WO2008007318A2 - Detergent compositions - Google Patents

Abstract

This invention relates to laundry detergent compositions comprising bacterial alkaline enzymes exhibiting endo-beta-l,4-glucanase activity (E.C. 3.2.1.4) and fabric hueing agents.

Description

DETERGENT COMPOSITIONS

FIELD OF THE INVENTION

This invention relates to laundry detergent compositions comprising a bacterial alkaline enzyme exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4) and a fabric hueing agent and processes for making and using such products.

BACKGROUND OF THE INVENTION

Cellulase enzymes have been used in detergent compositions for many years now for their known benefits of depilling, softness and colour care. However, the use of most of cellulases has been limited because of the negative impact that cellulase may have on the tensile strength of the fabrics' fibers by hydrolysing crystalline cellulose. Recently, cellulases with a high specificity towards amorphous cellulose have been developed to exploit the cleaning potential of cellulases while avoiding the negative tensile strength loss. Especially alkaline endo-glucanases have been developed to suit better the use in alkaline detergent conditions.

For example, Novozymes in WO02/099091 discloses a novel enzyme exhibiting endo-beta- glucanase activity (EC 3.2.1.4) endogenous to the strain Bacillus sp., DSM 12648; for use in detergent and textile applications. Novozymes further describes in WO04/053039 detergent compositions comprising an anti-redeposition endo-glucanase and its combination with certain cellulases having increased stability towards anionic surfactant and/or further specific enzymes. Kao's EP 265 832 describes novel alkaline cellulase K, CMCase I and CMCase II obtained by isolation from a culture product of Bacillus sp KSM-635. Kao further describes in EP 1 350 843, alkaline cellulase which acts favourably in an alkaline environment and can be mass produced readily because of having high secretion capacity or having enhanced specific activity.

We have found that the combination of alkaline bacterial endoglucanases and hueing agents deliver improved, synergistic whitening benefits. Without wishing to be bound by theory, it is believed that the following mechanisms are likely to give rise to such benefits: the endoglucanase enzyme hydrolyses amorphous cellulose present on the cotton surface, and thereby assists the removal of yellow soils and opens up the pore structure of the fabric making it more accessible to dye molecules. The resulting combination of improved yellow soil removal and improved shading colorant deposition leads to an improvement in fabric appearance. These combined effects hence contribute to a surprising improvement in visual perception and hence, in cleaning perception.

SUMMARY OF THE INVENTION

The present invention relates to compositions comprising a fabric hueing agent and a bacterial alkaline enzyme exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4).

SEQUENCE LISTINGS SEQ ID NO: 1 shows the amino acid sequence of an endoglucanase from Bacillus sp. AA349

SEQ ID NO: 2 shows the amino acid sequence of an endoglucanase from Bacillus sp KSM-S237

DETAILED DESCRIPTION OF THE INVENTION DEFINITIONS As used herein, the term "cleaning composition" includes, unless otherwise indicated, granular or powder-form all-purpose or "heavy-duty" washing agents, especially laundry detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy- duty liquid types; liquid fine-fabric detergents; as well as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-treat types. As used herein the term 'fabric hueing agent' means dyes or pigments which when formulated in detergent compositions can deposit onto a fabric when said fabric is contacted with a wash liquor comprising said detergent compositions thus altering the tint of said fabric through absorption of visible light. For the purposes of the present application, fluorescent whitening agents, also called optical brighteners, are not considered fabric hueing agents, as they exert their effects on fabric through emission, rather than absorption, of visible light.

COMPOSITIONS

The compositions of the present invention may contain from 0.00003% to 0.1%, from 0.00008% to 0.05%, or even from 0.0001% to 0.04% by weight of one or more fabric hueing agent and from 0.00005% to 0.15%, from 0.0002% to 0.02%, or even from 0.0005% to 0.01% by weight of pure enzyme, of one or more endoglucanase(s). The balance of any aspects of the aforementioned cleaning compositions is made up of one or more adjunct materials. SUITABLE ENDOGLUCANASE

The endoglucanase to be incorporated into the detergent composition of the present invention is one or more bacterial alkaline enzyme(s) exhibiting endo-beta-1,4-glucanase activity (E.C.

3.2.1.4).

As used herein, the term "alkaline endoglucanase", shall mean an endoglucanase having an optimum pH above 7 and retaining greater than 70% of its optimal activity at pH10.

Preferably, the endoglucanase is a bacterial polypeptide endogenous to a member of the genus Bacillus.

More preferably, the alkaline enzyme exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), is a polypeptide containing (i) at least one family 17 carbohydrate binding module (Family 17 CBM) and/or (ii) at least one family 28 carbohydrate binding module (Family 28 CBM). Please refer for example to: Current Opinion in Structural Biology, 2001, 593-600 by Y. Bourne and B. Henrissat in their article entitled: "Glycoside hydrolases and glycosyltransferases: families and functional modules" for the definition and classification of CBMs. Please refer further to Biochemical Journal, 2002, v361, 35-40 by A.B. Boraston et al in their article entitled: "Identification and glucan-binding properties of a new carbohydrate-binding module family" for the properties of the family 17 and 28 CBM' s.

In a more preferred embodiment, said enzyme comprises a polypeptide (or variant thereof) endogenous to one of the following Bacillus species:

Suitable endoglucanases for the compositions of the present invention are: 1) An enzyme exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4), which has a sequence of at least 90%, preferably 94%, more preferably 97% and even more preferably 99%, 100% identity to the amino acid sequence of position 1 to position 773 of SEQ ID NO: 1 (Corresponding to SEQ ID NO:2 in WO02/099091); or a fragment thereof that has endo-beta- 1,4-glucanase activity, when identity is determined by GAP provided in the GCG program using a GAP creation penalty of 3.0 and GAP extension penalty of 0.1. The enzyme and the corresponding method of production is described extensively in patent application WO02/099091 published by Novozymes A/S on December 12, 2002. Please refer to the detailed description pages 4 to 17 and to the examples page 20 to page 26. One of such enzyme is commercially available under the tradename Celluclean™ by Novozymes A/S.

GCG refers to the sequence analysis software package provided by Accelrys, San Diego, CA, USA. This incorporates a program called GAP which uses the algorithm of Needleman and Wunsch to find the alignment of two complete sequences that maximises the number of matches and minimises the number of gaps.

