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WO1995007970A1 - Produit pour laver la vaisselle contenant des enzymes lipolytiques et proteolytiques - Google Patents

Produit pour laver la vaisselle contenant des enzymes lipolytiques et proteolytiques Download PDF

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Publication number
WO1995007970A1
WO1995007970A1 PCT/US1994/009899 US9409899W WO9507970A1 WO 1995007970 A1 WO1995007970 A1 WO 1995007970A1 US 9409899 W US9409899 W US 9409899W WO 9507970 A1 WO9507970 A1 WO 9507970A1
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composition
alkyl
surfactant
compositions
weight
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PCT/US1994/009899
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English (en)
Inventor
Peter Robert Foley
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The Procter & Gamble 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
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP7501091A priority Critical patent/JPH09502462A/ja
Priority to AU77191/94A priority patent/AU7719194A/en
Priority to EP94927990A priority patent/EP0713525A1/fr
Publication of WO1995007970A1 publication Critical patent/WO1995007970A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • composition faces the challenge of deriving a formulation which meets a number of distinct consumer relevant
  • such a composition should be effective at removing soils from dirty "dishes" when used in a manual dishwashing process.
  • the term "dishes” is used herein in a generic sense, and encompases essentially any items which may be found in a dishwashing load, including chinaware,
  • glassware plasticware, hollowware and cutlery, including silverware.
  • the soils encountered in dishwashing will largely but not exclusively be food based. Particularly difficult soils to remove would include greasy soils, burnt or baked on food soils, dried on food soils, highly coloured soils derived from eg : highly coloured vegetables such as beetroot and tomato, as well as non-food soils such as lipstick on the rims of glasses or nicotine stains on saucers which have been used as ashtrays.
  • the dishwashing detergent should act such as to suspend these soils in the wash solution and thus prevent their redeposition onto the dishes, or onto the surface of the sink.
  • the manual dishwashing composition should be high sudsing and the sudsing should persist throughout the washing process.
  • the sudsing is used as an indicator by the person doing the washing up that the wash solution still contains active detergent ingredients. When the sudsing subsides the sink will generally be emptied and a fresh wash solution prepared.
  • the persistence of suds throughout the washing process is measured in the industry by various suds mileage indices.
  • the manual dishwashing composition should also be mild to the skin, and particularly to the hands. That is, it should not cause skin dryness, chapping or rougness when in contact with the skin. Such skin dryness, chapping or roughness largely results from the removal of natural oils, specifically epidermal lipids, from the skin.
  • the manual dishwashing composition should desirably be
  • compositions are formulated in a distinct way from, for example, machine dishwashing, laundry, and hard surface cleaner
  • Manual dishwashing compositions are usually unbuilt, and may contain added levels of Ca and Mg to aid cleaning performance. Laundry and automatic dishwashing
  • compositions typically contain high levels of builder.
  • Manual dishwashing compositions typically contain no bleaching components, which are by contrast common
  • Manual dishwashing detergent typically contain high levels of high-sudsing surfactant and often suds booster.
  • Machine laundry and dishwashing compositions are desirably low foaming and typically contain lower levels of surfactant.
  • Manual dishwashing compositions are formulated to perform well at near neutral pH.
  • Machine dishwashing and laundry compositions are typically alkaline with a pH of usually 9-11.
  • Bleach-containing hard-surface cleaner compositions are often acidic with a pH of less than 6.
  • composition is most usually a surfactant system, which will typically comprise from 5 to 80% by weight of the
  • the surfactant system has a primary soil removal purpose, and also acts so as to suspend the soils in solution and prevent redeposition of these soils.
  • the surfactant system should be effective at removing and suspending greasy soils.
  • Amylolytic, proteolytic and lipolytic enzymes are common components of laundry and machine dishwashing compositions, formulated in either granular or fluid (liquid/gel) form. Enzymes are not commonly recognized to be of use in manual dishwashing compositions.
  • Amylolytic enzymes, or amylases act to catalyse the hydrolysis of starch.
  • Proteolytic enzymes, or proteases act to catalyse the hydrolysis of peptide bonds in proteins.
  • Lipolytic enzymes, or lipases act to catalyse the hydrolysis of fats or oils, which comprise esters of glycerol and fatty acids, into these glycerol and fatty acid components.
  • proteolytic enzyme in compositions specifically formulated for use in manual dishwashing.
  • the specific utility of the combination of lipolytic enzyme with proteolytic enzyme in such compositons has not previously been recognized in the art. Indeed, the extensive art relating to the use of such enzymes, in combination, in machine dishwashing and laundry compositions, but neglecting to provide clear teaching of their utility in manual dishwashing, would seem to imply a prejudice against the use of these enzymes in manual dishwashing compositions.
