EP0504159B1 - Detergents liquides - Google Patents

Detergents liquides Download PDF

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Publication number
EP0504159B1
EP0504159B1 EP90916484A EP90916484A EP0504159B1 EP 0504159 B1 EP0504159 B1 EP 0504159B1 EP 90916484 A EP90916484 A EP 90916484A EP 90916484 A EP90916484 A EP 90916484A EP 0504159 B1 EP0504159 B1 EP 0504159B1
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EP
European Patent Office
Prior art keywords
weight
composition
polymer
preferred
compositions
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EP90916484A
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German (de)
English (en)
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EP0504159A1 (fr
Inventor
Peter Leonard Unilever Research Dawson
Johannes Cornelis Van De Pas
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB898927730A external-priority patent/GB8927730D0/en
Priority claimed from GB909014830A external-priority patent/GB9014830D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0504159A1 publication Critical patent/EP0504159A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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
    • 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
    • C11D3/227—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 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.
  • the present invention relates to liquid detergent compositions which contain low levels of detergent active materials.
  • 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-104 452 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 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 product which is occupied by the droplets. Generally speaking, when the volume fraction is around 0.6, the droplets are just touching (space-filling). This allows reasonable stability with an acceptable viscosity.
  • Detergent products for use on hard surfaces tend to contain relatively low levels of surfactant materials, say from 0.1 to 16 % weight of the compositions. These low levels of surface-active ingredients sometimes render it difficult to formulate detergent compositions of the lamellar droplet-type. Often products containing these low active levels are not entirely stable and/or have an unacceptable low viscosity.
  • EP-A-0,301,882 discloses structured liquid detergent compositions comprising polymers selected from polyethylene glycols, polyacrylates, polymaleates, polysugars, polysugarsulphonates and copolymers thereof to improve stability and/or lower viscosity.
  • compositions as disclosed in these applications comprise generally high levels (about 17 weight % or more) of surface active ingredients and/or high total levels of STP plus zeolite; or they comprise somewhat lower levels of active material in the presence of at least 8 % by weigth of STP.
  • Compositions as disclosed in these patent applications are herewith disclaimed from the scope of the present invention.
  • 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 C8 ⁇ 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 compositions according to the two above mentioned British patents are hereby disclaimed from the scope of the present invention.
  • the present invention relates to a detergent composition in liquid, gel or paste form, which yields no more than 10% by volume phase separation as evidenced by appearance of two or more separate phases when stored at 25°C for 21 days from the time of preparation, and which comprises a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition comprising from 0.1 to 16% by weight of surface active materials and no or less than 20% by weight of sodium tripolyphosphate plus zeolite builder material, said composition also comprising from 0.01 to 5% by weight of a deflocculating polymer; wherein said deflocculating polymer has a hydrophilic backbone and at least one hydrophobic side chain; and with the provisos that
  • the polymers will possibly at least partly be incorporated inside the droplets, this has the effect of decoupling the inter- and intra-droplet forces, i.e. the difference between the forces between individual surfactant molecules in adjacent layers within a particular droplet and those between surfactant molecules in adjacent droplets could become accentuated, in that the forces between the adjacent droplets are reduced. This will possibly lead to increased stability and less flocculation, especially at high electrolyte levels.
  • the polymer may actually form a linkage between two or more lamellar droplets, whereby an additional structure may be formed which provides a thickening effect.
  • compositions of the invention are physically stable.
  • physical 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 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.
  • deflocculating polymers in compositions which are unstable in the absence of deflocculating polymer, but stable in the presence of said polymer.
  • compositions of the invention may be pourable liquids, but also possible are products in gel or paste-form.
  • Gel or paste compositions according to the invention preferably have a viscosity of between 2,000 and 20,000 mPas at 21 s-1, more preferred between 5,000 and 15,000, most preferred from 8,000 to 12,000.
