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WO1995007969A1 - Produit pour laver la vaisselle a la main - Google Patents

Produit pour laver la vaisselle a la main Download PDF

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Publication number
WO1995007969A1
WO1995007969A1 PCT/US1994/009890 US9409890W WO9507969A1 WO 1995007969 A1 WO1995007969 A1 WO 1995007969A1 US 9409890 W US9409890 W US 9409890W WO 9507969 A1 WO9507969 A1 WO 9507969A1
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WO
WIPO (PCT)
Prior art keywords
composition
weight
alkyl
compositions
dishes
Prior art date
Application number
PCT/US1994/009890
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English (en)
Inventor
Michael Crombie Addison
Peter Robert Foley
Andrew Michael Allsebrook
Original Assignee
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
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP94927987A priority Critical patent/EP0719320A4/fr
Priority to AU77188/94A priority patent/AU7718894A/en
Priority to US08/605,125 priority patent/US5883062A/en
Publication of WO1995007969A1 publication Critical patent/WO1995007969A1/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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

  • the formulator of a dishwashing detergent composition faces the challenge of deriving a formulation which meets a number of distinct consumer relevant performance demands.
  • such a composition should be effective at removing soils from dirty "dishes" when used in a 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 on food soils, dried on food soils, highly coloured soils derived from, e.g. 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.
  • 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. Hard-surface cleaner compositions whilst occasionally unbuilt, typically do not contain added Ca or Mg to boost performance.
  • Manual dishwashing compositions typically contain no bleaching components, which are by contrast common components of laundry, machine dishwashing and hard-surface cleaner compositions.
  • Manual dishwashing compositions are typically formulated to perform well at near neutral pH.
  • Machine dishwashing, non- bleach containing hard surface cleaner compositions 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.
  • a further manual dishwashing habit involves contacting soiled dishes with a concentrated detergent product (e.g. using a spray dispenser), and allowing the product to remain on the surface of the dishes for a period of time.
  • the dishes may subsequently be rinsed by immersion in a water bath or passing under a stream of running water, with optionally manual rubbing of the surface of the dishes with, e.g. a sponge or cloth, or using the rinse cycle of an automatic dishwashing machine.
  • the dishes may be subjected to washing steps, utilising further detergent product, which may involve either a manual dishwashing method, or a washing method utilising an automatic dishwashing machine.
  • composition containing anionic surfactant and divalent cation (particularly Ca or Mg) having an acidic pH gives remarkable performance benefits, particularly greasy cleaning performance benefits, when employed in a dishwashing method in which, essentially, concentrated detergent product is applied directly to the surface of the dishes, preferably followed by rinsing of the dishes.
  • a fluid detergent composition suitable for use in a dishwashing method in which the detergent composition is applied to the dishes in essentially concentrated form, containing (a) from 1% to 80% by weight of the composition of anionic surfactant; and
  • composition is formulated such that the pH of a 1% solution of the composition in water, at 20°, is no more than 6.
  • composition is in the form of a liquid or a gel.
  • composition contains organic solvent components.
  • composition contains no builder salts.
  • composition contains no bleaching components.
  • said compositon contains additional surfactant selected from nonionic, cationic, zwitterionic, ampholytic and amphoteric surfactants.
  • a 1% by weight solution of said composition has a pH of from 3 to 6.
  • Said composition can be formulated to contain enzyme components.
  • the first essential component of the composition of the invention is anionic surfactant present at a level of from 1% to 80% by weight, preferably from 3% to 60% by weight, more preferably from 5% to 40% by weight of the composition.
  • the anionic surfactant may be, 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 ⁇ o ⁇ c 1 6 alkyl sulfate which has been ethoxylated with an average of from 0.5 to 20 moles of ethylene oxide per molecule, C 9 -C 1 7 acyl-N-(Cl-C4 alkyl) glucamine sulfate and mixtures thereof.
  • Alkyl ethoxy sulfate surfactants suitable for use herein comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C*LO ⁇ C 16 alcohol with an average of from 0.5 to 20, preferably from 0.5 to 12, ethylene oxide groups.
  • C 12 -C14 alkyl sulfate which has been 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 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, Cg-C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, paraffin sulfonates, and any mixtures thereof.
  • the salts e.g. alkali metal salts
  • C 9 -C 20 linear alkylbenzene sulfonates C 8 -C 22 primary or secondary alkane sulfonates
