EP1117770A1 - Laundry detergent and/or fabric care compositions comprising chemical components linked to a cellulose binding domain - Google Patents

Abstract

The present invention relates to an improved chemical entity which comprises a chemical component linked to an amino acid sequence comprising a Cellulose Binding Domain (CBD) having a binding constant (Kr) for crystalline cellulose (Kr-c) of at least 10 l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose. The present invention further relates to laundry detergent and/or fabric care compositions comprising such an improved chemical entity, providing improved fabric care and cleaning benefits and cost effectiveness.

Description

LAUNDRY DETERGENT AND/OR FABRIC CARE COMPOSITIONS COMPRISING CHEMICAL COMPONENTS LINKED TO A CELLULOSE BINDING DOMAIN

Field of the Invention

The present invention relates to an improved chemical entity comprising a chemical component linked to an amino acid sequence comprising a Cellulose Binding Domain (CBD) having a binding constant (Kr) for crystalline cellulose (Kr- c) of at least 10 l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose; and its incorporation in a laundry detergent and/or fabric care composition.

Background of the invention

Modern laundry detergent and/or fabric care compositions contain various detergent ingredients having one or more purposes in obtaining fabrics which are not only clean, fresh and sanitised but also have retained appearance and integrity. Therefore, detergent components such as perfumes, soil release agents, fabric brightening agents, fabric softeners, chelants, bleaching agents and catalysts, dye fixatives and enzymes, have been incorporated in laundry detergent and/or fabric care compositions. In using such detergent components, it is important that some of these compounds deposit on the fabrics so as to be effective during or after the laundering and/or fabric care process. One such example is the use of cellulase enzymes for treatment of fabrics which consist largely of cellulose. The cellulose structures are depolymerized or cleaved into smaller and thereby more soluble or dispersible fractions. This activity in particular on fabrics provides cleaning, rejuvenation, softening and generally improved hand-feel characteristics to the fabric structure. However, it has been difficult to incorporate cellulase enzymes into modern detergents in an effective manner. In this regard, those skilled in the art have sought to use minimal amounts of cellulase to their fullest effectiveness by ensuring that most, if not all, of the cellulase enzyme comprised in the detergent composition deposits on the fabric. For example, optimum cellulases would generally have a binding domain especially suitable for celluloses. Thus guaranteeing that most of the cellulase enzyme included in the detergent composition will deposit or otherwise bind to the fabric during the laundering cycle to achieve its desired results.

Accordingly, there remains a need to formulate laundry detergent and/or fabric care compositions wherein the chemical components have a stronger and enhanced deposition on fabrics, which results in an improved performance during typical washing / fabric care cycles. There is also a need to ensure that chemical components remain more effectively and longer on the fabric or fiber during the additional steps of rinsing and during wear. There also remains a need for such components to be formulated in a more cost-effective manner.

The above objectives has been met by formulating laundry detergent and/or fabric care compositions comprising an improved chemical entity which comprises a chemical component linked to an amino acid sequence comprising a Cellulose Binding Domain (CBD) having a binding constant for crystalline cellulose (Kr-c) of at least 10 l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose.

WO 91/10732 describes novel derivatives of cellulase enzymes combining a core region derived from an endoglucanase producible by a strain of Bacillus spp., NICMB 40250 with a CBD derived from another cellulase enzyme, or combining a core region derived from another cellulase enzyme with a CBD derived from said endoglucanase, for improved binding properties. WO94/07998 describes cellulase variants of a cellulase classified in family 45, comprising a CBD, a Catalytically Active Domain (CAD) and a region linking the CBD to the CAD, wherein one or more amino acid residues have been added, deleted or substituted and /or another CBD is added at the opposite end of the CAD. W095/16782 relates to the cloning and high level expression of novel truncated cellulase proteins or derivatives thereof in Trichoderma longibrachiatum comprising different core regions with several CBDs. WO97/01629 describes cellulolytic enzyme preparation wherein the mobility of the cellulase component may be reduced by adsorption to an insoluble or soluble carrier e.g. via the existing or newly introduced CBD. W097/28243 describes a process for removal or bleaching or soiling or stains from cellulosic fabrics wherein the fabric is contacted in aqueous medium with a modified enzyme which comprises a catalytically active amino acid sequence of a non-cellulolytic enzyme selected from amylases, proteases, lipases, pectinases and oxidoreductases, linked to an amino acid sequence comprising a cellulose binding domain and a detergent composition comprising such modified enzyme and a surfactant. WO98/00500 discloses a composition comprising a protein deposition aid having a high affinity for fibers or a surface and having a benefit agent attached / adsorbed thereto.

However, none of these documents disclose an improved chemical entity with improved deposition which comprises a chemical component linked to an amino acid sequence comprising a Cellulose Binding Domain having a binding constant for crystalline cellulose (Kr-c) of at least 10 l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose. Thereby defining an improved chemical entity which has a very high affinity for cellulose and is especially adapted to selectively bind cotton fibers, i.e. crystalline cellulose, Avicel, and/or amorphous cellulose; and which provides new, superior, enhanced and/or more cost-effective performance of the chemical components in a laundry and/or fabric care application.

Summary of the invention

The present invention relates to an improved chemical entity comprising a chemical component which is linked to an amino acid sequence comprising a Cellulose Binding Domain having a binding constant (Kr) for crystalline cellulose (Kr-c) of at least 10 l/gcellulose - preferably at least 20l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose - preferably 5l/gcellulose. This improved chemical entity has a very high affinity for cellulose and is especially adapted to selectively bind cotton fibers, i.e. crystalline cellulose, Avicel, and/or amorphous cellulose.

The present invention further relates to laundry detergent and/or fabric care compositions comprising one or more improved chemical entity(ies). These compositions provide a new, improved and superior, more cost effective performance of the chemical components.

In addition, the present invention relates to the use of the improved chemical entity to efficiently and effectively deposit a chemical component onto a fabric.

Detailed description of the invention

The present invention relates to an improved chemical entity comprising a chemical component linked to an amino acid sequence comprising a cellulose binding domain specifically selected for having a binding constant (Kr) for crystalline cellulose (Kr-c) of at least 10 l/gcellulose - preferably at least 20l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose - preferably at least 5l/gcellulose.

The object of the present invention is to increase and/or enhance the performance and cost effectiveness of a chemical component by increasing its deposition ability. This object is achieved by the formulation of an improved chemical entity which comprises a chemical component linked to an amino acid sequence comprising a selected cellulose binding domain. It has been surprisingly found that such improved chemical entities wherein the CBD has been particularly selected for its increased deposition to cellulose, more readily affix or otherwise come into contact with the fabric. Thereby it results in new, greater and/or enhanced performance of the chemical component at the fabric surface or when released during or after the laundry and/or fabric care process. Accordingly, this allows to formulate compositions in a more cost-effective manner, with substantially augmented deposition and hence enhanced benefits of the chemical entity.

The present invention encompasses chemical entities with one or more chemical component(s) linked to one or more amino acid sequence(s) comprising one or more cellulose binding domain(s), potentially with one or more linking region(s).

Cellulose Binding Domain (CBD)

In the present context, the terms "amino acid sequence comprising a Cellulose Binding Domain (CBD)" are intended to indicate an amino acid sequence capable of effecting binding of the cellulase to a cellulosic substrate (e.g., as described in P. Kraulis et al., Determination of the three-dimensional structure of the C terminal domain of cellobiohydrolase I from Trichoderma reesei. A study using nuclear magnetic resonance and hybrid distance geometry-dynamically simulated annealing. Biochemistry 28:7241-7257, 1989). The classification and properties of cellulose binding domains are presented in P. Tomme et al., in the symposium "Enzymatic degradation of insoluble polysaccharides" (ACS Symposium Series 618, edited by J.N. Saddler and M.H. Penner, ACS, 1995).

Cellulose-binding (and other carbohydrate-binding) domains are polypeptide amino acid sequences which occur as integral parts of large polypeptides or proteins consisting of two or more polypeptide amino acid sequence regions, especially in hydrolytic enzymes (hydrolases) which typically comprise a catalytic domain containing the active site for substrate hydrolysis and a carbohydrate- binding domain for binding to the carbohydrate substrate in question. Such enzymes can comprise more than one catalytic domain and one, two or three carbohydrate-binding domains, and they may further comprise one or more polypeptide amino acid sequence regions linking the carbohydrate-binding domain(s) with the catalytic domain(s), a region of the latter type usually being denoted a "linker" or "linking region".

Examples of hydrolytic enzymes comprising a cellulose-binding domain are cellulase, xylanases, mannanases, arabinofuranosidases, acetylesterases and chitinases. "Cellulose-binding domains" have also been found in algae, e.g. in the red alga porphyra purpurea in the form of a non-hydrolytic polysaccharide- binding protein [see P. Tomme et al., Cellulose-binding domains - Classification and Properties in Enzymatic Degradation of Insoluble Carbohydrates , John N. Saddler and Michael H. Penner (Eds.), ACS Symposium Series, No. 618 (1996)]. However, most of the known CBDs (which are classified and referred to by P. Tomme et al. (op. cit.) as "cellulose-binding domains") are derived from cellulases and xylanases.

In the present context, the term "cellulose-binding domain" is intended to be understood in the same manner as in the latter reference (P. Tomme et al., op. cit. ) The P. Tomme et al. reference classifies more than 120 "cellulose-binding domains" into 10 families (l-X) which may have different functions or roles in connection with the mechanism of substrate binding. However, it is to be anticipated that new family representatives and additional families will appear in the future.

In proteins/polypeptides in which CBDs occur (e.g. enzymes, typically hydrolytic enzymes such as cellulases), a CBD may be located at the N or C terminus or at an internal position.

The part of a polypeptide or protein (e.g. hydrolytic enzyme) which constitutes a CBD per se typically consists of more than about 30 and less than about 250 amino acid residues. For example, those CBDs listed and classified in Family I in accordance with P. Tomme et al. (op. cit.) consist of 33-37 amino acid residues, those listed and classified in Family lla consist of 95-108 amino acid residues, those listed and classified in Family VI consist of 85-92 amino acid residues, whilst one CBD (derived from a cellulase from Clostridium thermocellum) listed and classified in Family VII consists of 240 amino acid residues. Accordingly, the molecular weight of an amino acid sequence constituting a CBD per se will typically be in the range of from about 4kD to about 40kD, and usually below about 35kD.

Cellulose binding domains can be produced by recombinant techniques as described in H. Stalbrand et al., Applied and Environmental Microbiology, Mar. 1995, pp. 1090-1097; E. Brun et al., (1995) Eur. J. Biochem. 231, pp. 142-148; J.B. Coutinho et al., (1992) Molecular Microbiology 6(9), pp. 1243-1252 In order to isolate a cellulose binding domain of, e.g. a cellulase, several genetic engineering approaches may be used. One method uses restriction enzyme to remove a portion of the gene and then to fuse the remaining gene-vector fragment in frame to obtain a mutated gene that encodes a protein truncated for a particular gene fragment. Another method involves the use of exonucleases such as Ba131 to systematically delete nucleotides either externally from the 5' and the 3' ends of the DNA or internally from a restricted gap within the gene. These gene-deletion methods result in a mutated gene encoding a shortened gene molecule whose expression product may then be evaluated for substrate- binding (e.g. cellulose-binding) ability. Appropriate substrates for evaluating the binding ability include cellulosic materials such as Avicel ™ and cotton fibres. Other methods include the use of a selective or specific protease capable of cleaving a CBD, e.g. a terminal CBD, from the remainder of the polypeptide chain of the protein in question.

Selected Cellulose Binding Domains

The present invention relates to an improved chemical entity wherein the chemical component is linked to one or more an amino acid sequence comprising one or more Cellulose Binding Domain(s) characterised by having a binding constant (Kr) for crystalline cellulose (Kr-c) of at least 10 l/gcellulose, preferably 20l/gcellulose and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose, preferably 5l/gceIlulose; hereinafter referred to as "selected CBD".

The relative binding constant (Kr) for binding to regenerated cellulose

(amorphous - PASC phosphoric acid swollen cellulose), crystalline cellulose

(bacterial microcrystalline cellulose - BMCC), or Avicel (microcrystalline cellulose - Avicel PH101) at 4°C and pH 7.0 is defined as Kr = [Nrj]K_a (as described in P.E. Johnson et al., (1996) Biochem. 35, 13895-13906) and determined from the slope of a plot of 1/[X_D] vs 1/[Xf], using a double-weighted, least-squares analysis; wherein [Nrj] is the concentration of binding sites in the absence of ligand (mol(g of cellulose)^-''), K_a is the equilibrium association constant (L mol^" _> [Xb] '^{s tne} concentration of bound ligand (mol (g of cellulose)^-'') and [Xf] is the concentration of free ligand (molar) (N.R. Gilkes et al., (1992) J. Biol. Chem. 267, pp. 6743-6749).

Microcrystalline cellulose (Avicel PH101) can be obtained from FMC International (Little Island, County Cork, Ireland). Bacterial microcrystalline cellulose (BMCC) can be prepared from cultures of Acetobacter xylinum (ATCC 23769) as described in Gilkes at al. 1992 (supra). Regenerated cellulose (PASC) can be obtained by phosphoric-acid treatment of Avicel PH101 as reported in J. B. Coutinho at al., (1992) Mol. Microbiol. 6, 1243-1252.

Suitable CBDs for the present invention are derived from a fungal or a bacterial strain, preferably from Family I, II, III, or IV according the current classification [See P. Tomme et al. (op cit.)]. Preferred CBDs are CBDs selected from the fungal strain Family I having a binding constant for Avicel (Kr-A) and/or amorphous cellulose (Kr-a) of at least 1.5 l/gcellulose. Also preferred are CBDs selected from the bacterial strain Family II, III, or IV and having a binding constant for crystalline cellulose (Kr-c) of at least 10 l/gcellulose, more preferably 20 l/gcellulose; and/or a binding constant for Avicel (Kr-av) and/or amorphous cellulose (Kr-am) of at least 5 l/gcellulose.

