EP0633308A1 - Composition détergente liquide à base de surfactant non ionique très moussant - Google Patents

Composition détergente liquide à base de surfactant non ionique très moussant Download PDF

Info

Publication number
EP0633308A1
EP0633308A1 EP94401590A EP94401590A EP0633308A1 EP 0633308 A1 EP0633308 A1 EP 0633308A1 EP 94401590 A EP94401590 A EP 94401590A EP 94401590 A EP94401590 A EP 94401590A EP 0633308 A1 EP0633308 A1 EP 0633308A1
Authority
EP
European Patent Office
Prior art keywords
liquid detergent
ethylene oxide
surfactant
detergent composition
moles
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.)
Granted
Application number
EP94401590A
Other languages
German (de)
English (en)
Other versions
EP0633308B1 (fr
Inventor
Rita Erilli
Gilbert S. Gomes
Stephen Repinec
Ronald Kern
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26784034&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0633308(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0633308A1 publication Critical patent/EP0633308A1/fr
Application granted granted Critical
Publication of EP0633308B1 publication Critical patent/EP0633308B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to novel light duty liquid detergent compositions with high foaming properties, containing a nonionic surfactant, a specific group of anionic surfactants, and a Zwitterionic betaine surfactant wherein the surfactants are dissolved in an aqueous medium.
  • Nonionic surfactants are in general chemically inert and stable toward pH change and are therefore well suited for mixing and formulation with other materials. The superior performance of nonionic surfactants on the removal of oily soil is well recognized. Nonionic surfactants are also known to be mild to human skin. However, as a class, nonionic surfactants are known to be low or moderate foamers. Consequently, for detergents which require copious and stable foam, the application of nonionic surfactants is limited. There have been substantial interest and efforts to develop a high foaming detergent with nonionic surfactants as the major ingredient. Little has been achieved.
  • 4,329,335 also discloses a shampoo containing a betaine surfactant as the major ingredient and minor amounts of a nonionic surfactant and of a fatty acid mono- or di-ethanolamide.
  • U.S. Patent No. 4,259,204 discloses a shampoo comprising 0.8-20% by weight of an anionic phosphoric acid ester and one additional surfactant which may be either anionic, amphoteric, or nonionic.
  • U.S. Patent No. 4,329,334 discloses an anionic-amphoteric based shampoo containing a major amount of anionic surfactant and lesser amounts of a betaine and nonionic surfactants.
  • U.S. Patent No. 3,935,129 discloses a liquid cleaning composition based on the alkali metal silicate content and containing five basic ingredients, namely, urea, glycerin, triethanolamine, an anionic detergent and a nonionic detergent.
  • the silicate content determines the amount of anionic and/or nonionic detergent in the liquid cleaning composition.
  • the foaming property of these detergent compositions is not discussed therein.
  • U.S. Patent No. 4,129,515 discloses a heavy duty liquid detergent for laundering fabrics comprising a mixture of substantially equal amounts of anionic and nonionic surfactants, alkanolamines and magnesium salts, and, optionally, zwitterionic surfactants as suds modifiers.
  • U.S. Patent No. 4,224,195 discloses an aqueous detergent composition for laundering socks or stockings comprising a specific group of nonionic detergents, namely, an ethylene oxide of a secondary alcohol, a specific group of anionic detergents, namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant which may be a betaine, wherein either the anionic or nonionic surfactant may be the major ingredient.
  • a specific group of nonionic detergents namely, an ethylene oxide of a secondary alcohol
  • anionic detergents namely, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol
  • amphoteric surfactant which may be a betaine, wherein either the anionic or nonionic surfactant may be the major ingredient.
  • the prior art also discloses detergent compositions containing all nonionic surfactants as shown in U.S. Patent Nos. 4,154,706 and 4,329,336 wherein the shampoo compositions contain a plurality of particular nonionic surfactants in order to effect desirable foaming and detersive properties despite the fact that nonionic surfactants are usually deficient in such properties.
  • U.S. Patent No. 4,013,787 discloses a piperazine based polymer in conditioning and shampoo compositions which may contain all nonionic surfactant or all anionic surfactant.
  • U.S. Patent No. 4,450,091 discloses high viscosity shampoo compositions containing a blend of an amphoteric betaine surfactant, a polyoxybutylenepolyoxyethylene nonionic detergent, an anionic surfactant, a fatty acid alkanolamide and a polyoxyalkylene glycol fatty ester.
  • U.S. Patent No. 4,595,526 describes a composition comprising a nonionic surfactant, a betaine surfactant, an anionic surfactant and a C12-C14 fatty acid monoethanolamide foam stabilizer.
  • a high foaming, nonionic based, liquid detergent composition containing a nonionic surfactant, a supplementary high foaming ethoxylated alkyl ether sulfate anionic surfactant and a supplementary foaming zwitterionic surfactant selected from betaine type surfactants as the three essential ingredients wherein the composition does not contain any amine oxide, calcium carbonate, polymeric or clay thickeners, abrasive, clays, silicas, alkyl glycine surfactant, cyclic imidinium surfactant, or more than 3.0 wt. % of a fatty acid or a metal salt of the fatty acid compounds.
  • None of the above-cited patents discloses a high foaming, nonionic based, liquid detergent composition containing a nonionic surfactant as a major active ingredient and lesser amounts of a magnesium salt of C8-C18 ethoxylated alkyl ether sulfate surfactant, an alkali metal salt of an alkyl sulfate surfactant, and a supplementary foaming zwitterionic surfactant selected from betaine type surfactants as the four essential ingredients, wherein the nonionic ingredient constitutes more than 50% of the total surfactant content.