  • Liquid compositions of the invention preferably have a viscosity of less than 2,500 mPas at 21 s-1 and more than 25 mPas at 21 s-1, more preferred less than 2,000 mPas and more than 50 mPas, most preferred less than 1,500 mPas and more than 100 mPas, e.g about 1,000 mPas.
  • compositions of the invention are more viscous than a corresponding composition without the deflocculating polymer.
  • the increase of viscosity by adding the polymer at a level of 1.0 wt % is at least 10 %, more preferred more than 20 %, especially preferred more than 35 %.
  • 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), polymers as described in this patent have a hydrophilic backbone and at least one hydrophobic side chain.
  • the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitutes 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 unsaturates C1 ⁇ 6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol.
  • Suitable monomer units are acrylic acid, methacrylic acid, maleic acid, vinyl acetic acid, glucosides, ethylene oxide and glycerol.
  • the 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 6.0 and 13.0.
  • the solubility is more than 1 g/l, more preferred more than 5 g/l most preferred more than 10 g/l.
  • 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 (I): Wherein: Q2 is a molecular entity of formula (Ia): wherein: R1 represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-or is absent; R2 represents from 1 to 50 independently selected alkyleneoxy groups preferably ethylene oxide or propylene oxide groups, or is absent , provided that when R3 is absent and R4 represents hydrogen or contains no more than 4 carbon atoms, then R2 must contain an alkyleneoxy group preferably more than 5 alkyleneoxy groups with at least 3 carbon atoms; R3 represents a phenylene linkage, or is absent; R4 represents hydrogen or a C1 ⁇ 24 alkyl or C2 ⁇ 24 alkenyl group, with the provisos that
  • Q1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q1 in any direction, in any order, therewith possibly resulting in a branched polymer.
  • Q1 is trimethyl propane triacrylate (TMPTA), methylene bisacrylamide or divinyl glycol.
  • n is at least 1; z and v are 1; and (x + y + p + q + r) : z is from 4 : 1 to 1,000 : 1, preferably from 6 : 1 to 250 : 1; in which the monomer units may be in random order; and preferably either p and q are zero, or r is zero; R7 and R8 represent -CH3 or -H; R9 and R10 represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phosphonate, phosphate, hydroxy, carboxyl and oxide groups, preferably they are selected from -SO3Na, -CO-O-C2H4-OSO3Na, -CO-O-NH-C(CH3)2-SO3Na, -CO-NH2, -O-CO-CH3, -OH;
  • Preferably polymers for use in compositions of the invention which are of relatively high pH (say 10 or more) are substantially free of hydrolysable
  • Particularly preferred polymers for use in high pH compositions of the invention comprise hydrophilic backbones constituted by acid groups such as acrylic acid and at least one hydrophobic side chain which is constituted of from 5 to 75 relatively water-insoluble alkoxy groups such as propoxy units optionally linked to the hydrophylic backbone via an -poly-alkoxy linkage constituted of from 1-10 relatively watersoluble alkoxy groups such as ethoxy units.
  • polymers for use in compositions of the invention are described in WO 91/06623, WO 91/06622 and GB-A-2,237,813.
  • polymers described in those patent applications especially the use of polymers in accordance with WO 91/06622 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 89201530.6; EP 346 995) of between 500 and 100,000, more preferred from 1,000 to 20,000, especially preferred from 1,500 to 10,000 most preferred from 2,800 to 6,000.
  • 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 %.
  • the ratio of hydrophobic or ionic monomers to hydrophilic or nonionic monomers is from 1 : 1 to 1 : 100, preferably 1 : 4 to 1 : 25.
  • polymers comprising two or more hydrophobic or ionic monomers.
  • polymers for this purpose are of relatively high molecular weight, say more than 2,000, preferably from 4,000 to 100,000, more preferred from 6,000 to 50,000.
  • relatively high mW polymers say less than 5,000
  • higher mW polymers say above 5,000
  • compositions of the invention also comprise detergent active materials, preferably at a level of from 0.1 to 16% by weight of the composition, more preferred at a level of 2 to 12 % by weight, most preferred from 4 to 11 % 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, sub-classes and specific materials described in 'Surface Active Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.II 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, München & 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 (C6-C18) 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 phosphine oxides and dialkyl sulphoxides.
  • the level of nonionic surfactants is more than 0.2 % by weight of the composition, preferably from 0.5 to 6.0% by weight of the composition, more preferred from 1.0 to 5.0 %.
  • 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 (C8-C18) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) 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 (C8-C18) 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 amides of methyl taurine; alkane