More preferred CBDs for the purpose of the present invention are selected from : CBD E3 cellulase from Thermomonospora fusca, CBD Cellulozome from Clostridium cellulovorans commercially available from Sigma, CBD family 45 originating from the fungal Humicola Insolens cellulase sold under the tradename "Carezyme" by Novo Nordisk A/S, and/or mixtures thereof. Carezyme is an endoglucanase from family 45, derived from Humicola insolens DSM1800, having a molecular weight of about 43kDa and exhibiting cellulolytic activity.

The linking region

The improved chemical entities of the present invention may further comprise one or more linking region(s). The term "linking region" is intended to indicate a region that adjoins the selected CBD(s) and connects it to the chemical component(s). Suitable linking regions, if encompassed in the improved chemical entity of the present invention, are characterized by having one or more attachment point(s) for a chemical component and one or more moiety that will covalently bind to the selected CBD. Preferably, the linking regions of the present invention will encompass at least one attachment point to the cellulose binding domain and more than one reactive group available to attach a chemical component, hereinafter referred to as a "polyreactive linking region". When present, this linking region can be achieved chemically or by recombinant techniques.

Suitable linking regions for the purpose of the present invention are : 1) Suitable are the polyethylene glycol derivatives described in the Shearwater polymers, Inc. catalog of January 1996, such as the nucleophilic PEGs, the carboxyl PEGs, the electrophilically activated PEGs, the sulfhydryl-selective

PEGs, the heterofunctional PEGs, the biotin PEGs, the vinyl derivatives, the

PEG silanes and the PEG phospholipids. In particular, suitable non-amino acid linking regions are the heterofunctional PEG, (X-PEG-Y) polymers from

Shearwater such as PEG(NPC)2, PEG-(NH2)2, t-BOC-NH-PEG-NH2, t-BOC-

NH-PEG-CO2NHS, OH-PEG-NH-tBOC, FMOC-NH-PEG-CO2NHS or PEG(NPC)2 MW 3400 from Sigma.

2) Other suitable linking regions are glutaric dialdehyde 50 wt% solution in water from Aldrich, disuccinimidyl suberate (DSS) form Sigma, γ-maleimidobutyric acid

N-hydroxysuccinimide ester (GMBS) from Sigma, 1-ethyl-3-(3- dimethylaminopropyl)carbodiimide hydrochloride (EDC) from Sigma and dimethyl suberimidate hydrochloride (DMS) from Sigma, 1-ethyl-3-(3- dimethylaminopropyl) carbodiimide, N-ethyl-5-phenylisoaxolium-3-sulphonate, 1- cyclohexyl-3(2morpholinoethyl) carbodide metho-p-toluene sulphonate, N- ethoxycarbonyl-2-ethoxy 1 ,2, dihydroquinoline or glutaraldehyde.

3) Also suitable are the crosslinkers described in the 1999/2000 Pierce Products Catalogue from the Pierce Company, under the heading "Cross linking reagents : the SMPH, SMCC, LC-SMCC compounds, and preferably the Sulfo-KMUS compound.

Preferred linking regions therefrom are PEG(NPC)2, (NH2)2-PEG, t-BOC-NH- PEG-NH2, MAL-PEG-NHS, VS-PEG-NHS polymers from Shearwater and/or the Sulfo-KMUS compound from Pierce.

Suitable polyreactive linking regions include polyacrylic acid/ maleic acid polymers, polyvinyl alcohol polymers and/or amine-containing compounds as described in co-pending application PCT/US98/20491 filed on September 30, 1998 by P&G, hereby incorporated by reference. Such amine-containing compounds include amino aryl derivatives, polyamines, substituted amines and amides, glucamines, dendrimers / chitosan saccharides, amine derivatives polysaccharides and peptidic polymers.

1) Poly acrylic acid/maleic acid : Suitable poly acrylic acid, maleic acid and/or mixtures thereof are those wherein one of the acid moiety is covalently bond to a NH2 group present in the amino acid sequence of the selected CBD. The other acid units are the reactive groups available as potential attachment groups for chemical components via their alcohol/amine groups.

2) Poly vinyl alcohol polymers. These polymers can still comprise or not the moiety containing the polymerisation initiator. - Without the acid moiety containing initiator of polymerisation, this polymer can be linked for example, to the reactive group of aspartic or glutamic acid present in the amino acid sequence of the selected CBD via an esterification reaction. The poly vinyl alcohol polymer does further comprise hydroxyl reactive groups available for attachment of acid/aldehyde containing chemical components.

- With an acid moiety containing initiator of polymerisation, this acid moiety of the initiator of polymerisation of the polymer for example, can be linked for example, to a NH2 group present in the amino acid sequence of the selected CBD. The poly vinyl alcohol polymer does further comprise hydroxyl reactive groups available for attachment of acid/aldehyde containing chemical components.

3) Also suitable are amine-containing compounds as described in co-pending application PCT/US98/20491 filed on September 30, 1998 by P&G, hereby incorporated by reference and having the following general structure : B-(NH2)n; wherein B is a carrier material, and n is an index of value of at least 1. Preferred B carriers are inorganic or organic carriers. By "inorganic carrier", it is meant carrier which are non-or substantially non carbon based backbones.

Preferred primary amines, among the inorganic carriers, are those selected from mono or polymers or organic-organosilicon copolymers of amino derivatised organo silane, siloxane, silazane, alumane, aluminum siloxane, or aluminum silicate compounds. Typical examples of such carriers are: organosiloxanes with at least one primary amine moiety like the diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the organoaminosilane (C6H5) 3SiNH2 described in: Chemistry and Technology of Silicone, W. Noll, Academic Press Inc. 1998, London, pp 209, 106).

Preferred primary amines, among the organic carriers, are those selected from aminoaryl derivatives, polyamines, amino acids and derivatives thereof, substituted amines and amides, glucamines, dendrimers, the polyvinylamines with a MW of from 600-50K; amino substituted polyvinylalcohol with a MW ranging from 400-300,000; polyoxyethylene bis [amine]; polyoxyethylene bis [6- aminohexyl]; N,N'-bis-(3-aminopropyl)-1 ,3-propanediamine linear or branched; 1 ,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.

Preferred aminoaryl derivatives are the amino-benzene derivatives including the alkyl esters of 4-amino benzoate compounds, and more preferably selected from ethyl-4-amino benzoate, phenylethyl-4-aminobenzoate, phenyl-4- aminobenzoate, 4-amino-N'-(3-aminopropyl)-benzamide, and mixtures thereof.

Polyamines suitable for use in the present invention are polyethyleneimines polymers, poly[oxy(methyl-1 ,2-ethanediyl)], -(2-aminomethylethyl)-(2- aminomethyl-ethoxy)- (= C.A.S No. 9046-10-0); poly[oxy(methyl-1 ,2-ethanediyl)], -hydro-)~(2-aminomethylethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1 ,3- propanediol (= C.A.S. No. 39423-51-3); commercially available under the tradename Jeffamines T-403, D-230, D-400, D-2000; 2,2',2"- triaminotriethylamine; 2,2'-diamino-diethylamine; 3,3'-diamino-dipropylamine, 1 ,3 bis aminoethyl-cyclohexane commercially available from Mitsibushi and the C12 Sternamines commercially available from Clariant like the C12 Sternamin(propylenamine)n with n=3/4, and mixtures thereof. Preferred polyamines are polyethyleneimines commercially available under the tradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA.

Preferred substituted amines and amides for use herein are selected from nipecotamide, N-coco-1 ,3-propenediamine; N-oleyl-1 ,3-propenediamine; N- (tallow alkyl)-1 ,3-propenediamine; 1 ,4-diamino cyclohexane; 1 ,2-diamino- cyclohexane; 1 ,12-diaminododecane, and mixtures thereof.

Other primary amine compounds suitable for use herein are the glucamines, preferably selected from 2,3,4,5,6-pentamethoxy-glucamine; 6-acetylglucamine, glucamine, and mixture thereof.

Also preferred compounds are the polyethylenimine and/or polypropylenimine dendrimers and the commercially available Starburst polyamidoamines (PAMAM) dendrimers, generation G0-G10 from Dendritech and the dendrimers Astromols, generation 1-5 from DSM being DiAminoButane PolyAmine DAB (PA)x dendrimers with x = 2nx4 and n being generally comprised between 0 and 4.

Still other preferred primary amine compounds are : - polyvinylamines with a molecular weight (MW) ranging from 600, 1200, 3K, 20K, 25K or 50K;

- amino substituted polyvinylalcohol with a MW ranging from 400-300,000;

- polyoxyethylene bis [amine] available from e.g. Sigma;

- polyoxyethylene bis [6-aminohexyl] available from e.g. Sigma; - N,N'-bis-(3-aminopropyl)-1 ,3-propanediamine linear or branched (TPTA) - 1 ,4-bis-(3-aminopropyl) piperazine (BNPP).

The more preferred compounds are ethyl-4-amino benzoate, polyethyleneimine polymers commercially available under the tradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; glucamine; the diaminobutane dendrimers Astramol, polyvinylamines with a MW ranging from 600, 1200, 3K, 20K, 25K or 50K; amino substituted polyvinylalcohol with a MW ranging from 400-300,000; polyoxyethylene bis [amine]; polyoxyethylene bis [6-aminohexyl]; N,N'-bis-(3-aminopropyl)-1 ,3-propanediamine linear or branched; 1 ,4-bis-(3-aminopropyl) piperazine, and mixture thereof. Most preferred primary amine compounds are selected from ethyl-4-amino benzoate, polyethyleneimine polymers commercially available under the tradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; the diaminobutane dendrimers Astramol, N,N'-bis-(3-aminopropyl)- 1 ,3-propanediamine linear or branched; 1 ,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.Even most preferred compounds are those selected from ethyl- 4-amino benzoate, polyethyleneimine polymers commercially available under the tradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA; N,N'-bis-(3-aminopropyl)-1 ,3-propanediamine linear or branched, 1 ,4-bis-(3-aminopropyl) piperazine, and mixtures thereof.

Most preferred polyreactive linking regions for use in the present invention are amino acids and their derivatives, especially ester and amide derivatives. These peptidic polymers are linked to the selected CBD via a peptidic linkage. More preferred compounds are those providing enhanced surface substantivity due to its structural feature.

Suitable amino acids have the following functionality of formula:

R=H, (L)-R*,

Suitable amino acids for use herein are selected tyrosine, tryptophane, lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine, phenylalanine, proline, glycine, serine, histidine, threonine, methionine, and mixture thereof. Homopolymers with the same amino acids or heteropolymers with different amino acids are suitable. For example, the amino acids Serine, Threonine and Tyrosine possess the reactive hydroxyl group, the Cysteine present a reactive SH group, the Asparagine and Glutamine amino acids possess a reactive amido group and the Lysine a reactive amino group. The linking will preferably be achieved on the Tyrosine, Cysteine or Lysine. Especially, the free NH2 group from a Lysine amino acid or of the terminal amino acid within the peptidic polymer is used as attachment points for chemicals containing aldehyde, ene one, ketone, or acid or halogene moeities

Also suitable compound are the amino acid derivatives selected from tyrosine ethylate, glycine methylate, tryptophane ethylate and mixture thereof, These peptidic polymers can be attached to the amino acid sequence comprising a cellulose binding domain, by recombinant technology. An example of the recombinant technique describing the expression of an enzyme with the CBD of different origin is described in S. Karita et al., (1996) Journal of Fermentation and Bioengineering, Vol. 81 , No. 6, pp. 553-556. The polyreactive linking region can comprise from 1 to about 100 amino acid residues, in particular of from 2 to 40 amino acid residues, e.g. from 2 to 15 amino acid residues. It is preferred to use amino acids which are less favoured by the surrounding proteases. Indeed, any combination of amino acids can be selected to achieve maximal weight efficiency and protease stability. Suitable amino acid linking regions are the Humicola insolens family 45 cellulase linker, the NifA gene of Klebsiella pneumoniae-C\P linker, the E. coli OmpA gene-CiP linker, the E3 cellulase Thermomonospora fusca linker and the CenA cellulase linker; preferably the Humicola insolens family 45 cellulase linker and the E3 cellulase Thermomonospora fusca linker.

Depending on the intended activity of the attached chemical component, said chemical components can be linked permanently or temporarily to the selected CBD and/or linking region. Therefore, the present invention further encompasses chemical entities wherein the chemical component is linked to the selected CBD and/or linking region by a weak bond. Said weak bond is a bond which can be enzymatically cleaved, oxidized, cleaved by light radiation and/or hydrolysed during or after the wash/fabric care process in order to release the chemical component(s). Examples of weak bonds are Shiff-base or beta-amino-ketone bonds.

The chemical components

The present invention relates to an improved chemical entity comprising a chemical component linked to a selected CBD. The chemical component is within the context of the present invention any compound which gives a desirable effect on a fibre or fabric. The chemical components encompassed in the improved chemical entity are preferably selected from perfumes, hygiene agents, insect control agents, fabric softening agents, soil release agents, bleaching agents, dye fixatives agents, brighteners, surfactants and/or mixtures thereof. More preferred components are the perfume components, insect control agents, hygiene agents, bleaching agents, and/or mixture thereof.

In addition to these chemical entities, the compositions of the present invention can comprise the same chemical components unmodified. The chemical component of the present invention may be encapsulated. Suitable encapsulating material includes starches, poly(vinylacetate), urea/formaldehyde condensate based materials. Especially suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1 ,464,616. Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins are, preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.

Perfumes

Most consumers have come to expect scented laundry products and to expect that fabrics which have been laundered also have a pleasing fragrance. It is also desired by consumers for laundered fabrics to maintain the pleasing fragrance over time. Perfume additives make laundry compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance to fabrics treated therewith. However, the amount of perfume carryover from an aqueous laundry bath onto fabrics is often marginal and does not last long on the fabric. Fragrance materials are often very costly and their inefficient use in rinse added fabric softener compositions and ineffective delivery to fabrics from the rinse results in a very high cost to both consumers and fabric softener manufacturers. Industry, therefore, continues to seek for more efficient and effective fragrance delivery in laundry detergent and/or fabric care compositions, especially for improvement in the provision of long-lasting fragrance to the rinsed fabrics. Therefore, industry continues to seek improved alternatives for generating fragrances through economic and effective means.

