EP1141204A1 - Detergent compositions comprising a pectate lyase and a low foaming nonionic surfactant - Google Patents

Abstract

The present invention relates to detergent compositions comprising a pectate lyase and a low foaming nonionic surfactant for providing improved plant-based soils/stains, spotting and filming performance as well as improved cleaning performance on greasy soils and suds or foam suppression.

Description

DETERGENT COMPOSITIONS COMPRISING A PECTATE LYASE AND A LOW FOAMING NONIONIC SURFACTANT

Field of the Invention

The present invention relates to detergent compositions comprising a pectate lyase and a low foaming nonionic surfactant.

Background of the invention

Performance of a detergent product 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. Therefore, detergent compositions include nowadays a complex combination of active ingredients which fulfill certain specific needs. In particular, current detergent formulations generally include surfactants and detergent enzymes providing cleaning and fabric care benefits.

Removal of stains stemming from plants, wood, mould-clay based soils, muddy soils, and fruits is one of today's toughest cleaning task; especially with the trend toward low wash temperatures. These stains typically contain complex mixtures of fibrous material based mainly on carbohydrates and their derivatives : fibres and cell wall components. 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 to remove. Specific examples of such soils would include orange juice, tomato juice, banana, mango or broccoli soils. Indeed, pectin polymers are important constituents of plant cell walls. Pectin is a hetero-polysaccharide with a backbone composed of alternating homogalacturonan (smooth regions) and rhamnogalacturonan (hairy regions). The smooth regions are linear polymers of 1 ,4-linked alpha-D-galacturonic acid. The galacturonic acid residues can be methyl-esterified on the carboxyl group to a varying degree, usually in a non-random fashion with blocks of polygalacturonic acid being completely methyl-esterified. The substrates on which pectin containing stains are commonly found can be fabrics, dishware or hard surfaces.

In addition, the complex nature of everyday "body" soils typically found on pillow cases, T-shirts, collars and socks, provides a continuous thorough cleaning challenge for detergents. These soils are difficult to remove completely due in part to their interaction with the pectin components in the primary cell walls of cotton fibers comprising cotton containing fabrics, and often residues build up on such fabric leading to dinginess and yellowing. Moreover, body fluid stains, such as blood and menstrual fluids, are often difficult to remove effectively from a soiled item, especially when the stains have been aged. Everyday body soils are also found on sanitary and kitchen surfaces such as bathtubs, toilet bowls and dishware.

Dishwashing and hard surface cleaning, in particular automatic dishwashing in domestic appliances, is an art very different from fabric laundering. Domestic fabric laundering is normally done in purpose-built machines having a tumbling action. These are very different from spray-action domestic automatic dishwashing appliances. The spray action in the latter tends to cause foam. Foam can easily overflow the low sills of domestic dishwashers and slow down the spray action, which in turn reduces the cleaning action. In addition, in horizontal axis machine laundry system, foam generation can also be a significant problem. Thus in both machine dishwashing and laundry, the use of common foam-producing detergent surfactants may be restricted.

One solution to this foaming problem has been to include a suds suppressor, typically a silicone suds suppressor. However, this solution while it works to a certain extent in fabric laundering compositions, fails in domestic dishwashers. The high shear forces involved in domestic dishwashers breaks down the silicone suds suppressors, so any suds suppressors present at the start of the wash is gone before the end. The silicone suds suppressors are not robust enough to survive in the environment of a domestic dishwasher. Even in laundry applications, while less shear than that in a domestic dishwasher, there is still a drop off in suds suppression towards the end of the washing cycle, because of the break down of the silicone suds suppressor. One alternative would be increase the amount of silicone suds suppressor present, however the cost of silicone suds suppressors and the fact that they have a tendency to redeposit on hydrophobic surfaces, such as plastic and polyestert, makes this an undesirable solution. There remains today the need for a viable and cost effective alternative to silicone suds suppressor suitable for use in automatic dishwashers as well as laundry washing machines.

Moreover, many compositions heretofore proposed for cleaning dishware and hard surfaces have had aesthetic and technical disadvantages, not the least of which is undesirable spots and films on the cleaned surfaces. These undesirable spots and films may be caused by redeposition of soils and cleaning agents such as surfactants which have a low solubility in water. Alternatively, the composition may provide desirable results with respect to undesirable spots and films, and provide excellent cleaning but be totally unsuitable because of the high foam it produces.

In addition, there continues to be a need for better cleaning, especially for reduction of spotting and filming and removal of greasy soils.

Accordingly, the need remains for compositions which can deliver improved plant- and dirt-based soils/stains removal, improved spotting and filming benefits as well as greasy soil removal while providing improved spotting and filming reduction benefits, as well as providing suds suppression which is robust enough to survive the washing environment in which it is deployed.

Pectin degrading enzymes are known to provide soil/stain removal benefits when used in washing and cleaning operations, specifically to provide the removal of a broad range of plant and fruit based stains and enhance the body soil cleaning profile of the detergent compositions. By pectin degrading enzyme it is meant herein any enzyme which acts to break down pectin substances and pectin related substances. Pectin degrading enzymes can be classified according to their preferential substrate, highly methyl-esterified pectin or low methyl-esterified pectin and polygalacturonic acid (pectate), and their reaction mechanism, beta- elimination or hydrolysis. Pectin degrading enzymes can be mainly endo-acting, cutting the polymer at random sites within the chain to give a mixture of oligomers, or they may be exo-acting, attacking from one end of the polymer and producing monomers or dimers. Several pectinase activities acting on the smooth regions of pectin are included in the classification of enzymes provided by the Enzyme Nomenclature (1992) such as pectate lyase (EC 4.2.2.2), pectin lyase (EC 4.2.2.10), polygalacturonase (EC 3.2.1.15), exo-polygalacturonase (EC 3.2.1.67), exo-polygalacturonate lyase (EC 4.2.2.9) and exo-poly-alpha- galacturonosidase (EC 3.2.1.82). The pectin degrading enzymes are natural mixtures of the above mentioned enzymatic activities.

Each type of pectin degrading enzyme has a unique profile of substrate specificity, activity and stability under different hardness, pH, temperature, surfactant and other detergent ingredient matrix conditions. Pectin degrading enzymes are specifically directed to degrade pectin substances and in particular plant cell walls. In particular, pectate lyase enzymes are directed to the cleavage of α-D-(1,4) glycosidic bonds in poly-D-galacturonans by the mechanism of β- elimination. These pectate lyase enzymes further help as well the removal of mixed stains / soils comprising pectin substances and other components. However, soils / stains which are not sensitive to pectate lyases such as non- pectin carbohydrates, lipids, proteins and their derivatives may block the accessibility of the pectin substances to the enzymes and necessitate a further strong detergent ingredient.

Low foaming nonionic surfactants are known in the art : U.S. Patent 4,272,394, issued June 9, 1981 , U.S. Patent 5,294, 365, issued March 15, 1994 U.S. Patent No. 4,248,729, issued February 3, 1981 ; U.S. Patent No. 4,284,532, issued August 18, 1981 ; U.S. Patent No. 4,627,927, issued December 9, 1986; U.S. Patent No. 4,790,856, issued December 13, 1988; U.S. Patent No. 4,804,492, issued February 14, 1989; U.S. Patent No. 4,770,815, issued September 13, 1989; U.S. Patent No. 5,035,814, issued July 30, 1991 ; U.S. Patent No. 5,047,165, issued September 10, 1991 ; U.S. Patent No. 5,419,853, issued May 30, 1995; U.S. Patent No 5,294,365, issued March 15, 1994; GB Application No. 2,144,763, published March 13, 1985; GB Application No. 2,154,599, published September 9, 1985; WO Application No. 9,296,150, published April 16, 1992; WO 94/22800, published October 13, 1994, WO 93/04153, published March 4, 1993, WO 97/22651 , published June 26, 1997, EP Application No. 342,177, published November 15, 1989 and "Glyceryl Bisether Sulfates. 1 : Improved Synthesis" Brian D. Condon; Journal Of the American Chemical Society, Vol. 71 , no. 7 (July 1994).

It has been surprisingly found that detergent compositions, and in particular, a dish or hard surface cleaning composition, comprising a pectate lyase and a low- foaming nonionic surfactant, either alone or in combination with other surfactants, provide improved plant-based soil/stains and dirt, mud removal, spotting and filming performance as well as improved cleaning performance on greasy soils while also providing suds or foam suppression. While not wishing_to be bound by theory, it is believed the low foaming nonionic surfactants of the present invention deliver superior spotting and filming benefits via improved sheeting action. As for improved cleaning performance, such benefits are shown when the low foaming nonionic surfactants of the present invention are employed in conjunction with a pectate lyase as disclosed in detail herein. Lastly, the low foaming nonionic surfactants of the present invention also act to reduce the suds or foaming associated with food soils or various other cleaning agents and allow the use of soluble surfactants, which are high sudsing, such as amine oxides.

It has been surprisingly found that a unique surfactant system containing a low foaming nonionic surfactant can maximise the pectate lyase enzyme cleaning efficiency. It has also been surprisingly found that detergent compositions comprising a pectate lyase and a low foaming nonionic surfactant, provide superior cleaning due to the synergistic effect of the low foaming nonionic surfactant removing greasy stains, especially at low temperature and the pectate lyase degrading the pectin components of soil/stains and/or in the laundry context, the pectin components of the fabrics that binds or otherwise interact with such soil/stains, making them difficult to remove. This surfactant - enzyme mixed system delivers an outstanding cleaning effect, especially on food stains and body soils.

The use of pectin degrading enzymes in detergent has already been recognised in the art. The use of pectin enzyme is also recognised for the cleaning of contact lenses (US 4,710,313 - J60196724). Enzymes having a pectinase activity are described in DE 36 35 427 to increase the capacity of the detergent for removing inorganic dirt, e.g. sludges, from laundry without damaging the fibres and without discoloration to allow the use of zeolites and polycarbonate builders which have a lower capacity for dispersing inorganic materials than the phosphates. Benefits for the use of pectin enzymes in detergent formulations, particularly those designed for use in laundry, dishwashing and household cleaning operations have been recognised in WO95/25790. JP 60226599 describes detergent compositions comprising conventional detergent actives and a cellulase and hydrolase such as hemicellulase, pectinase, amylase or protease. The combination of cellulase and hydrolase is said to give a good washing effect on inorganic fouling together with enzymatic activity. WO95/09909 describes an enzyme preparation comprising modified enzyme selected from the group of amylase, lipase, oxidoreductase, pectinase or hemicellulase; the modified enzyme having an improved performance due to an alkaline pi and/or increased surface activity obtained by chemical modification or amino acid substitution. Modified pectin and/or pectolytic and/or hemi-cellulolytic and /or lipolytic enzymes are applied advantageously in the papermaking industry and modified amylase and/or lipase in laundry and dishwashing.

In particular, Pectate lyases have been cloned from different bacterial genera such as Erwinia, Pseudomonas, Klebsiella, Streptomyces, Penicillium, Bacteroides, Thermomonospora, Fusarium, Aspergillus and Xanthomonas. Also from Bacillus subtilis (Nasser et al. (1993) FEBS 335:319-326) and Bacillus sp. YA- 4 (Kim et al. (1994) Biosci. Biotech. Biochem. 58:947-949) cloning of a pectate lyase has been described. Purification of pectate lyases with maximum activity in the pH range of 8-10 produced by Bacillus pumilus (Dave and Vaughn (1971) J. Bacteriol. 108:166-174), B. polymyxa (Nagel and Vaughn (1961) Arch. Biochem. Biophys. 93:344-352), B. stearothermophilus (Karbassi and Vaughn (1980) Can. J. Microbiol. 26:377-384), Bacillus sp. (Hasegawa and Nagel (1966) J. Food Sci. 31 :838-845) and Bacillus sp. RK9 (Kelly and Fogarty (1978) Can. J. Microbiol. 24:1164-1172) has been reported. WO 98/45393 discloses detergent compositions containing protopectinase with remarkable detergency against muddy soiling.

