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EP0724013A1 - Giessfähige Waschmittelkonzentrate, die nach Verdünnung mit Wasser gleiche oder erhöhte Viskosität zeigen - Google Patents

Giessfähige Waschmittelkonzentrate, die nach Verdünnung mit Wasser gleiche oder erhöhte Viskosität zeigen Download PDF

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Publication number
EP0724013A1
EP0724013A1 EP96200101A EP96200101A EP0724013A1 EP 0724013 A1 EP0724013 A1 EP 0724013A1 EP 96200101 A EP96200101 A EP 96200101A EP 96200101 A EP96200101 A EP 96200101A EP 0724013 A1 EP0724013 A1 EP 0724013A1
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EP
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Prior art keywords
concentrate
viscosity
surfactants
composition
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96200101A
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English (en)
French (fr)
Inventor
Hoai-Chau Cao
Patricia Pagnoul
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Colgate Palmolive Co
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Colgate Palmolive Co
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Filing date
Publication date
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Publication of EP0724013A1 publication Critical patent/EP0724013A1/de
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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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes

Definitions

  • This invention relates to aqueous detergent concentrates adapted to be diluted by the consumer prior to use.
  • Aqueous liquid concentrates such as laundry, fine fabric and dishwasher detergents are normally provided with a high content of active ingredients such that, when diluted by the consumer per packaging instructions, the diluted product will contain an amount of active ingredients normally present in a non-concentrated product.
  • Concentrated liquids tend to exhibit a higher viscosity due to the high content of surfactants, builders, electrolytes and other components present in the concentrate. Concentrates having viscosities in excess of 10,000 cps (mPas) tend to be difficult to pour from the packaging container, while pourable concentrates tend to have insufficient viscosity on the other hand when appropriately diluted by the consumer, thereby reducing consumer appeal. Also, surfactants present at high levels in such concentrates tend to form closely spaced, suspended lamellar structures which tend to contact one another after periods of storage, resulting in a flocculation phenomenon which destabilizes the suspension and leads to a marked increase in product viscosity.
  • One approach to dealing with poor post-dilution viscosity is to include in the liquid concentrate formulation one or more organic or inorganic thickening agents such as swelling clays, alumina, gums, polymeric materials or cellulosic polymers.
  • organic or inorganic thickening agents such as swelling clays, alumina, gums, polymeric materials or cellulosic polymers.
  • thickening additives tends to worsen the problem of concentrate pourability and imparts only a minimal viscosity increase to the diluted concentrate.
  • Hydrophilic polymeric materials have also been used in liquid detergent concentrates as viscosity control agents.
  • U.S. Patent 4,715,969 discloses that the addition of less than about 0.5% by weight of a polyacrylate polymer, e.g., sodium polyacrylate, having a molecular weight from about 1,000 to 5,000, to aqueous detergent compositions containing primarily anionic surfactants will stabilize the viscosity of the composition and prevent a major increase in viscosity after a period of storage of the formulated composition.
  • EPO 301,883 discloses similar compositions containing from about 0.1 to 20% by weight of a viscosity reducing, water soluble polymer such as polyethylene glycol, dextran or a dextran sulfonate.
  • a liquid detergent concentrate which exhibits a sufficiently low viscosity such that it is pourable as a free flowing liquid from its packaging container and which also exhibits a viscosity after appropriate dilution with water which is preferably at least equal to the viscosity of the original, undiluted concentrate.
  • the present invention provides pourable aqueous detergent concentrate compositions comprising a micellar dispersion of a mixture of at least two surfactants having differing resistance to electrolytic salting out and a dissolved electrolyte salt, which concentrate has a viscosity of less than about 2500 cps (mPas) and which contains the electrolyte salt at a concentration such that, upon dilution of the concentrate with a designated amount of water, the micellar surfactant dispersion is converted at least partially or totally into a lamellar phase dispersion, thereby providing a diluted concentrate having a viscosity in excess of 200 cps, and more preferably a viscosity at least equal to and generally higher than the viscosity of the undiluted concentrate.
  • mPas cps