  • lipolytic enzyme which acts such as to hydrolyse grease
  • lipolytic enzyme acts such as to hydrolyse grease
  • a further reason for the implied prejudice might rest in the belief that the fatty acid products obtained when oils or fats are broken down by lipolytic enzyme may act as suds suppressors, thereby impending the desired high sudsing performance.
  • containing compositions are employed in a wash process including a soaking step.
  • the soaking step can involve immersing the soiled articles in a dilute solution
  • a highly concentrated solution of the composition can be applied directly to the surface of the dishes, being allowed to remain there for a period of time, prior to subsequent rinsing/washing steps.
  • manual dishwashing compositions containing proteolytic enzyme and lipolytic enzyme may be formulated which have desirable skin mildness properties.
  • composition containing certain surfactant systems which act such as to stabilize the enzymes.
  • composition containing a surfactant system, lipolytic enzyme and proteolytic enzyme suitable for use in a manual dishwashing method.
  • composition is in the form of a liquid or a gel.
  • composition contains no builder salts.
  • composition contains no bleaching
  • composition contains from 5% to 80% by weight of said surfactant system, wherein the surfactant system comprises surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants.
  • surfactant system comprises surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants.
  • said composition is high sudsing.
  • the first essential component of the compositions in accordance with the invention is lipolytic enzyme (lipase) which is preferably present at levels of active lipolytic enzyme of from 0.001% to 2% by weight, more preferably 0.005% to 1% by weight, most preferably from 0.01% to 0.5% by weight of the compositions.
  • lipolytic enzyme lipase
  • the lipase is preferably bacterial in origin being
  • Lipase from chemically or genetically modified mutants of these strains are also included herein. Mixtures of lipase from various strains are included herein, though not preferred.
  • a preferred lipase is derived from Pseudomonas
  • pseudoalcaligenes which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S.
  • Lipases herein are preferably compatible with surfactants. They are preferably stable in the present compositions and improve cleaning when they are included in the present compositions.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced by Pseudomonas flluorescens. This lipases described in Japanese Patent Application 53-20487, laid open February 24, 1987. It is available under the trade name Lipase P Amano. A method for testing immunological cross-reaction with Amano P antibody is described in U.S. Patent 4,707,291, Thorn et al, issued November 17, 1987.
  • a lipase unit is defined as the amound of lipase which produces 1 umol of titratable butyric acid per minute in a pH stat, where pH is 7.0, temperature is 30°C, and
  • substrate is an emulsion of ributyrin and gum arabic in the presence of Ca++ and NaCl in phosphate buffer.
  • the second essential component of the compositions in accordance with the invention is proteolytic enzyme
  • proteolytic enzyme which is preferably present at a level of from 0.005% to 2% active enzyme by weight of the composition.
  • the proteolytic enzyme is preferably incorporated at a level such that the weight ratio of active lipolytic enzyme to active proteolytic enzyme is from 20:1 to 1:20,
  • Preferred commercially available protease enzymes include those sold under the tradenames Alcalase and Savinase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands).
  • Amylolytic (amylase) enzyme may be incorporated into the compositions in accordance with the invention at a
  • composition preferred level of from 0.005% to 2% active enzyme by weight of the composition.
  • Preferred amylases include, for example, alpha-amylases obtained from a special strain of B licheniforms, described in more detail in GB 1,269,839 (Novo). Preferred
  • amylases include for example,
  • Rapidase sold by International Bio-Synthetics Inc
  • Termamyl sold by Novo Industries A/S.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
  • the compositions herein may further comprise from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and
  • Suitable chlorine scavenger anions are widely available, indeed ubiquitous, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as
  • ethylenediaminetetracetic acid or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
  • Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.
  • the chlorine scavenger function can be performed by several of the ingredients separately listed under better recognized functions, (e.g., other components of the invention
  • formulation chemists generally recognize that combinations of reducing agents such as thiosulfate with strong oxidizers such as percarbonate are not wisely made unless the reducing agent is protected from the oxidizing agent in solid-form composition.
  • reducing agents such as thiosulfate
  • strong oxidizers such as percarbonate
  • ammonium salts such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such