  • Cg-C 24 olefin sulfonates Cg-C 24 olef
  • Anionic alkyl ethoxy carboxylate surfactant Anionic alkyl ethoxy carboxylate surfactant
  • Alkyl ethoxy carboxylates suitable for use herein include those with the formula RO(CH CH 2 0)x CH C00-M + wherein R is a C 12 to 16 alkyl group, x ranges from 0 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- ⁇ 3 , 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.
  • Anionic alkyl polvethoxy polycarboxylate surfactant Anionic alkyl polvethoxy polycarboxylate surfactant
  • Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include those having the formula: R - O - ( CH - CH - 0) X - R3
  • R is a C to C ⁇ g alkyl group, x is from 1 to 25, R- ⁇ and 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 ⁇ or R2 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.
  • Secondary soap surfactants (aka “alkyl carboxyl 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, e.g. p-octyl benzoic acid.
  • 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 (CH2)y, wherein y can be O or an integer from 1 to 4, x is an integer from 4 * co 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 carboxyl on the ring.)
  • Still another class of secondary soaps comprises secondary carboxyl compounds of the formula CH 3 (CHR) k -(CH 2 ) ro -(CHR) n -CH(COOM) (CHR) 0 -(CH2) p -(CHR) q -CH 3 , wherein each R is C- -C ⁇ alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18.
  • 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 C1-C5 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-l-undecanoic acid, 2- ethyl-1-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l- octanoic acid and 2-pentyl-l-heptanoic acid.
  • Other anionic surfactants are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2- ethyl-1-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l- octanoic acid and 2-pentyl-l-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- j ⁇ - C*L monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 1 4 diesters) , N-acyl sarcosinates, sulfates of alkylpolys
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • compositions of the invention contain as the second essential component divalent ion, selected from calcium and magnesium ions, at a level of from 0.05% to 10% by weight, preferably from 0.5% to 8% by weight, more preferably from 1% to 6% by weight, most preferably from 1.5% to 5% by weight of the composition.
  • compositions containing polyhydroxy fatty acid amide Preferably, from 0.05% to 5%, more preferably from 0.25% to 4% most preferably from 0.5% to 3% by weight of the composition of calcium ions may be included in the detergent compositions herein. It has additionally been found for compositions containing polyhydroxy fatty acid amide that the presence of calcium greatly improves the cleaning of greasy soils.
  • the calcium ions can, for example, be added as a chloride, hydroxide, oxide, formate or acetate, or nitrate salt. If the anionic surfactants are in the acid form, the calcium can be added as a calcium oxide or calcium hydroxide slurry in water to neutralise the acid.
  • 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 2:1 to 1:10, for compositions of the invention.
  • Magnesium Preferably, from 0.05% to 5%, most preferably from 0.2% to 4%, most preferably from 0.5% to 3% by weight of the composition, by weight, of magnesium ions are preferably added to the liquid detergent compositions of the invention.
  • the inclusion of magnesium provides for improved product stability.
  • 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.
  • Malic, maleic or acetic acid, or salts thereof, 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.
  • malic, maleic or acetic acid, or salts thereof may be added at levels of from 0.05% to 10% by weight of the composition and a molar ratio with calcium of from 0.01:1 to 1:10.
  • compositions in accord with the invention will be formulated such that the compositions have a pH in a 1% solution water at 20°C of less than 6.0, preferably between 3.0 and 6.0, more preferably between 3.0 and 5.0, most preferably between 3.5 and 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 preferably contain additional surfactant selected from nonionic, cationic, zwitterionic, ampholytic, and amphoteric surfactants, and any mixtures thereof, at a level of from 1% to 60%, preferably from 2% to 30%, most preferably from 3% to 15% by weight of the composition.
  • Any surfactant is preferably formulated to be compatible with any enzyme components.
  • the surfactant system comprises from 5% to 90% by weight, more preferably from 30% to 70% by weight of the surfactant system of anionic surfactant, and from 5% to 60% by weight, more preferably from 15% to 50% by weight of the surfactant of nonionic surfactant.
  • 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 polvhydroxy fatty acid amide surfactant Nonionic polvhydroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula:
  • R 1 is H, C1-C 4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, or a mixture thereof, preferable C1-C 4 alkyl, more preferably C- ⁇ or C 2 alkyl, most preferably C-*_ alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight-chain C 7 -C-L 9 alkyl or alkenyl, more preferably straight-chain Cg-C- ⁇ alkyl or alkenyl, most preferably straight-chain 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 (preferably ethoxylated or propoxylated) thereof.
