AU6637790A

AU6637790A - Liquid detergents

Info

Publication number: AU6637790A
Application number: AU66377/90A
Authority: AU
Inventors: Cornelis Johannes Buytenhek; Hidde Frankena; Johannes Cornelis Van De Pas
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1989-12-01
Filing date: 1990-10-22
Publication date: 1991-06-26
Also published as: BR9007879A; ZA909645B; EP0502860A1; CA2069618A1; JPH05501574A; WO1991008280A1

Description

LIQUID DETERGENTS

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. In particular 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' .

The presence of 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^~ ¹J. 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. When 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.

It has been described in our non-prepublished European patent application 89201530.6 (EP 346 995) to incorporate deflocculating polymers comprising a hydrophilic backbone and one or more hydrophobic sidegroups in lamellar structured aqueous liquid detergent compositions for increasing the stability and/or decreasing the viscosity. The use of other deflocculating polymers in lamellar structured aqueous detergent compositions is described in our non- prepublished British patent applications 8924479.2, 8924478.4 and 8924477.8. Compositions as described in the above mentioned patent applications comprise relatively high levels, say about 37 % or more of water.

It has now been recognised that 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.

Accordingly the present invention relates to 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.

It is well-known in the art to formulate 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.

Preferably compositions of the invention are physically stable. In the context of the present invention, 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. Generally 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. Specific examples of 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. Preferably the solubility is more than lg/1, more preferred more than 5 g/1 most preferred more than 10 g/1.

Preferably 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:

Q² is a molecular entity of formula (la)

wherein: R R¹¹ rreepprreesents -CO-O-, -0-, -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 Cι_2₄ alkyl or C₂_ 4 alkenyl group, with the provisos that a) when R¹ represents -0-CO-, R² and R³ must be absent and R⁴ must contain at least 5 carbon atoms; b) when R² is absent, R⁴ is not hydrogen and when also R³ is absent, then R⁴ must contain at least 5 carbon atoms;

R⁵ represents hydrogen or a group of formula -COOA⁴;

R⁶ represents hydrogen or Cχ- alkyl; and

A¹, A², A³ and A⁴ are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C₁_₄, or (C₂H4θ)tH wherein t is from 1-50, and wherein the monomer units may be in random order.

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. Preferably 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 p and q are zero and/or r is zero; most preferably p, q, y and r are zero.

R⁷ and R⁸ represent -CH₃ or -H;

R⁹ and R¹⁰ represent substituent groups such as amino, amine, amide, sulphonate, sulphate, phophonate, phosphate, hydroxy, carboxyl and oxide groups, preferably they are selected from -S0₃Na, -CO-0-C₂H4~ OS0₃Na, -CO-0-NH-C(CH₃)₂-S0₃Na, -CO-NH₂, -0-CO-CH₃, - OH;

Preferably polymers for use in compositions which are of relatively high pH (say 10 or more) 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.

Other preferred polymers for use in compositions of the invention are described in our copending Brithish patent applications 8924479.2, 8924478.4 and 8924477.6. Of the polymers described in those patent applications, especially the use of polymers in accordance with British patent application 8924478.4 is preferred. These polymers are constituted of nonionic monomers and ionic monomers, wherein the ionic monomers are from 0.1 to 50 % by weight of the polymer.

Especially preferred polymers of this type are of the

wherein: x, z and n are as above;

- R³ and R⁴ represent hydrogen or C₁_4 alkyl;

- R² represents -CO-0-, -0-, -0-CO-, -CH₂-, -CO-NH-, or is absent;

- R¹ represents -C₃H₆-N⁺-(CH₃) ₃ (Cl~) , -C₂H₄-OS0₃~(Na⁺) , -S0₃~(Na⁺),

-C₂H₄ Nτ+^(,CH₃)₃ Cl^", -C₂H₄ ΪτT+ (C₂H₆)₃ Cl^"

-CH₂ Nι+^τ (CH₃)₃ Cl^", -CH₂ ITτ+-- (C₂H₆)₃ Cl^" or benzyl-S0₃ ^" (Na⁺) ;

- R^a is CH₂, C₂H4, C₃Hg or is absent;

- R-^**-^* represents form 1 to 50 independently selected alkylene oxide groups, preferably ethylene oxide groups or is absent;

- R^c represents -OH or -H; and wherein if R²,R^a and R^b are absent, then R^c is not -H.

