EP0222557B1 - Composition détergente liquide - Google Patents

Composition détergente liquide Download PDF

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Publication number
EP0222557B1
EP0222557B1 EP19860308453 EP86308453A EP0222557B1 EP 0222557 B1 EP0222557 B1 EP 0222557B1 EP 19860308453 EP19860308453 EP 19860308453 EP 86308453 A EP86308453 A EP 86308453A EP 0222557 B1 EP0222557 B1 EP 0222557B1
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European Patent Office
Prior art keywords
surfactant
carbon atoms
groups
alkyl
average
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EP19860308453
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German (de)
English (en)
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EP0222557A3 (en
EP0222557A2 (fr
Inventor
Eugene Joseph Pancheri
Young Sik Oh
Rodney Mahlon Wise
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to AT86308453T priority Critical patent/ATE95834T1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • the invention relates to aqueous high sudsing liquid detergent compositions containing specified amounts and types of polymeric surfactants especially useful in the washing of tableware, kitchenware and other hard surfaces.
  • compositions incorporating polymeric surfactants are known in the art.
  • EP-A-0105556 discloses an aqueous liquid dishwashing detergent composition containing a mixture of anionic, alkoxylated nonionic and alkyl polysaccharide surfactants that provide enhanced drainage of rinse water from articles washed by the compositions.
  • suitable nonionic surfactants include the condensate of ethylene oxide, propylene oxide and a compound containing hydroxyl or amine groups onto which the alkylene oxides can be polymerised.
  • EP-A-0083223 also discloses detergent compositions incorporating alkylene oxide homo- and co-polymers for grease and oil emulsification.
  • EP-A-0024711 discloses concentrated aqueous anionic surfactant solutions incorporating the mono- and/or di-sulfates of poly C2-C3 alkylene glycols of MW >600 as viscosity modifiers, optionally together with unsulfated C2-C3 polyalkylene glycols of MW >1500.
  • compositions of this invention have superior ability to handle grease.
  • the performance of a detergent composition for cleaning tableware and kitchen utensils is evaluated by its ability to handle grease.
  • the detergent solution should readily remove grease and minimize its redeposition.
  • compositions and methods which can be employed during dishwashing operations to improve the appearance of kitchen utensils and articles.
  • Such compositions and methods should provide improved removal of grease in conventional dishwashing soil removal operations while maintaining the sudsing attributes of an acceptable dishwashing detergent composition.
  • a high sudsing liquid detergent composition with enhanced grease handling ability containing by weight:
  • Dishware, glassware, and other tableware and kitchenware are washed in water solutions of the detergent composition, generally at a weight concentration of from 0.05% to 0.4% of the composition in water at a temperature of from 15.6°C (60°F) to 48.9°C (120°F).
  • liquid detergent compositions of the present invention contain two essential components:
  • Optional ingredients can be added to provide various performance and aesthetic characteristics.
  • compositions of this invention contain from 5% to 50% by weight of an anionic surfactant or mixtures thereof preferably comprising at least 5%, more preferably at least 8%, and most preferably more than 10% of an alkyl polyethoxylate (polyethylene oxide) sulfate having from 10 to 20, preferably from 10 to 16 carbon atoms in the alkyl group and containing from 1 4 to 10, preferably from 1 to 8, most preferably from 1 to 6 ethoxy groups on the average.
  • Preferred compositions contain from 20% to 40% of anionic surfactant by weight.
  • anionic detergents can be broadly described as the water-soluble salts, particularly the alkali metal, alkaline earth metal, ammonium or amine salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from 8 to 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Included in the term "alkyl” is the alkyl portion of acyl radicals.
  • Examples of the anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the salts of compatible cations, e.g.
  • alkyl sulfates especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms), alkyl benzene, or alkyl toluene, sulfonates, in which the alkyl group contains from 9 to 15 carbon atoms, the alkyl radical being either a straight or branched aliphatic chain; paraffin sulfonates or olefin sulfonates in which the alkyl or alkenyl group contains from 10 to 20 carbon atoms; sodium C10 ⁇ 20 alkyl glyceryl ether sulfonates, especially those ethers of alcohols derived from tallow and coconut oil; coconut oil fatty acid monoglyceride sulfates and sulfonates; alkylphenolpolyethylene oxide ether sulfates with from 1
