CA2066623C - Liquid detergents containing deflocculating polymers - Google Patents

Abstract

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 said composition having a pH of more than 12.5

Description

J

LIOUID DETERGENTS CONTAININ DEFLOCCULATIN POLYMER
The present invention is concerned with aqueous liquid detergent compositions which contain sufficient detergent-active material and, optionally, sufficiently dissolved electrolyte to result in a structure of lamellar droplets dispersed in a continuous aqueous phase.
Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry: Industrial Applications', J. Wiley & Sons, Letchworth 1980.
Such lamellar dispersions are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending particulate solids such as detergency builders or abrasive particles. Examples of such structured liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342;
EP-A-38 101; EP-A-140 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplet are called 'spherulites'.
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 WO 91 /05844 PCT/EP90/0166 i a which is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.
The viscosity and stability of the product depend on the volume fraction of the liquid which is occupied by the droplets. Generally speaking, when the volume fraction is around 0.6 (say from 0.5 to 0.7), the droplets are just touching (space-filling). This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 1 Pas at a shear rate of 21s-1). This volume fraction also endows useful solid-suspending properties., A problem in the formulating of liquid detergent compositions is to prevent the occurence of flocculation. 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 is an object of the invention to minimise flocculation of liquid detergent compositions of the lamellar droplet type. It is a second object of the present invention to formulate stable liquid detergent compositions which are of relative high pH and relative low viscosity.
It has been suggested in GB 1,506,427 to formulate liquid detergent compositions containing five essential ingredients in specific relative amounts. The compositions described contain from 3-12 % by weight of a potassium alkylbenzenesulphonate, 2-8 % by weight of a potasssium soap of a Cg_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 malefic anhydride with vinylmethylether, ethylene or styrene, partially l0 esterified with the nonionic detergent active material.
GB 1,589,971 relates to similar compositions wherein part of the alkali metal tripolyphosphate is replaced by tetrapotassium pyrophosphate. The pH of the exemplified compositions is 12.5, which would generally be too low for certain purposes such as for example the industrial cleaning of fabrics, the viscosity of the products is 550 mPas or more at 30 s-1.
Surprisingly, it has now been found that stable liquid detergent compositions of the lamellar droplet type and of high pH and acceptable viscosity, can be formulated, provided that they comprise a deflocculating polymer.
Suitable deflocculating polymers are for example polymers comprising a hydrophilic backbone and one or more hydrophobic sidechains.
Accordingly the present invention relates to a liquid detergent composition comprising a dispersion of lamellar droplets of detergent 3 o active materials in an aqueous continuous phase, said composition comprising a deflocculating polymer selected from the group of:

3a (i) polymers comprising a hydrophilic backbone and one or more hydrophobic side-chains, with the proviso that, when the composition comprises from 3% to 12% of a potassium alkyl benzene sulphonate, from 2% to 8% of a potassium fatty acid soap, from 0.5 to 5% of a nonionic surfactant, and from 1 to 25% of potassium or sodium tripolyphosphate and/or tetrapotassium pyrophosphate, all percentages being by weight, the weight ratio of said sulphonate to said soap being from 1:2 to 6:1, the weight ratio of said sulphonate to said nonionic surfactant being from 3:5 to 25:1, and the total amount or said sulphonate, soap and nonionic surfactant being from 7.5 to 20% by weight, then the deflocculating polymer does not consist solely from 0.1 to 2% by weight of a partially esterified neutralised co-polymer of malefic anhydride with vinylmethyl ether, ethylene or styrene; and (ii) polymers consisting of nonionic monomers and ionic monomers, wherein the ionic monomer is from 0.1 to 50% by weight of the polymer, said composition having a pH of more than 12.5 and yielding no more than 10% by volume phase separation when stored at 25° C for 21 days from the time of preparation.
Preferably compositions of the invention are stable. In the context of the present invention, stability for------------------------------------------------------------these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable' compositions will yield no more than 10 %, preferably no more than 5 %, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
Compositions of the invention have a pH of more than 12.5, more preferred more than 13.0, especially preferred more than 13.5. These high pH values render the products of the invention especially suitable for the preparation of liquid detergent compositions intended for use in the industrial cleaning of fabrics.
Compositions of the invention preferably have a viscosity of less than 2,500 especially less than 1,000 mPas at 21 s-1, more preferred less than 750 mPas, most preferred less than 500 mPas, especially preferred between 100 and 400 mPas at 21 s-1.
Suitable deflocculating polymers for use in compositions of the present invention are for instance described in our copending European patent application 89201530.6 (EP 346 995). Generally the hydrophilic backbone of the polymer is predominantly linear ( the main chain of the backbone constitues at least 50 %, preferably more than 75 %, most preferred more than 90% by weight of the backbone), suitable monomer constituents of the hydrophilic backbone are for example unsaturated C1_6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, malefic anhydride and saturated polyalcohols such as glycerol. Examples of suitable monomer units are acrylic acid, methacrylic ~' i o V~'O 91 /05844 PCf/EP90/01667 ~; : ~0~6623 acid, malefic 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 5 ambient temperature and a pH of between 10.0 and 15Ø
Preferably the solubility is more than lg/1, more preferred more than 5 g/1 most preferred more than 10 g/1. Most preferably. the hydrophilic backbone remains soluble in these concentrations in the presence of up to 40 % by weight of electrolytes (e. g. sodium citrate).
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:
R8 R~ ( H- CH2___C___ CH2____C___ _Q1 __ _Q2_ _H
R10 R9 r q P
wherein:
Q2 is a molecular entity of formula (Ia):

~o~~b'z~

--~ CH2-~ CH CH CH CH C
1 ~ 2 ( 3 ~5 1 C02A x C02A C02A y R R

R
~Ia) R4 wherein:
R1 represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-or is absent; especially it has been found that a -CO-O
linkage is more stable at high pH values than a -O-CO-link.
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 a C2_24 alkenyl group, with the provisos that a) when R1 represents -O-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 ~'O91/05844 ~ PCT/EP90/0166i 2066fi23 also R3 is absent, then R4 must contain at least carbon atoms;
R5 represents hydrogen or a group of formula -COOA4;

R6 represents hydrogen or C1-4 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 (C2H40)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 either p and q are zero, or r is zero;
R~ 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-O-C2H4-OS03Na, -CO-O-NH-C(CH3)2-S03Na, -CO-NH2, -O-CO-CH3, -OH;
Preferably polymers for use in compositions of the invention are substantially free of hydrolysable groups such as carbonyl groups for increased polymer stability at high pH values. Particularly preferred polymers for use in 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 a poly-alkoxy linkage constituted of from 1-10 relatively watersoluble alkoxy groups such as ethoxy units. Other preferred polymers are copolymers of acid groups such as acrylic acid and alpha olefins comprising at least 5 carbon atoms. Polymers as in formula IA, wherein R1 is -CO-O-are more preferred than polymers wherein R1 is -O-CO-, because of the better stability at high pH's of the former .
Other preferred polymers for use in compositions of the invention are described in our copending non-prior-published PCT patent applications WO/91/06622 (published 16 May 1991) and WO/91/06623 (published 16 May 1991) and our co-pending non-prior-published British patent application GB 2,237,813 (published 15 May 1991).
Of the polymers described in those patent applications, especially the use of polymers in accordance with our non-prior-published patent application WO/91/06623 (published 16 May 1991) is preferred. These polymers are constituted of nonionic monomers and ionic monomers, wherein the ionic monomer is from 0.1 to 50 % by weight of the polymer. Especially preferred polymers of this type are of the formula:
p.~ ,x~y -'.~ i ~.~~ :off Jd, ,.~ , .