  • a high foaming liquid detergent can be formulated with a nonionic surfactant which has desirable cleaning properties, mildness to the human skin.
  • An object of this invention is to provide novel, liquid aqueous detergent compositions containing a nonionic surfactant, an ethoxylated alkyl (ether) sulfate anionic surfactant, and a zwitterionic betaine surfactant, wherein the composition does not contain amine oxide, alkali metal carbonate, polymeric or clay thickeners, clays, abrasives, alkyl glycine surfactants, cyclic imidinium surfactants, silicas or more than 3 wt. % of a fatty acid or a metal salt of a fatty acid.
  • a further object of this invention is to provide novel, nonionic based, liquid detergent compositions containing a major amount of nonionic surfactant supplemented with lesser amounts of a magnesium salt of an ethoxylated alkyl ether sulfate surfactant, a sodium salt of an alkyl sulfate surfactant, and a zwitterionic betaine surfactant, wherein the composition does not contain any amine oxide, fatty acid alkanolamides, clay, silica, abrasive, clay or polymeric thickeners, alkali metal or alkaline earth metal carbonate or more than 3 wt.% of a fatty acid or its metal salt.
  • Still another object of this invention is to provide a novel, liquid detergent with desirable high foaming and cleaning properties which is mild to the human skin.
  • the novel, high foaming, light duty liquid detergent of this invention comprises three essential surfactants: a water soluble, ethoxylated, nonionic surfactant; a foaming water soluble, zwitterionic surfactant selected from the class of betaines; and an ethoxylated alkyl ether sulfate surfactant, wherein the ingredients are dissolved in an aqueous vehicle, and the composition does not contain any amine oxide, alkanolamide ingredients.
  • the present invention relates to a high foaming, nonionic based, liquid detergent comprising a nonionic surfactant selected from the group consisting of water soluble primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkyl phenol ethoxylates and alcohol ethylene oxide propylene oxide condensates; a water soluble zwitterionic betaine surfactant; ethoxylated alkyl ether sulfate surfactants: and optionally a C8 ⁇ 14 alkyl sulfate surfactant wherein the ingredients are dissolved in an aqueous vehicle.
  • a nonionic surfactant selected from the group consisting of water soluble primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkyl phenol ethoxylates and alcohol ethylene oxide propylene oxide condensates; a water soluble zwitterionic betaine surfactant; ethoxyl
  • the total amount of surfactants may constitute 18 %-55 %, preferably 20 % - 40 %, most preferably 25 % - 35 %, by weight of the liquid composition.
  • the invention relates to a high foaming, nonionic surfactant-based, light duty, liquid detergent comprising approximately, by weight :
  • a preferred composition is a liquid detergent composition further including 1.0 to 15 % of a cosolubilizing agent selected from the group consisting of C2-C3 mono- and di-hydroxy alkanols, water soluble salts of C1-C3 alkyl substituted benzene sulfonate hydrotropes and mixtures thereof.
  • a cosolubilizing agent selected from the group consisting of C2-C3 mono- and di-hydroxy alkanols, water soluble salts of C1-C3 alkyl substituted benzene sulfonate hydrotropes and mixtures thereof.
  • the high foaming nonionic based light duty liquid detergent compositions of the instant invention comprise approximately by weight : 10 to 25 wt. % of a water soluble nonionic surfactant; 8 to 16 wt. % of an ethoxylated alkyl ether sulfate and 2 to 12 wt. % of a betaine surfactant; and 47 to 80 wt. % of water, wherein the compositions do not contain any amine oxides, calcium carbonate, polymeric or clay thickeners, abrasives, clays, silicas, alkyl glycine surfactants, cyclic imidinium surfactants, or more than 3 wt. % of a fatty acid or a metal salt of the fatty acid.
  • the invention also relates to a high foaming, nonionic surfactant-based, light duty, liquid detergent comprising approximately, by weight :
  • Said composition comprises approximately by weight : 10 to 20 wt. %, more preferably 11 to 17 wt. % of a nonionic surfactant; 0.5 to 8 wt. % more preferably 1 to 7 wt. % of an alkali metal or ammonium salt of a C8-C14 alkyl sulfate surfactant; 8 to 16 wt. % of a magnesium salt of a C8-C18 ethoxylated alkyl ether sulfate surfactant and 2 to 10 wt. %, more preferably 3 to 9 wt.
  • composition does not contain any amine oxide, fatty acid alkanolamide, alkali metal or alkaline earth metal carbonate, clay, silica, abrasive, clay or polymeric thickener or more than 3 wt. % of fatty acid or its metal salt.
  • a preferred composition is a liquid detergent composition which includes, in addition, 1% to 15% by weight of a solubilizing agent which is a C2-C3 mono or dihydroxy alkanol or a water soluble salts of C1-C3 alkyl substituted benzene sulfonate hydrotropes and mixtures thereof.
  • a solubilizing agent which is a C2-C3 mono or dihydroxy alkanol or a water soluble salts of C1-C3 alkyl substituted benzene sulfonate hydrotropes and mixtures thereof.
  • the nonionic surfactant which constitutes the major ingredient in the liquid detergent composition is present in amounts of 10 to 25 %, preferably 15 to 20 % by weight of the composition and provides superior performance in the removal of oily soil and mildness to human skin.
  • the water soluble nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxidepropylene oxide condensates on primary alkanols, such a Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI).
  • the nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups.
  • any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic detergent. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements.
  • the nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with 16 moles of ethylene oxide (EO), tridecanol condensed with 6 moles of EO, myristyl alcohol condensed with 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EO per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