However, the synergistic combination of a pectate lyase and a low foaming nonionic surfactant, for superior cleaning performance, i.e. improved plant-based soil/stains and dirt, mud removal, spotting and filming performance as well as improved cleaning performance on greasy soils and suds or foam suppression in a detergent composition, has never been previously recognised.

Summary of the invention

The present invention relates to detergent compositions, including laundry and/or fabric care, dishwashing and hard surfaces compositions, comprising a pectate lyase and low foaming nonionic surfactant for providing improved plant-based soils/stains and body soils, spotting and filming performance as well as improved cleaning performance on greasy soils and suds or foam suppression.

Detailed description of the invention

The present invention relates to detergent compositions comprising a pectate lyase and low foaming nonionic surfactant.

Each type of pectin degrading enzyme has a unique profile of substrate specificity, activity and stability under different hardness, pH, temperature, surfactant and other detergent ingredient matrix conditions. Pectin degrading enzymes are specifically directed to degrade pectin substances and in particular plant cell walls. In particular, pectate lyase is a pectin degrading enzyme which splits the α-1 ,4,glucoside bond of polygalacturonic acids found in pectin substances, to create a double bound between C4 and C5.

Pectate lyase enzymes further help the removal of mixed stains / soils comprising pectin substances and other components. However, soils / stains which are not sensitive to pectate lyases such as non-pectin carbohydrates, lipids, proteins and their derivatives may block the accessibility of the pectin substances to the enzyme and necessitate a further strong detergent ingredient.

It has been surprisingly found that detergent compositions comprising a pectate lyase and a low foaming nonionic surfactant, provide superior cleaning due to the synergistic effect of the low foaming nonionic surfactant removing greasy stains, especially at low temperature and the pectate lyase degrading the pectin components of soil/stains and/or in the laundry context, the pectin components of the fabrics that binds or otherwise interact with such soil/stains, making them difficult to remove. This surfactant - enzyme mixed system delivers an outstanding cleaning effect, especially on food stains and body soils.

It has been surprisingly further found that significant improvements in spotting and filming characteristics and, when used in conjunction with a pectate lyase and a high cloud point surfactants, in the removal of plant-, dirt-based and food stains; body soils and greasy soils relative to conventional surfactants, are provided via the low foaming nonionic surfactants of the present invention. It has been surprisingly found that in addition to delivering superior cleaning benefits also provide good suds control. This suds control can be clearly seen in the presence of high sudsing surfactants, such as amine oxides, or in the presence of high sudsing soils, such as pectin- and protein-containing soils.

The Pectate Lyase enzyme

An essential element of the detergent composition of the present invention is a pectate lyase enzyme.

Pectate lyase is classified within the classification of enzymes provided by the Enzyme Nomenclature (1992) as EC 4.2.2.2. Said enzyme is known to split the α-1 ,4,glucoside bond of galacturonic acid found in pectin substances, creating a double bond between C4 and C5 and is substantially free for other pectin degrading activities, i.e having less than 25%, preferably less than 15%, more preferably less than 5% by weight of the enzyme compound of other pectin degrading enzyme activities.

Pectate lyases have been cloned from different bacterial genera such as Erwinia, Pseudomonas, Klebsiella, Streptomyces, Penicillium, Bacteroides, Thermomonospora, Fusarium, Aspergillus and Xanthomonas. Also from Bacillus subtilis (Nasser et al. (1993) FEBS 335:319-326) and Bacillus sp. YA-14 (Kim et al. (1994) Biosci. Biotech. Biochem. 58:947-949) cloning of a pectate lyase has been described. Purification of pectate lyases with maximum activity in the pH range of 8-10 produced by Bacillus pumilus (Dave and Vaughn (1971) J. Bacteriol. 108:166-174), B. polymyxa (Nagel and Vaughn (1961) Arch. Biochem. Biophys. 93:344-352), B. stearothermophilus (Karbassi and Vaughn (1980) Can. J. Microbiol. 26:377-384), Bacillus sp. (Hasegawa and Nagel (1966) J. Food Sci. 31:838-845) and Bacillus sp. RK9 (Kelly and Fogarty (1978) Can. J. Microbiol. 24:1164-1172) has been reported. WO 98/45393 discloses detergent compositions containing protopectinase with remarkable detergency against muddy soils.

Further suitable pectate lyases for use in the present invention are the protopecfinases having an optimum reaction pH of 7.0 or higher when polygalacturonic acid is used as a substrate such as described in WO98/45393 and the pectic acid lyase having the amino acid sequence SEQ no 1 of EP 870 843 or having such amino acid sequence with one or more amino acid being deleted, added or substituted.

Preferred are the pectate lyase enzymes described in the international co- pending application PCT/DK98/00515, internationally filed on November 24, 1998 :

- A pectate lyase comprising a first amino acid sequence consisting of seven (7) amino acid residues having the following sequence: Asn Leu Asn Ser Arg Val Pro (NLNSRVP);

- A pectate lyase which is : i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482 or DSM 8721 , or by a Bacillus species having a 16S rDNA sequence homology to Bacillus agaradhaerens, DSM 8721 , of at least 99%, or ii) a polypeptide comprising an amino acid sequence as shown in positions

27-359 of SEQ ID NO:2 of PCT/DK98/00515, or iii) an analogue of the polypeptide defined in i) or ii) which is at least 45% homologous with said polypeptide, or iv) is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, provided that the arginine in position 240, and optionally also the arginine in position 245, is conserved and the derived polypeptide is at least 42% homologous with said polypeptide, or v) is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form;

- A pectate lyase which is : i) a polypeptide produced by Bacillus licheniformis, ATCC 14580, or by a

Bacillus species having a 16S rDNA sequence homology to Bacillus licheniformis, ATCC 14580, of at least 99%, or ii) a polypeptide comprising an amino acid sequence as shown in positions 28-341 of SEQ ID NO:4 of PCT/DK98/00515, or iii) an analogue of the polypeptide defined in i) or ii) which is at least 45% homologous with said polypeptide, or iv) is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, provided that the arginine in position 233, and optionally also the arginine in position 238, is conserved and the derived polypeptide is at least 42% homologous with said polypeptide, or v) is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form; - A pectate lyase which is : i) a polypeptide produced by a Bacillus species having the 16S rDNA sequence of SEQ ID NO:14 of PCT/DK98/00515or by a Bacillus species having a 16S rDNA sequence homology to SEQ ID NO:14 of

PCT/DK98/00515higher than 97.3%; or ii) a polypeptide comprising an amino acid sequence as shown in positions 181-509 of SEQ ID NO:6 of PCT/DK98/00515, or iii) an analogue of the polypeptide defined in i) which is at least 50% homologous with said polypeptide, or iv) is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, provided that the arginine in position 390, and optionally also the arginine in position 395, is conserved and the derived polypeptide is at least 44% homologous with said polypeptide, or v) is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form, - A pectate lyase which is : i) a polypeptide produced by the species Bacillus halodurans, or ii) a polypeptide comprising an amino acid sequence as shown in positions

42-348 of SEQ ID NO:8 of PCT/DK98/00515, or iii) an analogue of the polypeptide defined in i) or ii) which is at least 45% homologous with said polypeptide, or iv) is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, provided that the arginine in position 240, and optionally also the arginine in position 245, is conserved and the derived polypeptide is at least 40% homologous with said polypeptide, or v) is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form, - A pectate lyase which is i) a polypeptide produced by a Bacillus species having the 16S rDNA sequence of SEQ ID NO: 13 of PCT/DK98/00515or by a Bacillus species having a 16S rDNA sequence homology to SEQ ID NO: 13 of

PCT/DK98/00515higher than 98.1%; or ii) a polypeptide comprising an amino acid sequence as shown in positions 25-335 of SEQ ID NO:10 of PCT/DK98/00515, or iii) an analogue of the polypeptide defined in i) or which is at least 45% homologous with said polypeptide, or iv) is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, provided that the arginine in position 227, and optionally also the arginine in position 232, is conserved and the derived polypeptide is at least 41% homologous with said polypeptide, or v) is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form.

Similarly preferred is the pectate lyase enzyme in the international co-pending application PCT/DK98/00514, internationally filed on November 24, 1998 and which is : i) a polypeptide produced by Bacillus licheniformis, ATCC 14580, or ϋ) a polypeptide comprising an amino acid sequence as shown in positions 28-221 of SEQ ID NO:4 of PCT/DK98/00514, or iϋ) an analogue of the polypeptide defined in i) or ii) which is at least

60% homologous with said polypeptide, or iv) is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, provided that the lysines in positions 133 and 155 and the arginine in position 158 are conserved and the derived polypeptide is at least 66% homologous with positions 60-158 of SEQ ID NO:4 of PCT/DK98/00514, or v) is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form.

More preferred pectate lyases for the purpose of the present invention are those having optimum activity at pH's >7.0 and derived from Streptomyces fradiae, Streptomyces nitrosporeus, Erwinia carotovora, Bacillus spheroides, Thermomonospora fusca, Pseudomonas solanacearum, Bacteroides thetaiotaomicron, Fusarium solani, Xanthomonas campestris, Bacillus agaradhaerens, and/or Bacillus licheniformis.

Most preferred pectate lyase for the purpose of the present invention is the Pectate lyase from Bacillus agaradhaerens, NCIMB 40482 or DSM 8721.

The pectate lyase is incorporated into the detergent compositions of the present invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001 % to 0.02% pure enzyme by weight of the composition. The pectate lyase of the invention, in addition to the enzyme core comprising the catalytically domain, may also contain a cellulose binding domain (CBD), the cellulose binding domain and enzyme core (the catalytically active domain) of the enzyme being operably linked. The cellulose binding domain (CBD) may exist as an integral part of the encoded enzyme, or a CBD from another origin may be introduced into the enzyme thus creating an enzyme hybrid. In this context, the term "cellulose-binding domain" is intended to be understood as defined by Peter Tomme et al. "Cellulose-Binding Domains: Classification and Properties" in "Enzymatic Degradation of Insoluble Carbohydrates", John N. Saddler and Michael H. Penner (Eds.), ACS Symposium Series, No. 618, 1996. This definition classifies more than 120 cellulose- binding domains into 10 families (l-X), and demonstrates that CBDs are found in various enzymes such as cellulases, xylanases, mannanases, arabinofuranosidases, acetyl esterases and chitinases. CBDs have also been found in algae, e.g. the red alga Porphyra purpurea as a non-hydrolytic polysaccharide-binding protein, see Tomme et al., op.cit. However, most of the CBDs are from cellulases and xylanases, CBDs are found at the N and C termini of proteins or are internal. Enzyme hybrids are known in the art, see e.g. WO 90/00609 and WO 95/16782, and may be prepared by transforming into a host cell a DNA construct comprising at least a fragment of DNA encoding the cellulose- binding domain ligated, with or without a linker, to a DNA sequence encoding the pectate lyase enzyme and growing the host cell to express the fused gene. Enzyme hybrids may be described by the following formula: CBD - MR - X wherein CBD is the N-terminal or the C-terminal region of an amino acid sequence corresponding to at least the cellulose binding domain; MR is the middle region (the linker), and may be a bond, or a short linking group preferably of from about 2 to about 100 carbon atoms, more preferably of from 2 to 40 carbon atoms; or is preferably from about 2 to about 100 amino acids, more preferably of from 2 to 40 amino acids; and X is an N-terminal or C-terminal region of the pectate lyase of the invention.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Nowadays, it is common practice to modify wild-type enzymes via protein / genetic engineering techniques in order to optimise their performance efficiency in the detergent 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 or chelant 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 metal binding sites to increase chelant stability.

