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WO1999033946A1 - Produits a action detachante amelioree contenant des enzymes - Google Patents

Produits a action detachante amelioree contenant des enzymes Download PDF

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Publication number
WO1999033946A1
WO1999033946A1 PCT/US1998/027127 US9827127W WO9933946A1 WO 1999033946 A1 WO1999033946 A1 WO 1999033946A1 US 9827127 W US9827127 W US 9827127W WO 9933946 A1 WO9933946 A1 WO 9933946A1
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WO
WIPO (PCT)
Prior art keywords
composition
enzyme
organic polymer
water soluble
surfactant
Prior art date
Application number
PCT/US1998/027127
Other languages
English (en)
Inventor
Hoai-Chau Cao
Marie-Christine Houben
Patricia Pagnoul
Patrick Durbut
Guy Broze
Anne-Marie Misselyn
Original Assignee
Colgate-Palmolive Company
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 Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to AU20062/99A priority Critical patent/AU2006299A/en
Publication of WO1999033946A1 publication Critical patent/WO1999033946A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to enzyme-containing compositions.
  • Detergent compositions are generally formulated to contain one or more anionic surfactant materials, builder materials, electrolyte materials and other adjuvants such as enzymes dispersed or dissolved in an aqueous medium. They are generally formulated at an alkaline pH of above 7, e.g., 8-12, and generally contain buffer ingredients and/or builder materials which will maintain an alkaline pH in both the detergent composition if it is a liquid, and in the wash water to which the detergent composition is added.
  • the main reason for the development of basic pH is to insure that the anionic surfactant components, enzymes or other organic components present in the composition remain solubilized and dispersed in the wash water and that greasy or oily stains removed from soiled clothing are also dispersed in the wash water.
  • liquid detergent composition An example of a liquid detergent composition is found in U.S. Patent 5,108,644 which discloses a liquid detergent concentrate comprising a mixture of nonionic polyalkoxy-lated anionic surfactants, a salting out electrolyte/ builder and a water soluble, viscosity reducing polymer which may be a polyethylene glycol.
  • the composition is formulated to have an alkaline pH of around 11, as shown in Table II.
  • premium commercial liquid laundry detergents are formulated to contain about 30%, by weight, or more of active ingredients, predominantly surfactants and builders, often including minor amounts of enzyme such as protease, amylase or lipase depending on the particular type of soil and stain being targeted for removal.
  • active ingredient levels below about 25%, and particularly below about 20%, commercial liquid laundry detergents are formulated to provide a less costly product to the consumer, while being generally less efficacious for cleaning the wide array of soils and stains which are capable of being laundered by the premium liquid detergents at normal dosage.
  • a surfactant selected from the group consisting of anionic, nonionic, and amphoteric surfactants and mixtures thereof; said composition being free of a quaternary nitrogen- containing cationic compound;
  • composition providing a cleaning performance in the wash bath due to the presence of the organic polymer which is superior to the cleaning provided by an otherwise identical composition which is free of said water soluble organic polymer.
  • compositions containing detergents and enzyme are formulated to contain less than about 25% by weight of active ingredients, and preferably about 20% or less of active ingredients which as herein defined comprises surfactant, builder, polymer and enzyme.
  • the invention also provides for a method for washing fabrics comprising forming a dilute aqueous solution of the enzyme- containing composition described above and then subjecting fabric material to washing action in said aqueous solution.
  • compositions of the invention contain two essential components: enzyme and organic polymer as herein described.
  • the compositions will advantageously also include one or more surfactants and optionally a builder.
  • the compositions of the invention are able to provide useful and efficacious fabric care or fabric cleaning effects by the proper selection of enzyme and in the absence of any surfactant .
  • the key to improved cleaning performance in accordance with this invention is the presence in the composition of a water soluble organic polymer which is miscible with the enzymes or surfactant, if present, in the composition.
  • the water soluble polymers are not themselves known as active cleaning agents, these polymer molecules have an affinity for both the active ingredients and the fabric surface. They thus serve to "link" enzyme molecules and the fiber surfaces of fabrics being washed, thereby carrying these actives into closer and more intimate contact with such surfaces. This allows effective cleaning to be carried out over a wide range of pH in the washing bath, from slightly acid up to highly alkaline aqueous medium.
