EP0495858B1 - Detergents liquides - Google Patents

Detergents liquides Download PDF

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Publication number
EP0495858B1
EP0495858B1 EP90915470A EP90915470A EP0495858B1 EP 0495858 B1 EP0495858 B1 EP 0495858B1 EP 90915470 A EP90915470 A EP 90915470A EP 90915470 A EP90915470 A EP 90915470A EP 0495858 B1 EP0495858 B1 EP 0495858B1
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EP
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Prior art keywords
weight
composition
compositions
composition according
polymer
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EP90915470A
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German (de)
English (en)
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EP0495858A1 (fr
Inventor
Johannes Cornelis Van De Pas
Frederik Jan Unilever Research U.S.Inc Schepers
Rudolf Cornelis Stefanus Verheul
Peter Graham Montague
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Diversey Inc
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Unilever PLC
Unilever NV
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Priority claimed from GB898927728A external-priority patent/GB8927728D0/en
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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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention is concerned with aqueous liquid detergent compositions which contain sufficient detergent-active material and, optionally, sufficiently dissolved electrolyte to result in a structure of lamellar droplets dispersed in a continuous aqueous phase.
  • Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry: Industrial Applications', J. Wiley & Sons, Letchworth 1980.
  • Such lamellar dispersions are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending particulate solids such as detergency builders or abrasive particles. Examples of such structured liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-140 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplet are called 'spherulites'.
  • lamellar droplets in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and electron microscopy.
  • the droplets consist of an onion-like configuration of concentric bi-layers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.
  • the viscosity and stability of the product depend on the volume fraction of the liquid which is occupied by the droplets. Generally speaking, when the volume fraction is around 0.6 (say from 0.5 to 0.7), the droplets are just touching (space-filling). This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 1 Pas at a shear rate of 21s- 1 ). This volume fraction also endows useful solid-suspending properties.
  • a problem in the formulating of liquid detergent compositions is to prevent the occurence of flocculation.
  • flocculation occurs between the lamellar droplets at a given volume fraction, the viscosity of the corresponding product will increase due to the formation of a network throughout the liquid.
  • Flocculation may also lead to instability reflected in phase separation of the product.
  • compositions containing five essential ingredients contain from 3-12 % by weight of a potassium alkylbenzenesulphonate, 2-8 % by weight of a potasssium soap of a C 8 - 22 fatty acids or polymers thereof and 0.5 to 5 % by weight of a nonionic detergent active material, wherein the relative ratios of the active ingredients are within narrowly defined ranges.
  • compositions according to this patent comprise from 1-25 % of an alkali metal tripolyphosphate and from 0.1-2 % of a specific copolymer of maleic anhydride with vinylmethylether, ethylene or styrene, partially esterified with the nonionic detergent active material.
  • GB 1,589,971 relates to similar compositions wherein part of the alkali metal tripolyphosphate is replaced by tetrapotassium pyrophosphate.
  • the pH of the exemplified compositions is 12.5, which would generally be too low for certain purposes such as for example the industrial cleaning of fabrics, the viscosity of the products is 550 mPas or more at 30 s-1.
  • Suitable deflocculating polymers are for example polymers comprising a hydrophilic backbone and one or more hydrophobic sidechains.
  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition comprising a deflocculating polymer selected from the group of:
  • compositions of the invention are stable.
  • stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable' compositions will yield no more than 10 %, preferably no more than 5 %, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
  • compositions of the invention have a pH of more than 12.5, more preferred more than 13.0, especially preferred more than 13.5. These high pH values render the products of the invention especially suitable for the preparation of liquid detergent compositions intended for use in the industrial cleaning of fabrics.
  • compositions of the invention preferably have a viscosity of less than 2,500 especially less than 1,000 mPas at 21 s-1, more preferred less than 750 mPas, most preferred less than 500 mPas, especially preferred between 100 and 400 mPas at 21 s-1.
  • Suitable deflocculating polymers for use in compositions of the present invention are for instance described in our copending European patent application 89201530.6 (EP 346 995).
  • the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitues at least 50 %, preferably more than 75 %, most preferred more than 90% by weight of the backbone)
  • suitable monomer constituents of the hydrophilic backbone are for example unsaturated C, - 6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol.
  • hydrophilic backbone made from the backbone constituents in the absence of hydrophilic side-groups is relatively water-soluble at ambient temperature and a pH of between 10.0 and 15.0.
  • solubility is more than 1 g/I, more preferred more than 5 g/I most preferred more than 10 g/I.
  • electrolytes e.g. sodium citrate.
  • the hydrophobic sidegroups are composed of relatively hydrophobic alkoxy groups for example butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains having from 5 to 24 carbon atoms.
  • the hydrophobic groups may be connected to the hydrophilic backbone via relatively hydrophilic bonds for example a poly ethoxy linkage.
  • Preferred polymers are of the formula: wherein:
  • compositions of the invention are described in our copending non-prior-published PCT patent applications WO/91/06622 (published 16 May 1991) and WO/91/06623 (published 16 May 1991) and our co-pending non-prior-published British patent application GB 2,237,813 (published 15 May 1991).
  • polymers described in those patent applications especially the use of polymers in accordance with our non-prior-published patent application WO/91/06623 (published 16 May 1991) is preferred.
  • These polymers are constituted of nonionic monomers and ionic monomers, wherein the ionic monomer is from 0.1 to 50 % by weight of the polymer.
  • Especially preferred polymers of this type are of the formula: wherein: x, z and n are as above;
  • polymers for use in compositions have a molecular weight (as determined as in our co- pending European patent application 346 995) of between 500 and 100,000, more preferred from 1,000 to 20,000, especially preferred from 1,500 to 10,000.
  • Polymers for use in compositions of the invention may for example be prepared by using conventional aqueous polymerisation procedures, suitable methods are for example described in the above mentioned co-pending European patent application.
  • the deflocculating polymer will be used at from 0.01 to 5 % by weight of the composition, more preferably from 0.1 to 3.0, especially preferred from 0.25 to 2.0 %.
