CA2069618A1 - Liquid detergents - 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 from 1-35 % by weight of water.

Description

LIOUID DE~ERGENTS ~ f~

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 r~latively low levels of water.

Lamellar dropleLs are a par~icular class OL surfactant struc'ures waich, int~r alia, are already ~nown from a variety OL references, e.g. ~.A.Barnes, 'Detergents', Ch.2. in ~.Walters (Ed), 'Rh~ometry: Industrial Applic~tior.s', 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 e~amples where solid particles are suspended are discloced 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.

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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.
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The viscosity and stability of the product depend on the volume L^raction of the liquid which is occupied by the dropl~-s Gener211y speaking, when the volume fraction is around 0.6, Lhe droplets are just touching (space-filling). This allows reasonable stability with an accep~able -~iscosi~y (say no ~,o~e than 2.S Pas, preferably no more than 1 Pas at a shear rate of 2ls~
). This volume frac~ion also endows useful solid-suspending propertles.

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.
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It has been described in our non-prepublished European patent appIica~ion 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 a~ueous detergent compositions is described in our non-` prepublished British patent applications 8924479.2, ; 8924478.4 and 8924477.8. Compositions as described in ~ . .
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_~ 3 the above mentioned patent applications compriserelatively high levels, say about 37 % or more of water.

It has now been recognised that deflocculating polymers can also be us2d for -che stabilisation and/or viscosity reduction of lamellar structured aqueous liquid detergent composiLions comprising relatively low levels of water.
~: 10 ` According1l~ the present inv2ntion relates to a liquid detergen~ CGmpOsition com?r'sing a dispersion of lamellar droplets OL deterger.~ astive materlals in an - aqueo~s continuous phasc, sa d composition somprisins a defloccula~ing polymer and from 1-~5 % by weight OI
wàter.

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 2S may be observed in lamellar structured detergent compositions; also ' these prior art compositions are often not of acceptable V15Cosity and/or physical stability.
: . , Preferably compositions of the invention are physically j 30 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 manufacturin~ and retail requirements. That is, the 'physically stable' compositions will yield no more ' 35 lO %, 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 ., .
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WO9l/08280 ~ PCT/EP90/01791 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 predo-..inan_ly l n_ar (_h2 mair. chaln of the backbone constitu,_s at leas~ 50 ~, preîera,ly more than 75 %, mcst preîerrod more than 90% by weight of the backbonej, sui~abie monomer constituenls of the hydro?hilic bac~bone are for e~ample unsaturated C1_6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alXoxy units, maleic anhydride and saturated polyalcohols such as glycerol. Speci~ic 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/l, more preferred more than 5 g/l most preferred more than 10 g/l.

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.

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WO91/08280 ~CT/EP90/01791 ~ ~ $ ~ ~.D ~
Preferred polymers are of the formula:

S H t CH --- - ;-- t~----~ _j __ Q1 ---tQ~ -H

wherein:

Q2 is a molecula,- ea~ity ol ormula ~Ia):

~-H2--CH~C --CH~ f5_ c CO2A1 J x lCO~A2 CO2A JY ¦ R I

`! R3 .,, 1.

~ 25 (Ia) R~
:~' , z wherein:
~: Rl represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-~;. 30 or is absent;
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~ R2 represents from l 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 ~ carbon atoms, then R2 must .: contain an alkyleneoxy group preferably more than 5 ' alkyleneoxy groups with at least 3 carbon atoms;

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~ 6 R3 represents a phenylene linkage, or is absent;

R4 represents hydrogen or a C1_24 alkyl or C2_24 al~enyl group, with the provisos that a) when Rl represents -O-Co-, R2 and R3 must be absent and R4 must ^ontain at least ~ carbon atoms;
b) when R2 is absent, R4 is not hydrogen and when also R3 is absent, then R~ must contain at least 5 carbon atoms;
R5 represents n~drogen or a group of formula -CooA4;

R6 represen~s hydrogen or C1_ alkyl; and Ai, A2, A- and A~ are independently selected from hydrogen, al~ali metals, al~aline earth metals, ammonium and amine bases and Cl_4, or (C2H4O)tH wherein t is from 1-50, and wherein the monomer units may be in random order.
l is a multifunctional monomer, allowing the branching of the poly~er, 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 prop~ane 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 preferàbly 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, sul?hate, phophonate, phosphate, hyd~roxy, carboxyl and oxide groups, .

