Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides

Definitions

• the present invention relates to detergent c mpositions comprising a pectate lyase and specific surfactant selected from a . n aftiine oxide surfactant and/or a mid-chain branched anionic surfactant.
• detergent compositions include nowadays a complex combination of active ingredients which fulfil certain specific needs.
• current detergent formulations generally include surfactants and detergent enzymes providing cleaning and fabric care benefits.
• 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.
• 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.
• Amine oxide surfactants have been used since a very long time in the detergency industry and are known to provide good cleaning benefits, especially on grease / lipids soils.
• Anionic surfactants have been used since a very long time in the detergency industry.
• mid-chain branched anionic surfactants were developed such as described in WO97/39091 and WO97/38956 and in the co-pending US applications US97/06485, US97/06474, US97/06339, US97/06476 and US97/06338. These mid-chain branched anionic surfactants are characterised by having the ability to couple with high hydrophobicity, a low temperature solubility and a high hardness tolerance.
• mid-chain branched are especially useful in cool or cold water laundry washing conditions, even in temperatures as low as 20°C-5°C. It has also been found that a combination of two or more of these mid-chain branched surfactants can provide a surfactant mixture that is even higher in surfactancy and has better low temperature water solubility.
• 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.
• 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.
• 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.
• 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.
• pectate lyase enzymes are directed to the cleavage of ⁇ -D-(1 ,4) glycosidic bonds in poly-D-galacturonans by the mechanism of ⁇ - elimination. These pectate lyase enzymes further help as well the removal of mixed stains / soils comprising pectin substances and other components.
• 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. It has been surprisingly found that a unique surfactant system containing a surfactant selected from an amine oxide surfactant and/or a mid-chain branched anionic surfactant, can maximise the pectate lyase enzyme cleaning efficiency.
• detergent compositions comprising a pectate lyase and such selected surfactant, provide superior cleaning due to the synergistic effect of the selected surfactant removing greasy stains and the pectate lyase degrading the pectin components of such soils and/or in a laundry context, the pectin components of the fabric that can bin or otherwise interact with such soils, making them difficult to remove.
• This surfactant - enzyme mixed system delivers an outstanding cleaning effect, especially on these plant-based stains and body soils.
• such removal of greasy stains is particularly effective with mid-chain branched anionic surfactant at low temperature.
• pectin degrading enzymes in detergent has already been recognised in the art.
• 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.
• JP 60226599 describes detergent composition comprising conventional detergent actives and a cellulase and hydrolase such as hemicellulase, pectinase, amylase or protease.
• 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.
• 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.
• the present invention relates to detergent compositions, including laundry and/or fabric care, dishwashing and hard surfaces compositions, comprising a pectate lyase and a surfactant selected from an amine oxide surfactant and/or mid-chain branched anionic surfactant.
• These compositions provide superior cleaning performance, especially on plant-based stains and body soils.
• the present invention relates to detergent compositions comprising a pectate lyase and a surfactant selected from an amine oxide surfactant and/or mid-chain branched anionic surfactant, for providing superior cleaning performance.
• a pectate lyase and a surfactant selected from an amine oxide surfactant and/or mid-chain branched anionic surfactant, for providing superior cleaning performance.
• 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.
• pectate lyase is a pectin degrading enzyme which splits the ⁇ -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.
• 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.
• a unique surfactant system comprising a surfactant selected from an amine oxide surfactant and/or mid-chain branched anionic surfactant, can maximise the pectate lyase cleaning efficiency.
• Such surfactants are known to provide superior cleaning, stain removal and in a laundry and/or fabric care context, whiteness maintenance and especially greasy/oily stain removal.
• an amine oxide surfactant and/or a mid-chain branched anionic surfactant with a pectate lyase enzyme achieves high substrate specificity, high solution activity and high flexibility towards a variety of wash conditions and applications needs. It has been found that such combination leads to performance synergy in soil and stain cleaning, especially on food stains/soils and body soils.
