CA1336385C - Liquid detergents - Google Patents

Abstract

Greater flexibility in selecting components for stable aqueous dispersions of surfactant lamellar droplets, and improved possibilities for formulating concentrated forms of such dispersions are provided by incorporating in the composition, a deflocculating polymer having a hydrophilic backbone and at least one hydrophobic side-chain.

Description

1 336385 C 3247 (R) ~TOUTD D~T~GENTS

The present lnvention 1B conc~rned with aqueou6 liquid detergent compo~itions which contain sufficient detergent-active material and, option~lly, sufficiently olved electrolyte to result in a 6tructure of lamellar droplets disper~ed in a continuous aqueous pha6e.

L~mellar droplets are a particular clas~ of 6urfactant 6tructures which, ~nter ~ , are already known from a variety of references, e.g. H.A.Barnes, 'Detergent6', Ch.2. in X.Walter6 (Ed), 'Rheometry: Indu6trial ~pplications', J. Wiley & Son6, Letchworth 1980.
Such lamellar di6per6ion~ are u6ed to endow propertie6 6uch a6 con6umer-preferred flow behaviour and/or turbid appc~rance. Many are al60 capable of 6u6pending particulate 601id6 such as detergency builders or abrasive particle~. Examples of 6uch stru~Lu~6d liquid6 without su6pended solid~ are given in US patent 4 244 840, whil6t examples where solid particles are suspended are di6closed in Fpecifications EP-A-160 342, published November 6, 1985; EP-A-38 101, published October 21, 1981;
EP-A-140 452, published May 8, 1985 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, published August 21, 1985, where the lamellar droplet are called 'spherulites' .

The presence of lamellar droplet6 in a liquid detergent product may be detected by means known to those 6killed ln the art, for example optical technique~, v~rlous rheometrical mea~urement6. X-ray or neutron diffraction, and electron micro6copy.
The droplets consist of an onion-like configur tion of concentric bi-layers of surfactant molecule~, between which 18 trapped water or electrolyte ~olution (aqueous ,L - .

2 1 33 ~3 ~5 C 3247 (R) ph_ge). Sy6tem6 in which such droplet6 are close-p~cked provide a very deslrable combination of physlcal stability and ~olid-su6psn~1n~ propertie~ with u~eful flow propertles.

m e vi~cosity and stabillty of the product ~sp~n~ on the volume fraction of the liguid which 18 occupied by the droplet~. Generally sreA~n~, the higher the volume fraction of the dispersed lamellar pha6e (droplets), the better the stability. However, higher volume frAction~
also lead to increa~ed vi6cosity which in the limit can re~ult in an unpourable product. Thi6 result6 in a compromise being reached. When the volume fraction i6 around 0.6, or higher, the droplets are ~u6t to~rh1~
(6pace-filling). Thi6 allow6 reasonable stability with an acceptable visco6ity (6Ay no more thAn 2.5 Pa6, preferably no more than l Pa6 at a shear r_te of 21 This volume fraction also endow6 u eful ~olid-~u6pen~n~
propertie6. Conductivity me_~urement6 are known to provide a u6eful way of mea~uring the volume fraction, when compared with the conductivity of the continuou6 pha se .

Fig. 1 6how6 a pilot of viscosity against l_mellar ph_6e volume fraction for a typical compo6ition of known kind:

Surfactant6* 20 Na-~ormate 5 or 7.5 Na-citrate 2aq lO
30 Borax 3.5 *~Tinopal CBS-X 0.1 PerfumQ 0.15 Water hal ar -e ~NaDoBS/LES/*~Neodol 23-6.5. See Ta~le 3 in Examples for raw ~aterial specifications.

~Denotes trade mark 1 33638~

3 C 3247 (R) It will be seen that there iB a window ho~n~A by lower volume fraction of 0.7 coLlLD~Gl,ding to the onset of in6tability and an upper volume fraction of 0.83 or 0.9 correspQ~A~n~ to a vi6coslty of l Pas or 2 Pas, respectively. Thi6 iB only one ~uch pilot and in many cases the lower volume fraction can be 0.6 or ~lightly lower.

A complicating factor in the relationship between stability and vi6c06ity on the one hand and, on the other, the volume fraction of the lamellar droplets is the degree of flocculation of the droplets. When flocculation occur6 between the lamellar droplets at a given volume fraction, the viscosity of the corresponding product will increase owing to the formation of a network throughout the liquid.
Flocculation may also lead to instability because deformation of the lamellar droplets, owing to flocculation, will make their packing more efficient.
Conseguently, more lamellar droplets will be required for stabilization by the space-filling mechAn~sm, which will again lead to a further increase of the viscosity.

The volume fraction of droplets is increased by increasing the surfactant concentration and flocculation between the lamellar droplets occur6 when a certain threshold value of the electrolyte concentration is ~.oEEcd at a given level of surfactant (and fixed ratio beL-~een any different ~urfactant components). Thus, in practice, the effects referred to above mean that there i8 a limit to the amount6 of ~urfactant and electrolyte which can be incorporated whilst still having an acceptable product. In principle, higher ~urfactant levels are required for increased detergency (cle~n~nq performance). Increased electrolyte level6 can al~o be used for better detergency, or are sometimes sought for e~cond~ry benefits ~uch as building.

1 3 3 6 3 8 5 C 3247 (R) We have now found that the AepenAency of ~tability and/or visco6ity upon volume fraction can be favourably infl~nse~ by il.~Gl~o~ating a deflocculating polymer compri6ing a hydrophilic bac~hone and one or more hydrophobic ~ide-r-h~~.

The deflocc~ ting polymer allow6, if desired, the incorporation of greater amount6 of surfactant~ and/or electrolyte6 than would otherwise be compatible with the need for a 6table, low-viscosity product. It also allows (if de6ired) incorporation of greater amounts of certain other ingredient6 to which, hitherto, lamellar disper~ion~ have been highly 6tability-6en6itive.
Further detail6 of these are given hereinbelow.

The present invention allows formulation of stable, pourable product6 wherein the volume fraction of the lamellar pha6e i6 O.S, 0.6 or higher, but with combinations or concentrations of ingredients not possible hitherto.

The volume fraction of the lamellar droplet phase may be determined by the following method. The composition is centrifuged, 6ay at 40,000 G for 12 hour6, to separate the composition into a clear (continuou6 agueous) layer, a turbid active-rich (lamellar) layer and (if solid6 are su6pended) a 601id particle layer. The conductivity of the continuou6 aqueous phase, the lamellar pha6e and of the total compo6ition before centrifugation are mea6ured. From the6e, the volume fraction of the lamellar pha6e iB calculated, using the ~L~yyeman ~quation, a6 disclosed in American Physics, 24, 636 (1935). When applying the equation, the conductivity of the total composition must be corrected for the conductivity inhibition owing to any 6u6pen~ 601ids present. The degree of correction nece66Ary can be 1 3 3 63 8 5 C 3247 (R) determined by measuring the con~l~ctivity of a model 6y6tem. Thi6 has the formulation of the total compogition but without any surfactant. The difference in conductivity of the model ~ystem, when continuously tirred tto disperse the ~olids) and at rest (80 the solld6 ~ettle), lndicates the effect of ~uspended solid6 in the real compo6ition. Alternatively, the real composition may be sub~ected to mild centrifugation (say 2,000 G for 1 hour) to ~u6t remove the solid6. The conductivity of the upper layer 18 that of the su6pending base (aqueou~ continuous phase with dispersed lamellar phase, minus 601id6).

It 6hould be noted that, if the centrifugation at 40,000 G fail6 to yield a separate continuous phase, the conductivity of the aforementioned model 6ystem at rest can 6erve as the conductivity of the continuous aqueous phase. For the conductivity of the lamellar phase, a value of 0.8 can be used, which is typical for most systems. In any event, the contribution of this term in the equation is often negligible.

Preferably, the vi6c06ity of the aqueous continuous phase is les6 than 25 mPas, most preferably less than 15 mPas, especially less than 10 mPas, these viscosities being measured using a capillary vi6cometer, for example an Ostwald vi6cometer.

Sometimes, it iB preferred for the compositions of the present invention to h~ve 601id-6uspen~n~ properties (i.e. capable of ~u~pen~ng ~olid particles). m erefore, in many preferred examples, ~u6pended solids are present. However, ~ometimQs it may also be preferred that the compositions of the present lnvention do not have 601id 6uspen~ng properties, thi6 ls al60 illustrated ln the examples.

6 1 336385 C 3247 (R) In practical terms, i.e. as determining product propertie~, the term 'deflocculating' ln rQspect of the polymer means that the equivalent compositlon, ~inus the polymer, ha6 a ~lgnificantly higher viscosity and/or becomes unstable. It 18 not lnt~n~ to ~mbrace polymer6 which would both incrsase the viscosity ~n~ not ~nhA~-e the ~tability of the composition. It iB also not lntenAe~ to ombrace polymers which would lower the vi6cocity ~imply by a dilutlon effect, i.e. only by adding to the volume of the continuou6 phase. Nor does lt lnclude those polymers which lower viscosity only by reducing the volume fraction (6hr~nklng) of the l~mellar droplets, as disclosed ln our European p~tent application EP 301 883, published February 1, 1989.Thus,although within the ambit of the present invention, relatively high levels of the deflocculating polymers Ç~a be used in those ~ystem6 where a viscosity reduction is brought about; typically levels a6 low a~ from about 0.01% by weight to about 1.0% by weight can be capable of reducing the viscosity at 21 ~-1 by up to 2 orders of magnitude.

E~pecially preferred embodiments of the pre~ent invention exhibit les6 phase separation on storage and have a lower viscosity than an equivalent composition without any of the deflocculating polymer.

Without being bound by any particular interpretation or theory, the applicants have hypothesized that the polymers exert their action on the composition by the following mec~A~i~m. The hydrophobic side-chain(s) could be incorporated only in the outer bi-layer of the droplet~, leaving the hydrophilic bac~hore over the out~lde of the droplets and additionally the polymers could also be incorporated deeper lnside the droplet.
When the hydrophobic side cha~nQ are only incorporated in the outer bilayer of the droplets, thi~ has the 7 1 336385 C 3247 (R) effect of ~coupling the inter- and intra-droplet forces i.e. the difference between the force~ between individual 6urfactant molecule6 ln ad~acent layer6 within a particular droplet and those between surfactant S molecules in ad~acent droplet6 could become accentuated in that the forces between ad~acent droplets are reduced. This will generally result in an increased ~tability due to less flocculation and a decrease in viscosity due to smaller forces ~ en the droplets resulting in greater aist~nc~ between ad~acent droplets.

When the polymer6 are incorporated deeper inside the droplet6 also les6 flocculation will occur, resulting in an increa6e in stability. The influence of these polymers within the droplet6 on the viscosity i6 governed by two opposite effect6 : firstly the pre6ence of deflocculating polymer6 will decrease the forces between ad~acent droplets resulting in greater dist~ce~
between the droplets, generally resulting in a lower vi6c06ity of the system; secondly the force6 be~cen the layer6 within the droplet6 are egually reAl~re~ by the pr~ence of the polymers in the droplet, thi6 generally re6ults in an increa6e in the water layer thickness, therewith increasing the lamellar volume of the droplets, therewith increasing the vi6cosity. The net effect of these two opposite effect6 may result in either a decrease or an increase in the viscosity of the product.
It is conventional in patent specifications relating to agueou6 structured liguid detergents to define the stability of the composition in terms of the volume separation observed during storage for a predetermined period at a fixed temperature. In fact, this can be an over-simpli6tic definition of what i6 observed in practice. Thus, it i6 appropriate here to give a more 1 3 3 6 3 8 5 C 3247 (R) detailed de6cription.

For lamellar droplet di6per6ions, where the volume fraction of the lamellar phase i6 below 0.6 and the droplet6 are flocculated, in6tability i6 inevitable and i6 ob6erved a6 a gro66 pha6e separation occurring in a relatively 6hort time. When the volume fraction iB below 0.6 but the droplet6 are not flocculated, the composition may be stable or unstable. When it i6 unstable, a pha6e separation occur6 at a slower rate than in the flocculated ca6e and the degree of pha6e ~eparation i6 le6s.