  • the water soluble organic polymers useful in the present invention are those which are capable of forming hydrogen bonds with enzymes and/or the surfactants present in the detergent composition at an acidic or near neutral pH.
  • Such polymers include polyvinyl alcohols, alkoxylated polyhydric alcohols, polycellulose (e.g. carboxy methyl cellulose) , polysaccharides, polyalkylene glycols, vinyl pyrrolidone polymers and like materials containing hydroxyl, ether and/or anhydride functionalities .
  • Useful alkoxylated polyhydric alcohols are represented by the formula: R'
  • w equals one to four and x, y and z have a value between 0 and 60, more preferably 0 to 40, provided that (x+y+z) equals about 2 to about 100, preferably about 4 to about 24 and most preferably about 4 to about 19, and wherein R' is either hydrogen atom or methyl group.
  • a preferred ethoxylated polyhydric alcohol is glycerol 6E0.
  • m is about 20 to about 350 more preferably about 70 to about 110.
  • Preferred organic polymers which are both water soluble and are iscible with or soluble in anionic surfactants include polyethylene glycol, polypropylene glycol and mixtures thereof having a molecular weight in the range of from about 200 to 20,000, preferably from about 500 to 10,000 and most preferably from about 500 to 5,000.
  • Other preferred polymers include vinylpyrrolidone polymers, which includes polyvinylpyrrolidone as well as water soluble copolymers of vinylpyrrolidone with up to 50 mole % of copolymerizable unsaturated hydrophilic monomers such as acrylic monomers.
  • the molecular weight of the vinyl pyrrolidone polymers may range from about 4,000 to 200,000, more preferably from about 10,000 to 50,000.
  • the organic polymer is present in the composition in an amount sufficient to enhance the cleaning performance of the detergent composition generally at a level of from about 0.1 to about 5 wt%, more preferably at a level of from about 0.25 to 2.5 wt%.
  • the function of the organic polymer in the compositions of the invention is fundamentally distinct from the use of polymers such as polyethylene glycol in liquid detergent compositions described in the prior art.
  • polymers such as polyethylene glycol in liquid detergent compositions described in the prior art.
  • polymer such as polyethylene glycols, polyacrylates and polyacrylate/maleic co-polymers are disclosed as additives to certain structural liquid detergents for the purpose of reducing viscosity in the liquid composition.
  • the polymer enhances the performance and activity of the enzyme and, if present, the surfactant, and provides no viscosity reduction or builder effect or anti-encrustation effect, the characteristic function of conventional polymer additives to laundry detergent compositions known in the art.
  • compositions in accordance with the invention contain at least about 5 wt% of an anionic surfactant.
  • the composition may optionally also contain a nonionic surfactant or an amphoteric surfactant .
  • a mixture of an anionic and nonionic surfactant is often preferred from the standpoint of efficient cleaning.
  • Suitable anionic surfactants include the water-soluble alkali metal salts having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (Cg-C ⁇ g) alcohols produced, for example, from tallow or coconut oil; sodium and potassium alkyl (C9-C20) benzene sulfonates, particularly sodium linear secondary alkyl (C]_o ⁇ c i5) benzene sulfonates; sodium alkyl glycerol ether sulfates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (Cg-C ] _
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides and alkyl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
  • Specific nonionic surfactant compounds are alkyl (Cg-C ⁇ _g) primary or secondary linear or branched alcohols condensed with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • nonionic surfactant compounds include long chain tertiary amine oxides, long-chain tertiary phosphine oxides, dialkyl sulfoxides, fatty (Cg-C ⁇ g) esters of glycerol, sorbitan and the like, alkyl polyglycosides, ethoxylated glycerol esters, ethyoxylated sorbitans and ethoxylated phosphate esters .
  • the preferred non-ionic surfactant compounds are those of the ethoxylated and mixed ethyoxylated-propyloxylated (Cg-C ⁇ g) fatty alcohol type, containing 2-11 EO groups.