  • compositions of the invention also comprise detergent active materials, preferably at a level of from 1 to 70% by weight of the composition, more preferred a level of 5 to 40 % by weight, most preferred from 10 to 35 % by weight.
  • the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • surfactants may be chosen from any of the classes, subclasses and specific materials described in 'Surface Active Agents' Vol.1, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.ll by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in 'Tensid-Taschenbuch', H.Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, 1981.
  • 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 or alkyl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary phospine oxides and dialkyl sulphoxides.
  • salting out resistant active materials such as for example described in EP 328 177, especially the use of alkyl poly glycoside surfactants such as for example disclosed in EP 70 074. Also alkyl mono glucosides may be used.
  • the level of nonionic surfactants is more than 1 % by weight of the composition, preferably from 2.0 to 20.0% by weight of the composition, more preferred from 5.0 to 19 %, especially preferred from 10.0 to 18.0 %.
  • compositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials.
  • Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates 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 l8 ) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 -C l8 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid
  • the preferred anionic detergent compounds are sodium (C 11 -C 15 ) alkyl benzene sulphonates, sodium (C 16 -C 18 ) alkyl sulphates and primary (ClO-C24) alkyl sodium or potassium sulphate.
  • the level of the above mentioned anionic surfactant materials is from 1-15 % by weight of the composition.
  • low levels of these anionic materials are used, for example less than 5 %, more preferred less than 3 % by weight of the composition, especially preferred less than 2.5 %.
  • the weight ratio of the above mentioned synthetic anionic surfactant materials to the nonionic surfactant materials is less than 1:2, more preferred less than 1:3, especially preferred from 1:4 to 1:10.
  • an alkali metal soap of a mono- or di-carboxylic acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • the level of soap in compositions of the invention is from 5-35 % by weight of the composition, more preferred from 10-25 %.
  • compositions optionally also contain electrolyte in an amount sufficient to bring about lamellar structuring of the detergent-active material.
  • the compositions contain from 1 % to 60%, especially from 10 to 45% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is those electrolytes which have a lyotropic number of less than 9.5.
  • some salting-in electrolyte (as defined in the latter specification) may also be included.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • detergency builder material some or all of which may be electrolyte.
  • some detergent active materials such as for example soaps, also have builder properties.
  • Examples of phosphorus-containing inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. For many reasons, including environmental reasons it is however preferred to minimise the amount of phosphate builders.
  • Especially the amount of alkali metal phosphate builders, such as sodium tripolyphosphate is preferably less than 0.5 % by weight of the composition, more preferred less than 0.1 %, especially preferred compositions of the invention are substantially free of phosphate builder materials.
  • non-phosphorus-containing inorganic detergency builders when present, include water- soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites. For high pH compositions according to the invention the use of silicate builders is preferred, these materials are especially advantageous because of their buffering capacities at pH values above 12.5.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • electrolytes which promote the solubility of other electrolytes
  • potassium salts to promote the solubility of sodium salts.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid.
  • compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a reference 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000.
  • Use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
  • compositions of the present invention are of low viscosity (less than 500 mPas at 21 s-1) and are substantially free of suspended solid materials such as undissolved builder materials.
  • level of less soluble builder materials such as sodium tripolyphosphate is less than 1 %, more preferred less than 0.5 %, more preferred less than 1 %, most preferred the builder material for use in compositions of the invention are completely water-soluble.
  • the level of non-soap builder material is from 5-40 % by weight of the composition, more preferred from 5 to 25 % by weight of the composition. Especially preferred is the use of from 5-20 % by weight of the composition of a silicate builder material, preferably a metasilicate builder material.
  • compositions of the invention comprise from 5 to 99 % by weight of water, more preferred from 10- 50 %, most preferred from 15 to 40 %.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), antiredeposition agents, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • fabric softeners such as clays, amines and amine oxides
  • lather depressants oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate
  • compositions of the invention may be prepared by any conventional method for the preparation of liquid detergent compositions.
  • a preferred method involves the dispersing of the electrolyte ingredient together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the builder material, the deflocculating polymer and the detergent active material under light stirring and finally cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
  • the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 %, more preferred from 0.1 to 3% by weight.
  • compositions were made by adding the KOH plus the silicate ingredients to water of ambient temperature under stirring followed by the addition of the deflocculating polymer.
  • the detergent active materials are premixed and subsequently added to the aqueous mixture. Finally the remaining ingredients are added.
  • the pH of the compositions is around 14.0.
  • composition A had a viscosity of 280 mPas at 21 s- 1
  • composition B of 490 mPas at 21 s-1
  • compositions C-F had viscosities of about 300 mPas.
  • Composition G (comparison) was unstable (more than 10 % phase separation upon storage for three weeks), no viscosity was measured of this composition.
  • Compositions A-F were stable lamellar dispersions of active materials in the aqueous base. The lamellar phase volume of these compositions was from 0.5 to 0.67.
  • the pH of the compositions was 14 or more.
  • the performance of the compositions was tested by washing at 60 °C at a dosage of 5 g/I in the presence of standard stained clothes AS 9. The following scores were obtained:
  • composition I had a viscosity of 1,680 mPas at 21 s -1
  • composition II had a viscosity of 648 mPas at 21 s -1 .
  • Both compositions had a pH of 14 or more.
  • compositions had a pH of 14 or more, all formulations were physically stable for more than 1 month upon storage at 37 ° C.
  • compositions had a pH of more than 14.
  • the viscosity of composition A was 504 mPas at 21 s -1
  • the viscosity of composition B was 384 mPas at 21 s- 1.