When the volume fraction of the lamellar pha6e i6 below 0.6, whether the droplets are flocculated or not, it i6 pos6ible to define 6tability in the conventional manner.
In the context of the present invention, 6tability for these sy6tems can be defined in term6 of the maximum separation compatible with most manufacturing and retail requirement6. That i6, the 'stable' composition6 will yield no more than 2% by volume phase 6eparation a6 evi~ence~ by appearance of 2 or more 6eparate layers when 6tored at 25-C for 21 days from the time of preparation.
In the ca6e of the compo6itions where the lamellar pha6e volume fraction iB 0.6 or greater, it i6 not alway6 ea6y to apply thi6 definition. In the ca6e of the pre6ent invention, 6uch 6y6tem6 may be 6table or un6table, according to whether or not the droplet6 are florc~ ted. For tho6e that are un6table, i.e.
flocculated, the degree of pha6e separation may be relatively small, e.g. a6 for the un6table non-flocculated 6y6tems with the lower volume fraction.
However, in thi6 ca6e the phase 6eparation will often not man$fest it6elf by the appearance of a di6tinct layer of continuous phase but will appear distributed as 9 1 336385 C 3247 (R) 'cracks' throughout the product. The onset of these cracks appearing and the volume of the materlal they contain are almost impossible to measure to a very high degree of accuracy. However, those skilled in the art will be able to a~certain lnstabillty becau~e the preFenc~ of a distrlbuted eparate phase greater than 2%
by volume of the total compositlon wlll readily be vl~ually identifiable by ~uch per~ons. Thus, ln formal terms, the above-mentioned definition of 'stable' is also applicable in these ~ituations, but di~regarding the requirement for the pha~e ~eparation to appear as ~eparate layers.

Especially preferred embodiment6 of the present invention yield less than 0.1% by volume visible phase separation after storage at 25-C for 90 days from the time of preparation.

It must also be realized that there can be 60me difficulty in determining the vi6cosity of an unstable liquid.

When the volume fraction of the lamellar phase is less than 0.6 and the ~ystem is deflocculated or when the volume fraction is 0.6 or greater and the system is flocculated, then pha6e ~eparation occurs relatively slowly and me~n~ngful viscosity measurement can u~ually be determined quite readily. For all compositions of the present invention it i6 usually preferred that their vi~cosity is not greater than 2.5 Pas, most preferably no ~ore than 1.0 Pas, and especially not greater than 750 mPas at a shear rate of 2l6-l.

When the volume fraction of the lamellar phase is le6s than 0.6 and the droplets are flocculated, then often the rapid phase ~eparation occurring makes a preci6e determination of viscosity rather difficult. However, it lo 1336385 C 3247 (R) 1B usu~lly pos6ible to obtain a figure whlch, whilst approxiate, i6 still ~uff$cient to indicate the effect of the deflocculating polymer in the compositions according to the pre~ent invention. Where this difficulty arises in the compo~ition~ ~xemplified here~nhelow, lt is indicated accordingly.

The compo6ition~ according to the invention may contain only one, or a mixture of deflocculating polymer types.
The term 'polymer types' iB used bec~u6e, in practice, nearly all polymer samples will have a spectrum of 6tructures and molecular weights and often impurities.
Thus, any 6tructure of deflocculation polymers decribes in this 6pecification refers to polymers which are believed to be effective for deflocculation pu~o~e~ as defined hereabove. In practice these effective polymers may constitute only part of the polymer 6ample, provided that the amount of deflocculation polymer in total i8 6ufficient to effect the desired deflocculation effects.
Furthermore, any 6tructure described herein for an individual polymer type, refer6 to the 6tructure of the predominating deflocculating polymer 6pecies and the molecular weight 6pecified i6 the weight average molecular weight of the deflocculation polymer6 in the polymer mixture.

The hydrophilic backhone of the polymer generally i6 a linear, brAnche~ or lightly crosslinked molecular composition contAin~ng one or more types of relatively hydrophilic monomer units. Preferably the hydrophilic monomers are ~ufficiently water soluble to form at least a 1 % by weight ~olution when dissolved in water. The only limitations to the structure of the hydrophilic backbone are that the polymer must be 6uitable for incorporation in an active-structured aqueous liquid detergent composition and that a polymer corre6ponding to the hydrophilic backbone made from the backbone 11 1 3 3 6 3 8 5 C 3247 (R) monomeric constituents is relatively soluble in water, in that the ~olubility in water at ~mhient temperature and at a pH of 3.0 to 12.5 is preferably more than 1 g/l, more preferred more than 5 g/l, most preferred more than 10 g/l.

Preferably the ~lyd~o~hilic backbone i6 predominantly linear; more preferably the main chain of the backho~P
constitutes at least 50 % by weight, preferably more than 75 %, most preferred more than 90 % by weight of the backbone.

The hydrophilic backbone i6 composed of monomer units, which can be selected from a variety of unit6 available for the preparation of polymers. The polymers can be linked by any possible chemical link, although the following types of linkages are preferred:
O~ o o -O-, -C-O, -C-C-, -C-O-, -C-N-, -~-N-, -~-OH
Examples of types of monomer unit6 are:
( i) Unsaturated Cl_6 acids, ethers, alcohols, aldehydes, ketones, or esters. Preferably these monomer units are mono-unsaturated. Examples of ~uitable monomers are acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, aconitic acid, citraconic acid, vinyl-methyl ether, vinyl sulphonate, vinylalcohol obtained by the hydrolysi6 of vinyl acetate, acrolein, allyl alcohol and vinyl acetic acid.
( ii) Cyclic units, either being unsaturated or comprising other ~ OU~3 capable of forming lnter-monomer linkages. In l~nk~g the~e monomers the ring-structure of the monomers may either be kept intact, or the ring 6tructure may be di6rupted to form the backbone structure. Examples of cyclic monomer units are 6ugar units, for instance 6accharides and glucosides; alkoxy 12 1 336385 C 3247 (R) units ~uch as ethylene oxide and hydroxy propylene oxide; and maleic anhydride.

(iii) Other unit~, for example glycerol or other 6atur~ted polyalcohol6.

Each of the above mentioned monomer units may be sub~tituted with ylG~ uch a~ amino, amine, amide, sulphonate, sulphate, pho~phonate, phosphate, ~dloxy, carboxyl and oxide y~OU~_.

The hydrophilic backbone of the polymer i8 preferably composed of one or two monomer types but al60 po~sible i~ the use of three or more different monomer types in one hydrophilic backhone. Examples of preferred hydrophilic backhones are : homopolymers of acrylic acid, copolymer6 of acrylic acid and maleic acid, poly 2-hydroxy ethyl acrylate, poly6accharide~, cellulo~e ethers, polyglycerols, polyacrylamide6, polyvinylalcohol/polyvinylether copolymer~, poly sodium vinyl sulphonate, poly 2-~ulphato ethyl methacrylate, polyacrylamido methyl propane sulphonate and copolymers of acrylic acid and tri methyl propane tr~acrylate.

Optionally the hydrophilic backbone may contain 6mall amounts of relatively hydrophobic units, e.g. those derived from polymers having a ~olubility of less than 1 g/l in water, provided that the overall solubility of the hydrophilic polymer bac~hQ~ 6till sati6fies the solubility requirements a6 specified hereabove. Example~
of relatively water insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyethylene, pol~ ylene, poly~yLene, poly~ylene oxide, propylene oxide and polyhydroxy propyl acetate.
Preferably the hydrophobic side c~ c are part of a monomer unit which is incorporated in the polymer by 13 1 336385 C 3247 (R) copolymerising hydrophobic monomers and the hydrophilic monomers making up the bac~hone of the polymer. The hydrophobic 6ide çhA~nR for this u6e prefer_bly include tho6e which when isolated from their linkage are relatively water in~oluble, i.e. preferably 1e6~ than 1 g/l more preferred less than 0.5 g/l, most preferred less than 0.1 g/l of the hydrophobic monomer~, will dissolve in water at ambient temperature and a pH of 3.0 to 12.5.
Prefer_bly the hydrophobic moleties are ~el-cted from 6iloYAne6, 6aturated and unsaturated alkyl ÇhA ~ nC, e.g.
having from 5 to 24 carbon atoms, preferably from 6 to 18, most preferred from 8 to 16 carbon atoms, and are optionally bonded to the hydrophilic backhQne via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, pol~.u~oxy or butyloxy (or mixtures of 6ame) linkage having from 1 to 50 alkoxylene ylo~
Alternatively the hydrophobic 6ide chain may be com~
of relatively hydrophobic alkoxy y~o~, for example butylene oxide and/or propylene oxide, in the absence of alkyl or alkenyl y~OU~. In 60me forms, the 6ide-chain(s) will essentially have the character of a nonionic 6urfactant.
In this context it can be noted that UK patent 6pecifications GB 1 506 427 A and GB 1 589 971 A
disclose aqueou6 compositions including a ¢arboxylate polymer partly esterified with nonionic 6urface side-ch~nR. The compositions according to these referencesare hereby disclaimed from the 6cope of the present invention. The particular polymer described there (a partially esterified, neutralized co-polymer of ~aleic anhydride with vinylmethyl ether, ethylene or 6tyrene, present at from 0.1 to 2% by weight of the total composition) was not only difficult to make, but found only to work for a very narrow co~centration range of five 6eparate ingredients, 6aid all to be essential for 14 1 3 3 6 3 85 C 3247 (R) 6tability. The particul~r products are very alkaline (pH
12.5). In contrast, the present invention provides a broad class of readily preparable polymers, usable in a wide range of detergent lamellar droplet aqueous S disper6ion6.

Thus, one a6pect of the ~ ent invention provides a liquid detergent composition comprising a di6persion of lamellar droplet6 in an aqueous continuou6 pha6e, the composition having a pH less than 12.5 and yielding no ~ore th~n 2% by volume phAse separation when stored at 25-C for 21 days from the time of 6eparation, and further compri6ing a deflocculating polymer having a hydrophilic backbone and at lea6t one hydrophobic side-chain.

Preferably though, all compositions according to thepresent invention have a pH le66 than 11, most preferably less than 10.
US Patents 3 235 505, 3 328 309 and 3 457 176 describe the use of polymers having relatively hydrophilic backhonec and relatively hydrophobic 8ide-rhA i n~ as 6tabilizers for emul6ion6. However, these product6 are un6table according to the definition of stability hereinbefore.

Another aspect of the present invention provides a liquid detergent composition which yield6 no more than 2% by volume pha6e separation when 6tored at 25-C for 21 days from the time of preparation and comprise6 a disper6ion of Iamellar droplets in an aqueou6 continuous phase and al60 comprises a deflocculating polymer having a hydrophilic backbone and at least one hydrophobic 6ide-chain, with the proviso that when the composition comprises from 3% to 12% of a pota6sium alkyl benzene sulphonate, from 2% to 8% of a pota6sium fatty acid 1 3 3 6 3 8 5 C 3247 (R) soap, from 0.5 to 5% of a nonionic surfactant, and from 1 to 25% of ~odium tripolyphosphate and/or tetrapota6sium ~.G~ho6phate, all percentage~ being by weight, the weight ratio of 6aid sulphonate to ~aid 60ap being from 1:2 to 6:1, the weight ratio of said ~ulphonate to said nonionic surfactant being from 3:5 to 25:1, and the total amount of 6aid ~ulphonate, ~oap and nonionic ~urfactant being from 7.5 to 20% by weight, then the decoupling polymer doe6 not consist ~olely of from 0.1 to 2~ by weight of a partially esterified, neutralised co-polymer of maleic anhydride with vinylmethyl ether, ethylene or 6tyrene.

Preferably, the deflocculating polymer has a lower 6pecific vi6c06ity than those di6closed in GB 1 506 427 A and GB 1 589 971 A, i.e a 6pecific vi6c06ity le66 than 0.1 measured a6 lg in 100 ml of methylethylketone at 25-C. Specific vi6cosity is a dimensionle66 vi6c06ity-related property which i8 indep6n~Pnt of shear rate and i6 well known in the art of polymer 6cience.