-WO91/08280 ~2~r~ PCT/EP90/01791 preferably they are selected from -SO3Na, CO-O-C2H4-OSO3Na, -CO-O-NH-C(CH3)2-SO3Na, -CO-NH2, -O-CO-C~3, -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 prefe red polymers for use in high pH compositions comprise hydrophilic backbones constituted by acid groups s~ch 2S acrylic acid and at least one hydrophobic side chain ~hich is c5ns tituted of from 5 to 75 relatively w2cer-insoluDle al~.o~y ; groups such as propo~:y unit, op~ional~y lin~.ed to the hydrophylic backbone via an poly-al,;o~y iin~age constituted of from l-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, especial-ly 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.
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Especially preferred polymers of this type are of the formula: .~
S ~HC~2- lc~2l ~

~o ~ P ~ (II) pjC I ~n j~:

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;
: _ Rl represents -C3H6-N+-(CH3)3(Cl-), ~`,!' -C2H4-OSO3 (Na+), -SO3 (Na+), -C2H4 N+(CH3)3 Cl , -C2H4 N (C2H6)3 Cl ' -CH2 N+ (CH3)3 Cl , -C~2 N (C2H5)3 Cl or ; 25 benzyl-SO3 (Na+);
:~l - Ra is CH2, C2H4, C3H6 or is absent;
~' - Rb represents form l to 50 independently ., selected alkylene:oxide groups, preferably ethylene oxide groups or is absent;
: 30 - Rc represents -OH or -H;
and wherein if R2,Ra and Rb are absent, then Rc is not -H-~ ~ .

'' ' ' ' '' : ' Other preferred polymers have the formula:

5 R5 16 ~ 13 4 CH - CH / \ CH - C~

HC _ CH HC _c _ ~ HC_c _ CH jHC - O H

~ l CIH _ O 1~ i:2~ ~2 (III) _ 15 I Wherein:
-- X = Xl + X2 - x,z and n are as defined above _ R1 represents -CH2O- or -O-;
- R2 represents -CH2COO~Na+, -C3H6ON+(CH3)3Cl or C3H6 N~ (CH3)3 Cl - R3 and R4 represents -OH, CH2OH, -O(C3H6O)p-H, i -CH2-O(C3H6O)p-H or -OCH2COO Na+, -O-C3H6ON+(CH3)3Cl- or -0- C3~5 N~ (C~3)3 Cl-- R5 represents ~OH, -NH-CO-CH3 or -O(C3H6O)p-H
- R6 represents -OH,-CH2OH, -CH~-OCH3,~-O(C3H6O)p-H or -CH2-O-(c3H6O)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 ' .

WO91/08280 ~ir~ ~ PCT/EP90/01791 european patent application. Another suitable method for the preparation of defloc~ulating polymers is described in example I.

Compositions according to the invention comprise from 1-35 % by weight o wa~er, prererably rrom ~-32 %, more . preferred from lO-27 %, most preferred from 12-23 %.
Gene-,-ally the deiloccula~ing poly~er will be used at from O.Ol to 5 ~ by weight of the composition, more lO pre-^erabl1 ~r~m 0' to 3.~ ?, especially preferred from 0.2~ ~o 2.0 -;.
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Preferably, composi~ions o~ ~h~ invention have a pH of ~ between ~ and l~, more preferred between 6 and 12 : 15 especial~y pre~ red from 7 to ll.
. :, - , Compositions of the invention preferably have a viscosity of less than 2,000 mPas at 21 s-l, more ; preferred less than 1,500 mPas, most preferred less than l,000 mPas, especially preferred between lO0 and 750 mPas at 21 s-l.

~ Compositions of the invention also comprise detergent j acti~ mate_izls, preferably at a level of from l 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 ~5 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.

. 35 In the widest definition the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionis, cationic, nonionic, zwitterionic and amphoteric species, and (provided WO9l/08280 ~'r~3~ PCT/EP90/01791 . . .

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 currenc edition of "McCutcheon's Emulsifiers & Detergents" published by the ~cCutcheon division of Manufacturing Confoction~rS
Company or in 'Tensid-Taschenbuch', H.Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, l9~1.

