EP0839905A1 - Enzymhaltige Schaum-Reinigungsmittel-Zusammensetzung - Google Patents

Enzymhaltige Schaum-Reinigungsmittel-Zusammensetzung Download PDF

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Publication number
EP0839905A1
EP0839905A1 EP96203075A EP96203075A EP0839905A1 EP 0839905 A1 EP0839905 A1 EP 0839905A1 EP 96203075 A EP96203075 A EP 96203075A EP 96203075 A EP96203075 A EP 96203075A EP 0839905 A1 EP0839905 A1 EP 0839905A1
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EP
European Patent Office
Prior art keywords
foam
composition
enzymes
weight
foam composition
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.)
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EP96203075A
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English (en)
French (fr)
Inventor
David Xavante Cumming
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP96203075A priority Critical patent/EP0839905A1/de
Priority to JP10521504A priority patent/JP2000508370A/ja
Priority to BR9712883-0A priority patent/BR9712883A/pt
Priority to PCT/US1997/019407 priority patent/WO1998020100A1/en
Priority to ARP970105160A priority patent/AR010057A1/es
Publication of EP0839905A1 publication Critical patent/EP0839905A1/de
Withdrawn legal-status Critical Current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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043—For use with aerosol devices
    • 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
    • C11D2111/42—

Definitions

  • the present invention relates to a cleaning composition, in the form of a foam, which comprises a surfactant system and enzymes.
  • 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.
  • Enzymes have been used for many years in both granular and liquid laundry detergents.
  • EP-A-0 677 577 discloses a foaming detergent composition for cleaning textile fabrics which may comprise enzymes such as protease, alcalase, lipase, cellulase.
  • the present invention is concerned with a means of delivering a foam comprising enzymes which is both highly efficient and cost-effective. It is an objective of the present invention to provide a foam detergent to enhance the appearance of the fabric surface without causing unacceptable wear or tensile strength loss of the fabric. It is a further objective of the present invention to provide a foaming composition with good enzyme stability.
  • a foam composition comprises from 0.0001% to 0.005% pure protease enzyme protein by weight of the total foam composition.
  • the foam composition further comprises 0.00001% to 0.0005%, and more preferably from 0.00005% to 0.00025%, pure cellulase enzyme protien by weight of the total foam composition.
  • the foam composition is dispensed from a packaged product comprising a sealed container, preferably an aerosol can; and a dispensing means, preferably a foam dispensing nozzle; and further comprising a propellant gas, wherein the propellant gas comprises carbon dioxide, nitrous oxides, air or mixtures thereof. Carbon dioxide is most preferred.
  • a method of cleaning textile fabrics comprising the steps of :
  • 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.
  • the gas "bubbles" of the dispersed phase can vary in size from 50 micrometers to several millimetres.
  • the quality of the foam is determined by assessing various foam quality attributes, such as: 1) the appearance of the foam as it is determined by the uniformity of the bubble size distribution, as well as by the actual bubble sizes, wherein small and uniformly sized bubbles are generally preferred; 2) the thickness of the foam as it is determined by the apparent foam viscosity, wherein a greater apparent foam viscosity is generally preferred; 3) the density of the foam which is preferably less than 250g/l, more preferably less than 150 g/l, and most preferably less than 100 g/l; and 4) the drainage of the liquid from the foam upon standing on a solid surface, wherein slow drainage of the liquid is generally preferred.
  • various foam quality attributes such as: 1) the appearance of the foam as it is determined by the uniformity of the bubble size distribution, as well as by the actual bubble sizes, wherein small and uniformly sized bubbles are generally preferred; 2) the thickness of the foam as it is determined by the apparent foam viscosity, wherein a greater apparent foam viscosity is generally preferred; 3)
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the ethanolamine, sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., monoethanolamine, sodium or potassium tallow and coconut soap.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ethanolamine, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • water-soluble salts preferably the alkali metal, ethanolamine, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • alkyl sulfates especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil
  • alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383; and methyl ester sulphonates.
  • linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11 -C 13 LAS.
  • alkyl glyceryl ether sulfonates especially those ethers of higher alcohols derived from tallow and coconut oil; coconut oil fatty acid monoglyceride sulfonates and sulfates; salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
  • Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
  • Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield 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, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 1 to 25 moles of ethylene oxide per mole of alcohol, especially 2 to 7 moles of ethylene oxide per mole of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms; and condensation products of propylene glycol with ethylene oxide.
  • polyhydroxy fatty acid amides which may be prepared by reacting a fatty acid ester 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 C12-C20 fatty acid methyl ester.