  • the level of the above mentioned anionic surfactant materials is from 0.5-15 % by weight of the composition, preferably from 1 to 12 %, more preferred from 2 to 10 %, most preferred from 3 to 8 %.
  • 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.
  • oleic acid 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, potassium, ammonium and alkanol amine soaps of these acids can be used.
  • the level of soap in compositions of the invention is from 0.1 to 5 % by weight of the composition, more preferred from 0.2 to 3%, especially preferred from 0.5 to 2%.
  • 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.
  • compositions optionally also contain electrolyte in an amount sufficient to bring about lamellar structuring of the detergent-active material.
  • compositions Preferably contain from 0.1% to 60% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
  • some salting-in electrolyte (as defined in the latter specification) may also be included.
  • compositions according to the present invention include no or low levels of detergency builder material selected from STP and zeolites.
  • level of these builder materials is less than 20 % by weight, more preferred less than 5 %, most especially preferred less than 1 % by weight, most preferably compositions of the invention are substantially free from these builder materials.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates and silicates, examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates and silicates.
  • 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, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid.
  • Products according to the invention preferably are used for the cleaning of surface areas, preferred embodiments of the invention are all purpose cleaners; liquid abrasive cleaners and bleach liquids.
  • All purpose cleaners of the invention preferably contain from 1-15 % by weight of surface active ingredients, more preferred from 2-14 %, most preferred from 3-13 %.
  • the surface active materials are selected from the group of anionic surfactant materials and nonionic surfactant materials, or mixtures thereof.
  • anionic surfactants of the alkyl aryl sulphonate and/or primary alkyl sulphate type are used in combination with nonionic materials which are alkoxylated fatty alcohols or alkylpolyglycosides and fatty acid materials or their soaps.
  • the viscosity of all purpose cleaners in accordance with the invention is preferably from 40 to 1,800 mPas at 21 s-1, more preferred from 45 to 1,500, most preferred from 50 to 1,200.
  • the pH of the compositions is preferably from 4-13, more preferred from 6-12, most preferred from 8-11.
  • Liquid abrasive cleaners in accordance with the invention preferably comprise from 1-15 % by weight of surface active ingredients, more preferred from 2-14 %, most preferred from 3-13 %.
  • the surface active materials are selected from the group of anionic surfactant materials and nonionic surfactant materials or mixtures thereof.
  • anionic surfactants of the alkyl aryl sulphonate and/or primary alkyl sulphate type are used in combination with nonionic materials which are alkoxylated fatty alcohols and/or alkylpolyglycosides and fatty acid materials or their soaps.
  • liquid abrasive cleaners will comprise solid particles for polishing and abrasion.
  • a substantial proportion (say more than 50 %) of the insoluble solid particles is of small particle size, preferably not larger than 10 micrometer.
  • Examples of these materials are calcites and solid particles of potassium sulphate, silica, bicarbonate, alumina, borax, calcium carbonate, magnesium carbonate and feldspar.
  • calcite is used.
  • the level of abrasive material is from 2-70 % by weight of the composition, more preferred from 10- 60 %, most preferred from 20-50 %. Especially preferred is the use of calcite abrasives.
  • the viscosity of liquid abrasive cleaners in accordance with the invention is preferably from 300 to 2,500 mPas at 21 s-1, more preferred 400-2,000, most preferred 500-1,500.
  • the pH of the compositions is preferably from 6-14 more preferred from 7-12, most preferred from 8-11.
  • Liquid bleach compositions of the invention will comprise one or more bleaching ingredients such as for example chlorine bleaches, peroxy bleaches, persulphate bleaches or hydrogen peroxide.
  • the robustness of the compostion will be provided by a lamellar structure of surface active ingredients.
  • the level of surface active ingredients will be relatively low, say from 0.1 to 10 % by weight of the composition, more preferred from 0.5 to 8 %, most preferred from 1.0 to 6%.
  • the level of bleach ingredients preferably corresponds to from 0.1-25 % by weight of the composition of available active chlorine and/or hydrogenperoxide, more preferred from 0.5-20 %, most preferred from 1-10%.
  • the viscosity of liquid bleach compositions in accordance with the invention is preferably from 10 to 1,000 mPas at 21 s-1, more preferred 30 to 500, most preferred 80-200.
  • the pH of the compositions is preferably from 2-14 more preferred from 4-12, most preferred from 6-11.
  • bleach compositions of the invention also comprise one or more bleach stabilising agents.