The present invention encompasses an improved perfume entity wherein at least one chemical component is a perfume compound linked to a selected CBD. The perfume compound is linked to the selected CBD and/or linking region via a weak bond. It is believed that improved substantivity of the perfume will be achieved by linking perfume compounds to a selected CBD.

Without wishing to be bound by theory, it is believed that the slow hydrolysis of the weak bond within the improved perfume entity will improve the release of the perfume. Indeed, after the wash or fabric care process, the weak bond will be hydrolysed and the perfume will be released. It has been surprisingly found that these improved perfume entities provide increased pleasing and long-lasting fragrance, through economic and effective means.

For example, it is known that alcohols represent key notes in perfumery. However, many alcohols are too volatile to remain in a perceptible way on dry fabrics and/or are not sufficiently fabric substantive to deposit on fabric in an optimum way such as in a softening through-the-wash process. The linking of these perfumery alcohols to the selected CBD and/or linking region can be achieved for instance via an ester bond to a carboxylic group of the polyreactive linking region or to a molecule of succinic acid which is itself linked to a hydroxy group of the polyreactive linking region.

A further example are the perfumery aldehydes known to provide a fresh note on fabrics and especially on dry fabrics. However many perfumery aldehydes do not deposit substantially enough on the fabrics and/or are too volatile. A known solution to the art consists in using a second perfumery material containing an amine group to form a Shift base. Said Shiff bases present a higher residuality on the fabrics but have poor fabric substantivity and cause a change in the aldehyde perfume character.

Therefore, the improved perfume entities encompassed in the present invention provide a high fabric substantivity which results in the reduction of the perfume waste in the wash of fabric care drain, as well as superior perfume retention and deposition on the fabrics throughout the wash. Moreover, these improved perfume entities provide significant release of the perfume on laundered dry fabrics giving long-lasting fragrance. Furthermore, the amine groups encompassed within the selected CBD and/or linking region of the present invention do not have any odour impact nor change the perfume character. Fully-formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic origin. The range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation. In this list of perfume ingredients, some are commercial names conventionally known to one skilled in the art, and also includes isomers. Such isomers are also suitable for use in the present invention. A typical disclosure of suitable ketone and/or aldehydes, traditionally used in perfumery, can be found in "Perfume and Flavor Chemicals", Vol. I and II, S. Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5. Preferred for the purpose of the present invention are the aldehydes or ketones based products.

- Natural products such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil;

- Alcohols such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol;

- Aldehydes such as citral, Helional™, alpha-hexyl-cinnamaldehyde, hydroxycitronellal, Lilial™ (p-tert. butyl-alpha -methyldihydrocinnamaldehyde), methylnonylacetaldehyde, 1 -decanal, benzaldehyde, florhydral, 2,4-dimethyl-3- cyclohexen-1-carboxaldehyde; cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenal, and mixture thereof;

- Ketones such as allylionone, alpha-ionone, beta -ionone, isoraldein (isomethyl- alpha -ionone), methylionone, Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone, Iso-E-Super, 2,4,4,7-Tetramethyl- oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof;

- Esters such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxolate, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc.; - Lactones such as gamma-undecalactone, various components often used in perfumery, such as musk ketone, indole, p-menthane-8-thiol-3-one, and methyl- eugenol;

- Acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a United States Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-lndanes, see U.S. Pat. No. 5 ,084,440, issued January 28, 1992, assigned to Givaudan Corp. ; - Recent synthetic specialties include the enol ethers of alkyl-substituted oxo- tetralins and oxo-indanes as described in U.S. Pat. 5,332,725, July 26, 1994, assigned to Givaudan; or Schiff Bases as described in U.S. Pat. 5,264,615, December 9, 1991 , assigned to Givaudan.

When encompassed in the compositions of the present invention, these improved perfume entities will be comprised generally at a level of from 0.001% to 20%, preferably from 0.01% to 5% by weight of the composition.

Hygiene agents

The present invention encompasses an improved hygiene entity wherein at least one chemical component is a hygiene agent, linked to an amino acid sequence comprising a selected CBD. The hygiene agent will be linked to the selected CBD and/or linking region via weak bond in order to release the active material upon time during or after the wash or fabric care process. Preferably, the hygiene agent comprises an hydroxyl, carboxyl or aldehyde reactive moiety. It has been surprisingly found that such improved hygiene entities provide an extremely long lasting and very efficient control of the micro-organism growth on stored and weared fabrics. This improved hygiene entity can be incorporated in a laundry detergent and/or fabric care composition of the present invention.

Sanitisation includes all positive effects obtained by the inhibition or reduction of microbial activity on fabrics and other surfaces, such as the prevention of malodour development and bacterial/fungal growth. For example, it provides prevention of malodour development on stored and weared fabrics. In particular, the composition of the present invention will inhibit or at least reduce the bacterial and/or fungal development on moist fabric waiting for further laundry processing and thereby preventing the formation of malodour. The term hygiene agents herein encompasses fungicides and antimicrobials that when applied to fabric respectively prevent or reduce the growth of fungi or bacteria. The sanitisation benefits of the laundry detergent and/or fabric care compositions of the present invention can be evaluated by the Minimum Inhibitory Concentration (MIC) as described in Tuber. Lung. Dis. 1994 Aug; 75(4):286-90; J. Clin. Microbiol. 1994 May; 32(5): 1261 -7 and J. Clin. Microbiol. 1992 Oct; 30(10):2692- 7.

Preferred antibacterial compounds are pentadecanol, cinamaldehyde, ionone, glutaraldehyde, citronellal. Other suitable antimicrobial compounds with an hydroxyl, carboxyl or aldehyde moiety are described in Parfums Cosmetiques Actualites No 125, Nov, 1995, 51-4. Other suitable antibacterial components are the Nerodol which can for example be linked to the carboxylic groups or succinic acid linked to the alcohol group of the selected CBD and/or linking region. A further example are the compounds Cipamaldehyde and/or Beta ionone which can form for example a Shiff base or β-amino ketone with the NH2 groups of the selected CBD and/or linking region.

Also suitable are the microbicidally active ingredients described in the handbook of Disinfectants and Antiseptics edited by J.M. Ascenzi and in W097/46218 such as 2-hydroxydiphenyl ether, phenol derivatives, diphenyl compounds, benzyl alcohols, chlorhexidine, C12-14 alkylbetaines and C8-18 fatty acid amido alkylbetaines, amphoteric surfactants, trihalocarbanilides and quaternary ammonium salts. Also suitable are the cationic germicides described in EP 843 002 and in W098/24314 and the antibacterial agents triclosan, triclocarban, DMDM hydantoin, piroctone olamine, zinc pyrithione, selenium disulfide, climnazole and 3-methyl-4-(1-methylethyl)phenol also therein described. Other examples of suitable fungicides are given in WO94/10286 (Henkel), CA943 429 (Unilever) and US3,426,024 (Henkel). Preferred antimicrobials are 2- thiocyanomethylthiobenzothiazole (Busan 30 WB ex Buckmann), butyl 4- hydroxy benzoate (Butyl Parabens ex Nipa Labs), propyl 4-hydroxy benzoate (Propyl Parabens ex Nipa Labs), Terpineol, Borneol, Fenchyl alcohol, trichlorocarbanilidem, Irgasan DP300 (2,4,4'-trichloro 2'hydroxydiphenylehter) and the higher homologues of hydroxybenzoate esters. Further examples of bactericides used in the hygiene agent entities of this invention include formaldehyde, 2-bromo-2-nitro-propane-1 ,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline- 3-one sold by Rohm and Haas Company under the trade name Kathon.

Also suitable hygiene agents include : 1- or 2-hexadecanol, 2-tetradecanol, 1- pentadecanol, 1-Undecanol, 2-dodecanol, 1-Tridecanol, nerolidiol, hinokitiol, tropolone, berberine, citronellic acid, Curcumin, 2-Mercaptopyridine N-oxide, Ellagic acid (dihydrate), 3-t-Butyl-5-methyl salicylic acid, 3-, 4- or 5-methyl salicylic acid, 1-nonanol, Decylalcohol, Cinamaldehyde, S- or R-Citronellal, Citronellol, Beta-ionone, Thujone, Coumarin and derivatives, Geraniol, Citral, Thymol, Iso-butyl- or Isopropyl-quinoline, 2-butyl-5-methylphenol, 2-Mercapto-3- pyrodinol, Perillyl alcohol, 6-hydroxy-1 ,3-benzoxathiol-2-one, BOAT, (Iso)- Eugenol, Menth-1-en-9-ol, 2-t-Butyl-4-methylphenol, Kojic acid, Camphene, Carveol, Dihydroxycarvecol, Isojasmone, Methol, Cineol, Terpinol, Camphor, 2-t- Butyl-methyl phenol, 2-Tridecanone, Acetyl salicylic acid, Salicylaldoxime, Undecyclenic aldehyde, Nerol, 3,5,5-trimethyl-1-hexanol, Adipic acid, Thiosalicylic acid, OH-Benzoic acid, 2-Methylbenzothiazole, 2- Aminobenzothiazole, Caryophyllene, Allyl-isocyanate, Carvone, Alpha-pinene, Salicylic acidfrole, Alpha-ionone, 2OH- or 30H-Phenethyl alcohol, Trimethoxy BP, Undecylic aldehyde, Cineole, Anisaldehyde, Bornyl acetate, Salicylhydroxamic, Benzofuran Car., Syringaldehyde.

Preferably, the levels of hygiene agent entity should be such that they prevent bacterial and fungi growth on fabrics, rather than merely preventing growth within the laundry detergent and/or fabric care compositions per se. When encompassed in the compositions of the present invention, these improved hygiene entities will be comprised generally at a level of from 0.00001% to 20%, preferably from 0.001% to 5% by weight of the total composition.

Insect Control agents

The present invention encompasses improved insect control entities wherein at least one chemical component is an insect control agent, linked to an amino acid sequence comprising a selected CBD. It has surprisingly been determined that such improved insect control entities provide a much longer lasting insect control by the slow release of the insect control agent. Such improved insect control agent entities can be incorporated into laundry detergent and/or fabric care compositions.

Such improved insect control entities are linked to the selected CBD and/or linking region preferably via a weak bond in order to release upon time the active material. For example, these materials can be linked to the NH2 group present in the selected CBD and/or linking region via a Shiff base or Michael reaction.

The term insect control agent refers to both insecticides and insect repellents either individually or as mixtures. Examples of insect repellents can be found in Kirk-Othmer Encyclopedia of Chemical technology, Fourth edition, volume 13, pages 474 to 478. Suitable insect repellents include aldehyde based compounds such as Citronellal and Rotundial, ene one based compounds such as Butopyronoxyl (Indalone TM), benzyl benzoate, bioallethrin and dimethrin, N,N- diethyl toluamide ("DEET"), N,N-diethyl benzamide, p-menthane-3,8-diol, 1S,3S,4S,6S-carene-3,4diol (Sumitomo - US5,130,136), 1-piperidinecarboxylic acid, 2-(2-hydroxyethyl)-, 1-methylpropylester, 1-(3cyclohexen-1-yl carbonyl)- 2methylpiperidine, 1-(3-cyclohexen-1-yl carbonmyl) piperidine, N,N-diethyl mandelamide, isopulegol hydrate, ethyl-3(N-butyl-N-acetyl) aminopropionate, diisopropyladipate, α-biasal, psearmint oil, benzyl alcohol, N,N- diethylphenylacetamide, vitamin E, citronella oil, coconut oil, cedar oil, geraniol, lemon grass oil, thyme oil, reosemary oil, mint oil, geranium oil, eugenol, 3- acetyl-2-(2-,6-dimethyl-5-heptenyl) oxazolidine, (2- hydroxymethylcyclohexyl)acetic acid lactone and eucalyptol. Other insect control agents are based on pyrethroid insecticides, in particular 3-phenoxybenzyl-DL- cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate (permethrin). W098/17772 describes the insect repellent agent 3-(N- butylacetamino) ethyl propionate for use in detergents.

Preferred insect repellents are aldehyde based compounds such as Citronellal and Rotundial. When encompassed in the compositions of the present invention, these improved insect control entities will be comprised generally at a level of from 0.1% to 40%), preferably from 0.1% to 10% by weight of the composition.

Bleaching agents

The present invention encompasses an improved bleaching entity wherein at least one chemical component is a bleaching agent, linked to an amino acid sequence comprising a selected CBD. Said bleaching agent can be selected from hydrophilic bleach activators, hydrophobic bleach activators, metal catalysts and/or photoactivated bleaches. It has been surprisingly found that the bleaching action with such improved bleaching entities results in improved and increased stain/soil bleaching/removal and whiteness maintenance. Also encompassed in the present invention, are laundry detergent and/or fabric care compositions comprising such improved bleaching entities.

Without wishing to be bound by theory, it is believed that improved stain/soil bleaching/removal and whiteness maintenance results in the generation of oxygen radicals, peracetic acid or peracid perhydrolysis occurring very close the fabric. Said peracetic acid or peracid is less dilute in the wash solution due to the bleach entity of the present invention being very efficiently deposited onto the fabric and thereby improving the bleaching action on the fabric.

Preferably, the bleach activator is linked to the selected CBD via a linking region, more preferably via a polyreactive linking region. Without wishing to be bound by theory, it is believed that the presence of such a linking region provides flexibility to the bleach activator enabling it to move around the CBD and perform its bleaching action more efficiently on the fabric.

1) Hydrophilic bleach activator : For example, Tetra Acetyl Ethylene Diamine (TAED) is a current bleach activator used in laundry detergent and forms peracetic acid in presence of H202. It is known that the two NH2 groups of the Ethylene Diamine are diacetylated to form TAED. Without wishing to be bound by theory, it is believed that the diacetylation of the free NH2 groups of the selected CBD and/or linking region, forms a substantive fabric hydrophilic bleach activator. Hydrophilic bleach activator of the TAED type can be linked for example via a diacetylation reaction to any NH2 groups of the selected CBD and/or linking region of the present invention.