• the synergistic cleaning benefits observed with the detergent compositions of the present invention is the result of the selected surfactant of the present invention, promoting the removal of greasy soils bound to the fabric by pectins and that the pectate lyase hydrolysing the pectin network which entraps a variety of soils species.
• the amine oxide and/or mid-chain branched anionic surfactants provide superior removal of hydrophobic soils such as body soils, mechanical and grease/oil, especially at low temperature, by emulsifying such soils and reducing their melting points.
• the pectate lyase enzyme is believed to further aid the cleaning action by removing the pectin containing compounds found in a number of dirt, mud and plant-based soils as well as the natural pectin found on cotton fabric.
• the combination of improved hydrophobic soil removal with the removal of the pectin containing compounds of soils that can entrap other spoils materials is believed responsible for the synergistic, superior cleaning, whitening and stain removal observed with the detergent compositions of the present invention.
• 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 ⁇ -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, PenicilHum, Bacteroides, The ⁇ nomonospora, 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.
• 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 protopectinases 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.
• 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
• 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/DK98/00515 or by a Bacillus species having a 16S rDNA sequence homology to SEQ ID NO:14 of
• 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/DK98/00515 or by a Bacillus species having a 16S rDNA sequence homology to SEQ ID NO:13 of PCT/DK98/00515 higher 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
• pectate lyase enzyme described in the international co- pending application PCT/DK98/00514, internationally filed on November 24, 1998 and published under WO99/27083 and which is :
• D a polypeptide produced by Bacillus licheniformis, ATCC 14580, or ⁇ ) a polypeptide comprising an amino acid sequence as shown in positions 28-221 of SEQ ID NO:4 of PCT/DK98/00514, or iii) 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.
• CBD cellulose-binding domain
• 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.
• 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.
• 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 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
• 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.
• the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
• 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.
• 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 selected surfactant is the selected surfactant
• the second essential element of the detergent compositions of the present invention is a specific surfactant selected from an amine oxide being a semi-polar surfactant and/or a mid branched anionic surfactant.
• the detergent compositions of the present invention generally comprise from 0.1% to 15%, preferably from 0.1% to 10%, more preferably less than 5% by weight of the total composition of such amine oxide.
• Suitable amine oxides for the purpose of the present invention are described in "Surface active agent and Detergent" Volk I and II by Schwatrz et al..
• suitable amine oxides are the 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
• R ⁇ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms
• R 4 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
• each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
• the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
• Preferred amine oxide surfactants include C ⁇ ⁇ o- -
• the mid-chain branched surfactant The mid-chain branched anionic surfactants of the present invention are described in WO97/38957, WO97/39090, WO97/38956, WO97/39901 and WO97/38972 and in WO97/39091.
• the detergent compositions of the present invention generally comprise from 0.1 % to 50%, preferably from 0.5% to 40% more preferably from 1 % to 35% by weight of the total composition of one or more longer alkyl chain, mid-chain branched surfactant compounds of the formula:
• a D is a hydrophobic mid-chain branched alkyl moiety, having in total 9 to 22 carbons in the moiety, preferably from 12 to about 18, having: (1 ) a longest linear carbon chain attached to the - X - B moiety in the range of from 8 to 21 carbon atoms; (2) one or more C-) - C3 alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is attached directly to a carbon of the longest linear carbon chain at a position within the range of the position 2 carbon, counting from position 1 carbon (#1) which is attached to the - X - B moiety, to the position of the terminal carbon minus 2 carbons, (the ( ⁇ - 2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the A D -X moieties in the above formula is within the range of greater than 11 to 20, preferably 14.5 to about 18, more preferably from about 15 to about 17; (I)
• Preferred surfactant systems herein comprise longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A D moiety is a branched primary alkyl moiety having the formula:
• R, R 1 , and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably methyl), provided R, R1 , and R2 are not all hydrogen and, when z is 0, at least R or R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13.
• mid-chain branched surfactant compounds of the surfactant system certain points of branching (e.g., the location along the chain of the R, Rl , and/or R2 moieties in the above formula) are preferred over other points of branching along the backbone of the surfactant.