  • bleach stabilising agents Especially preferred for this purpose are phosphonates and stannates. Phosphonate bleach stabilisation materials are available under the trade-name Dequest (ex Monsanto).
  • 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, 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), anti-redeposition 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 such as inorganic salts such as sodium sulphate
  • fluorescent agents such as fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), anti-redeposition
  • 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 deflocculating polymer ingredient in water before the formation of a lamellar droplet structure for example before the addition of the detergent active materials thereto.
  • the polymer together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the surfactant active materials, and builder material or other electrolyte ingredients under stirring and finally cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
  • Ingredient % wt Composition A B anionic 1) 6.0 6.0 soap 2) 1.0 1.0 nonionic 3) 3.0 3.0 sodium carbonate 7.3 7.3 perfume 4) 0.7 0.7 preservative 5) 0.1 0.1 polymer 6) 0.25 -- water balance 1) Sodium salt of DOBS 102 (ex Shell) 2) Potassium coconut soap 3) Dobanol 23 6.5 EO (ex Shell) 4) GC 234 E (ex Quest) 5) formalin 6) polymer A-11 disclosed in EP 346 995.
  • the viscosity of the compositions was measured at 1 s-1, 21 s-1 and 1000 s-1. The results were the following: Shear rate s ⁇ 1 A B viscosity in mPas 1 4800 2900 21 450 290 1000 54 38
  • compositions C, D, E and F were made as in example I
  • Ingredient % wt C D E F anionic 1) 4.0 4.0 6.0 6.0 soap 2) 1.0 1.0 1.0 1.0 nonionic 3) 5.0 5.0 3.0 3.0 sodium carbonate 7.3 7.3 10.0 10.0 perfume 4) 0.25 0.25 0.25 0.25 polymer 6 ) 0.25 -- 0.25 -- 1) Sodium salt of DOBS 102 (ex Shell) 2) Potassium coconut soap 3) Dobanol 23 6.5 EO (ex Shell) 4) GC 234 E (ex Quest) 6) polymer A-11 disclosed in EP 346 995.
  • compositions D and F were unstable and showed more than 10 % phase separation upon storage for 3 weeks at ambient temperature. Compositions C and E did not show phase separation under these conditions.
  • This example illustrates that detergent compositions of low active level can be made more stable by incorporating therein a deflocculating polymer in accordance with the invention.
  • a liquid abrasive cleaner according to the invention was made by preparing a base composition by adding the ingredients in the order as indicated in example I, followed by mixing 65 parts by weight of the base composition with 35 parts by weight of calcite under stirring Base composition
  • Ingredient G H anionic 1) 6.0 6.0 soap 2) 1.0 1.0 nonionic 3) 3.0 3.0 sodium carbonate 7.3 7.3 perfume 4) 7.0 7.0 preservative 5) 1.0 1.0 polymer 6) 0.25 -- water balance calcite 7) 35 35 1) Sodium salt of DOBS 102 (ex Shell) 2) Potassium coconut soap 3) Dobanol 23 6.5 EO (ex Shell) 4) GC 234 E (ex Quest) 5) formalin 6) polymer A-11 disclosed in EP 346 995.
  • composition G had a viscosity of 540 mPas at 21 s-1, composition H had a viscosity of 290 mPas at 21 s-1. Both compositions were stable at ambient temperature. Compositions G to H were used for the cleaning of shiny stainless steel surfaces. Composition H gave a greasy look to the surface, which was disliked by the consumers. Composition G did not give a greasy appearance.
  • a bleach composition was prepared by preparing a base composition by the method as described in example I, followed by the addition of the peroxide ingredient. All percentages indicate the amount of ingredients in the final composition.
  • compositions K and L The pH of the compositions was adjusted with NaOH to 8.25. All compositions were physically stable, although some chemical instability due to decomposition of the bleach was noted for compositions K and L.
  • Composition K had a viscosity of 269 mPas at 21 s-1
  • composition L had a viscosity of 173 mPas.
  • Composition M had a viscosity of 268 mPas
  • the viscosity of composition N was 191 mPas.
  • composition Q was the same as in the previous examples.
  • Composition S contained a polymer substantially as in the previous examples except that the molecular weight is 3.8 and R4 is stearyl.
  • composition P had a viscosity at 21 s-1 of 120 mPas.
  • the viscosity of compositions Q, R and S was 200, 230 and 280 mPas.
  • This example illustrates that an increase in viscosity can also be obtained when varrying the ratio of hydrophobic monomers to hydrophilic monomers in the deflocculating polymer, or by using other hydrophobic groups.
  • An abrasive cleaner of formulation T was made as in Example I.
  • the abrasive cleaner of formulation U was prepared by mixing the calcite into water, followed by addition of the polymer, the detergent active materials and the electrolytes followed by the addition of the remaining ingredients.
  • Ingredient (% wt) T U DOBS 102 3.9 3.9 Na Prifac 7901 0.65 0.65
  • Dobanol 23.6.5 EO 1.95 1.95 Na2 CO3 3.58 4.55 Calcite 35.0 35.0 polymer 1) 0.5 0.32 perfume 0.5 0.5 water balance 1)
  • Polymer A-11 of EP 346 995 25:1, acrylic acid/laurylmethacrylic acid polymer of mW 3,500)
  • Composition U had a viscosity of 1,000 mPas at 21 s ⁇ 1