2) Hydrophobic bleach activators such as Nonanoyl benzene sulphonate, are current bleach activators used in laundry detergent. It has been surprisingly found that the phenolic moiety can be replaced by the one present in the tyrosine amino acid present in the selected CBD and/or linking region. Active hydrophobic bleach activator precursors such as nonanyl unit can be linked to the phenol group of an amino acid such as tyrosine present in the peptidic selected CBD and/or linking region. Similarly, if there is no phenol entity available in the selected CBD and/or linking region, a phenol unit can be linked to a group NH2 in this selected CBD and/or linking region. Hydrophobic bleach activators in general can be linked to the selected CBD and/or linking region for example by a reaction on NH2 groups. Other examples of suitable hydrophobic bleach activators are nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG) or Phenolsulfonate ester of N-nonanoyl-6- aminocaproic acid (NACA-OBS, described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.

Also suitable bleach activators are the activators based on a caprolactam leaving group such as benzoyl caprolactam and quaternary ammonium hexanoyl caprolactam; the imides activators such as N-nonanoyl-N-methyl acetamide and unsymetrical acyclic imide bleach activator of the following formula as disclosed in the Procter & Gamble co-pending patent applications US serial No. 60/022,786 (filed July 30, 1996) and No. 60/028,122 (filed October 15, 1996) :

wherein Ri is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C-j-Cs, linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group.. These bleach activators can for example be linked to any NH2 groups of the polyreative linking region. Also suitable are the pre-fromed peracid such as nonylamido peroxy adipic acid and N,N-phtaloylaminoperoxy caproic acid and the Di-acyl peroxides such as dobenzoyl peroxide.

3) Metal catalysts : A third type of bleach activator that can be encompassed in the improved bleaching entity of the present invention, are the below described metal catalysts. For example, these catalysts can be linked via their capping cyclo azo moieties to NH2 groups of the selected CBD and/or linking region. Examples of Metal-containing catalysts for use in bleach compositions, include cobalt-containing catalysts such as Pentaamine acetate cobalt(lll) salts and manganese-containing catalysts such as those described in EPA 549 271 ; EPA 549 272; EPA 458 397; US 5,246,621 ; EPA 458 398; US 5,194,416 and US 5,114,611. Bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3.

4) Photoactivated bleach : Another group of suitable bleach activators that can be encompassed in the improved bleaching entity of the present invention, are the photoactivated bleaches. For example, the linking can be achieved between the NH2 groups of and the benzyls groups of these photoactivated bleaches, activated via a preliminary bromination.

Suitable photoactivated bleaching agents are the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically, the compositions herein will contain about 0.025% to about 1.25%, by weight of sulfonated zinc phthalocyanine.

In addition to this improved bleaching entity, the compositions of the present invention can further comprise bleaching species such as hydrogen peroxide, PB1 , PB4 and percarbonate with a particle size of 400-800 microns, typically be present at levels of from 1 % to 25% by weight of the total composition. When encompassed in the compositions of the present invention, these improved bleaching entities will be generally comprised at a level of from 0.001 % to 40%), preferably from 0.1% to 10% by weight of the total composition.

Fabric softening agents

The present invention encompasses an improved fabric softening entity wherein at least one chemical component is a fabric softening agent, linked to an amino acid sequence comprising a selected CBD. It has been surprisingly found that such improved fabric softening entities provide anti-wrinkling, anti-bobbling, and anti-shrinkage properties to fabrics, as well as fabric softness. These improved fabric softening entities can be incorporated in a laundry detergent and/or fabric care composition.

In recent years, consumer desirability for durable press fabric garments, particularly cotton fabric garments, has risen. Durable press garments include those garments which resist wrinkling of the fabric both during wear and during the laundering process. Durable press garments can greatly decrease the hand work associated with laundering by eliminating ironing sometimes necessary to prevent wrinkling of the garment. However, in most commercially available durable press fabrics, the fabric's ability to resist wrinkling is reduced over time as the garment is repeatedly worn and laundered. Therefore, the improved fabric softening entities of the present invention aid in eliminating this problem by providing excellent anti-wrinkling properties due to effective desposition of the improved fabric softening entity on the fabric.

Suitable fabric softening agents are dialkyl units that can be linked for example, by dialkylation of the NH2 groups comprised in the selected CBD and/or linking region. Preferably such fabric softening entities will not comprise a weak bond.

Dialkyl units suitable for the compositions of the present invention can be extracted from the following cationic softening surfactants currently used in the laundry detergent and/or fabric care context. The alkyl, or alkenyl chain will contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched. Specific examples of the alkyl or alkenyl chains herein include : 1) N,N-di(tallowyl-oxy-ethyl);

2) N,N-di(2-tallowyloxy-2-oxo-ethyl);

3) N,N-di(2-tallowyloxyethylcarbonyloxyethyl); 4)N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl);

5) N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl); and

6) 1 ,2-ditallowyloxy; and mixtures of any of the above materials. Preferred alkyl chains for the purpose of the present invention N,N-di(tallowoyl- oxy-ethyl), where the tallow chains are at least partially unsaturated.

Other suitable fabric softening agents include quaternary ammonium softening compounds having a solubility in water at pH2.5 and 20°C of less than 10g/l. It is particularly advantageous if the fabric softening agent is a quaternary ammonium compound in which at least one long chain alkyl group is connected to the quaternary ammonium compound via at least one ester link. Suitable cationic softeners are described in US4,137,180 (Naik) and WO93/23510.

Also suitable as softening components are clay or silicone.

Suitable clays include a three layered smectite clay, preferably having a cationic exchange capacity as described in GB 1 ,400,898 and in USP 5,019,292.

Especially preferred are clays which are 2:1 layer phyllosilicates possessing a lattice charge efficiency in the range of 0.2 to 0.4g equivalent per half unit cell as described in EP 350 288 (Unilever).

Also encompassed in the present invention are any polymeric lubricant suitable for softening a fabric. These include silicone and in particular those described in

GB1.549.180; EP 459 821 (Unilever) and EP 459 822 (Unilever).

When encompassed in the present invention, these improved fabric softening entities will be comprised generally at a level of from 0.5% to 50%, preferably from 1% to 30%, more preferably from 2% to 15% by weight of the composition.

Dye fixative agents

The present invention encompasses an improved dye fixative entity wherein at least one chemical component is a dye fixative agent, linked to an amino acid sequence comprising a selected CBD. It has been surprisingly found that such improved dye fixative entities provide enchanced anti-wear properties and colour appearance. Also encompassed in the present invention are laundry detergent and/or fabric care compositions comprising an improved dye fixative entity.

Indeed, coloured garments have a tendency to wear and show colour appearance losses. A portion of this colour appearance loss may be attributed to abrasion in the laundering process, particularly in automatic washing machines and automatic laundry dryers. Dye fixative agents are well-known, commercially available materials which are designed to improve the appearance of dyed fabric by minimising the loss of dye from fabrics due to washing. Many dye fixatives are cationic, and are based on various quatemized or otherwise cationically charged organic nitrogen compounds. Fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981 , Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) from Crosfield; INDOSOL E-50 (February 27, 1984, Ref. No. 6008.35.84; polyethyleneamine-based) from Sandoz; SANDOFIX TPS, which is also available from Sandoz and is a preferred polycationic fixative for use herein and SANDOFIX SWE (cationic resinous compound), REWIN SRF, REWIN SRF-0 and REWIN DWR from CHT-Beitlich GMBH. Other cationic dye fixative agents are described in "Aftertreatments for improving the fastness of dyes on textile fibres" by Christopher C. Cook (REV. PROG. COLORATION Vol. 12, 1982).

Further suitable dye fixative agents for use in the present invention are ammonium compounds such as fatty acid - diamine condensates e.g. the hydrochloride, acetate, metosulphate and benzyl hydrochloride of oleyldiethyl aminoethylamide, oleylmethyl-diethylenediaminemethsulphate, monostearyl- ethylene diaminotrimethylammonium methosulphate and oxidised products of tertiary amines; derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrins.

When encompassed in the compositions of the present invention, these improved dye fixative entities will be comprised generally at a level of from 0.01% to 30%, preferably from 0.1% to 15% by weight of the composition.

Soil release agents The present invention encompasses an improved soil release entity wherein at least one chemical component is a soil release agent, linked to an amino acid sequence comprising a selected CBD. It has been surprisingly found that such improved soil release entities provide better deposition of the soil release agent onto the fabric and therefore better soil release performance. Also encompassed in the present invention are laundry detergent and/or fabric care compositions comprising such improved soil release entity.

Suitable soil release agents for the present invention are ethylene glycols oligomers, polyethylene glycol and derivatives such as transesterified polyethylene glycols, and propylene polyoxy ethylene. Other suitable soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and

European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula :

(CH3(PEG)43)o.75(POH)o.25[T-PO)2.8(T-PEG)o.₄]T(PO- H)o.25(( EG)43CH₃)o.75 where PEG is -(OC2H4)O-,PO is (OC3H6O) and T is (PCOC5H4CO).

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 ends by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 342. Other soil release agents currently used in the detergent context are those of U.S. 4,968,451 , November 6, 1990 to J.J. Scheibel and E.P. Gosselink: such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1 ,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end- capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711 ,730, December 8, 1987 to Gosselink et al, for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721 ,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31 , 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400. Another preferred soil release agent is a sulfonated end-capped type described in US 5,415,807.

When encompassed in the compositions of the present invention, these improved soil release entities will be comprised generally at a level of from 0.01% to 20%, preferably from 0.1% to 5% by weight of the total composition.

Brighteners

The present invention encompasses an improved brightener entity wherein at least one chemical component is a brightener, linked to an amino acid sequence comprising a selected CBD. It has been surprisingly found that such improved brightener entities provide increased deposition of the brightener onto the fabric and therefore better whiteness maintenance performance. In addition, it has been found that various brighteners not currently used in the detergent field could also be used in the present invention thanks to their increased fabric substantivity, in particular during a softening-through-the-wash process. Preferably, such improved brightener entities will not comprise a weak bond. Also encompassed are laundry detergent and/or fabric care compositions comprising an improved brightener entity.

Suitable brighteners for compositions of the present invention are :

- Carbocycles types of compounds such as distyrylbenzenes, distyrylbiphenyls and divinylstibenes,

- Triazinylaminostilbenes,

- Stilbenyl-2H-triazoles such as stilbenyl-2H-naphtol[1 ,2-d]triazoles and bis(1 ,2,3-triazol-2-yl)stilbenes,

- Benzoxazoles such as stilbenylbenzoxazoles and bis(benzoxazoles), - Furans, Benzo[b]furnas and Benzimidazoles such as bis(benzo[b]furan-2- yl)biphenyls and cationic benzimidazoles,

- 1 ,3-Diphenyl-2-pyrazolines

- Coumarins

- Naphtalimides - 1 ,3,5-triazin-2-yl-Derivatives.

For example, a brightener of the Coumarin type can be attached to the NH2 group or to an amido group from the selected CBD and/or linking region. Preferred are the bleach-stable brighteners such as 1 ,4-di(2- methylaminostyryl)benzene.

Other suitable brighteners that can be linked to the selected CBD according to the present invention are the hydrophilic optical brighteners having the structural formula:

wherein R-i is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. - When in the above formula, Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the rinse added compositions herein.

- When in the above formula, R<| is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy

Corporation.

- When in the above formula, R-| is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Other suitable optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino- stilbene-2:2' - disulphonate, disodium 4,4' - bis-(2,4-dianilino-s-triazin-6- ylamino)stilbene-2:2' - disulphonate, monosodium 4',4" -bis-(2,4-dianilino-s-tri- azin-6 ylamino)stilbene-2-sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyl- N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2' - disulphonate, disodium 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. 95201943.8. When encompassed in the compositions of the present invention, these improved brightener entities will be generally comprised at a level of from 0.001% to 10%, preferably of from 0.005% to 3.5% by weight of the composition.

Other suitable chemical components

Other suitable chemical components which may be linked to a selected cellulose binding domain in accordance with the present invention are latex and resins. Latex are defined as materials suitable for refining the drape of fabric. Suitable materials include a polyvinylacetate homopolymer such as 9802 (Vinamul). Resins prevent the formation of pills on the fabrics. Suitable resins are Knittex BE from Ciba-Geigy or silicas such as Crosanol NS from Crosfiled.

LAUNDRY DETERGENT AND FABRIC CARE COMPONENTS

The laundry detergent and/or fabric care compositions of the invention will comprise at least one additional detergent and/or fabric care component. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.

As already mentioned supra, all the components that may be linked to a selected Cellulose Binding Domain in accordance with the present invention, can also be incorporated into the laundry detergent and/or fabric care compositions of the present invention in their unmodified, conventional form.

The chemical entities of the present invention are generally incorporated into the laundry detergent and/or fabric care compositions at a level of from 0.00001% to 50%, preferably from 0.001% to 20%, more preferably from 0.1% to 10% by weight of the total composition.

When formulated as compositions suitable for use in a laundry machine washing method, the compositions of the invention preferably contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional detergent components. The laundry detergent and/or fabric care compositions of the present invention preferably further comprise a detergent ingredient selected from cationic surfactants, dye transfer inhibiting polymers, builders - in particular zeolite A and sodium tripolyphosphate - and/or clays.

The compositions of the invention may for example, be formulated as hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions. Pre-or post treatment of fabric include gel, spray and liquid fabric care compositions. A rinse cycle with or without the presence of softening agents is also contemplated. The compositions of the invention can also be used as detergent additive products in solid or liquid form. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process.

The laundry detergent and/or fabric care compositions according to the invention can be liquid, paste, gels, bars, tablets, spray, foam, powder or granular forms. Granular compositions can also be in "compact" form, the liquid compositions can also be in a "concentrated" form. If needed the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 600 to 950 g/litre of composition measured at 20°C.