  • alkyl sulfate salts which can be employed in the instant detergent compositions include sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, and magnesium: lauryl sulfates, stearyl sulfates, palmityl sulfates, decyl sulfates, myristyl sulfates, tallow alkyl sulfates, coconut alkyl sulfates, C12 ⁇ 15 alkyl sulfates and mixtures of these surfactants.
  • Preferred alkyl sulfates include the C12 ⁇ 15 alkyl sulfates.
  • Suitable alkylbenzene, or alkyltoluene, sulfonates include the alkali metal (lithium, sodium, and/or potassium), alkaline earth (preferably magnesium), ammonium and for alkanolammonium salts of straight, or branched-chain, alkylbenzene, or alkyltoluene, sulfonic acids.
  • Alkylbenzene sulfonic acids useful as precursors for these surfactants include decyl benzene sulfonic acid, undecyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tridecyl benzene sulfonic acid, tetrapropylene benzene sulfonic acid and mixtures thereof.
  • Preferred sulfonic acids as precursors of the alkyl-benzene sulfonates useful for compositions herein are those in which the alkyl chain is linear and averages 11 to 13 carbon atoms in length.
  • the preferred anionic surfactants herein which are essential if there are no, e.g., magnesium ions or betaine surfactant present, are alkylpolyethoxylate sulfates having the formula RO(C2H4O) x SO3M wherein R is alkyl of from 10 to 20 carbon atoms, x is from 1/4 to ten on the average, treating alkyl sulfates as if they had 0 ethoxy groups, preferably from 1 2 to eight, most preferably from one to six, and M is a water-soluble compatible cation such as those disclosed hereinbefore.
  • the alkylpolyethoxylate sulfates useful in the present invention are sulfates of condensation products of ethylene oxide and monohydric alcohols having from 10 to 20 carbon atoms.
  • R has 10 to 16 carbon atoms.
  • the alcohols can be derived from natural fats, e.g., coconut oil or tallow, or can be synthetic. Such alcohols can be reacted with from 1 2 to 20, especially from one to 14, and more especially from one to eight, molar proportions of ethylene oxide and the resulting mixture of molecular species is sulfated and neutralized.
  • the computed average degree of ethoxylation should be more than 0.25, preferably more than 0.6.
  • the other anionic surfactant can be treated as if it were an alkyl sulfate to compute the average degree of ethoxylation.
  • alkylpolyethoxylate sulfates of the present invention are sodium coconut alkylpolyethoxylate (3) ether sulfate, magnesium C12 ⁇ 15 alkylpolyethoxylate (3) ether sulfate, and sodium tallow alkylpolyethoxylate (6) ether sulfate.
  • a particularly preferred example is a water soluble, e.g. magnesium, C12 ⁇ 13 alkylpolyethoxylate (1) ether sulfate.
  • Preferred alkyl polyethoxylate sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from 10 to 16 carbon atoms and an average degree of ethoxylation of from 1 to 8 moles of ethylene oxide.
  • the compositions should contain magnesium ions, and/or at least 10%, preferably at least 15% by weight of the anionic surfactant, of the preferred alkyl polyethoxylate sulfates described hereinbefore. It is preferred that the compositions of this invention, including those that contain the preferred alkylpolyethoxylate sulfates, also contain magnesium and/or calcium ions, most preferably magnesium ions, to act as cations for a portion of the anionic surfactant. If the composition is to be used primarily in water containing more than 0.17 ppm Ca++ of hardness, added magnesium may not be essential. In use, from 10% to 100%, preferably from 20% to 90%, of the anionic surfactant should be the magnesium salt.
  • the surfactant system minus the polymeric surfactant should preferably reduce the interfacial tension to below 0.25 Pa.cm, preferably below 0.2 Pa.cm , against triolein at a concentration of 0.2% and a temperature of 115°F (46°C) in a spinning drop Tensiometer.
  • Interfacial tension is lowered by any detergent surfactant, but the efficiency can be improved by selection of surfactants which have longer alkyl chain lengths, use of cations such as magnesium which minimize charge effects when anionic surfactants are used, and use of anionic surfactants combined with cosurfactants like trialkylamine oxides which form complexes with the anionic surfactant.
  • cations such as magnesium which minimize charge effects when anionic surfactants are used
  • anionic surfactants combined with cosurfactants like trialkylamine oxides which form complexes with the anionic surfactant.
