CA2262790A1

CA2262790A1 - Detergent compositions comprising alkaline polygalacturonase

Info

Publication number: CA2262790A1
Application number: CA002262790A
Authority: CA
Inventors: Ivan Maurice Alfons Jan Herbots; Andre Cesar Baeck
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1996-08-09
Filing date: 1996-08-09
Publication date: 1998-02-19
Also published as: IL128418A0; AU6951496A; JP2000507640A; CZ42799A3; EP0925347A1; AR009027A1; WO1998006809A1; HUP0000459A2

Abstract

The present invention relates to detergent compositions, including dishwashing, hard surface cleaning and laundry compositions containing an alkaline polygalacturonase enzyme for improved overall cleaning performance and enhanced stain/soil removal benefits and in particular improved removal of plant, dried-on fruit and vegetables juice soils/stains.

Description

W098/0~09 PCT~S96/12963 DETERGENT COMPOSITIONS COMPRISING ALKALINE
POLYGALACTURONASE

FIELD OF THE INVENTION

This invention relates to detergent compositions, including household cleaning, dishwashing and laundry compositions, comprising an alkaline polygalacturanase enzyme substantially free of other pectic enzymes.

BACKGROUND OF THE INVENTION

The overall performance of a detergent product, for use in washing or cleaning method, such as a laundry or dishwashing method, is judged by a number of factors, including the ability to remove soils, and the ability to prevent the redeposition of the soils, or the breakdown products of the soils on the articles in the wash.

Removal of stains stemming from plants, wood, mould-clay based soil and fruits is one of today~s toughest cleaning task; in particular with the trends to move to low wash temperatures. These stains typically contain complex mixtures of fibrous material based mainly on carbohydrates and their derivatives : fibres and cell wall components.

W098/06809 2 PCT~S96/12963 Plant based soils are additionally accompanied with amylose, sugars and their derivatives.

Food soils are often difficult to remove effectively from a soiled substrate. Highly coloured or 'dried-on' soils derived from fruit and/or vegetable juices are particularly challenging soils to remove. Specific examples of such soils would include orange juice, tomato juice, banana, mango or broccoli soils. The substrates can be fabrics, dishware or hard surfaces.

Pectic substances are found in, for example, fruit juices. The pectic substances act to hold dispersed particulates in suspension in such fruit juices, which will tend to be viscous and opaque in nature. Pectic enzymes are commonly used in the fruit/vegetable juice processing industry in the clarification of juices by breakdown of the pectic substances therein (depectinization).

German Patent Specification 3,635,427, published April 23, 1985 by Lion Corporation, is directed to phosphate-free detergents for cleaning clothes containing enzymes with pectinase activity, which is said to include such enzymes as polygalacturonase, pectin lyase, and/or pectinesterase.
However, aside from the general teachings therein relating to mixtures of these pectinase enzymes for the removal of inorganic soiling from clothes, the only specific teaching regarding an individual pectinase enzyme is found in Example 3, where the enzyme (designated "Enzyme D") is characterized as containing a large quantity of pectin lyase. Table III provides the results of the evaluation of this Enzyme D in a detergent formulation, indicating that this high pectin lyase mixture has the highest ~ pectinase activity (lO~) and one of the higher detergency values (83~) in combination with water-soluble high molecular compounds by comparison to the other enzyme compositions reported.

W098/0~09 3 PCT~S96/12963 Benefits for the specific use of polygalacturanase enzymes which is substantially free from other pectic enzymes in detergent formulations, particularly those designed for use in laundry, dishwashing and household cleaning operations have been recognized in the copending US patent application US08/529816.

It is an object of the present invention to provide laundry, dishwashing or household detergent compositions which provide improved soil / stain removal benefits when used in washing and cleaning operations.

According to the present invention, it has now been surprisingly found that the polygalacturonase enzyme having at least 10%, preferably 25~, more preferably 40~ of its optimum activity, at a pH ranging from 7 to ll and in particular with an optimum activity at a pH ranging from 7-ll improves significally the removal of a broad range of plant and fruit based stains and enhances the realistic item cleaning profile of the detergent compositions.

Indeed, the inclusion of alkaline polygalacturonase enzyme provides in particular improved removal of dried-on fruit and vegetables juice soils/stains.

In addition, it has been found that the alkaline polygalacturonase enzyme substantially free of other pectic enzymes presents improved compatibility and enhanced activity in the wash solution thereby providing improved removal of body, dried-on fruit and vegetables juice soils/stains, especially when stemming from heavy duty laundry or dishwashing compositions. It has also been found that the alkaline polygalacturonase enzyme substantially free of other pectic enzymes demonstrates a better compatibility with detergent matrix, e.g. during product process and shelf life.

W O 98/06809 4 rCTrUS96/12963 Furthermore, it has also been surprisingly been found that the inclusion of dispersants, particularly organic polymer dispersants, is of great value in detergent compositions containing alkaline polygalacturonase enzymes.
The dispersants aid dispersion of the breakdown products of the enzymatic soil degradation, thus preventing their redeposition on articles on the wash.

Improved cleaning performance has been also observed when the alkaline polygalacturonase enzymes are combined with other detergent enzymes. Enzymatic bleaching system or conventional activated bleach system together with alkaline polygalacturonase enzymes provides enhanced performance benefits on a wider range of stains.

Furthermore, polymers providing dye transfer inhibition combined with alkaline polygalacturonase enzymes results in improved whiteness maintenance and /or soil release properties.

SUMMARY OF THE INVENTION

The present invention relates to detergent compositions, including dishwashing, hard surface cleaning and laundry compositions comprising an alkaline polygalacturonase enzyme substantially free of other pectic enzymes for improved overall cleaning performance and enhanced stain / soil removal benefits and in particular improved removal of plant, dried-on fruit and vegetables juice soils/stains.

DETAILED DESCRIPTION OF THE INVENTION

Alakaline Polygalacturanase enzymes W098/~809 5 PCT~S96/12963 An essential component of the detergent compositions of the invention is an alkaline polygalacturanase enzyme.
The term "alkaline" is intended to cover polygalacturonase enzyme having an enzymatic activity of at least 10~, preferably 25~, more preferably 40~ of its optimum activity, at a pH ranging from 7 to 11 and to cover polygalacturonase enzyme having an optimum activity at a pH
ranging from 7 to 11. The enzymatic activity can be measured according to the "Assay of APGase" described by K.
Horikoshi in Agr. Biol. Chem, Vol 36(2), 286.