2) Also suitable are the alkaline endoglucanase enzymes described in EP 1 350 843A published by Kao corporation on October 8, 2003._ Please refer to the detailed description [0011] to [0039] and examples 1 to 4 [0067] to [0077] for a detailed description of the enzymes and its production. The alkaline cellulase variants are obtained by substituting the amino acid residue of a cellulase having an amino acid sequence exhibiting at least 90%, preferably 95%, more preferably 98% and even 100% identity with the amino acid sequence represented by SEQ. ID NO:2 (Corresponding to SEQ. ID NO: 1 in EP 1 350 843 on pages 11-13) at (a) position 10, (b) position 16, (c) position 22, (d) position 33, (e) position 39, (f) position 76, (g) position 109, (h) position 242, (i) position 263, (j) position 308, (k) position 462, (1) position 466, (m) position 468, (n) position 552, (o) position 564, or (p) position 608 in SEQ ID NO:2 or at a position corresponding thereto with another amino acid residue

Examples of the "alkaline cellulase having the amino acid sequence represented by SEQ. ID NO:2" include Egl-237 [derived from Bacillus sp. strain KSM-S237 (FERM BP-7875), Hakamada, et al., Biosci. Biotechnol. Biochem., 64, 2281-2289, 2000]. Examples of the "alkaline cellulase having an amino acid sequence exhibiting at least 90% homology with the amino acid sequence represented by SEQ. ID NO:2" include alkaline cellulases having an amino acid sequence exhibiting preferably at least 95% homology, more preferably at least 98% homology, with the amino acid sequence represented by SEQ. ID NO:2. Specific examples include alkaline cellulase derived from Bacillus sp. strain 1139 (EgI- 1139) (Fukumori, et al., J. Gen. Microbiol., 132, 2329-2335) (91.4% homology), alkaline cellulases derived from Bacillus sp. strain KSM-64 (Egl-64) (Sumitomo, et al., Biosci. Biotechnol. Biochem., 56, 872-877, 1992) (homology: 91.9%), and cellulase derived from Bacillus sp. strain KSM-N131 (Egl-N131b) (Japanese Patent Application No. 2000-47237) (homology: 95.0%).

The amino acid is preferably substituted by: glutamine, alanine, proline or methionine, especially glutamine is preferred at position (a), asparagine or arginine, especially asparagine is preferred at position (b), proline is preferred at position (c), histidine is preferred at position (d), alanine, threonine or tyrosine, especially alanine is preferred at position (e), histidine, methionine, valine, threonine or alanine, especially histidine is preferred at position (f), isoleucine, leucine, serine or valine, especially isoleucine is preferred at position (g), alanine, phenylalanine, valine, serine, aspartic acid, glutamic acid, leucine, isoleucine, tyrosine, threonine, methionine or glycine, especially alanine, phenylalanine or serine is preferred at position (h), isoleucine, leucine, proline or valine, especially isoleucine is preferred at position (i), alanine, serine, glycine or valine, especially alanine is preferred at position (j), threonine, leucine, phenylalanine or arginine, especially threonine is preferred at position (k), leucine, alanine or serine, especially leucine is preferred at position (1), alanine, aspartic acid, glycine or lysine, especially alanine is preferred at position (m), methionine is preferred at position (n), valine, threonine or leucine, especially valine is preferred at position (o) and isoleucine or arginine, especially isoleucine is preferred at position (p).

The "amino acid residue at a position corresponding thereto" can be identified by comparing amino acid sequences by using known algorithm, for example, that of Lipman- Pearson's method, and giving a maximum similarity score to the multiple regions of simirality in the amino acid sequence of each alkaline cellulase. The position of the homologous amino acid residue in the sequence of each cellulase can be determined, irrespective of insertion or depletion existing in the amino acid sequence, by aligning the amino acid sequence of the cellulase in such manner (Fig. 1 of EP 1 350 843). It is presumed that the homologous position exists at the three- dimensionally same position and it brings about similar effects with regard to a specific function of the target cellulase.

With regard to another alkaline cellulase having an amino acid sequence exhibiting at least 90% homology with SEQ. ID NO:2, specific examples of the positions corresponding to (a) position 10, (b), position 16, (c) position 22, (d) position 33, (e) position 39, (f) position 76, (g) position 109, (h) position 242, (i) position 263, (j) position 308, (k) position 462, (1) position 466, (m) position 468, (n) position 552, (o) position 564 and (p) position 608 of the alkaline cellulase (Egl-237) represented by SEQ. ID NO: 2 and amino acid residues at these positions will be shown below:

3) Also suitable is the alkaline cellulase K described in EP 265 832A published by Kao on May 4, 1988. Please refer to the description page 4, line 35 to page 12, line 22 and examples 1 and 2 on page 19 for a detailed description of the enzyme and its production. The alkaline cellulase K has the following physical and chemical properties:

• (1) Activity: Having a Cx enzymatic activity of acting on carboxymethyl cellulose along with a weak C₁ enzymatic activity and a weak beta-glucoxidase activity;

• (2) Specificity on Substrates: Acting on carboxymethyl cellulose(CMC), crystalline cellulose, Avicell, cellobiose, and p-nitrophenyl cellobioside(PNPC);

• (3) Having a working pH in the range of 4 to 12 and an optimum pH in the range of 9 to

10;

• (4) Having stable pH values of 4.5 to 10.5 and 6.8 to 10 when allowed to stand at 40°C for 10 minutes and 30 minutes, respectively;

• (5) Working in a wide temperature range of from 10 to 65 °C with an optimum temperature being recognized at about 40°C;

• (6) Influences of chelating agents: The activity not impeded with ethylenediamine tetraacetic acid (EDTA), ethyleneglycol-bis-(β-aminoethylether) N,N,N',N"-tetraacetic acid (EGTA), N,N-bis(carboxymethyl)glycine (nitrilotriacetic acid) (NTA), sodium tripolyphosphate (STPP) and zeolite; • (7) Influences of surface active agents: Undergoing little inhibition of activity by means of surface active agents such as sodium linear alkylbenzenesulfonates (LAS), sodium alkylsulfates (AS), sodium polyoxyethylene alkylsulfates (ES), sodium alpha- olefinsulfonates (AOS), sodium alpha- sulfonated aliphatic acid esters (alpha-SFE), sodium alkylsulfonates (SAS), polyoxyethylene secondary alkyl ethers, fatty acid salts

(sodium salts), and dimethyldialkylammonium chloride;

• (8) Having a strong resistance to proteinases; and

• (9) Molecular weight (determined by gel chromatography): Having a maximum peak at 180,000 + 10,000.

