EP0964909A1 - Produits de nettoyage contenant une enzyme alcaline de decomposition du xylane et une enzyme de degradation de constituants parietaux non vegetaux - Google Patents

Produits de nettoyage contenant une enzyme alcaline de decomposition du xylane et une enzyme de degradation de constituants parietaux non vegetaux

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Publication number
EP0964909A1
EP0964909A1 EP97914893A EP97914893A EP0964909A1 EP 0964909 A1 EP0964909 A1 EP 0964909A1 EP 97914893 A EP97914893 A EP 97914893A EP 97914893 A EP97914893 A EP 97914893A EP 0964909 A1 EP0964909 A1 EP 0964909A1
Authority
EP
European Patent Office
Prior art keywords
enzyme
alkyl
compositions
enzymes
cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97914893A
Other languages
German (de)
English (en)
Inventor
Ivan Maurice Alfons Jan Herbots
Rosa Laura Moese
Andre Cesar Baeck
Alfred Busch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0964909A1 publication Critical patent/EP0964909A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the present invention relates to cleaning compositions, including laundry, dishwashing, household cleaning and oral/dental compositions, comprising a xylan degrading alkaline enzyme and a non-plant cell walls degrading enzyme.
  • Performance of a cleaning product, for use in washing or cleaning method is judged by a number of factors, including the ability to remove soils, and the ability to prevent the redeposition of the soils, or the breakdown products of the soils on the articles in the wash.
  • stains stemming from plants, wood, mould- clay based soil and fruits are on of the thoughest cleaning challenge. Especially in the laundry processes wherein the tendency is to move to low wash temperatures and shorter washing cycles.
  • These stains typically contain complex mixtures of fibrous material, based mainly on carbohydrates and their derivatives, fibre and cell wall components.
  • such stains are generally accompanied by amylose, sugars and their derivatives.
  • Specific examples of such soils would include orange, tomato, banana, tea, mango, broccoli, spinash soils and grass.
  • food soils are often difficult to remove effectively from a soiled item. Highly coloured or 'dried-on' soils derived from fruit and/or vegetables are particularly challenging soils to remove.
  • processed or cooked vegetables and fruits often contain non-plant cell walls materials used for the processing, cooking and flavouring of the food : butter, milk, eggs, oils such as soya or olive oil, thickeners, sweeteners such as sugar. These material are often based on proteins, fats and/or starches.
  • the items can be fabrics, hard surfaces and dishware such as plasticware, glassware or chinaware, or teeth and mouth.
  • cleaning compositions comprising a xylan degrading alkaline enzyme and a non-plant cell walls degrading enzyme, especially a protease, lipase and/or amylase.
  • the present invention relates to a laundry and/or fabric care composition
  • a laundry and/or fabric care composition comprising a xylan degrading alkaline enzyme and a non-plant cell walls degrading enzyme, especially a protease, lipase and/or amylase, which enhances fabric realistic items cleaning and whitening.
  • the present invention relates to dishwashing or household cleaning compositions comprising a xylan degrading alkaline enzyme and a non-plant cell walls degrading enzyme, especially a protease, lipase and/or amylase and in a third embodiment, the present invention relates to oral/dental care compositions comprising a xylan degrading alkaline enzyme and a non-plant cell walls degrading enzyme, especially a protease, lipase and/or amylase.
  • Xylan degrading enzymes like xylanase are commonly used in the paper/pulp industry and to a lesser extent also in the starch/baking industry.
  • WO 94/01 532 is disclosed a method for producing enzymes from strains of the alkalophilic species Bacillus sp. AC 1 3. Enzymes obtainable from these strains are proteases, xylanases and cellulases as well. The protease and cellulase enzymes are demonstrated to be valuable for use in detergents while on the other hand xylanase is shown to be of use in processes for treatment of lignocellulosic pulp i.e. the paper pulp industry.
  • xylanase enzymes are overexpressed by microbial strains constructed via genetic techniques free of cellulolytic enzymes. These xylanase enzymes are described for use in a variety of applications like the bleaching of wood pulps and the modification of cereals and grains for use in baking and the production of animal feeds.