  • a higher alcohol e.g., an alkanol containing 8 to 18
  • Neodol ethoxylates which are higher aliphatic, primary alcohol containing 9-15 carbon atoms, such as C9-C11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12 ⁇ 13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12 ⁇ 15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14 ⁇ 15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like.
  • Neodol ethoxylates such as C9-C11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12 ⁇ 13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12 ⁇ 15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12
  • Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
  • HLB hydrophobic lipophilic balance
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
  • nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from 8 to 18 carbon atoms in a straight- or branched chain alkyl group with 5 to 30 moles of ethylene oxide.
  • alkyl phenol ethoxylates include nonyl phenol condensed with 9.5 of EO per mole of nonyl phenol, dinonyl phenol condensed with 12 moles of EO per mole of dinonyl phenol, dinonyl phenol condensed with 15 moles of EO per mole of phenol and diisoctylphenol condensed with 15 moles of EO per mole of phenol.
  • nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
  • Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic detergent ingredient in the described shampoo.
  • These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
  • the water-soluble zwitterionic surfactant which is also an essential ingredient of present liquid detergent composition, constitutes 2 to 12%, preferably 3 to 10%, by weight and provides good foaming properties and mildness to the present liquid detergent.
  • the zwitterionic surfactant is a water soluble betaine having the general formula: wherein R1 is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, or the amido radical: wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4; R2 and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4 is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one hydroxyl group.
  • Typical alkyldimethyl betaines include decyl dimethyl betaine or 2-(N-decyl-N, N-dimethyl-ammonia) acetate, coco dimethyl betaine or 2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, etc.
  • the amidobetaines similarly include cocoamidoethylbetaine, cocoamidopropyl betaine and the like.
  • a preferred betaine is coco (C8-C18) amidopropyldimethyl betaine.
  • anionic sulfate and sulfonate surfactants which may be used in the detergent of this invention are water soluble such as triethanolamine and include the sodium, potassium, ammonium and ethanolammonium salts of C8-C14 alkyl sulfates such as lauryl sulfate, myristyl sulfate and the like; linear C8-C18 alkyl benzene sulfonates; preferably C9-C16 or C10-C15.
  • the preferred sulfate surfactant is a C8 to C14 alkyl sulfate and is present in the composition at a concentration of about 0.5 to 8 wt. %.
  • a preferred alkylbenzene sulfonate is a linear alkylbenzene sulfonate having a higher content of 3-phenyl (or higher) isomers and a correspondingly lower content (well below 50%) of 2-phenyl (or lower) isomers, such as those sulfonates wherein the benzene ring is attached mostly at the 3 or higher (for example 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low.
  • Preferred materials are set forth in U.S. Patent 3,320,174, especially those-in which the alkyls are of 10 to 13 carbon atoms.
  • AEOS.xEO ethoxylated alkyl ether sulfate
  • R-(OCH2 CH2)x OSO3M wherein x is about 1 to 22, more preferably about 1 to about 10 and R is an alkyl group having about 8 to 18 carbon atoms and more preferably about 12 to about 15 carbon atoms and natural cuts for example C12 ⁇ 14, C12-C13 and C12 ⁇ 15 and M is an alkali earth metal cation such as magnesium.
  • ethoxylated sulfate salts having the formula: R'(OCH2-CH2) n OSO3M wherein R' is alkyl of 8 or 9 to 18 carbon atoms, n is 1 to 22, preferably 1 to 5, and M is a magnesium cation.
  • R' is alkyl of 8 or 9 to 18 carbon atoms
  • n is 1 to 22, preferably 1 to 5
  • M is a magnesium cation.
  • the ethoxylated alkyl ether sulfates may be made by sulfating the condensation product of ethylene oxide and C8 ⁇ 18 alkanol, and neutralizing the resultant product.
  • the ethoxylated alkyl ether sulfates differ from one another in the number of carbon atoms in the alcohols and in the number of moles of ethylene oxide reacted with one mole of such alcohol.
  • Preferred ethoxylated alkyl ether sulfates contain 10 to 6 carbon atoms in the alcohols and in the alkyl groups thereof.
  • Na(AEOS.XEO) surfactant provides a detergent system which coacts with the nonionic surfactant to product a liquid detergent composition with desirable foaming, foam stability and detersive properties.
  • the resultant homogeneous liquid detergent exhibits the same or better foam performance, both as to initial foam volume and stability of foam in the presence of soils, and cleaning efficacy as an anionic based light duty liquid detergent (LDLD) as shown in the following Examples.
  • LDLD light duty liquid detergent
  • aqueous medium comprising water and optionally, solubilizing ingredients such as alcohols and dihydroxy alcohols such as C2-C3 mono- and di-hydoroxy alkanols, e.g. ethanol, isopropanol and propylene glycol.
  • solubilizing ingredients such as alcohols and dihydroxy alcohols such as C2-C3 mono- and di-hydoroxy alkanols, e.g. ethanol, isopropanol and propylene glycol.
  • Suitable water soluble hydrotropic salts include sodium, potassium, ammonium and mono-, di- and thriethanolammonium salts of (C1-C3) alkyl substituted benzene sulfonate hydrotropes.
  • the aqueous medium is primarily water, preferably said solubilizing agents are included in order to control the viscosity of the liquid composition and to control low temperature cloud clear properties.
  • the proportion of solubilizer generally will be from 0.5% to 8%, preferably 1% to 7%, by weight of the detergent composition with the proportion of ethanol, when present, being 5% of weight or less in order to provide a composition having a flash point above 46° C.