Preferably such enzyme is obtained by isolation from a culture product of Bacillus sp KSM-

635.

Cellulase K is commercially available by the Kao Corporation: e.g. the cellulase preparation Eg- X known as KAC® being a mixture of E-H and E-L both from Bacillus sp. KSM-635 bacterium. Cellulases E-H and E-L have been described in S. Ito, Extremophiles, 1997, vl, 61-66 and in S. Ito et al, Agric Biol Chem, 1989, v53, 1275-1278.

4) The alkaline bacterial endoglucanases described in EP 271 004A published by Kao on June

15, 1988 are also suitable for the purpose of the present invention. Please refer to the description page 9, line 15 to page 23, line 17 and page 31, line 1 to page 33, line 17 for a detailed description of the enzymes and its production. Those are:

Alkaline Cellulase K-534 from KSM 534, FERM BP 1508,

Alkaline Cellulase K-539 from KSM 539, FERM BP 1509,

Alkaline Cellulase K-577 from KSM 577, FERM BP 1510,

Alkaline Cellulase K-521 from KSM 521, FERM BP 1507, Alkaline Cellulase K-580 from KSM 580, FERM BP 1511,

Alkaline Cellulase K-588 from KSM 588, FERM BP 1513,

Alkaline Cellulase K-597 from KSM 597, FERM BP 1514,

Alkaline Cellulase K-522 from KSM 522, FERM BP 1512,

Alkaline Cellulase E-II from KSM 522, FERM BP 1512, Alkaline Cellulase E-III from KSM 522, FERM BP 1512. Alkaline Cellulase K-344 from KSM 344, FERM BP 1506, and Alkaline Cellulase K-425 from KSM 425, FERM BP 1505.

5) Finally, the alkaline endoglucanases derived from Bacillus species KSM-N described in JP2005287441A, published by Kao on the October 20^th, 2005, are also suitable for the purpose of the present invention. Please refer to the description page 4, line 39 to page 10, line 14 for a detailed description of the enzymes and its production. Examples of such alkaline endoglucanases are:

Alkaline Cellulase Egl-546H from Bacillus sp. KSM-N546 Alkaline Cellulase EgI-115 from Bacillus sp. KSM-Nl 15 Alkaline Cellulase EgJ- 145 from Bacillus sp. KSM-N145 Alkaline Cellulase Egl-659 from Bacillus sp.KSM-N659 Alkaline Cellulase Egl-640 from Bacillus sp.KSM-N440

Also encompassed in the present invention are variants of the above described enzymes obtained by various techniques known by persons skilled in the art such as directed evolution.

FABRIC HUEING AGENTS

Fluorescent whitening agents emit at least some visible light. In contrast, fabric hueing agents can alter the tint of a surface as they absorb at least a portion of the visible light spectrum. Suitable fabric hueing agents include dyes and dye-clay conjugates, and may also include pigments. In one aspect, suitable fabric hueing agents include those fabric hueing agents that satisfy the requirements of Test Method 1 in the Test Method Section of the present specification. Suitable dyes include small molecule dyes and polymeric dyes.

Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (CI.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red, or mixtures thereof, for example:

(1) Tris-azo direct blue dyes of the formula

where at least two of the A, B and C napthyl rings are substituted by a sulfonate group, the C ring may be substituted at the 5 position by an NH₂ or NHPh group, X is a benzyl or naphthyl ring substituted with up to 2 sulfonate groups and may be substituted at the 2 position with an OH group and may also be substituted with an NH₂ or NHPh group.

(2) bis-azo Direct violet dyes of the formula:

where Z is H or phenyl, the A ring is preferably substituted by a methyl and methoxy group at the positions indicated by arrows, the A ring may also be a naphthyl ring, the Y group is a benzyl or naphthyl ring, which is substituted by sulfate group and may be mono or disubstituted by methyl groups.

(3) Blue or red acid dyes of the formula

where at least one of X and Y must be an aromatic group. In one aspect, both the aromatic groups may be a substituted benzyl or naphthyl group, which may be substituted with non water- solubilising groups such as alkyl or alkyloxy or aryloxy groups, X and Y may not be substituted with water solubilising groups such as sulfonates or carboxylates. In another aspect, X is a nitro substituted benzyl group and Y is a benzyl group

(4) Red acid dyes of the structure

or

where B is a naphthyl or benzyl group that may be substituted with non water solubilising groups such as alkyl or alkyloxy or aryloxy groups, B may not be substituted with water solubilising groups such as sulfonates or carboxylates.

(5) Dis-azo dyes of the structure

wherein X and Y, independently of one another, are each hydrogen, C₁-C₄ alkyl or C₁-C₄-alkoxy, Ra is hydrogen or aryl, Z is C₁-C₄ alkyl; C₁-C₄-alkoxy; halogen; hydroxyl or carboxyl, n is 1 or 2 and m is 0, 1 or 2, as well as corresponding salts thereof and mixtures thereof (6) Triphenylmethane dyes of the following structures

and mixtures thereof.

In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159 and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Acid Violet 17, Acid Violet 43, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, Direct Violet 51 and mixtures thereof.

In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.

In another aspect, suitable small molecule dyes include photobleaches which satisfy the requirements of Test Method 1 in the Test Method Section. Such materials function as both fabric hueing dyes and also as photobleaching agents, i.e. they generate bleaching species on exposure to light. Suitable photobleaches include catalytic photobleaches selected from the group consisting of water soluble phthalocyanines of the formula:

in which: PC is the phthalocyanine ring system;

Me is Zn; Fe(II); Ca; Mg; Na; K; Al-Z₁; Si(IV) ; P(V); Ti(IV); Ge(IV);

Cr(VI); Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI) ;

Z₁ is a halide; sulfate; nitrate; carboxylate; alkanolate; or hydroxyl ion; q is 0; 1 or 2; r is 1 to 4;

Qi₁ is a sulfo or carboxyl group; or a radical of the formula -SO₂X₂-Ri -X3⁺; - 0-Ri-X₃ ⁺; or -(CH₂),-Yi⁺; in which

R₁ is a branched or unbranched C₁-Cg alkylene; or 1,3- or 1,4-phenylene;