  • stabilised, modified enzymes In WO 92/1 9726 are disclosed stabilised, modified enzymes.
  • the naturally occurring amino acids (other than proline) have been substituted with a proline residue at one or more positions.
  • modified enzymes amylases, lipases, cellulases, xylanases and peroxidases are mentioned.
  • Said stabilised, modified enzymes can be used in detergent compositions.
  • EP 709 452 recognises the benefits for use of xylanase at low levels in cleaning formulations.
  • WO 95/35362 describes cleaning compositions containing plant cell walls degrading enzymes such as pectinases and/or hemicellulases and/or optionally cellulases.
  • the cleaning properties of the xylanases enzymes were tested in non-enzymes containing detergents.
  • the present invention relates to cleaning compositions comprising a xylan degrading alkaline enzyme and a non-plant cell walls degrading enzyme, especially a protease, lipase and/or amylase, which significantly improve the removal of a broad range of plant based stains.
  • An essential component of the cleaning compositions of the invention is a xylan degrading alkaline enzyme.
  • the cleaning compositions of the present invention significantly improve the removal of a broad range of plant based stains.
  • the cleaning compositions of the present invention enhance fabric realistic items cleaning and whitening.
  • the xylan degrading alkaline enzyme is capable of attacking specific parts of plant/fruit cell constituents, breaking them down and facilitating removal during the wash process. This goes by random endo-hydrolysis of the xylan component or by successive exo-hydrolysis of xylose residues from the non- reducing end of the xylan polymer chain or by removal of substituents such as acetyl, 4-O-methyl glucuronic side chains, the L-arabinose side chains and ferulic acid cross linkages and p-coumaric side chains from the xylan polymer of the plant/fruit cells. Moreover, the xylan degrading activity enhances the accessibility of other detergent ingredients such as non-plant cell walls degrading enzymes, at the stain/soil.
  • xylan degrading enzyme it is meant herein any enzyme which degrade, for instance hydrolyse and/or modify, xylan containing polymers which are associated with hemicellulose and other plant polysaccharides.
  • xylan degrading alkaline enzyme it is meant a xylan degrading enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a pH ranging from 7 to 12.
  • a xylan degrading enzyme having its maximum activity at a pH ranging from 7 to 1 2.
  • the xylan degrading alkaline enzyme can be a single xylan degrading activity species or a mixture of the iso-enzymes obtained via the purification of the crude xylan degrading alkaline enzyme mixure.
  • the xylan degrading enzymes of interest are the endo- and exo-Xylanases hydrolysing Xylan in endo- or in exo fashion: endo-1 ,3 beta Xylosidase (E.G. 3.2.1 .32) , the endo-1 ,4-beta Xylanase (E.C. 3.2.1 .8), 1 ,3-beta D Xylans Xylohydrolase,(E.C. 3.2.1 .72), 1 ,4 -beta D Xylans Xylohydrolase,(E.C. 3.2.1 .37).
  • Xylan degrading alkaline enzymes of interest remove substitutions from the main xylan polymer such as Acetylxylan esterase ; Glucuronoarabinoxylan endo-1 ,4-xylanase (E.C. 3.2.1 .1 36), arabinosidase (E.C.3.2.1 .55) and ferulic esterase and coumaric acid esterase. These enzymes remove respectively the acetylation , 4-O-methyl glucuronic side chains ; the L-arabinose side chains and ferulic acid cross linkages and p- coumaric side chains from the main xylan polymer.
  • the xylan degrading alkaline enzymes can be produced as the wild types by alkalophilic micro-organisms, but also the genes encoding the xylan degrading alkaline enzymes can be cloned and expressed in suitable hosts.
  • the cloned xylan degrading alkaline enzymes are either the natural wild types or the protein engineered enzymes for improved compatibility with detergents.
  • micro-organisms suitable for the production of the enzymes are listed : Bacillus species: AC13(NCIMB 40482); SD 902 (FERM P-13356); BX-1 ; BX-2; BX-3; BX-4 ; DSM 71 197; W2 (FERM P- 7221 ); W4 (FERM P-7223); C-%(-2 (FERM P-1 698); TAR-1 ; V1 -4; 41 M 1 ; K-1 2; B. stearothermophilus; B. polymyxa; B. circulans; Thermotoga species: T. neopolitama; T.