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Abstract

Composition détergente comprenant une dispersion de gouttelettes lamellaires de matériaux à activité détergente en phase continue aqueuse. Ladite composition comprend de 0,1 à 16 % en poids de matériaux tensio-actifs, moins de 20 % en poids de STP avec du matériau adjuvant à zéolithe, ou n'en comprend pas du tout, ainsi qu'un polymère défloculant; à condition que (a) lorsque les matériaux tensio-actifs représentent entre 12 % et 16 % en poids de la composition, la composition comprend moins de 7 % en poids de STP avec du matériau adjuvant à zéolithe, ou n'en comprend pas du tout; et que (b) lorsque la composition comprend entre 3 % et 12 % en poids d'un sulfoné benzénique d'alkyle de potassium, entre 2 % et 8 % en poids d'un savon d'acide gras de potassium, entre 0,5 % et 5 % en poids d'un tensio-actif non ionique, et entre 1 % et 25 % en poids de STP et/ou de pyrophosphate de tétrapotassium, le rapport de poids entre ledit sulfoné et ledit tensio-actif non ionique étant compris entre 3:5 et 25:1, et la quantité totale de sulfoné, de savon et de tensio-actif non ionique étant comprise entre 7,5 et 20 % en poids, alors le polymère défloculant n'est pas uniquement constitué d'entre 0,1 et 2 % en poids d'un copolymère neutralisé et partiellement estérifié d'anhydride maléique avec de l'éther vinylméthylique, de l'éthylène ou du styrène.

Claims (4)

  1. Une composition détergente à l'état liquide ou sous la forme de gel ou de pâte, qui ne donne pas plus de 10 % en volume de séparation de phases comme montré par l'apparition de deux phases séparées ou plus quand elle est conservée à 25°C pendant 21 jours après sa préparation, et qui comprend une dispersion de gouttelettes lamellaires de matières à activité détergente dans une phase continue aqueuse, cette composition comprenant de 0,1 à 16 % en poids de matières tensioactives et pas du tout ou moins de 20 % en poids de matière adjuvante tripolyphosphate de sodium plus zéolite, cette composition comprenant aussi de 0,01 à 5 % en poids d'un polymère défloculant, ce polymère défloculant ayant un squelette hydrophile et au moins une chaîne latérale hydrophobe ; et avec les conditions que
    (a) quand la teneur en matières tensio-actives est comprise entre 12 % et 16 % du poids de la composition, alors la composition ne comprend pas du tout ou comprend moins de 7 % en poids de matière adjuvante tripolyphosphate de sodium plus zéolite ; et
    (b) quand la composition comprend de 3 % à 12 % d'un alcoyl benzène sulfonate de potassium, de 2 % à 8 % d'un savon potassique d'acide gras, de 0,5 % à 5 % d'un agent tensio-actif non-ionique et de 1 % à 25 % de tripolyphosphate de sodium et/ou de pyrophosphate tétrapotassique, tous les pourcentages étant en poids, le rapport en poids du sulfonate à l'agent tensio-actif non-ionique étant compris entre 3:5 et 25:1, et la quantité totale du sulfonate, du savon et de l'agent tensio-actif non-ionique étant comprise entre 7,5 % et 20 % en poids,
    alors le polymère défloculant n'est pas constitué uniquement de 0,1 % à 2 % en poids d'un copolymère neutralisé, partiellement estérifié, d'anhydride maléique avec l'oxyde de vinyle et de méthyle, l'éthylène ou le styrène.
  2. Une composition selon la revendication 1, qui est à l'état liquide.
  3. Une composition selon la revendication 1 ou 2, qui comprend au moins un polymère défloculant qui n'est pas à base d'un copolymère d'anhydride maléique avec l'oxyde de méthyle et de vinyle, l'éthylène ou le styrène.
  4. Une méthode de préparation d'une composition détergente selon l'une quelconque des revendications précédentes, dans laquelle le polymère défloculant est dispersé dans l'eau avant l'addition des matières à activité détergente.
EP90916484A 1989-12-07 1990-11-12 Detergents liquides Expired - Lifetime EP0504159B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB898927730A GB8927730D0 (en) 1989-12-07 1989-12-07 Liquid detergents
GB8927730 1989-12-07
GB909014830A GB9014830D0 (en) 1990-07-04 1990-07-04 Liquid detergents
GB9014830 1990-07-04
PCT/EP1990/001885 WO1991009108A1 (fr) 1989-12-07 1990-11-12 Detergents liquides