• the formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A D moieties useful according to the present invention.
• surfactant compounds wherein in the above formula the A D moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom).
• mid-chain branched surfactants compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulfonate and, even more preferably, sulfate surfactants. It should be understood that for the purpose of the invention, it may be preferred that the surfactant system comprises a mixture of two or more mid-chain branched primary alkyl sulfate or sulphonate surfactants.
• Preferred mid-chain branched primary alkylsulfate surfactants are of the formula
• These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms.
• the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 11 to 20, preferably 14.5 to about 17.5.
• the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 11 to 20, preferably 14.5 to about 17.5.
• R, R 1 , and R 2 are each independently selected from hydrogen and C1-C3 alkyl group (preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R 1 , and R 2 are not all hydrogen. Further, when z is 1 , at least R or R 1 is not hydrogen.
• M is hydrogen or a salt forming cation depending upon the method of synthesis.
• salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula
• R 3 , R 4 , R 5 and R 6 are independently hydrogen, C1-C22 alkylene, C4- C22 branched alkylene, C-
• Preferred cations are ammonium (R 3 , R 4 , R 5 and R6 equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.
• the monoalkanol ammonium compounds of the present invention have R 3 equal to CJ -CQ alkanol, R 4 , R 5 and R 6 equal to hydrogen; dialkanol ammonium compounds of the present invention have R 3 and R 4 equal to C ⁇
• Preferred alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas:
• Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred is sodium. Further regarding the above formula, w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1 ; and w + x + y + z is an integer from 8 to 14.
• a preferred mid-chain branched primary alkyl sulfate surfactant is, a C16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and having 1 , 2, or 3 branching units (i.e., R, R 1 and/or R 2 ) of in total 3 carbon atoms, (whereby thus the total number of carbon atoms is at least 16).
• Preferred branching units can be one propyl branching unit or three methyl branching units.
• Another preferred surfactant system of the present invention have one or more branched primary alkyl sulfates having the formula
• the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 11 to 20, preferably 14.5 to about 17.5;
• R 1 and R 2 are each independently hydrogen or C1-C3 alkyl;
• M is a water soluble cation;
• x is from 0 to 11 ;
• y is from 0 to 11 ;
• z is at least 2; and
• x + y + z is from 9 to 13; provided R-* and R 2 are not both hydrogen.
• the surfactant system comprises at least 20% by weight of the system, more preferably at least 60% by weight , even more preferably at least 90% by weight of the system, of a mid chain branched primary alkyl sulfates, preferably having R ⁇ and R 2 independently hydrogen or methyl, provided R 1 and R 2 are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably from 15 to 17, more preferably from 16-17.
• preferred surfactant systems are those, which comprise at least about 20%, more preferably at least 60%, even more preferably at least 905 by weight of the system, of one or more mid-chain branched alkyl sulfates having the formula: CH 3
• Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11 -methyl pentadecanol sulfate, 12- methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecan
• Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2, 3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2, 5-methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2, 10-methyl tetradecanol sulfate, 2,11-methyl tetradecanol sulfate, 2,12- methyl tetradecanol sulfate, 2, 3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2, 5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol
• branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions:
• M is preferably sodium
• branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:
• M is preferably sodium
• the mid-chain branched encompasses in the present invention can be manufactured according to the process described in WO97/38956. Such process prepares mid- to near mid-chain branched olefins (primarily, methyl branched at or near the mid-chain region). Such materials are then used as the basic feedstock which provides the hydrophobic portion of branched-chain detersive surfactants.
• the process herein is designed to provide branched reaction products which are primarily (85%, or greater) alpha-olefins, and which are then converted into hydrophobes in the Oxo-reaction sequence noted hereinafter.
• branched alpha-olefins contain from about 11 to about 18 (avg.) total carbon atoms and comprise a linear chain having an average length in the 10-18 region.
• the branching is predominantly mono-methyl, but some di-methyl and some ethyl branching may occur.