The "compact" form of the compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition. The inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides. A preferred filler salt is sodium sulphate. Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents. Typically the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

Surfactant system

The laundry detergent and/or fabric care compositions according to the present invention will preferably further comprise a surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants. Preferred surfactants are cationic surfactants. It has been surpringly found that the compositions of the present invention further comprising a surfactant, will provide superior, enhanced cleaning and fabric care, including colour care, fabric appearance, fabric anti-wear propeties, anti-static properties and/or softeness.

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

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

Cationic detersive surfactants suitable for use in the laundry detergent and/or fabric care compositions of the present invention are those having one long- chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula : [R2(OR3)_y][R (OR³)y]2R⁵N+X-

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

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

Formula I whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :

Formula II

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

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

Preferred quaternary ammonium surfactants are those as defined in formula I whereby Ri is C8, C-|o ^or mixtures thereof, x=o, R3, R4 = CH3 and R₅ = CH₂CH₂OH.

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

R<| R2R3R4N⁺X- (i)

wherein R-j is Cs-C-ig alkyl, each of R2, R3 and R4 is independently C-1-C4 alkyl, C-1-C4 hydroxy alkyl, benzyl, and -(C2H4Q)_XH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl. The preferred alkyl chain length for R-| is C12-C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C-|2-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein R-| is

CH2-CH2-O-C-C-12-I4 alkyl and R2R3R4 are methyl). II 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.

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

1) ditallow dimethylammonium chloride (DTDMAC);

2) dihydrogenated tallow dimethylammonium chloride; 3) dihydrogenated tallow dimethylammonium methylsulfate;

4) distearyl dimethylammonium chloride;

5) dioleyl dimethylammonium chloride;

6) dipalmityl hydroxyethyl methylammonium chloride;

7) stearyl benzyl dimethylammonium chloride; 8) tallow trimethylammonium chloride;

9) hydrogenated tallow trimethylammonium chloride;

10) C-|2^_14 alkyl hydroxyethyl dimethylammonium chloride;

11) C-12-18 ^a' dihydroxyethyl methylammonium chloride;

12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC); 13) di(tallow-oxy-ethyl) dimethylammonium chloride;

14) ditallow imidazolinium methylsulfate;

15) 1-(2-tallowylamidoethyl)-2-tallowyl imidazolinium methylsulfate.

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

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

(I) (II)

wherein Q is selected from -O-C(O)-, -C(0)-0-, -0-C(0)-0-, -NR4-C(0)-, -C(0)-

NR4-;

R¹ is (CH₂)_n-Q-T² or T3; R² is (CH₂)_m-Q-T4 or T5 or R3;

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

R⁴ is H or C-1-C4 alkyl or C1-C4 hydroxyalkyl;

T 1 , T2, T³, T⁴, T^ are independently C-| 1-C22 alkyl or alkenyl; n and m are integers from 1 to 4; and X- is a softener-compatible anion.

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

The alkyl, or alkenyl, chain T^ , T², T^, T⁴, T^ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein τ1 , T2, T³, T⁴, T^ represents the mixture of long chain materials typical for tallow are particularly preferred. Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :

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

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

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

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

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

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

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

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal™ CO-630, marketed by the GAF Corporation; and Triton™ X- 45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxy lates). The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol^M 15-S-9 (the condensation product of C-11-C-15 linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the condensation product of C-|2- i4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodof 45.9 (the condensation product of C14-C-15 linear alcohol with 9 moles of ethylene oxide), Neodol^M 23-3 (the condensation product of C-|2-C-|3 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro™ EOB (the condensation product of C-13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA 030 or 050 (the condensation product of Ci2-C-|4 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.

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

R2θ(C_nH_2nO)t(glycosyl)_x

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

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available Plurafac^M LF404 and 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 consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000. Examples of this type of nonionic surfactant include certain of the commercially available 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 C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C8-C-|8 alcohol ethoxylates (preferably C<|fj avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.

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

R² - C - N - Z,

II I o R1

wherein R1 is H, or R¹ is C-ι_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C-| ^«|_15 alkyl or C<|β-18 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids

(i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:

O II

R - CH - C - OR⁴

I SO3M wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof,

R⁴ is a C1-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 mono-ethanolamine, 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-|o-C"|6 alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a

C-|o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C^<ιo-C2θ alkyl component, more preferably a C-12-C18 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 C12-C16 are preferred for lower wash temperatures (e.g. below about 50°C) and C-iβ-18 alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).

Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent and/or fabric care compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C22 primary of secondary alkanesulfonates, C8-C24 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, C8-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates

(especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ)k-CH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to

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

When included therein, the laundry detergent compositions of the present invention typically comprise from about 1 % to about 40%, preferably from about

3% to about 20% by weight of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mS03M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10- 24 alkyl component, preferably a C12- 20 alkyl or hydroxyalkyl, more preferably C12-

C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C<|2-Ci8 alkyl polyethoxylate (1.0) sulfate (C^<|2-C^<|8E(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (Ci2-CiδE(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C-|2-Ci8E(3.0)M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (C-|2-C-|8E(4.0)M), wherein M is conveniently selected from sodium and potassium.

Further highly preferred anionic surfactants are the mid-chain-branched anionic surfactants described in the co-pending US applications Serial Nos. US97/06485, US97/06474, US97/06339, US97/06476 and US97/06338 and in WO97/39091 , hereby incorporated by reference. The compositions of the present invention generally comprise from 0.1% to 50%, preferably from 0.5% to 40% more preferably from 1% to 35% by weight of the total composition of one or more longer alkyl chain, mid-chain branched surfactant compounds of the formula: A^D - X - B wherein: (I) A^D is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to

22 carbons in the moiety, preferably from 12 to about 18, having: (1) a longest linear carbon chain attached to the - X - B moiety in the range of from 8 to 21 carbon atoms; (2) one or more C-| - C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the - X - B moiety, to the position of the terminal carbon minus 2 carbons, (the (ω - 2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the A^-X moieties in the above formula is within the range of greater than 11 to 20, preferably 14.5 to about 18, more preferably from about 15 to about 17;

(II) B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, alkylated quats, alkyated/polyhydroxyalkylated quats, alkylated quats, alkylated/polyhydroxylated oxypropyl quats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and sulfonated fatty acids; and (III) X is selected from -CH2- and -C(O)-. Preferred mid-banched anionic surfactants are of the above formula wherein the

A^D moiety is a branched primary alkyl moiety having the formula:

R Rl R2

I I I

CH₃CH₂(CH₂)_wCH(CH₂)_xCH(CH₂)_yCH(CH₂)_r wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, Ri, and R3 branching, is from 13 to 19; R, R^"1, and R2 are each independently selected from hydrogen and C1-C3 alkyl, preferably methyl, provided R, R¹, and R2 are not all hydrogen and, when z is 0, at least R or R¹ is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13. More preferably, said surfactant has the formula:

CH₃ CH₃ (CH₂)_aCH (CH₂)_bCH₂ OSθ₃M

CH₃ CH₃

CH₃ (CH₂)_dCH (CH₂)_e CHCH₂ OSO₃M or mixtures thereof; wherein M represents one or more cations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11 , a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11 ; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11 , d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11 ; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; whereby, when more than one of these sulfate surfactants is present in the surfactant system, the average total number of carbon atoms in the branched primary alkyl moieties is from 11 to 20, preferably 14.5 to 18. Particularly preferred is said surfactant which has an A^D - X moiety comprising from 11 to 20, preferably 16 to 18 carbon atoms and B is a sulfate group.

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

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

When included therein, the laundry detergent and/or fabric care compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1%) to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergent and/or fabric care compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.

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

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

0

R3(OR⁴)XN(R5)2

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

These amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. When included therein, the laundry detergent and/or fabric care 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 laundry detergent and/or fabric care 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 R-1 NH2 wherein R^ is a Cβ-C-12, preferably Cβ-Cio alkyl chain or R4X(CH2)n_> X is -0-,-C(0)NH- or -NH- R4 is a Cg-C^ alkyl chain n is between 1 to 5, preferably 3. R-| alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.

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

Suitable tertiary amines for use herein include tertiary amines having the formula R1 R2R3N wherein R1 and R2 are C-j-Cs alkylchains or

R5

— ( CH₂ — CH θ )χH

R3 is either a C6-C12, preferably Cβ-Cio alkyl chain, or R3 is R4X(CH2)n. whereby X is -0-, -C(0)NH- or -NH- R4 is a C4-C12, n is between 1 to 5, preferably 2-3. R5 is H or C1-C2 alkyl and x is between 1 to 6 . R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or

R₅ ( CH₂ CH θ )χH

where R5 is H or CH3 and x = 1-2. Also preferred are the amidoamines of the formula:

o

Ri — C-NH— ( CH₂ )— N— ( R₂ ) n 2

wherein R-j is CQ-C-\2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C-1-C4

Most preferred amines of the present invention include 1-octylamine, 1- hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N coco 1- 3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyl- dimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyl- dimethylamine. The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n- dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

Conventional detergent enzymes

Suitable enzymes for use in the compositions of the present invention include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, mannanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. A preferred combination is a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.

The cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Preferred are these cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ^"43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801 , Genencor, published September 29, 1994. 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). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, W096/17994 and W095/24471.

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

Enzymatic system may be used as bleaching agents : 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.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.

Enhancers are generally comprised at a level of from 0.1 % to 5% by weight of total composition. Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4- carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10- methylphenoxazine (described in WO 94/12621) and substitued syringates (C3- C5 substitued alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

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

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1 ,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 LipaseR ^ar|d LipomaχR (Gist-Brocades) and LipolaseR and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitables are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever. Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A- 88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).

The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and β. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®. MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades. Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in W091/02792 and their variants described in WO 95/23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A" herein. Suitable is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in WO 91/06637. Genetically modified variants, particularly of Protease C, are also included herein. A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101 , +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and WO95/10592. The "protease D" variants have preferably the amino acid substitution set 76/103/104, more preferably the substitution set N76D/S103A/V104I. Also suitable is a carbonyl hydrolase variant of the protease described in WO95/10591 , having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101 , +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending patent application published under W098/55634). More preferred proteases are multiply-substituted protease variants. These protease variants comprise a substitution of an amino acid residue with another naturally occuring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue positions corresponding to positions 1 , 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21 , 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61 , 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101 , 102, 104, 106, 107, 109, 111 , 114, 116, 117, 119, 121 , 123, 126, 128, 130, 131 , 133, 134, 137, 140, 141 , 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181 , 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209, 210, 211 , 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251 , 252, 253, 254, 255, 256, 257, 258, 259, 260, 261 , 262, 263, 265, 268, 269, 270, 271 , 272, 274 and 275 of Bacillus amyloliquefaciens subtilisin; wherein when said protease variant includes a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than amino acid residue positions corresponding to positions 27, 99, 101 , 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens subtilisin and/or multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occuring amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amyloliquefaciens subtilisin as described in PCT application Nos. PCT/US98/22588, PCT/US98/22482 and PCT/US98/22486 all filed on October 23, 1998 from The Procter & Gamble Company. Preferred multiply substituted protease variants have te amino acid substitution set 101/103/104/159/232/236/245/248/252, more preferably

101 G/103A/1041/159D/232V/236H/245R/248D/252K according to the numbering of Bacillus amyloliquiefaciens subtilisin. The proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001 % to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.

Amylases (α and/or β) can be included for removal of carbohydrate-based stains. WO94/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in cleaning compositions include both - and β-amylases. α- Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo). Other suitable amylases are stability-enhanced amylases described in W094/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, W095/26397 and W096/23873 (all by Novo Nordisk). Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® .Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases : α-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. Preferred are variants of the above enzymes, described in W096/23873 (Novo Nordisk). Preferably, the variants are those demonstrating improved thermal stability, more preferably those wherein at least one amino acid residue equivalent to F180, R181 , G182, T183, G184, or K185 has been deleted from the parent α-amylase. Particularly preferred are those variants having improved thermal stability which comprise the amino acid deletions R181^* + G182^* or T183^* + G184^*. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermal stability and a higher activity level are described in W095/35382.

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

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned. Said enzymes are normally incorporated in the laundry detergent and/or fabric care compositions of the present invention, at levels from 0.0001% to 2% of pure enzyme by weight of the composition. The enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).

Other suitable ingredients for use in the compositions of the present invention, are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31 , 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines. A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261 ,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971 , Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Colour care and fabric care benefits

Other suitable technologies which provide a type of colour care benefit can also be included. Examples of these technologies are metallo catalysts for colour maintenance. Such metallo catalysts are described in copending European Patent Application No. 92870181.2. Dye fixing agents, polyolefin dispersion for anti-wrinkles and improved water absorbancy, perfume and amino-functional polymer for colour care treatment and perfume substantivity are further examples of colour care / fabric care technologies and are described in the co-pending Patent Application No. 96870140.9, filed November 07, 1996.

Other suitable fabric softening may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-BO 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A- 0 299 575 and 0 313 146. Preferably, the laundry detergent and/or fabric care compositions of the present invention will comprise a smectite clay. It has been surprisingly found that such compositions provide enhanced anti-wrinkle properties, static control, fabric softeness and fabric anti-wear properties. Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added as a dry mixed component to the remainder of the formulation.

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

Bleaching agent

Other detergent ingredients that can be included in the laundry detergent and/or fabric care compositions of the present invention include bleaching agents. The bleaching agent component for use herein can be any of the bleaching agents useful for cleaning compositions including oxygen bleaches as well as others known in the art. The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.

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

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 the compositions of the present invention are described in our co-pending applications USSN 08/136,626, PCT/US95/07823, W095/27772, W095/27773, W095/27774 and W095/27775.

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

Builder system

The compositions according to the present invention will preferably further comprise a builder system, preferably selected from zeolite and/or sodium tripolyphosphate. It has been surpringly found that the laundry detergent and/or fabric care compositions of the present invention further comprising a builder provide additional, enhanced cleaning and fabric care, including fabric appearance, fabric anti-wear properties and/or anti-static properties.

Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopoly- phosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.