WO 91/05844 PC1'/EP90/01667 .066623 . . -.
R4 1 i R:

R2 R' Ra R: ( I I ) Rb c x wherein: x, z and n are as above; .
- R3 and R4 represent hydrogen or Cl-4 alkyl;
- R2 represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-, or is absent;
- R1 represents -C3H6-N+-(CH3)3(Cl-), -C2H4-OS03-(Na+). -S03 (Na+), -C2H4 N+(CH3)2 C1-, -C2H4 N+ (C2H6)2 C1-, -CH2 N+ (CH3)2 C1-, -CH2 N+ (C2H6)2 C1- or benzyl-S03- (Na+);
- Ra is CH2, C2H4, C3H6 or is absent;
- Rb represents form 1 to 50 independently selected alkylene oxide groups, preferably ethylene oxide groups or is absent;
- Rc represents -OH or -H;
and wherein if R2,Ra and Rb are absent, then Rc is preferably not -H.

VVO 91/05844 PCT/EP90/0166 i Other preferred polymers have the formula:

CH CH CH- O CH--CH

H H HC---O CH HC O CH HC H

CH O CH CH O
-CH

xl x2 z (III) Wherein:
- x = xl + x2 - x,z and n are as defined above - R1 represents -CH20- or -O-;
- R2 represents -CH2C00-Na+ or -C3H60N+(CH3)3C1-- R3 and R4 represent -OH, CH20H, -O(C3H60)p-H, -CH2-O(C3H60)p-H or -OCH2C00-Na+ or -O-C3H60N+(CH3)3C1-- R5 represents -OH, -NH-CO-CH3 or -O(C3H60)p-H
- R6 represents -OH,-CH20H, -CH2-OCH3, -O(C3H60)p-H or -CH2_O-(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 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 V1'O 91/05844 PCT/EP90/OI667 11 .
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.
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 %.
Compositions of the invention also comprise detergent active materials, preferably at a level of from 1 to by weight of the composition, more preferred a level of 5 to 40 % by weight, most preferred from 10 to 35 % by weight.
In the case of blends of surfactants, the precise proportions of each component which will result in lamellar structures will depend on the types) and amounts) 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., WO 91 /05844 PCT/EP90/0166 i ~06fib~3 12 Carl Hanser Verlag, Miinchen & 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-Clg) 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.
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.
Preferably the level of nonionic surfactants is more than 1 % by weight of the composition, preferably from 2.0 to 20.0% by weight of the composition, more preferred from 5.0 to 19 %, especially preferred from 10.0 to 18.0 %.
Compositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials. Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl V1'O 91/05844 - PCT/EP90/01667 portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (Cg-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-Clg) 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 (Cg-20) with sodium bisulphate and those derived from reacting paraffins with S02 and C12 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-C20 alpha-olefins, with S03 and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates, sodium (C16-C18) alkyl sulphates and primary (C10-C24) alkyl sodium or potassium sulphate.
Generally the level of the above mentioned anionic surfactant materials is from 1-15 % by weight of the composition. Preferably, however, low levels of these anionic materials are used, for example less than 5 %, f. .~ ~. ~~~~b'Z3 more preferred less than 3 % by weight of the composition, especially preferred less than 2.5 %.
Preferably the weight ratio of the above mentioned synthetic anionic surfactant materials to the nonionic surfactant materials is less than 1:2, more preferred less than 1:3, especially preferred from 1:4 to 1:10.
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, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used. Preferably the level of soap in compositions of the invention is from 5-35 % by weight of the composition, more preferred from 10-25 %.
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 those electrolytes which have a lyotropic 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.

W'O 91/05844 PCT/EP90/01667 .~~.: s , ~ ~osss~~
Examples of phosphorus-containing inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of 5 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 10 of phosphate builders. Especially the amount of alkali metal phosphate builders, such as sodium tripolyphosphate is preferably less than 0.5 % by weight of the composition, more preferred less than 0.1 %, especially preferred compositions of the invention are 15 substantially free of phosphate builder materials..
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. For high pH compositions according to the invention the use of silicate builders is preferred, these materials are especially advantageous because of their buffering capacities at pH values above 12.5.
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.