X₂ is -NH-; or -N-C₁-C₅ alkyl; X₃ ⁺ is a group of the formula

or, in the case where R₁ = C₁-C₈alkylene, also a group of the formula

Yi⁺ is a group of the formula

t is 0 or 1 where in the above formulae

R₂ and R3 independently of one another are C₁-C₆ alkyl

R₄ is C₁-C₅ alkyl; C₅-C₇ cycloalkyl or NR₇R₈;

R₅ and R₆ independently of one another are C₁-C₅ alkyl;

R₇ and R₈ independently of one another are hydrogen or C₁-C₅ alkyl; R₉ and R₁O independently of one another are unsubstituted C₁-C₆ alkyl or C₁-C₆ alkyl substituted by hydroxyl, cyano, carboxyl, carb-C₁-C₆ alkoxy, C₁-C₆ alkoxy, phenyl, naphthyl or pyridyl; u is from 1 to 6;

A₁ is a unit which completes an aromatic 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain one or two further nitrogen atoms as ring members, and

B₁ is a unit which completes a saturated 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain 1 to 2 nitrogen, oxygen and/or sulfur atoms as ring members; Q₂ is hydroxyl; C₁- C₂₂ alkyl; branched C3-C₂₂ alkyl; C₂- C₂₂ alkenyl; branched C3-C₂₂ alkenyl and mixtures thereof; C₁-C₂₂ alkoxy; a sulfo or carboxyl radical; a radical of the formula

a branched alkoxy radical of the formula

an alkylethyleneoxy unit of the formula

or an ester of the formula

COOR₁₈ in which

B₂ is hydrogen; hydroxyl; C₁-C₃₀ alkyl; C₁- C₃₀ alkoxy; -CO₂H; -CH₂COOH; -SO₃-M₁; - OSO₃-M₁ ; -PO₃ ² M₁ ; -OPO₃ ² M₁ ; and mixtures thereof;

B₃ is hydrogen; hydroxyl; -COOH; -SO₃-M₁; -OSO₃ M₁ or C₁-C₆ alkoxy;

M₁ is a water-soluble cation;

T₁ is-O-; or-NH-;

X₁ and X₄ independently of one another are -0-; -NH- or -N-C₁-C₅alkyl; R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo group and salts thereof; a carboxyl group and salts thereof or a hydroxyl group; at least one of the radicals R₁₁ and

R₁₂ being a sulfo or carboxyl group or salts thereof,

Y₂ is -0-; -S-; -NH- or -N-C₁-C₅alkyl;

R₁₃ and R₁₄ independently of one another are hydrogen; C₁-C₆ alkyl; hydroxy-C₁-C₆ alkyl; cyano-C₁-C₆ alkyl; sulfo- C₁-C₆ alkyl; carboxy or halogen-C₁-C₆ alkyl; unsubstituted phenyl or phenyl substituted by halogen, C₁-C₄ alkyl or C₁-C₄ alkoxy; sulfo or carboxyl or R₁₃ and

R₁₄ together with the nitrogen atom to which they are bonded form a saturated 5- or 6- membered heterocyclic ring which may additionally also contain a nitrogen or oxygen atom as a ring member; Ri5 and R₁₆ independently of one another are C₁-C₆ alkyl or aryl-C₁-C₆ alkyl radicals;

R₁₇ is hydrogen; an unsubstituted C₁-C₆ alkyl or C₁-C₆ alkyl substituted by halogen, hydroxyl, cyano, phenyl, carboxyl, carb-C₁-C₆ alkoxy or C₁-C₆ alkoxy;

R₁₈ is C₁- C₂₂ alkyl; branched C₃-C₂₂ alkyl; C₁-C₂₂ alkenyl or branched C₃- C₂₂ alkenyl; C₃-

C₂₂ glycol; C₁-C₂₂ alkoxy; branched C₃-C₂₂ alkoxy; and mixtures thereof; M is hydrogen; or an alkali metal ion or ammonium ion,

Z₂ ^" is a chlorine; bromine; alkylsulfate or arylsulfate ion; a is 0 or 1 ; b is from 0 to 6; c is from 0 to 100; d is O; or l; e is from 0 to 22; v is an integer from 2 to 12; w is 0 or 1 ; and A- is an organic or inorganic anion, and s is equal to r in cases of monovalent anions A- and less than or equal to r in cases of polyvalent anions, it being necessary for A_s- to compensate the positive charge; where, when r is not equal to 1, the radicals Qi can be identical or different, and where the phthalocyanine ring system may also comprise further solubilising groups;

Other suitable catalytic photobleaches include (i) xanthene dyes and mixtures thereof; and (ii) those selected from the group consisting of sulfonated zinc phthalocyanine, sulfonated aluminium phthalocyanine, Eosin Y, Phoxine B, Rose Bengal, C.I. Food Red 14 and mixtures thereof.

In another embodiment, fabric hueing dyes include photobleach-dye conjugates. Such materials contain at least one chromogen and at least one photobleach moiety in the same molecule. These include materials comprising at least one Zn-, Ca-, Mg-, Na-, K-, Al-, Si-, Ti-,

Ge-, Ga-, Zr-, In- or Sn-phthalocyanine to which at least one dyestuff is attached through a covalent bonding. Examples of suitable materials are given below.

Suitable polymeric dyes include polymeric dyes selected from the group consisting of olymers containing conjugated chromogens (dye-polymer conjugates) and polymers with hromogens co-polymerised into the backbone of the polymer and mixtures thereof. n another aspect, suitable polymeric dyes include polymeric dyes selected from the group onsisting of fabric-substantive colorants sold under the name of Liquitint® (Milliken, partanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive ye and a polymer selected from the group consisting of polymers comprising a moiety selected om the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In still another aspect, suitable polymeric dyesnclude polymeric dyes selected from the group consisting of Liquitint® (Milliken, Spartanburg, outh Carolina, USA) Violet CT, carboxymethyl cellulose (CMC) conjugated with a reactive lue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold y Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code -ACMC and mixtures thereof.

Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof. In another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of one cationic/basic dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through 11, and a clay selected from the group consisting of 20

Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof. In still another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green Gl C.I. 42040 conjugate, Montmorillonite Basic Red Rl C.I. 45160 conjugate, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate, Hectorite Basic Green Gl C.I. 42040 conjugate, Hectorite Basic Red Rl C.I. 45160 conjugate, Hectorite C.I. Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate, Saponite Basic Green Gl C.I. 42040 conjugate, Saponite Basic Red Rl C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate and mixtures thereof.