  • the solubilizing ingredient will be propylene glycol.
  • Another extremely effective solubilizing or cosolubilizing agent used at a concentration of 0.1 to 5 wt. percent, more preferably 0.5 to 4.0 weight percent is isethionic acid or an alkali metal salt of isethionic acid having the formula wherein X is hydrogen or an alkali metal cation, preferably sodium.
  • solubilizing ingredients also facilitate the manufacture of the inventive compositions because they tend to inhibit gel formation.
  • various coloring agents and perfumes such as the Uvinuls, which are products of GAF Corporation; sequestering agents such as ethylene diamine tetraacetates; magnesium sulfate heptahydrate; pearlescing agents and opacifiers; pH modifiers; etc.
  • the proportion of such adjuvant materials, in total will normally not exceed 15% of weight of the detergent composition, and the percentages of most of such individual components will be 0.1% to 5% by weight and preferably less than 2% by weight.
  • Sodium formate can be included in the formula as a perservative at a concentration of 0.1 to 4.0%.
  • Sodium bisulfite can be used as a color stabilizer at a concentration of 0.01 to 0.2 wt.%.
  • Typical perservatives are dibromodicyano-butane, citric acid, benzylic alcohol and poly (hexamethylene-biguamide) hydro-chloride and mixtures thereof.
  • compositions can contain 0 to 5 wt. %, more preferably 1 to 4.0 wt. % of an alkyl polysaccharide surfactant.
  • the alkyl polysaccharides surfactants which are used in conjunction with the aforementioned surfactant have a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing from 1.5 to 10, preferably from 1.5 to 4, most preferably from 1.6 to 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units).
  • the number x indicates the number of saccharide units in a particular alkyl polysaccharide surfactant.
  • x can only assume integral values.
  • the physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values.
  • the hydrophobic group (R) can be attached at the 2-, 3-, or 4- positions rather than at the 1-position, (thus giving e.g.
  • glucosyl or galactosyl as opposed to a glucoside or galactoside).
  • attachment through the 1- position i.e., glucosides, galactoside, fructosides, etc.
  • additional saccharide units are predominately attached to the previous saccharide unit's 2-position. Attachment through the 3-, 4-, and 6- positions can also occur.
  • the preferred alkoxide moiety is ethoxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 20, preferably from 10 to 18 carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to 30, preferably less than 10, alkoxide moieties.
  • Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.
  • the alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in admixture with alkyl polysaccharides, the alkyl monosaccharides are solubilized to some extent.
  • the use of alkyl monosaccharides in admixture with alkyl polysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
  • the preferred alkyl polysaccharides are alkyl polyglucosides having the formula R2O(C n H2 n O)r(Z) x wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to 10, preferable 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7.
  • a long chain alcohol R2OH
  • an acid catalyst to form the desired glucoside
  • the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (R1OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside.
  • a short chain alcohol C1 ⁇ 6
  • R2OH longer chain alcohol
  • the short chain alkylglucoside content of the final alkyl polyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkyl polyglucoside.
  • the amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polysaccharide surfactant is preferably less than 2%, more preferably less than 0.5% by weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than 10%.
  • alkyl polysaccharide surfactant is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkyl polysaccharide surfactants.
  • alkyl polyglucoside is used to include alkyl polyglycosides because the stereochemistry of the saccharide moiety is changed during the preparation reaction.
  • APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, PA.
  • APG 625 has: a pH of 6 to 10 (10% of APG 625 in distilled water); a specific gravity at 25°C of 1.1 g/ml; a density at 25°C of 9.1 Ibs/gallon; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C, 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
  • compositions can contain a silk derivatives as part of the composition and generally constitute 0.01 to 3.0 % by weight, preferably 0.1 to 3.0% by weight, most preferably 0.2 to 2.5% by weight of the liquid detergent composition.
  • the silk fibers may be used in the form of powder in preparing the liquid detergent or as a powder of a product obtained by washing and treating the silk fibers with an acid.
  • silk fibers are used as a product obtained by hydrolysis with an acid, alkali or enzyme, as disclosed in Yoshiaki Abe et al., U.S. Patent No. 4,839,168; Taichi Watanube et al., U.S. Patent No. 5,009,813; and Marvin E. Goldberg, U.S. Patent No. 5,069,898, each incorporated herein by reference.
  • Another silk derivative which may be employed in the composition of the present invention is protein obtained from degumming raw silk, as disclosed, for example, in Udo Hoppe et al., U.S. Patent No. 4,839,165, incorporated herein by reference.
  • the principal protein obtained from the raw silk is sericin which has an empirical formula of C15H25O3N5 and a molecular weight of 323.5.
  • a silk derivative for use in the liquid detergent composition of the present invention is a fine powder of silk fibroin in nonfibrous or particulate form, as disclosed in Kiyoshi Otoi et al., U.S. Patent No. 4,233,212, incorporated herein by reference.
  • the fine powder is produced by dissolving a degummed silk material in at least one solvent selected from, for example, an aqueous cupriethylene diamine solution, an aqueous ammoniacal solution of cupric hydroxide, an aqueous alkaline solution of cupric hydroxide and glycerol, an aqueous lithium bromide solution, an aqueous solution of the chloride, nitrate or thiocyanate of calcium, magnesium or zinc and an aqueous sodium thiocyanate solution.
