MXPA99004232A - Foam detergent composition with enzymes - Google Patents

Abstract

The present invention relates to a cleaning composition, in the form of a low density foam, which comprises a surfactant system and enzymes. The cleaning composition comprises from 0.0001%to 0.005%pure protease enzyme protein by weight of the total foam composition. The invention also relates to a packaged product for dispensing the foam, preferably an aerosol package, as well as to a method for cleaning textile fabrics using the foam.

Description

COMPOSITION DETERGENT IN THE FORM OF FOAM WITH ENZYMES DESCRIPTIVE MEMORY The present invention relates to a cleaning composition, in the form of a foam, comprising a system of surfactant and enzymes. The invention also relates to a packaged product for dispensing the foam, preferably an aerosol package, as well as a method for cleaning textile materials using the foam. Enzymes have been used for many years in both granular and liquid washing detergents. The co-pending European patent application of the applicant number 962001705.9, of June 19, 1996, claims detergent compositions consisting of 0.0001% to 0.5% by weight of pure protein protease enzyme. Alternate ways of providing washing detergents are now being considered. EP-A-0 677 577 of October 18, 1995, describe a detergent composition in the form of a foam for cleaning textile materials that can consist of enzymes such as protease, alcalase, lipase, cellulase.

It has now been found that the enzymatic activity provided by a washing detergent in the form of foam is much larger than that provided by a comparable liquid or granular washing detergent having the same enzyme system (weight by weight). The present invention also relates to means for supplying a foam consisting of enzymes that are very efficient and cost effective. It is an object of the present invention to provide a detergent in the form of foam to improve the appearance of the surface of the fabric without causing unacceptable wear or loss of tensile strength of the TV. It is a further object of the present invention to provide a foam composition with good enzyme stability.

BRIEF DESCRIPTION OF THE INVENTION According to the invention, these objects are achieved by a composition in the form of a foam consisting of 0.0001% to 0.005% pure protease enzyme protein by weight of the total foam composition In a preferred embodiment of the present invention the composition in the form of foam further comprises 0.00001% to 0.0005%, and more preferably 0.00005% to 0.00025%, of pure cellulase enzyme protein by weight of the total composition in the form of foam.

In a further embodiment of the invention the composition in the form of a foam is dispensed from a packaged product comprising a sealed container, preferably an aerosol can; and a means for dispensing it, preferably a nozzle for dispensing foam; and it further comprises a driving gas, wherein the driving gas consists of carbon dioxide, nitrous oxides, air or mixtures thereof. Carbon dioxide is the most preferred. In a further aspect of the invention there is provided a method for cleaning textile materials, comprising the steps of: (i) forming a foam composition as defined above, (ii) dissolving or dispersing the foam in water for form an aqueous solution; and either subsequently or simultaneously (iii) shaking cleaned textile materials in the aqueous solution.