  • Most preferred is the reaction product of N-methyl glucamine (which may be derived from glucose) with C12-C20 fatty acid methyl ester.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R 4 R 5 R 6 R 7 N + X - , wherein R 4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R 5 , R 6 and R 7 are each C 1 to C 7 alkyl preferably methyl; X - is an anion, e.g. chloride.
  • Examples of such trimethyl ammonium compounds include C 12 - 14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
  • surfactants that may be used in the compositions of the present invention include C10-C18 glycerol ethers, C10-18 alkyl polyglycoside and their corresponding sulphated polyglycosides, alkyl ester sulphonates, and oleoyl sarcosinate.
  • the proteolytic enzymes are incorporated in the detergent compositions of the present invention 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 (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or non purified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants.
  • 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 International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
  • Other preferred proteases include those of WO 95/10591 A to Procter & Gamble.
  • 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.
  • 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.
  • Preferred protease for use in the present invention are SAVINASE® and the proteases described in EP 215 446 and WO95/10591 at a level of from 0.0001% to 0.005%, preferably from 0.0002% to 0.002%, more preferably 0.0005% to 0.001% pure potease enzyme protein by weight of total composition in foam deterget compositions.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 93/07263 A and WO 93/07260 A to Genencor International, WO 89/08694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for foam detergent formulations are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques.
  • Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 94/01532 A to Novo.
  • the detergent compositions can in addition to and protease enzymes further comprise one or more enzymes which 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, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases chondroitinase, laccase or mixtures thereof.
  • a preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • 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 1800.
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
  • suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
  • Peroxidase enzymes are used in combination with 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 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.00001% to 0.001%, preferably 0.00005% to 0.00025% of active enzyme protein by weight of the detergent composition. (These levels correspond to 0.005 CEVU/g to 0.2 CEVU/g, preferably 0.02 CEVU/g to 0.1 CEVU/g).
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • lipases such as M1 Lipase R and Lipomax R (Gist-Brocades) and Lipolase R and Lipolase Ultra R (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation.
  • Suitable cutinases are described in WO 94/14963 and WO 94/14964. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
  • WO/94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases.
  • Other amylases known for use in detergent 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. 1,296,839 (Novo).
  • ⁇ -amylases examples are Termamyl®, Ban® and Fungamyl®, 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.
  • Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • enzyme oxidation scavengers which are described in the copending European patent application 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • the foam of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • neutral water-soluble salts examples include the 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 may be incorporated into the present invention.
  • water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ethanolamine, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhydroxysulfonates. Preferred are the sodium, ethanolamine and ammonium salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the salts of ethylene diphosphonic acid, the salts of ethane 1-hydroxy-1,1-diphosphonic acid and the salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed 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.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • Another component of the foaming compositions useful herein comprises nonaqueous, viscosity by reducing, organic solvent (s).
  • solvent is used herein to connote non-surface active or low surface active materials that dissolve into the detergent composition matrix having a vicosity reduction effect on the composition. This effect is generally a result of their interaction with the surfactant-water system present in the formulations preventing the formulation of liquid crystal phases.
  • solvent is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • the non-aqueous organic materials which are employed as solvents herein can be liquids of high or low polarity.
  • 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 ethers.
  • Other polar materials useful in some cases are glycerols, glycols and short chain ethoxylated alcohols (short chain nonionic surfactants)
  • the short chain nonionic surfactants for use herein are alkoxylated alcohols according to the formula : R O (A)n H, wherein R is a C6 to C10 straight or branched, hydrocarbon chain and n, representing the average ethoxylation degree, is from 1 to 10, or mixtures thereof.
  • R is a C6 to C10 straight or branched, hydrocarbon chain and n, representing the average ethoxylation degree, is from 1 to 10, or mixtures thereof.
  • A is ethylene oxide or propylene oxide or mixtures thereof.