  • Detergent compositions in accord with the invention will preferably be formulated such that during use in aqueous cleaning operations, particularly those where a dilute solution of the detergent composition is employed, the wash solution will have a pH of between about 5.0 and about 8.0.
  • Compositions for use in such aqueous cleaning operations themselves preferably have a pH as a 1% solution in water at 20°C of between about 5.5 and about 8.5, most preferably between about 6.8 and ⁇ bout 7.8.
  • compositions may be formulated for use in dishwashing methods in which the detergent composition is applied to the dishes in
  • compositions for use in such methods may be formulated to have a pH, as a 1% solution in water, of from 3 to 6, preferably from 3.5 to 4.5.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art. Dilute hydrochloric acid is preferred for downward pH adjustment, and sodium hydroxide for upward pH adjustment.
  • compositions of the invention contain a surfactant system at a level of from 5 % to 80 %, preferably from 10 % to 60 %, most preferably from 15 % to 50 % by weight of the composition.
  • the surfactant system is preferably formulated to be compatible with the enzyme components.
  • the surfactant system is most preferably formulated such that it promotes, or at least does not degrade, the stability of the enzymes in these
  • the surfactant system comprises surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants, and any mixtures thereof.
  • the surfactant system comprises from 5% to 95% by weight, more preferably from 30% to 70% by weight of the surfactant system of anionic surfactant, and from 5% to 95% by weight, more preferably from 30% to 70% by weight of the surfactant system of nonionic surfactant.
  • the weight ratio of nonionic surfactant to anionic surfactant is preferably greater than 1:1.
  • the anionic surfactant may be essentially any anionic surfactant, including anionic sulfate, sulfonate or carboxylate surfactant.
  • Anionic sulfate surfactant is essentially any anionic surfactant, including anionic sulfate, sulfonate or carboxylate surfactant.
  • the anionic sulfate surfactant may be any organic sulfate surfactant. It is preferably selected from the group consisting of C 10 -C 16 alkyl sulfate which has been
  • Alkyl ethoxy sulfate surfactants suitable for use herein comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C 10 -C 16 alcohol with an average of from 0.5 to 20, preferably from 0.5 to 12, ethylene oxide groups.
  • ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.
  • the counterion for the anionic sulfate surfactant component is preferably selected from calcium, sodium, potassium, magnesium, ammonium, or alkanol-ammonium, and mixtures thereof, with calcium and magnesium being preferred for cleaning and sudsing respectively.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include, for example, the salts (e.g. alkali metal salts) of C 9 -C 20 linear alkylbenzene sulfonates, C 8 -C 22 primary or secondary alkane sulfonates, C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, paraffin sulfonates, and any mixtures thereof.
  • Anionic alkyl ethoxy carboxylate surfactant e.g. alkali metal salts
  • Alkyl ethoxy carboxylates suitable for use herein include those with the formula RO(CH 2 CH 2 O)x CH 2 COO-M + wherein R is a C 12 to C 16 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20%, preferably less than 15%, most preferably less than 10%, and the amount of material where x is greater than 7, is less than 25%, preferably less than 15%, most preferably less than 10%, the average x is from 2 to 4 when the average R is C 13 or less, and the average x is from 3 to 6 when the average R is greater than C 13 , and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred alkyl ethoxy carboxylates
  • Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include those having the formula:
  • R is a C 6 to C 18 alkyl group, x is from 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R 1 or R 2 is a succinic acid radical or hydroxysuccinic acid radical, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Anionic secondary soap surfactant is selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R 1 or R 2 is a succinic acid radical or hydroxysuccinic acid radical, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • surfactants useful herein are those which contain a carboxyl unit connected to a secondary carbon. It is to be understood herein that the secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates.
  • the secondary soap surfactants should contain no ether linkages, no ester linkages and no hydroxyl groups. There should be no nitrogen atoms in the head-group (amphiphilic portion).
  • the secondary soap surfactants usually contain 11-13 total carbon atoms, although slightly more (e.g., up to 16) can be tolerated.
  • a highly preferred class of secondary soaps useful herein comprises the secondary carboxyl materials of the formula R 3 CH(R 4 )COOM, wherein R 3 is CH 3 (CH 2 )x and R 4 is CH 3 (CH 2 )y, wherein y can be 0 or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most preferably 8.
  • Another class of secondary soaps useful herein comprises those carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the formula R 5 -R 6 -COOM, wherein R 5 is C 7 -C 10 , preferably C 8 -C 9 , alkyl or alkenyl and R 6 is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R 5 can be in the ortho, meta or para position relative to the
  • Still another class of secondary soaps comprises secondary carboxyl compounds of the formula