  • amphoteric surfactants which can be used in the compositions of the present invention are betaines and those which can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • betaines those which can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Examples of compounds falling within this definition are sodium 3 -dodecylaminopropionate, sodium 3 -dodecylaminopropane sulfonate, N-alkyltaurines, such as prepared by reacting dodecylamine with sodium isothionate, N-higher alkyl aspartic acids and the products sold under the trade name "Miranol”.
  • betaines useful herein include alkylamido betaines, alkylamino betaines, alkyl betaines and sulfobetaines .
  • the high alkyl betaines are represented by coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha- carboxymethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis (2-hydroxyethyl) carboxy methyl betaine, stearyl bis- (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma- carboxypropyl betaine, lauryl bis- (2- hydroxypropyl ) alpha- carboxymethyl betaine, etc.
  • the sulfo- betaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl bis- (2- hydroxyethyl ) sulfopropyl betaine, amino betaine amidosulfobetaines, and the like.
  • betaines include 1- (lauryl, dimethylammonio) acetate-1- (myristyl dimethylammonio) propane- 3 -sulfonate, 1- (myristyl dimethylamino) -2 -hydroxypropane- 3 -sulfonate, cocoamidoethylbetaine and cocoamidopropylbetaine .
  • amphoteric surfactants are the glycinate derivatives of the formula:
  • R is a hydrocarbon group, preferably a Cg to C20 aliphatic
  • R 1 is hydrogen or a Ci to C_ alkyl, preferably hydrogen or methylene
  • T is hydrogen or W, preferably W
  • W is R 2 COOM wherein M is hydrogen, alkali metal, alkaline earth metal, ammonium or substituted ammonium, such as lower alkanolamine, e.g., triethanolamine, x is 2 to 3 and y is 2 to 4, and R 2 is a Ci to C ⁇ , alkylene.
  • a preferred amphoteric surfactant is of the formula
  • R is an aliphatic hydrocarbon group, preferably a
  • M is alkali metal
  • y is 3 to 4. More preferably R is tallowalkyl (which is a mixture of stearyl, palmityl and oleyl in the proportions in which they occur in tallow), M is sodium and y is about 3.5, representing a mixture of about equal parts of the amphoteric surfactant wherein y is 3 and such amphoteric surfactant wherein y is 4.
  • Preferred amphoteric surfactants of this type are available commercially under the trade name AmpholakTM 7TX obtainable from Kenobel AB, a unit of Nobel Industries, Sweden.
  • the amount of surfactant in the composition is advantageously from about 5% to about 75%, more usually from about 5% to about 30%, and most preferably from about 5% to about 15% by weight of the composition.
  • the anionic surfactant is at least 40% by weight of such mixture.
  • the nonionic surfactant when present, is used in an amount of from about 0.5 to 10%, preferably from about 1 to 8% by weight and the amphoteric surfactant when present, can comprise from about 0.3 to 15%, preferably 1 to 10%, most preferably from about 1 to 8% by weight, based on the total composition.
  • the composition may also contain one or more detergency builders.
  • the selection of particular builders from those known in the art is dictated, in part, by the pH of the liquid detergent composition itself, or the pH which it generates in the wash water.
  • the builder For detergent composition intended to provide an acidic or near neutral wash medium, it is preferred that the builder not be a material that will generate a significantly basic pH above about 7.5, preferably not above 7.0, in the wash water or in the detergent composition itself if it is in the form of a liquid.
  • known builders such as Zeolites are less preferred as the main builder component when operating at low pH conditions because of proton exchange from the acidic detergent medium with the alkali metal, e.g., sodium cation, of the zeolite after a period of storage.
  • preferred builders at low pH wash water conditions include organic builders, for example, polycarboxylate builders, such as aminopolycarboxylates , for example, sodium and potassium ethylene-diamine tetraacetate; sodium and potassium nitrotriacetate; and the polyacetal polycarboxylates, such as those described, for example, in U.S. Patent Nos. 4,144,226 and 4,315,092.
  • polycarboxylate builders such as aminopolycarboxylates , for example, sodium and potassium ethylene-diamine tetraacetate
  • sodium and potassium nitrotriacetate sodium and potassium nitrotriacetate
  • polyacetal polycarboxylates such as those described, for example, in U.S. Patent Nos. 4,144,226 and 4,315,092.