As used herein, "substantially free of other pectic enzymes" means polygalacturanase enzyme-containing compositions which contain less than 50% of pectic enzymes which are not alkaline polygalacturanase enzymes, preferably less than about 25~, more preferably less than about 10~, and most preferably less than about 5~. Such pectic enzymes include, for example, the pectin methylesterases which hydrolyse the pectin methyl ester linkages, and the pectin transeliminases or lyases which act on the pectic acids to bring about non-hydrolytic cleavage of alpha-1-4 glycosidic linkages to form unsaturated derivatives of galacturonic acid.

The alkaline polygalacturanase enzyme is preferably incorporated into the compositions in accordance with the invention at a level of from 0.0001~ to 2%, preferably from 0.0005~ to 0.5~, more preferably from 0.001~ to 0.1~ pure enzyme by weight of the total composition.

By alkaline polygalacturanase enzyme it is meant herein any enzyme which acts to break down pectic substances by cleaving the glycosidic bonds between galacturonic acid molecules. Pectic substances may be found in plant tissues, and are common constituents of fruit juices such as orange, tomato and grape juices.

W098/0~09 6 PCT~S96/12963 Pectic substances contain galacturonic acids and/or their derivatives.

Pectic substances include pectins and pectic acids.
Pectins are, in general, polymers made up of chains of galacturonic acids joined by alpha-1-4 glycosidic linkages.
Typically, in natural pectins approximately two-thirds of the carboxylic acid groups are esterified with methanol.
Partial hydrolysis of these methyl esters gives low methoxyl pectins, which tend to form gels with calcium ions. Complete methyl ester hydrolysis gives pectic acids.

Alkaline polygalacturanase enzymes herein include naturally derived alkaline polygalacturanase enzymes and any variants obtained by, for example, genetic engineering techniques.

Alkaline polygalacturonase enzymes are produced by alkalophilic microorganisms e.g. bacterial, fungal and yeast microorganisms such as Bacillus species. Preferred microorganisms are Bacillus firmus, bacillus circulans and bacillus subtilis as described in JP 56131376 and JP
56068393. Said enzymes can also be produced by the Erwinia species. Preferred are E. chrysanthemi, E. carotovora, E.
amylovora, E. herbicola, E. dissolvens as described in JP
59066588, JP 63042988 and in World J. Microbiol.
Microbiotechnol. ~8, 2, 115-120) 1992. Said alkaline degrading pectin enzymes can also be produced by Bacillus species as disclosed in JP 73006557 and Agr. Biol. Chem.
(1972), 36(2) 285-93.

Pectin degrading enzymes are produced by alkalophilic microorganisms e.g. bacterial, fungal and yeast microorganisms such as Bacillus species. Preferred microorganisms are Bacillus firmus, Bacillus circulans and Bacillus subtilis as described in JP 56131376 and JP
56068393. Pectin decomposing enzymes include galacturan-W098/06~9 7 PCT~S96tl2963 1/4-~-galacturonase (EC 3.2.1.67), poly-galacturonase activities (EC3.2.1.15, pectin esterase (EC 3.1.1.11), pectate lyase (EC 4.2.2.2) and their iso enzymes and they can be produced by the Erwinia species. Preferred are E.
chrysanthemi, E. carotovora, E. amylovora, E. herbicola, E.
dissolvens as described in JP 59066588, JP 63042988 and in World J. Microbiol. Microbiotechnol. (8, 2, 115-120) 1992.
Said pectin enzymes can also be produced by Bacillus species as disclosed in JP 73006557 and Agr. Biol. Chem.
(1972), 36(2) 285-93. Such enzymes may be used following purification to isolate polygalacturanase enzymes substantially free of other pectic enzyme. Preferred are pectic enzyme compositions consisting essentially of polygalacturanase enzymes.

Nowadays, it is common practice to modify wild-type enzymes via protein / genetic engineering techniques in order to optimise their performance efficiency in the cleaning compositions of the invention. For example, the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased. Alternatively, the variant may be designed such that the optimal pH, bleach stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular cleaning application.

In particular, attention should be focused on amino acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility. The isoelectric point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase in isoelectric point may help to improve compatibility with anionic surfactants. The stability of the enzymes may be further enhanced by the creation of e.g. additional salt bridges and enforcing calcium binding sites to increase chelant stability.

W098/06809 8 PCT~S96/12963 Dispersants It has also been surprisingly been found that the inclusion of dispersants, particularly organic polymer dispersants, is of great value in detergent compositions containing alkaline polygalacturonase enzymes. The dispersants aid dispersion of the breakdown products of the enzymatic soil degradation, thus preventing their redeposition on articles on the wash.

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 cleaning compositions of the present invention.

The compositions of the invention may contain a lime soap peptiser compound, which has 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 C.A. Bergman, W098/0~9 9 PCT~S96/12963 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 CaCo3 (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 C16-C1g dimethyl amine oxide, C12~Clg alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C12-Cls 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 /

W O 98/0680g 10 rCT~US96/12963 hydrophobic bleach formulations can also be used as lime soap peptisers compounds.

Detergent enzymes Improved removal of a broad range of plant and fruit based stains is achieved with a combination of alkaline polygalacturonase enzymes with other detergent enzyme.

Synergistic effects are observed from detergent compositions comprising an alkaline polygalacturonase enzyme and a cellulase, xylanase and/or protease.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
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 WO91/17243.

0 98/06809 11 rcTruss6ll2s63 Suitable xylanases include the commercail available xylanases like Pulpzyme HB and SP431 (Novo Nordisk), Lyxasan (Gist-Brocades), Optipulp and Xylanase (Solvay).

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B.
licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, 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 International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. 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.
Other preferred proteases include those of WO 95/10591 A to Procter & Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & ~amble. A
recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
In more detail, 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 W098/06809 12 PCT~S96/12963 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 W095/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No.
08/322,677, filed October 13, 1994. Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO91/06637 and the protease BLAP2 described in WO91/02792.

Improved plant and fruit stains / soils removal is observed with detergent compositions of the present invention further comprising starch-, sugar- and their derivatives-degrading enzymes such as amylase, gluco amylase, dextranase, pullulanase, invertase, laccase insulinase.

Suitable amylases (a and/or ~) to be included in the - detergent compositions of the present invention are W094~02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also W094/18314, Genencor, published August 18, 1994; WO95/10603, Novo Nordisk A/S, published April 20, 1995 and W096/05295, genencor, published February 22, 1996.
Other amylases known for use in cleaning compositions include both a- and ~-amylases. a-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 amylase are stability-enhanced amylases including Purafact Ox AmR
described in WO 94/18314, published August 18, 1994 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Examples of W098/0~09 13 PCT~S96/12963 commercial a-amylases products are Termamyl~, Ban~
,Fungamyl~ and Duramyl , all available from Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases :
a-amylases characterised by having a specific activity at least 25~ higher than the specific activity of Termamyl~ at a temperature range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Phadebas~ a-amylase activity assay. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.