  • 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 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.
  • Pulpzyme HB and Pulpzyme HC from Novo Nordisk and xylanase L1 20000 from Solvay are commercial available xylan degrading alkaline enzymes.
  • Said xylan degrading alkaline enzyme is incorporated into the compositions of the present invention preferably at a level of from 0.0001 % to 2%, more preferably from 0.0005% to 0.5%, most preferred from 0.001 % to 0.05% pure enzyme by weight of the composition.
  • the non-plant cell walls degrading enzyme The non-plant cell walls degrading enzyme
  • the cleaning compositions further comprise one or more non-plant cell walls degrading enzymes which provide cleaning performance and/or fabric care benefits.
  • non-plant cell wall degrading enzymes it is meant to exclude the three broad enzyme classes of cellulases, hemicellulases and pectinases (Ward and Young (1 989), CRC Critical Rev. in Biotech. 8, 237-274).
  • Cellulolytic enzymes have been traditionally divided into three classes : endoglucanases, exoglucanases or cellobiohydrolases and ⁇ -glucosidases (Knowles, J. et al. (1 987) TIBTECH 5, 255-261 ).
  • pectinases examples include pectin esterase, pectin lyase, pectate lyase and endo- or exo- polygalacturonase (Pilnik and Voragen (1 990) Food Biotech 4, 31 9-328), enzymes degrading hairy regions such as rhamnogalacturonase and accessory enzymes (Schols et al. ( 1 990), Carbohydrate Res. 206, 1 05-1 1 5; Searle Van Leeuw et al. ( 1 992) Appl. Microbiol. Biotech. 38, 347-349). Galactanase, arabinase, lichenase and mannase are some hemicellulose degrading enzymes.
  • Non-plant cell walls degrading enzymes include enzymes selected from the group of protein degrading enzymes such as proteases, Keratanase, from the group of starch-and starch-derivatives degrading enzymes like: alfa-,beta- and iso-amylases, pullulanase, from the group of polysaccharide degrading enzymes such as isomaltase, glucoamylase, dextranase, mycodextranase, invertase, lactase, insulinase and from the group of oligosaccharide degrading enzymes such as lysozym, endoglycosidaseH, alfa- and beta-N-acetylgalactosaminidases, neuraminidase, chondroitinase, hesperinidase, hyaluronidase and chitinase.
  • enzymes selected from the group of esters and fat's and wax-hydrolysing enzymes like lipase, phospholipases, esterases and cutinases and enzymes of the group of oxidoreductases such as peroxidases, laccases. Preferred are those enzymes being of the alkaline type.
  • Preferred enzymes that can be included in the cleaning compositions of the present invention include lipases.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 1 9.1 54, 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 M 1 Lipase ⁇ ar, d Lipomax R (Gist-Brocades) and LipolaseR and Lipolase Ultra ⁇ (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 95/2261 5 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 cleaning composition at levels from 0.0001 % to 2% of pure enzyme by weight of the detergent composition.
  • Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and 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.
  • proteases include ALCALASE ® , DURAZYM ® and SAVINASE ® from Novo and MAXATASE ® , MAXACAL®, PROPERASE ® and MAXAPEM® (protein engineered Maxacal) from Gist- Brocades.
  • proteases also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761 .8, filed April 28, 1 987 (particularly pages 1 7, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1 986, 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 1 23, and alanine replaced threonine at position 274.
  • Protease C is described in EP 9091 5958:4, corresponding to WO 91 /06637, Published May 1 6, 1 991 . 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.
  • 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 516200 by Unilever.
  • the proteolytic enzymes are incorporated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.
  • Amylases can be included for removal of carbohydrate- based stains.
  • WO94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91 /00353; FR 2,676,456; EP 285, 123; EP 525,610; EP 368,341 ; and British Patent specification no.