  • a solvent selected from, for example, an aqueous cupriethylene diamine solution, an aqueous ammoniacal solution of cupric hydroxide, an aqueous alkaline solution of cupric hydroxide and glycerol, an aqueous lithium bromide solution, an aqueous solution of the chloride, nitrate or thiocyanate of calcium, magnesium or zinc and an aqueous sodium thiocyanate solution.
  • the resulting fibroin solution
  • the dialyzed aqueous silk fibroin solution having a silk fibroin concentration of from 3 to 20% by weight, is subjected to at least one treatment for coagulating and precipitating the silk fibroin, such as, for example, by the addition of a coagulating salt, by aeration, by coagulation at the isoelectric point, by exposure to ultrasonic waves, by agitation at high shear rate and the like.
  • at least one treatment for coagulating and precipitating the silk fibroin such as, for example, by the addition of a coagulating salt, by aeration, by coagulation at the isoelectric point, by exposure to ultrasonic waves, by agitation at high shear rate and the like.
  • the resulting product is a silk fibroin gel which may be incorporated directly into the liquid detergent composition or the same may be dehydrated and dried into a powder and then dissolved in the liquid detergent composition.
  • the silk material which may be used to form the silk fibroin includes cocoons, raw silk, waste cocoons, raw silk waste, silk fabric waste and the like.
  • the silk material is degummed or freed from sericin by a conventional procedure such as, for example, by washing in warm water containing a surfact-active agent or an enzyme, and then dried.
  • the degummed material is dissolved in the solvent and preheated to a temperature of from 60 to 95°C, preferably 70 to 85°C. Further details of the process of obtaining the silk fibroin are discussed in U.S. Patent No. 4,233,212.
  • a preferred silk derivative is a mixture of two or more individual amino acids which naturally occur in silk.
  • the principal silk amino acids are glycine, alanine, serine and tyrosine.
  • a silk amino acid mixture resulting from the hydrolysis of silk of low molecular weight and having a specific gravity of at least 1 is produced by Croda, Inc. and sold under the trade name "CROSILK LIQUID” which typically has a solids content in the range of 27 to 31% by weight. Further details of the silk amino acid mixture can be found in Wendy W. Kim et al., U.S. Patent No. 4,906,460, incorporated herein by reference.
  • a typical amino acid composition of "CROSILK LIQUID” is shown in the following Table.
  • compositions can contain a viscosity modifying solvent at a concentration of 0.1 to 5.0 weight percent, more preferably 0.5 to 4.0 weight percent.
  • the viscosity modifying agent is an alcohol of the formula wherein
  • the 3-methyl-3-methoxy butanol is commercially available from Sattva Chemical Company of Stamford, Connecticut and Kuraray Co., Ltd., Osaka, Japan.
  • the instant composition can contain 0.1 to 4.0% of a protein selected from the group consisting of hydrolyzed animal collagen protein obtained by an enzymatic hydrolysis, lexeine protein, vegetal protein and hydrolyzed wheat protein and mixtures thereof.
  • the present light duty liquid detergents such as dishwashing liquids are readily made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition.
  • the nonionic surfactant be mixed with the solubilizing ingredients, e.g., ethanol and, if present, prior to the addition of the water to prevent possible gelation.
  • the nonionic based surfactant system is prepared by sequentially adding with agitation the anionic surfactant and the betaine to the nonionic surfactant, cosolubilizing agent and water, and then adding with agitation the formula amount of water to form an aqueous solution of the surfactant system.
  • mild heating up to 100°C.
  • the viscosities are adjustable by changing the total percentage of active ingredients. No polymeric or clay thickening agent is added. In all such cases the product made will be pourable from a relatively narrow mouth bottle (1.5 cm. diameter) or opening, and the viscosity of the detergent formulation will not be so low as to be like water.
  • the viscosity of the detergent desirably will be at least 100 centipoises (cps) at room temperature, but may be up to 1,000 centipoises as measured with a Brookfield Viscometer using a number 3 spindle rotating at 18 rpms. Its viscosity may approximate those of commercially acceptable detergents now on the market.
  • the detergent viscosity and the detergent itself remain stable on storage for lengthy periods of time, without color changes or settling out of any insoluble materials.
  • the pH of this formation is substantially neutral to skin, e.g., 4.5 to 8 and preferably 5 to 5.5.
  • the compositions of the instant invention are optically clear - that is they exhibit a light transmission of at least 95%, more preferably at least 98%.
  • the foam quality and detersive property is equal to or better than standard light duty liquid detergents while using a nonionic surfactant as the primary surfactant and minimal amounts of anionic surfactant, thereby achieving a mild, non-irritating liquid detergent.
  • the Shell Foam and Shake Foam Height test were run against a control sample of a commercial Palmolive Skin Sensitive formulation manufactured by Colgate-Palmolive Co.
  • the designation "s” means that the sample being tested has the same value as the commercial sample.
  • the designation "-” means that the value obtained is less than the value obtained for the commercial sample.
  • the designation "+” means that the value obtained is superior to the value obtained for the commercial sample.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
EP94401590A 1993-07-09 1994-07-08 Composition détergente liquide à base de surfactant non ionique très moussant Revoked EP0633308B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US9151293A 1993-07-09 1993-07-09
US9151393A 1993-07-09 1993-07-09
US91512 1993-07-09
US91513 1993-07-09