Suitable pigments include pigments selected from the group consisting of flavanthrone, indanthrone, chlorinated indanthrone containing from 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide, wherein the imide groups

5 may be unsubstituted or substituted by C1-C3 -alkyl or a phenyl or heterocyclic radical, and wherein the phenyl and heterocyclic radicals may additionally carry substituents which do not confer solubility in water, anthrapyrimidinecarboxylic acid amides, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper

10 phthalocyanine containing up to 14 bromine atoms per molecule and mixtures thereof.

In another aspect, suitable pigments include pigments selected from the group consisting of Ultramarine Blue (CI. Pigment Blue 29), Ultramarine Violet (CI. Pigment Violet 15) and mixtures thereof. In one aspect, Applicant's invention does not include Ultramarine Blue.

15 The aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used). Suitable fabric hueing agents can be purchased from Aldrich, Milwaukee, Wisconsin, USA; Ciba Specialty Chemicals, Basel, Switzerland; BASF, Ludwigshafen, Germany; Dayglo Color Corporation, Mumbai, India; Organic Dyestuffs Corp., East Providence, Rhode Island, USA; Dystar, Frankfurt, Germany; Lanxess, Leverkusen, 21

Germany; Megazyme, Wicklow, Ireland; Clariant, Muttenz, Switzerland; Avecia, Manchester, UK and/or made in accordance with the examples contained herein.

Adjunct Materials

5 While not essential for the purposes of the present invention, the non-limiting list of adjuncts illustrated hereinafter are suitable for use in the instant compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance cleaning performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the cleaning composition as is the case with perfumes, colorants, dyes or the like. The precise nature

10 of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used. Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, additional enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed

15 peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 Bl and 6,326,348 Bl that are incorporated by reference. When one or more

20 adjuncts are present, such one or more adjuncts may be present as detailed below:

Bleaching Agents - The cleaning compositions of the present invention may comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include other photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids and mixtures thereof. In general, when a bleaching agent is used, the compositions of 25 the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent by weight of the subject cleaning composition. Examples of suitable bleaching agents include:

(1) other photobleaches for example Vitamin K3;

(2) preformed peracids: Suitable preformed peracids include, but are not limited to, compounds 30 selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxone ®, and 22 mixtures thereof. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R-(C=O)O-O-M wherein R is an alkyl group, optionally branched, having, when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and 5 M is a counterion, for example, sodium, potassium or hydrogen;

(3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof. In one aspect of the invention the inorganic perhydrate salts are selected from the group consisting of sodium salts of perborate,

10 percarbonate and mixtures thereof. When employed, inorganic perhydrate salts are typically present in amounts of from 0.05 to 40 wt%, or 1 to 30 wt% of the overall composition and are typically incorporated into such compositions as a crystalline solid that may be coated. Suitable coatings include, inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty

15 soaps; and

(4) bleach activators having R-(C=O)-L wherein R is an alkyl group, optionally branched, having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group. Examples of suitable leaving groups are benzoic

20 acid and derivatives thereof - especially benzene sulphonate. Suitable bleach activators include dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS). Suitable bleach activators are also disclosed in WO 98/17767. While any suitable bleach activator may be employed, in one aspect

25 of the invention the subject cleaning composition may comprise NOBS, TAED or mixtures thereof.

When present, the peracid and/or bleach activator is generally present in the composition in an amount of from about 0.1 to about 60 wt%, from about 0.5 to about 40 wt % or even from about 0.6 to about 10 wt% based on the composition. One or more hydrophobic peracids or precursors 30 thereof may be used in combination with one or more hydrophilic peracid or precursor thereof. 23

The amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.

Surfactants - The cleaning compositions according to the present invention may comprise a 5 surfactant or surfactant system wherein the surfactant can be selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semi- polar nonionic surfactants and mixtures thereof. When present, surfactant is typically present at a level of from about 0.1% to about 60%, from about 1% to about 50% or even from about 5% to about 40% by weight of the subject composition.

10 Builders - The cleaning compositions of the present invention may comprise one or more detergent builders or builder systems. When a builder is used, the subject composition will typically comprise at least about 1%, from about 5% to about 60% or even from about 10% to about 40% builder by weight of the subject composition.

Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts

15 of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders and polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-

2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine

20 tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Chelating Agents - The cleaning compositions herein may contain a chelating agent. Suitable chelating agents include copper, iron and/or manganese chelating agents and mixtures thereof. 25 When a chelating agent is used, the subject composition may comprise from about 0.005% to about 15% or even from about 3.0% to about 10% chelating agent by weight of the subject composition.

Dye Transfer Inhibiting Agents - The cleaning compositions of the present invention may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting

30 agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and 24 polyvinylimidazoles or mixtures thereof. When present in a subject composition, the dye transfer inhibiting agents may be present at levels from about 0.0001% to about 10%, from about 0.01% to about 5% or even from about 0.1% to about 3% by weight of the composition.

Fluorescent whitening agent - The cleaning compositions of the present invention will preferably

5 also contain additional components that may tint articles being cleaned, such as fluorescent whitening agent. Any fluorescent whitening agent suitable for use in a laundry detergent composition may be used in the composition of the present invention. The most commonly used fluorescent whitening agents are those belonging to the classes of diaminostilbene-sulphonic acid derivatives, diarylpyrazoline derivatives and bisphenyl-distyryl derivatives. Examples of the

10 diaminostilbene-sulphonic acid derivative type of fluorescent whitening agents include the sodium salts of:

4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulphonate,

4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino) stilbene-2.2'-disulphonate,

4,4'-bis-(2-anilino-4(N-methyl-N-2-hydroxy-ethylamino)-s-triazin-6-ylamino) stilbene-2,2'- 15 disulphonate,

4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)stilbene-2,2'-disulphonate,

4,4'-bis-(2-anilino-4(l-methyl-2-hydroxy-ethylamino)-s-triazin-6-ylamino) stilbene-2,2'- disulphonate and,

2-(stilbyl-4"-naptho-l.,2':4,5)-1,2,3-trizole-2"-sulphonate.

20 Preferred fluorescent whitening agents are Tinopal® DMS and Tinopal® CBS available from Ciba-Geigy AG, Basel, Switzerland. Tinopal® DMS is the disodium salt of 4,4'-bis-(2- morpholino-4 anilino-s-triazin-6-ylamino) stilbene disulphonate. Tinopal® CBS is the disodium salt of 2,2'-bis-(phenyl-styryl) disulphonate.