  • amylases are stability-enhanced amylases described in WO94/1 8314, published August 1 8, 1 994 and WO96/05295, Genencor, published February 22, 1 996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/1 0603, published April 95. Also suitable are amylases described in EP 277 21 6, WO95/26397 and WO96/23873 (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.
  • WO95/26397 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 WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • amylolytic enzymes are incorporated in the cleaning compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned. Said enzymes are normally incorporated in the cleaning composition at levels from 0.0001 % to 2% of pure enzyme by weight of the cleaning composition. The enzymes can be added as separate single ingredients
  • enzyme oxidation scavengers which are described in Copending European Patent application 9287001 8.6 filed on January 31 , 1 992.
  • 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, 1 39, January 5, 1 971 to McCarty et al. Enzymes are further disclosed in U.S. 4, 101 ,457, Place et al, July 1 8, 1 978, and in U.S. 4,507,21 9, Hughes, March 26, 1 985. 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. 3,600,31 9, August 17, 1 971 , Gedge et al, EP 1 99,405 and EP 200,586, October 29, 1 986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,51 9,570. A useful Bacillus, sp. AC1 3 giving proteases, xylanases and cellulases, is described in WO 9401 532 A to Novo.
  • the cleaning compositions of the invention may also contain additional cleaning components.
  • additional cleaning components and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • the present invention relates to a laundry and/or fabric care composition comprising a xylan degrading alkaline enzyme and a bleaching agent (Examples 1 -1 4).
  • the present invention relates to dishwashing or household cleaning compositions (Examples 1 5-21 ) and in a third embodiment, the present invention relates to oral/dental care compositions (Examples 22-24).
  • the cleaning compositions according to the invention can be liquid, paste, gels, bars, tablets, powder or granular forms.
  • Granular compositions can also be in "compact” form, the liquid compositions can also be in a "concentrated” form.
  • compositions of the invention may for example, be formulated as hand and machine dishwashing compositions, hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions, and compositions for use in general household hard surface cleaning operations.
  • Compositions containing such xylan degrading enzyme can also be formulated as oral /dental care compositions.
  • compositions containing xylan degrading alkaline enzyme can provide fabric cleaning, stain removal, whiteness maintenance, softening, color appearance and dye transfer inhibition when formulated as laundry detergent compositions.
  • compositions of the invention When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.
  • a surfactant 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.
  • compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the density of the laundry detergent compositions herein ranges from 400 to 1 200 g/litre, preferably 600 to 950 g/litre of composition measured at 20°C.
  • compositions herein are 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 1 7-35% by weight of the total composition.
  • the filler salt is present in amounts not exceeding 1 5% of the total composition, preferably not exceeding 1 0%, 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 cleaning compositions according to the present invention can also be in a "concentrated form", in such case, the liquid cleaning compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • 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.
  • the cleaning compositions according to the present invention generally comprise a surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.
  • the surfactant is typically present at a level of from 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 cleaning 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.
  • Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 1 5 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal ⁇ M CO-630, marketed by the GAF Corporation; and TritonTM ⁇ . 45 / ⁇ -1 14, ⁇ -100 and X-1 02, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • 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 1 5-S-9 (the condensation product of C-] -] -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 , 1 986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 1 6 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 1 6 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 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 1 0 to about 1 8, preferably from about 1 2 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
  • the glycosyl is preferably derived from glucose.
  • 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
  • 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 1 500 to about 1 800 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. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 1 1 ,000.
  • nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are Cg-C-
  • Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.
  • R ⁇ is H, or R ⁇ is C1.4 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 ⁇ 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 C -C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 ( 1 975), pp. 323-329.
  • 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 ⁇ is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R ⁇ is a Ci -C ⁇ 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 ⁇ is C-] 0" l 6 alky' and R ⁇ is methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R ⁇ is C 1 0 -C 1 6 alkyl.
  • alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C1 0- 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C -
  • R preferably is a C1 0- 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C -
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium,
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • alkyl chains of C1 2- 1 6 are preferred for lower wash temperatures (e.g. below about 50°C) and C-
  • Other anionic surfactants useful for detersive purposes can also be included in the cleaning compositions of the present invention.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • soap C -C22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • C g-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C-
  • the cleaning 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 C-
  • R is an unsubstituted 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 C1 2- 18 alkyl polyethoxylate (1 .0) sulfate (C-
  • the cleaning compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described herein.