Abstract

Composition de détergent liquide comprenant une dispersion de gouttelettes lamellaires de matériaux à activité détergente dans une phase continue aqueuse. Ladite composition comprend un polymère défloculant et présente un pH supérieur à 12,5.

Claims (7)

1. Composition détergente liquide comprenant une dispersion de gouttelettes lamellaires de matières détergentes actives en une phase aqueuse continue, ladite composition comprenant un polymère défloculant choisi parmi les suivants :
i) des polymères comprenant un édifice de base hydrophile et une ou plusieurs chaîne(s) latérale(s) hydrophobe(s) à la condition que :
quand la composition comprend de 3 à 12% d'un alkylbenzènesulfonate de potassium, de 2 à 8% d'un savon d'acide gras de potassium, de 0,5 à 5% d'un tensioactif non ionique et de 1 à 25% de tripolyphosphate de potassium ou de sodium et/ou de pyrophosphate tetrapotassique, tous les pourcentages étant en poids, le rapport pondéral dudit sulfonate audit savon étant compris entre 1:2 et 6:1, le rapport pondéral dudit sulfonate audit tensioactif non ionique étant compris entre 3:5 et 25:1 et le total desdits sulfonate, savon et tensioactif non ionique étant compris entre 7,5 et 20% en poids, alors le polymère défloculant ne consiste pas seulement en 0,1 à 2% en poids d'un copolymère neutralisé partiellement estérifié d'anhydride maléique avec l'éther vinylméthylique, l'éthylène ou le styrène; et
ii) des polymères consistant en monomères non ioniques et monomères ioniques, le monomère ionique représentant de 0,1 à 50% en poids du polymère,