  • compositions of the present invention contain from 0.1% to 10%, preferably from 1/2% to 4%, and most preferably from 1/2% to 2%, of the polymeric surfactant described generically hereinbefore and discussed in detail hereinafter.
  • the surfactant contains a hydrophilic group comprising polyethylene oxide and/or ethyleneimine groups containing from 1 to 500 ethylene oxide and/or ethyleneimine derived moieties.
  • the polymeric surfactant also contains at least one hydrophobic group, preferably comprising polyalkylene oxide groups wherein the alkylene contains from three to six, most preferably three, carbon atoms and the molecular weight is from 400 to 60,000.
  • the alkylene groups containing from 7 to 18, preferably from 10 to 18, carbon atoms can also be used, abut preferably only short chain relatively nonoleophilic alkyl or acyl groups containing less than ten carbon atoms are pendant on the polymeric surfactant.
  • Preferred surfactants are block copolymers comprising one or more groups that are hydrophilic and which contain mostly ethylene oxide groups and one or more hydrophobic groups which contain mostly propylene oxide groups attached to the residue of a compound that contained one or more hydroxy or amine groups onto which the respective alkylene oxides were polymerized, said polymers having molecular weights of from 400 to 60,000, an ethylene oxide content of from 10% to 90% by weight and a propylene oxide content of from 10% to 90% by weight.
  • Preferred surfactants are those in which propylene oxide is condensed with an amine, especially ethylenediamine to provide a hydrophobic base having a molecular weight of from 350 to 55,000, preferably from 500 to 40,000. This hydrophobic base is then condensed with ethylene oxide to provide from 10% to 90%, preferably from 20% to 80% ethylene oxide. Reverse structures in which the ethylene oxide is condensed first are also desirable. These structures are especially easy to formulate into desirable single phase liquid compositions.
  • the polypropylene glycol portion can be replaced by an alkyl, or alkylene group containing from 5 to 18, preferably from 8 to 16 carbon atoms.
  • compositions of this invention contain from 0% to 10%, preferably from 1% to 8%, of suds stabilizing nonionic surfactant or mixtures thereof.
  • Suds stabilizing nonionic surfactants operable in the instant compositions are of two basic types: fatty acid amides and the trialkyl amine oxide semi-polar nonionics.
  • the amide type of nonionic surface active agent includes the ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from 8 to 18 carbon atoms and represented by the general formula: R1-CO-N(H) m (R2OH) 2-m wherein R1 is a saturated or unsaturated, aliphatic hydrocarbon radical having from 7 to 21, preferably from 11 to 17 carbon atoms; R2 represents a methylene or ethylene group; and m is 1 or 2.
  • Specific examples of said amides are coconut fatty acid monoethanol amide and dodecyl fatty acid diethanol amide.
  • acyl moieties may be derived from naturally occurring glycerides e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • the monoethanol amides and diethanolamides of C12 ⁇ 14 fatty acids are preferred.
  • Amine oxide semi-polar nonionic surface active agents comprise compounds and mixtures of compounds having the formula: wherein R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms, R2 and R3 are each a methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl radical and n is from 0 to 10. Particularly preferred are amine oxides of the formula: wherein R1 is a C10 ⁇ 14 alkyl and R2 and R3 are methyl or ethyl.
  • the preferred sudsing characteristics of the compositions of the invention are those which will provide the user of the product with an indication of cleaning potential in a dishwashing solution. Soils encountered in dishwashing act as suds depressants and the presence or absence of suds from the surface of a dishwashing solution is a convenient guide to product usage. Mixtures of anionic surfactants and suds stabilizing nonionic surfactants are utilized in the compositions of the invention because of their high sudsing characteristics, their suds stability in the presence of food soils and their ability to indicate accurately an adequate level of product usage in the presence of soil.
  • the ratio of anionic surfactants to suds stabilizing nonionic surfactants in the composition will be in a molar ratio of from 11:1 to 1:1, and more preferably from 8:1 to 3:1.
  • compositions of the invention can desirably contain optional surfactants, especially ampholytic and/or zwitterionic surfactants.
  • optional surfactants especially ampholytic and/or zwitterionic surfactants.