  • the invention also provide a method for preparing a diluted detergent concentrate having a viscosity at least about equal to and generally higher than the viscosity of the undiluted concentrate comprising:
  • Figure 1 is a graph plotting viscosity characteristics of a dispersed surfactant system in the micellar and lamellar phases as a function of electrolyte concentration.
  • Figure 2 is a graph plotting viscosity enhancement of a detergent concentrate of the invention as a function of the degree of dilution with water.
  • surfactants When surfactants are solubilized in electrolyte-free water, they exhibit different phase structures in accordance with concentration and degree of water solubility. At concentrations of less than about 30-40 wt%, surfactants usually form the micellar isotropic solution "L" phase. These micelles are aggregates of surfactant molecules, too small to be visible through an optical microscope. These micelles tend to form spherical shapes at lower concentrations and become cylindrical in shape at higher concentrations within this range. Micellar solutions look and behave in most cases as true clear solutions with very low viscosity, e.g., generally less than about 200 cps.
  • Lamellar phases are anisotropic phases composed of successive bilayers of surfactant arranged in parallel and separated by a liquid medium, usually an aqueous medium. Lamellar phase solutions are less viscous than M phase solutions even though they contain less water. This reduction in viscosity is due to the ease with which the parallel layers can slide over each other during shear. Lamellar phase solutions are, however, generally more viscous than micellar phase solutions.
  • surfactants form a hydrated solid.
  • Some surfactants such as the non-ionics tend to form a liquid phase containing dispersed water droplets of micelle size.
  • micellar dispersions of certain combinations of surfactants having differing resistance to electrolytic salting out can be converted at relatively low surfactant concentrations into and out of lamellar phase dispersions as a function of the concentration of water soluble electrolyte added to the dispersion.
  • Figure 1 demonstrates the development of a lamellar, more viscous phase within a micellar surfactant dispersion containing a certain concentration range of electrolyte, and reversion to the micellar phase above and below that concentration range.
  • concentrated micellar phase detergents containing up to about 60 wt% of surfactants and containing a water soluble electrolyte at a concentration in excess of the concentration which promotes conversion of the micelle phase to the lamellar phase can be diluted with water to the point where the electrolyte concentration falls within the lamellar phase-promoting concentration range for the particular system.
  • Dilution levels of the concentrate may generally range from about 0.5 to about 5 volumes of water per volume of concentrate. Conversion of the micelle dispersion into a lamellar dispersion produces an increase in viscosity of the detergent composition which at least equals, and normally will exceed, the viscosity of the undiluted, micellar phase concentrate.
  • the combination of surfactants which may be used in the present invention may be selected from anionic, non-ionic, cationic and amphoteric species, including mixtures containing different species or mixtures of different surfactants within the same species.
  • Suitable anionic surfactants include the water-soluble alkali metal salts having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil; sodium and potassium alkyl (C 9 -C 20 ) benzene sulfonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulfonates; sodium alkyl glycerol ether sulfates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (C 8 -C 18
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides and alkyl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
  • Specific nonionic surfactant compounds are alkyl (C 6 -C 18 ) primary or secondary linear or branched alcohols condensed with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • nonionic surfactant compounds include long chain tertiary amine oxides, long-chain tertiary phosphine oxides, dialkyl sulfoxides, fatty (C 8 -C 18 ) esters of glycerol, sorbitan and the like, alkyl polyglycosides, ethoxylated glycerol esters, ethyoxylated sorbitans and ethoxylated phosphate esters.
  • the preferred non-ionic surfactant compounds are those of the ethoxylated and mixed ethyoxylated-propyloxylated (C 6 -C 18 ) fatty alcohol type, containing 2-11 EO groups.
  • amphoteric surfactants which can be used in the compositions of the present invention are betaines and those which can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • betaines those which can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Examples of compounds falling within this definition are sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropane sulfonate, N-alkyltaurines, such as prepared by reacting dodecylamine with sodium isothionate, N-higher alkyl aspartic acids and the products sold under the trade name "Miranol”.