  • the species M can be any suitable, especially water-solubilizing, counterion, e.g., H, alkali metal, alkaline earth metal, ammonium, alkanolammonium, di- and tri- alkanolammonium, and C 1 -C 5 alkyl substituted ammonium.
  • Sodium is convenient, as is diethanolammonium.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
  • anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of
  • sulfosuccinate especially saturated and unsaturated C 12 -C 18 monoesters
  • diesters of sulfosuccinate especially saturated and unsaturated C 6 -C 14 diesters
  • N-acyl especially saturated and unsaturated C 12 -C 18 monoesters
  • sarcosinates sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH 2 CH 2 O)] k C 2 COO-M + wherein R is a C 8 -C 22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated
  • Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.
  • Nonionic polyhvdroxy fatty acid amide surfactant Nonionic polyhvdroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula:
  • R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, or a mixture thereof, preferable C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight-chain C 7 -C 19 alkyl or alkenyl, more preferably straight-chain C 9 -C 17 alkyl or alkenyl, most preferably straight-chain C 11 -C 17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup high fructose corn syrup
  • high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH2-OH 2 , -CH(CH 2 OH)-(CHOH) n -, -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR')(CHOH)-CH 2 OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylate
  • glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
  • R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1- deoxymannityl, 1-deoxymaltotriotityl, etc.
  • the most preferred polyhydroxy fatty acid amide has the general formula:
  • R 2 is a straight chain C 11 -C 17 alkyl or alkenyl group.
  • polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein.
  • the polyethylene oxide condensates are
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
  • the alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
  • Most preferred are the condensation products of alcohols having an alkyl group containing from 10 to 14 carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12 -C 14 Primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C 12 -C 13 linear alcohol with 6.54 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and KyroTM EOBN (the condensation product of C 13 -C 15 alcohol with 9 moles ethylene oxide), marketed by The Procter
  • hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containng from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • alkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16, carbon atoms.
  • the alkyl group is a
  • the alkyl group can contain up to about 3 hydroxyl groups and/or the
  • polyalkyleneoxide chain can contain up to about 10,
  • alkyl polysaccharides are octyl, nonyldecyl,
  • undecyldodecyl tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galatoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
  • the preferred alkylpolyglycosides have the formula:
  • R 2 O(C n H 2n O)t(glycosyl) x
  • R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
  • Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
  • Fatty acid amide surfactants suitable for use herein are those having the formula: O
  • R 6 C N(R 7 )2 wherein R 6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and -(C 2 H 4 O) x H, where x is in the range of from 1 to 3.
  • Ampholytic surfactants can be incorporated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for examples of ampholytic
  • Suitable amphoteric surfactants for use herein include the alkyl amphocarboxylic acids of the formula:
  • R is a C 8 -C 18 alkyl group, and R i is of the general formula:
  • R 1 R 1 wherein R 1 is a (CH 2 ) x COOM or CH 2 CH 2 OH, and x is 1 or 2 and M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred R alkyl chain length is a C 10 to C 14 alkyl group.
  • amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the
  • amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • Amine oxides useful, as amphoteric surfactants, in the present invention include those compounds having the formula:
  • R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms;
  • R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof;
  • x is from 0 to 3, preferably 0;
  • each R 5 is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1, ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxyethyl amine oxides.
  • examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide,
  • dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide Preferred are C 10 -C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions herein. See U.S. Patent No.
  • the betaines useful, as zwitterionic surfactants, in the present invention are those compounds having the formula R(R') 2 N + R 2 COO- wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group or C 10-16 acylamido alkyl group, each R 1 is typically C 1 -C 3 alkyl, preferably
  • methyl,m and R 2 is a C 1 -C 5 hydrocarbyl group, preferably a C 1 -C 3 alkylene group, more preferably a C 1 -C 2 alkylene group.
  • suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl
  • acylamidohexyldiethyl betaine 4[C 1 acylmethylamidodiethylammonio]-1-carboxybutane; C 16-18 acylamidodimethylbetaine; C 12-16 acylamidopentanediethylbetaine; [C 12-16 acylmethylamidodimethylbetaine.
  • betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10 - 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • R is a hydrocarbon group having from 7 to 22 carbon atoms