The low foaming nonionic surfactant

The second essential element of the detergent compositions of the present invention is low foaming nonionic surfactant (referred hereinafter as "LFNI)".

The detergent compositions of the present invention generally comprise from 0.01% to 15%, preferably from 0.25% to 4% by weight of a low-foaming nonionic surfactant.

One suitable low foaming nonionic surfactant for the purpose of the present invention is the low foaming surfactant described in the co-pending US application US serial No. 60/057025 filed by the Procter and Gamble Company on August 2, 1997 and is selected from the ether-capped poly(oxyalkylated) alcohols having the formula:

R O[CH₂CH(R3)O]_x[CH₂]kCH(OH)[CH2]jOR2 wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; R^ is H, or a linear aliphatic hydrocarbon radical having from about 1 to about 4 carbon atoms; x is an integer having an average value from 1 to about 40, wherein when x is 2 or greater R3 may be the same or different and k and j are integers having an average value of from about 1 to about 12, and more preferably 1 to about 5 further wherein when x is 15 or greater and R^ is H and methyl, at least four of R^ are methyl, further wherein when x is 15 or greater and R3 includes H and from 1 to 3 methyl groups, then at least one R^ is ethyl, propyl or butyl, further wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof.

R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from about 6 to about 22 carbon atoms with about 8 to about 18 carbon atoms being most preferred. Additionally, R2 may be selected from hydrocarbon radicals which are ethoxylated or propoxylated. H or a linear aliphatic hydrocarbon radical having from about 1 to about 2 carbon atoms is most preferred for R3. Preferably, x is an integer having an average value of from about 1 to about 20, more preferably from about 6 to about 15.

As described above, when, in the preferred embodiments, x is greater than 2, R^ may be the same or different. That is, R3 may vary between any of the alkyleneoxy units as described above. For instance, if x is 3, R^may be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO). Of course, the integer three is chosen for example only and the variation may be much larger with a higher integer value for x and include, for example, multiple (EO) units and a much small number of (PO) units. However, when x is 15 or greater and R^ is H and methyl, at least four of R3 are methyl, further wherein when x is 15 or greater and R3 includes H and from 1 to 3 methyl groups, then at least one R^ is ethyl, propyl or butyl.

Preferred surfactants as described above include those that have a low cloud point of less than about 20°C. These low cloud point surfactants may then be employed in conjunction with a high cloud point surfactant as described in detail below for superior grease cleaning benefits.

More preferred according to the present invention are those surfactants wherein k is 1 and j is 1 so that the surfactants have the formula:

R¹0[CH₂CH(R3)O]_xCH₂CH(OH)CH2θR² where R¹ , R² and R3 are defined as above and x is an integer with an average value of from about 1 to about 30, preferably from about 1 to about 20, and even more preferably from about 6 to about 18. Most preferred are surfactants wherein R1 and R² range from about 9 to about 14, R3 is H forming ethyleneoxy and x ranges from about 6 to about 15.

Basically, the alcohol surfactants of the present invention comprise three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.

Generally speaking, the ether-capped poly(oxyalkylene) alcohol surfactants of the present invention may be produced such as described in the co-pending US application US serial No. 60/054702 filed by the Procter and Gamble company on August 2, 1997, by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention.

The process comprises the first step of providing a glycidyl ether having the formula:

where R² is defined as above. Various glycidyl ethers are available from a number of commercial sources including the Aldrich Chemical Company. Alternatively, the glycidyl ether may be formed from the reaction of a linear or branched, aliphatic or aromatic alcohol of the formula R²OH where R² is defined as above and an epoxide of the formula: o

*^ where X is a suitable leaving group. While a number of leaving groups may be employed in the present invention, X is preferably selected from the group consisting of halides including chloride, bromide, and iodide, tosylate, mesylate and brosylate, with chloride and bromide being even more preferred with chloride being the most preferred (e.g. epichlorohydrin).

The linear or branched alcohol and the epoxide are preferably reacted at ratios ranging from about 0.5 equivalents alcohol to 2 equivalents epoxide with 0.95 equivalents alcohol to 1.05 equivalents epoxide more typical under acidic conditions for catalysis purposes. Acids which may be employed as catalyst include mineral acids, including but not limited to H2SO4 and H3PO4 and Lewis acids including, but not limited to, TiC-4, Ti(O'Pr)4, ZnC-4, SnC j, AICI3, and BF3-OEt₂. Preferred catalysts include the Lewis acids with SnC-4 and BF3-OEt₂ being the most preferred. The catalysts are preferably employed at amounts of about 0.1 mol % to about 2.0 mol % with 0.2 mol % to about 1.0 mol % being more typical.

While the reaction may be conducted in the presence of a suitable solvent such as benzene, toluene, dichloromethane, tetrahydrofuran, diethylether, methyl tert- butylether or the like, the reaction is preferably conducted neat or in the absence of solvent. Lastly, the reaction is conducted at temperatures preferably ranging from about 40°C to about 90°C, more preferably from about 50°C to about 80°C, and most preferably from about 55°C to about 65°C. Upon completion of the reaction, the mixture is treated with a basic material to form the glycidyl ether. The basic material is preferably a strong base such as a hydroxide. Preferred hydroxides include alkali metal hydroxides with sodium being the typical choice. However, one of ordinary skill in the art will recognize that other basic materials may also be employed. The basic material is preferably added at levels of from about 0.5 equivalents to about 2.5 equivalents, with 0.95 equivalents to 2.0 equivalents being more preferred and 1.0 to 1.5 equivalents being the most preferred.

The product glycidyl ether may then be collected after optional filtration, drying and distillation according to the methods well-known in the art. To form the surfactant, an ethoxylated alcohol having the formula:

wherein R^ and x are defined as before in an amount of from about 0.80 to about 1.5 equivalents is combined with a catalyst as described hereinbefore and heated to a temperature ranging from about 50°C to about 95°C and more preferably from about 60°C to about 80°C. The glycidyl ether is then added to the mixture and reacted for from about 0.5 hours to about 30 hours, more preferably from about 1 hour to about 24 hours.

The ether-capped poly(oxyalkylated) alcohol surfactant product is then collected by means common in the art such as filtration. If desired, the surfactant may be further treated by stripping, distillation or various other means before use. The surfactants made the process disclosed herein may contain related impurities which will not adversely affect performance.

Also suitable for the purpose of the present invention are the low foaming nonionic surfactants polyoxypropylene / polyoxyethylene / polyoxypropylene reverse block polymer hereinafter described. They encompass non-silicone, nonphosphate polymeric materials further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing and laundry.

Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers. The PO/EO/PO polymer-type surfactants are well-known to have foam suppressing or defoaming action, especially in relation to common food soil ingredients such as egg.

A particularly preferred LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (Ciβ-C o alcohol), preferably a C-is alcohol, condensed with an average of from about 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.

The LFNI can optionally contain propylene oxide in an amount up to about 15% by weight. Other preferred LFNI surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference.

Highly preferred LFNI's include ethoxylated monohydroxy alcohol or alkyl phenol and additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound; the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNI comprising from about 20% to about 100%, preferably from about 30% to about 70%, of the total LFNI. Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound. Polymeric compounds made from a sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom, such as C-J2-18 aliphatic alcohols. Certain of the block polymer surfactant compounds designated PLURONIC® and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the compositions of the invention. A particularly preferred LFNI contains from about 40% to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend comprising about 75%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block co-polymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.

Suitable for use as LFNI in the compositions are those LFNI having relatively low cloud points and high hydrophilic-lipophilic balance (HLB). Cloud points of 1% solutions in water are typically below about 32°C and preferably lower, e.g., 20°C, for optimum control of sudsing throughout a full range of water temperatures.

LFNIs which may also be used include those POLY-TERGENT® SLF-18 nonionic surfactants from Olin Corp., and any biodegradable LFNI having the melting point properties discussed hereinabove.

These and other nonionic surfactants are well known in the art, being described in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein.

Particularly preferred in the present invention include mixed nonionic surfactants. While a wide range of nonionic surfactants may be selected from for purposes of the mixed nonionic surfactant systems useful in the present invention compositions, it is preferred that the nonionic surfactants comprise both a low cloud point surfactant as represented by the ether capped poly(oxyalkylated) alcohol surfactant and high cloud point nonionic surfactant(s) as described as follows. "Cloud point", as used herein, is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the "cloud point" (See Kirk Othmer, pp. 360- 362, hereinbefore).

As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30°C, preferably less than about 20°C, and most preferably less than about 10°C and is represented by the ether-capped poly(oxyalkylated) alcohols as described herein.

Of course, other low-cloud point surfactants may be included in conjunction with the ether-capped poly(oxyalkylated) surfactants. Such optional low-cloud point surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/ polyoxypropylene (PO/EO/PO) reverse block polymers. Also, such low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation). These nonionic surfactants can optionally contain propylene oxide in an amount up to about 15% by weight. Other preferred nonionic surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. Optional low cloud point nonionic surfactants additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound. Block polyoxyethylene-polyoxypropylene polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound. Certain of the block polymer surfactant compounds designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such surfactants are typically useful herein as low cloud point nonionic surfactants. As used herein, a "high cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of greater than 40°C, preferably greater than about 50°C, and more preferably greater than about 60°C. Preferably the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

It is also preferred for purposes of the present invention that the high cloud point nonionic surfactant further have a hydrophile-lipophile balance ("HLB"; see Kirk Othmer hereinbefore) value within the range of from about 9 to about 15, preferably 11 to 15. Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another preferred high cloud point nonionic surfactant is derived from a straight or preferably branched chain or secondary fatty alcohol containing from about 6 to about 20 carbon atoms (Cβ-C₂o alcohol), including secondary alcohols and branched chain primary alcohols. Preferably, high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9/11 or C^ 1/15 branched alcohol ethoxylates, condensed with an average of from about 6 to about 15 moles, preferably from about 6 to about 12 moles, and most preferably from about 6 to about 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.

The preferred nonionic surfactant systems useful herein are mixed high cloud point and low cloud point nonionic surfactants combined in a weight ratio preferably within the range of from about 10:1 to about 1 :10. Preferred are compositions comprising such mixed nonionic surfactant systems wherein the sudsing (absent any silicone suds controlling agent) is less than 2 inches, preferably less than 1 inch, determined as follows:

The equipment useful for these measurements are: a Whirlpool Dishwasher (model 900) or a Miele Dishwasher (model G7750) equipped with clear plexiglass door, IBM computer data collection with Labview and Excel Software, proximity sensor (Newark Corp. - model 95F5203) using SCXI interface, and a plastic ruler.

The data is collected as follows. The proximity sensor is affixed to the bottom dishwasher rack on a metal bracket. The sensor faces downward toward the rotating dishwasher arm on the bottom of the machine (distance approximately 2 cm. from the rotating arm). Each pass of the rotating arm is measured by the proximity sensor and recorded. The pulses recorded by the computer are converted to rotations per minute (RPM) of the bottom arm by counting pulses over a 30 second interval. The rate of the arm rotation is directly proportional to the amount of suds in the machine and in the dishwasher pump (i.e., the more suds produced, the slower the arm rotation).

The plastic ruler is clipped to the bottom rack of the dishwasher and extends to the floor of the machine. At the end of the wash cycle, the height of the suds is measured using the plastic ruler (viewed through the clear door) and recorded as suds height.

Detergent components

The detergent compositions of the invention will preferably comprise further additional detergent components. The precise nature of these additional component, 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 detergent compositions according to the invention can be liquid, paste, gels, bars, tablets, spray, foam, powder or granular. Granular compositions can also be in "compact" form and the liquid compositions can also be in a "concentrated" form. Tablet compositions can be in single phase or multiple phase form.