  • Suitable surfactants for use herein can readily be made by condensing alcohols having the desired chain length with propylene or ethylene oxide, or mixtures thereof.
  • Suitable short chain alkoxylated for use herein are commercially available from several suppliers, for example Dehydrol O4® from Henkel (C8EO4), Mergital C4® from Sidobre (C8EO4), and Imbentin AG/810/050® and AG/810/080® from Kolb (respectively C8-10EO5 and C8-10EO8).
  • Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein include alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
  • a preferred type of nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra-C 2 -C 3 alkylene glycol mono C 2 -C 6 alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cello
  • nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs).
  • PEGs polyethylene glycols
  • Such materials are those having molecular weights of at least about 150.
  • PEGs of molecular weight ranging from about 200 to 600 are most preferred.
  • non-polar, nonaqueous solvent comprises lower molecular weight methyl esters.
  • Such materials are those of the general formula : R 1 -C(O)-OCH 3 wherein R 1 ranges from 1 to about 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the nonaqueous, organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, used in the foaming compositions herein.
  • a solvent component will generally be utilized in an amount of from about 1% to 60% by weight of the composition. More preferably, the nonaqueous, organic solvent will comprise from about 5% to 40% by weight of the composition, most preferably from about 10% to 25% by weight of the composition.
  • Foam stabilising agents may also be employed in the compositions of the present invention.
  • alyphatic alcohols such as straight chain saturated alcohols of 12 to 18 carbon atoms e.g. cetyl alcohol, stearyl alcohol, myristyl alcohol and mixtures thereof.
  • Polymers including polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, polypeptides, polysaccharides, cellulose derivatives; and also natural and synthetic gums and resins such as guar gum, xanthan gum, carageenan, sodium alginate and caseinate may also be used in the present invention.
  • Textile fabrics are any materials made from cloth, including garments such as shirts, blouses, socks, skirts, trousers, jackets, underwear etc, and also including tablecloths, towels, curtains etc.
  • the definition of textile fabrics as used herein does not include carpets and similar floor coverings.
  • Textile fabrics which are to be used in the present invention are commonly made by weaving or knitting. Many different fibres may be used to produce woven, knitted or other types of textile fabric including synthetic fibres (such as polyester, polyamide, etc.) and natural fibres from plants (such as cotton, hemp) and from animals (such as wool, angora, silk). Blends of different fibres are also commonly used.
  • synthetic fibres such as polyester, polyamide, etc.
  • natural fibres such as cotton, hemp
  • animals such as wool, angora, silk
  • the foam of the present invention is much more concentrated and comprises less water than conventional suds.
  • the foam of the present invention preferably comprises 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.
  • Most preferred foams for use as cleaning compositions comprise at least 10% by weight, preferably at least 20% by weight of anionic surfactant.
  • suds which are formed in conventional washing process when detergents are diluted prior to washing, are formed from quite dilute solutions typically 100g of product in 10 litres of water.
  • the result is a wash liquor which comprises about 99% by weight of water.
  • a layer of suds may form on the surface of the wash liquor, the composition of the suds being similar to that of the wash liquor itself.
  • the surfactant content of the suds will normally be much less than 1%, typically less than 0.3%. Consequently the difference between the foam of the present invention and the suds of a conventional washing process will be understood.
  • suds are often considered undesirable in the washing process and antisuds agents are often employed to reduce or control them.
  • the solution of detergent active agents is the medium of transport of the actives to the fibre surface
  • the presence of suds can diminish washing performance. This is because the detergent actives which are in the suds are no longer dissolved in the washing liquor itself, and are not therefore efficiently transported to the fibre surface.
  • the packaged product of the present invention comprises a sealed container, such as an essentially cylindrical bottle, having a dispensing means such as a nozzle.
  • the container contains the composition and propellant gas.
  • Suitable containers may be made from any material, especially aluminium, tin-plate, plastics including PET, OPP, PE or polyamide and including mixtures, laminates or other combinations of these.
  • 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.
  • the propellant gas of the present invention comprises either liquid propellants or compressed gas propellants.
  • liquid propellants are fluorocarbons, chlorofluorocarbons, H-chlorofluorocarbons, methane, ethane, propane, butane, pentane.
  • compressed gas propellants are carbon dioxide, nitrogen or nitrous oxides (especially N2O), air, ammonia and dimethyl ether. Most preferred is carbon dioxide because of environmental and flamability considerations.
  • the gas may be pressurised at the time of packing.
  • the product may be physically separated from a compressed gas by a membrane such as rubber under tension.
  • a means for pressurising the gas subsequently by mechanical action may be provided (so-called "pump and spray” systems).
  • Metering nozzles which dispense a predetermined amount of foam are also available and useful in the present invention.
  • Metering valves are disclosed in WO9108965 (Precision Valve Co) and EP-A 616953 (3M Co).
