WO1991008280A1 - Detergents liquides - Google Patents

Detergents liquides Download PDF

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Publication number
WO1991008280A1
WO1991008280A1 PCT/EP1990/001791 EP9001791W WO9108280A1 WO 1991008280 A1 WO1991008280 A1 WO 1991008280A1 EP 9001791 W EP9001791 W EP 9001791W WO 9108280 A1 WO9108280 A1 WO 9108280A1
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WO
WIPO (PCT)
Prior art keywords
polymer
composition
weight
backbone
preferred
Prior art date
Application number
PCT/EP1990/001791
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English (en)
Inventor
Cornelis Johannes Buytenhek
Hidde Frankena
Johannes Cornelis Van De Pas
Original Assignee
Unilever N.V.
Unilever Plc
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Priority to BR909007879A priority Critical patent/BR9007879A/pt
Publication of WO1991008280A1 publication Critical patent/WO1991008280A1/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
    • C11D3/227—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
    • 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
    • C11D3/228—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
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines 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.
  • the present invention relates to lamellar structured detergent compositions which comprise relatively low levels of water.
  • 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. alters (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 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, 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 J. 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.
  • deflocculating polymers can also be used for the stabilisation and/or viscosity reduction of lamellar structured aqueous liquid detergent compositions comprising relatively low levels of water.
  • 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 and from 1-35 % by weight of water.
  • liquid detergent compositions which comprise no or only low levels of water
  • these compositions are however generally not of the lamellar droplet type and therefore they often do not have the advantages such as solid suspending properties, robustness, and sometimes tolerance to electrolyte levels etc as may be observed in lamellar structured detergent compositions; also these prior art compositions are often not of acceptable viscosity and/or physical stability.
  • compositions of the invention are physically stable.
  • physical stability for these systems can be defined in terms of the maximum phase separation compatible with most manufacturing and retail requirements. That is, the 'physically 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. Ideally compositions of the invention yield no visible phase separation when stored at 25 °C for 21 days.
  • 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 unsaturated C- ⁇ g 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 hydrophobic side-groups is relatively water-soluble at ambient temperature and a pH of between 6.5 and 14.5.
  • the solubility is more than lg/1, more preferred more than 5 g/1 most preferred more than 10 g/1.
  • 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:
  • Q 2 is a molecular entity of formula (la)
  • R 2 represents from 1 to 50 independently selected alkyleneoxy groups preferably ethylene oxide or propylene oxide groups, or is absent, provided that when R 3 is absent and R 4 represents hydrogen or contains no more than 4 carbon atoms, then R 2 must contain an alkyleneoxy group preferably more than 5 alkyleneoxy groups with at least 3 carbon atoms; R 3 represents a phenylene linkage, or is absent;
  • R 4 represents hydrogen or a C ⁇ _2 4 alkyl or C 2 _ 4 alkenyl group, with the provisos that a) when R 1 represents -0-CO-, R 2 and R 3 must be absent and R 4 must contain at least 5 carbon atoms; b) when R 2 is absent, R 4 is not hydrogen and when also R 3 is absent, then R 4 must contain at least 5 carbon atoms;
  • R 5 represents hydrogen or a group of formula -COOA 4 ;
  • R 6 represents hydrogen or C ⁇ - alkyl
  • a 1 , A 2 , A 3 and A 4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C 1 _ 4 , or (C 2 H4 ⁇ )tH wherein t is from 1-50, and wherein the monomer units may be in random order.
  • Q 1 is a multifunctional monomer, allowing the branching of the polymer, wherein the monomers of the polymer may be connected to Q 1 in any direction, in any order, therewith possibly resulting in a branched polymer.
  • Q 1 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 p and q are zero and/or r is zero; most preferably p, q, y and r are zero.
  • R 7 and R 8 represent -CH 3 or -H
  • R 9 and R 10 represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phophonate, phosphate, hydroxy, carboxyl and oxide groups, preferably they are selected from -S0 3 Na, -CO-0-C 2 H4 ⁇ OS0 3 Na, -CO-0-NH-C(CH 3 ) 2 -S0 3 Na, -CO-NH 2 , -0-CO-CH 3 , - OH;
  • polymers for use in compositions which are of relatively high pH are substantially free of hydrolysable groups such as carbonyl groups for increased polymer stability at high pH values.
  • Particularly preferred polymers for use in high pH compositions 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.
  • Especially preferred polymers of this type are of the
  • R 3 and R 4 represent hydrogen or C 1 _4 alkyl
  • - R 2 represents -CO-0-, -0-, -0-CO-, -CH 2 -, -CO-NH-, or is absent;
  • R 1 represents -C 3 H 6 -N + -(CH 3 ) 3 (Cl ⁇ ) , -C 2 H 4 -OS0 3 ⁇ (Na + ) , -S0 3 ⁇ (Na + ),