  • organic builders of the polycarboxylate type include the water-soluble salts, especially sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene polycarboxylic acids, carboxymethyloxy succinic acid, cis-cyclohexane hexacarboxylic acid, and the like.
  • Citric acid salt e.g., potassium or sodium citrate
  • the citric acid salt also serves a dual function as a builder and an electrolyte which helps maintain the surfactant micelles dispersed in the aqueous liquid medium.
  • Such builders may be used for alkaline pH wash water conditions.
  • Such builders include phosphates such as alkali metal polyphosphates , and alkali or alkaline earth metal silicates, carbonates, and bicarbonates, as well as water- insoluble aluminosilicate zeolite, such as zeolite A.
  • Sodium tripolyphosphate is especially preferred but other phosphate builders such as tetrasodium pyrophosphate can also be used. Mixtures of sodium tripolyphosphate and sodium carbonate as disclosed in U.S. Patent 4,842,769 are also useful.
  • the zeolites useful in the present invention include the crystalline, amorphous and mixed crystalline-amorphous zeolites of either natural or synthetic origin. It is preferred that the zeolites rapidly and effectively counteract hardness cations, such as calcium, magnesium, iron and the like to soften the wash water before such hardness ions adversely react with any other components of the detergent composition.
  • the preferred zeolites have a high calcium ion exchange capacity, normally from about 200 to 400 or more, milliequivalents of calcium carbonate hardness per gram of the aluminosilicate ("meq./g.”). It is preferred that the zeolite used has a calcium capacity between about 250 to 350 meq./g.
  • the finely divided synthetic zeolite builder particles preferred in the practice of this invention will have the formula
  • the water insoluble crystalline aluminosilicates used are often characterized by having a network of substantially uniformly sized pores in the range of about 3 to 10 Angstroms, often being about 4A (normal) . This size is determined by the unit structure of the zeolite crystal.
  • the zeolite should be an univalent cation- exchanging zeolite, i.e., it should be an aluminosilicate of an univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, ammonium or hydrogen.
  • the univalent cation of the zeolite molecular sieve is an alkali metal cation, preferably sodium or potassium and most preferably sodium.
  • Crystalline zeolites that are good ion exchangers for use in the invention include zeolites of the following crystalline structure groups: A, X, Y, L, mordenite and erionite.
  • the A, X and Y types are preferred.
  • These crystalline types of zeolites are well-known in the art and are described in Zeolite Molecular Sieves by Donald W. Beck, published in 1974 by John Wiley & Sons. Typical commercially available zeolites of the types mentioned above are listed in Table 9.6, at pages 747-749, of the Beck text, which table is incorporated herein by reference.
  • the builder is used at generally low levels of from about 0 to about 25 wt% of the detergent composition, more preferably from about 0 to 10 wt% of said composition.
  • compositions of the invention contain one or more enzymes which are active against biodegradable stains, e.g., starches, vegetable and blood, and which are also active at a pH of about 5 to about 12.
  • the present invention allows the use of enzymes which ordinarily would not be active at a wash water pH of below about 7.5 but which become active at a lower pH in the present composition because of the presence of the water soluble polymer component .
  • Enzymes which may be used include amylolytic enzymes (alpha amylases) , alkaline and neutral proteases, lipolases, cellulases and the like, and mixtures thereof .
  • Alkaline or neutral proteolytic enzymes suitable for the present composition include the various commercial liquid enzyme preparations which have been adapted for use in detergent compositions. Enzyme preparations in powdered form are also useful although, as a general rule, less convenient for incorporation into a built liquid detergent composition.
  • suitable liquid enzyme preparations include "Alcalase” and “Savinase”, trademarked products sold by Novo Industries, Copenhagen, Denmark, and "Maxatase”, “Maxacal”, “Maxaperm” and “AZ-Protease” sold by Gist-Brocades, Delft, The Netherlands.
  • alpha-amylase liquid enzyme preparations are those sold by Novo Industries and Gist-Brocades under the tradenames "Termamyl” and “Maxamyl", respectively.
