. A detergent composition according to claim 7 wherein said other enzyme is a protease.

9. A detergent composition according to claims 7-8 wherein said other enzyme is a lipase.

10. A detergent composition according to claims 1-9 which is in the form of a detergent additive.

11. Use of a combination of .alpha.-amylases in detergent compositions for odor control.