  • the apparatus In order for the apparatus to be effective in the method of the present invention it should deliver the foam at a rate of at least 3g per second of foam from the sealed container, more preferably at a rate of at least 10 g per second.
  • the method of the present invention may be used to wash textile fabrics by hand (referred to herein as "handwash”).
  • handwash The foam is dispensed onto or around the textile fabrics to be washed, or dissolved (usually in water) to form a wash liquor.
  • the whole surface of the fabrics is then exposed to the "neat” foam, or to the wash liquor. It is believed that the foam ensures easy and even distribution of enzymes, either in "neat” form, or when dissolved to form a wash liquor, which promotes rapid and effective enzyme activity without causing fabric damage due to localised high concentration of enzymes.
  • the textile fabrics may be left to soak in the foam or wash liquor for anything 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.
  • the method of the present invention is particularly well-suited to hand washing of delicate textile fabrics.
  • textile fabrics comprising high levels of wool or silk may be advantageously treated in this way.
  • One particular benefit is a marked reduction in local fabric damage which may occur when conventional laundry processes are used.
  • conventional laundry processes the composition, the soiled textile fabrics and water are all brought together in a suitable container.
  • At the beginning of the process there are very high local concentrations of enzymes as the composition begins to dissolve in the water, but it has been homogeneously distributed in the water.
  • Such high local concentrations in solution if they happen to be present on or close to the fabric can cause local fabric damage.
  • This type of local fabric damage is avoided according to the method of the present invention. Because all of the enzymes are uniformly distributed throughout the large volume of the foam there are no local concentrations of active materials which might cause fabric damage.
  • a typical handwash composition will comprise some or all of the following components : surfactants (anionic, nonionic, cationic, amphoteric, zwitterionic), detergent builders and chelating agents, soil release polymers, optical brightener, dye transfer inhibition polymer, perfume, enzymes, colorants.
  • surfactants anionic, nonionic, cationic, amphoteric, zwitterionic
  • detergent builders and chelating agents soil release polymers
  • optical brightener dye transfer inhibition polymer
  • perfume enzymes, colorants.
  • Surfactants are preferably present at a level of from 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 most preferably about 30% by weight of the composition.
  • Detergent builders such as fatty acids, citric acid, succinic acid, phosphate, zeolite are preferably present at a level of from 10% to 90% by weight of the composition, preferably 10% to 50% of the composition, more preferably from 12% to 20% by weight of the composition.
  • Chelating agent such as phosphonate are preferably present at a level of from 0% to 5%, more preferably from 0.1% to 3% by weight of the composition.
  • An alternative washing method of the present invention may be used to wash textile fabrics in a conventional washing machine or, alternatively, if no added water is required, in a conventional drying machine (both cases referred to herein as "machine wash”).
  • the foam of the present invention is simply dispensed into the drum of the machine either before or after the soiled textile fabrics have been loaded.
  • the wash cycle may be completed by any combination of washing, rinsing, conditioning and/or drying steps, during any one of which additional wash or rinse additives may be introduced into the machine drum.
  • compositions suitable for machine wash foams are similar to those described above for handwash foams.
  • Liquid laundry compositions were prepared by mixing the components according to the compositions in Table 1. Then each composition was packed into metal containers, each container having a nominal capacity of 405 cubic centimetres. The cans were filled with 250 ml of liquid detergent and then were pressurised with carbon dioxide while shaking, until it equilibrates to a can pressure of about 10 bars of carbon dioxide at about 20 °C.
  • All the cans are fitted with a 3 x 1.0 mm diameter standard valve (Code No. 045380 supplied by Valve Precision), without a dip tube and a straight whipped cream nozzle. In order to expel the foam out of the can, the can must be in an inverted position.
  • Example 1 Alkyl sulphate 7.4 Alkyl ethoxy sulphate 6.4 Nonionic C12/C15 E7 10.6 NMG 4.0 Fatty acid 8.8 Citric acid 0.9 Propane diol 9.7 Ethanol 0.7 Monoethanolamine 6.8 Boric acid 4.5 Ca acetate 0.1 EDDS 1.3 Soil release polymer 0.2 PTMS 0.03 Ethoxylated TPP 0.3 PVNO 0.2 Perfume 1.6 PEG 200 25.0 ENZYME SYSTEM: Pure Protease protein 0.00075 Pure Cellulase protein 0.0001 Pure Lipase protein 0.004 Pure Amylase protein 0.009 Water balance to 100 NMG is C12/C14 N-methyl glucamide. Ethoxylated TEP is ethoxylated tetraethy
EP96203075A 1996-11-05 1996-11-05 Enzymhaltige Schaum-Reinigungsmittel-Zusammensetzung Withdrawn EP0839905A1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP96203075A EP0839905A1 (de) 1996-11-05 1996-11-05 Enzymhaltige Schaum-Reinigungsmittel-Zusammensetzung
JP10521504A JP2000508370A (ja) 1996-11-05 1997-10-28 酵素を含むフォーム洗剤組成物
BR9712883-0A BR9712883A (pt) 1996-11-05 1997-10-28 Composição deter0gente de espuma com enzimas
PCT/US1997/019407 WO1998020100A1 (en) 1996-11-05 1997-10-28 Foam detergent composition with enzymes
ARP970105160A AR010057A1 (es) 1996-11-05 1997-11-05 Composicion espumante, producto envasado para dispensar dicha composicion y metodo de limpieza de telas