Some polymers having a hydrophilic backbone and hydrophobic 6ide-chains are known for thicken~ ng isotropic agueou6 liquid detergent6, for example from European Patent Specification EP-A-244 006. However, there i6 no suggestion in 6uch reference6 that polymer6 of thi6 general type are usable as stabilizers and/or viscosity-reducing agents in (anisotropic) lamellar droplet dispersion6.
In the compo6ition6 of the pre6ent invention, it is possible to u6e deflocculating polymer6 wherein the hackhone of the polymer is of anionic, cationic, nonionic, zwitterionic or amphoteric nature. Po66ibly the polymer backbones have a 6tructure generally corresponding to a 6urfactant 6tructure, and independently of whether or not the backbone has such a 16 1 336385 C 3247 tR) form, the ~ide-chain(s) may also have structures generally correspo~ng to anionic, cationic, zwitterionic or amphoteric surfactants. The only restriction is that the side-chain(6) ~hould have hydrophobic character, relative to the polymer hAc~ho~.
However, the choice of overall polymer types will usually be limited by the urfactants in the composition. For ~xample, polymers with any cationic 6urfactant ~tructural features would be le~s preferred in combination with anionic ~urfactants, and vice versa.

One preferred class of polymers for use in the compositions of the present invention comprises those of general formula (I) R

C02Al ~x C02A2 Co2A3 Y X5 R
R2 (I) ~ ~ , z n wherein:
Z iB l; (X + y): Z iB from 4 : 1 to 1,000 : 1, preferably from 6 : 1 to 250 : 1; in which the monomer unit~ may be in random order; y preferably being from O up to a maximum equal to the value of x; and n is at least 1;

Rl represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-. 17 1 33 63 85 C 3247 (R) or i8 absent;

R2 represents from 1 to 50 indepen~ntly 6elected alkyleneoxy ~ou~ preferably ethylene oxide or ~lG~ylene oxide ~.ou~, or i8 ah~nt~
provided that when R3 is absent and R4 ~e~ ~Fents Lyd~o~en or contains no more than 4 carbon atoms, then R2 must contain an alkyleneoxy group with at least 3 carbon atoms;
R3 .eyle-ents a phenylene linkage, or is absent;

R4 represents hydrogen or a Cl_24 alkyl or C2-24 alkenyl group, with the provisos that a) when Rl represents -0-C0-, 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 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 Cl_4 alkyl; and Al, A2, A3 and A4 are ~nAepe~ently selected from hydrogen, alkali metals, alkaline earth meta~s, ~mmonium and amine bases and Cl_4.
Another clas6 of polymers for use in compositions of the present invention comprise those of formula (II) 18 1 336385 C 3247 tR) R8 ~ R7 H CH2----C CH2----C Ql Q2----H

,r ~ , v g , P
~ , n wherein:

Q2 i6 a molecular entity of formula, tIIa):
~ ~ ~ R6 H- CHz CH CH CH CH C H

C02Al, x ~ C02A2 Co2A3~y RS. R

(IIa) X3 ~ ~ z wherein z and R1-6 are as defined for formula (I);
Al-4, Are a6 defined for formula (I) or ( C2H4O )tH, wherein t iB from 1-50 , A~nd wherein the monomer units may be in random order;
Ql i6 _ multifunctional monomer, _llowing the brAnr-h~ng of the polymer, wherein the monomer6 of the polymer may be cc.--.ected to Ql in _ny direction, in any order, therewith pog~ibly resulting in _ branched polymer. Preferably Ql i~
trimethyl propane triacrylate (TMPTA), methylene bi~acrylamide or divinyl glycol.

l9 C 3247 (R) n and z are a6 defined above; v i6 l; and (x + y +
p + q + r ) : z i6 from 4 : l to l,000 : l, preferably from 6 : l to 250 : l; in which the monomer unit~ may be in random order; and preferably either p and q are zero, or r i6 zero;

R7 and R8 ~Le_~nt -CH3 or -H;

R9 and RlO represent substituent ~ou~ such a6 amino, amine, amide, 6ulphonate, sulphate, phophonate, pho6phate, hydroxy, carboxyl and oxide groups, preferably they are 6elected from -SO3Na, -C0-O-C2H4-OS03Na, -C0-O-NH-C(CH3)2-S03Na, -CO-NH2, --O-CO-CH3, --OH ;

A third class of polymers for use in composition6 of the present invention comprise those of formula (III):

' ~ R6 2 5 OAl ~x R5 ~l R5 Rl2 R3 (III) ~ R

wherein:

X i6 from 4 to l,000, preferably from 6 to 250; n i6 1, Z and Rl-6 are as defined in formula I, wherein the monomer6 unit6 may be in random order:

C 3247 (R) Al i~ a~ defined above for formula I, or -CO-CH2-C(OH)CO2Al-CH2-CO2Al, or may be a br~ch~n~ point whereto other molecule~ of formula (III) are attached.

Examples of molecule6 of th$~ formula are hydrophobically modified polyglycerol ethers or hydrophobically modified conADnQ~tion polymer6 of polyglycerol and citric acid anhydride.

Other ~uitable materials have the formula (IV) Rll Rll ~ ~ R12 Rll Rll CH----CH CH Q ~H----CH

HO--CH HC--O-- ~ 3c o-- ~H Hf-O--H

CH O CH----CH -H O

R12 ~ Rll Rll ~- R

(IV) ~4 i n Wherein :

Z~ n and Al are as defined for formula I, (x + y) : z i6 from 4 :1 to 1,000 t~ 1, preferably from 6 : 1 to 2S0 : 1; wherein the monomer units may be 3 5 in random order.

Rl i~ a~ defined above for formula I,or can be 21 1 ~3 b3 85 C 3247 (R) -CH2-0-, -CH2-0-CO-, -NH-CO-;

R2-4 are aB defined ln formula I:

Rll represents -OH, -NH-CO-CH3, -SO3Al or -OSO3Al:

R12 repre~ent~ -OH, -CH2OH, -CH2OS03Al, COOAl, -CH2-OCH3:

Example~ of molecule6 of thi~ formula are hydrophobically modifled polydextran, -dextran 6ulphonates, and -dextran sulphate6 and the commercially available lipoheteropoly6accharide6 ~Emulsan or ~Biosan LP-31 (ex Petroferm).
Other ~uitable polymer material6 have the following formula (V):

, I
~CHOH----~OH CH----O

H--O--CH CH-C--CH CH--O----H
` / \

~H20R2H ~ 11 (V) ~4 ~ ~ , z, n Wherein:

*~Denotes trade mark 22 C 3247 (R) z, n and R1-6 are _8 defined above for formula I;
and x i6 as defined for formula III;

Simil~r materi~ls are di6closed in GB 2,043,646.

Other ~uitable polymers are hydrophobically modified con~e~Ation polymer6 of -hydroxy acids of formula (VI):
~ , ~

R4*-C--- ----o--C--C--C----o--l--C----oR2--R4*

~ S S ~x ~ 'Y (VI) wherein:
If z i6 the total of R4 yLO~ then the ratio (x + y) : z is from 4 : 1 to 1,000 : 1, preferably from 6 : 1 to 250 : 1; R4* is R4 or -H;
R2 and R4 _re as defined above for formula I;
and S is 6elected from -H, -COOAl, -CH2COOAl, -CH(COOAl)2, (-CH2COOAl)2H~ wherein Al is as defined for formula I or i6 R4;

with the proviso that at least one R4 group i6 present as _ 6ide chain;

Example6 of 6uitable polymer backbones are polymalate, polytartronate, polycitrate, polyglyconate: or mixture6 thereof.

Other 6uitable polymer6 are hydrophobically modified polyacetals of formula (VII):

23 C 3247 (R) ~ CH2----0 C---R4 1 ~ ~v S--f--S
S--l--S (VII) H ~x Wherein:

x, z, S and R4 are as defined above for formula VI;
and wherein at least one R4 group is present as a side chain; and v is 0 or 1;
~n any particular sample of polymer materials in which polymers of the above formulas are in the form of a salt, usually, ~ome polymers will be full ~alts (Al-A4 all other than hydrogen), some will be full acids (Al-A4 all hydrogen) and some will be part-salts (one or more of Al-A4 hydrogen and one or more other than hydrogen).

The ~alts of the polymer6 of the above formula~ may be formed with any organic or inorganic cation defined for Al-A4 and which iB capable of forming a water-soluble salt with a low molecular weight carboxylic acid.
Preferred are the alkali metal salt6, eepecially of ~odium or pota~sium.
The above general formulas are to be construed as including those mixed copolymer forms wherein, within a 24 1 3 3 6 3 8 5 C 3247 (R) particular polymer molecule where n i6 2 or greater, Rl-R12 differ bct~-~en individual monomer unit6 therein.

One preferred ~ub-class comprise6 those polymers which contain sub~tantially no ~aleic acid (or sterified form thereo~) ~onomer unit~.

Al~ho~gh in the polymer~ of the above formulas ~nd their ~alt6, the only requirement i~ that n i8 at lea6t 1, x ( + y + p + q ~ r) i~ at lea6t 4 ~nd that they fulfil the definition6 of the deflocculating effect hereinbefore described (stabilizing and/or vi6cosity lowering), it i6 helpful here to indicate 60me preferred molecular weights. Thi6 is preferable to indicating values of n. However, it must be realized that in practice there is no method of determining polymer molecular weights with 100% accuracy.

As already referred to above, only polymer6 of which the value of n i~ equal to or more than 1 are believed to be effective a deflocculating polymer6. In practice however generally a mixture of polymer6 will be u6ed.
For the purpose of the present invention it i6 not necessary that the polymer mixtures as used have an average value of n which i6 equal or more than one;
al60 polymer mixtures of lower average n value may be u~ed, provided that an effective amount of the polymer molecules have one or more .. ~ ou~ y~ nt on the type and amount of polymer u6ed, the amount of effective polymer a6 calculated on the ba6i~ of the total polymer fraction ~ay be relatively low, for example samples having an average n-value of about 0.1 have been found to be effective a6 deflocculation polymer6.
Gel permeation chromatography (GPC) is widely u6ed to measure the molecular weight distribution of water-25 1 336385 C 3247 (R) soluble polymers. By thi6 method, a calibration isconstructed from polymer etA~Ards of known molecular weight and a ~ample of unknown molecular weight di~tribution i8 compared with this.
S

When the ~ample and ~tA~Ards are of the same chemical composition, the a~Lo~imate true molecular weight of the sample can be calculated, but if such ~tAn~Ards are not available, it is common practice to use 60me other well characterized ~tAnAard~ as a reference. The molecular weight obtA~e~ by such means is not the absolute value, but is useful for comparative purposes.
Sometimes it will be less than that resulting from a theoretical calculation for a dimer.
It is possible that when the ~ame sample is measured, relative to different 6ets of st~Ards~ different molecular weights can be obtained. We have found this to be the case when using (say) polyethylene glycol, polyacrylate and poly ~yLene sulphonate stA~Ards. For the compositions of the present invention exemplified hereinbelow, the molecular weight is specified by reference to the appropriate GPC st~An~Ard.

For the polymers of formula (I to VII) and their salt6, it is preferred to have a weight average molecular weight in the region of from 500 to 500,000, preferably from 750 to 100,000 most preferably from 1,000 to 30,000, especially from 2,000 to 10,000 when measured by GPC u6ing polyacrylate stAn~Ards. For the ~uL~oses of thi6 definition, the molecular weights of the 6t~n~Ards are measured by the absolute intrin6ic visco6ity method described by Noda, T60ge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710-719.

AB well as the polymer~ of the above formulas and their 26 1 3363~5 C 3247 (R) ~alt6, many other suitable polymers are known, although previously, not for $nclusion in l~mellar dispersion6 of surfact nt. Such known polymers are described, for example, in R.R~rcAll and T.Corner, Colloids and 8urfaces, 17 (1986) 25-38; R~rcall and Corner, ~ , PP. 39-49: European Patent Application6 EP-A-57 875, published August 18, 1982 and EP-A-99 179, published January 25, 1984;US Patent 4 559 159 ~nd ~R Patent GB 1 052 924.
These references also disclose methods for making the polymers therein 10 described and which, by analogy, those skilled in the art will be capable of adapting for preparing other polymers for use in the present invention.
The polymers may also be made by methods generally analogous to any of those described in any of patent documents EP-A-244 066, published November 4, 1987, US 3 235 505, US 3 328 309 and US 3 457 176 referred to hereinbefore.