Another suitable inorganic builder material is layered silicate, e.g. SKS-6

(Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2θ5).

Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821 ,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241 , lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1 ,1 ,3-propane tricarboxylates described in British Patent No. 1 ,387,447. Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261 ,829, 1 ,1 ,2,2-ethane tetracarboxylates, 1 ,1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1 ,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6-hexane -hexa-carboxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the compositions of the present invention include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid. Preferred builders are zeolite A and sodium tripolyphosphate. Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid. Preferred builder systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.

Other builder materials that can form part of the builder system for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates. Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A- 1 ,596, 756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 5% to 80% by weight of the composition preferably from 10% to 70% and most usually from 30% to 60% by weight.

Chelating Agents

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

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraamine- hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like. If utilized in the compositions of the present invention these chelating agents will generally comprise from about 0.1% to about 15%, preferably from about 0.1% to about 3.0%) by weight of the compositions.

Suds suppressor

Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components. A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 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-butyl-octanol which are commercially available under the trade name Isofol 12 R.

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

Especially preferred silicone suds controlling agents are described in Copending European Patent application N°92201649.8. Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.

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

Dispersants

The laundry detergent and/or fabric care composition of the present invention can also contain dispersants : Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1 , 596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 1 ,000 to 100,000. Especially, copolymer of acrylate and methylacrylate such as the 480N having a molecular weight of 4000, at a level from 0.5-20% by weight of composition can be added in the laundry detergent and/or fabric care compositions of the present invention.

The compositions of the present invention may contain a lime soap peptiser compound, which has preferably a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap peptiser compound is preferably present at a level from 0% to 20% by weight. A numerical measure of the effectiveness of a lime soap peptiser is given by the lime soap dispersant power (LSDP) which is determined using the lime soap dispersant test as described in an article by H.C. Borghetty and CA. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950). This lime soap dispersion test method is widely used by practitioners in this art field being referred to, for example, in the following review articles; W.N. Linfield, Surfactant science Series, Volume 7, page 3; W.N. Linfield, Tenside surf, det., volume 27, pages

159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in 30ml of water of 333ppm CaCθ3 (Ca:Mg=3:2) equivalent hardness.

Surfactants having good lime soap peptiser capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols. Exemplary surfactants having a LSDP of no more than 8 for use in accord with the present invention include C-|6- i8 dimethyl amine oxide, C-|2- i8 alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C12-C15 alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3

(LSDP=4), and the C14-C15 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the tradenames Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

Polymeric lime soap peptisers suitable for use herein are described in the article by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989). Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6- aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds.

Dye transfer inhibition

The laundry detergent and/or fabric care compositions of the present invention will preferably further comprise compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics. It has been surprinsinlgy found that the laundry detergent and/or fabric care composition of the present invention further comprising a dye transfer inhibiting agent, will provide superior, enhanced fabric care including colour appearance and/or fabric anti-wear properties.

Polymeric dye transfer inhibiting agents

The laundry detergent and/or fabric care compositions according to the present invention will preferably further comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into cleaning compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.

Especially suitable polymeric dye transfer inhibiting agents are polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Addition of such polymers also enhances the performance of the enzymes according the invention.

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

I

(I) A_x

I

R

wherein P is a polymerisable unit where 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 II II II

A is NC, CO, C, -0-,-S-, -N- ; x is O or 1 ;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-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 | |

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

I (R3)z

wherein R1 , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.

The N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both. Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

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

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

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

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

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1 :1000000. More preferably from 1 :4 to 1 :1000000, most preferably from 1 :7 to 1 :1000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferred PKa < 6. The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.

Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole :

The N-vinylimidazole N-vinyipyrrolidone polymers suitable for use in the compositions herein, have an average molecular weight range from 5,000-

1 ,000,000, preferably from 5,000-200,000.

Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N- vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.

The average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern

Methods of Polymer Characterization". Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from

8,000 to 30,000; most preferably from 10,000 to 20,000.

The N-vinyiimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.

The N-vinylimidazole N-vinylpyrrolidone copolymer 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 laundry detergent and/or fabric care 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 laundry detergent and/or fabric care compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.

e) Polyvinylimidazole :

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

f) Cross-linked polymers :

The laundry detergent and/or fabric care compositions of the present invention may also utilize cross-linked polymers. Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross- linked polymers entrap the dyes by swelling. Such cross-linked polymers are described in the co-pending patent application 94870213.9

Others

Other components such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, and/or coloring agents may be employed.

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

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

It is well known in the art that free chlorine in tap water rapidly deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the detergent enzymes. Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31 , 1992. Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2θ)_m(CH2)_nCH3 wherein m is 2-3 and n is 6-12. The side- chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.

Method of washing

The compositions of the invention may be used in essentially any washing, cleaning and/or fabric care methods, including soaking methods, pre-treatment methods, methods with rinsing steps for which a separate rinse aid composition may be added and post-treatment methods.

The process described herein comprises contacting fabrics with a laundering solution in the usual manner and exemplified hereunder. A conventional laundry method comprises treating soiled fabric with an aqueous liquid having dissolved or dispensed therein an effective amount of the laundry detergent and/or fabric care composition. Such methods are preferably carried out at 5°C to 95°C, especially between 10°C and 60°C. The pH of the treatment solution is preferably from 7 to 12.

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

In the detergent compositions, the enzymes levels are expressed by pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions. The abbreviated component identifications therein have the following meanings: LAS Sodium linear C-| -j_-|3 alkyl benzene sulphonate.

TAS Sodium tallow alkyl sulphate.

CxyAS Sodium Ci_x - Cι_v alkyl sulfate.

CxySAS Sodium Ci_x - Cι_v secondary (2,3) alkyl sulfate.

CxyEz C-|_x - C-|y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide.

CxyEzS C-|_X - C-|y sodium alkyl sulfate condensed with an average of z moles of ethylene oxide.

QAS R2-N+(CH3)2(C2H4θH) with R2 = C12-C14. QAS 1 R2.N+(CH3)2(C2H₄OH) with R2 = Cs-C-π . APA Cδ-10 amido propyl dimethyl amine. Soap Sodium linear alkyl carboxylate derived from a 80/20 mixture of tallow and coconut fatty acids.

STS Sodium toluene sulphonate.

CFAA C-12- 14 alkyl N-methyl glucamide.

TFAA C-16- 18 alkyl N-methyl glucamide.

TPKFA Ci2-Ci4 topped whole cut fatty acids.

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

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

DTDMAMS Ditalllow dimethyl ammonium methylsulfate. SDASA 1 :2 ratio of stearyldimethyl amine:triple-pressed stearic acid.

Silicate Amorphous Sodium Silicate (Siθ2:Na2θ ratio = 1.6-3.2). Zeolite A Hydrated Sodium Aluminosilicate of formula Na-|2(A1θ2Siθ2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).

Na-SKS-6 Crystalline layered silicate of formula δ-Na2Si2θ5 Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 and 850 micrometres.

Citric Anhydrous citric acid.

Borate Sodium borate

Carbonate Anhydrous sodium carbonate with a particle size between 200 and 900 micrometres. Bicarbonate Anhydrous sodium hydrogen carbonate with a particle size distribution between 400 and 1200 micrometres.

Sulphate Anhydrous sodium sulphate. Mg Sulphate Anhydrous magnesium sulfate. STPP Sodium tripolyphosphate. TSPP Tetrasodium pyrophosphate. MA/AA Random copolymer of 4:1 acrylate/maleate, average molecular weight about 70,000-80,000.

MA/AA 1 Random copolymer of 6:4 acrylate/maleate, average molecular weight about 10,000.

AA Sodium polyacrylate polymer of average molecular weight 4,500.

PB1 Anhydrous sodium perborate monohydrate of nominal formula NaBθ2.H2θ2-

PB4 Sodium perborate tetrahydrate of nominal formula NaBθ2.3H₂O.H2θ2-

Percarbonate Anhydrous sodium percarbonate of nominal formula 2Na2Cθ3.3H2θ2 .

TAED Tetraacetylethylenediamine. NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.

NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate. CBD-NACA-OBS Reaction product of Cellulose Binding Domain from the cellulase sold under the tradename Carezyme by Novo

Nordisk A/S, with polytyrosine linker, and (6- nonamidocaproyl) oxybenzene sulfonate molecules.

DTPA Diethylene triamine pentaacetic acid. HEDP 1 ,1-hydroxyethane diphosphonic acid. DETPMP Diethyltriamine penta (methylene) phosphonate, marketed by Monsanto under the Trade name Dequest

2060.

EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt

Photoactivated Sulfonated zinc phtalocyanine encapsulated in dextrin Bleach soluble polymer. Photoactivated Sulfonated alumino phtalocyanine encapsulated in Bleach 1 dextrin soluble polymer. Protease Proteolytic enzyme sold under the tradename Savinase,

Alcalase by Novo Nordisk A/S, the "protease D" variant with the substitution set N76D/S103A/V104I and the protease described in PCT application Nos.

PCT/US98/22588, PCT/US98/22482 and

PCT/US98/22486 with the amino acid substitution set

101 G/103A/1041/159D/232V/236H/245R/248D/252K.

Amylase Amylolytic enzyme sold under the tradename Termamyl

® and Duramyl® available from Novo Nordisk A/S and those variants having improved thermal stability with amino acid deletions R181^* + G182^* or T183^" + G184^*as described in W095/35382.

Lipase Lipolytic enzyme sold under the tradename Lipolase,

Lipolase Ultra by Novo Nordisk A/S and Lipomax by

Gist-Brocades.

Cellulase Cellulytic enzyme sold under the tradename Carezyme,

Celluzyme and/or Endolase by Novo Nordisk A/S.

CMC Sodium carboxymethyl cellulose. PVP Polyvinyl polymer, with an average molecular weight of

60,000.

PVNO Polyvinylpyridine-N-Oxide, with an average molecular weight of 50,000.

PVPVI Copolymer of vinylimidazole and vinylpyrrolidone, with an average molecular weight of 20,000.

Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl. Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2- yl) stilbene-2:2'-disulfonate.

Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to

100:1.

Suds Suppressor 12% Silicone/silica, 18% stearyl alcohol, 70% starch in granular form. Opacifier Water based monostyrene latex mixture, sold by BASF

Aktiengesellschaft under the tradename Lytron 621.

SRP 1 Anionically end capped poly esters. SRP 2 Diethoxylated poly (1 ,2 propylene terephtalate) short block polymer.

QEA bis((C2H5θ)(C2H4θ)_n)(CH3) -N⁺-C₆H₁₂-N⁺-(CH3) bis((C2H5θ)-(C2H4θ))_n, wherein n = from 20 to 30. PEI Polyethyleneimine with an average molecular weight of

1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen.

SCS Sodium cumene sulphonate.

HMWPEO High molecular weight polyethylene oxide. PEGx Polyethylene glycol, of a molecular weight of x . PEO Polyethylene oxide, with an average molecular weight of

5,000.

TEPAE Tetreaethylenepentaamine ethoxylate. CBD-Rotundial Reaction product of CBD from E3 cellulase from

Thermomonospora fusca with Rotundial molecules.

CBD-Damascone Reaction product of CBD Cellulozome from Clostridium cellulovorans , which is sold under the tradename

Cellulose Binding Domain by Sigma with α-Damascone molecules.

CBD-PRP1 Reaction product of CBD Cellulozome from Clostridium cellulovorans , which is sold under the tradename

Cellulose Binding Domain by Sigma; with polylysine linker, and 2, 4 dimethly - 3 - cyclohexan -1- carboxaldehyde

Example 1

According to the present invention, this example illustrates the coupling of a perfume citral, hygiene agent glutaraldehyde or insect control agent citronellal to the selected CBD : CBD Cellulozome from Clostridium cellulovorans. The reaction at equal mol takes place in mild conditions (pH 6 to 9.5, from 1 to 48hours / See for example Wirth, P at al 1991 Biorg.Chem 19, 133, 1991 and Chamow SM et al Bioconjugate chem, 4, 133 1994). The chemical components such as perfume (citral or 2, 4 dimethly - 3 - cyclohexan -1- carboxaldehyde), insect control agent (citronellal) and hygiene agent (glutaraldehyde) are linked to NH2 groups of the selected CBD and/or linking region via Schiffs base reaction. The reaction could also be completed in anhydrous ethanol that contain a drying agent such as Sodium Sulphate.

As the selected CBD has 10 Lysine and/or if there is a polyreactive linking region comprising more than one lysine, the reaction is identical with the appropriate number of chemicals per reacting group. For example, 10 equivalents of aldehyde will be added per mol of the selected CBD that contain 10 Lysines.

The selected CBD is non volatile and does not change the character of the aldehyde.

M e

Improved release on dry fabrics is obtained by the slow hydrolysis of the selected CBD / perfume linkage.