  • Cationic detersive surfactants suitable for use in the cleaning compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula :
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 1 8 carbon atoms in the alkyl chain, each R ⁇ is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH2OH)-, -CH 2 CH CH2-, and mixtures thereof; each R ⁇ is selected from the group consisting of C-
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I):
  • R1 is a short chainlength alkyl (C6-C1 0) 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 C1 -C4 and z is 1 or 2.
  • Preferred quat ammonium surfactants are those as defined in formula
  • R -] is Cg, C -
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
  • R1 is Cg-C-
  • each of R2, R3 and R4 is independently C1 -C4 alkyl, C1 -C4 hydroxy alkyl, benzyl, and -(C2H4Q) X H where x has a value from 2 to 5, and X is an anion.
  • R2, R3 or R4 should be benzyl.
  • is C1 2- 1 5 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • Suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C-
  • CH2 -CH2 -0-C-C 12 - i4 alkyl and R2R3R4 are methyl).
  • Typical cationic fabric softening components include the water- insoluble quaternary-ammonium fabric softening actives, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
  • Preferred cationic softeners among these include the following: 1 ) ditallow dimethylammonium chloride (DTDMAC);
  • 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-0,239,91 0.
  • the quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below :
  • Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR -C(O)-, C(O)-NR 4 -;
  • R 1 is (CH 2 ) n -Q-T 2 or T3 ;
  • R 2 is (CH 2 ) m -Q-T 4 or T 5 or R 3 ;
  • R 3 is C 1 -C4 alkyl or C 1 -C4 hydroxyalkyl or H;
  • R 4 is H or C1 -C4 alkyl or C1 -C4 hydroxyalkyl;
  • T 1 , T 2 , T 3 , T 4 , T ⁇ are independently C-
  • Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
  • the alkyl, or alkenyl, chain T ⁇ , T 2 , T 3 , T 4 , T ⁇ must contain at least 1 1 carbon atoms, preferably at least 1 6 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 ⁇ , T 2 , T 3 , T 4 , T ⁇ 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 :
  • N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride 1 ) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; 2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; 3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride; 4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
  • the cleaning compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1 % to about 8% by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the cleaning compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 1 8 carbon atoms, and at least one contains an anionic water- solubilizing group, e.g.
  • the cleaning compositions of the present invention typically comprise from 0.2% to about 1 5%, 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, 1 975 at column 1 9, line 38 through column 22, line 48, for examples of zwitterionic surfactants. When included therein, the cleaning compositions of the present invention typically comprise from 0.2% to about 1 5%, preferably from about 1 % to about 10% by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 1 8 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 1 0 to about 1 8 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 1 0 to about 1 8 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 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof 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 ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C-
  • the cleaning compositions of the present invention typically comprise from 0.2% to about 1 5%, preferably from about 1 % to about 10% by weight of such semi-polar nonionic surfactants.
  • the cleaning composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.
  • Suitable primary amines for use herein include amines according to the formula R1 NH2 wherein R-
  • alkyl chains may be straight or branched and may be interrupted with up to 1 2, 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 are preferred primary amines.
  • 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 R1 R2R3N wherein R1 and R2 are C-j -Cg alkylchains or
  • R3 is either a C ⁇ -C-1 2, preferably C ⁇ -Ci o alkyl chain, or R3 is R4X(CH2)r whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-C1 2, n is between 1 to 5, preferably 2-3.
  • R5 is H or C1 -C2 alkyl and x is between 1 to 6 .
  • R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary amines are R1 R2 3N where R1 is a C6-C1 2 alkyl chain, R2 and R3 are C1 -C3 alkyl or
  • Ri is C6-C1 2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1 -C4
  • Most preferred amines of the present invention include 1 -octylamine, 1 -hexylamine, 1 -decylamine, 1 -dodecylamine,C8-1 0oxypropylamine, N coco 1 -3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-1 0 amidopropyldimethylamine and C10 amidopropyldimethylamine.