25 Also preferred are fluorescent whitening agents of the structure:

HpNL ,NH

25 wherein Rl and R2, together with the nitrogen atom linking them, form an unsubstituted or Cl- C4 alkyl- substituted morpholino, piperidine or pyrrolidine ring, preferably a morpholino ring (commercially available as Parawhite KX, supplied by Paramount Minerals and Chemicals, Mumbai, India)

5 Other fluorescers suitable for use in the invention include the 1-3-diaryl pyrazolines and the 7- alkylaminocoumarins .

Suitable fluorescent brightener levels include lower levels of from about 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.

Dispersants - The compositions of the present invention can also contain dispersants. Suitable 10 water-soluble organic materials include 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.

Enzymes - In addition to the bacterial alkaline endoglucanase, the cleaning compositions can comprise one or more other enzymes which provide cleaning performance and/or fabric care

15 benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, other cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. In a

20 preferred embodiment, the compositions of the present invention will further comprise a lipase, for further improved cleaning and whitening performance. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase. When present in a cleaning composition, the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about

25 0.001% to about 0.5% enzyme protein by weight of the composition.

Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes. In case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a 30 boron compound, can be added to further improve stability. 26

Catalytic Metal Complexes - Applicants' cleaning compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little 5 or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water- soluble salts thereof. Such catalysts are disclosed in U.S. 4,430,243.

If desired, the compositions herein can be catalyzed by means of a manganese compound. Such 10 compounds and levels of use are well known in the art and include, for example, the manganese- based catalysts disclosed in U.S. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. 5,597,936; U.S. 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. 5,597,936, and U.S. 5,595,967.

15 Compositions herein may also suitably include a transition metal complex of ligands such as bispidones (WO 05/042532 Al) and/or macropolycyclic rigid ligands - abbreviated as "MRLs". As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per hundred million of the active MRL species in the aqueous washing medium, and will typically provide from about 0.005 ppm to

20 about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.

Suitable transition-metals in the instant transition-metal bleach catalyst include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-1,5,8,12- tetraazabicyclo[6.6.2]hexadecane.

25 Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. 6,225,464.

Solvents - Suitable solvents include water and other solvents such as lipophilic fluids. Examples of suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines, perfluorinated and 27 hydrofluoroether solvents, low-volatility nonfluorinated organic solvents, diol solvents, other environmentally-friendly solvents and mixtures thereof.

Softening system - the compositions of the invention may comprise a softening agent such as clay and optionally also with flocculants and enzymes; optionally for softening through the wash.

5

Processes of Making Compositions

The compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator, non- limiting examples of which are described in Applicants' examples and in U.S. 4,990,280; U.S. 20030087791A1; U.S. 20030087790A1; 10 U.S. 20050003983 Al; U.S. 20040048764A1; U.S. 4,762,636; U.S. 6,291,412; U.S. 20050227891 Al; EP 1070115A2; U.S. 5,879,584; U.S. 5,691,297; U.S. 5,574,005; U.S. 5,569,645; U.S. 5,565,422; U.S. 5,516,448; U.S. 5,489,392; U.S. 5,486,303 all of which are incorporated herein by reference.

15 Method of Use

The present invention includes a method for laundering a fabric. The method comprises the steps of contacting a fabric to be laundered with a said cleaning laundry solution comprising at least one embodiment of Applicants' cleaning composition, cleaning additive or mixture thereof. The fabric may comprise most any fabric capable of being laundered in normal consumer use

20 conditions. The solution preferably has a pH of from about 8 to about 10.5. The compositions may be employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. The water temperatures typically range from about 5 °C to about 90 °C. The water to fabric ratio is typically from about 1:1 to about 30:1.

25 TEST METHOD 1

Fabric hueing agents are known to those skilled in the art and are described in the present specification. In one non-limiting aspect, suitable fabric hueing agents may be defined by the following test: 28

1.) Fill two tergotometer pots with 800ml of Newcastle upon Tyne, UK, City Water (-12 grains per US gallon total hardness, supplied by Northumbrian Water, Pity Me, Durham, Co. Durham, UK).

2) Insert pots into tergotometer, with water temperature controlled at 30°C and agitation set at 5 40rpm for the duration of the experiment

3) Add 4.8g of IEC-B detergent (IEC 60456 Washing Machine Reference Base Detergent Type B), supplied by wfk, Bruggen-Bracht, Germany, to each pot.

4) After two minutes, add 2.0mg active colorant to the first pot.

5) After one minute, add 50g of flat cotton vest (supplied by Warwick Equest, Consett, 10 County Durham, UK), cut into 5cm x 5cm swatches, to each pot.

6) After 10 minutes, drain the pots and re-fill with cold Newcastle upon Tyne City Water (16°C)

7) After 2 minutes rinsing, remove fabrics

8) Repeat steps 3-7 for a further three cycles using the same treatments 15 9) Collect and line dry the fabrics indoors for 12 hours

10) Analyse the swatches using a Hunter Miniscan spectrometer fitted with D65 illuminant and UVA cutting filter, to obtain Hunter a (red-green axis) and Hunter b (yellow-blue axis) values.

11) Average the Hunter a and Hunter b values for each set of fabrics. If the fabrics treated with 20 colorant under assessment show an average difference in hue of greater than 0.2 units on either the a axis or b axis, it is deemed to be a fabric hueing agent for the purpose of the invention.

25 EXAMPLES

Unless otherwise indicated, materials can be obtained from Aldrich, P.O. Box 2060, Milwaukee, WI 53201, USA.

Examples 1-6

Granular laundry detergent compositions designed for handwashing or top-loading washing 30 machines. 29

Any of the above compositions is used to launder fabrics at a concentration of 600 - 10000 ppm in water, with typical median conditions of 2500ppm, 25°C, and a 25:1 water: cloth ratio. Examples 7-10

Granular laundry detergent compositions designed for front-loading automatic washing machines.

Any of the above compositions is used to launder fabrics at a concentration of 10,000 ppm in water, 20-90 °C, and a 5:1 water:cloth ratio. The typical pH is about 10.