Other carbohydrases combined with alkaline polygalacturonase enzymes show synergistic performance benefits, such as ~-glucanase (lichenase, laminarase) and exo-glucanase (lignase, tannase, pentosanase, malanase and hemi-cellulase) Finally, combinations of enzymes hydrolysing fat and waxes such as lipases, cutinases and wax esterases and alkaline polygalacturonase enzymes provide synergistic improved plant and fruit stains / soils removal 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 W098/06809 14 PCT~S96tl2963 Netherlands, and lipases ex Pseudomonas gladioli.
Especially suitable lipases are lipases such as M1 LipaseR
and LipomaxR (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 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).
The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001~ to 2~ of active enzyme by weight of the detergent composition.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels from 0.0001~ to 2~ of active enzyme by weight of the detergent composition. The enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g.
cogranulates ).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 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, W 0.98/06809 15 rCT~US96/12963 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.

Bleaching agent It has been found that a wider range of plant and/or fruit based stains / soils removal is achieved with detergent compositions comprising an enzymatic bleaching system or conventional activated bleach system in addition to the alkaline polygalacturonase enzyme.

Bleaching agents such as Hydrogen peroxide, PB1, PB4 and percarbonate with a particle size of 400-800 microns.
These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. When present oxygen bleaching compounds will typically be present at levels of from about 1~ to about 25~.

The bleaching agent component for use herein can be any of the bleaching agents useful for 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.

W098/0~09 16 PCT~S96/12963 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.

The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) 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 blèaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters such as disclosed in Copending European Patent Application No. 91870207.7.

Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent W098/0~09 17 PCT~S96/12963 compositions according to the invention are described in our co-pending applications USSN 08/136,626, PCT/US95/07823, W095/27772, W095/27773, W095/27774 and W095/27775.

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

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "stain and 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.

Preferred enhancers are substitued phenothiazine 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.

CA 02262790 l999-02-08 W 098/06809 18 rcT~uss6ll2s63 Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001g6 to 2~ of active enzyme by weight of the detergent composition.

Metal-containing catalysts for use in bleach compositions, include cobalt-containing catalysts such as Pentaamine acetate cobalt(III) 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.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033, 718.
Typically, detergent compositions will contain about 0. 025~
to about 1.25~, by weight, of sulfonated zinc phthalocyanine.

Dye transfer inhibition Enhanced whiteness maintenance and/or soil release properties have been observed when the detergent compositions of the present invention include compounds for inhibiting dye transfer from one fabric to another of CA 02262790 l999-02-08 W O 98/06809 19 PCTrUS96/12963 solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.

Polymeric dye transfer inhibiting agents The detergent compositions according to the present .

invention also comprise from 0.001~ to 10 ~, preferably from 0.01~ to 2~, more preferably from 0.05~ to 1~ by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into 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 contain units having the following structure formula :
p I

(I) AX
I
R

wherein P is a polymerisable unit, whereto the R-N-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both.

W098/06809 20 PCT~S96/12963 O O O
Il 11 11 A is NC, CO, C, -O-,-S-, -N- ; x is O or l;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O
group can be attached or wherein the nitrogen of the N-O group is part of these groups.

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

O O

(Rl)x -N- (R2~y =N- (Rl)x I

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

The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as W O 98/06809 21 rcT~us96ll2963 pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O
group is attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R
is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-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-W098/0~09 22 PCT~S96/12963 oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa ~ 7, more preferred PKa ~ 6.
The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 5,000-200,000.
Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-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 W098/06809 23 PCT~S96tl2963 5,000 to 50,000; more preferably from 8,000 to 30,000; most ~ preferably from 10,000 to 20,000.

The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0. 2, more preferably from 0.8 to 0. 3, most preferably from 0. 6 to 0.4 .

c) Polyvinylpyrrolidone The detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP'~) having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP
Corporation, New York, NY and Montreal, Canada under the product names PVP K- 15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP
K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000) . Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12;
polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262, 897 and EP-A-256,696) .

d) Polyvinyloxazolidone :

The detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye 098/0680g 24 PCT~S96/12963 transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.

e) Polyvinylimidazole :

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

f) Cross-linked polymers :

Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or 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 W098/06809 25 PCT~S96/12963 Deterqent components The cleaning compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.

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

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

Such compositions containing alkaline polygalacturonase enzyme can provide fabric cleaning, stain removal, whiteness maintenance, softening, color appearance and dye transfer inhibition when formulated as laundry detergent compositions.

When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric W098/06809 26 PCT~S96/12963 compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.

When formulated as compositions suitable for use in a laundry machine washing method, the compositions of the invention preferably contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional detergent components.

The compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.

If needed the density of the laundry detergent compositions herein ranges from 400 to 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 lO~, most preferably not exceeding 5~ by weight of the composition.

W098/0~09 27 PCT~S96/12963 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 cleaning compositions according to the present invention comprise a surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.
The surfactant is typically present at a level of from O.l~ to 60~ by weight. More preferred levels of incorporation are l~ to 35~ by weight, most preferably from l~ to 30~ by weight of cleaning 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.

.. ~ .. . .. .

WO 98/06809 28 PCTrUS96/12963 Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 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 IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about lO moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 WO 98/06809 29 PCTrUS96/12963 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporationi NeodolTM 45-9 ~the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C1s linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C14-C1s linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most 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 ~098/06~9 30 PCT~S96/12963 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 R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to 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 l-position). The additional glycosyl units can then be attached between their l-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 W098/0~09 31 PCT~S96/12963 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 PlurafacTM 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 Cg-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C1g alcohol ethoxylates (preferably C1o 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 Il I

W098/06809 32 PCT~S96/12963 O Rl _ wherein R1 is H, or R1 is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11_15 alkyl or C16_1g alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous 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 I I .
R3 - CH - C - oR4 I

wherein R3 is a Cg-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 monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is W0981068U9 33 PCT~S96/12963 Clo-C16 alkyl, and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates wherein R3 is C1o-C16 alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROS03M wherein R preferably is a C1o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C1o-C20 alkyl component, more preferably a C12-C1g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g. below about 50~C) and C16_18 alkyl chains are preferred for higher wash temperatures (e.g.
above about 50~C).
Other anionic surfactants useful for detersive purposes can also be included in the cleaning 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, Cg-C22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, Cg-C24 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 ... .