  • Another enzyme preparation which may be used is a powdered enzyme preparation containing alpha-amylase and a mixture of alkaline and neutral proteases available as CRD- Protease from the Monsanto Co of St. Louis, Missouri.
  • the enzymes are normally present in the composition at a level of from about 0.01 up to about 5 wt%, more preferably from about 0.1 to 2 wt%.
  • composition may also contain a suitable stabilizer system for the enzyme such as up to 1 wt% calcium chloride or the combination of boric acid, boric oxide or alkali metal borate and water soluble calcium salt.
  • a suitable stabilizer system for the enzyme such as up to 1 wt% calcium chloride or the combination of boric acid, boric oxide or alkali metal borate and water soluble calcium salt.
  • An optional, but often preferred additive is a higher fatty acid, which may be saturated or unsaturated, and may contain from about 10 to about 22 carbon atoms, preferably from about 12 to 20 carbon atoms. Oleic acid is especially preferred in amounts of from 0.1 to about 10% by weight of the composition.
  • These higher fatty acids function in the detergent compositions as anti-foaming agents and also function as soap surfactants in combination with neutralizing cations, e.g., sodium or potassium, present in the composition. They may be used alone for this anti-foaming function but are often used in combination with polysiloxane (silicone) anti- foaming agents.
  • the silicone anti-foaming agents will generally be present in minor amounts compared to the fatty acid. Suitable ratios (by weight) of the fatty acid anti-foaming agent to silicone anti- foaming agent may range from about 100:1 to 1:10, preferably 50:1 to 1:1, especially 30:1 to 2:1.
  • the present compositions may also contain one or more softening components known in the art .
  • Suitable softeners include swelling bentonite clays such as sodium and calcium montmorillonites, sodium saponites and sodium hectorites. These may be present in the detergent composition at levels of from about 0.5 to 20wt%, more preferably from about 5 to 15 wt%.
  • compositions of the invention may also be present in the compositions of the invention, for example, soil-suspending agents, thickening agents, sequesterants such as salts of ethylene diamine tetraacetic acid or analogous phosphonic acid salts, hydrotropes, corrosion inhibitors, dyes, perfumes, optical brighteners, suds boosters, germicides, e.g., quaternary ammonium salts, preservatives, e.g., quaternium 15, anti-tarnishing agents, opacifiers, oxygen- liberating bleaches such as sodium perborate or percarbonate with or without bleach precursors, buffers and the like.
  • sequesterants such as salts of ethylene diamine tetraacetic acid or analogous phosphonic acid salts, hydrotropes, corrosion inhibitors, dyes, perfumes, optical brighteners, suds boosters, germicides, e.g., quaternary ammonium salts, preservatives, e.g.,
  • Such other conventional materials may be used in the amounts they are normally used generally up to about 5% by weight, more preferably up to about 3% by weight, although higher amounts which do not interfere with the stability of the composition or give rise to an unacceptably high pH may be used, if desired.
  • compositions of the present invention may be in liquid or in granular form.
  • the liquid carrier for the liquid compositions of this invention is preferably water alone, but an aqueous carrier containing minor amounts of a lower alcohol, such as ethanol or isopropanol, may also be used in some cases.
  • water levels may be up to about 90% by weight of the composition, for example, from about 20% to about 90%, preferably from about 20% to 70%, by weight.
  • the water may be deionized, but usually tap water is sufficient.
  • the viscosity of the liquid composition is normally in the range of about 800 to 10,000 centipoises, preferably 2,000- 7,000 centipoises, but products of other suitable viscosities may also be useful.
  • the liquid detergent is pourable, stable, nonseparating and uniform.
  • pH modifiers such as water soluble bases, e.g., NaOH, KOH, amines, or ammonia, will be added to obtain the desired pH level.
  • the preferred pH will range from about 5 up to 7.5, more preferably from about 5.0 up to less than 7.0 and most preferably from about 5.5 up to 6.9.
  • the detergent composition is in the form of a liquid, the liquid will also exhibit a pH within these specified ranges.
  • Powder or granular forms of the present compositions may be prepared by conventional granulation techniques, such as spray drying, wherein a liquid formulation (crutcher slurry) is spray dried and the resulting granular product collected.