  • the level of anionic surfactant is less than 20%, the composition should not contain any substantial amount of conventional nonionic surfactant, e.g., an alkylpolyethoxylate, in addition to the polymeric surfactant.
  • conventional nonionic surfactants e.g., more than about three or four percent, tend to harm the sudsing ability of the composition.
  • anionic surfactants When larger amounts ( > 20%) of anionic surfactants are present it is sometimes desirable to have a low level, up to 5%, of conventional nonionic surfactants; "conventional” nonionic surfactants are, e.g., C8 ⁇ 18 alkyl polyethoxylates (4-15) or C8 ⁇ 15 alkyl phenol polyethoxylates (4-15).
  • Ampholytlc surfactants can be broadly described as derivatives of aliphatic amines which contain a long chain of 8 to 18 carbon atoms and an anionic water-solubilizing group, e.g. carboxylate, sulfonate or sulfate. Examples of compounds falling within this definition are sodium-3-dodecylamino propane sulfonate, and dodecyl dimethylammonium hexanoate.
  • Zwitterionic surface active agents operable in the instant composition are broadly described as internally-neutralized derivatives of aliphatic quaternary ammonium and phosphonium, and tertiary sulfonium compounds in which the aliphatic radical can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.
  • betaine detergent surfactants which synergistically interact with the polymeric surfactant to provide improved grease handling.
  • the betaine detergent surfactant has the general formula: wherein R is a hydrophobic group selected from alkyl groups containing from 10 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R6 is an alkyl group containing from one to 3 carbon atoms; and R7 is an alkylene group containing from one to 6 carbon atoms.
  • betaines dodecylamidopropyl dimethylbetaine; dodecyldimethylbetaine; tetradecyldimethylbetaine; cetyldimethylbetaine; cetylamidopropyldimethylbetaine, tetradecyldimethylbetaine, tetradecylamidopropyldimethylbetaine, and docosyldimethylammonium hexanoate and mixtures thereof.
  • Betaine surfactants are unique ingredients that provide exceptional benefits. When betaine surfactant and polymeric surfactant are combined with any anionic surfactant with, or without magnesium ions being present, superior grease holding benefits are provided.
  • Betaines containing a C12 ⁇ 14 alkyl provide a much bigger benefit when combined with polymeric surfactant than when used by themselves.
  • the betaine is preferably present at a level of from 1 2 % to 15% by weight of the formula, preferably from 1% to 10%, most preferably from 1% to 8%.
  • the ratio of anionic detergent surfactants to the betaine is from 1 to 80, preferably from 1 to 40, more preferably from 2 to 40.
  • the composition should preferably have a ratio of betaine to polymeric surfactant of more than 7:1, preferably more than 9:1.
  • Alcohols such as ethyl alcohol, and hydrotropes, such as sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related compounds (as disclosed in U.S. Patent 3,915,903), and urea, can be utilized in the interests of achieving a desired product phase stability and viscosity.
  • Alkanols containing from one to six carbon atoms, especially two, and especially ethyl alcohol can be present.
  • Ethyl alcohol at a level of from 0% to 15%, preferably from 1% to 6%, and potassium and/or sodium toluene, xylene, and/or cumene sulfonates at a level of from 1% to 6% can be used in the compositions of the invention.
  • the viscosity should be greater than 0.1 Pa.s, more preferably greater than 0.14 Pa.s, more preferably greater than 0.2 Pa.s for consumer acceptance.
  • the polymeric surfactant can be used to reduce the viscosity and provide phase stability, e.g., when either the preferred alkyl polyethoxylate sulfate or magnesium ions are present in the composition.
  • the percentage of ethylene oxide in the polymer should be less than 70%, preferably less than 50%.
  • Preferred compositions contain less than 2% alcohol and less than 3% hydrotrope and preferably essentially none while maintaining a viscosity of from 0.15 Pa.s to 0.5 Pa.s, preferably from 0.2 Pa.s to 0.4 Pa.s.
  • the percentage of ethylene oxide in the polymer should be more than 50%, preferably more than 70%.
  • the polymeric surfactant reduces viscosity for all water soluble anionic surfactants.
  • compositions of this invention contain from 20% to 90%, preferably from 30% to 80%, water.
  • compositions of this invention can contain up to 10%, by weight of selected detergency builders either of the organic or inorganic type.