  • R a is CH 2 , C 2 H4, C 3 Hg or is absent;
  • R c represents -OH or -H; and wherein if R 2 ,R a and R b are absent, then R c is not -H.
  • - R 1 represents -CH 2 0- or -0-;
  • R 2 represents -CH 2 COO ⁇ Na+, -C 3 H 6 ON + (CH 3 ) 3 C1 ⁇ or C 3 H 6 N + (CH 3 ) 3 Cl "
  • R 3 and R 4 represents -OH, CH 2 OH, -O(C 3 H 6 0) p -H, -CH 2 -0(C 3 H 6 0) p -H or -OCH 2 COO ⁇ Na + , -0-C 3 H 6 0N + (CH 3 ) 3 Cl ⁇ or -0- C3H6 N+ (CH3)3 Cl ⁇
  • R 5 represents -OH, -NH-CO-CH 3 or -0(C 3 H 6 0) p -H
  • R 6 represents -0H,-CH 2 0H, -CH 2 -0CH 3 , -0(C 3 H 6 0) p -H or -CH 2 -0-(C 3 H 6 0) p -H
  • - p is from 1 - .10.
  • 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.
  • 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. Another suitable method for the preparation of deflocculating polymers is described in example I.
  • compositions according to the invention comprise from
  • 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 have a pH of between 5 and 14, more preferred between 6 and 12 especially preferred from 7 to 11.
  • compositions of the invention preferably have a viscosity of less than 2,000 mPas at 21 s-1, more preferred less than 1,500 mPas, most preferred less than 1,000 mPas, especially preferred between 100 and 750 mPas at 21 s-1.
  • 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 30 to 65 % by weight, especially preferred from 40 to 60 % by weight, most preferred from 45 to 55 %.
  • 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, M ⁇ nchen & 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 (Cg-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.
  • the level of nonionic surfactants is from 2 to 50 % by weight of the composition, more preferably from 10 to 45 % by weight of the composition, more preferred from 11 to 40 %, especially preferred from 12 to 35 %.
  • 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 ⁇ 8 ) 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 i5) 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 18 ) 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 amide
  • the level of non-soap anionic surfactants is from 2 to 40 % by weight of the composition, more preferred from 5 to 37 %, most preferred from 7 to 35 % by weight of the composition.
  • the weight ratio of the above mentioned synthetic anionic surfactant materials to the nonionic surfactant materials is between 10 :1 and 1:10, more preferred between 5:1 and 1:5, especially preferred from 3:1 to 1:3.
  • 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, alk(en)yl succinates e.g. dodecyl succinate 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 advantageously be used.
  • the level of soap in compositions of the invention is from 1-40 % by weight of the composition, more preferred from 2-20 %, most preferred from 5 to 15 %.
  • 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.
  • 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 salting-out electrolytes have a lytropic 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.
  • phosphorous-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.
  • 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.
  • 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, nitrilitriacetic 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.
  • the total level of non-soap builder material is from 5-40 % by weight of the composition, more preferred from 5 to 35 % by weight of the composition. Especially preferred is the use of from 5-25 % by weight of the composition of a soluble organic builder material. Especially preferred is the use of a soluble builder materials such as citrate builders. The level of such builders is preferably from 2 to 40 % by weight of the compostion, more preferred from 7.5 to 30 %, especially preferred from 10 to 25 %, most preferred from 12.5 to 22.5%.
  • 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 triehloroisocyanuric 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) , 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 oxygen-releasing bleaching agents such as sodium perborate and sodium
  • 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 and the detergent active materials which are optionally premixed under stirring and finally cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
  • the defloccculating polymer may advantageously be added just before or after the detergent active materials.
  • 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.
  • a suitable method of preparing deflocculating polymers is the preparation of a 'backbone' polymer followed by a reaction thereof with one or more side groups.
  • Polymers comprising a hydrophilic backbone and one or more hydrophobic side groups (as for example described in our co-pending European patent application
  • 89201530.6 can be prepared by this method by reacting a hydrophilic 'backbone' polymer with one or more hydrophobic moieties.
  • Polymers comprising nonionic monomers and ionic monomers can be prepared by this method by reacting a nonionic 'backbone' polymer with one or more ionic groups.
  • An example of a suitable reaction between the backbone polymer and the side groups is an esterification reaction wherein acid- or hydroxy groups of the backbone polymer are esterified with hydroxy- or acid groups of the side groups.
  • the backbone polymer may comprise carboxylic acid groups which may be esterified with hydrophobic moieties such as fatty alcohols, fatty glycerol ethers, fatty di-hydroxy alcohols, alkoxylated fatty alcohols and alkyl polyglycosides.