DETAILED DESCRIPTION OF THE INVENTION The foam is a coarse dispersion of gas in a relatively small amount of liquid. The foams of the present invention are a continuous liquid phase comprising a composition, and a dispersed phase comprising a gas. Typically, the gas "bubbles" of the dispersed phase can vary in size from 50 microns to several millimeters. In general, the quality of the foam is determined by calculating various attributes of foam quality, such as: 1) the appearance of the foam as determined by the uniformity of the bubble size distribution as well as by the actual sizes of the foam bubbles, wherein bubbles of small and uniform size are generally preferred; 2) the thickness of the foam as determined by the apparent viscosity of the foam, wherein an apparent bulk viscosity of the foam is generally preferred; 3) the density of the foam which is preferably less than 250g / 1, more preferably less than 150g / 1, and even more preferably less than 100g / 1; and 4) trained foam liquid after remaining on a solid surface, wherein a slow drainage of liquid is generally preferred. The preferred components of the detergent in the form of foam will now be described in more detail. The water-soluble salts of the higher fatty acids, for example, "soaps", are anionic surfactants useful in the present compositions. These include alkali metal soaps such as the sodium, potassium, ethanolamine, ammonium, and alkylammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the salts of ethanolamine, sodium and potassium or the mixture of fatty acids derived from coconut oil and wood, for example, monoethanolamine, sodium or potassium tallow and coconut soap. Useful anionic surfactants also include the water soluble salts, preferably the alkali metal, ethanolamine, ammonium and alkylammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms. carbon and an ester group of sulfuric acid or sulfonic acid. (included in the term "alkyl" is the alkyl portion of the acyl groups). Examples of this group of synthetic surfactants are alkyl sulphates, especially those obtained by sulfating the higher alcohols (C8-C8 carbon atoms) as that produced by reducing the glycerides of wood or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in either straight or branched configuration, for example, those of the type described in US Patents. Nos. 2,220,099 and 2,477,383; and the methyl estersulfonates. Especially valuable are linear straight-chain alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C11-C13 LAS. Other anionic surfactants herein are the alkylglyceryl ether sulfonates, especially the ethers of higher alcohols derived from wood and coconut oil, the sulfonates and sulphates of coconut oil fatty acid monoglyceride; salts of alkylphenolethelene oxide ether sulfates containing from 1 to 10 ethylene oxide units per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and alkylethylene oxide ether sulfate salts containing 1 to 10 ethylene oxide units per molecule and wherein the alkyl group contains 10 to 20 carbon atoms. Other anionic surfactants useful herein include salt water-soluble salts of alpha-sulfonated fatty acid esters containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; the water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane portion; the alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles ethylene oxide; the water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; and alloy beta-alkyloxy sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane portion. Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. In fact, the preferred process uses anionic / non-ionic mixtures. Such non-ionic materials include compounds produced by the condensation of the alkylene oxide groups (hydrophilic in nature) with a hydrophobic organic compound., which can be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be easily adjusted to produce a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, for example, the condensation products of alkyl phenols having an alkyl group containing from 6 to 16 carbon atoms, in I know a chain configuration direct or branched hip, with 4 to 25 moles of ethylene oxide per mole of alkyl phenol.

Preferred nonionic surfactants are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in straight or branched chain configuration, with 1 to 25 moles of ethylene oxide per moles of alcohol, especially 2 to 7 moles of oxyethylene per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms; and the condensation products of propylene glycol with ethylene oxide.

Other preferred nonionic surfactants are the polyhydroxy fatty acid amides which can be prepared by reacting a fatty acid ether and an N-alkyl polyhydroxy amine. The preferred amine for use in the present invention is N- (R1) -CH2 (CH2OH) 4-CH2-OH and the preferred ester is a methyl ester of C12-C20 fatty acid. Most preferred is the reaction product of N-methylglucamine (which can be derived from glucose) with methyl ester or C12-C20 fatty acid. Methods of making polyhydroxy fatty acid amides have been described in WO 9206073 of April 16, 1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of solvents. In a highly preferred embodiment of the invention the N-methyl glucamide is reacted by a C12-C20 methyl ester. The semi-polar nonionic surfactants include water-soluble amine oxides containing an alkyl portion of 10 to 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of 10 to 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water soluble sulfoxides containing an alkyl portion of 10 to 18 carbon atoms, and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of 1 to 3 carbon atoms.

Ampholytic surfactants include aliphatic derivatives of tertiary amines and heterocyclic secondaries in which the aliphatic portion can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains a anionic water solubilizing group. Zwitterionic surfactants include aliphatic quaternary ammonium phosphonium derivatives, and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms. Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R7N + X ', wherein R4 is an alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6, and R are each C1 to C alkyl preferably methyl; X "is an anion, for example chloride Examples of such trimethyl ammonium compounds include alkyltrimethylammonium chloride of C-12-14 and cocalkyltrimethylammonium methosulfate Other surfactants which may be used in the compositions of the present invention include glycerol ethers of C10-18, C10-18 alkyl polyglycosides and their corresponding sulfated polyglycosides, alkyl estersulfonates, and oleylsarcosinate.