  • water-soluble inorganic builders which can be used, alone or in admixture with themselves and organic alkaline sequestrant builder salts, are alkali metal carbonates, phosphates, polyphosphates, and silicates.
  • Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, and potassium tripolyphosphate.
  • organic builder salts which can be used alone, or in admixture with each other or with the preceding inorganic alkaline builder salts, are alkali metal polycarboxylates, e.g., water-soluble citrates and tartrates, such as sodium and potassium citrate and sodium and potassium tartrate.
  • detergency builders have limited value in dishwashing detergent compositions and use at levels above 10% can restrict formulation flexibility in liquid compositions because of solubility and phase stability considerations. It is preferred that any builder used be relatively specific to control of calcium as opposed to magnesium, Citrates, tartrates, malates, maleates, succinates and malonates are especially preferred.
  • the detergent compositions of this invention can contain, if desired, any of the usual adjuvants, diluents and additives, for example, perfumes, electrolytes, enzymes, dyes, antitarnishing agents and antimicrobial agents, without detracting from the advantageous properties of the compositions.
  • adjuvants for example, perfumes, electrolytes, enzymes, dyes, antitarnishing agents and antimicrobial agents, without detracting from the advantageous properties of the compositions.
  • Alkalinity sources and pH buffering agents such as monoethanolamine, triethanolamine and alkali metal hydroxides can also be utilized.
  • the anionic surfactant is a C10-C20 alkylpolyethoxylate sulfate surfactant containing from 0.25 to 10 ethoxy groups per molecule on average
  • the pH should be above 6, preferably above 7 to avoid hydrolysis of the ester linkage.
  • the composition be substantially free of antibacterial agents such as N-trichloromethyl-thio-4-cyclohexene-1,2,dicarboximide for safety.
  • E stands for an ethoxylate group and P stands for a propoxylate group.
  • the base product contains 5% magnesium C12 ⁇ 13 alkyl sulfate, 23% mixed magnesium and ammonium C12 ⁇ 13 alkyl polyethoxylate (1) sulfate, 2.7% C12 ⁇ 13 alkyl dimethyl amine oxide; 5% ethyl alcohol, 3% sodium toluene sulfonate, about 60% water, and the balance being inorganic salts and minor ingredients.
  • grey cutting is determined by the following test.
  • a preweighed 250 cc. polypropylene cup has 3 cc. of a melted beef grease applied to its inner bottom surface. After the grease has solidified, the cup is reweighed. Then a 0.4% aqueous solution of the composition to be tested is added to the cup to completely fill it. The aqueous solution has a temperature of 46°C. After 15 minutes, the cup is emptied and rinsed with distilled water. The cup is dried and then weighed to determine the amount of grease removal. The amount removed by the base product is indexed at 100.
  • greyness is determined by modifying the above grease cutting test by using 10 ml of an easier to remove fat which is an 80/20 mixture of a solid vegetable shortening and a liquid vegetable shortening, lowering the detergent concentration to about 0.2%, and soaking for 30 minutes to allow equilibrium to occur.
  • the viscosity of the composition is greater than about 1.5 Pa.s and less than about 5 Pa.s centipoise.
  • This example demonstrates the large reductions in viscosity obtained by adding the polymeric surfactant.
  • the viscosity can be adjusted back up by reducing alcohol and/or hydrotrope levels. As can be seen, the higher the level of ethoxylate moieties in the polymers, the less the reduction in viscosity.
  • This test determines the effectiveness or strength of the grease emulsification by the detergent by measuring the level of grease deposition on a hydrophobic surface after its exposure to a detergent solution to which a grease has been added. This test models the actual situation of redeposition of greases onto later washed items, especially plastics.
  • the reference product used here is the base product.
  • the polymeric surfactant is added at the 1% level to the base.
  • a "*" indicates a statistically significant (LSD05) reduction in grease redeposition compared to the Base Product.
  • Tetronic 704 and Compound F did not excel in this test, but did perform well in the previous examples. Again, the Methocel® polymer does not provide sufficient benefit.
  • compositions of this invention When some of the compositions of this invention are first made, they are not at equilibrium. They typically require an aging period to reach equilibrium and exhibit the full benefit. A period of about two weeks, which is about equivalent to the normal time between making and use by the consumer is usually sufficient.