  • the backbone polymer is preferably free of carboxylic acid anhydride groups.
  • the backbone may comprise alcohol groups which may be esterified with hydrophobic moieties comprising acid groups such as fatty acids and fatty ethers carboxylates.
  • the backbone monomers comprise reactive groups, allowing the esterification, more preferred more than 75 % of the monomers comprise reactive groups, most preferred more than 90 %.
  • the reason for this is that the esterification reaction is an equilibrium reaction, and under normal conditions a small amount -say about 0.2-10 %- of the backbone reactive groups will be esterified. If the polymer 'backbone' contains relative high amounts of reactive groups, these relative low amounts of side groups are sufficient to provide deflocculating polymers.
  • Preferred _ circumstances for the esterification reaction are high concentrations of backbone polymers, relative high concentrations of the side-group moieties and a relatively low pH.
  • An especially preferred embodiment of a process for preparing the polymers is the reaction of a backbone polymer with hydrophobic or ionic moieties, wherein the hydrophobic or ionic moiety has surfactant properties.
  • An example of such a reaction is the esterification of a carboxylic acid group containing backbone with alkoxylated nonionic surfactant materials.
  • the use of surfactant materials as the source for the side-groups of the polymer has the advantage that this allows the in-situ preparation of deflocculating polymers, the polymer can be formed in the presence of an excess of surfactant materials under acid conditions; the part of the reactive surfactant materials that do not react with the backbone.in the equilibrium reaction will be present as detergent active materials in the final detergent composition.
  • the deflocculating polymer may be formed 'in- situ' in a composition containing all or a significant part of the ingredients of the final detergent composition.
  • the formation of the polymer takes place in a composition comprising the detergent active materials of the final detergent composition, but at a relatively low pH, say less than 6.0, more preferred less than 4.0, most pref rred less than 2.0.
  • the low pH can advantageously be provided by the presence of part of all of the anionic surfactants in non-neutralised form.
  • the reaction may then be stopped by neutralising the anionic surfactants, for example by the addition of an amount of NaOH and or KOH.
  • compositions were made by mixing the ingredients in the order listed
  • composition A B % t
  • Composition A was made by mixing the ingredients in the order listed under stirring.
  • Composition B was made by the same method, but the product was stored for 5 days at 52°C at a pH of about 0 after the addition of the polymer backbone.
  • Composition A was unstable (24% phase separation) and had a viscosity of 740 mPas at 21s -1 .
  • Composition B was stable (no phase separation) and had a viscosity of 1320 mPas at 21s -1 .
  • composition B it is believed that the increased stability of composition B can be explained by an esterification reaction between the polymer backbone and the Synperonic A7 component whereby a deflocculating polymer is formed.
  • compositions were made by mixing the ingredients in the listed order. After addition of the water the product was stored for a variable time period at 20°C and 60°C at a pH of 0.3.
  • the intermadiate product was stored at 20°C.
  • the product which was not stored but immediately further processed was unstable and had a viscosity of 600 mPas at 21 s -1 .
  • a storage period of 3 days gave a stable product having a viscosity of 50 mPas at 21 s -1 ; 6 days storage gave a viscosity of 150 mPas and a stable product; after 10 days storage the final product was still stable and had a viscosity of 320 mPas at 21 s "1 .
  • Unstable, highly viscous (about 600mPas) products were obtained without storage, or after a short period of storage. With 2 hours of storage the viscosity was 30 mPas; 3 hours storage gave a viscosity of 50 mPas; 8 hours storage gave a viscosity of 190 mPas, these three products were stable.
  • Photograph 1 is an electron-microscopy micrograph of a flocculated lamellar dispension, in accordance to Example I, Method A, Composition A.
  • Photograph 2 is an electron-microscopy micrograph of a deflocculated lamellar dispension, in accordance to Example I, Method A, Composition B.
  • composition were made by mixing the ingredients in the lister order.
  • the premixes were mixed and stored for 120 hours at a pH of 0.3.
  • compositions were made by dissolving the citrate material together with the minor ingredients in water of 50 °C, followed by the addition of the glycerol, borax, the deflocculating polymer and the detergent active materials under stirring and finally cooling the mixture.
  • compositions A-H were stable pourable liquid detergent compositions comprising a dispersion of lamellar droplets of detergent active material in an aqueous phase. This example illustrates that stable aqueous liquid detergent compositions can be obtained comprising water levels of less than 35 %.
  • composition was made by mixing the ingredients in the listed order:
  • compositions were made by mixing the ingredients in the order listed:
  • compositions were stable pourable liquid detergent compositions.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