  • 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, and 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)- CH2OH, where n is an integer from 3 to 5, inclusive, and R * is H or a cyclic or aliphatic monosaccharide, and alkoxylate derivative thereof. Most preferred are glycityls wherein n is 4, particularly -CH2 ⁇ (CHOH)4-CH2OH.
  • RI 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 preferred.
  • 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 1 5 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 1 4 ⁇ C 1 5 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C-*_2- Ci 3 linear alcohol with 6.54 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C1 4 -C1 5 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 -C15 alcohol
  • condensation produc s of ethylene oxide with a 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.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety.
  • the preferred alkyleneoxide 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 straight-chain saturated alkyl group.
  • the alkyl group can contain up to about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable 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 pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.
  • the preferred alkylpolyglycosides have the formula: R 0(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:
  • 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- -C ⁇ alkyl, C1-C 4 hydroxyalkyl, and
  • 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 surfactants.
  • Suitable amphoteric surfactants for use herein include the alkyl amphocarboxylic acids of the formula:
  • R is a Cg-C 18 alkyl group
  • Rj is of the general formula:
  • R 1 is a (CH 2 ) x COOM or CH 2 CH2OH, 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- ⁇ o to C1 4 alkyl group.
  • a preferred amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • Amine oxide surfactant 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 ⁇ o ⁇ 1 8 alkyl dimethyl amine oxides and C -Ci2 alkoxy ethyl dihydroxyethyl amine oxides.
  • examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide.
  • Preferred are C ⁇ Q -C ⁇ alkyl dimethylamine oxide, and C-Lo- 18 acylamido alkyl dimethylamine oxide.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions herein. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.
  • 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 Cg-C-Lg hydrocarbyl group, preferably a C 10 " c 16 alkyl group or C 10 -i 6 acylamido alkyl group, each R 1 is typically C1-C3 alkyl, preferably methyl,m and R 2 is a C1-C5 hydrocarbyl group, preferably a C-L-C 3 alkylene group, more preferably a ⁇ -C 2 alkylene group.
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; 0- ⁇ 2 - 14 acyla idopropylbetaine; Cg_i 4 acylamidohexyldiethyl betaine; 4 [ C ⁇ 4 - ⁇ acylmethylamidodiethylammonio]-l-carboxybutane; C- ⁇ g. ⁇ g acylamidodimethylbetaine; C 12 -1 6 acylamidopentanediethyl- betaine; [C 12 - 16 acylmethylamidodimethylbetaine.
  • Preferred betaines are Ci 2 - ⁇ g dimethyl-ammonio hexanoate and the C 10 - l g 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*L 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--*) 2 N + R 2 S ⁇ 3 ⁇ wherein R is a c 6 ⁇ c 1 8 hydrocarbyl group, preferably a C ⁇ -C ⁇ g alkyl group, more preferably a Ci 2 ⁇ 1 3 alkyl group, each R 1 is typically l ⁇ c 3 alkyl, preferably methyl, and R 2 is a C-j ⁇ -C hydrocarbyl group, preferably a C*L-C3 alkylene or, 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 composition.
  • the organic solvent system may be a mono, or mixed solvent system; but is preferably in mixed solvent system.
  • at least the major component of the solvent system is of low volatility.
  • 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.
  • 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 preffered.
  • Suitable solvents are benzyl alcohol, and diols such as 2-ethyl-l,3-hexanediol and 2,2,4-trimethl-l,3- pentanediol.
  • the low molecular weight, water-soluble, liquid polyethylene glycols are also suitable solvents for use herein.
  • alkane mono and diols especially the C ⁇ -Cg alkane mono and diols are suitable for use herein.
  • C1-C 4 monohydric alcohols eg: ethanol, propanol, isopropanol, butanol and mixtures thereof
  • ethanol particularly preferred.
  • the C1-C4 dihydric alcohols, including propylene glycol, are also preferred.
  • 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 Cg-C 2 o alkyl mono- or di-C2 ⁇ C 3 alkanolamides, especially monoethanolamides, diethanolamides, and isopropanolamides.
  • Preferred suds enhancing agents are C ⁇ Q -IS 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.
  • hydrotropes include polycarboxylates. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties. Particularly useful hydrotropes are alkylpolyethoxy polycarboxylate surfactants of the type as previously described herein.
  • alkyl amphodicarboxylic acid of the generic formula: (CH 2 ) X COO- RCNHCH 2 CH 2 N ⁇
  • R is a Cg to C- ⁇ g 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 preferably no more than 6.
  • 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 in accordance with the invention may contain enzyme components.
  • Suitable enzymes include those selected from lipolytic, a ylolytic and proteolytic enzymes.