  • A is the group (C(O))
  • n is 0 or 1
  • R 1 is hydrogen or a lower alkyl group
  • x is 2 or 3
  • y is an integer of 0 to 4
  • Q is the group -R 2 COOM wherein R 2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium
  • B is hydrogen or a group Q as defined.
  • the sultaines useful in the present invention are those compounds having the formula (R(R 1 ) 2 N + R 2 SO 3 - wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10 -C 16 alkyl group, more preferably a C 12 -C 13 alkyl group, each R i is typically C 1 -C 3 alkyl, preferably methyl, and R 2 is a C 1 -C 6
  • hydrocarbyl group preferably a C 1 -C 3 alkylene or
  • hydroxyalkylene group preferably, hydroxyalkylene group.
  • compositions of the invention will most preferably contain an organic solvent system present at levels of from 1% to 30% by weight, preferably from 3% to 25% by weight, more preferably form 5% to 20% by weight of the
  • Suitable organic solvent for use herein has the general formula
  • R is an alkyl, alkenyl, or alkyl aryl group having from 1 to 8 carbon atoms, and n is an integer from 1 to 4.
  • R is an alkyl group containing 1 to 4 carbon atoms, and n is 1 or 2.
  • Especially preferred R groups are n-butyl or isobutyl.
  • Water-soluble CARBITOL solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water- soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol.
  • Water-soluble CELLOSOLVE solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2-butoxyethoxyethanol being preferred.
  • Suitable solvents are benzyl alcohol, and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethl-1,3-pentanediol.
  • polyethylene glycols are also suitable solvents for use herein.
  • the alkane mono and diols especially the C 1 -C 6 alkane mono and diols are suitable for use herein.
  • the C1-C4 dihydric alcohols including propylene glycol, are preferred. It is preferred that monohydric alcohols, especially ethanol, are present at less than 6% by weight of the composition.
  • compositions of the present invention may comprise from 1% to 20%, preferably from 2% to 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, complex betaines, and certain nonionics.
  • a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, complex betaines, and certain nonionics.
  • Preferred amides are C 8 -C 20 alkyl mono- or di-C 2 -C 3
  • alkanolamides especially monoethanolamides
  • Preferred suds enhancing agents are C 10-18 acyl amide alkyl dimethyl amine oxides, betaines, condensation products of aliphatic alcohols with ethylene oxides, and
  • alkylpolysaccharides and mixtures thereof.
  • a hydrotrope is typically added to the compositions of the present invention, and may be present at levels of from 0.5% to 10%, preferably from 1% to 5%, by weight.
  • Useful hydrotropes include sodium, potassium, and ammonium xylene sulfonates, sodium, potassium, and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof.
  • polycarboxylates include polycarboxylates. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties.
  • hydrotropes are alkylpolyethoxy
  • polycarboxylate surfactants of the type as previously described herein.
  • An example of a commercially available alkylpolyethoxy polycarboxylate which can be employed herein is POLYTERGENT C, Olin Corporation, Cheshire, CT.
  • Another compound useful as a hydrotrope is alkyl
  • R is a C 8 to C 18 alkyl group
  • x is from 1 to 2
  • M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions.
  • the preferred alkyl chain length (R) is a C 10 to C 14 alkyl group and the dicarboxylic acid functionally is diacetic acid and/or dipropionic acid.
  • alkyl amphodicarboxylic acid is the amphoteric surfactant Miranol R 2CM Cone.manufactured by Miranol, Inc., Dayton, NJ.
  • compositions of the present invention are particularly useful when formulated to contain a lime soap dispersant compound which acts to disperse any insoluble lime soap salts which may be formed between the fatty acids produced by the lipolytic hydrolysis of fats/oils and calcium ions in the wash soluble, thereby preventing the deposition of these salts as spots or films on the articles in the wash, or as an unseemly ring around the rim of the sink.
  • Certain lime soap dispersant compounds may also provide improved product stability particularly where the product is formulated as a liquid product containing calcium ions.
  • a lime soap dispersant compound herein is defined as a compound, which has a lime soap dispersing power (LSDP), as of no more than 8, preferably no more than 7, most
  • the lime soap dispersant compound is typically present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.
  • compositions containing polyhydroxy fatty acid amide may be included in the detergent compositions herein. It has been found for compositions containing polyhydroxy fatty acid amide that the presence of calcium greatly improves the cleaning of greasy soils. This is especially true when the compositions are used in softened water, which contains few divalent ions.
  • the calcium ions can, for example, be added as a chloride, hydroxide, oxide, formate or acetate, or nitrate salt.
  • the calcium can be added as a calcium oxide or calcium
  • the calcium ions may be present in the compositions as salts.
  • the amount of calcium ions present in compositions of the invention may be dependent upon the amount of total anionic surfactant present herein.
  • the molar ratio of calcium ions to total anionic surfactant is preferably from 1:0.1 to 1:25, more preferably from 1:2 to 1:10, for compositions of the invention.