  • the most preferred amines for use in the compositions herein are 1 - hexylamine, 1 -octylamine, 1 -decylamine, 1 -dodecylamine.
  • Especially desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
  • the cleaning compositions can in addition to xylan degrading alkaline enzyme and non-plant cell walls degrading enzyme further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.
  • Said other plant cell wall degrading enzymes can be selected from the group of cellulose and hemi-cellulose degrading enzymes such as endo-and exo-cellulases and beta-glucosidases, the endo 1 -3/1 -4-beta glucanases and xyloglucanases, the pectin degrading enzymes pectin esterase, pectin lyase, pectate lyase, endo-and exo-polygalacturonase and rhamnogalacturonase and from the group of the galactanases, arabinases, lichenases, mannanases and laminarinases. Preferred are those enzymes being of the alkaline type.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A- 2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1 800.
  • Suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 41 5 amino acids; and a " 43kD endoglucanase derived from Humicola insolens, DSM 1 800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91 /1 7243.
  • suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21 801 , Genencor, published September 29, 1 994. Especially suitable cellulases are the cellulases having color care benefits.
  • cellulases examples include cellulases described in European patent application No. 91 202879.2, filed November 6, 1 991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91 /1 7243.
  • Peroxidase enzymes are used in combination with an enhancer and oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. 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. 91 202882.6, filed on November 6, 1 991 and EP No. 9687001 3.8, filed February 20, 1 996. Also suitable is the laccase enzyme.
  • 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 94/1 2621 ) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.
  • Said enzymes are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • 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, 1 39, January 5, 1 971 to McCarty et al. Enzymes are further disclosed in U.S. 4, 101 ,457, Place et al, July 1 8, 1 978, and in U.S. 4,507,21 9, Hughes, March 26, 1 985. 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 1 4, 1 981 .
  • Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,31 9, August 1 7, 1 971 , Gedge et al, EP 1 99,405 and EP 200,586, October 29, 1 986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,51 9,570. A useful Bacillus, sp. AC1 3 giving proteases, xylanases and cellulases, is described in WO 9401 532 A to Novo.
  • Fabric softening agents can also be incorporated into laundry cleaning and/or fabric care 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 5,01 9,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-BO 01 1 340 and their combination with mono C1 2-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 91 9. 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 31 3 146.
  • Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 1 5% 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 0.1 5% 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 bleaching agent is the bleaching agent
  • Additional optional detergent ingredients that can be included in the cleaning compositions of the present invention include bleaching agents such as hydrogen peroxide, PB1 , PB4 and percarbonate with a particle size of 400-800 microns.
  • 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 0,1 33,354 and U.S. Patent 4,41 2,934.
  • 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 dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1 -5% by weight.
  • the hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in US 4,41 2,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 1 20,591 ) 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), nonanoyloxybenzene-sulfonate (NOBS, described in US 4,41 2,934), 3,5,- trimethylhexanoloxybenzenesulf
  • 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 copending applications USSN 08/1 36,626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • 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, 194,41 6 and US 5, 1 14,61 1 .
  • 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.
  • sulfonated zinc phthalocyanine Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718.
  • cleaning compositions will contain about 0.025% to about 1 .
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine 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.
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2 ⁇ 5).
  • Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 ,368, 821 ,369 and 821 ,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241 , lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1 , 1 ,3-propane tricarboxylates described in British Patent No. 1 ,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261 ,829, 1 , 1 ,2,2-ethane tetracarboxylates, 1 , 1 ,3,3-propane tetracarboxylates and 1 , 1 ,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,082, 1 79, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1 ,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane- cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6- hexane -hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
  • Preferred builder 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 cleaning compositions of the present invention are soaps and 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 1 0% to 70% and most usually from 30% to 60% by weight.
  • the cleaning 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, triethylenetetraamine- hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to 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 3,81 2,044, issued May 21 , 1 974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1 987, to Hartman and Perkins.