In a first embodiment, the present invention relates to laundry detergent and/or fabric care compositions comprising a pectate lyase and a low foaming nonionic surfactant (Examples 1-15). In a second embodiment, the present invention relates to dishwashing or household detergent compositions (Examples 16-22).

The compositions of the invention may for example, be formulated as hand 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 and compositions for use in general household hard surface cleaning operations. When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group 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. Such compositions containing a pectate lyase and a low foaming nonionic can provide fabric cleaning, stain removal, and color appearance when formulated as laundry detergent compositions.

When formulated as compositions suitable for use in a machine dish wash method, the compositions of the invention preferably contain a low foaming nonionic surfactant, a builder system, and one or more 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.

The compositions of the invention can also be used as detergent additive products in solid or liquid form. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process.

If needed the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 500 to 950 g/litre of composition measured at 20°C. The "compact" form of the compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition. The inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides. A preferred filler salt is sodium sulphate. Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents. Typically the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

Suitable detergent compounds for use herein are selected from the group consisting of the below described compounds. Indeed, the compositions of the present invention comprise the low foaming nonionic surfactants as disclosed in detail herein and may optionally include various other detergent adjunct ingredients including, but not limited to, detersive enzymes (to assist with tough food cleaning, especially of starchy and proteinaceous soils), builder and a bleaching agent (such as a chlorine bleach or a source of hydrogen peroxide). Bleaching agents useful herein include chlorine oxygen bleaches (e.g., hypochlorite; no NaDCC) and sources of hydrogen peroxide, including any common hydrogen-peroxide releasing salt, such as sodium perborate, sodium percarbonate, and mixtures thereof. Also useful are sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont). In the preferred embodiments, additional ingredients such as water-soluble silicates (useful to provide alkalinity and assist in controlling corrosion), dispersant polymers (which modify and inhibit crystal growth of calcium and/or magnesium salts), chelants (which control transition metals), and pH control agents are present. Additional bleach-modifying materials such as conventional bleach activators, e.g. TAED and/or bleach catalysts, may be added, provided that any such bleach-modifying materials are delivered in such a manner as to be compatible with the purposes of the present invention. The present detergent compositions may, moreover, comprise one or more processing aids, fillers, perfumes, conventional enzyme particle-making materials including enzyme cores or "nonpareils", as well as pigments, and the like.

In general, materials used for the production of the compositions herein are preferably checked for compatibility with spotting/filming on surfaces such as glassware. Test methods for spotting/filming are generally described in the automatic dishwashing detergent literature, including DIN and ASTM test methods. Certain oily materials, especially at longer chain lengths, and insoluble materials such as clays, as well as long-chain fatty acids or soaps which form soap scum are therefore preferably limited or excluded from the instant compositions.

Amounts of the essential ingredients can vary within wide ranges, however preferred compositions herein (which typically have a 1% aqueous solution pH of above about 8, more preferably from about 9.5 to about 12, most preferably from about 9.5 to about 11) are those wherein there is present: from about 5% to about 90%, preferably from about 5% to about 75%, of builder; from about 0.1% to about 40%, preferably from about 0.5% to about 30%, of bleaching agent; from about 0.1% to about 15%, preferably from about 0.2% to about 10%, of the nonionic alcohol surfactant; from about 0.0001% to about 1%, preferably from about 0.001% to about 0.05%, of a metal-containing bleach catalyst (most preferred cobalt catalysts useful herein are present at from about 0.001% to about 0.01%); and from about 0.1% to about 40%, preferably from about 0.1% to about 20% of a water-soluble (two ratio) silicate. Such fully-formulated embodiments typically further comprise from about 0.1% to about 15% of a polymeric dispersant, from about 0.01% to about 10% of a chelant, and from about 0.00001% to about 10% of a detersive enzyme, though further additional or adjunct ingredients may be present. Detergent compositions herein in granular or tablet form typically limit water content, for example to less than about 7% free water, for best storage stability. Of course, the compositions may also be in liquid or gel form as well. While the present invention compositions may be formulated using chlorine- containing bleach additives, preferred compositions of this invention (especially those comprising detersive enzymes) are substantially free of chlorine bleach. By "substantially free" of chlorine bleach is meant that the formulator does not deliberately add a chlorine-containing bleach additive, such as a dichloroisocyanurate, to the preferred composition. However, it is recognized that because of factors outside the control of the formulator, such as chlorination of the water supply, some non-zero amount of chlorine bleach may be present in the wash liquor. The term "substantially free" can be similarly constructed with reference to preferred limitation of other ingredients.

By "effective amount" herein is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance cleaning of a soiled surface. Likewise, the term "catalytically effective amount" refers to an amount of metal-containing bleach catalyst which is sufficient under whatever comparative test conditions are employed, to enhance cleaning of the soiled surface. In automatic dishwashing, the soiled surface may be, for example, a porcelain cup with tea stain, a porcelain cup with lipstick stain, dishes soiled with simple starches or more complex food soils, or a plastic spatula stained with tomato soup. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some machines have considerably longer wash cycles than others. Some users elect to use warm water without a great deal of heating inside the appliance; others use warm or even cold water fill, followed by a warm-up through a built-in electrical coil. Of course, the performance of bleaches and enzymes will be affected by such considerations, and the levels used in fully-formulated detergent and cleaning compositions can be appropriately adjusted.

Surfactant system

Preferably, the detergent compositions of the present invention will comprise in addition to the low foaming nonionic surfactant, another surfactant system wherein the surfactant can be selected from cationic, anionic, other nonionic and/or mixtures thereof. Also suitable are ampholytic and/or zwitterionic and/or semi-polar surfactants.

The surfactant system comprising this low foaming nonionic surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation are 1% to 35% by weight, most preferably from 1% to 30% by weight of laundry detergent 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.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal™ CO-630, marketed by the GAF Corporation; and Triton™ X- 45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol 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 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include TergitofTM 15-S-9 (the condensation product of C-11-C-J5 linear alcohol with 9 moles ethylene oxide), Tergito.TM 24-L-6 NMW (the condensation product of C-|₂-Ci4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodofM 45.9 (the condensation product of C-14-C15 linear alcohol with 9 moles of ethylene oxide), Neodo.TM 3_3 (the condensation product of C-_{| 2}-C-|3 linear alcohol with 3.0 moles of ethylene oxide), Neodol^M 45-7 (the condensation product of C-14-C15 linear alcohol with 7 moles of ethylene oxide), Neodo-TM 45.5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro™ EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA O3O or O5O (the condensation product of C-ι₂-Ci4 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.

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

R²O(C_nH₂nO)t(glycosyl)_x

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

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available Plurafac^M LF404 and Pluronic™ surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40%) to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.

Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and CR-C-I S alcohol ethoxylates (preferably C-I Q avg.) having from 2 to 10 ethoxy groups, and mixtures thereof. Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.

R2 . c - N - Z, II I o R1

wherein Rl is H, or R1 is C<|_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, R^ is methyl, R² is a straight Cn_i5 alkyl or C16-I8 ^a' 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 Cs-C₂o carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.

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

O

II

R3 - CH - C - OR⁴

SO3M wherein R³ is a C8-C o hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a C<|-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 C<|rj-Ci6 alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C10-C16 alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cιrj-C₂o alkyl component, more preferably a C-|₂-C<|8 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, 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 C-|₂-Ci6 are preferred for lower wash temperatures (e.g. below about 50°C) and Ciβ-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, C8-C₂2 primary of secondary alkanesulfonates, Cs-C 4 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1 ,082,179, C8-C 4 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C^-C^s monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C-|₂ 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(CH₂CH₂O)k-CH₂COO-M+ wherein R is a Cs-C₂₂ alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).

When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mSO3M wherein R is an unsubstituted C-| Q-C 4 alkyl or hydroxyalkyl group having a C<|rj-C₂4 alkyl component, preferably a C<|₂-C₂o alkyl or hydroxyalkyl, more preferably Cι₂- Ci8 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C-|₂-C^<|8 alkyl polyethoxylate (1.0) sulfate (C_l2-Ci8E(1.0)M), Cι₂-C<|8 alkyl polyethoxylate (2.25) sulfate (C-|₂-C<|8E(2.25)M), C<|₂-C<|8 alkyl polyethoxylate (3.0) sulfate (Cι₂-CιsE(3.0)M), and C_{l 2}-C<|8 alkyl polyethoxylate (4.0) sulfate (Ci₂-C-|8E(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(OR3)_y]₂R5N+X-

wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH₂CH₂-, -CH₂CH(CH3)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, - CH₂CHOH-CHOHCOR6CHOHCH₂OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R§ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R§ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

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

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

Formula II

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

whereby X- is a counterion, preferably a halide, e.g. chloride or methylsulfate.

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

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

Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : Rι R₂R3R4N⁺X- (i)

wherein R-| is C8-C16 alkyl, each of R₂, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C₂H4o)χH where x has a value from 2 to 5, and X is an anion. Not more than one of R₂, R3 or R4 should be benzyl. The preferred alkyl chain length for R-j is C-| -C<|5 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 di hydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; ^12-15 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 Ri is

CH₂-CH₂-O-C-C<|₂_i4 alkyl and R₂R3R4 are methyl). II

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

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

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

1) ditallow dimethylammonium chloride (DTDMAC);

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

4) distearyl dimethylammonium chloride;

5) dioleyl dimethylammonium chloride;

6) dipalmityl hydroxyethyl methylammonium chloride;

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

9) hydrogenated tallow trimethylammonium chloride;

10) C-|2^_14 a'kyl hydroxyethyl dimethylammonium chloride;

11) C-.-J2-18 a'kyl di hydroxyethyl methylammonium chloride;

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

14) ditallow imidazoiinium methylsulfate;

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

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

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

(I) (II)

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

NR4-;

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

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

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

Ti , T², T3, τ4, T^ are independently C-j 1-C₂₂ alkyl or alkenyl; n and m are integers from 1 to 4; and X^" is a softener-compatible anion. Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.

The alkyl, or alkenyl, chain T^π , T², τ , τ4, T^ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein τ1 , T², τ , T , j5 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 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 selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula

0

R3(OR )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 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include C-|rj-Ci8 alkyl dimethyl amine oxides and C8-C<|₂ 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 co- surfactant selected from the group of primary or tertiary amines. Suitable primary amines for use herein include amines according to the formula R_π NH₂ wherein R-j is a C6-Cι_2> preferably CQ-C^ Q alkyl chain or R4X(CH₂)_n, X is -O-,-C(O)NH- or -NH- R4 is a Cg-C-^ alkyl chain n is between 1 to 5, preferably 3. R-| alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties. Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from 1-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 R-| R₂R3N wherein R1 and R2 are C-|-C8 alkylchains or

R₅

— ( CH₂ — CH θ )χH

R3 is either a C6-C-|₂ preferably Cβ-C-io alkyl chain, or R3 is 4X(CH₂)_n, whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-Cι_2j n is between 1 to 5, preferably 2-3. R5 is H or C-|-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 R-| R R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or

— ( CH₂ — CH θ )χH where R5 is H or CH3 and x = 1-2.