Most preferably, however, we havQ found that the polymers for use ln the composition~ of the pre~ent invention can be efficiently prepared using conventional aqueou6 polymerization procedures, but employing a process wherein the polymerization is carried out in the presence of a suitable cosolvent and wherein the ratio of water to co-solvent 18 carefully monitored so as to maintain the ratio of water to cosolvent egual or greater than unity durlng the reaction, thereby keeping the polymer, ~8 it form~, in a ~ufficlently mobile conditlon and to prevent unwanted homopolymerization and precipitation of the polymer from the hydrophobic monomer.
A preferre process for preparing the polymers provldes a product ln unigue form ~8 a relatively hlgh solids, low vlscosity, opaque or semi-opagus product lnterre~te between ~ true clear or llmpid solution, 35 and an emulsion consistlng entirely of non-agglomerated partlcles. The product exhibit6 no ;~,. ~

27 1 3 3 6 3 8 5 C 3247 (R~

gelling, coagulation or product 6eparation on stAn~n~
for at lea6t two week6. It i6 further preferably characterized in that upon dilution in water to 0.25 %
by weight, the turbidity of the re6ultant preparation 5 iB at least 10 Nephelometric Turbidity Units (N.T.~.~s).

Thi6 preferred proce6s i~ e6pecially ~uited to preparation of the polymers and 6alts according to formula (I and II) a6 hereinbefore defined.
The particular cosolvent choFcn for the reaction will vary depen~ng upon the particular monomer6 to be polymerized. The co-601vent 6elected should be mi6cible with water, di6solve at least one of the monomers, but not react with the monomer6 or with the polymer as it is produced and be 6ubstantially readily removed by 6imple distillation or azeotropic di6tillation procedures.

The particular co-601vent chosen for the reaction will vary dep~n~ng upon the particular monomers to be polymeri6ed. The cosolvent selected 6hould be mi6cible with water, dis601ve at least one of the monomers, but not react with the monomers or with the polymers a6 it is pro~llce~ and be 6ubstantailly readily removed by 6imple distillation or azeotropic distillation prGcedured. Suitable co-601vents include i60propanol, n-propanol, acetone, lower (Cl to C4) alcohols, ketones and e6ter6. Isopropanol and normal propanol are the most preferred.

The ratio of water to co-solvent i6 preferably carefully regulated. If too low an amount of co-solvent iB employed, precipitation of hydrophobic monomer or homopolymer may occur; too high a co-solvent level is more eYpencive and time-con6uming to remove, result6 in too high product viscosity and, in some cases, may 28 C 3247 (R) cau6e precipitation of the water-soluble polymer.

In some ca6e it is critical that the ration of water to cosovent i6 equal or greater than unity durlng the reaction.

The polymerization i8 carried out in the ~la~ence of free-radical initiators. Examples of water-soluble, free-radical initiators which are sultable for the polymerization are the usual thermal decomposition initiators 6uch as hydrogen peroxide, peroxydisulphate6, e6pecially sodium peroxydisulphate or ammonium peroxydisulphate, or azo-bi6(2-aminopropane) hydrochloride. Redox initiators such a6 tertiary butyl hydroperoxide/bisulphite;
tertiary butyl hydroperoxide/ sodium formaldehyde sulphoxylate; or hydrogen peroxide with a ferrous com~ou.,d can al60 be used.

Preferably, from 0.1 to 5% by weight, ba6ed on the sum of the monomers, of the initiators is present in the mixture. The polymerization takes place in an aqueous co-601vent medium, and the concentration i6 advantageously cho6en 80 that the agueou6 co-601vent solution contain6 from 10 to 55, preferably from 20 to 40% by weight of total monomer6. The reaction temperature can vary within wide limit6, but i6 advantageously r~oren to be from 60- to 150-C, preferably from 70- to 95-C. If the reaction is carried out at above the boillng point of water, a pre6sure-tight vessel, such a8 an autoclave, is chosen as the reaction ves6el.

Furthermore, the regulators co"~e"tionally used for free-radical polymerization in an aqueou6 medium, e.g.
thioglycolic acid or Cl to C4 ~ldehydes, or branching agent6, such a6 methylene bisacrylamide or divinyl 29 1 3 3 6 3 8 5 C 3247 (R) glycol or TMPTA, can be employed, the amounts being from 0.1 to 10% by weight preferably from 0.5 to 5% by weight, re6pectively, and the percentages being based on the total amount of the monomer6.

The turbidity of the prepared polymers may be measured using a Hach Model 2100A Turbidimeter. It wa~ ~ound that direct measurement on the polymers was not possible, and that u~eful rea~ngs could only be ~ade when the polymers were dilutes to 0.25 % by weight 601id contents with deionized water.

Generally, the deflocculating polymer will be used at from 0.01% to 5.0% by weight in the composition, most preferably from 0.1% to 2.0%.

Although it i6 possible to form lamellar disper6ions of surfactant in water alone, in many cases it is preferred for the aqueous continuous phase to contain di6solved electrolyte. As used herein, the term electrolyte means any ionic water-soluble material.
However, in lamellar di6per6ions, not all the electrolyte is nPce~c~rily dissolved but may be 6uspended as particles of solid becau6e the total 2S electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being ~ubstantially only in the suspended ~olid phase. Two or ~ore electrolytes may also be distributed approximately ~Lo~G.Lionally, between these two rha~e~. In p_rt, thi~ may ~p~n~ on ~ ~Aing, e.g. the order of addition of comron~nt~. On the other hand, the term '6alts' include6 all organic and inorganic materials which may be included, other than 6urfactants and water, whether or not they are ionic, and thi6 term encomrA~re~ the 6ub-set of the 1 33 63 85 c 3247 (R) electrolyte6 (water- soluble material6).

The only restriction on the total amount of detergent-active material and electrolyte (if any) is that in the compositions of the invention, together they must result in formation of an aqueous lamellar ~i~per~ion.
Thus, within the ambit of the present invention, a very wide variation in ~urfactant types and level~ iB pos-sible. The selection of ~urfactant types and their proportion6, in order to obtain a ~table liquid with the required 6tructure will be fully within the capability of those 6killed in the art. However, it can be mentioned that an important 6ub-cla66 of useful com-positions i6 tho~e where the detergent-active material compri6es blends of different 6urfactant types. Typical blends u6eful for fabric wA~h~ng composition~ include those where the primary surfactant(s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
In many (but not all) ca6es, the total detergent-active material may be present at from 2% to 60~ by weight of the total composition, for example from 5% to 40% and typically from 10% to 30% by weight. However, one preferred class of compositions compri6es at least 20%, mo6t preferably at least 25%, and especially at lea6t 30% of detergent-active material based on the weight of the total composition.
In the ca6e of blends of surfactants, the precise proportlons of each compo"~-"~ which will result in such ~tability and vi~cosity will depend on the type(~) and amount(6) of the electrolytes, as 18 the case with conventional ~tructured liqulds.

In the widest definition the detergent-active material in general, may comprise one or more ~urfactants, and may be ~elected from anionic, cationic, nonionic, 31 1 336385 C 3247 (R) zwitterlonic and amphoteric species, and (provided mutually compatible) mixture6 thereof. For example, they may be rho--n from any of the classes, sub-cla66es and ~pecific materials described in 'Surface Active Agents' Vol.I, by 8chwartz ~ Perry, Interscience 1949 and 'Surface Active Agents' Vol.II by 8chwartz, Perry &
Berch (Interscience 1958), in the current edition of ~NcCutch~Dn'~ Emulsifiers ~ Dete~gents" publi~hed by the ~cCutcheon divi~ion of Manufacturing Confectioners Company or in 'Tensid-Tar-h~nh~h', H.Stache, 2nd Edn., Carl ~n~er Verlag, Mllnchen & Wien, 1981.

Suitable nonionic surfactant6 include, in particular, the reaction product6 of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohol6, acids, amides or alkyl phenol~ with alkylene oxides, e6pecially ethylene oxide, either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C18) primary or secondary linear or brA~Ghe~ alcohol6 with ethylene oxide, and products made by con~ tion 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.

Sultable anionic surfactant6 are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radlcals containing from about 8 to about 22 carbon atoms, the term alkyl being used to lnclude the alkyl portion of higher acyl radicals.
Ex~mples of sultable synthetic anionic detergent compounds are ~odium and potassium alkyl sulphates, especially those obtained by 6ulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil, ~odium and pota~sium alkyl (Cg-C20) benzene 32 1 3 3 6 3 8 5 C 3247 (R) 6ulphonates, partieularly 60dlum llnear seron~ry alkyl (C10-Cl5) benzene sulphonates oodium alkyl glyeeryl ether 6ulphates, e6peeially those ethers of the higher aleohol6 derived from tallow or CG~O~ oil and synthetie aleohols derived from petroleum; ~odium çoeonut oil fatty monoglyeeride sulphates and 6ulphonate~; ~odium and potaselum ~alts of ~ulphurie aeid esters of higher (C8-C18) fatty aleohol-alkylene oxide, partieularly ethylene oxide, reaetion produets;
the reaetion produets of fatty ~eids sueh as eoeonut fatty aeid6 e6terified with isethionie aeid and neutr~lized with sodium hydroxide; sodium and pota66ium 6alts of fatty ~cid amide6 of methyl taurine; A 1 kAne monosulphonate6 ~ueh a6 those derived by reaeting alpha-olefin6 (C8-20) with sodium bisulphite and tho6e derived from re~cting paraffin6 with S02 and C12 and then hydrolyzing with a base to produce a random sulponate; and olefin 6ulphonate6, which term i6 usQd to describe the material made by reacting olefin6, particularlY C10-C20 alpha-olefin with S03 and then neutralizing and hydrolyzing the reaction product The preferred anionie detergent eompounds are sodium ~Cll-C15) alkyl benzene 6ulphonates and sodium (C16-C18) alkyl sulphates Also possible iB that part or all of the detergent aetive ~aterial is an ~tabilising 6urfaetant, whieh has an average alkyl ehain length greater than 6 C-atom6, and whleh hafi a salting out re~lstanee, greater then, or equal to 6 4 These ~tabili~ing ~urfaetantants are diselosed in CA 8803036 Examples of these ~aterlals are alkyl polyalkoxylated phosphates, alkyl polyAlkQxylated sulpho6ueelnates ~Alkyl diphenyloxide~ dl6ulpbonate~;
alkyl poly~aeeharides and ~lxtures thereof ~t 16 also possibl~, and ~ometlmes preferred, to 33 1 33~385 C 3247 (R) inelude an ~ i ~etal soap of a long ehain mono- or diearboxylie aeid for example one having from 12 to 18 earbon atoms. Typieal aeid6 of thi6 kind are oleie aeid, rieinoleie aeid, and fatty aeids derived from eastor oil, rape_~e~ oil, y~ U~ oil, ~-oeo~ oil, palmkernel oil or mixtures thereof. The sodium or pota6sium soaps of the6e aeids ean be u~ed.

Preferably the amount of water in the eomposition i8 from 5 to 95~, more preferred from 25 to 75%, mo~t preferred from 30 to 50%. E6pecially preferred le66 than 45% by weight.