Suitable nonionic surfactants include, in parricu~ar, the reaction products of compound, having a h~dro~;^oDic group and a reactive hydrogen atom, ror e~ample aliphatic alcohols, acids, amides or alkvl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C18) primary or secondary linear or branched alcohols wlth 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 o~ides and dialkyl sulpho~ides.
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, morepreferred from ll to 40 %, especially preferred from 12 to 35 %.
Compositions of the present invention may contain synthetic anionic surfactan' ingredients, which are preferably present in combination with the above mentioned nonionic materials. Suitable anionic ` surfactants are usually water-soluble al~ali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon : .

WO91/08280 ~ PCT/EP90/01791 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 o~tained by sulphating higher (C~-C18) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (Cg-C20) benzene sulphonates, particularly sodiur~ linear secondary alkyl (C10-Cl5) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especlally chos~ et`ners of the higher alcohols d-~ived ~_om tGll~ or _oconu_ oil and synthetic aicohols de- ved -rom pe~:-oleum; sodium coconut oil fatty ~?noglyce~ide sulphates and sulphonates; sodiu~ and po~~ssium sal~s of sulphuric acid esters of higher (Cg~C18) ~at~v alcohol-alkylene oxide, particularly ethylene oxide, reaction products;
- the reaction products of falty 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 SO2 and Cl2 and then hydrolyzin with a ba~e 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 reactlon product. The preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and sodium (C16-C18) alkyl sulphates.

Preferably the level of nor.-soap anionic surfactants is from 2 to 40 % by weight o, the composition, more preferred from 5 to 37 %, ..,ost preferred from 7 to 35 %
by weight of the composition.

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WO9l/08280 PCT/EP90/01791 Preferably the weight ratio of the above mentioned synthetic anionic surfactant materials to the nonionic surfactant materials is be~ween lO :1 and 1:10, more preferred between 5:1 and 1:5, especially preferred from 3:1 to 1:3.
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It is also possible, and sometimes preferred, to - include an alkali metal soap of a mono- or di-carbo~ylic acid, especially a soap of an acid having from 12 to 1 carbon atoms, for example oleic acid, ricinoleic acid, alk(en)yl succinates e.g. dodecyl succinate and ^atty acids derived from castor oil, rapeseed oil, groundnu-~
oil,coconut oil, palmkernel oil or mixtures th2reo.. 'rh~
sodium or potassium soaps of these acids can advantageously be used. Preferably the level of s02p in cbmpositions of the invention i5 from 1-40 % by weignt of the composition, more preferred from 2-20 ~, most preferred from 5 to 15 %.
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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 la~ter specification) may also be included.

In any event, it is preferred that compositions according to the present invention include detergency :::
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WO91/08280 ~'rq~ PCT/EP90/01791 .

builder material, some or all of which may be electrolyte. In this context it sr.ould be noted that some detergent active materials such as for example soaps, also have builder properties.
Examples of phosphorous-contalning inorganic detergency builders include the water-soluble salts, especially alXali met.~l2y opr.osprla_ea, o thophospha.ea, polyphosphates and phosphonates. Specific examples of inorganic phospha~e bulld~, in~'ul~ 50dium and potassium tripolyphcsphat2a, ~ho,;vl.a _s and hexametaphosphates. ?hosphon2_e se~-~es~ran-c buildera may also be useà. ~or many reasons, i-._luding en-~ironmen~al reasons it is howe~er prerer~ed to r~nimise 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 $odium salts. Thereby, the amount of dissolved electrolyte can be increased considerably (crystal dissolution) as described in UK
patent specification GB l 302 543.

Examples of organic detergen-y builders, when present, include the al~aline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodiu.." potassium, lithium, ammonium and substituted ammonium salts of ;, ..

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~ W~91/08280 F~ PCT/EP90/01791 : :

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 benefi_, especially building, because the part which is not - dissolved does not bring about the instability that would occur iL substantially all were dissolved. Typica 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 résistance of more than 5 grams sodium nitrilotriacetate in l00ml 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 l000. 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 .~ .

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WO91/08280 ~ir~ PCT/EP90/01791 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 lO to 25 ~, most preferred from 12.5 to 22.5%.