  • betaines useful herein include the high alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis(2-hydroxyethyl) carboxy methyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl) alpha-carboxyethyl betaine, etc.
  • high alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis(2-hydroxyethyl) carboxy methyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl di
  • the sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, amino betaine amidosulfobetaines, and the like.
  • betaines include 1-(lauryl, dimethylammonio) acetate-1-(myristyl dimethylammonio) propane-3-sulfonate, 1-(myristyl dimethylamino)-2-hydroxypropane-3-sulfonate, cocoamidoethylbetaine and cocoamidopropylbetaine.
  • Cationic surfactants which maybe used include mono C 8 -C 24 alkyl or alkenyl onium salts, especially mono-or polyammonium salts, imidazolinium salts, pyridinium salts or mixtures thereof.
  • Especially preferred cationics include the following: stearyldimethylbenzyl ammonium chloride; dodecyltrimethylammonium chloride; nonylbenzylethyldimethyl ammonium Nitrate; tetradecylpyridinium bromide; laurylpyridinium chloride; cetylpyridinium chloride; laurylisoquinoliumbromide; ditallow(hydrogenated)dimethyl ammonium chloride; dilauryldimethyl ammonium chloride; and stearalkonium chloride.
  • the surfactant or at least one of a combination of two or more surfactants used must possess a high resistance to salting out in the presence of an electrolyte such as potassium citrate or sodium chloride.
  • an electrolyte such as potassium citrate or sodium chloride.
  • high salting out resistance is meant that a 10% by weight aqueous solution of a particular surfactant should remain as a clear isotropic, stable solution where the aqueous solution contains about 4% by weight of dissolved citrate electrolyte.
  • a surfactant of low electrolyte resistance is one where a 10% by weight aqueous solution would form a cloudy, turbid or two phase solution in the presence of 4% by weight or less of potassium citrate.
  • high salting out resistant surfactants which can be used alone or as a mixture in the composition of this invention include C 12 - C 14 fatty alcohol ether sulfates (AEOS) with 2 or 3 moles of ethylene oxide, preferably 2 moles of ethylene oxide and mixtures thereof.
  • AEOS fatty alcohol ether sulfates
  • Some other high salting out resistant surfactants, e.g. betaines and AEOS surfactants having 4 or greater EO groups cannot be used as the sole surfactant because they do not provide the desired viscosity boost at relatively low electrolytic levels.
  • Low salting out resistant surfactants which cannot be used as the sole surfactant include linear alkyl benzene sulfonates (LAS) or the alkyl sulfates, since these tend to salt out in the presence of only 1% by weight electrolyte.
  • Other surfactants which can not be used alone include AEOS surfactants having a high EO content, e.g. 4 moles or greater and betaines, because, although they have a high resistance to electrolytic salting out, they do not exhibit a substantial viscosity boost when diluted with water.
  • the surfactants comprise a mixture of two or more surfactants, at least one of which has a high salting out resistance and at least one other of which has a low salting out resistance.
  • Such a combination provides the desired balance of electrolytic stability afforded by the electrolyte-resistant surfactant combined with a higher boost in viscosity provided by the non-electrolyte resistant surfactant when the surfactant phase is converted from the micellar phase to the lamellar phase upon dilution with water.
  • surfactants which may be used include AEOS (2EO) or AEOS (3EO) mixed with AEOS > (4EO); AEOS (2EO) blended with AEOS (3EO) (4:1 to 1:4 blend ratios); a mixture of a betaine, e.g.
  • cocoamidopropylbetaine with linear alkyl benzene sulfonate (3:1 to 1:1 blend ratios); a blend of C 8 to C 18 alkyl sulfates or sulfonates with AEOS (2 or 3EO) at 2:1 to 1:2 blend ratios; a ternary blend of C 8 to C 18 alkyl sulfate or sulfonate with a C 13 - C 15 fatty ethoxy alcohol (6-10 EO) and AEOS (2-3EO), blended at about equal parts of each surfactant; a ternary blend of a betaine, e.g. cocoamidoproplybetaine, with a C 13 - C 15 fatty ethoxy alcohol (6-10EO) and AEOS (2-3EO) and like combinations.
  • a betaine e.g. cocoamidoproplybetaine
  • surfactants When combined, such surfactants exhibit the desired balance of properties and stability required for the present invention. Accordingly, some trial and error may be required to determine the optimum surfactant combination.
  • Surfactants may be combined in the relative weight ratios of about 4:1 to 1:4 respectively.
  • a particularly preferred surfactant combination comprises a mixture of an anionic alkyl polyethoxy sulfate (AEOS) wherein the alkyl group contains from about 10 to 18 carbon atoms and the polyethyoxy is of 2 to 7 ethylene oxide groups, more preferably 2 or 3 ethylene oxide groups and a non-ionic ethoxylated fatty alcohol wherein the fatty alcohol contains from about 6 to 18 carbon atoms and containing 2-11 ethylene oxide groups, used in the relative proportion of 3:1 to 1:3.