Example 2 The following high density laundry detergent compositions were prepared according to the present invention :

I II III IV V VI

LAS 8.0 8.0 8.0 2.0 6.0 6.0

TAS - 0.5 - 0.5 1.0 0.1

C46(S)AS 2.0 2.5 - - - -

C25AS - - - 7.0 4.5 5.5

C68AS 2.0 5.0 7.0 - - -

C25E5 - - 3.4 10.0 4.6 4.6

C25E7 3.4 3.4 1.0 - - -

C25E3S - - - 2.0 5.0 4.5

QAS - 0.8 - - - -

QAS 1 - - - 0.8 0.5 1.0

Zeolite A 18.1 18.0 14.1 18.1 20.0 18.1

Citric - - - 2.5 - 2.5

Carbonate 13.0 13.0 27.0 10.0 10.0 13.0

Na-SKS-6 - - - 10.0 - 10.0

Silicate 1.4 1.4 3.0 0.3 0.5 0.3

Citrate - 1.0 - 3.0 - -

Sulfate 26.1 26.1 26.1 6.0 - -

Mg sulfate 0.3 - - 0.2 - 0.2

MA/AA 0.3 0.3 0.3 4.0 1.0 1.0

CMC 0.2 0.2 0.2 0.2 0.4 0.4

PB4 9.0 9.0 5.0 - - -

Percarbonate - - - - 18.0 18.0

TAED 1.5 0.4 1.5 - 3.9 4.2

NACA-OBS - 2.0 1.0 - - -

DETPMP 0.25 0.25 0.25 0.25 - -

SRP 1 - - - 0.2 - 0.2

EDDS - 0.25 0.4 - 0.5 0.5

CFAA - 1.0 - 2.0 - -

HEDP 0.3 0.3 0.3 0.3 0.4 0.4

QEA - - - 0.2 - 0.5

Protease 0.009 0.009 0.01 0.04 0.05 0.03

Amylase 0.002 0.002 0.002 0.006 0.008 0.008 I II III IV V VI

Cellulase 0.0007 0.0006 0.0007 0.0008 0.0007 0.001

Lipase 0.006 - - 0.01 0.01 0.01

Photoactivated 15 15 15 - 20 20 bleach (ppm)

PVNO/PVPVI - - - 0.1 - -

Brightener 1 0.09 0.09 0.09 - 0.09 0.09

Perfume 0.3 0.3 0.3 0.4 0.4 0.4

Silicone antifoam 0.5 0.5 0.5 - 0.3 0.3

CBD-Damascone 1.0 2.0 0.5 1.0 5.0 0.1

Density in g/litre 850 850 850 850 850 850

Miscellaneous and minors Up to 100%

Example 3

The following granular laundry detergent compositions of particular utility under European machine wash conditions were prepared according to the present invention :

I II Ill

LAS 5.5 7.5 7.0

TAS 1.25 1.9 0.3

C24AS/C25AS - 2.2 2.2

C25E3S - 0.8 1.0

C45E7 3.25 - 3.0

TFAA - - -

C25E5 - 5.5 -

QAS 0.8 - -

QAS 1 - 0.7 0.7

STPP 19.7 - -

Zeolite A - 19.5 17.0

NaSKS-6/citric acid (79:21) - 10.6 -

Na-SKS-6 - - 10.0

Carbonate 6.1 21.4 18.0

Bicarbonate - 2.0 2.0

Silicate 6.8 - - I II III

Citrate - - -

Sulfate 39.8 - 12.0

Mg sulfate - - -

MA/AA 0.5 1.6 1.0

CMC 0.2 0.4 0.4

PB4 5.0 12.7 -

Percarbonate - - 15.0

TAED 0.5 3.1 -

CBD-NACA-OBS 0.8 0.5 2.0

DETPMP 0.25 0.2 0.2

HEDP - 0.3 0.3

QEA - - -

Protease 0.009 0.03 0.02

Lipase 0.003 0.003 0.004

Cellulase 0.0006 0.0006 0.0007

Amylase 0.002 0.002 0.003

PVNO/PVPVI - - -

PVP 0.9 1.3 0.9

SRP 1 - - -

Photoactivated bleach (ppm) 15 27 20

Photoactivated bleach 1 (ppm) 15 - -

Brightener 1 0.08 0.2 0.15

Brightener 2 - 0.04 -

Perfume 0.3 0.5 0.3

Silicone antifoam 0.5 2.4 2.0

Density in g/litre 750 750 750

Miscellaneous and minors I up to 100%

Example 4

The following detergent formulations of particular utility under European machine wash conditions were prepared according to the present invention :

I II Blown Powder

LAS 6.0 5.0 11.0

TAS 2.0 - -

Zeolite A 24.0 - -

STPP - 27.0 24.0

Sulfate 4.0 6.0 13.0

MA/AA 1.0 4.0 6.0

Silicate 1.0 7.0 3.0

CMC 1.0 1.0 0.5

Brightener 1 0.2 0.2 0.2

Silicone antifoam 1.0 1.0 1.0

DETPMP 0.4 0.4 0.2

Spray On

Brightener 0.02 - -

C45E7 - - -

C45E2 2.5 2.5 2.0

C45E3 2.6 2.5 2.0

Perfume 0.5 0.3 0.5

Silicone antifoam 0.3 0.3 0.3

Dry additives

QEA - - -

EDDS 0.3 - -

Sulfate 2.0 3.0 5.0

Carbonate 6.0 13.0 15.0

Citric 2.5 - -

QAS 1 0.5 - -

Na-SKS-6 10.0 - -

Percarbonate 18.5 - -

PB4 - 18.0 10.0

TAED 0.5 2.0 -

CBD-NACA-OBS 2.0 1.0 3.0

CBD-PRP1 2.0 1.0 1.5

Cellulase 0.0004 0.0006 0.0006

Protease 0.03 0.03 0.03

Lipase 0.008 0.008 0.008 1 II III

Amylase 0.003 0.003 0.003

Brightener 1 0.05 - -

Miscellaneous and minors Up to 100%

Example 5

The following granular detergent formulations were prepared according to the present invention :

I II III IV V VI

Blown Powder

LAS 23.0 8.0 7.0 9.0 7.0 7.0

TAS - - - - 1.0 -

C45AS 6.0 6.0 5.0 8.0 - -

C45AES - 1.0 1.0 1.0 - -

C45E35 - - - - 2.0 4.0

Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0

MA/AA - 0.5 - - - 2.0

MA/AA 1 7.0 - - - - -

AA - 3.0 3.0 2.0 3.0 3.0

Sulfate 5.0 6.3 14.3 11.0 15.0 19.3

Silicate 10.0 1.0 1.0 1.0 1.0 1.0

Carbonate 15.0 20.0 10.0 20.7 8.0 6.0

PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0

DTPA - 0.9 0.5 - - 0.5

Brightener 2 0.3 0.2 0.3 - 0.1 0.3

Spray On

C45E7 - 2.0 - - 2.0 2.0

C25E9 3.0 - - - - -

C23E9 - - 1.5 2.0 - 2.0

Perfume 0.3 0.3 0.3 2.0 0.3 0.3

Agglomerates

C45AS - 5.0 5.0 2.0 - 5.0

LAS - 2.0 2.0 - - 2.0 I II III IV V VI

Zeolite A - 7.5 7.5 8.0 - 7.5

Carbonate - 4.0 4.0 5.0 - 4.0

PEG 4000 - 0.5 0.5 - - 0.5

Misc (Water etc.) - 2.0 2.0 2.0 - 2.0

Dry additives

QAS - - - - 1.0 -

Citric - - - - 2.0 -

PB4 - - - - 12.0 1.0

PB1 4.0 1.0 3.0 2.0 - -

Percarbonate - - - - 2.0 10.0

Carbonate - 5.3 1.8 - 4.0 4.0

NOBS 4.0 - 6.0 - - 0.6

Methyl cellulose 0.2 - - - - -

Na-SKS-6 8.0 - - - - -

STS - - 2.0 - 1.0 -

Culmene sulfonic - 1.0 - - - 2.0 acid

Protease 0.02 0.02 0.02 0.01 0.02 0.02

Lipase 0.004 - 0.004 - 0.004 0.008

Amylase 0.003 - 0.002 - 0.003 -

Cellulase 0.0003 0.0005 0.0005 0.0007 0.0005 0.0008

PVPVI - - - - 0.5 0.1

PVP - - - - 0.5 -

PVNO - - 0.5 0.3 - -

QEA - - - - 1.0 -

SRP 1 0.2 0.5 0.3 - 0.2 -

Silicone antifoam 0.2 0.4 0.2 0.4 0.1 -

Mg sulfate - - 0.2 - 0.2 -

CBD-Damascone - 2.0 1.0 - - -

CBD-Rotundial 1.0 0.5 0.1 3.0 2.0 5.0

Miscellaneous and minors Up to 100%

Example 6 The following nil bleach-containing detergent formulations of particular use in the washing of coloured clothing were prepared according to the present invention :

I II III

Blown Powder

Zeolite A 15.0 15.0 -

Sulfate - 5.0 -

LAS 3.0 3.0 -

DETPMP 0.4 0.5 -

CMC 0.4 0.4 -

MA/AA 4.0 4.0 -

Agglomerates

C45AS - - 11.0

LAS 6.0 5.0 -

TAS 3.0 2.0 -

Silicate 4.0 4.0 -

Zeolite A 10.0 15.0 13.0

CMC - - 0.5

MA/AA - - 2.0

Carbonate 9.0 7.0 7.0

Spray-on

CBD-Damascone 2.0 1.0 3.0

CBD-PRP1 3.0 - 4.0

Perfume 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0

Dry additives

MA/AA - - 3.0

Na-SKS-6 - - 12.0

Citrate 10.0 - 8.0

Bicarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO 0.5 0.5 0.5

Transferase 0.001 1.0 0.01

Substrate 0.1 - 5.0

Protease 0.03 0.02 0.05 1 II III

Lipase 0.008 0.008 0.008

Amylase 0.01 0.01 0.01

Cellulase 0.0008 0.001 0.001

Silicone antifoam 5.0 5.0 5.0

Sulfate - 9.0 -

Density (g/litre) 700 700 700

Miscellaneous and minors Up to 100%

Example 7

The following detergent formulations were prepared according to the present invention:

I II III IV

Base granule

Zeolite A 30.0 22.0 24.0 10.0

Sulfate 10.0 5.0 10.0 7.0

MA AA 3.0 - - -

AA - 1.6 2.0 -

MA/AA 1 - 12.0 - 6.0

LAS 14.0 10.0 9.0 20.0

C45AS 8.0 7.0 9.0 7.0

C45AES - 1.0 1.0 -

Silicate - 1.0 0.5 10.0

Soap - 2.0 - -

Brightener 1 0.2 0.2 0.2 0.2

Carbonate 6.0 9.0 10.0 10.0

PEG 4000 - 1.0 1.5 -

DTPA - 0.4 - -

Spray On

C25E9 - - - 5.0

C45E7 1.0 1.0 - -

C23E9 - 1.0 2.5 -

Perfume 0.2 0.3 0.3 -

CBD-Damascone 1.0 0.5 0.2 1.0 I II III IV

CBD-PRP1 3.0 5.0 1.0 -

Dry additives

Carbonate 5.0 10.0 18.0 8.0

PVPVI/PVNO 0.5 - 0.3 -

Pectinase 0.005 0.01 0.01 0.005

Protease 0.03 0.03 0.03 0.02

Lipase 0.008 - - 0.008

Amylase 0.002 - - 0.002

Cellulase 0.0002 0.0005 0.0005 0.0002

NOBS - 4.0 - 4.5

PB1 1.0 5.0 1.5 6.0

Sulfate 4.0 5.0 - 5.0

SRP 1 - 0.4 - -

Suds suppressor - 0.5 0.5 -

Miscellaneous and minors Up to 100%

Example 8

The following granular detergent formulations were prepared according to the present invention :

I II III

Blown Powder

Zeolite A 20.0 - 15.C

STPP - 20.0 -

Sodium sulfate - - 5.0

Carbonate - - 5.0

TAS - - 1.0

LAS 6.0 6.0 6.0

C68AS 2.0 2.0 -

Silicate 3.0 8.0 -

MA/AA 4.0 2.0 2.0

CMC 0.6 0.6 0.2

Brightener 1 0.2 0.2 0.1

DETPMP 0.4 0.4 0.1

STS _ _ 1.0 I II III

Spray On

C45E7 5.0 5.0 4.0

Silicone antifoam 0.3 0.3 0.1

Perfume 0.2 0.2 0.3

CBD-Rotundial 1.0 3.0 3.0

Dry additives

QEA - - 1.0

Carbonate 14.0 9.0 10.0

PB1 1.5 2.0 -

PB4 18.5 13.0 13.0

TAED 2.0 2.0 2.0

QAS - - 1.0

Photoactivated bleach 15 ppm 15 ppm 15 ppm

Na-SKS-6 - - 3.0

Laccase 0.02 0.06 0.003

Enhancer 1.0 0.8 0.8

Protease 0.03 0.03 0.007

Lipase 0.004 0.004 0.004

Amylase 0.006 0.006 0.003

Cellulase 0.0002 0.0002 0.0005

Sulfate 10.0 20.0 5.0

Density (g/litre) 700 700 700

Miscellaneous and minors Up to 100%

Example 9

The following detergent formulations were prepared according to the present invention:

I II III

Blown Powder

Zeolite A 15.0 15.0 15.0

Sulfate - 5.0 -

LAS 3.0 3.0 3.0 I II III

QAS - 1.5 1.5

DETPMP 0.4 0.2 0.4

EDDS - 0.4 0.2

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0

Agglomerate

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0

Spray On

CBD-Damascone 1.0 0.5 3.0

Perfume 0.3 0.3 -

C45E7 2.0 2.0 2.0

C25E3 2.0 - -

Dry Additives

Citrate 5.0 - 2.0

Bicarbonate - 3.0 -

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0

PB1 14.0 7.0 10.0

PEO - - 0.2

1 Bentonite clay - - 10.0

Mannanase 0.005 0.002 0.0008

Protease 0.03 0.03 0.03

Lipase 0.008 0.008 0.008

Cellulase 0.001 0.0007 0.001

Amylase 0.01 0.01 0.01

Silicone antifoam 5.0 5.0 5.0

Sulfate - 3.0 -

Density (g/litre I 850 850 850

Miscellaneous and minors Up to 100%

Example 10 The following detergent formulations were prepared according to the present invention:

I II III IV

LAS 18.0 14.0 24.0 20.0

QAS 0.7 1.0 - 0.7

TFAA - 1.0 - -

C23E56.5 - - 1.0 -

C45E7 - 1.0 - -

C45E3S 1.0 2.5 1.0 -

STPP 32.0 18.0 30.0 22.0

Silicate 9.0 5.0 9.0 8.0

Carbonate 11.0 7.5 10.0 5.0

Bicarbonate - 7.5 - -

PB1 3.0 1.0 - -

PB4 - 1.0 - -

CBD-NACA-OBS 1.5 0.8 - -

DETPMP - 1.0 - -

DTPA 0.5 - 0.2 0.3

SRP 1 0.3 0.2 - 0.1

MA/AA 1.0 1.5 2.0 0.5

CMC 0.8 0.4 0.4 0.2

PEI - - 0.4 -

Sulfate 20.0 10.0 20.0 30.0

Mg sulfate 0.2 - 0.4 0.9

Protease 0.03 0.03 0.02 0.02

Amylase 0.008 0.007 - 0.004

Lipase 0.004 - 0.002 -

Cellulase 0.0003 0.0001 0.0003 0.0001

Photoactivated bleach 30 ppm 20 ppm - 10 ppm

Perfume 0.3 0.3 0.1 0.2

CBD-Damascone - 1.0 0.5 2.0

Brightener 1/2 0.05 0.02 0.08 0.1

Miscellaneous and Minors up to 100%o Example 11

The following liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight) :