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Claims (9)

  1. Composition détergente liquide à fort pouvoir moussant ayant une capacité améliorée de détachage des graisses, contenant, en poids :
    (a) de 5% à 50% de tensioactif anionique;
    (b) de 0,1 à 10% de tensioactif polymère contenant des groupes oxyde d'éthylène et/ou oxyde de propylène polymérisés, ledit tensioactif polymère possédant une masse moléculaire de 400 à 60 000;
    (c) de 0% à 10% d'un tensioactif non ionique stabilisateur de mousse choisi parmi les amides d'acides gras, les oxydes de trialkylamines et des mélanges de ceux-ci;
    (d) de 0% à 10% d'un adjuvant de détergence choisi parmi les phosphates minéraux, les polyphosphates minéraux, les silicates minéraux, les carbonates minéraux, les carboxylates organiques, les phosphonates organiques, et des mélanges de ceux-ci;
    (e) de 0% à 15% d'un alcanol contenant de 1 à 6 atomes de carbone; et
    (f) de 20% à 90% d'eau,
    caractérisée en ce que ledit tensioactif polymère est choisi parmi les composés de formule



            1)   [R¹(R²O)n(R³O)m]y[R⁴]



    dans laquelle R¹ est un hydrogène, chaque R² ou R³ est un groupe alkylène contenant de 2 à 6 atomes de carbone, pas plus de 90% de ladite molécule comprenant des groupes R² ou R³ contenant deux atomes de carbone, les groupes R²O et R³O étant interchangeables; dans laquelle R⁴ est choisi parmi :
    i) les groupes alkylène contenant de 1 à 18 atomes de carbone,
    ii) les groupes poly(oxyde d'hydroxyalkylène) dans lesquels chaque groupe alkylène possède de 1 à 6 groupes hydroxy et contient de 3 à 8 atomes de carbone et il existe de 2 à 50 groupes oxyde d'hydroxyalkylène et de 2 à 50 groupes hydroxy,
    iii) (-NR²N=), et
    iv) =N-(R²NH)x-,
    où n a une valeur de 0 à 500, m a une valeur de 0 à 500, n+m a une valeur de 5 à 1000, x a une valeur de 2 à 50, et y a une valeur de 2 à 50 et est égal aux liaisons disponibles de R⁴;