Publications (2)

Publication Number Publication Date
EP0633308A1 true EP0633308A1 (fr) 1995-01-11
EP0633308B1 EP0633308B1 (fr) 1998-10-21

Family

ID=26784034

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94401590A Revoked EP0633308B1 (fr) 1993-07-09 1994-07-08 Composition détergente liquide à base de surfactant non ionique très moussant

Country Status (10)

Country Link
EP (1) EP0633308B1 (fr)
AT (1) ATE172487T1 (fr)
AU (1) AU6600394A (fr)
CA (1) CA2127657A1 (fr)
DE (1) DE69414040T2 (fr)
DK (1) DK0633308T3 (fr)
ES (1) ES2126080T3 (fr)
GR (1) GR940100343A (fr)
NZ (1) NZ260848A (fr)
PT (1) PT101539B (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996001101A1 (fr) * 1994-07-01 1996-01-18 The Procter & Gamble Company Compositions de desquamation
WO1996018712A1 (fr) * 1994-12-10 1996-06-20 Henkel Kommanditgesellschaft Auf Aktien Tensio-actifs non ioniques speciaux pour liquides a vaisselle utilises pour faire la vaisselle a la main
WO1997015650A1 (fr) * 1995-10-23 1997-05-01 Colgate-Palmolive Company Compositions detergentes liquides pour travaux legers
WO1997038073A1 (fr) * 1996-04-08 1997-10-16 Colgate-Palmolive Company Compositions liquides de nettoyage destinees a un usage non intensif
WO1997038072A1 (fr) * 1996-04-08 1997-10-16 Colgate-Palmolive Company Compositions liquides detergentes pour lavages delicats
US5681852A (en) * 1993-11-12 1997-10-28 The Procter & Gamble Company Desquamation compositions
WO1998002512A2 (fr) * 1996-07-15 1998-01-22 Colgate-Palmolive Company Detergent liquide a haut pouvoir moussant a base de tensioactif non ionique
WO1998005744A2 (fr) * 1996-08-07 1998-02-12 Colgate-Palmolive Company Compositions nettoyantes liquides pour travaux legers
WO1998005745A2 (fr) * 1996-08-08 1998-02-12 Colgate-Palmolive Company Compositions nettoyantes liquides pour travaux legers
WO1998036043A1 (fr) * 1997-02-13 1998-08-20 Colgate-Palmolive Company Compositions lavantes liquides travaux legers
US5821237A (en) * 1995-06-07 1998-10-13 The Procter & Gamble Company Compositions for visually improving skin
WO1998050507A1 (fr) * 1997-05-02 1998-11-12 Colgate-Palmolive Company Detergent liquide a base de tensio-actif non ionique a fort pouvoir moussant
WO2000015741A2 (fr) * 1998-09-11 2000-03-23 Colgate-Palmolive Company Compositions nettoyantes liquides
US6759382B2 (en) 2001-06-01 2004-07-06 Kay Chemical, Inc. Detergent composition containing a primary surfactant system and a secondary surfactant system, and a method of using the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1379678A (zh) 1999-10-01 2002-11-13 强生消费者公司 用个人护理组合物镇静人类的方法
GB2384563A (en) 2002-01-29 2003-07-30 Johnson & Johnson Consumer Method of measuring the stress or relaxation level of a mammal

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2361080A1 (de) * 1972-12-11 1974-06-12 Procter & Gamble Mildes shampoo
US3950417A (en) * 1975-02-28 1976-04-13 Johnson & Johnson High-lathering non-irritating detergent compositions
EP0155737A2 (fr) * 1984-03-21 1985-09-25 Shionogi & Co., Ltd. Compositions de shampooing peu irritantes
EP0181212A1 (fr) * 1984-11-07 1986-05-14 The Procter & Gamble Company Compositions détergentes liquides
EP0387063A2 (fr) * 1989-03-10 1990-09-12 Unilever Plc Compositions détergentes