  • Malic, maleic or acetic acid, or their salts, or certain lime soap dispersant compounds may be added to a
  • composition formulated to contain calcium to provide good product stability, and in particular to prevent the precipitation of insoluble calcium salts.
  • calcium is present, malic, maleic or acetic acid, or their salts can be added at levels of from 0.05% to 10% of the composition and a molar ratio with calcium of from 0.01:1 to 1:10.
  • magnesium ions are preferably added to the liquid detergent compositions of the invention for improved product stability, as well as improved sudsing.
  • the magnesium can be added by neutralization of the acid with a magnesium oxide or magnesium hydroxide slurry in water. Calcium can be treated similarly. This technique minimises the addition of chloride ions, which reduces corrosive properties.
  • the neutralized surfactant salts and the hydrotrope are then added to the final mixing tank and any optional ingredients are added before adjusting the pH.
  • compositions are fluid in nature, being for example liquids, gels, creams, foams or mousses.
  • Liquid compositions are fluid in nature, being for example liquids, gels, creams, foams or mousses.
  • the detergent compositions of the present invention are liquid detergent compositions. These preferred liquid detergent compositions typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixture of water and organic solvent.
  • a liquid carrier e.g., water, preferably a mixture of water and organic solvent.
  • the detergent compositions of the present invention may also be in the form of gels. Such compositions are
  • polyakenyl polyether typically formulated in polyakenyl polyether and having a molecular weight of from about 750,000 to about 4,000,000.
  • polycarboxylate polymer thickeners are the Carbopol 600 series resins available from B.F. Goodrich. Especially preferred are Carbopol 616 and 617. It is believed that these resins are more highly cross-linked than the 900 series resins and have molecular weights between about 1,000,000 and 4,000,000. Mixtures of polycarboxylate polymers as herein described may also be used in the present invention. Particularly preferred is a mixture of Carbopol 616 and 617 series resins.
  • the polycarboxylate polymer thickener is utilized
  • polymers of the present invention are utilized with clay in the composition of the present invention, a less desirable product, in terms of phase instability, results.
  • the polycarboxylate polymer is preferably used instead of clay as a thickening/stabilizing agent in the present compositions.
  • the polycarboxylate polymer is used as a thickening agent in the compositions of the present invention, it is typically present at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 2% by weight.
  • the thickening agents are preferably used to provide a yield value of from about 50 to about 350 and most
  • the yield value is an indication of the shear stress at which the gel strength is exceeded and flow is initiated. It is measured herein with a Brookfield RVT model viscometer with a T-bar B spindle at 25° utilizing a Helipath.
  • compositions herein include dyes, perfumes and opacifiers.
  • Opacifiers such as Lytron (Morton Thiokol, Inc.), a modified polystyrene latex, or ethylene glycol distearate can be added, preferably as a last step. Lytron can be added directly as a dispersion with mixing. Ethylene glycol distearate can be added in a molten state with rapid mixing to form pearlescent crystals. Opacifiers useful herein, particularly for light duty liquids, are typically present at levels from about 0.2% to about 10%, preferably from about 0.5% to about 6% by weight.
  • soiled dishes are contacted with an effective amount, typically from about 0.5g to about 20g (per 25 dishes being treated), preferably from about 3g to about 10g, of the composition of the present invention.
  • an effective amount typically from about 0.5g to about 20g (per 25 dishes being treated), preferably from about 3g to about 10g, of the composition of the present invention.
  • the actual amount of detergent composition used will be based on the judgement of user, and will depend upon factors such as the particular product formulation of the composition, the concentration of the composition, the number of soiled dishes to be cleaned and the degree of soiling of the dishes.
  • concentrated solution of the detergent composition is applied to the surface of the dishes to be washed.
  • concentrated solution of the composition it is meant no less than a 20% by weight, preferably no less than 50% by weight product dilution, and most preferably the
  • composition is applied in undiluted form.
  • the detergent can be enabled by use of an applicator such as a sponge, cloth or brush to which detergent has previously been applied, or in an alternative and preferred process the product is sprayed on to the surface of the dishes.
  • the detergent will typically be distributed on the surface of the dishes in such a way that heavily soiled areas are more heavily dosed than those where only light soiling is present.
  • the dishes may have been pre-rinsed or pre-soaked in water prior to application of the detergent, although this is not necessary,
  • the concentrated solution of the detergent composition is allowed to remain on the surface of dishes for a period of time.