Wherein:

- x,z and n are as defined above

- R¹ represents -CH₂0- or -0-;

- R² represents -CH₂COO~Na+, -C₃H₆ON⁺(CH₃) ₃C1~ or C₃H₆ N⁺ (CH₃)₃ Cl^"

- R³ and R⁴ represents -OH, CH₂OH, -O(C₃H₆0)_p-H, -CH₂-0(C₃H₆0)_p-H or -OCH₂COO~Na⁺, -0-C₃H₆0N⁺(CH₃)₃Cl~ or -0- C3H6 N+ (CH3)3 Cl~

- R⁵ represents -OH, -NH-CO-CH₃ or -0(C₃H₆0)_p-H

- R⁶ represents -0H,-CH₂0H, -CH₂-0CH₃, -0(C₃H₆0)_p-H or -CH₂-0-(C₃H₆0)_p-H

- p is from 1 - .10.

Preferably 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

1-35 % by weight of water, preferably from 5-32 %, more preferred from 10-27 %, most preferred from 12-23 %. Generally 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 %.

Preferably, 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 %.

In the case of blends of surfactants, the precise proportions of each component which will result in lamellar structures will depend on the type(s) and amount(s) of the electrolytes, as is the case with conventional structured liquids.

In the widest definition 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. For example, they 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, Mϋnchen & 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-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 phospine oxides and dialkyl sulphoxides.

Preferably 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. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C₈-Cι₈) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C₉-C₂₀) benzene sulphonates, particularly sodium linear secondary alkyl (C₁₀~^ci5) 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 monosulphonates such as those derived by reacting alpha-olefins (C₈-₂₀) with sodium bisulphite and those derived from reacting paraffins with S0₂ and Cl₂ and then hydrolyzing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C₁₀~ ₂o alpha-olefins, with S0₃ and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergent compounds are sodium (^cii~^ci5) alkyl benzene sulphonates and sodium (C^- C₁₈) alkyl sulphates.

Preferably 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. Preferably 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.

It is also possible, and sometimes preferred, to include 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. Preferably 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 %.

Also possible is the use of 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 compositions optionally also contain electrolyte in an amount sufficient to bring about lamellar structuring of the detergent-active material. Preferably 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. Optionally, some salting-in electrolyte (as defined in the latter specification) may also be included.

In any event, it is preferred that compositions according to the present invention include detergency builder material, some or all of which may be electrolyte. In this context it should be noted that some detergent active materials such as for example soaps, also have builder properties.

Examples of 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.

Examples of 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.

In the context of inorganic builders, we prefer to include electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts. Thereby, the amount of dissolved electrolyte can be increased considerably (crystal dissolution) as described in UK patent specification GB 1 302 543.

Examples of 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..

In the context of organic builders, it is also desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described in EP 301.882. This allows a viscosity reduction (due to the polymer which is dissolved) whilst incorporating a sufficiently high amount to achieve a secondary benefit, especially building, because the part which is not dissolved does not bring about the instability that would occur if substantially all were dissolved. Typical amounts are from 0.5 to 4.5% by weight.

It is further possible to include in the 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.

Preferably 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%.

Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for example 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.

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.

In use 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. The 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.

The invention will now be illustrated by way of the following Examples.

EXAMPLE I

Preparation of deflocculating polymer

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 (as for example described in our co-pending British patent application 8924478.4) 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.

If the backbone polymer is hydrophilic, two situations can be distinguished. Firstly, 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. In this situation, the backbone polymer is preferably free of carboxylic acid anhydride groups. Alternatively the backbone may comprise alcohol groups which may be esterified with hydrophobic moieties comprising acid groups such as fatty acids and fatty ethers carboxylates. Preferably at least 50 % of 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. This method avoids the waste of starting materials and also allows the preparation of the polymer at a late stage of the product formulation: in some cases, especially when low pH products are concerned, 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.

Preferably 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.

METHOD A

The following compositions were made by mixing the ingredients in the order listed

Composition A B % t

water 50.5 50.5

Marlon AS-3 ²) 21 21 Synperonic A7 9 9

Polymer backbone¹) 1.5 1.5

NaOH 3.0 3.0

NaCitrate 15 15

^!) Sokolan PA50 (ex BASF) , polyacrylate polymer of MW = 10K (PAA standards) . ²) Dodecyl benzene sulphonic acid (EX Hils)

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.