Examples 11-16

Heavy Duty Liquid laundry detergent compositions

Raw Materials and Notes For Composition Examples 1-16

Linear alkylbenzenesulfonate having an average aliphatic carbon chain length Cn-Cn supplied by Stepan, Northfield, Illinois, USA C_12-I4 Dimethylhydroxyethyl ammonium chloride, supplied by Clariant GmbH, Sulzbach,

Germany

AE3S is C₁₂-₁₅ alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA

AE7 is C₁₂-i₅ alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by

Huntsman, Salt Lake City, Utah, USA Sodium tripolyphosphate is supplied by Rhodia, Paris, France

Zeolite A was supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK

1.6R Silicate was supplied by Koma, Nestemica, Czech Republic

Sodium Carbonate was supplied by Solvay, Houston, Texas, USA

Polyacrylate MW 4500 is supplied by BASF, Ludwigshafen, Germany Carboxy Methyl Cellulose is Finnfix® BDA supplied by CPKelco, Arnhem, Netherlands

Savinase®, Natalase®, Termamyl®, Mannaway® and Liquanase® supplied by Novozymes,

Bagsvaerd, Denmark

Endoglucanase: Celluclean®, supplied by Novozymes, Bagsvaerd, Denmark

Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 is Tinopal® CBS-X, Sulphonated zinc phthalocyanine and Direct Violet 9 was Pergasol® Violet BN-Z all supplied by

Ciba Specialty Chemicals, Basel, Switzerland

Diethylenetriamine pentacetic acid was supplied by Dow Chemical, Midland, Michigan, USA

Sodium percarbonate supplied by Solvay, Houston, Texas, USA Sodium perborate was supplied by Degussa, Hanau, Germany

NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Eastman, Batesville, Arkansas, USA

TAED is tetraacetylethylenediamine, supplied under the Peractive® brand name by Clariant

GmbH, Sulzbach, Germany S-ACMC is carboxymethylcellulose conjugated with C.I. Reactive Blue 19, sold by Megazyme,

Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC.

Ultramarine Blue was supplied by Holliday Pigments, Kingston upon Hull, UK

Soil release agent is Repel-o-tex® PF, supplied by Rhodia, Paris, France

Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, Germany

Protease described in patent application US 6312936B1 supplied by Genencor International, Palo

Alto, California, USA

Na salt of Ethylenediamine-N,N'-disuccinic acid, (S, S) isomer (EDDS) was supplied by Octel,

Ellesmere Port, UK Hydroxyethane di phosphonate (HEDP) was supplied by Dow Chemical, Midland, Michigan,

USA

Suds suppressor agglomerate was supplied by Dow Corning, Midland, Michigan, USA

HSAS is mid-branched alkyl sulfate as disclosed in US 6,020,303 and US 6,060,443 C_12-I4 dimethyl Amine Oxide was supplied by Procter & Gamble Chemicals, Cincinnati, Ohio, USA

Nonionic is preferably a C₁₂-C₁₃ ethoxylate, preferably with an av degree of ethoxylation of 9.

Liquitint® Violet CT was supplied by Milliken, Spartanburg, South Carolina, USA)

* Numbers quoted in mg enzyme/ lOOg

¹ as described in US 4,597,898.. 2 available under the tradename LUTENSIT® from BASF and such as those described in WO

01/05874

Claims

CLAIMS What is claimed is:

1. A composition comprising a fabric hueing agent and a bacterial alkaline enzyme exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4).

2. A composition according to claim 1 wherein enzyme is a bacterial polypeptide endogenous to a member of the genus Bacillus.

3. A composition according to claims 1-2 wherein the enzyme is a polypeptide containing (i) at least one family 17 carbohydrate binding module and/or (ii) at least one family 28 carbohydrate binding module.

4. A composition according to claims 1-3 wherein the enzyme comprises a polypeptide endogenous to one of the following Bacillus species selected from the group consisting of: AA349 (DSM 12648), KSM S237, 1139, KSM 64, KSM N131, KSM 635 (FERM BP 1485), KSM 534 (FERM BP 1508), KSM 53 (FERM BP 1509), KSM 577 (FERM BP 1510), KSM 521 (FERM BP 1507), KSM 580 (FERM BP 1511), KSM 588 (FERM BP 1513), KSM 597 (FERM BP 1514), KSM 522 (FERM BP 1512), KSM 3445 (FERM BP 1506), KSM 425 (FERM BP 1505), and mixtures thereof.

5. A composition according to claims 1-4 wherein the enzyme is selected from the group consisting of:

(i) the endoglucanase having the amino acid sequence of positions 1 to position 773 of SEQ ID

NO:1;

(ii) an endoglucanase having a sequence of at least 90%, preferably 94%, more preferably 97% and even more preferably 99%, 100% identity to the amino acid sequence of position 1 to position 773 of SEQ ID NO: 1; or a fragment thereof has endo-beta-1,4-glucanase activity, when identity is determined by GAP provided in the GCG program using a GAP creation penalty of 3.0 and GAP extension penalty of 0.1; (iii) mixtures thereof.

6. A composition according to claims 1-4 wherein the enzyme is an alkaline endoglucanase variant obtained by substituting the amino acid residue of a cellulase having an amino acid sequence exhibiting at least 90%, preferably 95%, more preferably 98%, 100% identity with the amino acid sequence represented by SEQ. ID NO:2 at (a) position 10, (b) position 16, (c) position 22, (d) position 33, (e) position 39, (f) position 76, (g) position 109, (h) position 242, (i) position 263, (j) position 308, (k) position 462, (1) position 466, (m) position 468, (n) position 552, (o) position 564, and/or (p) position 608 in SEQ ID NO:2 and/or at a position corresponding thereto with another amino acid residue.

7. A composition according to claim 5 wherein the enzyme is characterised by at least one of the following substitutions:

(a) at position 10: glutamine, alanine, proline or methionine, preferably glutamine;

(b) at position 16: asparagine or arginine, preferably asparagine;

(c) at position 22: proline;

(d) at position 33: histidine;

(e) at position 39: alanine, threonine or tyrosine, preferably alanine;

(f) at position 76: histidine, methionine, valine, threonine or alanine, preferably histidine;

(g) at position 109: isoleucine, leucine, serine or valine, preferably isoleucine;

(h) at position 242: alanine, phenylalanine, valine, serine, aspartic acid, glutamic acid, leucine, isoleucine, tyrosine, threonine, methionine or glycine, preferably alanine, phenylalanine or serine;

(i) at position 263: isoleucine, leucine, proline or valine, preferably isoleucine;

(j) at position 308: alanine, serine, glycine or valine, preferably alanine;

(k) at position 462: threonine, leucine, phenylalanine or arginine, preferably threonine;

(1) at position 466: leucine, alanine or serine, preferably leucine;

(m) at position 468: alanine, aspartic acid, glycine or lysine, preferably alanine;

(n) at position 552: methionine;

(o) at position 564: valine, threonine or leucine, preferably valine; an/or

(p) at position 608: isoleucine or arginine, preferably isoleucine.