  • the precise length of this time period will depend on a number of factors including degree of soiling of the dishes, amount of detergent applied, the extent of any pre-rinsing or pre-soaking in water, and the nature of any subsequent rinsing or washing steps.
  • the dishes are subjected to a manual or machine washing or rinsing method, involving either further washing steps and use of detergent product, and/or to a manual or machine rinsing method.
  • the dishes are subjected solely to a manual or machine rinsing method.
  • the direct application method will typically comprise as a first step wetting the soiled dishes, by eg: immersing in a water bath without any liquid dishwashing detergent, or holding under a running tap.
  • a device for absorbing liquid dishwashing detergent such as a sponge, is then placed directly into a separate quantity of concentrated liquid or gel detergent composition for a period of time typically ranging from about 1 to about 5 seconds. The absorbing device, and consequently the undiluted detergent
  • composition is then contacted individually to the surface of each of the soiled dishes.
  • the absorbing device is typically contacted with each dish surface for a period of time range from 1 to 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
  • the contacting of the absorbing device to the dish surface is preferably
  • the dishes are rinsed manually by immersion in a water bath or by passing under a stream of running water, with typically further manual agitation of the dish surface.
  • the concentrated solution of detergent is applied to the surface of the dishes by any of the aforementioned means, and is allowed to remain on the dishes for an extended period of time of from 30 seconds to 24 hours, more typically from 5 minutes to 1 hour, preferably from 10 minutes to 30 minutes.
  • the dishes are subsequently subjected to a manual or machine dishwashing or rinsing method, preferably a rinsing method.
  • the composition used in the detergent pre-soak method contains suds
  • the suds suppressor at a level of from 0.01% to 15% by weight.
  • the suds suppressor may be any of these commonly known in the art including silicone suds suppressor.
  • large volume of a dilute solution of the detergent composition is employed.
  • the dishes alre preferably allowed to soak for a period of time, typically from 5 seconds to 30 minutes in the dilute solution.
  • Dilute solution washing methods include the "dilute
  • a liquid detergent composition In the typical dilute solution in sink method from about 3 ml. to 15 ml., preferably from 5 ml. to 10 ml. of a liquid detergent composition is combined with from 1,000 ml. to 10,000 ml., more typically from 3,000 ml. to 5,000 ml. of water in a sink having a volumetric capacity in the range of from 5,000 ml. to 20,000 ml., more typically from 10,000 ml. to 15,000 ml.
  • the detergent composition has a
  • surfactant concentration of from about 10 % to about 60 % by weight, preferably from about 45 % to about 50 % by weight.
  • the dishes are allowed to soak in the dilute detergent solution in the sink for a period of time of from 5 seconds to 30 minutes, preferably from 30 seconds to 10 minutes, before manual agitation.
  • the cloth, sponge or similar article may be immersed in the detergent
  • composition and water mixture prior to being contacted with the dish surface and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of the cloth, sponge or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
  • a detergent composition in a typical solution in bowl method from 1 ml. to 50 ml., prefrably from 2 ml. to 10 ml. of a detergent composition is combined with from 50 ml. to 2,000 ml., more typically from 100 ml. to 1,000 ml. of water in a bowl having a volumetric capacity in the range of from 500 ml. to 5,000 ml., more typically from 500 ml. to 2,000 ml.
  • the detergent composition has a surfactant concentration of from about 10 % to about 60 % by weight, preferably from about 15 % to about 50 % by weight.
  • the soiled dishes are immersed in the bowl containing the detergent composition and water, where they are cleaned by the soaking action of the solution, and by manual agitation of the soiled surface of the dish by contacting with a cloth, sponge or similar article.
  • the dishes are allowed to soak in the dilute detergent solution in the sink for a period of time of from 5 seconds to 30 minutes, preferably from 30 seconds to 10 minutes, before manual agitation.
  • the cloth, sponge or similar article may be immersed in the detergent
  • composition and water mixture prior to being contacted with the dish surface and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of the cloth, sponge or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
  • compositions in accord with the invention were prepared.
  • the lipase is a lipolytic enzyme sold under the tradename, lipolase, by Novo Industries A/S. Levels of active enzyme in the compositions are given. Commercial samples typically have an activity of about 2%.
  • the protease is proteolytic enzyme sold under the tradename, savinase, by Novo Industries A/S. Levels of active enzyme in the compositions are given. Commercial samples typically have an activity of about 1% to 4%.
  • compositions were prepared by mixing all of the surfactants with the exception of the glucamide.
  • the magnesium and calcium salts were then pre-dissolved into solution together with the maleic acid and added to the surfactant mixture with the remaining components. Finally the pH was trimmed to 7.3 using hydrochloric acid and the viscosity checked.