  • AEOS anionic alkyl polyethoxy sulfate
  • the surfactant combination may be present in the concentrate at a level of from about 10 to 60% by weight, more preferably from about 10 to 35% by weight.
  • Electrolytes which may be used in the present invention include one of a mixture of water soluble organic and inorganic salts.
  • Suitable inorganics include alkali or alkaline earth metal chlorides, sulfates, phosphates, acetates and nitrates such as sodium, magnesium, lithium or calcium chloride, potassium bromide, calcium sulfate and the like.
  • Organic salts include the citrates, formates and salts of ethylene diamine tetraacetic acid.
  • a preferred electrolyte is sodium or potassium citrate since it also contributes as a builder in detergent compositions in the amount used.
  • the amount of electrolyte present in any given concentrate is determined by first evaluating the concentration in a diluted product containing a given combination of surfactants where conversion from the micellar into the lamellar phase is achieved, and than multiplying that level of concentration by the dilution factor as hereinafter described.
  • the concentrate will normally contain electrolyte at a level in the range of from about 1 to about 30% by weight.
  • the detergent composition of the invention may be used in numerous applications such as heavy duty laundry detergents, dish detergents, household cleaners, shampoos, body douche and body lotions. Accordingly they may contain the usual quantities of one or more adjuvants such as phosphorous and non-phosphorous containing builders, fluorescent brighteners, dyes, perfumes, viscosity regulators, shampoo adjuvants, enzymes, bleaches, batericidies, fungicides, anti-foam agents, preservatives, stabilizers and skin conditioners.
  • the adjuvants should not, however, be of a type which will promote instability of the product on standing.
  • a stock fine fabric detergent formulation was prepared by mixing the following ingredients (as 100% active ingredients by weight) and in the following proportions in a high shear mixer: Deionized water 89.43% NI-7EO* 3.70 AEOS-3EO** 3.80 Coco amino betaine 1.50 Foam control - myristic acid 0.10 Foam control - lauric acid 0.70 Fragrance 0.35 Protein cosmetic 0.01 Opacifier 0.38 Preservative 0.03 Dye 0.0001 *NI-7EO is C 13 - C 15 fatty alcohol with 7EO. **AEOS-3EO is C 12 - C 14 fatty alcohol ether sulfate with 3EO.
  • the resulting product was a clear micellar dispersion having a viscosity of about 12 cps (12 mPas). Ph was adjusted to about 7.4 to 7.6 by addition of potassium hydroxide (50%). The product had a total active ingredient content of about 10.5%, of which about 9% is surfactant content.
  • a series of ten additional solutions (A-J) having the composition of Example 1 were prepared except that a combination of citric acid and potassium hydroxide (50%) at about a 1.0 to 0.9 weight ratio was added at appropriate weight levels to form solutions containing about 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10% by weight, respectively, of potassium citrate electrolyte. Ph of each was adjusted to 7.4 - 7.6 as above. Viscosity measurements were as follows: EXAMPLE ELECTROLYTE CONCENTRATION (WT%) VISCOSITY (CPS) 1 0 12 2A 1 20 2B 2 75 2C 3 390 2D 4 910 2E 5 1020 2F 6 625 2G 7 290 2H 8 175 2I 9 120 2J 10 100
  • Example 2E A concentrate having approximately double the concentration of active ingredients of Example 2E, which contained about 5% by weight electrolyte, was prepared as described above.
  • the concentrate had the following composition: Deionized water 67.9% NI-7E0 7.40 AEOS-3EO 9.00 Coco amino betaine 3.00 Foam control - myristic acid 0.10 Foam control - lauric acid 1.50 Citric acid (anhy) 5.00 KOH (50%) 4.40 Fragrance 0.70 Protein cosmetic 0.01 Opacifier 0.75 Preservative 0.07 Dye 0.0002
  • the pH of the concentrate was adjusted to 7.4 to 7.6 using 50% KoH as above.
  • the concentrate had a viscosity of 100-150 cps and formed a clear, isotropic micellar dispersion.
  • Total active ingredients were about 31.2% by weight, of which about 19.4% by weight is surfactant and about 9% by weight is potassium citrate electrolyte.
  • Portions of the concentrate were then diluted with varying amounts of tap water as illustrated in Figure 2.
  • the concentrate developed a marked increase in viscosity with increasing dilution up to a maximum value in the lamellar phase and then began to drop again with the reformation of a micellar solution.
  • the twice diluted product (one volume water per volume of concentrate) exhibited a viscosity in the range of 600-800 cps.
  • pourable detergent concentrates having a viscosity of 200 cps and less are readily converted, by simple mixing, into water diluted concentrates having a viscosity in excess of 400 cps which have considerable appeal to the consumer.