• the present process results in little (1%, or less) geminal branching, i.e., little, if any, "quaternary" carbon substitution. Moreover, little (less than about 20%) vicinal branching occurs.
• the present process provides alpha-olefins with: an average number of branches (longest chain basis) in the 0.4-2.5 range; of the branched material, there are essentially no branches on carbons 1 , 2 or on the terminal (omega) carbon of the longest chain of the branched material.
• the feedstock is subjected to an Oxo carbonylation process.
• a catalyst e.g., conventional cobalt carbonyl; see Kirk Othmer, below
• the detergent compositions of the invention will preferably comprise further additional detergent components.
• 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. It has been surprisingly found that the cleaning benefits of pectate lyase enzyme can be optimised and maximised with a time controlled release technology.
• the time controlled technology is a tablet wherein the pectate lyase is separated from the inhibiting / deactivating other detergent ingredients in a different product phase having a different solubility in the wash.
• pectate lyase enzyme can be achieved when said enzyme is incorporated into a tablet and such system delivers significant soil and stain cleaning benefits. It has further been found that such time controlled release technology allows a broader range of Pectate Lyases to be used, including those that show a high degree of instability in standard detergent matrices. Indeed, the pectate lyase and buffer materials can preferably be incorporated into the rapid dissolving portion of the tablet.
• pectate lyase is released earlier than the inhibiting / deactivating other detergent ingredients and that optimum pectate lyase activity is obtained at the beginning of the wash under buffered conditions, allowing the formulation in detergent of pectate lyases in the full range of available pectate lyases.
• Suitable tablets are detergent tablets which are not only sufficiently robust to withstand handling and transportation, but also at least a portion of which dissolves rapidly in the wash water providing rapid delivery of the pectate lyase enzyme. It is preferred that at least one phase of the tablet dissolves in the wash water within the first ten minutes, preferably five minutes, more preferably four minutes of the wash cycle of an automatic dishwashing or laundry washing machine.
• the washing machine is either an automatic dishwashing or laundry washing machine.
• the time within which the multi-phase tablet or a phase thereof or a detergent active component dissolves is determined according to DIN 44990 using a dishwashing machine available from Bosch on the normal 65°C washing program with water hardness at 18°H using a minimum of six replicates or a sufficient number to ensure reproducibility.
• the present invention relates to laundry detergent compositions comprising a pectate lyase and a surfactant selected from an amine oxide and/or a mid-chain branched anionic surfactant (Examples 1-18).
• the present invention relates to dishwashing or household detergent compositions (Examples 19-23).
• 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.
• 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.
• compositions suitable for use in a laundry machine washing method 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 an amine oxide can provide fabric cleaning, stain removal, and colour appearance when formulated as laundry detergent compositions.
• compositions suitable for use in a machine dish wash method 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.
• compositions of the invention can also be used as detergent additive products in solid or liquid form.
• Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process.
• the 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 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.
• the detergent compositions of the present invention will comprise in addition to the selected surfactant of the present invention, another surfactant system wherein the surfactant can be selected from cationic, nonionic, other anionic and/or mixtures thereof. Also suitable are ampholytic and/or zwitterionic surfactants.
• the surfactant system comprising this selected 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.
• 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.
• 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.
• nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X- 45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
• 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.
• 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.
• nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C-
• 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.
• 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
• R 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 PlurafacTM LF404 and PluronicTM surfactants, marketed by BASF.
• nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
• the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
• This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.
• Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
• Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C8-C-
• Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.
• R 1 is H, or R 1 is C-1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
• R 2 is C5.31 hydrocarbyl
• Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
• R 1 is methyl
• R 2 is a straight C-
• Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
• Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The
• Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
• alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula: O
• R 3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
• R 4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof
• 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.
• R 3 is C-
• R 4 is methyl, ethyl or isopropyl.
• the methyl ester sulfonates wherein R 3 is C ⁇ r -C-
• 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 C-10-C20 alkyl component, more preferably a C12-C-18 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.