The eompo~ition6 optionally al60 eontain electrolyte in an amount suffieient to bring about ~trueturing of the detergent-aetive material. Preferably tho~gh, the eompo~itions eontain from l~ to 60%, e6peeially from lO
to 45% of a ~alting-out eleetrolyte. Salting-out electrolyte ha~ the me~nq a-erlbed to in ~peclfication EP-A-79646,published May25,1983 Optionally, ome ~altlng-in electrolyte (a6 defined in the latter ~pecification) may also be included, provided if of a kind and in an amount eompatible with the other eomponent6 and the eomposition i6 6till in aeeordance with the definition of the invention elaimed herein. Some or all of the electrolyte (whether salting-in or salting-out), or any 6ub~tantially water-in~oluble ~alt whieh ~ay be pre~ent, may have detergeney builder propertie~. In any event, lt i6 preferred that eompositions aeeording to the present invention inelude detergeney builder material, some or all of whieh may be eleetrolyte. The builder material i~ any eapable of reduelng the level of free ealeium ions in the wash liguor _nd will preferably provide the eomposition with other benefieial propertie~ sueh as the generation of an a~Aline p~, the ~u6pension of soil removed from the ~abrie and the di6per~10n of the fabrie soften~ elay ,.

34 ¦ 336385 C 3247 (R) material.

Examples of pho6phorous-cont~n~n~ inorganic detergency builders, when ~r~ent, include the 5 water-~oluble salts, especially alkali metal ~,o~hc_~hates, orthopho6phate6, polyphosphates and pho6phonate6. 8pecific example6 of inorganic pho6phate builders include sodium and pota66ium tripolypho6phates, pho6phates and hexamet~rhosphate6.
10 Phosphonate ~equestrant builders may also be used.

Examples of non-pho6phorus-cont~ning inorganic detergency builders, when pre6ent, include 15 water-soluble alkali metal c~rhonAtes, bicarbonates, silicate6 and crystalline and amorphous aluminosilicates. Specific examples include 60dium carbonate (with or without calcite 6eeds), potassium carbonate, 60dium and potassium bicarbonates, silicates 20 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 601ubility of sodium salts. Thereby, the amount of di6601ved electrolyte can be increa6ed con6iderably (cry6tal di6601ution) a6 described in UK
patent specification GB 1 302 543.

Examples of organic detergency builders, when ~ ent, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates, ca boxymethyloxysuccinates, carboxymethyloxymalonates, ethylene diamine-N,N, disuccinic acid salt6, polyepo~y6uccinates, oxydi~cetates, triethylene tetramine hexacetic acid salts, N-alkyl imino diacetates or dipropionates, alpha -- 35 C 3247 (R) - 1 3363~5 sulpho- fatty acid salt6, dipicolinic acid ~lats, ox~A1~ed polysaccharides, polyhyd~oxy~lphonates and mixtures thereof.

Specific examples include ~odium, potassium, lithium, ammonium and sub6tituted ammonium salts of ethyleneA~minetetraacetic acid, nitrilitriacetic acid, oxydi6uccinic acid, melitic acid, benzene polycarboxylic acid6 and citric acid, tartrate mono succinate and tartrate di ~uccinate.

In the context of organic builders, it i6 al60 desirable to incorporate polymer6 which are only partly dis601ved in the aqueous continuous phase. Thi6 allows a visc06ity reduction (owing to the polymer which i6 dissolved) whil6t incorporating a sufficiently high amount to achieve a 6econdary benefit, especially building, because the part which is not di6601ved does not bring about the instability that would occur if 6ubstantially all were dis601ved.

Examples of partly di6solved polymer6 include many of the polymer and co-polymer6 6alt6 already known a6 detergency builder6. For example, may be u6ed (including building and non-building polymer6) polyethylene glycols, polyacrylates, polymaleates, poly6ugars, polysug~rsulphonate6 and co-polymer6 of any of the6e. Preferably, the partly dissolved polymer comprise6 a co-polymer which include6 an alkali metal salt of a polyacrylic, polymethacrylic or maleic acid or anhydride. Preferably, compo6ition6 with the6e co-polymer6 have a pH of above 8Ø In general, the amount of viscosity-reducing polymer can vary widely according to the formulation of the re6t of the composition. However, typical amount6 are from 0.5 to 4.5% by weight.

36 C 3247 ~R) It i6 further pos6ible to include in the composition6 of the pre~ent invention, alternatively, or in addition to the partly dis601ved polymer, yet another polymer which is sub6tantially totally soluble in the agueous phase and has an electrolyte re6i6tance of more than 5 grams 60dium nitrilotriacetate in 100 ml of a 5% by weight aqueous ~olution of the polymer, ~aid ~CQn~
polymer al~o having a vapour pressure in 20~ agueous 601ution, egual to or le66 than the vapour pre6sure of a reference 2% by weight or greater agueou6 ~olution of polyethylene glycol having an average molecular weight of 6,000; ~aid 6econd polymer having a molecular weight of at least 1,000.

The incorporation of the 601uble polymer permits formulation with improved 6tability at the same viscosity (relative to the composition without the 601uble polymer) or lower viscosity with the same stability. The soluble polymer can also reduce viscosity drift, even when it also brings about a viscosity reduction. Here, improved 6tability and lower viscosity mean over and above any such effects brought about by the deflocculating polymer.

It i~ especially preferred to incorporate the 601uble polymer with a partly dis601ved polymer which has a large insoluble compone~t. That i6 because although the building capacity of the partly di~olved polymer will be good (since relatively high quantitie~ can be stably incorporated), the vi6co~ity reduction will not be optimum (~ince little will be di~solved). Thus, the soluble polymer can usefully function to reduce the viscosity further, to an ideal level.

The soluble polymer can, for example, be incorporated at from 0.05 to 20% by weight, although usually, from 0.1 to 10% by welght of the total composition i~

37 1 33 63 ~5 C 3247 (R) ~ufficient, and especially from 0.2 to 3.5 -4.5~ by woight. It has boon found that the presenco of deflor~llAtlng polymer lncrease the tolerance for h~h9r 1QVO1B of oluble polymer without ~tability probl m~. A large nu~ber of different polymers ~ay be usQd as ~uch a ~oluble polymer, provided the lectrolyte resi~tance and vapour pressure roquirement~
are ~et. The former 18 ~easured as the amount of ~odium nltrilotriacetato ~NaNTA) ~olution nece~ry to reach the cloud point of 100 ml of a 5~ solution of the polymer in water at 25-C, with the sy6tem ad~usted to neutral pH, i.e. about 7. Thi6 is preferably effected using 60dium hydroxide. Most preferably, the electrolyte resi6tance is 10 g NaNTA, especially 15 g.
The latter indicates a vapour pres6ure low enough to have 6ufficient water b~n~1ng capability, as generally explained in the Applicants' specificatlon GB-A-2 053 249. Preferably, the measurement i8 effected with a reference solution at 10~ by weight aqueous concentration, especially 18%.

Typical classes of polymers which may be used as the 601uble polymer, provided they meet the above requirements, include polyethylene glycols, Dextran, Dextran sulphonates, polyacrylates and polyacrylate/
maleic acid co-polymers.

The 601uble polymer mu6t have an average~molecular weight of at least 1,000 but a minimum average ~ol~c~ r weight of 2,000 i8 preferred.

The use o~ p~rtly soluble and the use of soluble polymers as referred to above in detergent compositions iB ~e~cribed in our cope~A1ng Eu~opean patent applications EP 301 882, published Februa~ 1,1989 and EP 301 883, published February 1,1989.

Although it i8 poB6ibl0 to incorporate minor ~mounts 38 1 336385 C 3247 (R) of hydrotropes 6uch as lower alcohols (e.g. ethanol) or alkA~olamlne6 (e.g. triethanolamine), ln order to ensure lntegrlty of the lamellar di6per6ion we prefer that the compositlons of the pre6ent lnvention are cubstantially free from hydrotropes. By hyd~u~.o~e i~
msant ~ny water ~oluble agent which tends to e~han~e the solubillty of surfactants in aqueous ~olutlon.

Apart from the lngredient6 already mentioned, a number of optional ingredients may also be ~ nt, for oxample lather boosters 6uch a~ ~lkAnolamldes, particularly the monoethanolamides derived from palm kernel fatty acid6 and coconut fatty acid6, fabric 60fteners such a6 clay6, amine6 and amine oxide6, lather depressants, oxygen-releasing bleaching agents 6uch as sodium perborate and sodium percarbonate, peracid bleach p~a_ul_~rs, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorg~nic ~alts such as sodium sulphate, and, usually present in very ~inor amounts, fluorescent agent6, perfumes, enzymes 6uch a6 proteA~e~, amylase6 and lipases (incl~ n~ Lipola6e (Trade Mark) ex Novo), germicide6 and colourants.

Amongst these optional ingredient6, a6 mentioned previouRly, are agents to which lamellar dispersion6 without deflocculating polymer are highly stability-censitlvQ and by virtue of the present invention, can be in~ol~orated in higher, ~ore use~ul amounts. mese agents cau6e a problem in the ab~ence of deflocculating polymer because they tend to promote flocculation of the lamellar droplets. ~xamples of ~uch agent~ are solubl~ polymers, ~oluble builder such a~ ~uccinate buildorc, fluo~ ers like Bl~orhor RKH, T1~or~l LMS, and T~nopal DMS-X and Blankophor BBH as well a~ metal chelating agents, especially of the rho~rhon~te type, ~or oxample the~Dequestrange 601d by Mon~anto.

~Denotestrade mark 39 1 33 63 85 C 3247 tR) The invention will now be ~llustrated by way of the following Examples. In all Examples, unless stated to the contrary, ~11 percentages are by weight.

40 1 33 63 85 c 3247 (R) A. BASE COMPOSITIONS

Table la Composition of basie formulations i.e. without defloeeulating polymer.

Ingredient Basie formulation (% w/w) NaDoBS 28.0 24.5 19.7 26.7 26.1 Synperonic A7 6.5 9.9 7.9 10.7 10.5 Na Citrate 16.4 16.4 11.0 9.0 10.9 Water 49.0 49.2 61.4 53.6 52.5 Defloeeulating weight6 additional to basie polymer formulation Table lb Composition of basie formulations Ingredient Basic formulation (% w/w) NaDoBS 25.6 25.0 12.9 12.6 12.3 Synperonie A7 10.3 10.0 5.2 5.1 5.0 Na Citrate 12.8 14.7 12.9 14.8 16.5 Water 51.3 50.3 69.0 67.5 66.2 Defloeeulating weights additional to basie polymer formulation 41 1 336385c 3247 (R) Table lc Compo~ition of ba~ic formulation6.

TngredientBasic formulation (% w/w) Na DoBS 23.5 Synperonic A7 9.5 Na Citrate 19.7 Water 47.3 Deflocculating weights additional to basic formulation polymer IngredientBasic formulation (% w/w) Na DoBS 17.1 Dobanol 23-6.5 7.0 TrEA 2.0 Na-citrate 20.0 Deflocculatingif ~ny polymer Water up to 100 42 C 3247 (R) Table ld Compo~ition of ba6ic formulation~

InqredientBasic formulation (% w~w) Na DoBS 8.5 8.5 8.5 8.5 7.5 7.5 6.4 4.3 Synperonic A7 2.0 2.0 2.0 2.0 3.0 3.0 4.0 6.0 Na Oleate 2.7 5.4 8.1 10.8 8.1 10.8 - -Glycerol 5Ø
Borax ----------- 3-5 Deflocculating if any Polymer Water --- up to 100 43 C 3247 (R) Table le Compo6ition of ba6ic formulations.

Ingredient Basic formulation (% w/w~

~1 22 23 24 ~

Na DoBS 9.6 9.9 10.1 10.2 10.4 Na Oleate 16.2 16.6 16.9 17.2 17.6 Synperonic A7 6.0 5.3 4.8 4.4 4.0 Glycerol 5.0 Borax 3.5 Deflocculating if any polymer Water up to loO

44 C 3247 (R) Table lf Compo~ition of ba~ic formulations Ingredient Ba6ic formulation (% w/w~

Na DoBS 10.2 9.6 20.6 21.5 21.8 Na Oleate 16.9 15.9 - - -Synperonic A7 4.8 4.5 4.4 3.5 3.2 Glycerol 5.0 5.0 5.0 5.0 5.0 Borax 3.5 3.5 3.5 3.5 3.5 STP 15.0 15.0 22.0 22.0 22.0 Silicone oil/DB 1000.25 0.25 0.25 0.25 0.25 Gasil 200 2.0 2.0 2.0 2.0 2.0 Na SCMC 0.1 0.1 0.3 0.3 0.3 Tinopal CBS-X 0.1 0.1 0.1 0.1 0.1 Blancophor RKH 766 - - 0/0~2 0/0.2 0/0.2 Dequest 2060S - - 0.4 0.4 0.4 Perfume 0.3 0.3 0.3 0.3 0.3 ~lcalase 2.5L 0.5 0.5 0.5 0.5 0.5 Deflocculating if any polymer Water up to 100 ~Denotes trade mark .~
,. .