            2)   R¹-(OCH₂CH₂)x-R²-(OCH₂CH₂)y-OR¹



    dans laquelle R¹ est H, CH₃ ou CH₃(CH₂)n, où n est 1-17, ou leurs analogues insaturés, chaque x et y a une valeur de 2-500 et R² est O(CH₂)z-, où z a une valeur de 1-18, ou leurs analogues insaturés, le pourcentage de groupes -(OCH₂CH₂)- dans la molécule étant inférieur à 90%;
    Figure imgb0037
     dans laquelle x est égal à 8 et y est égal à 4 ou 14, ou x est égal à 17 et y est égal à 10.
    Figure imgb0038
     dans laquelle x est égal à 7,5 ou 16 et y est égal à 2,75;
    ladite composition ayant un pH supérieur à 6 lorsque la composition contient un tensioactif alkyl(en C₁₀-C₂₀)polyéthoxysulfate contenant en moyenne de 0,25 à 10 groupes éthoxy par molécule et ayant une viscosité supérieure à 0,1 Pa.s, ladite composition étant essentiellement dépourvue de tensioactif détergent alkylpolyéthoxylat non ionique lorsque la quantité de tensioactif anionique est inférieure à 20%, ledit tensioactif anionique étant un sel de tensioactif alkyl (en C₁₀-C₂₀)polyéthoxysulfate contenant en moyenne de 0,25 à 10 groupes éthoxy par molécule en l'absence d'ions magnésium ou de tensioactifs bétaïnes.
  2. Composition selon la revendication 1, dans laquelle il y a de 0,1% à 7%, de préférence de 0,5% à 4%, de tensioactif polymère.
  3. Composition selon l'une quelconque des revendications 1 et 2, dans laquelle le détergent anionique est choisi parmi les sels de sodium, d'ammonium, de monoéthanolammonium, de diéthanolammonium, de triéthanolammonium, de potassium et de magnésium d'alkylsulfates contenant 8-18 atomes de carbone, d'alkylbenzènesulfonates dans lesquels le groupe alkyle contient de 9 à 15 atomes de carbone et d'alkylpolyéthoxysulfates dans lesquels le groupe alkyle contient de 10 à 20 atomes de carbone et il y a en moyenne de 0,5 à 10 groupes éthoxylat, et des mélanges de ceux-ci.
  4. Composition selon l'une quelconque des revendications 1-3, dans laquelle il y a moins de 2% de tensioactif polymère et dans laquelle de 10% à 100% du tensioactif anionique se trouve sous la forme d'un sel de magnésium.
  5. Composition selon l'une quelconque des revendications 1-3, dans laquelle il y a au moins 8% d'un akylpolyéthoxysulfate contenant de 10 à 16 atomes de carbone dans le groupe alkyle et en moyenne de 0,5 à 8 groupes éthoxylat; dans laquelle de 20% à 90% du tensioactif anionique est le sel de magnésium.
  6. Composition selon l'une quelconque des revendications 1-4, dans laquelle le tensioactif anionique comprend au moins 10% d'alkylpolyéthoxysulfate dans lequel le groupe alkyle contient de 10 à 20 atomes de carbone et contenant en moyenne de 1 à 6 groupes éthoxylat, d'alkylsulfates contenant en moyenne de 8 à 18 atomes de carbone, et des mélanges de ceux-ci, et dans laquelle le tensioactif non ionique stabilisateur de mousse est un agent tensioactif non ionique semipolaire de type oxyde d'amine comprenant des composés répondant à la formule :
    Figure imgb0039
     dans laquelle R¹ est un radical alkyle, 2-hydroxyalkyle, 3-hydroxyalkyle ou 3-alcoxy-2-hydroxypropyle dans lequel les groupes alkyle et alcoxy contiennent respectivement de 8 à 18 atomes de carbone, R² et R³ représentent chacun un radical méthyle, éthyle, propyle, isopropyle, 2-hydroxyéthyle, 2-hydroxypropyle ou 3-hydroxypropyle, et n a une valeur de 0 à 10.
  7. Composition selon la revendication 4, lorsqu'elle dépend de la revendication 3, dans laquelle le tensioactif anionique est choisi parmi les mélanges d'alkylbenzènesulfonates dans lesquels le groupe alkyle contient de 9 à 15 atomes de carbone et d'alkylpolyéthoxysulfates dans lesquels le groupe alkyle contient de 10 à 16 atomes de carbone et qui contiennent en moyenne de 0,5 à 6 groupes éthoxylat, et dans laquelle le tensioactif non ionique stabilisateur de mousse est un amide d'acide gras représenté par la formule générale :