• an alkali metal cation e.g. sodium, potassium, lithium
• ammonium or substituted ammonium e.g.
• alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
• alkyl chains of C12-C-16 are preferred for lower wash temperatures (e.g. below about 50°C) and C-
• anionic surfactants useful for detersive purposes can also be included in the detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
• salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
• C8-C22 primary of secondary alkanesulfonates C8-C24 olefinsulfonates
• sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of
• alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C-18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-C-
• 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.
• alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12- C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
• R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C
• 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-
• the detergent 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 detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
• cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula : [R2(OR 3 ) y ][R (OR 3 )y] 2 R 5 N+X-
• R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
• each R 3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH 3 )-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof
• each R 4 is selected from the group consisting of C1-C4 alkyl, C-1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, - CH2CHOH-CHOHCOR 6 CHOHCH2OH wherein R ⁇ 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 R 4 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
• Quaternary ammonium surfactant suitable for the present invention has the formula (I):
• R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the 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,
• X" is a counterion, preferably a halide, e.g. chloride or methylsulfate.
• R6 is C-
• Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R-
• is C8-C16 alkyl
• each of R2, R3 and R4 is independently C-J-C4 alkyl, C-J-C4 hydroxy alkyl, benzyl, and -(C2H4o) x H where x has a value from 2 to 5, and X is an anion.
• R2, R3 or R4 should be benzyl.
• is C-12-C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
• Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
• quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide;
• CH2-CH2-O-C-C-12-14 alkyl and R2R3R4 are methyl).
• 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:
• DTDMAC ditallow dimethylammonium chloride
• DSOEDMAC di(stearoyloxyethyl) dimethylammonium chloride
• 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 :
• Q is selected from -O-C(O)-, -0(O)-O-, -O-0(O)-O-, -NR 4 -C(0)-, -C(O)-
• R 2 is (CH 2 ) m -Q-T 4 or T5 or R 3 ;
• R 3 is C1-C4 alkyl or C-1-C4 hydroxyalkyl or H;
• R 4 is H or C-1-C4 alkyl or C-1-C4 hydroxyalkyl;
• T 1 , T 2 , T 3 , T 4 , T 5 are independently C-11-C22 alkyl or alkenyl;
• n and m are integers from 1 to 4; and
• X" is a softener-compatible anion.
• softener-compatible anions include chloride or methyl sulfate.
• the alkyl, or alkenyl, chain T "1 , T 2 , T 3 , T 4 , 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 T 1 , T 2 , T 3 , T 4 , T 5 represents the mixture of long chain materials typical for tallow are particularly preferred.
• 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;
• the detergent 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 detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which 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.
• the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1 % to about 10% by weight of such ampholytic surfactants.
• Zwitterionic surfactants are also suitable for use in 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.
• the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.
• the detergent composition od 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-1 NH2 wherein R-
• X is -0-,-C(0)NH- or -NH-_ R4 is a C6-C12 alkyl chain n is between 1 to 5, preferably 3.
• R-j 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-1 R2R3N wherein R1 and R2 are C-j-Cs alkylchains or R 5 ( C H 2 CH ⁇ ) ⁇ H
• R3 is either a C ⁇ -C-12, preferably C ⁇ -C-io alkyl chain, or R3 is R4X(CH2) n . whereby X is -0-, -C(0)NH- or -NH- R4 is a C4-C-
• R5 is H or C1-C2 alkyl and x is between 1 to 6 .
• R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
• Preferred tertiary amines are R1 R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or
• is C ⁇ -C-
• 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.
• 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.
• 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.
• 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.
• bleaching agents that can be used encompasses the halogen bleaching agents.
• hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanu rates 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.
• bleach activators such as tetraacetylethylenediamine (TAED), nonanoyl-oxybenzene- sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzen
• 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) :
• R-j is a C7-C13 linear or branched chain saturated or unsaturated alkyl group
• R2 is a C-i-C ⁇ , linear or branched chain saturated or unsaturated alkyl group
• R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group.
• 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 W095/27775.