Also preferred are the amidoamines of the formula:

0

Ri — C— NH — ( CH₂ )— N — ( R₂ ) n 2 wherein R-| is Cβ-Cι₂ alkyl; n is 2-4, preferably n is 3; R₂ and R3 is C1-C4 Most preferred amines of the present invention include 1 -octylamine, 1- hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N coco 1- 3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyl- dimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyl- dimethylamine. The most preferred amines for use in the compositions herein are 1-hexylamine, 1 -octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n- dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

Bleaching agent

The detergent compositions of the present invention can further comprise a bleaching agent 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 detergent compositions including oxygen bleaches as well as others known in the art. The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- 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), nonanoyl-oxybenzene- sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG)or Phenolsulfonate ester of N-nonanoyl-6- aminocaproic acid (NACA-OBS, described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters such as disclosed in co-pending European Patent Application No. 91870207.7 and unsymetrical acyclic imide bleach activator of the following formula as disclosed in the Procter & Gamble co-pending patent applications US serial No. 60/022,786 (filed July 30, 1996) and No. 60/028,122 (filed October 15, 1996) :

wherein R-j is a C7-C-13 linear or branched chain saturated or unsaturated alkyl group, R₂ is a C-j-Cs, linear or branched chain saturated or unsaturated alkyl group and R3 is a C-1-C4 linear or branched chain saturated or unsaturated alkyl group.

Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co- pending applications USSN 08/136,626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775. 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.

Metal-containing catalysts for use in bleach compositions, include cobalt- containing catalysts such as Pentaamine acetate cobalt(lll) salts and manganese-containing catalysts such as those described in EPA 549 271 ; EPA 549 272; EPA 458 397; US 5,246,621 ; EPA 458 398; US 5,194,416 and US 5,114,611. Bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3.

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 aluminium 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.

Builder system

The detergent compositions of the present invention can further comprise a builder. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as 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 ,1 ,2,2-ethane tetracarboxylates, 1 ,1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1 ,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis.cis.cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6-hexane -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. Other 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.

Conventional detergent enzymes The detergent compositions can in addition to the pectate lyase enzyme further comprise one or more enzymes which provide cleaning performance, fabric care and/or sanitisation benefits.

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

A preferred combination is a detergent composition having cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.

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 Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A" herein. Suitable is the protease called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein. A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101 , +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and 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 is a carbonyl hydrolase variant of the protease described in WO95/10591 , having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101 , +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending patent application US Serial No. 60/048,550, filed June 04, 1997).

Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever. The proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.

The cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.

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; and a ^"43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801 , Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471. Said cellulases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of pure enzyme by weight of the detergent composition.

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

Enhancers are generally comprised at a level of from 0.1% to 5% by weight of total composition. Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4- carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10- methylphenoxazine (described in WO 94/12621) and substitued syringates (C3- C5 substitued alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.

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

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

Amylases (α and/or β) can be included for removal of carbohydrate-based stains. WO94/02597, Novo Nordisk A/S published February 03, 1994, describes detergent compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in detergent compositions include both α- and β-amylases. α- Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo). Other suitable amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk). Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® .Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases : α- amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). 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 WO95/35382. The amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Nowadays, it is common practice to modify wild-type enzymes via protein / genetic engineering techniques in order to optimise their performance efficiency in the detergent 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 or chelant 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. Special attention must be paid to the cellulases as most of the cellulases have separate binding domains (CBD). Properties of such enzymes can be altered by modifications in these domains.

Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure 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 co-pending European Patent application 92870018.6 filed on January 31 , 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January

5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261 ,868, Hora et al, April 14, 1981.

Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August

17, 1971 , Gedge et al, EP 199,405 and EP 200,586, October 29, 1986,

Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Colour care and fabric care benefits

Technologies which provide a type of colour care benefit can also be included. Examples of these technologies are metallo catalysts for colour maintenance. Such metallo catalysts are described in co-pending European Patent Application No. 92870181.2. Dye fixing agents, polyolefin dispersion for anti-wrinkles and improved water absorbancy, perfume and amino-functional polymer (PCT/US97/16546) for colour care treatment and perfume substanfivity are further examples of colour care / fabric care technologies and are described in the co-pending Patent Application No. 96870140.9, filed November 07, 1996.

Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di- long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.

Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight. These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.

Chelating Agents

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

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine- hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions.

Suds suppressor

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

Such suds suppressor system are described in Co-pending European Patent application N 92870174.7 filed 10 November, 1992. Especially preferred silicone suds controlling agents are described in co-pending European Patent application N°92201649.8. Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.

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

Others

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

Especially suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1 ,464,616. Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxyiic 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 monofuncfional 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 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 disclosed in EP 753 567.

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.

Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH3(PEG)43)o.75(POH)o.₂₅[T-PO)₂.₈(T-PEG)o.4]T(PO- H)θ.25((PEG)₄₃CH3)o.75

where PEG is -(OC₂H4)O-,PO is (OC3H6O) and T is

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 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 342.

It is well-known in the art that free chlorine in tap water rapidly deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1 % by weight of total composition, in the formulas will provide improved through the wash stability of the detergent enzymes. Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31 , 1992.

Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(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.

Dispersants

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

The compositions of the invention may contain a lime soap peptiser compound, which has preferably a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap peptiser compound is preferably present at a level from 0% to 20% by weight.

A numerical measure of the effectiveness of a lime soap peptiser is given by the lime soap dispersant power (LSDP) which is determined using the lime soap dispersant test as described in an article by H.C. Borghetty and C.A. Bergman, J.

Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950). This lime soap dispersion test method is widely used by practitioners in this art field being referred to, for example, in the following review articles; W.N. Linfield, Surfactant science Series, Volume 7, page 3; W.N. Linfield, Tenside surf, det., volume 27, pages 159-163,

(1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in 30ml of water of 333ppm CaCθ3 (Ca:Mg=3:2) equivalent hardness. Surfactants having good lime soap peptiser capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.

Exemplary surfactants having a LSDP of no more than 8 for use in accord with ^• the present invention include C-|6-C-i8 dimethyl amine oxide, C-ι₂-Ci8 alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly Cι₂-C-|5 alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3 (LSDP=4), and the C14-C15 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the tradenames Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

Polymeric lime soap peptisers suitable for use herein are described in the article by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6- aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds.

Dye transfer inhibition

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

Polymeric dye transfer inhibiting agents

The detergent compositions according to the present invention also comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers 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) A_x

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.

O O O

II II II A is NC, CO, C, -O-.-S-, -N- ; x is O or 1 ; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-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 :

0 O

1 I

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

I (R3)z wherein R1 , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-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 pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-O group is attached to the R-group.

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

Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of 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-O functional group is attached to said R groups. Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.

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

The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The N-vinylimidazole N-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 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 available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A- 256,696).

d) Polyvinyloxazolidone :

The detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from about 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 polyvinyiimidazoles 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. _*-

63

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

Method of washing

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, dishware or any other hard surface with a cleaning solution in the usual manner and exemplified hereunder. A conventional laundry method comprises treating soiled fabric with an aqueous liquid having dissolved or dispensed therein an effective amount of the laundry detergent and/or fabric care composition. 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 3-10 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. A conventional hard surface method comprises treating soiled hard items with e.g. a sponge, brush, clothe, etc. with an aqueous liquid having dissolved or dispensed therein an effective amount of the hard surface cleaner and/or with such composition undiluted. It also encompasses or the soaking in a concentrated solution or in a large volume of dilute solution of the detergent composition.

The process of the invention 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 12.

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

In the following laundry detergent and/or fabric care 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:

LFNI 1 : Ether-capped poly(oxyalkylated) alcohol is C-]2/14-alkyl-

Cg/ι ι -alkyl ethoxylated ether capped alcohol surfactant and is prepared as follows :

Neodol® 91-8 (16.60 g, 0.0325 mol Shell Chemical Co.) is placed in to a 250ml three necked round bottom flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The contents of the flask are dried under vacuum at 75°C for 15 minutes after establishing an Argon atmosphere, Tin (IV) Chloride (0.25 ml, 2.1 mmol Aldrich) is added to the flask via syringe. The mixture is heated to 60 °C at which point C_π2/i4-alkyl glycidyl ether (10.00 g, 0.039 mol) is added dropwise over 15 min while maintaining a temperature of 75-80°C. After stirring for 18 h at 60 °C. The mixture stirs for an additional hour at 75°C until the glycidyl ether is consumed, as determined by TLC. The mixture is cooled to room temperature and diluted with 1 ml of water. The solution is passed through a 170 g of silica gel (Aldrich 227196, 7x12 diameter) while eluting with 5% Methanol (40 ml) dichloromethane. The filtrate is concentrated by rotary evaporation and then stripped in a Kugelrohr oven (70 °C, 0.1 mm Hg for 30 minutes) to yield product as an oil.

LFNI 2 LF404 EO-PO-EO block copolymer from BASF

LAS Sodium linear C-| <|_^«|3 alkyl benzene sulphonate.

TAS Sodium tallow alkyl sulphate.

CxyAS Sodium C-ix - C-|y alkyl sulfate.

CxySAS Sodium Cι_x - Ciy secondary (2,3) alkyl sulfate.

MB AS Mid-branched alkyl sulfate.

CxyEz Ciχ - C-jy predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide.

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

CxEOy Cy alcohol with an average of ethoxylation of y.

High Cloud Point Tergitol 15S9 (Union Carbide)

Nonionic (HCNI)

QAS R₂.N+(CH3)₂(C₂H OH) with R₂ = C<|₂-C_l4.

SADS Sodium C14-22 alkyl disulfate of the formula 2-R.C4H7.-

1 ,4-(SO4-)2 where R = C10-18.

MES x-sulpho methyl ester of C18 fatty acid. APA Cδ-io amido propyl dimethyl amine. Soap Sodium linear alkyl carboxylate derived from a 80/20 mixture of tallow and coconut fatty acids.

Neodol xy-z C1x-C1z linear primary alcohol z ethoxylate.

CFAA Ci2-C-|4 alkyl N-methyl glucamide.

TFAA Ci6"C-18 ^a"*y' N-methyl glucamide.

TPKFA Cι₂-C^«|4 topped whole cut fatty acids.

DEQA Di-(tallow-oxy-ethyl) dimethyl ammonium chloride. DEQA (2) Di-(soft-tallowyloxyethyl) hydroxyethyl methyl ammonium methylsulfate.

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

Silicate Amorphous Sodium Silicate (SiO :Na₂O ratio = 1.6-

3.2:1).

Metasiiicate Sodium metasiiicate (SiO₂:Na₂O ratio = 1.0). Zeolite A Hydrated Sodium Aluminosilicate of formula

Naι₂(A1O₂SiO₂)-|₂. 27H O having a primary particle size in the range from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).

Na-SKS-6 Crystalline layered silicate of formula δ-Na₂Si₂Os

Citrate Tri-sodium citrate dihydrate.

Citric Anhydrous citric acid.

Borate Sodium borate

Carbonate Anhydrous sodium carbonate.

Bicarbonate Sodium hydrogen carbonate.

Sulphate Anhydrous sodium sulphate.

STPP Sodium tripolyphosphate.

TSPP Tetrasodium pyrophosphate.

MA/AA Random copolymer of 4:1 acrylate/maleate, average molecular weight about 70,000-80,000.

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

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

Polycarboxylate Copolymer comprising mixture of carboxylated monomers such as acrylate, maleate and methyacrylate with a MW ranging between 2,000-80,000 such as

Sokolan commercially available from BASF, being a copolymer of acrylic acid, MW4.500.

PB1 Anhydrous sodium perborate monohydrate. PB4 Sodium perborate tetrahydrate of nominal formula

NaBO₃.4H₂O. Percarbonate Anhydrous sodium percarbonate of nominal formula 2.74

Na₂CO3.3H₂O₂ .

NaDCC Sodium dichloroisocyanurate.

TAED Tetraacetyl ethylene diamine.

NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.

NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate. DOBS Decanoyl oxybenzene sulfonate in the form of the sodium salt.

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

2060.

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

Chelant Chelant selected from EEDS, HEDP, DTPA, DETPMP and/or mixtures thereof.

MnTACN Manganese 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane.

Photoactivated Sulfonated zinc phtalocyanine encapsulated in dextrin

Bleach soluble polymer.

Photoactivated Sulfonated alumino phtalocyanine encapsulated in

Bleach 1 dextrin soluble polymer.