C 3247 (R) Table lq Composition of basic formulation6 IngredientBasic formulation (% w/w) Na DoBS 9.8 12.3 Synperonic A7 2.3 2.9 Glycerol 5.0 6.3 Borax 3.5 4.4 STP 25.0 31.3 Water 54.4 42.8 Deflocculating weights additional to basic formulation polymer~

46 C 3247 (R) Table lh Composition of basic formulations.

Ingredients Basic formulation ~% w/w~

NaDoBS c......... 21.5........ >
Synperonic A7 ~......... .3.5........ >
Glycerol ~......... .5Ø....... >
Borax <......... .3.5........ >

Silicon oil <......... Ø25....... ~
Gasil 200 <......... .2Ø....... >
Na SCMC <......... Ø3........ >
Tinopal CBS-X <......... Ø1........ >
Dequest 2060S (as 100~) <......... Ø4........ >
Perfume <......... Ø3........ >
Alcalase 2.5L <......... Ø5........ >
Deflocculating polymer <......... Ø75....... >
Water <......... 39.9........ >

47 C 3247 (R) Table li Compo61tion of b~sic formulation6 Ingredients Basic formulation (~ w/wl 41 42 ~ 44 45 NaDoBS 9.6 9.4 9.2 8.9 8.3 Na-Oleate 15.9 15.6 15.3 14.7 13.7 Synperonic A7 4.5 4.4 4.3 4.2 3.9 Glycerol 5.0 4.9 4.8 4.6 4.3 Borax 3.5 3.4 3.4 3.2 3.0 KTP - 2.0 3.8 7.4 13.8 STP 15.0 14.7 14.4 13.9 12.9 Silicon oil 0.25 0.25 0.24 0.23 0.22 Gasil 200 2.0 2.0 1.9 1.9 1.7 Na-SCMC 0.1 0.1 0.1 0.1 0.1 Tinopal CBS-X 0.1 0.1 0.1 0.1 0.1 Perfume 0.3 0.3 0.3 0.27 0.26 Alcalase 2.5L 0.5 0.5 0.5 0.46 0.43 Deflocculating polymer0.75 0.74 0.72 0.69 0.65 Water 42.5 41.6 40.9 39.4 36.6 48 C 3247 (R) Table lk Composition of ba6ic formulations Inqredient Basic formulation (9~w/w) NaDoBS 27.1 31.5 33.9 Synperonic A7 11.5 13.4 14.5 Na Citrate 15.3 13.8 12.9 Water 46.1 41.3 38.7 Deflocculating Weights additional to polymer ba6ic formulations 49 C 3247 (R) Table 11 ComDosition of basic formulations Inqredient Basic formulation (%w/w) NaLAS 6.2 - - - 6.3 5.2 -K LAS - 6.5 6.5 6.3 - -- 6.3 N~Oleate 8.8 - - - - - -X Laurate - - 3.8 - 3.8 3.2 -X Oleate - 9.4 5.5 9.2 5.5 4.6 9.2 ~;ynperonic A7 10.0 3.5 10.0 10.0 10.0 8.4 -Synperonic A3 - - - - - - 10.0 Glycerol 5.0 5.0 5.0 5.0 5.0 3.64 3.64 Borax 3.5 3.5 3.5 Boric-acid - - - 2.28 2.28 1.66 1.66 ROH - - - 1.0 1.0 0.75 0.75 KTP 7.0 STP 15.0 20.0 19.0 20.0 19.0 20.0 20.0 Ga6il 200 2.0 2.0 1.5 1.5 2.0 -Silicon oil 0.25 0.25 0.3 0.25 0.25 0.05 0.05 Tinopal CBS-X 0.1 0.1 0.1 0.1 0.1 0.1 0.07 Na-CMC 0.3 0.3 0.1 0.3 0.3 0.3 0.3 Dequest 2060S
(as 100%) 0.4 0.4 0.4 0.4 0.4 0.3 0.3 Alcalase 2.5L 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Perfume 0.3 0.3 0.3 0.3 0.3 0.25 0.3 Deflocculating 0/ 0/ 0/ 0/ 0/ 0/ 0/
Polymer (if any) 0.75 0.75 0.75 0.75 0.75 0.75 0.60 Water up to 100 C 3247 (R) Table lm Composition of ba6ic formulations Ingredient Ba6ic formulation r%w/w~
56 57 58 59 ~0 NaLAS 7.9 7.9 11.5 8.1 10.0 K Oleate 1.0 1.0 - - -5ynperonic A7 2.25 2.25 2.7 5.4 4.0 Glycerol 4.8 4.8 6.7 6.7 6.7 Borax 3.1 3.1 4.7 4.7 4.7 STP 23.0 23.0 8.1 8.1 8.1 Na-CMC 0.1 0.1 Tinopal CBS-X 0.1 0.1 Silicone 0.25 0.25 -Gasil 200 2.0 2.0 Perfume 0.3 0.3 Dequest 2060S 0.2 0.4 (as 100%) Alcalase 2.5L 0.5 0.5 Water up to 100 Deflocculatingweights additional to polymerbasic formulation 51 C 3247 (R) Table ln Com~osition of basie formulation6 Ingredient ~ic formulation (%w/w~

Na DoBs 9.1 17.3 6.4 Synperonie A7 3.6 1.8 3.5 Na Oleate - - -R Oleate - - 8.2 Na Stearate - 0.9 X Laurate - - 5.7 Glyeerol 8.1 3.0 5.0 Borie-aeid - - 2.28 XOH - - 2.2 NaOH 1.0 Borax 5.8 2.0 Na-eitrate - 5.0 Citrie-acid 1.5 - 1.50 Zeolite A4 25.3 30.0 20.0 NaCMC - 0.3 0.3 Tinopal CBS-X - 0.13 0.1 Silieon DB100 - - 0.25 Dequest 2060S - - 0.4 (as 100%) Perfume - O.22 0.3 Alealase 2.34L - 0.5 0.5 Defloeeulating 0/0.5 0/0.5 0/0.5 polymer (if any) Water up to 100 pH 8.8 9.1 7.7 52 C 3247 (R) Table lp Composition of basic formulations Inqredient Basic formulation (%w/w) Na Dobs 14.4 10.3 6.2 11.0 13.6 12.3 12.3 Synperonic A7 11.6 19.3 27.0 13.8 17.0 15.4 15.4 Na Oleate 8.7 6.23.7 6.7 8.2 7.5 7.5 Na Laurate 5.9 4.32.6 4.6 5.7 5.1 5.1 Na2CO3 4.0 4.04.0 4.0 4.0 2.0 6.0 Glycerol 5.0 Borax 3.5 Dequest 2066 (as 100%) 0.4 Silicon DB100 0.1 Savinase 0.3 Amylase 0.1 Tinopal CBS-X 0.1 Perfume 0.3 Deflocculating 0/1.0 polymer (if any) Water up to 100 pH 9.7-10.0 1 3363~5 53 C 3247 (R) Table lq Composition of basic formulations Ingredient Basic formulation (%w/w) 71 72 73 74 ~ 76 77 Na Dobs 14.4 10.3 11.0 12.3 13.6 12.3 12.3 8ynperonic A7 11.6 19.3 13.8 15.4 17.0 15.4 15.4 Na Oleate 8.7 6.26.7 7.5 8.2 7.5 7.5 Na Laurate 5.9 4.34.6 5.1 5.7 5.1 5.1 X2S04 6.0 6.06.0 6.0 6.0 1.0 3.0 Glycerol 5.0 Borax 3.5 Dequest 2066 (as 100~) 0.4 Silicon DB100 0.1 Savinase 0.3 Amylase 0.1 Tinopal CBS-X 0.1 Perfume 0.3 Deflocculating 0/1.0 polymer (if any) Water up to 100 pH 8.3-8.8 54 C 3247 (R) Table lr Composition of basic formulations Ingredient Basic formulation (%w/w) Na Dobs 14.4 10.3 6.2 9.2 11.3 10.3 10.3 ~ynperonic A7 11.6 19.3 27.0 17.3 21.3 19.3 19.3 Na Oleate 8.7 6.2 3.7 5.6 6.9 6.2 6.2 Na Laurate 5.9 4.3 2.6 3.8 4.7 4.3 4.3 Na-citrate.2aq 10.0 10.0 10.0 10.0 10.0 6.0 12.0 Glycerol 5.0 Bor~x 3.5 Deque~t 2066 (as 100%) 0.4 Silicon DB100 0.1 Savinase 0.3 Amylase 0.1 Tinopal CBS-X 0.1 Perfume 0.3 Deflocculating 0/1.0 polymer (if any) Water up to 100 pH 7.0-9.8 S5 C 3247 (R) Table ls Composition of basic formulations Ingredient Basic formulation (%w/w) Na Dobs 14.4 10.3 11.3 9.2 11.3 10.3 10.3 8ynperonic A7 11.6 19.3 17.4 17.3 21.3 19.3 19.3 Na Oleate 8.7 6.2 6.9 5.6 6.9 6.2 6.2 Na ~urate 5.9 4.3 4.7 3.8 4.7 4.3 4.3 Na-CMOS (75%) 10.0 10.0 10.0 10.0 10.0 8.0 12.0 Glycerol 5.0 Borax 3.5 Deque~t 2066 (as 100%) 0.4 Silicon DB100 0.1 Savinase 0.3 Amylase 0.1 Tinopal CBS-X 0.1 Perfume 0.3 Deflocculating 0/1.0 polymer (if any) Water up to 100 pH 8.2 - 9.0 56 C 3247 (R) Table lt Composition of basic formulAtions Tn~redient Basic formulation (%w/w) NaDobs 10.2 K Dobs - 10.7 Synperonic A7 19.3 19.3 Na Oleate 10.3 K Oleate - 10.9 Glycerol 5.0 5.0 80rax 3.5 3.5 Na-citrate 2aq 10.0 Na2C03 - 4.0 Sokalan CP5 2.5 Dequest 2066 (as 100%) 0.4 0.4 Silicon DB100 0.3 0.3 Tinopal CBS-X 0.5 0.5 Savina~e 0.3 0.3 Amylase 0.1 0.1 Perfume 0.1 0.1 Dye 0.3 0.3 Deflocculating 0/1.0 0/1.0 polymer (in any) water up to 100 57 C 3247 (R) R. PREPARATION OF POLYMF~S

The following i6 the method used to prepare the polymer hereinafter designated by the reference A-15. All other polymer6 of Table 2a-2g can be prepared in priciple in an analogous manner.

A monomer mixture was prepared consisting of a hydrophilic monomer (acrylic acid 216g, 3.0 moles) ~nd a hydrophobic monomer tMethacrylester 13 (Trade Mark), average chain length 13 carbon atoms, available from Rohm, 32g, 0.12 moles). This gave a molar ratio of hydrophilic to hydrophobic monomer of 25:1.

To a 2 litre glass round bottomed reaction vessel, equipped with a condenser, stainless steel paddle stirrer, and thermometer, was added 600 g of an aqueous mixture of isopropanol and water, consisting of 400 g deionized water and 200g isopropanol. This gave a molar ratio of water, cosolvent mixture to total weight of monomers of 2.42:1 and a water to isopropanol ratio of 2:1.

The monomer mixture was pumped into the reaction vessel over a period of about 3 hours, keeping the reaction mass at 80-85-C, with simultaneous introduction over a period of 4 hours, by pumping in an independent stream, of an initiator solution consisting of lOOg of a 4% aqueous solution of 60dium persulphate.
~0 After addition of the lnitiator, the ratio of water and cosolvent to polymer had risen to 2.81:1 and the water to isopropanol ratio to 2.5:1. The reaction contents were held at 80-85-C for a period of about one further hour, giving a total time from the start of the monomer and initiator additions of about 5 hours.