PROTEOLITIC ENZYMES The proteolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 0.005%, preferably from 0.0002% to 0.002%, more preferably from 0.0005% to 0.001% pure protease enzyme protein by weight of the composition . The proteolytic enzyme can be of animal, vegetable or microorganism origin (preferred). The most preferred is the proteolytic cerin enzyme of bacterial origin. Purified or non-purified forms of this enzyme can be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as they are variants of nearby structural enzyme. Suitable proteases are subtilisins that are obtained from particular strains of B. subtilis and ß. Licheniformis (subtilisin BPN and BPN '). A suitable protease is obtained from a Bacillus separator, which has a maximum activity through the pH scale of 8-12, developed and marketed as ESPERASER 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. The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784 to Novo. Other suitable proteases include ALCALASER, DURAZIMR and SAVINASAR from Novo and MAXATASER, MAXACALR, PROPERASER and MAXAPEMR (engineered maxacal protein) from International Bio-Synthe / tics, Inc., The Netherlands; as well as protease A as described in EP 130,756 A, of January 9 of 1985 and protease B as described in EP 303,761 A, of April 28, 1987 and EP 130,756 A, of January 9, 1985. See also a high pH protease of Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. Other preferred proteases include those of WO 95/10591 A a Procter & Gamble. When desired, a protease having decreased absorption 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. In more detail, the protease referred to as "Protease D" is a hydrolaza carbonyl variant having an amino acid sequence not found in nature, which is derived from a hydrolase carbonyl precursor by replacing a different amino acid by a plurality of amino acid residues at a position in the hydrolase carbonyl equivalent to the plus 76 position, 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 numeration of subtilicin Bacillus amyloliquefaciens as described in WO95 / 10591 and in the patent application of C. Ghosh , and others, "Bleaching Compositions Comprising Protease Enzymes" that has the US serial number No. 08 / 322,677, of October 13, 1994. Also suitable for the present invention are the proteases described in the patent applications EP 251 446 and WO91 / 06637. The preferred protease for use in the present invention is SAVINASER and the proteases described in EP 215 446 and WO95 / 10591 at a level of 0.0001% to 0.005%, preferably from 0.0002% to 0.002%, more preferably 0.0005% to 0.001% of pure protease enzyme protein by weight of the total composition in detergent compositions in the form of foam. A scale of enzyme materials and means for their incorporation into synthetic detergent compositions is also described in WO 93/07263 A and WO 93/07260 A to Genecor International, WO 89/08694 A to Novo, and E.U.A. 3,553,139, January 5, 1971 to McCarty and others. Enzymes are further described in E.U. A. 4,101, 457, Place and others, July 18, 1978, and in E.U.A. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for detergent formulations in the form of foam are described in E.U.A. 4,261, 868, Hora et al., April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in E.U.A. 3,600,319, August 17, 1971, Gedge et al., EP 199, 405 and EP 200, 586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. A Bacillus, useful sp. AC13 that gives proteases, xylanases and cellulases, is described in WO 94/01532 A to Novo. The detergent compositions can in addition to and protease enzymes consist in addition to one or more enzymes that provide cleaning performance and / or fabric care benefits. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, gluco-amylases, amylases, xylanases, lipases, esterases, cutinases, pectinases, reductases, oxidases, phenoloxidase, lipoxygenases, linginases, pullulanase, tanases, pentosanas, malanases, β-glucanases, arabinosidases, chondroitinase, laccase or mixtures thereof. A preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase in conjunction with one or more plant cell wall degrading enzymes. Cellulases useful in the present invention include bacterial or fungal cellulases. Preferably, they will have an optimum pH of between 5 and 9. 5. Suitable cellulases are described in U.S. Pat. 4,435,307, Barbesgoard et al., Which describes fungal cellulase produced from Humicola insolens. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. Examples of such cellulases are the cellulases produced by a strain of Humicola insolens (Humicola grísea var.thermoidea), particularly the humicola strain DSM 1800. Other suitable ceiulases are the cellulases originated from Humicola insolens having a molecular weight of 50KDa, and a point isoelectric of 5.5 and contain 415 amino acids. Particularly suitable cellulases are cellulases that have color care benefits. Examples of such cellulases with the cellulases described in European Patent Application No. 91202879.2, of 6 November 1991 (Novo). The peroxidase enzymes are used in combination with oxygen sources, for example percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching solution", that is, to avoid the transfer of inks or pigments removed from substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, linginase, and haloperoxidases such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813 and in European Patent Application EP No. 91202882.6 of November 6, 1991, Said cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.00001% to 0.001% preferably 0. 00005% to 0.00025% active enzyme protein by weight of the detergent composition, (these levels correspond to 0.005 CEVU / g a 0. 2 CEVU / g, preferably 0.02 CEVU / g to 0.1 CEVU / g).