V1'O 91/05844 PCT/EP90/0166 i f~u~~b~

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 100m1 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 V1'O 91/05844 PCT/EP90/0166i 1~ '~.~66fi23 weight.
Especially preferred compositions of the present invention are of low viscosity (less than 500 mPas at 21 s-1) and are substantially free of suspended solid materials such as undissolved builder materials.
Preferably the level of less soluble builder materials such as sodium tripolyphosphate is less than 1 %, more preferred less than 0.5 %, more preferred less than 1 %, most preferred the builder material for use in compositions of the invention are completely water-soluble.
Preferably the level of non-soap builder material is from 5-40 % by weight of the composition, more preferred from 5 to 25 % by weight of the composition. Especially preferred is the use of from 5-20 % by weight of the composition of a silicate builder material, preferably a metasilicate builder material.
Preferably compositions of the invention comprise from 5 to 99 % by weight of water, more preferred from 10-_50 %, most preferred from 15 to 40 %.
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 trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as ~c~~c~ ~~

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, the deflocculating polymer and the detergent active material under light stirring and finally cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
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.
The names "Marion", "Prifac", "Priolene", "Plurafac", "Marlipal", "Synperonic" and "Tinopal" used in the Examples are Trade Marks.
>, _ ..

V1'O 91/05844 ~ PCT/EP90/01667 20.6623 19 : : : ~ ,., EXAMPLE I
The following compositions were made by adding the KOH
plus the silicate ingredients to water of ambient temperature under stirring followed by the addition of the deflocculating polymer. The detergent active materials are premixed and subsequently added to the aqueous mixture. Finally the remaining ingredients are added. The pH of the compositions is around 14Ø
Ingredient A B C D E F G
% (wt) ABS (Marlon AS3) - 2.3 2 4 - - -Soap (Prifac 9470) 16 18.7 -- -- - --Soap (Priolene 6902) -- 16 16 16 16 15 --Nonionic (Plurafac LF403) 14 14 7.2 10 9 9 9 Nonionic (Marlipal 13/60)- - 4.8 -- 6 6 6 Neutral waterglass (100%)10 10 10 10 10 10 10 KOH (100%) 13.7 14.5 14 10 13 13 13 Polymer 1) 1 1 1 1 1 1 --Water <--------balance ----------->

1) polymer A-11 as described in EP 346 995 Composition A had a viscosity of 280 mPas at 21 s-1, composition B of 490 mPas at 21s-1, compositions C-F had viscosities of about 300 mPas. Composition G
(comparison) was unstable (more than 10 % phase separation upon storage for three weeks), no viscosity was measured of this composition. Compositions A-F were stable lamellar dispersions of active materials in the aqueous base. The lamellar phase volume of these compositions was from 0.5 to 0.67.

2~~4~~623 20 Example II
The following compositions were prepared as in example I
Ingredient(%wt) I II III IV

Plurafac LF403 27 12 12 12 LAS (Marlon AS3) 6 5 5 12 oleate 6 19 19 12 sodium citrate l0 l0 7.5 10 KOH 5.1 6.4 8.8 7.5 Neutral waterglass(34 %) 7.5 7.5 15 7.5 polymerl) 1.5 1.5 1.5 1.5 water <----- ----balance----- ---->

viscosity (mPas at 21 s-1) 444 264 348 288 1) polymer A-11 as described in EP 346 995 The pH of the compositions was 14 or more.
The performance of the compositions was tested by washing at 60 °C at a dosage of 5 g/1 in the presence of standard stained clothes AS 9. The following scores were obtained:
Composition I II III IV
cleaning score 53 63 64 59 Example III
The following compositions were made as in the previous examples:
Ingredient (% wt) I II

Surfactantsl) 40 40 sodium citrate 7.5 7.5 Neutral water glass 5 5 polymer2) 1.0 --polymer3) -- 1.5 water <--balance-->

1) mixture of Synperonic A7, Marlon AS3 and Oleate in a weight ratio of 2.5 . 1 . 2.
2) a copolymer of acrylic acid and alpha (C12) olefinic monomers in a mole ratio of 20 . 1 and a molecular weight of 4800.
3) polymer A-11 as described in EP 346 995 Composition I had a viscosity of 1,680 mPas at 21 s-1, composition II had a viscosity of 648 mPas at 21 s-1.
Both compositions had a pH of 14 or more.