Publications (2)

Publication Number Publication Date
EP0504159A1 EP0504159A1 (fr) 1992-09-23
EP0504159B1 true EP0504159B1 (fr) 1994-05-04

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EP90916484A Expired - Lifetime EP0504159B1 (fr) 1989-12-07 1990-11-12 Detergents liquides

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EP (1) EP0504159B1 (fr)
JP (1) JP2823355B2 (fr)
AU (1) AU652543B2 (fr)
BR (1) BR9007902A (fr)
DE (1) DE69008735T2 (fr)
ES (1) ES2052279T3 (fr)
WO (1) WO1991009108A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8029772B2 (en) 2001-12-21 2011-10-04 Rhodia Inc. Stable surfactant compositions for suspending components
US8828364B2 (en) 2007-03-23 2014-09-09 Rhodia Operations Structured surfactant compositions

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
US6090762A (en) * 1993-05-07 2000-07-18 Albright & Wilson Uk Limited Aqueous based surfactant compositions
IL132948A0 (en) * 1997-06-04 2001-03-19 Toto Ltd Method for surface pretreatment before formation of photocatalytic hydrophilic film and detergent and undercoat composition for use in the same
DE19836808A1 (de) * 1998-08-14 2000-02-24 Basf Ag Verdickungsmittel für tensidhaltige Zusammensetzungen
GB9914671D0 (en) * 1999-06-24 1999-08-25 Albright & Wilson Uk Ltd Structured surfactant systems

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0301882A1 (fr) * 1987-07-31 1989-02-01 Unilever Plc Compositions détergentes liquides

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Publication number Priority date Publication date Assignee Title
US3235505A (en) * 1961-09-20 1966-02-15 Monsanto Co Detergent processes
NL297876A (fr) * 1963-10-21
US3457176A (en) * 1964-10-16 1969-07-22 Monsanto Co Liquid detergent processes
GB8310529D0 (en) * 1983-04-19 1983-05-25 Unilever Plc General-purpose cleaning composition
US4826618A (en) * 1984-02-22 1989-05-02 Diversey Corporation Stable detergent emulsions
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents
CA2066623C (fr) * 1989-10-12 2001-03-06 Johannes Cornelis Van De Pas Detersifs liquides des polymeres deflocucants
JPH05501574A (ja) * 1989-12-01 1993-03-25 ユニリーバー・ナームローゼ・ベンノートシヤープ 液体洗剤

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0301882A1 (fr) * 1987-07-31 1989-02-01 Unilever Plc Compositions détergentes liquides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8029772B2 (en) 2001-12-21 2011-10-04 Rhodia Inc. Stable surfactant compositions for suspending components
US8394361B1 (en) 2001-12-21 2013-03-12 Rhodia Operations Stable surfactant compositions for suspending components
US8828364B2 (en) 2007-03-23 2014-09-09 Rhodia Operations Structured surfactant compositions

Also Published As

Publication number Publication date
JP2823355B2 (ja) 1998-11-11
JPH05502249A (ja) 1993-04-22
BR9007902A (pt) 1992-09-15
AU652543B2 (en) 1994-09-01
ES2052279T3 (es) 1994-07-01
DE69008735T2 (de) 1994-08-25
WO1991009108A1 (fr) 1991-06-27
AU6649290A (en) 1991-07-18
DE69008735D1 (de) 1994-06-09
EP0504159A1 (fr) 1992-09-23

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