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomas group such as Pseudomas stutzeri ATCC 19.154, as described in British Patent 1, 372, 034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the Pseudomas Fluorescent IAM 1057 microorganism. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P " Amano, "hereafter referred to as M1 LipaseR and LipomaxR (Gist-Brocades). Especially suitable lipases are lipases such as Lipolase® and Lipolase Ultra® (Novo) which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.5] that can be considered as a special type of lipase, ie lipases that require interfacial activation. Suitable cutinases are described in WO / 94/14963 and WO 94/14964. The addition of cutinases to detergent compositions has been described in for example WO-A-88/09367 (Genencor). The lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.001% to 2% active enzyme by weight of the detergent composition.

Amylases (a and / or ß) can be included for removal of carbohydrate-based stains. WO / 94/02597, Novo Nordisk A / S of February 3, 1994, describes cleaning compositions that incorporate mutant amylases. Other known amylases for use in detergent compositions include both a- and β-amylases. The amylases are known in the art and include those described 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 in the English patent specification No. 1, 296,839 (Novo). Examples of commercial a-amylases products are Termamyl®, Ban® and Fungamyl®, all available from Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized as 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 a pH value in the scale from 8 to 10, measured by the Phadebas® α-amylase activity meter. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher level of activity are described in W095 / 35382. The enzymes mentioned above may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Enzymes can be added as separate ingredients alone (pills, granules, stabilized liquids, etc. that contain an enzyme) or as mixtures of two or more enzymes (for example cogranulates). Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in co-pending European patent application 92870018.6 of January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines. The foam of the present invention may contain neutral or alkaline salts having a solution pH of 7 or greater, and may be either organic or inorganic in nature. The detergency builder salt helps to provide the desired density and bulk to the detergent granules herein. Although some of the salts are inert, many of them also function as detergency builders in the wash solution. Examples of neutral water-soluble salts include those of alkali metal, ethanolamine, ammonium or substituted ammonium chlorides, fluorides and sulfates. The sodium, ethanolamine and ammonium salts of the above are preferred. Citric acid and, in general, any other organic or inorganic acid can be incorporated in the present invention. Other useful water soluble salts include the compounds commonly known as builders. The detergency builders are generally selected from the different water-soluble ammonium or substituted ammonium, polyphosphate, phosphonate, polyphosphonate, carbonate, silicates, borate and polyhydroxysulfonate phosphates. Sodium, ethanolamine and ammonium salts are preferred over the above. Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphates, pyrophosphates, polymeric metaphosphates having a degree of polymerization of 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the salts of ethylene diphosphonic acid, the salts of ethane 1-hydroxy-1,1-diphosphonic acid and the salts of ethane, 1,1,1-triphosphonic acid. Other phosphorus builder compounds are described in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference. In general, however, phosphates are preferably avoided for environmental reasons. Examples of inorganic, non-phosphorus builders are sodium and potassium carbonates, bicarbonate, sesqu carbonate, decahydrate, tetraborate, and silicate having a molar ratio of SiO2 to alkali metal oxide of 0.5 to 4.0, preferably from 1.0 to 2.4. Another component of the foam compositions useful herein consists of non-aqueous, organic, viscosity reducing solvent (s). The term "solvent" is used herein to connote non-surface or low surface activity active materials that dissolve in the matrix of the detergent composition that has a viscosity reducing effect on the composition. This effect is generally a result of its interaction with the surfactant-water system present in the formulations to avoid the formulation of liquid crystal phases. The term "solvent" does not mean that it requires that the solvent material be capable of in effect dissolving all of the components of the detergent composition added thereto. The non-organic aqueous materials that are used as solvents herein may be high or low polarity liquids. High-polarity liquids suitable as solvents are, for example, short-chain alcohols (ethanol, propanol, propane-diol, etc.), short-chain aldehydes (methylal, acetaldehyde, etc.), short-chain ketones (acetone, propanone, etc.) and short chain esters. Other polar materials useful in some cases are glycerols, glycols and short chain ethoxylated alcohols (short chain surfactants). The short chain surfactants for use herein are alkoxylated alcohols according to the formula: R O (A) n H, wherein R is a direct or branched hydrocarbon chain of C6 to C10, and n, representing the average degree of ethoxylation, is from 1 to 10, or mixtures thereof. A is ethylene oxide or propylene oxide or mixtures thereof.