WO1993009215A1 (fr) * 1991-11-07 1993-05-13 The Procter & Gamble Company Systeme de stabilisation des couleurs dans des compositions detergentes liquides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2361080A1 (de) * 1972-12-11 1974-06-12 Procter & Gamble Mildes shampoo
US3950417A (en) * 1975-02-28 1976-04-13 Johnson & Johnson High-lathering non-irritating detergent compositions
EP0155737A2 (fr) * 1984-03-21 1985-09-25 Shionogi & Co., Ltd. Compositions de shampooing peu irritantes
EP0181212A1 (fr) * 1984-11-07 1986-05-14 The Procter & Gamble Company Compositions détergentes liquides
EP0387063A2 (fr) * 1989-03-10 1990-09-12 Unilever Plc Compositions détergentes
WO1993009215A1 (fr) * 1991-11-07 1993-05-13 The Procter & Gamble Company Systeme de stabilisation des couleurs dans des compositions detergentes liquides

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5681852A (en) * 1993-11-12 1997-10-28 The Procter & Gamble Company Desquamation compositions
AU703079B2 (en) * 1994-07-01 1999-03-11 Procter & Gamble Company, The Desquamation compositions
WO1996001101A1 (fr) * 1994-07-01 1996-01-18 The Procter & Gamble Company Compositions de desquamation
WO1996018712A1 (fr) * 1994-12-10 1996-06-20 Henkel Kommanditgesellschaft Auf Aktien Tensio-actifs non ioniques speciaux pour liquides a vaisselle utilises pour faire la vaisselle a la main
US5821237A (en) * 1995-06-07 1998-10-13 The Procter & Gamble Company Compositions for visually improving skin
WO1997015650A1 (fr) * 1995-10-23 1997-05-01 Colgate-Palmolive Company Compositions detergentes liquides pour travaux legers
WO1997038073A1 (fr) * 1996-04-08 1997-10-16 Colgate-Palmolive Company Compositions liquides de nettoyage destinees a un usage non intensif
WO1997038072A1 (fr) * 1996-04-08 1997-10-16 Colgate-Palmolive Company Compositions liquides detergentes pour lavages delicats
AU719890B2 (en) * 1996-04-08 2000-05-18 Colgate-Palmolive Company, The Light duty liquid cleaning compositions
WO1998002512A2 (fr) * 1996-07-15 1998-01-22 Colgate-Palmolive Company Detergent liquide a haut pouvoir moussant a base de tensioactif non ionique
WO1998002512A3 (fr) * 1996-07-15 1998-06-25 Colgate Palmolive Co Detergent liquide a haut pouvoir moussant a base de tensioactif non ionique
WO1998005744A2 (fr) * 1996-08-07 1998-02-12 Colgate-Palmolive Company Compositions nettoyantes liquides pour travaux legers
WO1998005744A3 (fr) * 1996-08-07 1998-06-25 Colgate Palmolive Co Compositions nettoyantes liquides pour travaux legers
WO1998005745A3 (fr) * 1996-08-08 1998-07-09 Colgate Palmolive Co Compositions nettoyantes liquides pour travaux legers
WO1998005745A2 (fr) * 1996-08-08 1998-02-12 Colgate-Palmolive Company Compositions nettoyantes liquides pour travaux legers
WO1998036043A1 (fr) * 1997-02-13 1998-08-20 Colgate-Palmolive Company Compositions lavantes liquides travaux legers
WO1998050507A1 (fr) * 1997-05-02 1998-11-12 Colgate-Palmolive Company Detergent liquide a base de tensio-actif non ionique a fort pouvoir moussant
WO2000015741A2 (fr) * 1998-09-11 2000-03-23 Colgate-Palmolive Company Compositions nettoyantes liquides
WO2000015741A3 (fr) * 1998-09-11 2000-09-21 Colgate Palmolive Co Compositions nettoyantes liquides
AU755741B2 (en) * 1998-09-11 2002-12-19 Colgate-Palmolive Company, The Liquid cleaning compositions
US6759382B2 (en) 2001-06-01 2004-07-06 Kay Chemical, Inc. Detergent composition containing a primary surfactant system and a secondary surfactant system, and a method of using the same