W098/0~09 34 PCT~S96112963 sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated Cl2-Clg monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-Cl2 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(CH2CH20)k-CH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from l to lO, 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 l~
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 Clo-C24 alkyl or hydroxyalkyl group having a ClO-C24 alkyl component, preferably a Cl2-C20 alkyl or hydroxyalkyl, more preferably Cl2-Cl8 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.), W O 98/06809 35 PCTrUS96/12963 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 ~uaternary 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 C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-ClgE(l.0)M)~ C12-C18 alkyl polyethoxylate (2 .25) sulfate (C12-C1gE(2 .25)M), C12-C1g alkyl polyethoxylate (3.0) sulfate (C12-ClgE(3.0)M), and C12-C1g alkyl polyethoxylate (4.0) sulfate (C12-C1gE(4.0)M), wherein M is conveniently selected from sodium and potassium.

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

Cationic detersive surfactants suitable for use in the cleaning compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula :
[R2(oR3)y]~R4(0R3)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-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose .__._ . .. .

W098/06809 36 PCTrUS96/12963 polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15;
and X is any compatible anion.

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

~o ~ ~Rs X-Formula I
whereby Rl is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :
o Formula II

y is 2-4, preferably 3.
whereby R2 is H or a Cl-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 (Cl-C3) or alkoxylated alkyl of the formula III, whereby X~ is a counterion, preferably a halide, e.g.
chloride or methylsulfate.

H

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

W O 98/06809 3 7 PCTrUS96/12963 Preferred quat ammonium surfactants are those as defined in formula I whereby Rl is C8, Clo or mixtures thereof, x=o, R3, R4 = CH3 and Rs = CH2CH20H.

Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
RlR2R3R4N X ( i ) wherein Rl is Cg-C16 alkyl, each of R2, R3 and R4 is independently Cl-C4 alkyl, Cl-C4 hydroxy alkyl, benzyl, and -(C2H40)XH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for Rl 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;
C12_15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein Rl is W098/0~09 38 PCT~S96/12963 CH2-CH2-O-C-C12_14 alkyl and R2R3R4 are methyl).
o di-alkyl imidazolines [compounds of formula (i)].

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

Typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives, 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) C12-14 alkyl hydroxyethyl dimethylammonium chloride;

11) Cl2-l8 alkyl dihydroxyethyl methylammonium chloride;

12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC)i 13) di(tallowoyloxyethyl) dimethylammonium chloride;

14) ditallow imidazolinium methylsulfate;

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

W098/0~09 39 PCT~S96/12963 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 :

R3\ R3 \/ 1 + N -(cH2)n-clH-cH2 X~
+ N-(CHk~-Q--T X R3 Q
Rl Tl T2 or (I) (II) wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR4-C(o)-, -C(o)-NR4-;
R1 is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is Cl-C4 alkyl or C1-C4 hydroxyalkyl or Hi R4 is H or Cl-C4 alkyl or Cl-C4 hydroxyalkyl;
Tl, T2, T3, T4, T5 are independently Cll-C22 alkyl or alkenyl;
n and m are integers from 1 to 4; and X~ is a softener-compatible anion.

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

The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched.

.. _....

Tallow ls a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein T1, T2, T3, T4, T5 represents the mixture of long chain materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :

1) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl 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 cleaning compositions of the present invention typically comprise from 0.2~ to about 25~, preferably from about 1~ to about 8~ by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the cleaning 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 W098/0~09 41 PCT~S96/12963 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 cleaning 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 cleaning 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 cleaning 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 _ _, .. . . . . .. . .

W 098/06809 42 PCT~US96112963 selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atomsi and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula o R3(oR4)xN(R5) 2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from O to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include Clo-C18 alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.

When included therein, the cleaning 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 cleaning 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 RlN~2 wherein R1 is a C6-C12 W098/06809 43 PCT~S96/12963 preferably C6-C10 alkyl chain or R4X(CH2)n, X is -O-,-C(O)NH- or -NH-, R4 is a C6-C12 alkyl chain n is between 1 to 5, preferably 3 . R1 alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from l-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2 -ethylhexyl-oxypropylamine, lauryl amido propylamine and amido propylamine.

Suitable tertiary amines for use herein include tertiary amines having the formula R1R2R3N wherein Rl and R2 are C1-C8 alkylchains or - (C112-CH - O ~H
R3 is either a C6-C12, preferably C6-C1o alkyl chain, or R3 is R4X (CH2)n, whereby X is -O-, -C(O) NH- or -NH- R4 is a C4 -C12, n is between 1 to 5, preferably 2-3. 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 Rl is a C6-C12 alkyl chain, R2 and R3 are Cl-C3 alkyl or Rl 5 - (CH2-CH - O ~H
where R5 is H or CH3 and x = 1- 2.

Also preferred are the amidoamines of the formula:

Rl - C-NH -(CH2n- N -(R2)2 W 0 98/06809 44 PCT~US96/12963 wherein R1 is C6-C12 alkyl; n is 2 -4, preferably n is 3; R2 and R3 is C1-C4 Most preferred amines of the present invention include l-octylamine, 1-hexylamine, l-decylamine, 1-dodecylamine,C8-lOoxypropylamine, N coco 1-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

Color care benefits Technologies which provide a type of color care benefit can also be included. Examples of these technologies are metallo catalysts for color maintenance. Such metallo catalysts are described in copending European Patent Application No. 92870181.2.

Builder system The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine W098/0~09 45 PCT~S96/12963 pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g. SKS-6 ~Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2O5).
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~l~2~2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane .

W 098/06809 46 PCT~US96/12963 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 -hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1, 425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

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

A suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or W 098/06809 47 PCT~US96/12963 magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
.

Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite 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.

Suds suppressor CA 02262790 l999-02-08 W O 98/06809 48 PCT~US96/12963 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, 199 2.
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.

W 098/06809 49 PCTrUS96/12963 The suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.

Others Other components used in cleaning compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.

Especially suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616.

Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.

Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ~.

CA 02262790 l999-02-08 W O 98/0680g 50 PCTAUS96/12963 ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.5~ to 10~ by weight, more preferably from 0.75~ to 8%, most preferably from 1~ to 6~ by weight of the composition.

Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-~2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis-~2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' - disulphonate, monosodium 4',4'' bis-(2,4-dianilino-s-tri-azin-6 ylamino)stilbene-2-sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2' disulphonate, di-sodium 4,4' -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2' disulphonate, di-so-dium 4,4'bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylami-no)stilbene-2,2'disulphonate, sodium 2(stilbyl-4''-(naphtho-1',2':4,5)-1,2,3 - triazole-2''-sulphonate and 4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred brighteners are the specific brighteners of copending European Patent application No. 95201943.8.

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

CA 02262790 l999-02-08 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-O 272 033 has the formula (CH3(PEG)43)0.75(poH)o.25[T-po)2.8(T-pEG)o.4]T( H)0.25((pEG)43cH3)o.75 where PEG is -(OC2H4)O-,po is (OC3H60) and T is ( pcOC6H4 CO ) .

Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46~ by weight of dimethyl terephthalic acid, about 1696 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 ... . . . ..... , . ,,, ............. ~

CA 02262790 l999-02-08 W 098/06809 52 PCT~US96/12963 method of preparation are described in detail in EPA 311 342.

Is is well known in the art that free chlorine in tap water rapidly deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1~ by weight of total composition, in the formulas will provide improved through the wash stability of the pectin enzyme. 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 ~(CH2CH2O)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.

Softening agent~

Fabric softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-l 400 898 and in USP
5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-Al 514 CA 02262790 l999-02-08 276 and EP-B0 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.

Levels of smectite clay are normally in the range from 2g~ to 20~, more preferably from 5~6 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 5g6 by weight, normally from 1~ to 3g6 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 29~, 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.

Method of washinq The compositions of the invention may be used in essentially any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.

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

. _ ...... . . .

W098/06809 54 PCT~S96/12963 The process of the inventlon is conveniently carried out in the course of the cleaning process. The method of cleaning is preferably carried out at 5~C to 95~C, especially between 10~C and 60~C. The pH of the treatment solution is preferably from 7 to ll.

A preferred machine dishwashing method comprises treating soiled articles with an aqueous liquid having dissolved or dispensed therein an effective amount of the machine diswashing or rinsing composition. A conventional effective amount of the machine dishwashing composition means from 8-60 g of product dissolved or dispersed in a wash volume from 3-lO litres.

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

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

In the detergent compositions, the enzymes levels are expressed by pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions. The abbreviated component identifications therein have the following meanings:

LAS : Sodium linear C12 alkyl benzene sulphonate W098/0~9 55 PCT~S96/12963 TAS : Sodium tallow alkyl sulphate CXYAS : Sodium C1x - C1y alkyl sulfate 25EY : A C12_C1s predominantly linear primary alcohol condensed with an average of Y
moles of ethylene oxide CXYEZ : A ClX - Cly predominantly linear primary alcohol condensed with an average of Z
moles of ethylene oxide XYEZS : ClX - Cly sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole QAS R2.N+(CH3)2 ~C2H40H) with R2 = C12-C14 Soap : Sodium linear alkyl carboxylate derived from a 80/20 mixture of tallow and coconut oils.

Nonionic : C13-C1s mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh.

CFAA : C12-C14 alkyl N-methyl glucamide TFAA : C16-C1g alkyl N-methyl glucamide.

TPKFA : C12-C14 topped whole cut fatty acids.

W 098/06809 56 PCT~US96112963 DEQA : Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.

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

Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by Shell Chemical CO.

Silicate : Amorphous Sodium Silicate (SiO2:Na2O
ratio = 2.0) NaSKS-6 : Crystalline layered silicate of formula â-Na2si2o5 .

Carbonate : Anhydrous sodium carbonate with a particle size between 200 ~m and 900~m.

Bicarbonate : Anhydrous sodium bicarbonate with a particle size between 400 ~m and 1200~m.

STPP : Anhydrous sodium tripolyphosphate MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000 PA30 : Polyacrylic acid of average molecular weight of approximately 8,000.

Terpolymer : Terpolymer of average molecular weight approx. 7,000, comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20 W098/~09 57 PCT~S96/12963 480N : Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500.

Polyacrylate : Polyacrylate homopolymer with an average molecular weight of 8,000 sold under the tradename PA30 by BASF GmbH

Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(AlO2SiO2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers Citrate : Tri-sodium citrate dihydrate of activity 86,4~ with a particle size distribution between 425 ~m and 850 ~m.

Citric : Anhydrous citric acid PB1 : Anhydrous sodium perborate monohydrate bleach, empirical formula NaBO2.H2O2 PB4 : Anhydrous sodium perborate tetrahydrate Percarbonate : Anhydrous sodium percarbonate bleach of empirical formula 2Na2CO3.3H2O2 TAED : Tetraacetyl ethylene diamine.

NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.

Photoactivated : Sulfonated zinc phtlocyanine Bleach encapsulated in dextrin soluble polymer.

PAAC : Pentaamine acetate cobalt(III) salt.

CA 02262790 l999-02-08 W 098/06809 58 PCTrUS96/12963 Paraffin : Paraffin oil sold under the tradename Winog 70 by Wintershall.

BzP : Benzoyl Peroxide.

Poly : Alkaline polygalacturonase as described galacturonase in Agr. Biol. Chem. (1972) 36(2) 285-93.

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

Amylase : Amylolytic enzyme sold under the tradename Purafact Ox Am~ described in WO 94/18314, sold by Genencor; Termamyl~
, Fungamyl~ and Duramyl , all available from Novo Nordisk A/S and those described in W095/26397.

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

Cellulase : Cellulytic enzyme sold under the tradename Carezyme, Celluzyme and/or Endolase by Novo Nordisk A/S.

CMC : Sodium carboxymethyl cellulose.

HEDP : l,l-hydroxyethane diphosphonic acid.

W 098/06809 59 rCTAUS96112963 DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.

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

PVPVI : Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl-imidazole and vinyl-pyrrolidone.

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 : Polydimethylsiloxane foam controller antifoam with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

Granular Suds : 12~ Silicone/silica, 18~ stearyl Suppressor alcohol,70~ starch in granular form SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone.

SRP 2 : Diethoxylated poly (1,2 propylene terephtalate) short block polymer.

Sulphate : Anhydrous sodium sulphate.

HMWPEO : High molecular weight polyethylene oxide W O 98/06809 60 rCT~US96112963 PEG : Polyethylene glycol.

BTA : Benzotriazole Bismuth nitrate : Bismuth nitrate salt NaDCC : Sodium dichloroisocyanurate Encapsulated : Insoluble fragrance delivery technology perfume utilising zeolite 13x, perfume and a particles dextrose/glycerin agglomerating binder.