Surfactants suitable for use herein can be readily made by condensing alcohols having the desired chain length with propylene oxide or ethylene, or mixtures thereof. Short chain alkoxylation suitable for use herein is commercially available from several suppliers, for example Dehydrol 04® by Henkel (C8EO4), Mergital C4® by Sidobre (C8EO4), and lmbentin AG / 810 / 050® and AG / 810 / 080® by Kolb (respectively C8-10E05 and C8- 10EO8). Suitable types of low polarity solvents useful in the non-aqueous liquid detergent compositions herein include lower alkylene glycols of alkylene glycol, low molecular weight polyethylene glycols, low molecular weight methyl esters and amides, and the like. A preferred type of low polarity, non-aqueous solvent for use herein comprises the C2-C6 mono alkyl ethers of C2-C3 mono-, di-, tri-, or tetraalkylene glycol. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of this type have been marketed under the trademarks Dowanol, Carbitol and Cellosolve Another preferred type of non-aqueous, low polarity organic solvent useful herein comprises low molecular weight polyethylene glycols (PEGs). Such materials are those that have molecular weights of at least 150. Low molecular weight PEGs in the range of 200 to 600 are most preferred. Another preferred type of non-aqueous, non-polar solvent comprises the low molecular weight methyl ester. Such materials are those of the general formula R1-C (O) -OCH3 wherein R1 is on the scale of 1 to 18.

Examples of suitable low molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate. The organic, non-aqueous solvent (s) used should, of course, be compatible and nonreactive with other components of the composition, used in the foam compositions herein. Such a solvent component will generally be used in an amount of 1% to 60% by weight of the composition. More preferably, the non-aqueous organic solvent will comprise from 5% to 40% by weight of the composition, more preferably from 10% to 25% by weight of the composition. Foam stabilizing agents can also be used in the compositions of the present invention. Especially preferred are aliphatic alcohols such as the straight chain saturated alcohols of 12 to 18 carbon atoms, for example cetyl alcohol, stearyl alcohol, myristyl alcohol and mixtures thereof. The polymers including polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polypeptides, polysaccharides, cellulose derivatives; and also synthetic and natural gums and resins such as guar gum, xanthan gum, carrageenan, alginate and sodium caffeinate can also be used in the present invention. Textiles are any material made from fabric, including clothing such as shirts, blouses, socks, skirts, briefs, bags, underwear, etc., and also including tablecloths, towels, curtains, etc. The definition of textile materials as used herein does not include carpets and similar floor coverings. The textile materials that are to be used in the present invention are commonly made by braiding or weaving. Many different fibers can be used to produce braided types, fabrics or other types of textiles including synthetic fibers (such as polyester, polyamide, etc.) and natural fibers from plants (such as cotton, hemp) and from animals (such as wool), angora, silk). Mixtures of different fibers are also commonly used. It is important to distinguish between the foam of the present invention and the foams that are commonly found in everyday washing procedures. The foam of the present invention is much more concentrated and contains less water than conventional foams. The foam of the present invention preferably consists of less than 25%, and more preferably less than 15% by weight of water. The foam of the present invention preferably comprises at least 18% by weight, and more preferably at least 25% by weight of a surface active agent. The most preferred foams for use as cleaning compositions comprise at least 10% by weight, preferably at least 20% by weight of anionic surfactant. On the other hand, the foams, which are formed in conventional washing processes when the detergents are diluted before washing, are formed from fairly dilute solutions, typically 100 g of product in 10 liters of water. The result is a washing liquid comprising almost 99% by weight of water. A layer of foam can be formed on the surface of the washing liquid, the composition of the foams being similar to that of the washing liquid itself. The surfactant content of the foams will normally be much less than 1%, typically less than 0.3%. Consequently, the difference between the foam of the present invention and the foams of conventional washing processes will be understood. It will also be recognized by the person skilled in the art that foams are often considered undesirable in washing processes and antifoaming agents are often used to reduce or control them. In a washing process in which the solution of detergent active agents is the means of transporting the active ingredients to the surface of the fiber, the presence of foams can decrease the washing efficiency.

This is because the detergent actives that are in the foams do not dissolve any more in the wash liquid itself, and therefore are not efficiently transported to the surface of the fiber. The packaged product of the present invention comprises a sealed container, such as an essentially cylindrical bottle, having a means for dispensing as a nozzle. The container contains the composition and propellant gas. Suitable containers can be made of any material, especially aluminum, tinplate, plastics including PET, or PP, PE or polyamide and including blends, laminates or other combinations thereof. The foam is dispensed when the nozzle is activated and the detergent is released together with the propellant gas. The propellant gas expands to form many "bubbles" within the composition thereby creating the foam.