  • the crutcher slurry also preferably will contain one or a mixture of granulation aids such as sodium sulfate, silicates, clays and other well known material as such as disclosed in U.S. Patents 5024778 and 5332513.
  • the amount of such granulation aids will generally range from about 10 to 50 wt%.
  • the water content of such granular detergents generally ranges from about 5 to 15 wt%.
  • compositions of this invention are suitable for use as laundry detergents, dish washer detergents, hard surface cleaners, shampoos, body lotions and the like and may be modified by inclusion of specific known ingredients to accommodate these applications, e.g., dispersing agents, skin conditioning agents, anti-dandruff agents and the like.
  • compositions in accordance with the invention may be used to formulate compositions in accordance with the invention.
  • a portion of the aqueous medium may be added to a mixing vessel and the surfactant components, when present, may be mixed therewith in any suitable order, followed by addition of builder, acidic components and sufficient neutralizing base, e.g., KOH, to produce the desired pH.
  • Softeners, enzyme, water soluble polymer, minors, e.g., perfume, optical brighteners, foam control agents, and the balance of water may then be added and mixing continued to form an aqueous dispersion.
  • Granular forms of the detergent may be prepared by spray drying a liquid formulation to a water content of up to about 15 wt%, followed by the addition of any volatiles after spray dry processing.
  • compositions of the invention are generally added to wash water at levels in the range of about 0.05 to 0.30 wt%.
  • compositions in the form of liquids are preferably added at levels in the range of from about 60 to 240 ml per load; powder compositions are preferably used at levels of about 60 to 300 grams per load.
  • Formulation A is typical of a conventional detergent formulation containing enzyme, zeolite builder, clay softener and formulated to a pH of about 8.2.
  • Formulation B a comparative composition, is free of Zeolite builder and contains citric acid (neutralized to potassium citrate) and is adjusted to a pH of about 6.0.
  • Formulation C is within the present invention and is similar to Formulation B except that it contains a water soluble polyethylene glycol polymer having a molecular weight of about 4000 (PEG 4000) . Ingredients were mixed in the order shown in Table 1.
  • the difference between prototypes B and C is the presence of 0.7 wt% of the polymer linker in C.
  • MIELETM European tumble type front loading washing machine
  • Figs. 1 and 2 show respectively the greasy (sensitive to surfactants) and the bio-stains (sensitive to enzymes) removal performance of these products.
  • the detergency expresses the difference ( ⁇ Rd) between the reflectance Rd before washing and the reflectance Rd after washing.
  • the term "Krefeld” refers to an artificial, particulate soiled cotton fabric (code WFK 10c) supplied by wfK-Testgewebe G bh of Germany.
  • Figure 2 shows the cleaning performances of enzyme sensitive stains between the conventional product A and the composition of the invention C. It can be observed that, due to the inappropriate medium - low pH - the enzymes in formulation B are not fully active resulting in a strong drop of soil removal performance on all stains: cocoa, groundnut/milk and blood/milk/ink. The incorporation of 0.7% PEG 4000 as in formulation C again corrects this tremendous weakness .
  • Formulation D is typical of a conventional powder formulation containing anionic surfactant
  • Formulation E is a comparative composition similar to D except that it contains "SOKALAN” DCS from BASF corporation, which is a powdered mixture of adipic, glutaric and succinic acids, added to impart an acidic wash water pH after the powder is dispersed in the wash water medium.
  • Formulation F is within the scope of the present invention and is similar to Formulation E except that it also contains the polyethylene glycol linker polymer. The ingredients were mixed in the order shown in Table 2.
  • Example 3 Two liquid detergent formulations were prepared having a composition, by weight, as shown in Table 4. The description of the particular surfactants, polymer and enzyme is the same as that noted in Table 1 of Example 1.
  • Formulation G is a conventional detergent liquid formulation containing a low level of active ingredients, below 20% by weight of the composition.