            R¹-CO-N(H)m(R²OH)2-m



    dans laquelle R¹ est un radical hydrocarboné aliphatique, saturé ou insaturé, de 7 à 21 atomes de carbone, R² représente un groupe méthylène ou éthylène; et m est égal à 1 ou 2 et il y a de 2% à 8% dudit amide d'acide gras.
  8. Composition selon l'une quelconque des revendications 1-3, dans laquelle il y a de 0,5% à 4% de tensioactif polymère, tensioactif dans lequel la quantité d'oxyde d'éthylène est inférieure à 70% en poids, ladite composition contenant moins de 2% d'alcanol et moins de 3% d'un produit hydrotrope et ayant une viscosité de 0,15 à 0,5 Pa.s.
  9. Composition selon la revendication 8, dans laquelle il y a moins de 2% de tensioactif polymère, tensioactif dans lequel la quantité d'oxyde d'éthylène dans le tensioactif polymère est inférieure à 50% en poids, et dans laquelle la viscosité est de 0,2 à 0,4 Pa.s.
EP19860308453 1985-10-31 1986-10-30 Composition détergente liquide Expired - Lifetime EP0222557B1 (fr)

Priority Applications (1)

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AT86308453T ATE95834T1 (de) 1985-10-31 1986-10-30 Fluessige reinigungsmittelzusammensetzung.

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US79353085A 1985-10-31 1985-10-31
US793530 1985-10-31
US91856786A 1986-10-20 1986-10-20
US918567 1986-10-20

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EP0222557A3 EP0222557A3 (en) 1988-09-28
EP0222557B1 true EP0222557B1 (fr) 1993-10-13

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JPS6386798A (ja) * 1986-09-30 1988-04-18 花王株式会社 台所用液体洗浄剤組成物
GB8924479D0 (en) * 1989-10-31 1989-12-20 Unilever Plc Detergent compositions
US5382376A (en) * 1992-10-02 1995-01-17 The Procter & Gamble Company Hard surface detergent compositions
CN1082998C (zh) * 1994-06-17 2002-04-17 普罗格特-甘布尔公司 手洗衣用组合物
GB2313602A (en) * 1996-05-31 1997-12-03 Procter & Gamble Detergent compositions
EP0916720A1 (fr) * 1997-11-17 1999-05-19 The Procter & Gamble Company Compositions liquides antibactériennes pour la vaisselle
US6701940B2 (en) 2001-10-11 2004-03-09 S. C. Johnson & Son, Inc. Hard surface cleaners containing ethylene oxide/propylene oxide block copolymer surfactants
WO2015030768A1 (fr) * 2013-08-29 2015-03-05 Colgate-Palmolive Company Compositions liquides aqueuses
USD815838S1 (en) 2016-07-15 2018-04-24 Colgate-Palmolive Company Toothbrush
EP3489336B1 (fr) 2017-11-27 2020-05-13 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
CA3081829A1 (fr) * 2017-11-27 2019-05-31 The Procter & Gamble Company Composition liquide de detergent pour laver la vaisselle a la main

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CA995092A (en) 1972-07-03 1976-08-17 Rodney M. Wise Sulfated alkyl ethoxylate-containing detergent composition
DE3066054D1 (en) 1979-09-01 1984-02-09 Henkel Kgaa Watery tenside concentrates and process for the improvement of the flowing property of difficultly movable watery tenside concentrates
CA1206060A (fr) 1981-12-24 1986-06-17 Peter K. Church Systeme d'emulsification de l'huile et de la graisse
EP0105556A1 (fr) 1982-09-30 1984-04-18 THE PROCTER & GAMBLE COMPANY Composition détergente liquide contenant des tensides nonioniques et ioniques
US4483787A (en) * 1983-12-28 1984-11-20 The Procter & Gamble Company Concentrated aqueous detergent compositions
DE3568455D1 (en) * 1984-05-23 1989-04-06 Rhone Poulenc Chimie Detergent compositions containing copolymers based on polyoxyethylene and polyoxyalkylene used as antisoil redeposition agents, and process for their preparation

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DE3689165D1 (de) 1993-11-18
EP0222557A3 (en) 1988-09-28
FI87086B (fi) 1992-08-14
DK522786A (da) 1987-05-01
FI864424A (fi) 1987-05-01
CA1299962C (fr) 1992-05-05
MX165143B (es) 1992-10-29
EP0222557A2 (fr) 1987-05-20
DK522786D0 (da) 1986-10-31
FI864424A0 (fi) 1986-10-30
AU6454286A (en) 1987-05-07
FI87086C (fi) 1992-11-25
DE3689165T2 (de) 1994-05-05
AU589225B2 (en) 1989-10-05

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