Propellant gas The propellant gas of the present invention comprises either liquid propellants or compressed gas propellants. Examples of liquid propellants are fluorocarbons, chlorofluorocarbons, H-chlorofluorocarbons, methane, ethane, propane, butane, pentane. Examples of compressed gas propellants are carbon dioxide, nitrogen or nitrous oxide (especially N2O), air, ammonia and dimethyl ether. The most preferred is carbon dioxide due to environmental and flammability considerations. Various ways of pressurizing the propellant gas are known in the art. For example, gas can be pressurized at the time of packing. The product can be physically separated from a compressed gas by a membrane such as rubber under tension. Alternatively a means for pressurizing the gas subsequently by mechanical action may be provided (the so-called "pump and sprinkler" system). Various devices for supplying foams are described in US-A 364 031 of November 15, 1994 entitled "Foam Dispensing Nozzles and Dispensers Employing Said Nozzles". Any nozzle or nozzle / valve assembly that provides a means for releasing the mixture of detergent ingredients from the container and providing a foam is suitable for use in the present invention. Valve Precision Company (Valve Precision in France) provides a scale of nozzle assemblies for different applications including shaving foams and carpet cleaners under various trade names including CityR, MontegoR, Power JetR, VulcanR and ViscoR. Nozzles are available that disperse the foam both horizontally and vertically (when the container is held upright). Metering nozzles are also available that dispense a predetermined amount of foam and are useful in the present invention. The metering valves are described in W09108965 (Precision Valve Co) and EP-A 616953 (3M Co). In order for the apparatus to be effective in the method of the present invention it must supply the foam at a rate of at least 3 g per second of foam from the sealed container, more preferably at a rate of at least 10 g per second.

Cleaning method The method of the present invention can be used to wash textile materials by hand (referred to herein as "hand washing"). The foam is poured on or around the textile materials to be washed, or dissolved (usually in water) to form a washing liquid. The entire surface of the fabrics is then exposed to the foam "pure", or to the washing liquid. It is believed that the foam ensures an easy and uniform distribution of enzymes, either in "pure" form, or when it dissolves to form a wash liquid, which promotes rapid and effective enzyme activity without causing damage to the fabric. at a high localized concentration of enzyme. The textile materials can be soaked in the foam or washing liquid for up to several days, or even weeks. However, it is preferred that the soaking time is between 1 minute and 24 hours, preferably between 5 minutes and 4 hours. Normally textile materials will be subsequently rinsed using clean water in order to remove any remaining detergent. The method of the present invention is particularly well suited for hand washing of delicate textiles, in particular textile materials comprising high levels of wool or silk can advantageously be treated in this way. A particular benefit is a marked reduction in the local damage to the fabric that can occur when conventional washing procedures are used. In conventional washing processes the composition, the ed textile material and the water are joined in a suitable container. At the beginning of the procedure, there are very high local concentrations as the composition begins to dissolve in the water, but has been homogeneously distributed in the water. Such high concentrations in the solution, if they happen to be present in or near the fabric, can cause local damage to the fabric. This type of local damage to the fabric is avoided according to the method of the present invention. Because all enzymes are uniformly distributed throughout the entire volume of foam there are no local concentrations of active materials that could cause damage to the fabric. A typical hand washing composition will consist of some or all of the following components: surfactants (anionic, nonionic, cationic, amphoteric, zwitterionic), builders and chelating agents, release polymers, optical brighteners, polymer inhibition of color transfer, perfume, enzymes, dyes. The surfactants are preferably present at a level of 10% to 90% by weight of the composition, preferably 20% to 80% of the composition, more preferably from 25% to 50% of the composition and more preferably 30% by weight of the composition. the composition. Builders such as fatty acids, citric acids, succinic acid, phosphate, zeolite are preferably present at a level of 10% to 90% by weight of the composition, preferably 10% to 50% by weight of the composition, more preferably 12% to 20% by weight of the composition. The chelating agent as phosphonate is preferably present at a level of 0% to 5%, more preferably 0.1% to 3% by weight of the composition. An alternate washing method of the present invention can be used to wash textiles in a conventional washing machine or, alternatively, if water is not required to be added, in a conventional drying machine (both cases referred to herein as "machine wash"). The foam of the present invention is simply delivered into the drum of the machine either before or after the soiled textile material has been loaded. Most commercially available washing machines have automatic washing cycles. If the water is added during the cycle most of the foam components will dissolve or be dispersed in the water, probably resulting in a layer of foam in the machine. As noted above, these foams having a high water content and a low content of surfactants should not be considered as foams within the meaning of the present invention. The washing cycle may be completed with any combination of washing, rinsing, conditioning, and / or drying steps, during which any additional washing or rinsing additives may be introduced into the drum of the machine. Suitable compositions for machine wash foam are similar to those described above for hand wash foam.