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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)
  • Enzymes And Modification Thereof (AREA)

Abstract

L'un des aspects de la présente invention porte sur un produit comprenant un système de tensioactifs ainsi que des enzymes lipolytiques et des enzymes protéolytiques et servant au lavage à la main de la vaisselle. De préférence, ledit produit se présentera sous forme de gel ou de liquide et ne contiendra ni sels (adjuvants pour détergents), ni agents de blanchiment.
PCT/US1994/009899 1993-09-14 1994-09-01 Produit pour laver la vaisselle contenant des enzymes lipolytiques et proteolytiques WO1995007970A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP7501091A JPH09502462A (ja) 1993-09-14 1994-09-01 脂肪分解およびタンパク質分解酵素を含んでなる機械式食器洗い組成物
AU77191/94A AU7719194A (en) 1993-09-14 1994-09-01 Machine dishwashing composition comprising lipolytic and proteolytic enzymes
EP94927990A EP0713525A1 (fr) 1993-09-14 1994-09-01 Produit pour laver la vaisselle contenant des enzymes lipolytiques et proteolytiques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP93307239 1993-09-14
EP93307239.9 1993-09-14

Publications (1)

Publication Number Publication Date
WO1995007970A1 true WO1995007970A1 (fr) 1995-03-23

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EP (1) EP0713525A1 (fr)
JP (1) JPH09502462A (fr)
CN (1) CN1133609A (fr)
AU (1) AU7719194A (fr)
CZ (1) CZ76196A3 (fr)
WO (1) WO1995007970A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0740697B1 (fr) * 1994-01-21 2003-04-23 Buckman Laboratories International, Inc. Enzymes pour eaux de bains recreatifs

Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
ATE257509T1 (de) * 1997-01-23 2004-01-15 Procter & Gamble Waschmittelzusammensetzungen mit verbesserter physikalischer stabilität bei niedriger temperatur
CN102604754B (zh) * 2012-02-03 2013-07-03 深圳市绿微康生物工程有限公司 生物酶清洗剂及其制备方法
EP3284811B1 (fr) * 2015-06-04 2018-12-12 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
CN106833946A (zh) * 2015-12-04 2017-06-13 深圳市芭格美生物科技有限公司 餐具生物酶清洗液及其制备方法和应用
CN106967516A (zh) * 2017-03-31 2017-07-21 湖南尔瞻智能科技有限公司 一种机洗餐具洗涤剂及其制备方法

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US3707504A (en) * 1969-12-19 1972-12-26 Procter & Gamble Detergent composition containing proteolytic enzyme elaborated by thermoactinomyces vulgaris atcc 15734
US4908150A (en) * 1989-02-02 1990-03-13 Lever Brothers Company Stabilized lipolytic enzyme-containing liquid detergent composition
US5112518A (en) * 1988-06-09 1992-05-12 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic dishwashing composition containing a chlorine-type bleaching agent
US5223179A (en) * 1992-03-26 1993-06-29 The Procter & Gamble Company Cleaning compositions with glycerol amides

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US3697451A (en) * 1969-01-02 1972-10-10 Witco Chemical Corp Stable enzyme containing liquid detergent
US4566985A (en) * 1984-09-19 1986-01-28 Applied Biochemists, Inc. Method of cleaning using liquid compositions comprising stabilized mixtures of enzymes
US4959179A (en) * 1989-01-30 1990-09-25 Lever Brothers Company Stabilized enzymes liquid detergent composition containing lipase and protease

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US3707504A (en) * 1969-12-19 1972-12-26 Procter & Gamble Detergent composition containing proteolytic enzyme elaborated by thermoactinomyces vulgaris atcc 15734
US5112518A (en) * 1988-06-09 1992-05-12 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic dishwashing composition containing a chlorine-type bleaching agent
US4908150A (en) * 1989-02-02 1990-03-13 Lever Brothers Company Stabilized lipolytic enzyme-containing liquid detergent composition
US5223179A (en) * 1992-03-26 1993-06-29 The Procter & Gamble Company Cleaning compositions with glycerol amides

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0740697B1 (fr) * 1994-01-21 2003-04-23 Buckman Laboratories International, Inc. Enzymes pour eaux de bains recreatifs

Also Published As

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EP0713525A4 (fr) 1996-06-05
CZ76196A3 (en) 1996-08-14
CN1133609A (zh) 1996-10-16
AU7719194A (en) 1995-04-03
EP0713525A1 (fr) 1996-05-29
JPH09502462A (ja) 1997-03-11

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