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.

METHOD B

The following 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.

8.2

In a first set of tests 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. When storing the intermediate at 60°C, similar results were obtained. 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.

Again it is believed that the increase instability and a decrease in viscosity can be explained by a reaction between the Sokolan CP5 polymer backbone and the Synperonic A7 material whereby a deflocculating polymer is formed. The occurence of deflocculation in composition B is nicely illustrated in the attached Micrographs 1,2.

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.

METHOD C

The following composition were made by mixing the ingredients in the lister order.

-*) The premixes were of the following composition: Ingredients % wt D E F

Water 5.0 10.0 20.0

Sokalan CP5 0.3 0.6 1.2

Marlon AS3 1.0 2.0 4.0

Synperonic A7 0.4 0.8 1.5

The premixes were mixed and stored for 120 hours at a pH of 0.3.

Product D was just unstable, whereas products E and F are perfectly stable, having viscosities of 640 and 1750 mPas at 21 S^_1. Since products D-F were made of the same starting materials, it is believed that the differences as observed are due to the fact that in compositions E and F more esterification of the polymer has taken place, therewith resulting in an increase in stability. EXAMPLE II

The following 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.

INGREDIENT A B C D E G H

detergent base¹) 44 47 49 52 54 58 63 sodium citrate 12 12 12 12 12 12 12 glycerol 5 5 5 5 5 5 5 borax 3.5 3.5 3.5 3.5 3.5 3.5 3.5 minors²) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 polymer³) 1 1 1 1 1 1 1 water 34 31 29 26 24 20 15

--) mixture of Synperonic A7, Na-Las and Oleate soap in weight ratios of 1:3:1.

²) 0.2% fluorescer (Tinopal) , 0.3 % perfume.

3) polymer All disclosed in EP 89201530.6 (EP 346 995)

(deflocculating polymer of formula I, wherein q, p and r are 0, v=l, x=25, y=0, R¹ is - CO - 0 -, R² is absent R³ is absent, R⁴ is - C₁₂H₂5, R⁵ is -H, R⁶ is - CH₃ and A¹ is Na. The molecular weight of the polymer is about 3.5 K) .

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 %. EXAMPLE III

The following composition was made by mixing the ingredients in the listed order:

Ingredient (wt %)

¹) polymer as in example II.

The product was stable (no visible phase separation) and had a pH of 9.0 and a viscosity of 710 at 21 s-1. A corresponding composition minus the deflocculating polymer is unstable (more than 10 % phase separation after storage for 21 days at 25°C) . EXAMPLE IV

The following compositions were made by mixing the ingredients in the order listed:

INGRDIENT (wt %) A B

water

KOH

NaOH Na Citrate 2aq

Glycerol

Borax

Zeolite 4A

Synperonic A7 Priolene 6902

Prifac 7904

Dobanic 113

Polymer ¹)

Savinase Amylase

Tinopal CBS-X

Perfume

1) Polymers as in Example II

Both compositions were stable pourable liquid detergent compositions.

Claims

1. 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.

2. A composition according to claim 1, wherein the deflocculating polymer has a hydrophilic backbone and at least one hydrophobic side-claim.

3. A composition according to claim 1, wherein the deflocculating polymer consists of nonionic monomers and ionic monomers wherein the ionic monomers constitute from 0.1 to 50 % by weight of the polymer.

4. A composition according to claim 1 being physically stable and wherein the corresponding composition minus the polymer has a significantly higher viscosity and or becomes unstable.

5. A composition according to claim 1 comprising 2-50 wt% of nonionic surfactants

2-40 wt% non-soap anionic surfactants

1-40 wt% of soap

2-40 wt% of soluble organic builder material.

6. Method for the treatment of fabrics, wherein fabrics are contacted with an aqueous liquor comprising from 0.1 to 10 % by weight of a composition according to claim 1.

7. Method for the preparation of a detergent composition in accordance with claim 1, comprising the mixing of the ingredients into water, wherein the deflocculating polymer is added just before or after the addition of the detergent active materials.

8. Method of preparing a deflocculation polymer having a hydrophibic backbone and at least one hydrophobic side-chain, or consisting of nonionic monomers and ionic monomers wherein the ionic monomers constitute from 0.1 to 50% by weight of the polymer, comprising the preparation of a backbone polymer followed by a reaction thereof with a hydrophobic moiety or one or more ionic groups.