Composition détergente liquide comprenant une dispersion de gouttelettes lamellaires de matières actives détergentes en phase continue aqueuse. Ladite composition comprend un polymère défloculant et entre 1 et 35 % en poids d'eau.
PCT/EP1990/001791 1989-12-01 1990-10-22 Detergents liquides WO1991008280A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BR909007879A BR9007879A (pt) 1989-12-01 1990-10-22 Composicao detergente liquida e processo para o tratamento de tecidos e para a preparacao de uma composicao detergente e de um polimero desfloculante

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP89203053.7 1989-12-01
EP89203053 1989-12-01

Publications (1)

Publication Number Publication Date
WO1991008280A1 true WO1991008280A1 (fr) 1991-06-13

Family

ID=8202515

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/001791 WO1991008280A1 (fr) 1989-12-01 1990-10-22 Detergents liquides

Country Status (7)

Country Link
EP (1) EP0502860A1 (fr)
JP (1) JPH05501574A (fr)
AU (1) AU6637790A (fr)
BR (1) BR9007879A (fr)
CA (1) CA2069618A1 (fr)
WO (1) WO1991008280A1 (fr)
ZA (1) ZA909645B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0623670A2 (fr) 1993-05-07 1994-11-09 ALBRIGHT & WILSON UK LIMITED Compositions tensioactives à base aqueuse
WO1996000277A1 (fr) * 1994-06-23 1996-01-04 Unilever N.V. Compositions pour le lavage de la vaisselle
US5597508A (en) * 1989-10-31 1997-01-28 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent composition containing deflocculating polymer with ionic monomers
WO1997011145A1 (fr) * 1995-09-18 1997-03-27 Colgate-Palmolive Company Compositions detergentes liquides aqueuses concentrees
EP0798372A2 (fr) * 1996-03-29 1997-10-01 Unilever N.V. Composition détergente
US5750489A (en) * 1994-05-13 1998-05-12 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent compostions containing structuring polymers for enhanced suspending power and good pourability
US6090762A (en) * 1993-05-07 2000-07-18 Albright & Wilson Uk Limited Aqueous based surfactant compositions
US6288137B1 (en) 1993-08-04 2001-09-11 Lvmh Recherche Process for preparing an aqueous composition in gel form and compositions obtainable from this process, especially a composition containing vesicles, in particular liposomes
EP1256620A1 (fr) * 2001-05-08 2002-11-13 Kao Corporation Composition de détergent liquide

Families Citing this family (2)