The isopropanol was then substantially removed from 58 C 3247 (R) - the reaction product by azeotropic di6tillation under vacuum, until the re6idual 160propanol content wa6 le66 than 1% a6 mea6ured by direct ga6 601id chromatography u6ing a flame ionization detector.

The polymer wa6 l~e~ lized to approximately pH 7 by a~ g~ at 40-C and below, 230 grams (2.76 moles) of 48%
caustic 60da ~olution with water added back a6 ne~e~Fary to bring the solids to approximately 35%.
The product was an opaque vi6cou6 product, having a 601id~ content of approximately 35% and a vi6cosity of 1500 cps at 23-C a6 mea6ured by a Brookfield Synchro-Lectric vi6cometer model RVT, spindle 4, at 20 rpm.

The molecular weight distribution of the polymer produced was measured by aqueous gel permeation chromatography, u6ing an ultra violet detector 6et at 215 nm. The number average (Mn) and weight average (Mw) molecular weight6 were mea6ured from the chromatogram 80 produced, using fractionated sodium polyacrylate st~n~Ards to con6truct a calibration graph. The molecular weight of 25 the6e 6tAn~Ards had been measured by the absolute intrin6ic vi6c06ity method de6cribed in the aforementioned reference of Noda, T6uge and Naga6awa .

The polymer proAl~ce~ had a Mn of 1600 and Mw of 4300.
The pH of the product wa6 7.0 and an 0.25 ~ by weight 601ution on solid6 had a turbidity of 110 N.T.U.'~.

In the following Table6 2a, 2b, 2c, the ~tructure6 of variou6 deflocculating polymer6 are given u6ing the notation of the general formula (I). Co-polymer6 are designated by the prefix A- (Tables 2a, 2b) whilst multi-polymers are designated by the prefix B- (Table 2c).

59 C 3247 tR) In Table 2b, although the polymers are stated to be sodium 6alts (Al, A4 - Na), some samples are only partially neutralised (some of Al, A4 ~ H). The degree of neutralisation iB indicated by way of the a~oximate pH of the 6ample.

Instead of guoting a value for n according to formula (I-VII), we prefer to ~pecify the weight average molecular weight (NW) as measured by GPC with polyacrylate ~tan~rd6 as hereinbefore described. It is believed that this will be more me~ngful to those skilled in the art.

In each Table, 60me moieties are common to each 6ample thus:-Table 2a: y is zero, Rl is -C0-0- and Al i6 Na.

Table 2b: y is zero, Rl i6 -C0-0-, R2 and R3 are ab6ent and Al is Na.

Table 2c: y is zero, R3 is absent, R5 is -H and Al i6 Na.
Table 2d: Rl is -C0-0-, R2 and R3 are absent, R4 is -C12 H25, R6 i6 methyl and Al, A2 and A3 are all Na.

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71 C 3247 (R) Examples 1-301: 1336385 ~ffect of deflocculating polYmers on physical Droperties of li~uid deterqent formulations.

Exam~le Basic Polymer % Product ViscositY
Com~o- ~YE~ Stability m Pas at 6ition ~ls-l 1 1 - - Unstable1430-1740 2 1 A-l 0.5 Stable 260 3 1 A-l 1.0 Stable 100 4 1 A-l 2.0 Stable 140 1 A-2 0.5 Stable 260 6 1 A-2 1.0 Stable 70 7 1 A-2 2.0 Stable 100 8 1 A-3 0.5 Stable 280 9 1 A-3 1.0 Stable 440 2 - - Unstable2560 11 2 A-l 0.5 Stable 35 12 2 A-l 1.0 Stable 35 13 2 A-l 2.0 Stable 35 14 2 A-2 0.5 Stable 35 2 A-2 1.0 Stable 35 16 2 A-2 2.0 Stable 35 17 2 A-4 0.5 Stable 80 18 2 A-4 1.0 Stable 110 19 2 A-4 2.0 Stable 210 1 - - Unstable1430-1740 21 1 A-14 0.25 Stable 130 22 1 A-14 0.50 Stable 70 23 1 A-14 1.0 Stable 35 24 1 A-14 2.0 Stable 60 1 3363~5 72 C 3247 (R) Example Basic Polvmer ~ Product Viscosity Compo- ~YE~ Stability m Pas at sition 2lS-l 1 A-5 0.5 Stable 480 26 1 A-4 0.5 Stable 340 27 1 A-4 1.0 Stable 440 28 1 A-4 2.0 Stable 130 29 3 - - Unstable 500 3 A-l 0.5 Stable 290 31 3 A-l 1.0 Stable 1220 32 3 A-l 2.0 Stable 1520 33 3 A-2 0.5 Stable 530 34 4 - - Un~table1600 4 A-l 0.5 Stable 630 36 4 A-2 0.5 Stable 500 37 8 - - Unstable190 39 8 A-2 1 Stable 1570 9 - - Unstable 90 41 9 A-2 1 Stable 610 42 10 - - Unstable 40 43 10 A-2 1 Stable 240 44 5 - - Unstable1380 A-2 1 Stable 200 46 6 - - Unstable2400 47 6 A-2 1 Stable 70 48 7 - - Unstable2300 49 7 A-2 1 Stable 40 2 - - Unstable2560 Sl 2 A-2 1 Stable 60 52 6 - - Unetable1600-2070 53 6 A-7 0.50 8table 80 54 6 A-7 1.0 Stable 100 6 A-7 2.0 Stable 120 73 C 3247 (R) ~mple ~asic PolYmer % Product Vl~cosity Compo- $YE~ Stability ~ Pas at ~ition ~16-56 6 A-8 0.25 Stable 160 57 6 A-8 0.50 8table 190 58 6 A-8 1.0 8table 460 59 6 A-ll 0.5 Stable 700 6 A-ll 1.0 Stable 760 61 2 - - Unstable1160-2560*
62 2 A-7 0.5 Stable 130 63 2 A-7 1.0 Stable 80 64 2 A-7 2.0 Stable 120 2 A-8 1.0 Stable 100 66 2 A-8 2.0 Stable 120 67 2 A-9 0.5 Stable 150 68 2 A-9 1.0 Stable 110 69 2 A-9 2.0 Stable 200 74 C 3247 (R) ExamPleBasic PolYmer % Product Vi6cosity Compo- Pe Stability m Pa6 at 6ition 216-l 2 - - Un6table1160-2560*
71 2 A-10 0.5 StAble 410 72 2 A-10 1.0 Stable 330 73 2 A-ll 1.0 St~ble 140 74 2 A-ll 2.0 Stable 210 6 - - Unstable1600-2070*
76 6 A-12 2.0 Stable 70 77 6 A-6 1.0 Stable 50 78 6 A-6 2.0 Stable 70 79 6 A-13 2.0 Stable 70 ___ _____ 2 - - Un6table1160-2560*
81 2 A-12 2.0 Stable 80 82 2 A-6 1.0 Stable 100 83 2 A-6 2.0 Stable 100 84 2 A-13 2.0 Stable 90 11 - - Un6table **
86 11 A-12 1.0 Stable 120 87 11 A-12 2.0 Stable 120 88 11 A-13 2.0 Stable 120 89 12 - - Unstable **
12 A-l 0.1 Stable 20 91 12 A-l 2.0 Stable 70 C 3247 (R) mple Basic PolYmer % Product Vi6co~ity Compo- ~y~e Stability m Pas at 6ition 21s-1 92 13 - - Unstable 660 93 13 A-2 0.5 8table 540 94 13 A-2 1.0 Stable 600 14 - - Unstable 700 96 14 A-2 1.0 Stable 160 97 14 A-2 2.0 8table 700 98 15 - - Unstable 2240 99 15 A-2 2.0 Stable 300 100 16 - - Un~table ~9000 101 16 A-2 2.0 Stable 150 102 17 - - Unstable 730 103 17 A-2 0.5 Stable 300 104 17 A-2 1.0 Stable 990 105 18 - - Unstable 2490 106 18 A-2 0.5 Stable 100 107 18 A-2 1.0 Stable 510 108 18 A-2 2.0 Stable 380 109 19 - - Unstable 950 110 19 A-2 0.5 Stable 670 111 20 - - Unstable 950 112 20 A-2 2.0 Stable 1430 113 21 - - Unstable 2730 114 21 A-l 0.5 Stable 750 115 22 - - Un~table 5550 116 22 A-l 0.5 Stable 430 117 23 - - Unstable 6630 118 23 A-l 0.5 Stable 220 119 24 - - Unstable 7950 120 24 A-l 0.5 Stable 270 121 25 - - Unstable 8620 122 25 A-l 0.5 Stable 270 ~ 336385 76 C 3247 (R) Example Basic Polymer % Product Vi6cositY
Como- TY~e StabilitY m Pas at ~ition 21~-1 123 26 - - Un6table5970 124 26 A-l 0.5 Stable 800 125 26 - - Un~table5970 126 26 A-6 1.0 Stable 700 127 26 A-7 0.5 Stable 1080 128 26 A-8 0.5 8table 1510 129 26 A-ll 0.5 Stable 1060 130 27 - - Un~table5050 131 27 A-l 0.25 Stable 760 132 27 A-l 0.50 Stable 660 133 27 A-l 0.75 Stable 850 134 27 A-l 1.0 Stable 1180 135 27 A-ll 0.50 Stable 660 136 27 A-ll 0.75 Stable 750 137 27 A-ll 1.0 Stable 850 138 29 - - Stable>9000 139 29 A-ll 0.5 Stable 1060 140 30 - - Stable~9000 141 30 A-ll 0.5 Stable 900 142 31 - - Stable~9000 143 31 A-ll 0.5 Stable 1820 144 32 - - Stable>9000 145 32 A-ll 0.5 Stable 1240 146 33 - - Stable~9000 147 33 A-ll 0.5 Stable 810 148 34 - - Un6table170 149 34 A-2 1 Stable 1400 150 35 - - Unstable6000 151 35 A-2 0.5 Stable 350 152 35 A-2 1 Stable 600 153 35 A-2 2 Stable 2000 77 C 3247 tR) am~le Basic PolYmer ~ Product V.scosity Compo- ~YE~ Stability m'as at ~ition 2_s-154 36 A-ll 0.75 8table1820 155 37 A-ll 0.75 Stable1110 156 38 A-ll 0.75 Stable750 157 3g A-ll 0.75 Stable590 158 40 A-ll 0.75 Stable500 159 41 A-ll 0.75 Stable860 160 42 A-ll 0.74 Stable670 161 43 A-ll 0.72 Stable530 162 44 A-ll 0.69 Stable400 163 45 A-ll 0.65 Stable490***
_____________ _ 164 6 A-16 1 Stable 50 165 6 A-16 2 Stable 70 166 2 A-16 1 Stable100 167 2 A-16 2 Stable100 ______ _ 168 2 A-46 1 Stable 60 169 2 A-47 1 Stable 50 170 2 A-47 2 Stable 50 171 2 A-48 2 Stable1160 172 2 A-49 2 Stable2440 173 2 A-34 2 Stable 60 174 2 A-35 2 Stable 70 175 2 A-18 0.5 Stable 75 176 2 A-18 1.0 Stable 40 177 2 A-18 2.0 Stable 40 178 2 A-ll 0.5 Stable 70 179 2 A-ll 1.0 Stable 70 180 2 A-ll 2.0 Stable 60 181 2 A-36 1.0 Stable 90 182 2 A-36 2.0 Stable180 ~ 336385 78 C 3247 (R) .
Example Basic PolYmer % Product V-scositY
ComDo- IYE~ StabilitY mPas at sition 2_E-l 183 2 A-37 2.0 Stable 1380 184 2 A-38 1.0 Stable 125 185 2 A-39 2.0 Stable 310 186 2 A-21 0.5 Stable 100 187 2 A-21 1.0 Stable 150 188 2 A-21 2.0 Stable 1280 189 2 A-20 0.5 Stable 75 190 2 A-20 1.0 Stable 220 191 2 A-20 2.0 Stable 6580 192 2 A-l9 0.5 Stable 940 193 2 A-l9 1.0 Stable 530 194 2 A-l9 2.0 Stable 4290 195 2 A-23 0.5 Stable 1090 196 2 A-23 1.0 Stable 1170 197 2 A-23 2.0 Stable 4920 198 2 A-40 0.5 Stable 190 199 2 A-40 1.0 Stable 430 200 2 A-40 2.0 Stable 4700 201 2 A-41 1.0 Stable 300 202 2 A-41 2.0 Stable 1580 203 2 A-42 1.0 Stable 120 204 2 A-42 2.0 Stable 350 205 2 A-43 2.0 Stable 4150 206 46-48 - - Unstable4000-6000*
207 46 A-ll 0.5 Stable 90 208 46 A-ll 1.0 Stable 110 209 47 A-ll 1.0 Stable 620 210 48 A-ll 1.0 Stable 2230 211 38 - - Unstable5000-6000*
212 38 A-ll 1.0 Stable 560 213 38 A-18 0.5 Stable 460 214 38 A-18 1.0 Stable 510 215 38 A-l9 0.3 Stable 1240 216 38 A-l9 0.5 Stable 1040 79 C 3247 (R) Example Basic Polymer % Product Vi6cosity Com~o- ~YE~ Stability mPas at ition ~1-6=