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96203075A EP0839905A1 (de) 1996-11-05 1996-11-05 Enzymhaltige Schaum-Reinigungsmittel-Zusammensetzung

Publications (1)

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EP0839905A1 true EP0839905A1 (de) 1998-05-06

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EP96203075A Withdrawn EP0839905A1 (de) 1996-11-05 1996-11-05 Enzymhaltige Schaum-Reinigungsmittel-Zusammensetzung

Country Status (5)

Country Link
EP (1) EP0839905A1 (de)
JP (1) JP2000508370A (de)
AR (1) AR010057A1 (de)
BR (1) BR9712883A (de)
WO (1) WO1998020100A1 (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5965507A (en) * 1995-06-08 1999-10-12 Procter & Gamble Company Cleaning compositions comprising chondroitinase
WO2002094973A1 (en) * 2001-05-19 2002-11-28 Sun Chemical Group B.V. Bio-active de-inking or cleaning foam
WO2005026306A1 (en) * 2003-09-11 2005-03-24 The Procter & Gamble Company Methods of formulating enzyme cocktails, enzyme cocktails for the removal of egg-based and grass-based stains and/or soils, compositions and products comprising same
EP1913931A1 (de) * 2006-10-06 2008-04-23 TOWA Enzyme Co., Ltd. Mikrobläschen-Waschmittelzusammensetzung, Mikrobläschen-Waschverfahren und Mikrobläschen-Waschvorrichtung
US8809246B2 (en) 2009-11-12 2014-08-19 Thales Inc. Braided hair washing method
WO2014199151A2 (en) * 2013-06-13 2014-12-18 Reckitt Benckiser (Brands) Limited Product
EP3415603A1 (de) * 2017-06-13 2018-12-19 The Procter & Gamble Company Verbraucherprodukt
EP3418370A1 (de) * 2017-06-13 2018-12-26 The Procter & Gamble Company Verbraucherprodukt
US10640903B2 (en) 2017-06-13 2020-05-05 The Procter & Gamble Company Process for treating at least one garment
EP4134423A1 (de) * 2021-08-12 2023-02-15 Henkel AG & Co. KGaA Sprühbare wäschevorbehandlungszusammensetzung