KOH : 100~ Active solution of Potassium Hydroxide pH : Measured as a 1~ solution in distilled water at 20~C.

W098/06809 61 PCT~S96/12963 Example 1 The following laundry detergent compositions were prepared in accord with the invention:

I II III IV V VI
LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3 4 QAS - 0.8 0.8 - 0.8 0.8 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5. 1.5 1.5 1.5 1.5 DETPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.3 0.3 0.3 0.3 Poly 0.005 0.01 0.05 0.01 0.02 0.08 galacturonase Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026 Amylase 0.0009 0.0009 0.0009 0.0009 0.0009 0.0009 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Photoactivated 15 15 15 15 15 15 bleach (ppm) Brightener 10.09 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 Silicone 0.5 0.5 0.5 0.5 0.5 0.5 antifoam Misc/minors to 100%
Density in 850 850 850 850 850 850 g/litre _ .. . . , .. . , .. , . ,, . .. .. _ ., W098/06809 62 PCT~S96/12963 Example 2 The following granular laundry detergent compositions of bulk density 750 g/litre were prepared in accord with the invention:

I II III

LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 QAS 0.8 2.0 2.0 STPP 19.7 Zeolite A - 19.5 19.5 NaSKS-6/citric acid - 10.6 10.6 (79:21) Carbonate 6.1 21.4 21.4 Bicarbonate - 2.0 2.0 Silicate 6.8 Sodium sulfate 39.8 - 14.3 PB4 5.0 12.7 TAED 0.5 3.1 DETPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 Poly galacturonase 0.001 0.02 0.005 Protease 0.0026 0.0085 0.045 Lipase 0.003 0.003 0.003 Cellulase 0.0006 0.0006 0.0006 Amylase 0.0009 0.0009 0.0009 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 Photoactivated 15 ppm 27 ppm 27 ppm bleach (ppm) Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0.04 Encapsulated perfume0.3 0.3 0.3 particles Silicone antifoam 0.5 2.4 2.4 Minors/misc to 100~

Example 3 The following detergent formulations, according to the present invention were prepared, where I is a phosphorus-containing detergent composition, II is a zeolite-containing detergent composition and III is a compact detergent composition:

I II III
Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 C45AS 9.0 6.0 13.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DETPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated 0.02 0.02 0.02 bleach Poly galacturonase 0.05 0.05 0.01 Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.002 0.003 0.001 Dry mixed sodium 3.0 3.0 5.0 sulfate Balance (Moisture &100.0 100.0 100.0 Miscellaneous) Density (g/litre) 630 670 670 . _ , ,, , _, ... . . .

W098/0~09 64 PCT~S96/12963 ExamPle 4 The following nil bleach-containing detergent formulations of particular use in the washing of colored clothing, according to the present invention were prepared:
I II III
Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 5.0 LAS 3.0 3.0 DETPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 4.0 4.0 Agglomera tes 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 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On ~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 NaSKS-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 Poly galacturonase 0.05 0.005 0.02 Protease 0.026 0.016 0.047 Lipase 0.009 0.009 0.009 Amylase 0.005 0.005 0.005 Cellulase 0.006 0.006 0.006 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 9.0 0.0 Balance tMoisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 700 700 700 W098/06809 65 PCT~S96/12963 Example 5 The following detergent formulations, according to the present invention were prepared:

II III IV
LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 - -C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 Bicarbonate - 7.5 DETPMP 0.7 1.0 SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Poly 0.08 0.04 0.05 0.01 galacturonase Protease 0.008 0.01 0.026 0.026 Amylase 0.007 0.004 - 0.002 Lipase 0.004 0.002 0.004 0.002 Cellulase 0.0015 0.0005 Photoactivated 7Oppm 45ppm - lOppm bleach (ppm) Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 NOBS 2.0 1.0 Balance 100 100 100 100 (Moisture and Miscellaneous) W098/06809 66 PCT~S96112963 Example 6 The following detergent formulations, according to the present invention were prepared:

I II III IV
Blown Powder Zeolite A 30.0 22.0 6.0 6.7 Na SkS-6 - - _ 3.3 Polycarboxylate - - - 7.1 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 14.0 12.0 22.0 21.5 C45AS 8.0 7.0 7.0 5.5 Cationic - - - 1.0 Silicate - 1.0 5.0 11.4 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 10.0 DETPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 3.2 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Poly galacturonase0.005 0.01 0.01 0.005 Protease 0.052 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 0.009 Amylase 0.001 0.001 0.001 0.001 Cellulase 0.0002 0.0002 0.0002 0.0002 NOBS - 6.1 4.5 3.2 PB1 1.0 5.0 6.0 3.9 Sodium sulfate - 6.0 - to balance Balance (Moisture 100 100 100 and Miscellaneous) W098/06809 67 PCT~S96/12963 Example 7 The following high density and bleach-containing detergent formulations, according to the present invention were prepared:
I II III

- Blown Powder Zeolite A15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3 0 QAS - 1.5 1.5 DETPMP 0.4 0.4 0.4 CMC 0.4 0.4 0 4 MA/AA 4.0 2.0 2.0 Agglomerates 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 Perfume 0.3 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 Polyethylene oxide of MW - - 0.2 5,000,000 Bentonite clay - - 10.0 Poly galacturonase 0.005 0.01 0.08 Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.005 0.005 0.005 Cellulase 0.002 0.002 0.002 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 850 W O g8/06809 68 rcTrusg61l2963 Exam~le 8 The following high density detergent formulations, according to the present invention were prepared:

I II
Agglomerate C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 o 5 DETPMP 0.4 0.4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Adds HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.8 Poly galacturonase 0.02 0. 05 Protease 0.04 0.04 Lipase 0.009 0.009 Cellulase 0.004 0.004 Amylase 0. 005 0. 005 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 Balance (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850 W098/06809 69 PCT~S96/12963 Example 9 The following granular detergent formulations, according to the present invention were prepared:

I II III IV V
LAS 21.0 25.0 18.0 18.0 Coco C12-14 AS - - - - 21.9 AE3S - - 1.5 1.5 2.3 Decyl dimethyl - 0.4 0.7 0.7 0.8 hydroxyethyl NH4+Cl Nonionic 1.2 - o g 0 5 Coco C12-14 Fatty - - - - 1.0 Alcohol STPP 44.0 25.0 22.5 22.5 22.5 Zeolite A 7.0 10.0 - - 8.0 MA/AA - - o.g o.g SRPl 0.3 0.15 0.2 0.1 0.2 CMC 0.3 2.0 0.75 0.4 1.0 Carbonate 17.5 29.3 5.0 13.0 15.0 Silicate 2.0 - 7.6 7.9 Poly galacturonase0.0050.01 0.007 0.01 0.01 Protease 0.0070.007 0.007 0.007 0.007 Amylase - 0.004 0.004 0.004 0.004 Lipase 0.0030.003 0.003 Cellulase - 0.001 0.001 0.001 0.001 NOBS - - - 1.2 1.0 PB1 - - - 2.4 1.2 Diethylene triamine - - - 0.7 1.0 penta acetic acid Diethylene triamine - - 0.6 penta methyl phosphonic acid Mg Sulfate - - 0.8 Photoactivated bleach 45 50 15 45 42 ppm ppmppm ppm ppm Brightener 1 0.05 - 0.04 0.04 0.04 W 098/06809 70 PCT~US96/12963 Brightener 2 0.1 0.3 0.05 0.13 0.13 Water and Mlnors up to 100~

W098/06809 71 PCT~S96112963 Example 10 The following liquid detergent formulations, according to the present invention were prepared:
I II III IV V VI VII VIII
LAS 10.0 13.0 9.0 - 25.0 - - -C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFAA - - - 4.5 - 6.0 8.0 8.0 QAS - - - - 3.0 1.0 TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0 Rapeseed - - - 5.0 - -4 0 4 0 fatty acids Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenyl/ 12.0 10.0 - - 15.0 tetradecenyl succlnlc acld Oleic acid 4.0 2.0 1.0 - 1.0 - - -Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-Propanediol Mono Ethanol - - - 5.0 - - 9.0 9.0 Amine Tri Ethanol - - 8 Amine NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3 tetraethylene pentamine DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1 PVNO - - - - - -- 0.10 Poly .005 .005 .004 .003 .008 .005.003 .006 galacturonase Protease .016 .016 .013 .008 .048 .0160.01 .019 Lipase - .002 - .001 - - 003 .00 WO 98106809 72 PCTrUS96/12963 Amylase .002 .002.005 .004 .002 .008.005 .005 Cellulase - -- .ooo - - ooo ooo Boric acid 0.1 0.2- 2.0 1.0 1.52.5 2.5 Na formate - - 1.0 - - - _ _ Ca chloride - 0.01 - 0.01 Bentonite - - - - 4.0 4 0 clay Suspending - - - - 0.6 0.3 clay SD3 Balance 100 100 100 100 100 100 100 100 Moisture and Miscellaneous W098/06809 73 PCT~S96/12963 ExamPle 1 1 Granular fabric cleaning compositions which provide "softening through the wash" capability were prepared in accord with the present invention :

I II
45AS - 10.0 LAS 7.6 68AS 1.3 45E7 4.0 Coco-alkyl-dimethyl hydroxy- 1.4 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 o 4 o 4 P~31 15.0 Percarbonate - 15.0 TAED 5.0 5 0 Smectite clay 10.0 10.0 HMWPEO - 0.1 Poly galacturonase 0.01 0.01 Protease 0.02 0.1 Lipase 0.02 0.01 Amylase 0.03 0.005 Cellulase 0.001 Silicate 3.0 5.0 Carbonate 10.0 10.0 Granular suds suppressor 1.0 4.0 CMC 0.2 0.1 Water/minors Up to 100~

.. _~, .. , . ,. . ~

W O 98/06809 74 PCT~US96/12963 Exam~le 12 The following rinse added fabric softener composition was prepared in accord with the present invention :

Softener active 20.0 Poly galacturonase 0.01 Amylase 0.001 Cellulase 0.001 HCL 0.03 Antifoam agent 0.01 Blue dye 25ppm CaCl2 0.20 Perfume o.go Water / minors Up to 100~

W098/06809 75 PCT~US96/12963 Example 13 The following fabric softener composition was prepared in accord with the present invention :

I II III
DEQA 2.6 19.0 SDASA _ _ 70 0 Stearic acid of IV=O 0.3 _ _ Neodol 45-13 - - 13.0 Hydrochloride acid 0.02 0.02 Ethanol - - 1.0 PEG - 0.6 Poly galacturonase 0. 005 0.05 0.01 Perfume 1.0 1.0 0.75 Digeranyl Succinate - - 0.38 Silicone antifoam 0.01 0.01 Electrolyte - 60Oppm Dye lOOppm 50ppm 0.01 Water and minors 100~ 100~

Example 14 Syndet bar fabric cleaning compositions were prepared in accord with the present invention :

I II III IV
C26 AS 20.00 20.00 20.00 20.00 CFAA 5 0 5 0 5 o 5 0 ~AS (C11-13) 10.0 10.0 10.0 10.0 Sodium carbonate 25.0 25.0 25.0 25.0 Sodium pyrophosphate 7.0 7.0 7.0 7.0 STPP 7. 0 7.0 7.0 7.0 Zeolite A 5.0 5.0 5.0 5.0 CMC 0.2 0.2 0.2 0.2 Polyacrylate (MW 1400) 0.2 0.2 0.2 0.2 Coconut monethanolamide 5.0 5.0 5.0 5.0 Poly galacturonase 0.1 0.1 0.15 0.2 Amylase 0.01 0.02 0.01 0.01 Protease 0.3 - 0.5 0.05 Brightener, perfume 0.2 0.2 0.2 0.2 CaS04 1.0 1.0 1.0 1.0 MgSO4 1.0 1.0 1.0 1.0 Water 4.0 4.0 4.0 4.0 Filler* : balance to 100~

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

CA 02262790 l999-02-08 098/06809 77 PCTrUS96/12963 ExamPle 15 The following compact high density (0.96Kg/l) dishwashing detergent compositions I to VI were prepared in accord with the present invention:

I II III IV V VI
STPP - - 49.0 38.0 Citrate 33.0 17.5 - - 54.0 25.4 Carbonate - 17. 5 _ 20.0 14.0 25.4 Silicate 33.0 14.8 20.4 14.8 14.8 Metasilicate - 2. 5 2.5 PB1 1.9 9.7 7.8 14.3 7.8 PB4 8.6 Percarbonate - - - - - 6.7 Nonionic 1.5 2.0 1.5 1.5 1.5 2.6 TAED 4.8 2.4 2.4 - 2.4 4.0 HEDP 0.8 1.0 0.5 DETPMP 0.6 0.6 PAAC - - - 0.2 BzP - - - 4.4 Paraffin 0.5 0.5 0.5 0.5 0.5 0.2 Poly 0.07 0.05 0.1 0.1 0.08 0.01 galacturonase Protease 0.075 0.05 0.10 0.10 0.08 0.01 Lipase - 0.001 - 0.005 Amylase 0.01 0.0050.015 0.015 0.010.0025 BTA 0.3 0.3 0.3 0.3 0.8 Bismuth Nitrate - 0.3 PA30 4.0 Terpolymer - - - 4.0 480N - 6.0 2.8 Sulphate 7.1 20.8 8.4 - 0.5 1.0 pH (1~ solution) 10.8 11.0 10.9 10.8 10.9 9.6 ~ .. . . .. . .. . .