  • 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 1 5% by weight of the cleaning compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions. Suds suppressor
  • 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 1 26 published April 28, 1 977.
  • 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 1 2 R.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil ⁇ .
  • 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.
  • encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1 ,464,61 6.
  • 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 1 0% 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- yiamino)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 1 000-1 0000, 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. 41 1 6885 and 471 1 730 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)O-,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.
  • polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 1 6% by weight of propane -1 .2 diol, about 1 0% by weight ethylene glycol about 1 3% by weight of dimethyl sulfobenzoic acid and about 1 5% 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 31 1 342.
  • 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 9287001 8.6 filed January 31 , 1 992.
  • 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 90/01 81 5 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 H3 wherein m is 2-3 and n is 6-1 2.
  • 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 cleaning 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 1 00,000.
  • copolymer of acrylate and methylacrylate such as the 480N having a molecular weight of 4000, at a level from 0.5-20% by weight of composition can be added in the cleaning compositions of the present invention.
  • compositions of the invention may contain a lime soap peptiser compound, which preferably has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6.
  • 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 1 04, pages 71 -73, ( 1 989).
  • Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N- decanoyl-6-aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds.
  • the cleaning 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 cleaning compositions according to the present invention also comprise from 0.001 % to 10 %, preferably from 0.01 % to 2%, more preferably from 0.05% to 1 % by weight of polymeric dye transfer inhibiting agents.
  • Said polymeric dye transfer inhibiting agents are normally incorporated into cleaning compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
  • 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.
  • 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-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both.
  • the N-O group can be represented by the following general structures
  • R3 ( R3 ) z wherein R1 , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-O 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-O functional group is part of said R group.
  • R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O 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-O 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.
  • polymeric backbones examples include 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 1 0: 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 : 1 000000, most preferably from 1 :7 to 1 : 1 000000.
  • 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 5,000-200,000.
  • Highly preferred polymers for use in cleaning 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 1 0,000 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 1 1 3, "Modern Methods of Polymer Characterization” .
  • N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 1 0,000 to 20,000.
  • 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 cleaning 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 cleaning 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
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-1 5
  • PVP K-90 average molecular weight of 360,000.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 1 65 and Sokalan HP 1 2; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).
  • Polyvinyloxazolidone :
  • the cleaning 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 1 5,000.
  • Polyvinylimidazole :
  • the cleaning compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles have an average of about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 1 5,000.
  • 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.
  • compositions of the invention may be used in essentially any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.
  • the process described herein comprises contacting fabrics with a laundering solution in the usual manner and exemplified hereunder.
  • 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.
  • 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.
  • 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:
  • Nonionic C13-C-15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh.
  • TPKFA C12-C14 topped whole cut fatty acids.
  • DEQA Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
  • Neodol 45- 1 3 C1 4-C 1 5 linear primary alcohol ethoxylate sold by Shell Chemical CO.
  • Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m.
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size between 400 ⁇ m and 1 200 ⁇ m.
  • PA30 Polyacrylic acid of average molecular weight of approximately 8,000.
  • Terpolymer Terpolymer of average molecular weight approx. 7,000, comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • PAAC Pentaamine acetate cobalt(lll) salt PAAC Pentaamine acetate cobalt(lll) salt.
  • Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.
  • Alkaline Xylanase Xylan degrading alkaline enzyme sold under the tradename Pulpzyme HC and Pulpzyme HB by Novo Nordisk A/S, Xylanase L1 20000 by Solvay.
  • Protease Proteolytic enzyme sold under the tradename Savinase, Alcalase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem sold by Gist-Brocades and proteases described in patents WO91 /06637 and/or WO95/10591 and/or EP 251 446.
  • Amylase Amylolytic enzyme sold under the tradename Purafact Ox Am R described in WO 94/1 8314, WO96/05295 sold by Genencor; Termamyl ® , Fungamyl ® and Duramyl ® , all available from Novo Nordisk A/S and those described in WO95/26397.
  • Lipase Lipolytic enzyme sold under the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S
  • DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.
  • PVPVI Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl- imidazole and vinyl-pyrrolidone.