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5485705B2 (ja) * 2007-02-20 2014-05-07 ノボザイムス アクティーゼルスカブ 洗濯用酵素フォーム処理
DE102020119698A1 (de) 2020-07-27 2022-01-27 Karlsruher Institut für Technologie Katalytisch aktive Proteinschäume und Verfahren zu deren Herstellung

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EP0677577A1 (de) 1994-03-30 1995-10-18 The Procter & Gamble Company Reinigungsschaumzusammensetzungen und Verfahren zum Behandeln von Textilien

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US5462607A (en) * 1994-04-15 1995-10-31 United Laboratories, Inc. Method of cleaning using a foamed liquid
US5551989A (en) * 1994-04-15 1996-09-03 United Laboratories, Inc. Method of cleaning using a foamed liquid

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US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
FR2111162A5 (de) * 1970-10-08 1972-06-02 Akzo Nv
US3781212A (en) * 1972-10-27 1973-12-25 Townsend & Townsend Aerosol enzyme detergents stabilized with carbon dioxide
US4954286A (en) * 1988-04-14 1990-09-04 Lever Brothers Company Fabric pretreatment cleaning compositions
WO1995010591A1 (en) * 1993-10-14 1995-04-20 The Procter & Gamble Company Protease-containing cleaning compositions
EP0677577A1 (de) 1994-03-30 1995-10-18 The Procter & Gamble Company Reinigungsschaumzusammensetzungen und Verfahren zum Behandeln von Textilien

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5965507A (en) * 1995-06-08 1999-10-12 Procter & Gamble Company Cleaning compositions comprising chondroitinase
WO2002094973A1 (en) * 2001-05-19 2002-11-28 Sun Chemical Group B.V. Bio-active de-inking or cleaning foam
WO2005026306A1 (en) * 2003-09-11 2005-03-24 The Procter & Gamble Company Methods of formulating enzyme cocktails, enzyme cocktails for the removal of egg-based and grass-based stains and/or soils, compositions and products comprising same
EP1913931A1 (de) * 2006-10-06 2008-04-23 TOWA Enzyme Co., Ltd. Mikrobläschen-Waschmittelzusammensetzung, Mikrobläschen-Waschverfahren und Mikrobläschen-Waschvorrichtung
US7635671B2 (en) 2006-10-06 2009-12-22 Towa Enzyme Co., Ltd Microbubble washing composition, microbubble washing method, and microbubble washing apparatus
US8216557B2 (en) 2006-10-06 2012-07-10 Towa Enzyme Co., Ltd. Methods of treating skin disease, scalp disease, sensitive skin or suppressing hair loss with microbubble washing compositions
US8809246B2 (en) 2009-11-12 2014-08-19 Thales Inc. Braided hair washing method
WO2014199151A2 (en) * 2013-06-13 2014-12-18 Reckitt Benckiser (Brands) Limited Product
WO2014199151A3 (en) * 2013-06-13 2015-02-05 Reckitt Benckiser (Brands) Limited Process of producing a fabric treatment agent and method of pre-treating a garment / fabric
EP3415603A1 (de) * 2017-06-13 2018-12-19 The Procter & Gamble Company Verbraucherprodukt
EP3418370A1 (de) * 2017-06-13 2018-12-26 The Procter & Gamble Company Verbraucherprodukt
US10640903B2 (en) 2017-06-13 2020-05-05 The Procter & Gamble Company Process for treating at least one garment
EP4134423A1 (de) * 2021-08-12 2023-02-15 Henkel AG & Co. KGaA Sprühbare wäschevorbehandlungszusammensetzung

Also Published As

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JP2000508370A (ja) 2000-07-04
WO1998020100A1 (en) 1998-05-14
AR010057A1 (es) 2000-05-17
BR9712883A (pt) 2000-02-01

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