• the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
• an enzymatic system i.e. an enzyme and a substrate therefore
• 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.
• Non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
• photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines.
• these materials can be deposited upon the substrate during the washing process.
• 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.
• detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfon
• the detergent compositions of the present invention can further comprise a builder.
• 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
• SKS-6 is a crystalline layered silicate consisting of sodium silicate
• Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos.
• 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
• 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,
• Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S.
• 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.
• 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.
• 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.
• 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.
• 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, preferably a pectin lyase enzyme.
• 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, ⁇ -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.
• 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.
• pectate lyase enzymes are specifically directed to pectic acid chains of plant cell walls such as low methoxy pectins while pectin lyase is more specifically directed towards esterified pectin chains such as high methoxyl pectins.
• pectate lyases are metal and especially calcium sensitive, whereas pectin lyases do not require metals for stabilisation and optimum enzymatic activity.
• Pectin lyase enzyme is classified under the EC classification EC 4.2.2.10, is preferably substantially free of other pectic enzymes, and acts on the pectic acids to bring about non-hydrolytic cleavage of alpha-1-4 glycosidic linkages to give oligosaccharides with terminal 4-deoxy-6- ⁇ -D-galacto-enuronosyl groups.
• the pectin lyase of the present invention is substantially free of other pectic enzymes.
• pectin lyase enzyme-containing compositions which contain less than 25% of pectic enzymes which are not pectin lyase enzymes, preferably less than 15%, more preferably less than 5%.
• the enzymatic activity can be measured according to the "Assay of trans-eliminase activities toward pectin and pectic acid" described by K. Horikoshi in Agr. Biol. Chem, Vol 36(2), 286.
• Preferred pectin lyase for the purpose of the present invention is the pectin lyase described in the co-pending international patent application PCT/DK98/00514, internationally filed on November 24, 1998 and published under WO99/27083 and which is i) a polypeptide produced by Bacillus licheniformis, ATCC 14580, or ii) a polypeptide comprising an amino acid sequence as shown in positions 31-
• 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.
• Protease C 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.
• 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
• 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.
• 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.
• 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 W095/26398.
• cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
• 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.
• 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.
• cellulases examples include cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, W096/17994 and W095/24471. Said cellulases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of pure enzyme by weight of the detergent composition.
• 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.
• 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".
• 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.
• lipases such as M1 Lipase ⁇ anQl LipomaxR (Gist-Brocades) and Lipolase ⁇ and Lipolase Ultra R (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
• 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.
• 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 ( ⁇ and/or ⁇ ) 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 ⁇ - and ⁇ -amyiases.
• ⁇ - Amylases are known in the art and include those disclosed in US Pat. no.
• amylases are stability-enhanced amylases described in W094/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, W095/26397 and W096/23873 (all by Novo Nordisk).
• ⁇ -amylases examples are Purafect Ox Am® from Genencor and Termamyl®, Ban® .Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark.
• W095/26397 describes other suitable amylases : ⁇ - 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® ⁇ -amylase activity assay. Suitable are variants of the above enzymes, described in W096/23873 (Novo Nordisk).
• amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.
• 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.
• the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
• 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.
• 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 ).
• enzyme oxidation scavengers which are described in co-pending European Patent application 92870018.6 filed on January 31 , 1992.
• 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.
• 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.
• the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
• chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, 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.
• EDDS ethylenediamine disuccinate
• 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.
• MGDA water-soluble methyl glycine diacetic acid
• 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.
• 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.
• 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.
• 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.
• 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.
• suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1 ,464,616.
• Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins are.preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato.
• Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch.
• the N-Lok encapsulating material consists of a modified maize starch and glucose.
• the starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.
• Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
• Polymers of this type include the polyacrylates and maleic anhydride- acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl 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'
• 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
• PEG is -(OC2H4)0-,PO is (OC3H6O) and T is (PCOC6H4CO).
• 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.
• 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.
• 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 -(CH2CH2 ⁇ ) m (CH2) n CH3 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.