Apart from the ingredients already mentioned, a number of optional ingredients may also be prGsent, for example lather boosters such as alkanolamides, particularly the monoethanolamides der1Jed from ~alm kernel fatty acids and _~conut ~atty acids, -- -!b-i~
softeners such as clays, amii1es and am:Lne oxides ~ latne~
depressants, o~yyen-releasiny bleac:nlny agenrs such as sodium perborate and sodium percarbona~e, peracid bieach precursors, chlorine-releasing bieaching agents such as ;; trichloroisocyanuric acid, inorgani_ salts such as sod1um 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 conver~tional 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 temperaturej followed by the addition of the builder material and the detergent active materlals 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.
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In use the detergent compositions of the invention will be diluted with wash water to form a wash liquor for :, .

W091/0~280 ~ PCT/~P9OtO1791.
: 17 instance for use in a washing machine. The concentration of liquid detergent composition in the wash liquor is preferably from O.l to lO ~, more preferred from O.l to 3% by weight.
The invention wiIl now be illustrated by way of the following Examples.

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-''~ ' WO91/08280 ~ r~ PCT/EP9~/01791 EXAMPLE I

Preparation of deflocculatina ~olymer A suitable method of preparing deflocculatiny polymersis the preparation of a 'backbone' polymer CollG~ed by a reaction thereof with one or more side groups.
Polymers comprising a hydrophilic backboIie and one or more hydrophobic side groups ~as for exam?lQ dsscribed ; lO in our co-pending European patent z~plicz'ion 89201530.6) can be prepared by this m-~_hoa 3'~ r-~ctincj ;
hydrophilic 'backbone' polymer wi~.rl 5ne or `QO-~
hydrophobic moieties. Polymers comprisins nonionic monomers and ionic monomers (as for e~ample describe~l in our co-pénding British patent applica ion 892~7~.~) 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.

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, WO91/~8280 ~ .~.~8 PCT/EP90/01791 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 9O %. The reason for this is that the esterification reaction is an equilibrium reaction, and under normal conditions a small amount -say about 0.2-lO %- of the backbone reactive groups will be esterified. If the polymer 'bac~bone' contains relative high amounts of reactive groups, these relative low amounts of side groups are sufficient to provide deflocculating polymers. ~re~erred clrcumstances for the esterification reaction are high concentrations of backbone polymers, relative high concent~ations of the side-group moieties and a ~ 15 relatively low pH.
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;~ 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:
~,~ 35 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 :. .
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WO91/08280 ` PCT/EP90/0179l 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 or the final detergent composition, but at a relati-~ely 1GW
pH, say less than 6.0, more preferred less than 4.0, most preferred less than 2Ø The low pH can advantageously be provided by the presence of par' of all of the anionic surfactants in non-neu~_ali'sed ,_ ~,..
The reaclion may then be stopped Dy :neucrcllising ChG
anionic surfactants, for example by th2 addi~is~ c an amount of NaOH and or KOH.

lS METHOD A
.

; The following compositions were made by mixing the ingredients in the order listed Composition A B
% wt 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 30 1) Sokolan PA50 ~ex BASF), polyacrylate polymer of MW = lOK (PAA standards).
2) Dodecyl benzene sulphonic acid (EX Hils) Composition A was made by mixing the ingredients in the ~- 35 order listed under stirring. Composition B was made by the same method, but the product was stored for 5 days at 52C at a pH of about 0 after the addition of the polymer backbone.

. . , WO91/08280 ~ PC~/EP90/01791 . 21 Composition A was unstable (24% phase separation) and had a viscosity of 740 mPas at 2ls~l.
Composition B was stable (no phase separation) and had a viscosity of 1320 mPas at 2ls~l.