ladite composition ayant un pH supérieur à 12,5 et ne produisant pas plus de 10% en volume de séparation de phases quand on l'emmagasine à 25 ° C pendant 21 jours à partir du moment de sa préparation.
2. Composition selon la revendication 1, dont le pH est supérieur à 13,0.
3. Composition selon la revendication 1, dont la viscosité est inférieure à 500 mPa.s à 21 s-1.
4. Composition selon la revendication 1, qui comprend de 0,01 à 5,0% en poids de polymères défloculants.
5. Composition selon la revendication 1, comprenant de 5 à 40% en poids de matières détergentes actives.
6. Composition selon la revendication 5, comprenant de 5,0 à 19,0% d'un tensioactif non ionique.
7. Composition selon la revendication 1, comprenant de 5 à 20% d'un silicate adjuvant, ladite composition étant sensiblement exempte d'adjuvants phosphatés.
EP90915470A 1989-10-12 1990-10-04 Detergents liquides Expired - Lifetime EP0495858B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP89202580 1989-10-12
EP89202580 1989-10-12
GB898927728A GB8927728D0 (en) 1989-12-07 1989-12-07 Liquid detergents
GB8927728 1989-12-07
PCT/EP1990/001667 WO1991005844A1 (fr) 1989-10-12 1990-10-04 Detergents liquides

Publications (2)

Publication Number Publication Date
EP0495858A1 EP0495858A1 (fr) 1992-07-29
EP0495858B1 true EP0495858B1 (fr) 1995-01-25

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EP90915470A Expired - Lifetime EP0495858B1 (fr) 1989-10-12 1990-10-04 Detergents liquides

Country Status (8)

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EP (1) EP0495858B1 (fr)
AU (1) AU651797B2 (fr)
CA (1) CA2066623C (fr)
DE (1) DE69016449T2 (fr)
ES (1) ES2067766T3 (fr)
FI (1) FI921570A0 (fr)
NZ (1) NZ235599A (fr)
WO (1) WO1991005844A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101351869B1 (ko) * 2005-05-20 2014-01-15 로디아 인코포레이티드 구조화된 계면활성제 조성물

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2052279T3 (es) * 1989-12-07 1994-07-01 Unilever Nv Detergentes liquidos.
US5360432A (en) * 1992-10-16 1994-11-01 Shturman Cardiology Systems, Inc. Abrasive drive shaft device for directional rotational atherectomy
US5312427A (en) * 1992-10-16 1994-05-17 Shturman Cardiology Systems, Inc. Device and method for directional rotational atherectomy
US5356418A (en) * 1992-10-28 1994-10-18 Shturman Cardiology Systems, Inc. Apparatus and method for rotational atherectomy
US6090762A (en) * 1993-05-07 2000-07-18 Albright & Wilson Uk Limited Aqueous based surfactant compositions
SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
US9090861B2 (en) 2007-08-17 2015-07-28 Rhodia Asia Pacific Ltd. Structured soap compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3235505A (en) * 1961-09-20 1966-02-15 Monsanto Co Detergent processes
GB1506427A (en) * 1975-04-29 1978-04-05 Unilever Ltd Liquid detergent
MX167884B (es) * 1983-12-22 1993-04-20 Albright & Wilson Composicion detergente liquida
GB8718217D0 (en) * 1987-07-31 1987-09-09 Unilever Plc Liquid detergent compositions
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101351869B1 (ko) * 2005-05-20 2014-01-15 로디아 인코포레이티드 구조화된 계면활성제 조성물

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NZ235599A (en) 1992-05-26
ES2067766T3 (es) 1995-04-01
WO1991005844A1 (fr) 1991-05-02
FI921570A (fi) 1992-04-09
AU6540690A (en) 1991-05-16
EP0495858A1 (fr) 1992-07-29
FI921570A0 (fi) 1992-04-09
CA2066623C (fr) 2001-03-06
CA2066623A1 (fr) 1991-04-13
DE69016449T2 (de) 1995-06-08
AU651797B2 (en) 1994-08-04
DE69016449D1 (de) 1995-03-09

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