W O 98/0C809 78 PCT~US96/12963 ExamPle 16 The following granular dishwashing detergent compositions examples I to IV of bulk density 1.02Kg/L were prepared in accord with the present invention :

I II III IV V VI
STPP 30.0 30.0 30.0 27.9 34.5 26.7 Carbonate 30.5 30.5 30 5 23.0 30.5 2.80 Silicate 7.4 7.4 7 4 12.0 8.0 20.3 PBl 4.4 4.4 4.4 - 4 4 NaDCC - - - 2.0 - 1.5 Nonionic 0.75 0.75 0.75 1.9 1.2 0.5 TAED 1.0 1.0 - - 1.0 BzP - 1.4 Paraffin 0.25 0.25 0.25 Poly 0.01 0.01 0.01 0.05 0.01 0.05 galacturonase Protease 0.05 0.05 0.05 - 0.1 Lipase 0.005 - 0.001 Amylase 0.003 0.001 0.01 0.02 0.01 0.015 BTA 0.15 - 0.15 Sulphate 23.9 23.9 23.9 31.4 17.4 pH (1~ solution) 10.8 10.8 10.8 10.7 10.7 12.3 W098/06809 79 PCT~S96/12963 Example 17 The following detergent composition tablets of 25g weight were prepared in accord with the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:

I II III
STPP 48.8 47.5 Citrate 26.4 - -Carbonate - 5.0 Silicate 26.4 14.8 25.0 Poly galacturonase 0.007 0.01 0.05 Protease 0.03 0.075 0.01 Lipase 0.005 Amylase 0.01 0.005 0.001 PBl 1.6 7.8 PB4 6.9 - 11.4 Nonionic 1.2 2.0 1.1 TAED 4.3 2.4 0.8 DETPMP 0.65 Paraffin 0.4 0.5 BTA 0.2 0.3 PA30 3.2 Sulphate 25.0 14.7 3.2 pH (1~ solution) 10.6 10.6 11.0 ... ..

W09~06809 80 PCT~S96112963 Example l8 The following liquid dishwashing detergent compositions were prepared in accord with the present invention I to II, of density 1.40Kg/L :

I II
STPP 33.3 20.0 Carbonate 2.7 2.0 Silicate - 4.4 NaDCC l.l l.15 Nonionic 2.5 l.0 Paraffin 2.2 Poly galacturonase 0.005 0.05 Protease 0.03 0.02 Amylase 0.005 0.0025 KOH - 6.00 Sulphate l.6 pH (l~ solution) 9.l l0.0 W O 98/06809 8l PCT~US96/12963 Example 19 The following liquid hard surface cleaning compositions were prepared in accord with the present invention :

I II III IV V VI
Poly galacturonase 0.005 0.01 0.02 0.02 0.005 0.005 Amylase 0.01 0.002 0.005 0.02 0.001 0.005 Protease 0.05 0.01 0.02 0.03 0.005 0.005 EDTA* - - 2.90 2.90 - -Citrate - - - - 2.90 2.90 LAS 1.95 - 1.95 - 1.95 C12 AS - 2.20 - 2.20 - 2.20 NaC12(ethoxy) - 2.20 - 2.20 - 2.20 **sulfate C12 Dimethylamine - 0.50 - 0.50 - 0.50 oxide SCS 1.30 - 1.30 - 1.30 Hexyl Carbitol**6.306.30 6.30 6.30 6.30 6.30 Water Balance to 100 *Na4 ethylenediamine diacetic acid **Diethylene glycol monohexyl ether ***All formulas adjusted to pH 7 _. .. . .

W O 98/06809 82 rCTrUS96/12963 Example 20 The following spray composition for cleaning of hard surfaces and removing household mildew was prepared in accord with the present invention :

Poly galacturonase 0.01 Amylase 0.01 Protease 0.01 Sodium octyl sulfate 2.00 Sodium dodecyl sulfate 4.00 Sodium hydroxide 0. 80 Silicate (Na) 0.04 Perfume 0.35 Water/minors up to 100

Claims

1. A detergent composition comprising a polygalacturonase enzyme substantially free of other pectic enzymes having an enzymatic activity of at least 10%, preferably 25%, more preferably 40% of its optimum activity, at pH ranging from 7 to 11.

2. A detergent composition according to claim 1 wherein said polygalacturonase enzyme has an optimum activity at a pH ranging from 7 to 11.

3. A detergent composition according to claims 1-2 wherein said polygalacturonase enzyme is present at a level from 0.0001% to 2%, preferably from 0.0005% to 0.5%, more preferably from 0.001% to 0.1% pure enzyme by weight of total composition.

4. A detergent composition according to claims 1-3 comprising less than 25%, preferably less than 10%, more preferably less than 5% by weight of the polygalacturonase enzyme, of other pectic enzymes.

5. A detergent composition according to any of the preceding claims further comprising a dispersant.

6. A detergent composition according to any of the preceeding claim further comprising another detergent enzyme.

7. A detergent composition according to claim 6 wherein said detergent enzyme is selected from cellulase, protease, lipase and/or amylase.

8. A detergent composition according to any of the preceding claims further comprising an enzymatic bleach system.

9. A detergent composition according to any of the preceding claims further comprising a conventional activated bleach system with a Mn-based bleach catalyst.

10. A detergent composition according to any of the preceding claims further comprising a dye transfer inhibiting polymer.

11. A detergent composition according to any of the preceding claims characterised in that said composition is in the liquid, paste, gel, bar, tablets, powder or granular form.

12. A detergent additive comprising a polygalacturonase enzyme substantially free of other pectic enzymes having an enzymatic activity of at least 10%, preferably 25%, more preferably 40% of its optimum activity, at pH ranging from 7 to 11.

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

14. Use of a detergent composition according to claims 1-12 for cleaning hard surfaces such as floors, walls, bathroom tile and the like.

15. Use of a detergent composition according to claims 1-12 for hand and machine dishwashing.