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
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The fol.l.owlng com?ositions were made by mi~ing the ingredients in the listed order. After addition of the ~; water the product was stored for a variable time period at 20~C and 60DC at a pH of 0.3.
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Composition C
~, 20 % wt Marlon AS3 15.6 LES 2.l 25 SyperoniG A7 4.2 Sokolan CP~ 3.5 . Water 63.3 Na-citrate 9.5 NaOH l.9 to pH ~.2 In a first set of tests the intermadiate product was . . stored at 20C. The product which was not stored but ~ .
immediately further processed was unstable and had a `~ viscosity of 600 mPas at 21 5-1. A storage period of 3 : 35 days gave a stable product having a.viscosity of 50 mPas at 21 s~l; 6 days storage gave a viscosity of 150 mPas . and a stable product; after l0 days storage the final ~, product was still stable and had a viscosity of 320 mPas at 21 s~l.
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WO91/08280 ~ PCT/EP90/01791 When storing the intermediate at 60C, 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 ~iscosity was 30 mPas; 3 hours storage gave a viscosity of 50 mPas; 8 hours storage gave a viscosity of l90 mPas, these three products were stable.

Again it is believed that the increase instability and 2 decrease in viscosity can be explained by a reaction between the So~olan CP5 polymer bac',;bone and the Synperonic A7 material whereby a deflocculatiny pol~er is formed. The occurence of deflocculation in composition B is nicely illustrated in the attached Micrographs l,2~

Photograph l is an electron-mieroseopy micrograph of a flocculated lamellar dispension, in accordance to Example I, Method A, Composition A.

Photograph 2 is an eleetron-microscopy micrograph of a defloceulated lamellar dispension, in accordance to Examp'e I, Method A, Composition ~.

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

Ingredients % wt D E F
water 31.7 26.7 16.7 Sokalan CP5 2.7 2.4 1.8 Marlon AS 3 5.8 4.8 2.8 L~S (~7~) 8.9 8.9 8.9 Synperonic A7 2.0 1.7 1.0 Premix 1) 6.7 13.4 26.7 Citric acid 1.5 1.5 1.5 Glvcerol 8.0 8.0 8.0 Borax 5.7 . 5-7 5-7 Na O H (to pHg) 1.8 1.8 1.8 Zeolite A4 25 25 25 .'~ .
) 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.~. 0.8 1.5 The premixes were mixed and stored for 120 hours at a pH
of 0.3.
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Product D was just unstable, whereas products E and F
are perfectly stable, having viscosities of 640 and 1750 ~; mPas at 21 S-l. 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 pla e, the=ewith resulting in an increas~ in stabiliby.

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WO91/08280 '2~ PCT/EP90/01791 EXAMPLE II

The following compositions were made by dissol~ing 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 52 545~ 63 sodium cilrate 12 12 12 12 12 1212 glycerol 5 5 5 5 5 5 5 borax 3.5 3.5 3.5 3.5 3.5 3.53.
minors2) 0.5 0.5 0.5 0.5 0.5 0.
polymer3) water 34 31 29 26 24 2015 ~' 20 1) 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 P 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 - O -, 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 ~.
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WO91/08280 ~ PCT/EP90/01791 . 25 EXAMPLE III
The following composition was made by mixing the ingredien-ts in the listed order:

Ingredient (wt %) Water 32.7 Na-citrate 9.9 citric acid 2.2 CaCl2 0.2 Glycerol 4.3 Na-perborat2 l.2 Na-metaborate 3.2 NaLas 30.2 Synperonic A7 13.0 Deflocculating polymerl) l.0 Dequest 2060S 0.5 Tinopal CBS-X O.l Silicon oil (DB 30) 0.3 Alcalase 0.9 Perfume 0.3 l~ poly~2r as in examplé II.

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

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, WO91/08280 PCr/EP90/0179l ,~ ~r~ ~
.~3.~, EXAMPLE IV
The following compositions were made by mixing the ingredients in,the order listed:

INGRDIENT (wt %) A B

water 27.0 29.0 KOH -- 4.6 NaOH 2.3 --Na Citrate 2aq 10.0 15.0 :~ Glycerol 2.0 2.0 Borax 1.5 2.0 Zeolite 4A 25.0 --Synperonic A7 12.0 18.0 : Priolene 6902 3.6 5.4 Prifac 7904 2.4 3.6 Dobanic 113 12.0 18.0 : - . Polymer 1) 1.0 1.0 Savinase 0.6 0.6 ~ . 20 Amylase 0.2 0.2 ; Tinopal CBS-X 0.2 0.2 Perfume 0.4 0.4 1) Polymers 25 in Example II

Both compositions were stable pourable liquid detergent compositions.

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Claims (8)

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 or 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.