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1 .3.5-triazin- 2-yl) stilbene-2:2'-disulfonate.
  • Granular Suds 1 2% Silicone/silica, 1 8% stearyl alcohol, 70% starch Suppressor in granular form
  • SRP 1 SulfobenzoyI or sodium isethionate end capped esters with oxyethylene oxy and terephtaloyl backbone.
  • Encapsulated Insoluble fragrance delivery technology utilising zeolite perfume particles 1 3x, perfume and a dextrose/glycerin agglomerating binder.
  • Silica dental Precipitated silica identified as Zeodent 1 1 9 offered by abrasive J.M. Huber.
  • laundry detergent compositions were prepared in accord with the invention:
  • Brightener 1 0.2 0.2 0.2 -
  • Zeolite A 1 5.0 1 5.0 1 5.0
  • Brightener 1 0.05 0.04 0.04 0.04 Brightener 2 0.1 0.3 0.05 0.1 3 0.1 3
  • liquid detergent formulations according to the present invention were prepared:
  • Granular fabric detergent compositions which provide "softening through the wash” capability were prepared in accord with the present invention :
  • Example 13 The following fabric softener composition was prepared in accord with the present invention :
  • Syndet bar fabric detergent compositions were prepared in accord with the present invention :
  • detergent composition tablets of 25g weight were prepared in accord with the present invention by compression of a granular dishwashing detergent composition at a pressure of 1 3KN/cm 2 using a standard 1 2 head rotary press:
  • liquid dishwashing detergent compositions were prepared in accord with the present invention I to II, of density 1 .40Kg/L :
  • liquid dishwashing compositions were prepared in accord with the present invention :
  • liquid hard surface cleaning compositions were prepared in accord with the present invention :
  • a two-layer effervescent denture cleansing tablet was prepared in accord with the present invention :
  • Dentifrice compositions were prepared in accord with the present invention.
  • Sorbitol (70% aqueous 35.0 35.0 35.0 35.0 solution)
  • Titanium dioxide 0.5 0.5 0.5 0.5 0.5 0.5
  • Mouthwash compositions were prepared in accord with the present invention:
  • Glycerin 1 0.0 1 0.0 1 0.0 1 0.0 1 0.0

Abstract

La présente invention concerne des produits de nettoyage, y compris des produits de lessive, de vaisselle, d'entretien ménager et des produits d'hygiène buccale et/ou dentaire, contenant une enzyme alcaline de décomposition du xylane et une enzyme de dégradation de constituants pariétaux non végétaux.
EP97914893A 1997-03-07 1997-03-07 Produits de nettoyage contenant une enzyme alcaline de decomposition du xylane et une enzyme de degradation de constituants parietaux non vegetaux Withdrawn EP0964909A1 (fr)

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PCT/US1997/003557 WO1998039403A1 (fr) 1997-03-07 1997-03-07 Produits de nettoyage contenant une enzyme alcaline de decomposition du xylane et une enzyme de degradation de constituants parietaux non vegetaux

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EP0964909A1 true EP0964909A1 (fr) 1999-12-22

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AU2319399A (en) * 1999-01-14 2000-08-01 Procter & Gamble Company, The Detergent compositions comprising an enzyme system
AU2456499A (en) * 1999-01-14 2000-08-01 Procter & Gamble Company, The Detergent compositions comprising a pectate lyase and a metal bleach catalyst
WO2000042154A1 (fr) * 1999-01-14 2000-07-20 The Procter & Gamble Company Compositions detergentes renfermant une pectate lyase et un tensioactif anionique mi-ramifie
JP2002534596A (ja) * 1999-01-14 2002-10-15 ザ、プロクター、エンド、ギャンブル、カンパニー ペクチン酸リアーゼおよび特定の界面活性剤系を含有した洗剤組成物
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WO1998039403A1 (fr) 1998-09-11
AR011938A1 (es) 2000-09-13
ZA981889B (en) 1998-09-01
JP2001513139A (ja) 2001-08-28
AU2198097A (en) 1998-09-22
CA2282352A1 (fr) 1998-09-11
MA24492A1 (fr) 1998-10-01

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