PAAC Pentaamine acetate cobalt(lll) salt.

Paraffin Paraffin oil sold under the tradename Winog 70 by

Wintershall.

Pectate lyase Pectate lyase from Bacillus agaradhaerens, NCIMB

40482 or DSM 8721

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^R described in WO 94/18314, WO96/05295 sold by Genencor; Termamyl®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S and those described in WO95/26397 (sold under the tradename Natalase By Novo Nordisk).

Lipase Lipolytic enzyme sold under the tradename Lipolase Lipolase Ultra by Novo Nordisk A/S and Lipomax by Gist- Brocades.

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

CMC Sodium carboxymethyl cellulose. PVNO Polyvinylpyridine-N-Oxide, with an average molecular weight of 50,000.

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

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

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

Suds Suppressor 12% Silicone/silica, 18% stearyl alcohol,70% starch in granular form.

Opacifier Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621.

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

QEA bis((C₂H₅O)(C2H4O)_n)(CH₃) -N⁺-C₆H₁₂-N⁺-(CH3) bis((C H5θ)-(C₂H4θ))_n, wherein n = from 20 to 30.

SCS Sodium cumene sulphonate.

HMWPEO High molecular weight polyethylene oxide.

PEGX Polyethylene glycol, of a molecular weight of x. PEO Polyethylene oxide, with an average molecular weight of

5,000.

TEPAE Tetreaethylenepentaamine ethoxylate.

BTA Benzotriazole. pH Measured as a 1% solution in distilled water at 20°C.

Example 1

The following high density and bleach-containing laundry detergent compositions were prepared according to the present invention:

III

Blown Powder

Zeolite A 12.0 15.0

Sulfate - 5.0

LAS 3.0 3.0

C45AS 3.0 2.0 4.0

QAS - 1.5

DETPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 1.0 2.0 2.0

Agglomerates

QAS 1.0

LAS - 11.0 7.0

TAS 2.0 2.0 1.0

Silicate 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0

Agglomerate

NaSKS-6 15.0 12.0 5.0

LAS 8.0 7.0 4.0

Spray On

Perfume 0.3 0.3 0.3

C25E3 2.0 2.0 I II III

LFNI1 1.0 0.5 1.0

Dry additives

QEA 1.0 0.5 0.5

Citric/Citrate 5.0 - 2.0

Bicarbonate - 3.0 -

Carbonate 8.0 15.0 10.0

TAED and/ or NACA-OBS 6.0 - 5.0

NOBS - 2.0 -

Percarbonate/ PB1 14.0 7.0 10.0

Polyethylene oxide of MW - - 0.2

5,000,000

Bentonite clay - - 10.0

Citric acid 4.0 - 1.5

Pectate lyase 0.001 0.02 0.01

Protease 0.033 0.033 0.033

Lipase 0.008 0.008 0.008

Amylase 0.1 0.1 0.1

Cellulase 0.0014 0.0014 0.0014

Silicone antifoam 5.0 5.0 5.0

Sulfate - 3.0 -

Density (g/litre) 850 850 850

Moisture and miscellaneous Up to 100%

Example 2

The following laundry compositions, which may be in the form of granules or tablet, were prepared according to the present invention.

I II III IV V

Base Product

C45 AS/TAS 8.0 5.0 3.0 3.0 3.0

LAS 8.0 - 8.0 - 7.0

C25AE3S 0.5 2.0 1.0 - -

C25AE5/AE3 2.0 - 5.0 2.0 2.0

LFNI1 0.5 1.0 1.0 0.5 0.5 I II III IV V

QAS - - - 1.0 1.0

Zeolite A 20.0 18.0 11.0 - 10.0

SKS-6 (1) (dry add) - - 9.0 - -

MA/AA 2.0 2.0 2.0 - -

AA - - - - 4.0

Citrate - 2.0 - - -

Citric 2.0 - 1.5 2.0 -

DTPA 0.2 0.2 - - -

EDDS - - 0.5 0.1 -

HEDP - - 0.2 0.1 -

PB1 3.0 5.0 10.0 - 4.0

Percarbonate - - - 18.0 -

NOBS 3.0 4.0 - - 4.0

NACA OBS - - 2.0 - -

TAED - - 2.0 5.0 -

Carbonate 15.0 18.0 8.0 15.0 15.0

Sulphate 5.0 12.0 2.0 17.0 3.0

Silicate - 1.0 - - 8.0

Protease 0.003 0.005 0.001 0.05 0.03

Amylase 0.001 0.004 0.0035 0.0008 0.05

Pectate lyase 0.001 0.002 0.02 0.05 0.005

Minors 0.5 0.5 0.5 0.5 0.5

Perfume 0.2 0.3 0.5 0.2 0.1

Moisture and miscellaneous Up to 100%

Minors include Brightener / SRP1 / CMC / Photobleach / MgSO4 / PVPVI/ Suds suppressor /PEG.

Example 3

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

I II III

Agglomerate

QAS 2.0 - 2.0 I II III

MES - 2.0 -

LAS 6.0 - -

TAS - 2.0 -

C45AS 6.0 4.0 2.0

MBAS16.5, 1.9 4.0 - -

Zeolite A 15.0 6.0 -

Carbonate 4.0 8.0 4.0

MA/AA 4.0 2.0 -

CMC 0.5 0.5 -

DETPMP 0.4 0.4 -

Spray On

LFNI 1 0.5 0.5 0.5

C25E3 1.0 1.0 -

Perfume 0.5 0.5 0.5

Agglomerate

SKS-6 7.0 15.0 20.0

LAS 5.8 9.0 15.0

Zeolite - 0.9 -

Water 0.08 0.1 -

Dry Adds

EDDS/HEDP 0.5 0.3 0.5

NaSKS 6 (I) 5.0 6.0 4.0

Citrate - 1.0 -

Citric 2.0 - 2.0

NACA-OBS 4.1 - 5.0

TAED 0.8 2.0 -

Percarbonate 20.0 20.0 15.0

SRP 1 0.3 0.3 -

Pectate lyase 0.002 0.01 0.03

Protease 0.046 0.046 0.033

Lipase 0.008 0.008 0.006

Cellulase 0.0014 0.0014 0.001

Amylase 0.01 0.01 -

QEA 1.0 - 1.0

Silicone antifoam 1.0 0.5 0.5 _*-

73

I II III

Brightener 1 0.2 0.2 -

Brightener 2 0.2 - 0.2

Density (g/litre) 850 850 800

Moisture and miscellaneous Up to 100%

Example 4

The following laundry compositions, which may be in the form of granules or tablet, were prepared in accordance with the invention:

I II III IV V

Base Product

C45 AS TAS 8.0 5.0 3.0 3.0 3.0

LAS 8.0 - 8.0 - 7.0

C25AE3S 0.5 2.0 1.0 - -

LAS/NaSKS-6 5.0 17.0 9.0 20.0 15.0

C25AE5/AE3 2.0 - 5.0 2.0 2.0

LFNI1 0.5 0.5 0.5 0.5 0.5

HCNI 1.0 1.0 1.0 1.0 1.0

QAS - - - 1.0 1.0

Zeolite A 20.0 10.0 10.0 - 10.0

SKS-6 - - 2.0 - -

MA/AA 2.0 2.0 2.0 - -

AA - - - - 4.0

Citrate - 2.0 - - -

Citric 2.0 - 1.5 2.0 -

DTPA 0.2 0.2 - - -

EDDS - - 0.5 0.1 -

HEDP - - 0.2 0.1 -

PB1 3.0 5.0 10.0 - 4.0

PC - - - 18.0 -

NOBS 3.0 4.0 - - 4.0

NACA OBS - - 2.0 - -

TAED - - 2.0 5.0 -

Carbonate 15.0 18.0 8.0 15.0 15.0

Sulphate 5.0 12.0 2.0 17.0 3.0

Silicate - 1.0 - - 8.0 I II III IV V

Protease 0.001 0.004 0.008 0.001 0.05

Lipase 0.005 0.015 0.0004 0.001 0.003

Amylase 0.0008 0.005 0.01 0.005 0.004

Cellulase 0.0001 .00015 0.001 0.002 .0001

Pectate lyase 0.001 0.02 0.01 0.015 0.03

Minors 0.5 0.5 0.5 0.5 0.5

Perfume 0.2 0.3 0.5 0.2 0.1

Moisture and miscellaneous Up to 100%

Minors include Brightener / SRP1 / CMC / Photobleach / MgSO4 / PVPVI/ Suds suppressor /PEG.

Example 5

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

I II III IV

Agglomerate

QAS 2.0 - 2.0 -

MES - 2.0 - -

LAS 6.0 - - -

TAS - 2.0 - -

C45AS 6.0 4.0 2.0 -

MBAS16.5, 1.9 4.0 - - -

Zeolite A 15.0 6.0 - -

Carbonate 4.0 8.0 4.0 8.0

MA/AA 4.0 2.0 - 2.0

CMC 0.5 0.5 - 0.5

DETPMP 0.4 0.4 - 0.5

Spray On

LFNI2 0.5 0.4 0.4 0.4

C25E3 1.0 1.0 - -

Perfume 0.5 0.5 0.5 0.5 I II III IV

Agglomerate

SKS-6 7.0 15.0 20.0 10.0

LAS 5.8 9.0 15.0 10.0

Zeolite - 0.9 - -

C45 AS - 3.0 - -

Water 0.08 0.1 - 0.2

Dry Adds

EDDS/HEDP 0.5 0.3 0.5 0.8

NaSKS 6) 5.0 6.0 4.0 11.0

Citrate - 1.0 - -

Citric 2.0 - 2.0 4.0

NAC OBS 4.1 - 5.0 4.0

TAED 0.8 2.0 - 2.0

Percarbonate 20.0 20.0 15.0 17.0

SRP 1 0.3 0.3 - 0.3

Pectate lyase 0.01 0.02 0.001 0.002

Protease 0.046 0.046 0.033 0.016

Lipase 0.008 0.008 0.006 -

Cellulase 0.0014 0.0014 0.001 0.001

Amylase 0.6 0.6 - 0.3

QEA 1.0 - 1.0 1.0

Silicone antifoam 1.0 0.5 0.5 1.5

Brightener 1 0.2 0.2 - 6.2

Brightener 2 0.2 - 0.2 -

Density (g/litre) 850 850 800 775

Moisture and miscellaneous Up to 100%

Example 6

The following granular detergent were prepared in accordance with the present invention:

I II III IV I II III IV

Base granule

STPP - 22.0 - 15.0

Zeolite A 30.0 - 24.0 5.0

Sulfate 5.5 5.0 7.0 7.0

MA/AA 3.0 - - -

AA - 1.6 2.0 -

MA/AA (1) - 12.0 - 6.0

LAS 14.0 10.0 9.0 20.0

C45AS 8.0 7.0 9.0 7.0

C45AE11S - 1.0 - 1.0

MES 0.5 4.0 6.0 -

SADS 2.5 - - 1.0

Silicate - 1.0 0.5 10.0

Soap - 2.0 - -

Brightener 1 0.2 0.2 0.2 0.2

Carbonate 6.0 9.0 8.0 10.0

PEG 4000 - 1.0 1.5 -

DTPA - 0.4 - -

Spray on

LFNI 2 0.5 0.4 0.4 0.4

HCNI 0.4 0.4 0.5 1.0

C25E9 - - - 5.0

C45E7 1.0 1.0 - -

C23E9 - 1.0 2.5 -

Perfume 0.2 0.3 0.3 -

Dry additives

Carbonate 5.0 10.0 13.0 8.0

PVPVI/PVNO 0.5 - 0.3 -

Protease 0.033 0.033 0.033 0.0016

Lipase 0.008 - - 0.008

Amylase 0.0016 - - 0.0016

Cellulase 0.0002 0.0005 0.0005 0.0002

Pectate lyase 0.001 0.02 0.03 0.015

DTPA 0.5 0.3 0.5 1.0

PB1 5 3.0 10 4.0 I II Ill IV

NOBS/ TAED 0.5 0.3 0.5 0.6

Sulfate 4.0 5.0 -. 5.0

SRP1 - 0.4

Sud supressor - 0.5 speckle 0.9 2.7 1.2

Moisture and miscellaneous Up to 100%

Example 7

The following laundry detergent compositions were prepared in accordance with the present invention:

I II III IV V VI VII

LAS 12.0 16.0 23.0 19 18.0 20.0 16.0

C45AS 4.5 - - - 4.0

C45 E0.5S - - - - -

C45 E3S - - 2.0 - 1.0 1.0 1.0

C45E6.5S 2.0 2.0 - 1.3 - - 0.6

LFNI 1 1.0 0.5 0.5 1.0 1.0 0.5 0.5

C₈-C₁₄ alkyl dimethyl - - 1.0 0.5 2.0 hydroxy ethyl quaternary ammonium salt

Tallow fatty acid - - - - 1.0

Tallow alcohol ethoxylate - - - - - - -

(50)

STPP 23.0 25.0 24.0 22,0 20.0 15.0 20.0

Carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0

Sodium Polyacrylate 0.5 0.5 0.5 0.5 - - -

(45%)

MA/AA - - 1.0 1.0 1.0 2.0 0.5

Silicate (1 :6 ratio 3.0 6.0 9.0 8.0 9.0 6.0 8.0

Sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0

PB1 5.0 5.0 10.0 8.0 3.0 1.0 2.0

PEG MW -4000 (50%) 1.5 1.5 1.0 1.0 - - 0.5

CMC 1.0 1.0 1.0 - 0.5 0.5 0.5 I II III IV V VI VII

Citric . . . . . . .

NOBS/ DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3

TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5

SRP1 1.5 1.5 1.0 1.0 - 1.0 -

SRP2 - - - - 1.0 - 1.0

Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0

Mg sulphate - - - - 1.0 0.5 1.5

Chelant _ _ _ - 0.8 0.6 1.0

Protease 0.004 0.000 0.002 0.011 0.001 0.005 0.006 4 3

Amylase 0.001 .0014 .0008 .0012 0.005 .0004 0.002

Lipase .0014 .0009 .004 0.010 .0008 0.005 0.001

Cellulase .0001 .0008 .0002 .0001 .0001 .0003 .0004

Pectate lyase 0.001 0.02 0.01 0.001 0.002 0.015 0.03 speckle 2.5 4.1 4.2 4.4 5.6 5.0 5.2

Minors 1.0 1.0 1.0 1.0 0.5 1.5 1.0

Example 8

The following laundry detergent compositions were prepared in accordance with the present invention:

I II III IV

LAS 13.3 13.7 10.4 8.0

C45 AS 3.9 4.0 4.5 -

C45 E0.5S 2.0 2.0 - -

C45 E3S - - - -

C45E6.5S 0.5 0.5 0.5 5.0

LFNI 1 0.4 0.4 0.5 0.4

C₉-C₁₄ alkyl dimethyl hydroxy 1.0 - - 0.5 ethyl quaternary ammonium salt

Tallow fatty acid 0.5 - - -

Tallow alcohol ethoxylate (50) - - 1.0 0.3

STPP . 41.0 - 20.0 I II III IV

Zeolite A 26.3 - 21.3 1.0

Carbonate 23.9 12.4 25.2 17.0

Sodium Polyacrylate (45%) 3.4 0.0 2.7 -

MA/AA - - 1.0 1.5

Silicate (1 :6 ratio) 2.4 6.4 2.1 6.0

Sulfate 10.5 10.9 8.2 15.0

PB1 1.0 1.0 1.0 2.0

PEG MW -4000 (50%) 1.7 0.4 1.0 -

CMC 1.0 - - 0.3

Citric - - 3.0 -

NOBS/ DOBS 0.2 0.5 0.5 0.1

TAED 0.6 0.5 0.4 0.3

SRP 1 1.5 - - -

SRP2 - 1.5 1.0 1.0

Moisture 7.5 3.1 6.1 7.3

Mn sulphate - - - 1.0

Chelant - - - 0.5 speckles 0.5 1.0 3.0 0.5

Pectate lyase 0.001 0.01 0.005 0.002

Protease 0.003 0.004 0.03 0.005

Amylase 0.0015 0.005 0.005 0.005

Minors 1.0 1.0 1.0 1.0

Example 9

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

1 II III IV V

LAS 11.5 9.0 - 4.0 -

C25E2.5S - 3.0 18.0 - 16.0

C45E2.25S 11.5 3.0 - 16.0 -

C23E9 - 3.0 2.0 2.0 1.0

C23E7 3.2 _ . _ _ 1 II III IV V

LFNI 2 0.5 1.0 1.0 2.0 1.0

CFAA - - 5.0 - 3.0

TPKFA 2.0 - 2.0 0.5 2.0

Citric (50%) 6.5 1.0 2.5 4.0 2.5

Ca formate 0.1 0.06 0.1 - -

Na formate 0.5 0.06 0.1 0.05 0.05

SCS 4.0 1.0 3.0 1.2 -

Borate 0.6 - 3.0 2.0 3.0

Na hydroxide 6.0 2.0 3.5 4.0 3.0

Ethanol 2.0 1.0 4.0 4.0 3.0

1 ,2 Propanediol 3.0 2.0 8.0 8.0 5.0

Monoethanolamine 3.0 1.5 1.0 2.5 1.0

TEPAE 2.0 - 1.0 1.0 1.0

Pectate lyase 0.1 0.002 0.01 0.01 0.5

Protease 0.03 0.01 0.03 0.02 0.02

Lipase - - 0.002 - -

Amylase - - - 0.002 -

Cellulase - - 0.0002 0.0005 0.000

SRP 1 0.2 - 0.1 - -

DTPA - - 0.3 - -

PVNO - - 0.3 - 0.2

Brightener 1 0.2 0.07 0.1 - -

Silicone antifoam 0.04 0.02 0.1 0.1 0.1

Miscellaneous and water

Example 10

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

I II Ill IV I II III IV

LAS 10.0 13.0 9.0 - 25.0 - - -

C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0

C25E3S 1.0 . . 3.0 . 2.0 2.0 4.0 I II III IV I II III IV

C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0

TFAA - - - 4.5 - 6.0 8.0 8.0

LFNI 2 0.5 0.4 0.4 0.4 0.5 0.4 0.4 0.5

HCNI 0.4 0.4 0.5 0.3 0.3 0.6 0.4 0.5

APA - 1.4 - - 3.0 1.0 2.0 -

TPKFA 2.0 - 13.0 7.0 - 15.0 11.0 11.0

Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0

Dodecenyl / tetradecenyl 12.0 10.0 - - 15.0 - - - succinic acid

Rapeseed fatty acid 4.0 2.0 1.0 - 1.0 - 3.5 -

Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0

1 ,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0

Monoethanolamine - - - 5.0 - - 9.0 9.0

Triethanolamine - - 8.0 - - - 0.4 0.3

TEPAE 0.5 - 0.5 0.2 2.0 1.2 1.0 -

DETPMP 1.0 1.0 0.5 1.0

Pectate lyase 0.01 .001 .001 0.02 0.02 .002 .002 0.02

Protease 0.02 0.02 0.01 .008 - - .003 .003

Lipase - .002 - .002 .004 0.01 0.01 0.01

Amylase .004 .004 0.01 .008 - - .004 .003

Cellulase - - - .002 - - 0.2 0.1

SRP 2 0.3 - 0.3 0.1 1.0 1.5 2.5 2.5

Boric acid 0.1 0.2 1.0 2.0 4.0 4.0 - -

Ca chloride - 0.02 - 0.01 0.1 0.2 0.3 -

Brightener 1 - 0.4 - - 0.4 - - -

Suds suppressor 0.1 0.3 - 0.1 0.8 0.7 - -

Opacifier 0.5 0.4 - 0.3 8.0 7.5 8.0 8.2

NaOH up to pH 8.0 8.0 7.6 7.7

Miscellaneous and water

Example 11

The following liquid detergent compositions were prepared according to the present invention (Levels are given in parts by weight, enzyme are expressed in pure enzyme) : 1 II

LAS 28.0 19.0

C45AS 14.0 6.0

C13E8 3.0 3.0

LFNI 1 0.5 0.8

Oleic acid 3.0 2.5

Citric 5.0 5.0

Na hydroxide 0.4 4.0

Ca Formate 0.2 0.1

Na Formate - 0.5

Ethanol 7.0 -

Monoethanolamine 16.5 8.0

1 ,2 propanediol 6.0 5.5

Xylene sulfonic acid - 2.0

TEPAE 1.5 0.8

Protease 0.05 0.02

Pectate lyase 0.02 0.01

PEG - 0.7

Brightener 2 0.4 0.1

Perfume 0.5 0.3

Water and Minors

Example 12

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

I II

C45AS - 10.0

LAS 7.6 -

C68AS 1.3 -

C45E7 4.0 -

C25E3 - 5.0

LFNI 2 0.5 0.4 I II

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

Percarbonate - 15.0 TAED 5.0 5.0

Smectite clay 10.0 10.0 HMWPEO - 0.1 Pectate lyase 0.001 0.01 Protease 0.02 0.01 Lipase 0.02 0.01 Amylase 0.03 0.005 Cellulase 0.001 - Silicate 3.0 5.0 Carbonate 10.0 10.0 Suds suppressor 1.0 4.0 CMC 0.2 0.1 Miscellaneous and minors Up to 100%

Example 13

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

DEQA (2) 20.0 LFNI 2 0.4

Pectate lyase 0.001 Cellulase 0.001 HCL 0.03 Antifoam agent 0.01

Blue dye 25ppm

CaCI₂ 0.20

Perfume 0.90

Miscellaneous and water Up to 100%

Example 14

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

I II III IV V

DEQA 2.6 19.0 - - -

DEQA(2) - - - - 52.0

DTMAMS - - - 26.0 -

SDASA - - 70.0 42.0 40.2

LFNI 2 0.4 0.6 0.5 0.4 0.5

HCNI 0.3 0.3 0.4 0.3 0.5

Stearic acid of IV=0 0.3 - - - -

Neodol 45-13 - - 13.0 - -

HCL 0.02 0.02 - - -

Ethanol - - 1.0 - -

Pectate lyase 0.001 0.002 0.01 0.01 0.005

Perfume 0.3 1.0 0.75 1.0 1.5

Glycoperse S-20 - - - - 15.4

Glycerol monostearate - - - 26.0 -

Digeranyl Succinate - - 0.38 - -

Silicone antifoam 0.01 0.01 - - -

Electrolyte - 0.1 - - -

Clay - - - 3.0 -

Dye 10ppm 25ppm 0.01 - -

Water and minors 100% 100% - - -

Example 15 The following laundry bar detergent compositions were prepared according to the present invention (Levels are given in parts per weight, enzyme are expressed in pure enzyme) :

I II III VI V III VI V

LAS - - 19.0 15.0 21.0 6.75 8.8 -

C28AS 30.0 13.5 - - - 15.75 11.2 22.5

LFNI 1 0.5 0.4 0.4 0.6 0.8 0.5 0.3 0.8

Na Laurate 2.5 9.0 - - - - - -

Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25

Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0

Ca Carbonate 27.5 39.0 35.0 - - 40.0 - 40.0

Sulfate 5.0 5.0 3.0 5.0 3.0 - - 5.0

TSPP 5.0 - - - - 5.0 2.5 -

STPP 5.0 15.0 10.0 - - 7.0 8.0 10.0

Bentonite clay - 10.0 - - 5.0 - - -

DETPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7

CMC - 1.0 1.0 1.0 1.0 - - 1.0

Talc - - 10.0 15.0 10.0 - - -

Silicate - - 4.0 5.0 3.0 - - -

PVNO 0.02 0.03 - 0.01 - 0.02 - -

MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4

SRP 1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Pectate lyase 0.01 0.001 0.005 0.02 0.02 0.1 0.01 0.01