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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)
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EP96200101A 1995-01-30 1996-01-16 Giessfähige Waschmittelkonzentrate, die nach Verdünnung mit Wasser gleiche oder erhöhte Viskosität zeigen Withdrawn EP0724013A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US38047795A 1995-01-30 1995-01-30
US380477 1995-01-30
US49607195A 1995-06-28 1995-06-28
US496071 1995-06-28

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EP0724013A1 true EP0724013A1 (de) 1996-07-31

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Country Status (8)

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EP (1) EP0724013A1 (de)
AU (1) AU702446B2 (de)
BR (1) BR9600236A (de)
CA (1) CA2168307A1 (de)
NO (1) NO960377L (de)
NZ (1) NZ280841A (de)
SG (1) SG54105A1 (de)
TR (1) TR199600075A2 (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050520A1 (en) * 1997-05-06 1998-11-12 Colgate-Palmolive Company Detergent concentrates which increase in viscosity after dilution
US6274546B1 (en) 1997-11-26 2001-08-14 Henkel Kommanditgesellschaft Auf Aktien Stable high viscosity liquid detergents
DE10023438A1 (de) * 2000-05-12 2001-11-22 Henkel Kgaa Konzentrat zur Verdünnung unter Viskositätserhalt oder -erhöhung
US6342472B1 (en) 1997-11-26 2002-01-29 Henkel Kommanditgesellschaft Auf Aktien (Kgaa) Low-concentration highly viscous liquid detergents
WO2003010262A1 (de) * 2001-07-24 2003-02-06 Henkel Kommanditgesellschaft Auf Aktien Maschinelle geschirrspülmittel mit niederviskosen tensiden
WO2003014275A1 (en) * 2001-08-06 2003-02-20 3M Innovative Properties Company Thickening on dilution liquid soap
US6564813B1 (en) 1997-07-22 2003-05-20 Ecolab Gmbh & Co. Ohg Use of solutions containing enzymes for cleaning fermentation or storage tanks
EP1362908A1 (de) * 2001-01-23 2003-11-19 Kao Corporation Flüssiges waschmittel
US7026276B2 (en) 2001-07-24 2006-04-11 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Machine dishwashing detergents containing surfactants with a low dynamic surface tension
US7053032B2 (en) 2001-07-24 2006-05-30 Henkel Kommanditgesellschaft Auf Aktien Machine dishwashing detergents containing surfactants with specific diffusion coefficients

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EP0164895A2 (de) * 1984-05-11 1985-12-18 Unilever N.V. Detergens-Zusammensetzungen
EP0314232A2 (de) * 1987-10-27 1989-05-03 Unilever N.V. Verdickende Gele
EP0328177A2 (de) * 1988-02-10 1989-08-16 Unilever N.V. Flüssige Reinigungsmittel
EP0359308A2 (de) * 1988-09-16 1990-03-21 Unilever N.V. Flüssige Waschmittel
EP0418986A2 (de) * 1989-09-22 1991-03-27 Colgate-Palmolive Company Verfahren zum Absorbieren lipophilen Schmutzes von einer Ober- fläche in eine Flüssigkristall-Detergenszusammensetzung
EP0452106A2 (de) * 1990-04-10 1991-10-16 ALBRIGHT & WILSON UK LIMITED Konzentrierte wässrige Tensidlösung
EP0595590A2 (de) * 1992-10-30 1994-05-04 Diversey Corporation Nichtchlorierte Reinigungsmittel mit niedriger Alkalinität und hohem Zurückhalten
WO1994025561A1 (en) * 1993-05-05 1994-11-10 Novo Nordisk A/S Cleaning gel
WO1994028108A1 (en) * 1993-06-01 1994-12-08 Ecolab Inc. Thickened hard surface cleaner
WO1995002664A1 (en) * 1993-07-13 1995-01-26 Jeyes Group Plc Surfactant-containing compositions