ExamQle IV
The following compositions were made as in the previous examples Inqredient ($ wt) A B C D E

Nonionicl) 10 12 12 11.7 -Nonionic2) - - - - 12 Marlon AS3 4 5 2 - 2 Priolene 6903 - - 16 - -Priolene 6902 16 19 - 9.2 -Priolene 6900 . - - - - 16 Prifac 7904 - - - 6.4 -KO H 9.8 9.8 13 13.5 13.4 Neutral waterglass 10.2 10.2 9.9 10 10.2 Tinopal CBSX 0.2 0.2 - - -Polymer3) 1 1 2.8 1.8 -Polymer 4) - - - - 1 Water <--------balance------- -->

1) plurafac LF 403 2) marlipal 013/60 3) polymer A-11 of EP 346995 4) copolymer of acrylic acid and a monomer of the formula C=C
(~04) (PO) 18 in a molar ratio 25:1, having a molecular weight of 3100.
The compositions had a pH of 14 or more, all formulations were physically stable for more than 1 month upon storage at 37°C.

V~'O 91 /05844 PCT/EP90/01667 2O~f6623 EXAMPLE V
The following formulations were made by adding the ingredients in the listed order:
INGREDIENT (% wt) A B

water 8.5 8.5 sodium citrate 2aq 8.6 8.6 Neutral water glass (34 %) 22.5 22.5 KOH (50 %) 22.0 22.0 Polymer 1) (29 %) 3.4 --Polymer 2) (25 %) -- 3.4 Marlipal 013/60 16.0 16.0 Priolene 6902 12.7 12.7 Marlon AS3 6.3 6.3 1) a copolymer of acrylic acid and alpha (C12) olefinic monomers in a mole ratio of 33 . 1 and a molecular weigh' of 8700. -2) a copolymer of acrylic acid and alpha (C12) olefinic monomers in a mole ratio of 50 . 1 and a molecular weight of 7100.
Both compositions had a pH of more than 14. The viscosity of composition A was 504 mPas at 21 s-1, the viscosity of composition B was 384 mPas at 21 s-1.

Claims (7)

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 selected from the group of:
(i) polymers comprising a hydrophilic backbone and one or more hydrophobic side-chains, with the proviso that, when the composition comprises from 3% to 12% of a potassium alkyl benzene sulphonate, from 2% to 8% of a potassium fatty acid soap, from 0.5 to 5% of a nonionic surfactant; and from 1 to 25% of potassium or sodium tripolyphosphate and/or tetrapotassium pyrophosphate, all percentages being by weight, the weight ratio of said sulphonate to said soap being from 1:2 to 6:1, the weight ratio of said sulphonate to said nonionic surfactant being from 3:5 to 25:1, and the total amount or said sulphonate, soap and nonionic surfactant being from 7.5 to 20% by weight, then the deflocculating polymer does not consist solely from 0.1 to 2%
by weight of a partially esterified neutralised co-polymer of maleic anhydride with vinylmethyl ether, ethylene or styrene; and (ii) polymers consisting of nonionic monomers and ionic monomers, wherein the ionic monomer is from 0.1 to 50%
by weight of the polymer, said composition having a pH of more than 12.5 and yielding no more than 10% by volume phase separation when stored at 25° C
for 21 days from the time of preparation.

2. Composition according to claim 1 having a pH of more than 13Ø

3. Composition according to claim 1 having a viscosity of less than 500 mPa.s at 21 s-1.

4. Composition according to claim 1 comprising from 0.01 to 5.0% by weight of deflocculating polymers.

5. Composition according to claim 1 comprising from 5-40% by weight of detergent active materials.

6. Composition according to claim 5 comprising from 5.0-19.0% of nonionic surfactant.

7. Composition according to claim 1 comprising from 5-20% of a silicate builder material, said composition being substantially free of phosphate builder materials.