EXAMPLES The liquid washing compositions were prepared by mixing the components according to the compositions in Table 1. Each composition was then packed in metal containers, each container having a nominal capacity of 405 cubic centimeters. The cans were filled with 250 ml of liquid detergent and then pressurized with carbon dioxide while stirring, until equilibrated to a can pressure of 10 bars of carbon dioxide at 20 ° C. All cans were equipped with a standard 3 x valve 1. 0 mm in diameter (code number 045380 supplied by Valve Precision) without an immersion tube and a straight nozzle of whipped cream. In order to expel the foam out of the can, the can must be in an inverted position. The cans were allowed to stand for one day at room temperature (almost 20 ° C) before use. Immediately before use, the cans were shaken strongly by hand to ensure the homogeneity of the components inside the can.

EXAMPLE 1 Alkylsulfate 7.4 Alkylethoxysulfate 6.4 Nonionic C12 / C15 E7 10.6 NMG 4.0 Fatty acid 8.8 Citric acid 0.9 Propanediol 9.7 Ethanol 0.7 Monoethanolamine 6.8 Boric acid 4.5 Ca acetate 0.1 EDDS 1.3 Dirt release polymer 0.2 PTMS 0.03 Ethoxylated TPP 0.3 PVNO 0.2 Perfume 1.6 PEG 200 25.0 Enzyme system: Protein pure protein 0.00075 Pure cellulase protein 0.0001 Pure lipase protein 0.004 Pure amylase protein 0.009 Water rest at 100 NMG is N-methylglocamide of C12 / C14. Ethoxylated TEP is ethoxylated tetraethylenepentamine. PVNO is N-polyvinyl pyridine oxide. PTMS is propyltrimetroxylan.

Claims (8)

NOVELTY OF THE INVENTION CLAIMS

1. - A composition in the form of foam comprising a system of surfactant and enzymes, further characterized in that the composition in the form of foam comprises from 0.0001% to 0.005% protein pure protease enzyme by weight of the total composition in the form of foam .

2. A composition of foam form according to claim 1, further characterized in that the composition comprises additional enzymes selected from the group consisting of cellulase, hemicellulase, peroxidase, amylase, gioco-amylase, xylanase, lipase, esterase, cutinase, pectinase , reductase, oxidase, phenoloxidase, lipogenase, ligninase, pulosase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, chondroitinase, laccase or mixtures thereof.

3. A composition in the form of foam according to claim 2, further characterized in that the composition comprises additional enzymes selected from the group consisting of cellulase, amylase, lipase or mixtures thereof.

4. - A composition according to claim 1, further characterized in that it comprises 0.00001% to 0.0005% of pure cellulase enzyme protein by weight of the total composition in the form of foam.

5. A composition according to claim 4, further characterized in that it comprises 0.00005% to 0.00025% pure cellulase protein by weight of the total composition in the form of foam.

6. A packaged product for dispensing a composition according to any of claims 1 to 5, further characterized in that the packaged product comprises a sealed container, a means for dispensing, and further comprises a propellant gas, wherein the propellant gas comprises of carbon oxide, nitrous oxides, or mixtures thereof.

7. A packaged product according to claim 6, further characterized in that the packaged product comprises an aerosol container and a nozzle for supplying foam.

8. - A method for cleaning textile materials comprising the steps of: (i) forming a composition in the form of foam, the composition in the form of foam having the composition according to any of claims 1 to 5; (ii) dissolving or supplying the foam in water to form an aqueous solution; and either subsequently or simultaneously (iii) shaking cleaned textile materials in the aqueous solution.