Also Published As

Publication number Publication date
DE69414040D1 (de) 1998-11-26
EP0633308B1 (fr) 1998-10-21
AU6600394A (en) 1995-01-19
PT101539A (pt) 1995-05-04
ATE172487T1 (de) 1998-11-15
NZ260848A (en) 1996-08-27
DK0633308T3 (da) 1999-07-12
CA2127657A1 (fr) 1995-01-10
ES2126080T3 (es) 1999-03-16
GR940100343A (en) 1995-10-31
PT101539B (pt) 1999-12-31
DE69414040T2 (de) 1999-06-17

Similar Documents

Publication Publication Date Title
US5389305A (en) High foaming nonionic surfactant base liquid detergent
US5387375A (en) High foaming nonionic surfactant based liquid detergent
US5866529A (en) High foaming nonionic surfactant base liquid detergent comprising gelatin beads
US5561106A (en) High foaming light duty liquid detergent composition comprising partially esterified ethoxylated polyhydric alcohol solubilizing agent
US5385696A (en) High foaming nonionic surfactant based liquid detergent
US5389304A (en) High foaming nonionic surfactant base liquid detergent
EP0633308B1 (fr) Composition détergente liquide à base de surfactant non ionique très moussant
WO2000071653A1 (fr) Compositions liquides antibacteriennes pour le nettoyage de surfaces dures
EP1220882A1 (fr) Solution homogenes d'un agent de surface de sulfonate d'olefine alpha
US5610127A (en) High foaming nonionic surfactant based liquid detergent
EP0633307B1 (fr) Composition détergente liquide à base de surfactant non ionique très moussant
US5503779A (en) High foaming light duty liquid detergent
US5922662A (en) High foaming nonionic surfactant based liquid detergent
WO1995023204A1 (fr) Detergent liquide
US5955411A (en) High foaming nonionic surfactant based liquid detergent
EP0638638B1 (fr) Composition détergente liquide à base de surfactant non ionique très moussant
US5756441A (en) High foaming nonionic surfactant based liquid detergent
US5556577A (en) High foaming nonionic surfactant based liquid detergent
US5789370A (en) High foaming nonionic surfactant based liquid detergent
US6455482B1 (en) Light duty liquid cleaning compositions comprising a crosslinked polymer
US5869439A (en) High foaming nonionic surfactant based liquid detergent
US6140290A (en) High foaming nonionic surfactant based liquid detergent
WO1998005743A1 (fr) Detergent liquide fabrique a partir d'un surfactif non ionique tres moussant
WO1998050507A1 (fr) Detergent liquide a base de tensio-actif non ionique a fort pouvoir moussant

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19950704

17Q First examination report despatched

Effective date: 19950830

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981021

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981021

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981021

REF Corresponds to:

Ref document number: 172487

Country of ref document: AT

Date of ref document: 19981115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69414040

Country of ref document: DE

Date of ref document: 19981126

ITF It: translation for a ep patent filed
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2126080

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: HENKEL KGAA

Effective date: 19990720

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: HENKEL KGAA

Effective date: 19990720

NLR1 Nl: opposition has been filed with the epo

Opponent name: HENKEL KGAA

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20010618

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20010703

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20010713

Year of fee payment: 8

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020709

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20020722

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030201

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20030201

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20030808

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20030811

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030930

Year of fee payment: 10

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20040702

Year of fee payment: 11

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030709

27W Patent revoked

Effective date: 20040312

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 20040312