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0164895A2 (de) * 1984-05-11 1985-12-18 Unilever N.V. Detergens-Zusammensetzungen
EP0314232A2 (de) * 1987-10-27 1989-05-03 Unilever N.V. Verdickende Gele
EP0328177A2 (de) * 1988-02-10 1989-08-16 Unilever N.V. Flüssige Reinigungsmittel
EP0359308A2 (de) * 1988-09-16 1990-03-21 Unilever N.V. Flüssige Waschmittel
EP0418986A2 (de) * 1989-09-22 1991-03-27 Colgate-Palmolive Company Verfahren zum Absorbieren lipophilen Schmutzes von einer Ober- fläche in eine Flüssigkristall-Detergenszusammensetzung
EP0452106A2 (de) * 1990-04-10 1991-10-16 ALBRIGHT & WILSON UK LIMITED Konzentrierte wässrige Tensidlösung
EP0595590A2 (de) * 1992-10-30 1994-05-04 Diversey Corporation Nichtchlorierte Reinigungsmittel mit niedriger Alkalinität und hohem Zurückhalten
WO1994025561A1 (en) * 1993-05-05 1994-11-10 Novo Nordisk A/S Cleaning gel
WO1994028108A1 (en) * 1993-06-01 1994-12-08 Ecolab Inc. Thickened hard surface cleaner
WO1995002664A1 (en) * 1993-07-13 1995-01-26 Jeyes Group Plc Surfactant-containing compositions

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050520A1 (en) * 1997-05-06 1998-11-12 Colgate-Palmolive Company Detergent concentrates which increase in viscosity after dilution
US6799585B2 (en) 1997-07-22 2004-10-05 Ecolab Gmbh Co. Ohg Use of solutions containing enzymes for cleaning fermentation or storage tanks
US6564813B1 (en) 1997-07-22 2003-05-20 Ecolab Gmbh & Co. Ohg Use of solutions containing enzymes for cleaning fermentation or storage tanks
US6342472B1 (en) 1997-11-26 2002-01-29 Henkel Kommanditgesellschaft Auf Aktien (Kgaa) Low-concentration highly viscous liquid detergents
US6274546B1 (en) 1997-11-26 2001-08-14 Henkel Kommanditgesellschaft Auf Aktien Stable high viscosity liquid detergents
DE10023438A1 (de) * 2000-05-12 2001-11-22 Henkel Kgaa Konzentrat zur Verdünnung unter Viskositätserhalt oder -erhöhung
EP1362908A1 (de) * 2001-01-23 2003-11-19 Kao Corporation Flüssiges waschmittel
EP1362908A4 (de) * 2001-01-23 2004-09-08 Kao Corp Flüssiges waschmittel
WO2003010262A1 (de) * 2001-07-24 2003-02-06 Henkel Kommanditgesellschaft Auf Aktien Maschinelle geschirrspülmittel mit niederviskosen tensiden
US7026276B2 (en) 2001-07-24 2006-04-11 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Machine dishwashing detergents containing surfactants with a low dynamic surface tension
US7053032B2 (en) 2001-07-24 2006-05-30 Henkel Kommanditgesellschaft Auf Aktien Machine dishwashing detergents containing surfactants with specific diffusion coefficients
US7094739B2 (en) 2001-07-24 2006-08-22 Henkel Kommandigesellschaft Auf Aktien (Henkel Kgaa) Dishwasher machine detergents with low viscosity surfactants
WO2003014275A1 (en) * 2001-08-06 2003-02-20 3M Innovative Properties Company Thickening on dilution liquid soap
US6617293B2 (en) 2001-08-06 2003-09-09 3M Innovative Properties Company Thickening on dilution liquid soap

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NO960377L (no) 1996-07-31
TR199600075A2 (tr) 1996-08-21
NZ280841A (en) 1997-04-24
BR9600236A (pt) 1997-12-23
AU4211396A (en) 1996-08-08
NO960377D0 (no) 1996-01-29
CA2168307A1 (en) 1996-07-31
SG54105A1 (en) 1998-11-16
AU702446B2 (en) 1999-02-18

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