• 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.
• 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.
• LSDP lime soap dispersing power
• the lime soap peptiser compound is preferably present at a level from 0% to 20% by weight.
• LSDP lime soap dispersant power
• 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-
• 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- aminohexanoyljbenzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds.
• 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.
• the detergent compositions according to the present invention can 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.
• 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
• polyamine N-oxide polymers suitable for use contain units having the following structure formula :
• R wherein P is a polymerisable unit, whereto the R-N-0 group can be attached to or wherein the R-N-0 group forms part of the polymerisable unit or a combination of both.
• A is NC, CO, C, -0-,-S-, -N- ; x is O or 1 ; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
• the N-0 group can be represented by the following general structures :
• R1 , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
• the N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
• Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
• polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-0 group forms part of the R-group.
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
• Another class of said polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-0 group is attached to the R-group.
• polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.
• polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
• R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
• polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
• polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
• 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.
• 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.
• 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.
• 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.
• 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.
• N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1 ,000,000, preferably from
• 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
• 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
• 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 .
• 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.
• PVP polyvinylpyrrolidone
• 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).
• 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).
• 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.
• Polyvinylimidazole The detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
• Said polyvinylimidazoies 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.
• 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.
• 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.
• the cross- linked polymers entrap the dyes by swelling.
• Such cross-linked polymers are described in the co-pending patent application 94870213.9
• 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.
• 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.
• 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/surfaces 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 the soaking of a hard item 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 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:
• MES x-sulpho methyl ester of C18 fatty acid APA C8-10 a mido propyl dimethyl amine.
• Neodol xy-z C1x-C1y linear primary alcohol z ethoxylate Nonionic Mixed ethoxylated/propoxylated fatty alcohol e.g.
• Plurafac LF404 being an alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5.
• 2(A1 ⁇ 2Si ⁇ 2)i2- 27H20 having a primary particle size in the range from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).
• Citric Anhydrous citric acid Citric Anhydrous citric acid.
• TSPP Tetrasodium pyrophosphate
• PAAC Pentaamine acetate cobalt(lll) salt PAAC Pentaamine acetate cobalt(lll) salt.
• 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.
• DETPMP Diethyltriamine penta (methylene) phosphonate marketed by Monsanto under the Trade name Dequest 2060.
• Chelant Chelant selected from EEDS, HEDP, DTPA, DETPMP and/or mixtures thereof.
• Pectate lyase Pectate lyase from Bacillus agaradhaerens, NCI MB 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 W095/10591 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 W095/26397 (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.
• Pectin lyase Pectin lyase produced by Bacillus licheniformis, ATCC
• 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.
• Opacifier Water based monostyrene latex mixture, sold by BASF
• SRP 1 Anionically end capped poly esters.
• SRP 2 Diethoxylated poly (1 ,2 propylene terephtalate) short block polymer.
• HMWPEO High molecular weight polyethylene oxide.
• PEGX Polyethylene glycol, of a molecular weight of x.
• laundry compositions which may be in the form of granules or tablet, were prepared according to the present invention.
• Minors include Brightener / SRP1 / CMC / Photobleach / MgS04 / PVPVI/ Suds suppressor /PEG.
• laundry compositions which may be in the form of granules or tablet, were prepared according to the present invention.
• Minors include Brightener / SRP1 / CMC / Photobleach / MgS04 / PVPVI/ Suds suppressor /PEG.
• Minors include Brightener / SRP1 / CMC / Photobleach / MgS04 / PVPVI/ Suds suppressor /PEG.
• Brightener 1 0.2 0.2 0.2 0.2 0.2
• liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight, enzyme are expressed in pure enzyme) :
• Brightener 1 0.2 0.07 0.1 - -
• 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 III IV I II III IV
• Example 12 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) :
• Brightener 1 0.2 0.07 0.1 - -
• liquid detergent compositions were prepared according to the present invention (Levels are given in parts by weight, enzyme are expressed in pure enzyme) :
• Example14 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) :

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