217 38 A-l9 1.0 8table 3230 218 38 A-21 0.5 Stable 670 219 38 A-21 1.0 8table 1260 220 50 A-ll 0.75 Stable 730 221 49 A-ll 0.5 8table 1510 222 49 A-ll 0.75 Stable 770 223 49 A-ll 1.0 Stable 730 224 49 A-45 0.75 Stable 820 225 49 A-21 0.75 Stable 1060 226 49 A-21 0.40 Stable 2510 227 49 A-17 0.75 Stable 880 228 49 A-17 1.50 Stable 1510 229 49 A-36 0.75 Stable 680 230 49 A-44 0.75 Stable 880 231 49 A-24 0.75 Stable 540 232 49-55 - - Unstable4000-6000*
233 51 A-ll 0.75 Stable 800 234 52 A-ll 0.75 Stable 650 235 53 A-ll 0.75 Stable 680 236 54 A-ll 0.75 Stable 790 237 55 A-ll 0.65 Stable 600 238 56-57 - - UnstableNot measured 239 56 A-ll 0.25 Stable 880 240 57 A-ll 0.25 Stable 550 241 58 - - Unstable140 242 58 A-ll 0.5 Stable 1300 243 58 A-ll 2.0 Stable 2240 244 58 A-36 0.5 Stable 230 245 58 A-36 2.0 Stable 140 246 59 - - Unstable 80 247 59 A-ll 0.5 Stable 270 248 59 A-ll 2.0 Stable 1190 249 59 A-36 0.5 Stable 70 250 59 A-36 2.0 Stable 120 C 3247 (R) Example Basic PolYmer % Product V''~cosity Com~o- ~YE~ Stability m~as at sition 2_8-l -251 60 - - Stable 520 252 60 A-36 0.5 8table 380 253 60 A-36 2.0 8t~ble 220 254 60 A-36 4.0 Stable 210 255 61 - - Unstable340 256 61 0.5 A-ll 8table 780 257 61 0.5 A-17 8table 1370 258 61 0.5 A-18 8table 400 259 62 - - Unstable4000-6000*
260 62 0.5 A-ll Stable 940 261 63 0.5 A-ll Stable 740 262 2 2.0 B-l Stable 100 263 2 4.0 B-l Stable 360 264 2 2.0 B-10 Stable 1490 265 5 2.0 B-ll Stable 50 266 2 2.0 B-22 Stable 200 267 2 2.0 B-23 8table 140 268 2 2.0 B-24 Stable 200 269 5 2.0 B-25 Stable 1790 270 64-91 - - Unstable4000-6000*
271 64 1.0 A-ll Stable 190 272 65 1.0 A-ll Stable 2290 273 66 1.0 A-ll Stable 850 274 67 1.0 A-ll Stable 230 275 68 1.0 A-ll Stable 440 276 69 1.0 A-ll Stable 1130 277 70 1.0 A-ll Stable 230 278 71 1.0 A-ll Stable 190 279 72 1.0 A-ll Stable 570 280 73 1.0 A-ll Stable 370 281 74 1.0 A-ll Stable 290 282 75 1.0 A-ll Stable 600 283 76 1.0 A-ll Stable 140 284 77 1.0 A-ll Stable 700 81 C 3247 (R) ~mple Basic % Polymer Product V 6cosity Compo- ~YE~ 8tability m~as at sition 21s~

285 78 1.0 A-ll Stable 190 286 79 1.0 A-ll Stable 260 287 80 1.0 A-ll Stable 340 288 81 1.0 A-ll Stable 250 289 82 1.0 A-ll Stable 440 290 83 1.0 A-ll Stable 480 291 84 1.0 A-ll Stable 300 292 85 1.0 A-ll Stable 160 293 86 1.0 A-ll Stable 250 294 87 1.0 A-ll Stable 240 295 88 1.0 A-ll Stable 340 296 89 1.0 A-ll Stable 360 297 90 1.0 A-ll Stable 610 298 91 1.0 A-ll Stable 190 299 92/93 - - Unstable 4000-6000*
300 92 1.0 A-ll Stable 1000 301 93 1.0 A-ll Stable 220 302 5 2.0 A-50 Stable 350 * Unreliable result~ due to rapid phase separation.

** Cannot be measured due to very rapid phase 6eparation.

*** After 11 days storage; product shows increase of viscosity due to stirring/shear.

Although not specified, 6imilar results can be obtained with Deflocculating Polymers with 6tructures A25-33, B2-9 and B12-21 82 C 3247 (R) Electron Mi~o~a~hs The appended mic~yrsp~s show the effect of deflocculating polymers on the lamellar droplets. Photographs 1, 4 and 7 chow flocculated droplets without the polymer.
Photographs 2, 3, 5, 6 and 8 show the deflocculating effect of the polymer in compositions according to the yL~-ent invention.

83 C 3247 (R) Table 3 Raw Material Specification 5 ComponentS~ecification NaDoBS Na Dodecyl Benzene Sulphonate LES Lauryl ether sulph~te Synperonic A7 C12_1s ethoxylated alcohol, 7EO, ex ICI
Synperonic A3 C12_1s ethoxylated alcohol, 3EO ex ICI
STP Sodium Tripolyphosphate KTP Potassium Tripolyphosphate Silicone oil Foam depressor, ex Dow Corning 15 Gasil 200 Corrosion inhibitor, ex Crossfield Na-SCMC Na Carboxymethyl cellulose (Anti-redeposition agent) Tinopal CBS-X Fluorescer, ex Ciba-Geigy Blankophor Fluorescer, ex Bayer Dequest 2060S/2066 Metal chelating agent, ex Monsanto Alcalase 2.5L Proteolitic enzyme, ex Novo 84 C 3247 (R) Component Specification Dobanol 23-6.5 C12_13 ethoxylated alcohol, 6.5 EO, ex Shell Neodol 23-6.5 a~ nQh~nol 23-6.5 TrEA Triethanolamine Zeolite A4 Wes~alith P, ex Degu~sa Na-CMOS C~rhQxy-Methyl-Oxy-8uccinate, tri ~odium ~alt Sokalan CP5 Acrylic/Maleic builder polymer, ex BASF

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Claims (12)

1. A liquid detergent composition which yields no more than 2% by volume phase separation when stored at 25°C for 21 days from the time of preparation and comprises a dispersion of lamellar droplets in an aqueous continuous phase, and also comprises a deflocculating polymer having a hydrophilic backbone and at least one hydrophobic side-chain, the deflocculating polymer having a weight average molecular weight in the range of from 500 to 500,000 and being present in an amount of from 0.01%
to 5.0% by weight in the composition, 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 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 of said sulphonate, soap and nonionic surfactant being from 7.5 to 20% by weight, then the deflocculating polymer does not consist solely of from 0.1 to 2%
by weight of a partially esterified, neutralised co-polymer of maleic anhydride with vinylmethyl ether, ethylene or styrene.

2. A composition according to claim 1, wherein the polymer has the general formula (I) (I) wherein:
z is 1; (x + y) : z is from 4: 1 to 1,000: 1; in which the monomer units may be in random order; y being from 0 up to a maximum equal to the value of x; and n is at least 1;

R1 represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH- or is absent;

R2 represents from 1 to 50 independently selected alkyleneoxy 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 with at least 3 carbon atoms;

R3 represents a phenylene linkage, or is absent;

R4 represents hydrogen or a C1-24 alkyl or C2-24 alkenyl group, with the provisos that 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 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 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 of formula (II):
(II) wherein:
Q2 is a molecular entity of formula (IIa):

(IIa) wherein z and R1-6 are as defined for formula (I); A1-4, are as defined for formula (I) or (C2H4O)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.

n and z are as defined above; v = 1 and (x + y + p + q + r) : z is from 4 : 1 to 1,000 : 1, in which the monomer units may be in random order;

R7 and R8 represent -CH3 or-H;

R9 and R10 represent independantly selected groups selected from -SO3Na; -CO-O-C2H4-OSO3Na, -CO-O-NH-C(CH3)2-SO3Na, -CO-NH2, -O-CO-CH3, -OH;

3. A composition according to claim 1, wherein the polymer is of formula III:

(III) wherein:

x is from 4 to 1,000, n, z and R1-6 are as defined in formula I, wherein the monomers units may be in random order;

A1 is as defined above for formula I, or -CO-CH2-C(OH)-CO2A1-CH2-CHO2A1, or may be a branching point whereto other molecules of formula (III) are attached.

4. A composition according to claim 4, wherein the polymer is of the formula (IV) (IV) Wherein:
z, n and A1 are as defined above for formula I; (x+y):z is from 4:1 to 1,000:1, wherein the monomers may be in random order.

R1 is as defined above for formula I,or can be -CH2-O-, -CH2-O-CO-, -NH-CO-;

R2-4 are as defined in formula I;

R11 represents -OH, -NH-CO-CH3, or -OSO3A1;
R12 represents -OH, -CH2OH, -CH2OSO3A1, COOA1, -CH2-OCH3;
or of formula (V):

(V) Wherein:

z, n and R1-6 are as defined above for formula I; and x is as defined for formula III;

5. A composition according to claim 1, wherein the polymer has the formula VI:

wherein If z is the total of R4 groups, then the ratio (x+y): z is from 4 : 1 to 1,000 : 1,; R4* is R4 or -H.

R2 and R4 are as defined above for formula I;

as S is selected from -H, -COOA1, -CH2COOA1, -CH(COOA1)2, (CH2COOA1)2H, wherein A1 is as defined for formula I or is R4;

with the proviso that at least one R4 group is present as a side chain;

or of formula (VII):

Wherein:

x,z,S and R4 are as defined above for formula VII;

and wherein at least one R4 group is present as a side chain; v is 0 or 1.

wherein If z is the total of R4 groups, then the ratio (x+y) : z is from 4 : 1 to 1,000 : 1,; R4* is R4 or -H.

R2 and R4 are as defined above for formula I;

as S is selected from -H, -COOA1, -CH2COOA1, -CH(COOA1)2, (CH2COOA1)2H, wherein A1 is as defined for formula I or is R4;

with the proviso that at least one R4 group is present as a side chain;

or of formula (VII):

Wherein:

x,z,S and R4 are as defined above for formula VII;

and wherein at least one R4 group is present as a side chain; v is 0 or 1.

6. A composition according to claim 1, wherein the deflocculating polymer has a specific viscosity less than 0.1 (1g in 100ml methylethylketone at 25°C).

7. A composition according to claim 1 having a pH less than 11.

8. A composition according to claim 1, containing solid particles in suspension.

9. A composition according to claim 1, which yields less than 0.1% by volume visible phase separation after storage at 25°C for 90 days from the time of preparation.

10. A composition according to claim 1, comprising at least 30% by weight of detergent active material.

11. A composition according to claim 1, having a viscosity of no greater than 1 Pas at a shear rate of 21s-1.

12. A composition according to any one of claims 1 to 11 comprising less than 45% by weight of water.