  • Formulation H is in accordance with the invention and is similar to Formulation G except that it contains polyethylene glycol polymer as a linker.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des produits formulés pour diverses applications de détachage et d'entretien de textiles ainsi que pour le nettoyage des surfaces dures. On peut utiliser ces produits dans l'eau de lavage avec une large gamme de pH dans le bain de lavage, ou dans le cycle de rinçage d'une machine à laver automatique personnelle. Ces produits renferment une ou plusieurs enzymes en association avec au moins un polymère organique hydrosoluble, tel que le polyéthylèneglycol. Ces produits contiennent de préférence un agent de surface anionique.
PCT/US1998/027127 1997-12-29 1998-12-21 Produits a action detachante amelioree contenant des enzymes WO1999033946A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20062/99A AU2006299A (en) 1997-12-29 1998-12-21 Enzyme-containing compositions having improved cleaning power

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US99951497A 1997-12-29 1997-12-29
US08/999,514 1997-12-29

Publications (1)

Publication Number Publication Date
WO1999033946A1 true WO1999033946A1 (fr) 1999-07-08

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PCT/US1998/027127 WO1999033946A1 (fr) 1997-12-29 1998-12-21 Produits a action detachante amelioree contenant des enzymes

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AU (1) AU2006299A (fr)
WO (1) WO1999033946A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2607469A1 (fr) * 2011-12-20 2013-06-26 Unilever PLC Détergent liquide avec protéase et lipase
CN104194963A (zh) * 2014-09-19 2014-12-10 江苏万淇生物科技有限公司 无酶稳定剂的高浓缩含酶洗衣液
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
WO2022235720A1 (fr) * 2021-05-05 2022-11-10 The Procter & Gamble Company Procédés de fabrication de compositions de nettoyage et de détection de salissures
CN116194562A (zh) * 2022-12-21 2023-05-30 广州洁生日化有限公司 一种洗涤片

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185991A (en) * 1986-01-30 1987-08-05 Colgate Palmolive Co Liquid laundering composition with detergent softening properties
WO1994010284A1 (fr) * 1992-10-23 1994-05-11 The Procter & Gamble Company Detergents granulaires contenant une enzyme protease et un agent de blanchiment
EP0781839A1 (fr) * 1995-12-29 1997-07-02 Colgate-Palmolive Company Compositions contenant des enzymes ayant un pouvoir nettoyant amélioré

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185991A (en) * 1986-01-30 1987-08-05 Colgate Palmolive Co Liquid laundering composition with detergent softening properties
WO1994010284A1 (fr) * 1992-10-23 1994-05-11 The Procter & Gamble Company Detergents granulaires contenant une enzyme protease et un agent de blanchiment
EP0781839A1 (fr) * 1995-12-29 1997-07-02 Colgate-Palmolive Company Compositions contenant des enzymes ayant un pouvoir nettoyant amélioré

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2607469A1 (fr) * 2011-12-20 2013-06-26 Unilever PLC Détergent liquide avec protéase et lipase
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
US10723974B2 (en) 2012-09-10 2020-07-28 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
CN104194963A (zh) * 2014-09-19 2014-12-10 江苏万淇生物科技有限公司 无酶稳定剂的高浓缩含酶洗衣液
CN104194963B (zh) * 2014-09-19 2017-07-07 江苏万淇生物科技有限公司 无酶稳定剂的高浓缩含酶洗衣液
WO2022235720A1 (fr) * 2021-05-05 2022-11-10 The Procter & Gamble Company Procédés de fabrication de compositions de nettoyage et de détection de salissures
EP4095223A1 (fr) * 2021-05-05 2022-11-30 The Procter & Gamble Company Procédés de fabrication de compositions de nettoyage et de détection de salissures
CN116194562A (zh) * 2022-12-21 2023-05-30 广州洁生日化有限公司 一种洗涤片
WO2024130580A1 (fr) * 2022-12-21 2024-06-27 广州洁生日化有限公司 Feuille de détergent pour lessive
GB2629552A (en) * 2022-12-21 2024-10-30 Guangzhou Joyson Cleaning Products Co Ltd Laundry detergent sheet
GB2629552B (en) * 2022-12-21 2025-04-23 Guangzhou Joyson Cleaning Products Co Ltd Detergent sheet

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