  • Enzymes 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.
  • compositions may contain proteolytic enzyme (protease) which, where present, is preferably incorporated at a level of from 0.005% to 2% active enzyme by weight of the composition.
  • proteolytic enzyme proteolytic enzyme
  • 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) .
  • Amylolvtic enzyme Amylolytic (amylase) enzyme may be incorporated into the compositions in accordance with the invention at a preferred level, where present, of from 0.005% to 2% active enzyme by weight of the composition.
  • Amylases include, for example, alpha-amylases obtained from a special strain of B licheniforms, described in more detail in GB 1,269,839 (Novo).
  • Commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc, and Termamyl, sold by Novo Industries A/S.
  • compositions may contain lipolytic enzyme (lipase) which, where present, is preferably incorporated at levels of active lipolytic enzyme of from 0.001% to 2% by weight, more preferably 0.01% to 1% by weight, most preferably from 0.05% to 0.5% by weight of the compositions.
  • lipolytic enzyme lipase
  • the lipase is preferably bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp. or Thermomyces sp. or Pseudomonas pseudoalcaligenes or Pseudomas fluorescens.
  • 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 lipase derived from Pseudomonas pseudoalcaligenes is described in Granted European Patent, EP-B-0218272.
  • Another 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. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • 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 A ano. 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.
  • Preferred enzyme-containing compositions herein may comprise from 0.001% to 10%, preferably from 0.005% to 8%,most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene.glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
  • 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 inactivating the enzymes, especially under alkaline conditions.
  • chlorine bleach scavengers While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
  • 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 (EDTA) or alkali metal salt thereof, monoethanolamine (MEA) , and mixtures thereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • 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 including oxygen bleaches) , there is no requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a chemist's normal skill in avoiding the use of any scavenger which is majorly incompatible with other optional ingredients, if used.
  • 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 can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Patent 4,652,392, Baginski et al.
  • 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 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 preferably with essentially no clay thickening agent.
  • the polycarboxylate 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 preferably from about 75 to about 250.
  • 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 lOg, 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 lOg, 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.
  • a concentrated solution of the detergent composition is applied to the surface of the dishes t ⁇ 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.
  • 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 accompanied by concurrent scrubbing. Subsequently, 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 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 known silicone and fatty acid suds suppressors. Examples
  • compositions I- III are in accord with the invention, compositions IV and V are prior art compositions.
  • compositions were prepared by mixing all of the surfactants with the exception of any glucamide.
  • the magnesium salts were then pre-dissolved into solution added to the surfactant mixture with the remaining components. Finally the pH was trimmed and the viscosity checked.
  • soiled plastic slides were prepared by taking five preweighed clean 6.5cm x 5cm plastic slides, applying approximately 2g of greasy soil (9:1 mixture of vegetable oil, corn oil) to each slide, and placing the slides in a fridge overnight. Each slide was then weighed, to obtain the exact mass of soil applied, and placed in a separate Petri dish. One of the compositions I - V was then added to each soiled slide-containing Petri dish, such that the soiled slide was fully immersed in the detergent. Each slide was allowed to remain so immersed for 15 minutes, before being removed from the Petri dish and clipped, using a bulldog clip, onto a bar which was suspended between two retort stands, at a height of 28cm above the bench.
  • Each suspended slide was then sprayed for 20 seconds with a uniform spray of water, originating from a 'garden spray' positioned 50cm from the slide.
  • Each slide was then dried, by placing in an oven at 40°C, and reweighed to calculate the mass of soil removed by the soaking/rinsing process. The full test procedure was repeated four times for ecah test composition.
  • the average mass of soil removed for each composition was indexed to a standard reference, taken to be the mass of soil removed for composition IV.
  • the following grease removal indices were obtained:

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Abstract

Produit détergent fluide pour laver la vaisselle sous forme essentiellement concentrée dont les ingrédients sont: (a) de 1 % à 80 % en poids de tensioactifs anioniques et (b) de 0,05 % à 10 % en poids d'ions bivalents de magnésium et de calcium. La formule de ladite composition est telle qu'en solution à 20° dans l'eau, son pH reste inférieur à 6.
PCT/US1994/009890 1993-09-14 1994-09-01 Produit pour laver la vaisselle a la main WO1995007969A1 (fr)

Priority Applications (3)

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EP94927987A EP0719320A4 (fr) 1993-09-14 1994-09-01 Produit pour laver la vaisselle a la main
AU77188/94A AU7718894A (en) 1993-09-14 1994-09-01 Manual diswashing compositions
US08/605,125 US5883062A (en) 1993-09-14 1994-09-01 Manual dishwashing compositions

Applications Claiming Priority (2)

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EP93307238.1 1993-09-14
EP93307238 1993-09-14

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Cited By (2)

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EP2420557A1 (fr) * 2010-08-17 2012-02-22 The Procter & Gamble Company Procédé pour laver la vaisselle à la main avec une mousse de longue durée
US8921297B2 (en) 2010-08-17 2014-12-30 The Procter & Gamble Company Stable sustainable hand dish-washing detergents

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CN101798551B (zh) * 2010-04-30 2012-01-18 北京绿伞化学股份有限公司 一种浓缩型餐具洗涤剂及其制备方法

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EP2420557A1 (fr) * 2010-08-17 2012-02-22 The Procter & Gamble Company Procédé pour laver la vaisselle à la main avec une mousse de longue durée
US8921297B2 (en) 2010-08-17 2014-12-30 The Procter & Gamble Company Stable sustainable hand dish-washing detergents
US8968482B2 (en) 2010-08-17 2015-03-03 The Procter & Gamble Company Method for hand washing dishes having long lasting suds

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CN1057791C (zh) 2000-10-25
AU7718894A (en) 1995-04-03
EP0719320A1 (fr) 1996-07-03
CN1135236A (zh) 1996-11-06

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