Amylase - - 0.01 - - - 0.002 -

Protease - 0.004 - 0.003 0.003 - - 0.00c

Lipase - 0.002 - 0.002 - - - -

Cellulase - .0003 - - .0003 .0002 - -

PEO - 0.2 - 0.2 0.3 - - 0.3

Perfume 1.0 0.5 0.3 0.2 0.4 - - 0.4

Mg sulfate - - 3.0 3.0 3.0 - - -

Brightener 0.15 0.1 0.15 - - - - 0.1

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

Example 16 The following compact high density (0.96Kg/l) dishwashing detergent compositions were prepared according to the present invention :

I II III IV V VI

STPP - 51.0 51.0 - - 44.3

Citrate 17.0 - - 50.0 40.2 -

Carbonate 17.5 14.0 20.0 - 8.0 33.6

Bicarbonate - - - 26.0 - -

Silicate 15.0 15.0 8.0 - 25.0 3.6

Metasiiicate 2.5 4.5 4.5 - - -

PB1 10.0 8.0 8.0 - - -

PB4 - - - 10.0 - -

Percarbonate - - - - 11.8 4.8

HCNI 2.0 1.5 1.5 3.0 1.9 5.9

LFNI 1 1.0 1.5 0.5 2.0 1.0 3.0

TAED 2.0 - - 4.0 - 1.4

HEDP 1.0 - - - - -

DETPMP 0.6 - - - - -

MnTACN - - - - 0.01 -

PAAC - 0.01 0.01 - - -

Paraffin 0.5 0.4 0.4 0.6 - -

Pectate lyase 0.04 0.1 0.03 0.5 0.005 0.005

Protease 0.072 0.053 0.053 0.026 0.059 0.01

Amylase 0.012 0.012 0.012 0.021 0.021 0.006

Lipase - 0.001 - 0.005 - -

BTA 0.3 0.2 0.2 0.3 0.3 0.3

Polycarboxylate 6.0 - - - 4.0 0.9

Perfume 0.2 0.1 0.1 0.2 0.2 0.2

PH 11.0 11.0 11.3 9.6 10.8 10.9

Miscellaneous, sulfate and water Up to 100%

Example 17

The following granular dishwashing detergent compositions of bulk density 1.02Kg/L were prepared according to the present invention : I II III IV V VI

STPP 30.0 33.5 27.9 29.6 33.8 22.0

Carbonate 30.5 30.5 30.5 23.0 34.5 45.0

Silicate 7.0 7.5 12.6 13.3 3.2 6.2

Metasiiicate - 4.5 - - - -

Percarbonate - - - - 4.0 -

PB1 4.4 4.5 4.3 - - -

NADCC - - - 2.0 - 0.9

HCNI 1.0 0.7 1.0 1.9 0.7 0.5

LFNI 2 1.0 2.0 1.5 2.5 3.0 0.5

TAED 1.0 - - - 0.9 -

PAAC - 0.004 - - - -

Paraffin 0.25 0.25 - - - -

Pectate lyase 0.4 0.005 0.001 0.02 0.02 0.1

Protease 0.036 0.021 0.03 - 0.006 -

Amylase 0.03 0.005 0.004 - 0.005 -

Lipase 0.005 - 0.001 - - -

BTA 0.15 0.15 - - 0.2 -

Perfume 0.2 0.2 0.05 0.1 0.2 - pH 10.8 11.3 11.0 10.7 11.5 10.9

Miscellaneous, sulfate and water Up to 100%

Example 18

The following tablet detergent compositions were prepared according to 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 IV V VI VII VIII

STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0

Citrate 20.0 - - - 35.9 - - -

Carbonate 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0

Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2

Pectate lyase 0.1 0.001 0.01 0.4 0.02 0.02 0.1 0.005

Protease 0.042 0.072 0.042 0.031 0.052 0.023 0.023 0.029 I II III IV V VI VII VIII

Amylase 0.012 0.012 0.012 0.007 0.015 0.003 0.017 0.002

Lipase 0.005 - - - - - - -

PB1 14.3 7.8 11.7 12.2 - - 6.7 8.5

PB4 - - - - 22.8 - 3.4 -

Percarbonate - - - - - 10.4 - -

HCNI 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5

LFNI 2 1.0 0.5 0.5 1.3 2.4 1.6 1.0 0.5

PAAC - - 0.02 0.009 - - - -

MnTACN - - - - 0.007 - - -

TAED 2.7 2.4 - - - 2.1 0.7 1.6

HEDP 1.0 - - 0.9 - 0.4 0.2 -

DETPMP 0.7 - - - - - - -

Paraffin 0.4 0.5 0.5 0.5 - - 0.5 -

BTA 0.2 0.3 0.3 0.3 0.3 0.3 0.3 -

Polycarboxylate 4.0 - - - 4.9 0.6 0.8 -

PEG - - - - - 2.0 - 2.0

Glycerol - - - - - 0.4 - 0.5

Perfume - - - 0.05 0.2 0.2 0.2 0.2

Weight of tablet 20g 25g 20g 30g 18g 20g 25g 24g

PH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8

Miscellaneous, sulfate and water Up to 100%

Example 19

The following liquid rinse aid compositions were prepared according to the present invention :

I II III IV

HCNI 10.0 13.6 62.3 60.0

LFNI 1 2.0 3.0 4.0 2.0

Pectate lyase 0.001 0.01 0.0005 0.001

Propylene glycol - - 5.0 5.5

Citric 3.5 4.6 - -

SCS 10.0 7.7 - - pH of the liquid 3.0 2.5 7.2 7.2 Miscellaneous, solvent and water Up to 100%

Example 20

The following liquid hard surface cleaning compositions were prepared according to the present invention :

I II III IV V

Pectate lyase 0.005 0.1 0.02 0.02 0.005

Amylase 0.01 0.002 0.005 - -

Protease 0.05 0.01 0.02 - -

Hydrogen peroxide - - - 6.0 6.8

Acetyl triethyl citrate - - - 2.5 -

DTPA - - - 0.2 -

Butyl hydroxy toluene - - - 0.05 -

EDTA^* 0.05 0.05 0.05 - -

Citric / Citrate 2.9 2.9 2.9 1.0 -

LAS 0.5 0.5 0.5 - -

C12 AS 0.5 0.5 0.5 - -

C10AS - - - - 1.7

C12(E)S 0.5 0.5 0.5 - -

C12.13 E6.5 nonionic 7.0 7.0 7.0 - -

Neodol 23-6.5 - - - 12.0 -

Neodol 23-3 - - - - 1.5

Neodol 91-10 - - - - 1.6

LFNI 2 0.5 0.5 0.5 0.3 0.4

C25AE1.8S - - - 6.0

Na paraffin sulphonate - - - 6.0

Perfume 1.0 1.0 1.0 0.5 0.2

Propanediol - - - 1.5

Ethoxylated tetraethylene - - - 1.0 - pentaimine

2, Butyl octanol - - - - 0.5

Hexyl carbitoP^* 1.0 1.0 1.0 - -

SCS 1.3 1.3 1.3 - - pH adjusted to 7-12 7-12 7-12 4 - Miscellaneous and water Up to 100%

^*Na4 ethylenediamine diacetic acid ^**Diethylene glycol monohexyl ether

Example 21

The following spray composition for cleaning of hard surfaces and removing household mildew was prepared according to the present invention :

Pectate lyase 0.01

Amylase 0.01

Protease 0.01

Na octyl sulfate 2.0

Na dodecyl sulfate 4.0

Na hydroxide 0.8

LFNI 2 0.4

Silicate 0.04

Butyl carbitol* 4.0

Perfume 0.35

Water/minors up to 100%

*Diethylene glycol monobutyl ether

Example 22

The following disinfecting compositions were prepared according to the present invention.

I II III

Wipe Spray Liquid

H2O2 1.0 1.5 1.0

Na tetraborate 10.H2O - 1.0 -

C10 Amine Oxide - 0.9 0.9

C12-14 alkyl dimethyl amine oxide 0.4 - -

C7-10 AS - - 6.0

C9-11 EO10 - 0.05 -

C8-18 Fatty acid - 0.1 0.2 I II III

LFNI 1 0.5 0.4 0.4

Ethanol 9.0 1.0 2.5

Benzyl alcohol - 0.8 -

Propylene or diethylene glycol butyl ether 1.0 1.5 -

Poly(propylene glycol) monobutyl ether 0.2 - -

HEDP - 0.1 -

Butylated hydroxytoluene 0.01 0.06 0.03

Salicyclic acid 0.03 - 0.07

Pectate lyase 0.001 0.01 0.005

Perfume 0.1 0.3 0.3

Citric 0.7 - 1.5

Dye - - 2.0

NaOH - 0.1 -

Miscellaneous and water Up to 100%

Claims

1. A detergent composition comprising a pectate lyase and a low foaming nonionic surfactant.

2. A detergent composition according to claim 1 wherein the pectate lyase enzyme is comprised at a level of from 0.0001 % to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition

3. A detergent composifion according to claims 1-2 wherein said low foaming nonionic surfactant is comprised at a level of from 0.01% to 15%, preferably from 0.25% to 4% by weight of total composition.

4. A detergent composition according to claims 1-3 wherein said low foaming nonionic surfactant is an ether-capped poly(oxyalylated) alcohol surfactant having the formula:

R¹O[CH₂CH(R3)O]_x[CH₂]_kCH(OH)[CH₂]jOR²

wherein R^ and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer having an average value from 1 to 40, wherein when x is 2 or greater R³ may be the same or different and k and j are integers having an average value of from 1 to 12; further wherein when x is 15 or greater and R3 is H and methyl, at least four of R³ are methyl, further wherein when x is 15 or greater and R³ includes H and from 1 to 3 methyl groups, then at least one R³ is ethyl, propyl or butyl, further wherein R2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof.

5. A detergent composition according to claim 4 wherein Rl and R² are linear or branched, saturated or unsaturated, aliphatic hydrocarbon radicals having from 6 to 22 carbon atoms.

6. A detergent composition according to claims 4-5 wherein R1 and R² are linear, saturated, aliphatic hydrocarbon radicals having from 8 to 18 carbon atoms.

7. A detergent composition according to claims 4-6 wherein x is an integer having an average value of from 1 to 20, preferably from 6 to 15.

8. A detergent composition according to claims 4-7 wherein R³ is H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms.

9. A detergent composition according to claims 4-8 wherein said surfactant has a cloud point of less than 20°C.

10. A detergent composition according to claims 1-3 wherein said low foaming nonionic surfactant is a polyoxypropylene / polyoxyethylene / polyoxypropylene reverse block polymer.

11. A detergent composition according to claim 10 wherein said polyoxypropylene / polyoxyethylene / polyoxypropylene reverse block polymer is selected from those materials having cloud points less than

30°C.

12. A composition according to any of the preceding claims further comprising a high cloud point nonionic surfactant having a cloud point of greater than 40° C, the ratio of low cloud point to high cloud point nonionic surfactants being within the range of from 10:1 to 1 :10.

13. A method of cleaning a fabric, a dishware and/or a hard surface with a detergent composition according to any of the preceding.

14. A method for the suppression of suds in a laundry, dishwashing and/or hard surface cleaning context, said method comprising the step of adding an effective amount of a detergent composition according to any of the preceding claims.