* 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.
JP2002332498A (ja) * 2001-05-08 2002-11-22 Kao Corp 液体洗浄剤組成物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1068554A (en) * 1963-10-21 1967-05-10 Gen Aniline & Film Corp Liquid alkaline detergent compositions
US3457176A (en) * 1964-10-16 1969-07-22 Monsanto Co Liquid detergent processes
FR2309629A1 (fr) * 1975-04-29 1976-11-26 Unilever Nv Composition detergente liquide et son procede de preparation
US4454060A (en) * 1983-06-09 1984-06-12 Colgate-Palmolive Company Liquid detergent composition with a cationic foam stabilizing copolymer containing pendant quaternary nitrogen groups and pendant hydrophobic groups
EP0299691A1 (fr) * 1987-07-09 1989-01-18 Diversey Corporation Emulsions stables de détergent
EP0301882A1 (fr) * 1987-07-31 1989-02-01 Unilever Plc Compositions détergentes liquides
EP0346995A2 (fr) * 1988-06-13 1989-12-20 Unilever N.V. Produits détergents liquides

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1068554A (en) * 1963-10-21 1967-05-10 Gen Aniline & Film Corp Liquid alkaline detergent compositions
US3457176A (en) * 1964-10-16 1969-07-22 Monsanto Co Liquid detergent processes
FR2309629A1 (fr) * 1975-04-29 1976-11-26 Unilever Nv Composition detergente liquide et son procede de preparation
US4454060A (en) * 1983-06-09 1984-06-12 Colgate-Palmolive Company Liquid detergent composition with a cationic foam stabilizing copolymer containing pendant quaternary nitrogen groups and pendant hydrophobic groups
EP0299691A1 (fr) * 1987-07-09 1989-01-18 Diversey Corporation Emulsions stables de détergent
EP0301882A1 (fr) * 1987-07-31 1989-02-01 Unilever Plc Compositions détergentes liquides
EP0346995A2 (fr) * 1988-06-13 1989-12-20 Unilever N.V. Produits détergents liquides

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5597508A (en) * 1989-10-31 1997-01-28 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent composition containing deflocculating polymer with ionic monomers
EP0623670A2 (fr) 1993-05-07 1994-11-09 ALBRIGHT & WILSON UK LIMITED Compositions tensioactives à base aqueuse
EP0623670B2 (fr) † 1993-05-07 2010-01-20 Huntsman International Llc Compositions tensioactives à base aqueuse
US6090762A (en) * 1993-05-07 2000-07-18 Albright & Wilson Uk Limited Aqueous based surfactant compositions
US6177396B1 (en) * 1993-05-07 2001-01-23 Albright & Wilson Uk Limited Aqueous based surfactant compositions
EP0712422B2 (fr) † 1993-08-04 2003-08-13 Lvmh Recherche Procede de preparation d'une composition aqueuse sous forme de gel et l'utilisation de ce procede
US6288137B1 (en) 1993-08-04 2001-09-11 Lvmh Recherche Process for preparing an aqueous composition in gel form and compositions obtainable from this process, especially a composition containing vesicles, in particular liposomes
US6469084B2 (en) * 1993-08-04 2002-10-22 Lvmh Recherche Process for preparing an aqueous composition in gel form and compositions obtainable from this process, especially a composition containing vesicles, in particular liposomes
US5750489A (en) * 1994-05-13 1998-05-12 Lever Brothers Company, Division Of Conopco, Inc. Liquid detergent compostions containing structuring polymers for enhanced suspending power and good pourability
WO1996000277A1 (fr) * 1994-06-23 1996-01-04 Unilever N.V. Compositions pour le lavage de la vaisselle
US5719112A (en) * 1994-06-23 1998-02-17 Lever Brothers Company, Division Of Conopco, Inc. Dishwashing composition
WO1997011145A1 (fr) * 1995-09-18 1997-03-27 Colgate-Palmolive Company Compositions detergentes liquides aqueuses concentrees
EP0798372A2 (fr) * 1996-03-29 1997-10-01 Unilever N.V. Composition détergente
EP0798372A3 (fr) * 1996-03-29 1999-12-08 Unilever N.V. Composition détergente
EP1256620A1 (fr) * 2001-05-08 2002-11-13 Kao Corporation Composition de détergent liquide
US6894016B2 (en) 2001-05-08 2005-05-17 Kao Corporation Liquid detergent composition

Also Published As

Publication number Publication date
CA2069618A1 (fr) 1991-06-02
JPH05501574A (ja) 1993-03-25
BR9007879A (pt) 1992-09-29
ZA909645B (en) 1992-08-26
EP0502860A1 (fr) 1992-09-16
AU6637790A (en) 1991-06-26

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