8. A composition according to claims 6 and 7 wherein the enzyme is selected from the group consisting of the following endoglucanase variants: Egl-237, Egl-1139, Egl-64, Egl-N131b and mixtures thereof.

9. A composition according to claims 1-4 wherein the enzyme is an alkaline cellulase K having the following physical and chemical properties:

(1) Activity: Having a Cx enzymatic activity of acting on carboxymethyl cellulose along with a weak C₁ enzymatic activity and a weak beta-glucoxidase activity;

(2) Specificity on Substrates: Acting on carboxymethyl cellulose(CMC), crystalline cellulose, Avicell, cellobiose, and p-nitrophenyl cellobioside(PNPC);

(3) Having a working pH in the range of 4 to 12 and an optimum pH in the range of 9 to 10;

(4) Having stable pH values of 4.5 to 10.5 and 6.8 to 10 when allowed to stand at 40°C for 10 minutes and 30 minutes, respectively;

(5) Working in a wide temperature range of from 10 to 65°C with an optimum temperature being recognized at about 40°C;

(6) Influences of chelating agents: The activity not impeded with ethylenediamine tetraacetic acid (EDTA), ethyleneglycol-bis-(β-aminoethylether) N,N,N',N"-tetraacetic acid (EGTA), N,N-bis(carboxymethyl)glycine (nitrilotriacetic acid) (NTA), sodium tripolyphosphate (STPP) and zeolite;

(7) Influences of surface active agents: Undergoing little inhibition of activity by means of surface active agents such as sodium linear alkylbenzenesulfonates (LAS), sodium alkylsulfates (AS), sodium polyoxyethylene alkylsulfates (ES), sodium alphaolefinsulfonates (AOS), sodium alpha- sulfonated aliphatic acid esters (alpha-SFE), sodium alkylsulfonates (SAS), polyoxyethylene secondary alkyl ethers, fatty acid salts (sodium salts), and dimethyldialkylammonium chloride ;

(8) Having a strong resistance to proteinases; and

(9) Molecular weight (determined by gel chromatography): Having a maximum peak at 180,000 ± 10,000.

10. A composition according to claim 9 wherein the alkaline cellulase K is obtained by isolation from a culture product of Bacillus sp KSM-635.

11. A composition according to claims 1-3 wherein the enzyme is selected from the group consisting of:

Alkaline Cellulase K-534 from KSM 534, FERM BP 1508,

Alkaline Cellulase K-539 from KSM 539, FERM BP 1509,

Alkaline Cellulase K-577 from KSM 577, FERM BP 1510,

Alkaline Cellulase K-521 from KSM 521, FERM BP 1507,

Alkaline Cellulase K-580 from KSM 580, FERM BP 1511,

Alkaline Cellulase K-588 from KSM 588, FERM BP 1513,

Alkaline Cellulase K-597 from KSM 597, FERM BP 1514,

Alkaline Cellulase K-522 from KSM 522, FERM BP 1512,

Alkaline Cellulase E-II from KSM 522, FERM BP 1512,

Alkaline Cellulase E-III from KSM 522, FERM BP 1512.

Alkaline Cellulase K-344 from KSM 344, FERM BP 1506,

Alkaline Cellulase K-425 from KSM 425, FERM BP 1505, and mixtures thereof.

12. A composition according to claims 1-3 wherein the enzyme is selected from the group consisting of endoglucanases derived from Bacillus species KSM-N, preferably is the alkaline endoglucanase Egl-546H derived from Bacillus sp. KSM-N546.

13. A composition according to any of the preceding claims wherein the bacterial alkaline enzyme exhibiting endo-beta-1,4-glucanase activity is comprised at a level of from 0.00005% to 0.15%, preferably from 0.0002% to 0.02%, or more preferably from 0.0005% to 0.01% by weight of pure enzyme.

14. A composition according to any of the preceding claims wherein said fabric hueing agent is selected from the group consisting of dyes, dye-clay conjugates, and mixtures thereof.

15. A composition according the any of the preceding claims wherein said hueing agent is comprised at a level of from 00003% to 0.1%, preferably from 0.00008% to 0.05%, or more preferably from 0.0001% to 0.04% by weight.

16. The composition of Claim 14-15 wherein said dyes are selected from the group consisting of small molecule dyes, polymeric dyes, and mixtures thereof, and said dye-clay conjugates are selected from the group consisting of dye clay conjugates comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof.

17. The composition of Claims 14-16 wherein said small molecule dyes are selected from the group consisting of Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159 and mixtures thereof, said polymeric dyes are selected from the group consisting of polymers containing conjugated chromogens, polymers with chromogens co-polymerised into the backbone of the polymer and mixtures thereof, said dye- clay conjugates are selected from dye clay conjugates comprising a dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through 11, and a clay selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof.

18. The composition of Claim 15 comprising a small molecule dye selected from the group consisting of Acid Violet 17, Acid Violet 43, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, Direct Violet 51, and mixtures thereof.

19. The composition of Claim 15 comprising a small molecule dye selected from the group consisting of Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.

20. The composition of Claims 1-13 said wherein said dye is selected from the group consisting of sulfonated zinc phthalocyanine, sulfonated aluminium phthalocyanines, xanthene dyes and mixtures thereof, preferably is xanthene dyes, more preferably is erythrosine (food red 14).

21. A composition according to claims 1-14 wherein the fabric hueing agent is a dye-photobleach conjugate

22. The composition of any of the preceding claims said composition comprising an adjunct material, preferably a lipase enzyme.

23. A composition according to Claim 1 wherein said fabric hueing agent comprises a fabric hueing agent that is a dye and/or a dye-clay conjugates that satisfies the requirements of Test Method 1 of the present specification.

24. A process of cleaning and/or treating a surface or fabric comprising the steps of optionally washing and/or rinsing said surface or fabric, contacting said surface or fabric with the composition of any of the preceding claims, then optionally washing and/or rinsing said surface or fabric.