I II III IV V

LAS 11.5 8.8 - 3.9 -

C25E2.5S - 3.0 18.0 - 16.0

C45E2.25S 11.5 3.0 - 15.7 -

C23E9 - 2.7 1.8 2.0 1.0

C23E7 3.2 - - - -

CFAA - - 5.2 - 3.1

TPKFA 1.6 - 2.0 0.5 2.0

Citric (50%) 6.5 1.2 2.5 4.4 2.5

Ca formate 0.1 0.06 0.1 - -

Na formate 0.5 0.06 0.1 0.05 0.05

SCS 4.0 1.0 3.0 1.2 -

Borate 0.6 - 3.0 2.0 2.9

Na hydroxide 5.8 2.0 3.5 3.7 2.7

Ethanol 1.75 1.0 3.6 4.2 2.9

1 ,2 Propanediol 3.3 2.0 8.0 7.9 5.3

Monoethanolamine 3.0 1.5 1.3 2.5 0.8

TEPAE 1.6 - 1.3 1.2 1.2

Protease 0.03 0.01 0.03 0.02 0.02

Lipase - - 0.002 - -

Amylase - - - 0.002 -

Cellulase 0.001 0.0002 0.0002 0.0005 0.000

SRP 1 0.2 - 0.1 - -

DTPA - - 0.3 - -

PVNO - - 0.3 - 0.2

Brightener 1 0.2 0.07 0.1 - -

Silicone antifoam 0.04 0.02 0.1 0.1 0.1

CBD-Damascone 2.0 0.2 4.0 0.6 2.0

Miscellaneous and water Up to 100%

Example 12 The following liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight) :

I II III IV

LAS 10.0 13.0 9.0 -

C25AS 4.0 1.0 2.0 10.0

C25E3S 1.0 - - 3.0

C25E7 6.0 8.0 13.0 2.5

TFAA - - - 4.5

APA - 1.4 - -

TPKFA 2.0 - 13.0 7.0

Citric 2.0 3.0 1.0 1.5

Dodecenyl / tetradecenyl succinic 12.0 10.0 - - acid

Rapeseed fatty acid 4.0 2.0 1.0 -

Ethanol 4.0 4.0 7.0 2.0

1 ,2 Propanediol 4.0 4.0 2.0 7.0

Monoethanolamine - - - 5.0

Triethanolamine - - 8.0 -

TEPAE 0.5 - 0.5 0.2

DETPMP 1.0 1.0 0.5 1.0

Protease 0.02 0.02 0.01 0.008

Lipase - 0.002 - 0.002

Amylase 0.004 0.004 0.01 0.008

Cellulase 0.0005 0.0008 0.0003 0.002

SRP 2 0.3 - 0.3 0.1

Boric acid 0.1 0.2 1.0 2.0

Ca chloride - 0.02 - 0.01

Brightener 1 - 0.4 - -

Suds suppressor 0.1 0.3 - 0.1

Opacifier 0.5 0.4 - 0.3

CBD-Damascone 0.4 0.2 2.0 1.0

NaOH up to pH 8.0 8.0 7.6 7.7 Miscellaneous and water Up to 100% Example 13

The following liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight) :

I II III IV

LAC) ΔO.V

C25AS 13.0 18.0 15.0

C25E3S - 2.0 2.0 4.0

C25E7 - - 4.0 4.0

TFAA - 6.0 8.0 8.0

APA 3.0 1.0 2.0 -

TPKFA - 15.0 11.0 11.0

Citric 1.0 1.0 1.0 1.0

Dodecenyl / tetradecenyl succinic 15.0 - - - acid

Rapeseed fatty acid 1.0 - 3.5 -

Ethanol 7.0 2.0 3.0 2.0

1 ,2 Propanediol 6.0 8.0 10.0 13.0

Monoethanolamine - - 9.0 9.0

TEPAE - - 0.4 0.3

DETPMP 2.0 1.2 1.0 -

Protease 0.08 0.02 0.01 0.02

Lipase - - 0.003 0.003

Amylase 0.004 0.01 0.01 0.01

Cellulase 0.0003 0.0006 0.004 0.003

SRP 2 - - 0.2 0.1

Boric acid 1.0 1.5 2.5 2.5

Bentonite clay 4.0 4.0 - -

Brightener 1 0.1 0.2 0.3 -

Suds suppressor 0.4 - - -

Opacifier 0.8 0.7 - -

CBD-Damascone - 0.2 0.6 -

CBD-Rotundial 2.0 3.0 5.0 2.0

NaOH up to pH 8.0 7.5 8.0 8.2

Miscellaneous and water Up to 100% Example 14

The following liquid detergent compositions were prepared according to the present invention (Levels are given in parts by weight) :

I II

LAS 27.6 18.9

C45AS 13.8 5.9

C13E8 3.0 3.1

Oleic acid 3.4 2.5

Citric 5.4 5.4

Na hydroxide 0.4 3.6

Ca Formate 0.2 0.1

Na Formate - 0.5

Ethanol 7.0 -

Monoethanolamine 16.5 8.0

1 ,2 propanediol 5.9 5.5

Xylene sulfonic acid - 2.4

TEPAE 1.5 0.8

Protease 0.05 0.02

Cellulase 0.0003 0.0006

PEG - 0.7

Brightener 2 0.4 0.1

CBD-Rotundial 10.0 1.0

Perfume 0.5 0.3

Miscellaneous and water Up to 100%

Example 15

The following granular fabric detergent compositions which provide "softening through the wash" capability were prepared according to the present invention :

I II

C45AS - 10.0

LAS 7.6 1 II

C68AS 1.3 - C45E7 4.0 - C25E3 - 5.0

Coco-alkyl-dimethyl hydroxy1.4 1.0 ethyl ammonium chloride Citrate 5.0 3.0 Na-SKS-6 - 11.0 Zeolite A 15.0 15.0 MA/AA 4.0 4.0 DETPMP 0.4 0.4 PB1 15.0 -

Percarbonate - 15.0 TAED 5.0 5.0

Smectite clay 10.0 10.0 HMWPEO - 0.1 Protease 0.02 0.01 Lipase 0.02 0.01 Amylase 0.03 0.005 Cellulase 0.001 0.0009 Silicate 3.0 5.0 Carbonate 10.0 10.0 Suds suppressor 1.0 4.0 CMC 0.2 0.1

CBD-Damascone 0.8 1.2 Water/minors Up to 100%)

Example 16

The following rinse added fabric softener composition was prepared according to the present invention :

I II III

DEQA (2) 20.0 20.0 20.0 Cellulase D.001 0.001 0.001 HCL 0.03 0.03 0.03 I II III

Antifoam agent 0.01 0.01 0.01

Blue dye 25ppm 25ppm 25ppm

CaCl2 0.20 0.20 0.20

CBD-Rotundial 5.0 - 2.0

CBD-Damascone - 5.0 6.0

Perfume 0.90 0.90 0.90

Miscellaneous and water I Up to 100%

Example 17

The following fabric softener and dryer added fabric conditioner compositions were prepared according to the present invention :

I II III IV V

DEQA 2.6 19.0 - - -

DEQA(2) - - - - 51.8

DTMAMS - - - 26.0 -

SDASA - - 70.0 42.0 40.2

Stearic acid of IV=0 0.3 - - - -

Neodol 45-13 - - 13.0 - -

Hydrochloride acid 0.02 0.02 - - -

Ethanol - - 1.0 - -

Cellulase 0.0001 0.001 0.0005 0.005 0.0003

Perfume 1.0 1.0 0.75 1.0 1.5

Glycoperse S-20 - - - - 15.4

Glycerol monostearate - - - 26.0 -

Digeranyl Succinate - - 0.38 - -

Silicone antifoam 0.01 0.01 - - -

Electrolyte - 0.1 - - -

CBD-Damascone 0.6 1.0 2.0 0.4 3.0

CBD Rotundial 10.0 0.1 - 1.0 -

Clay - - - 3.0 -

Dye 10ppm 25ppm 0.01 - -

Water and minors 100% 100% - - - Example 18

The following laundry bar detergent compositions were prepared according to the present invention :

I II III VI V III VI V

LAS - - 19.0 15.0 21.0 6.75 8.8 -

C28AS 30.0 13.5 - - - 15.75 11.2 22.5

Na Laurate 2.5 9.0 - - - - - -

Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25

Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0

Ca Carbonate 27.5 39.0 35.0 - - 40.0 - 40.0

Sulfate 5.0 5.0 3.0 5.0 3.0 - - 5.0

TSPP 5.0 - - - - 5.0 2.5 -

STPP 5.0 15.0 10.0 - - 7.0 8.0 10.0

Bentonite clay - 10.0 - - 5.0 - - -

DETPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7

CMC - 1.0 1.0 1.0 1.0 - - 1.0

Talc - - 10.0 15.0 10.0 - - -

Silicate - - 4.0 5.0 3.0 - - -

PVNO 0.02 0.03 - 0.01 - 0.02 - -

MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4

SRP 1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Amylase - - 0.01 - - - 0.002 -

Protease - 0.004 - 0.003 0.003 - - 0.003

Lipase - 0.002 - 0.002 - - - -

Cellulase .0008 .0003 .0002 .0003 .0003 .0002 .0005 .0005

PEO - 0.2 - 0.2 0.3 - - 0.3

Perfume 1.0 0.5 0.3 0.2 0.4 - - 0.4

Mg sulfate - - 3.0 3.0 3.0 - - -

CBD- 1.0 - 2.5 1.0 3.0 - 0.2 0.4

Damascone

CBD-Rotundial 1.0 0.5 2.5 - 0.5 0.5 - 0.04

Brightener 0.15 0.1 0.15 - - - - 0.1

Photoactivated - 15.0 15.0 15.0 15.0 - - 15.0 bleach (ppm)

Claims

1. A chemical entity comprising a chemical component linked to an amino acid sequence comprising a cellulose binding domain characterised in that said amino acid sequence comprising a cellulose binding domain, has a binding constant for crystalline cellulose (Kr-c) of at least 10 l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or for amorphorous cellulose (Kr-am) of at least 1.5 l/g cellulose.

2. A chemical entity according to claim 1 wherein said amino acid sequence comprising a cellulose binding domain has a binding constant for crystalline cellulose (Kr-c) of at least 20 l/gcellulose, and/or a binding constant for Avicel (Kr-av) and/or for amorphorous cellulose (Kr-am) of at least 5 l/gcellulose.

A chemical entity according to claims 1-2 wherein said amino acid sequence comprising a cellulose binding domain having a binding constant for Avicel (Kr-av) and/or for amorphous cellulose (Kr-am) of at least 1.5 l/gcellulose, is selected from a fungal strain of Family I.

4. A chemical entity according to claims 1-2 wherein said amino acid sequence comprising a cellulose binding domain has a binding constant for crystalline cellulose (Kr-c) of at least 10 l/gcellulose, preferably 20l/gcellulose; and/or having a binding constant for Avicel (Kr-av) and/or for amorphous cellulose (Kr-am) of at least 5 l/gcellulose, is selected from a bacterial strain of Family II, III, or IV.

5. A chemical entity according to claims 1-4 wherein said amino acid sequence comprising a cellulose binding domain is selected from : CBD family 45 from the endoglucanase derived from Humicola insolens

DSM1800 with a molecular weight of about 43kDa, CBD E3 cellulase from Thermomonospora fusca, CBD Cellulozome from Clostridium cellulovorans, and/or mixtures thereof.

6. A chemical entity according to claims 1-5 wherein the chemical component is linked to said amino acid sequence comprising a cellulose binding domain via a linking region.

7. A chemical entity according to claim 6 wherein the linking region is a amino acid linking region.

8. A chemical entity according to claim 6 wherein the linking region is a polymer selected from PEG(NPC)2, (NH2)2-PEG, t-BOC-NH-PEG-NH2, MAL-PEG-NHS and/or VS-PEG-NHS polymers.

9. A chemical entity according to any of the preceding claims wherein said chemical component is linked to said amino acid sequence comprising a cellulose binding domain or to said linking region via a weak bond.

10. A chemical entity according to any of the preceding claims wherein said chemical component is selected from perfumes, hygiene agents, insect control agents, fabric softening agents, soil release agents, bleaching agents, dye fixatives agents, brigtheners, latex, resins, and/or mixtures thereof, preferably from perfumes, hygiene agents, insect control agents, and/or mixtures thereof.

11. A laundry detergent and/or fabric care composition comprising a laundry detergent and/or fabric care ingredient and a chemical entity according to any of the preceding claims.

12. A laundry detergent and/or fabric care composition according to claim 11 which is in the form of an additive, a pre-treatment, a post-treatment, a soaking treatment and/or a rinsing treatment composition.

13. A method of cleaning comprising the step of contacting a fabric with a chemical entity according to claims 1-10 or with a laundry detergent and/or fabric care composition according to claims 11-12 for providing fabric cleaning including soil and stain removal and/or fabric whiteness maintenance and/or fabric dye transfer inhibition.

14. A method comprising the step of contacting a fabric with a chemical entity according to claims 1-11 or with a laundry detergent and/or fabric care composition according to claims 11-12 for providing fabric care including anti-wrinkle, anti-bobbling, anti-shrinkage properties to fabrics, fabric softness, fabric freshness, color appearance and fabric anti-wear properties.

15. A method comprising the step of contacting a fabric with a chemical entity according to claims 1-10 or with a laundry detergent and/or fabric care composition according to claims 11-12 for providing sanifisation and/or insect control.