CA2069647A1

CA2069647A1 - Liquid detergents containing deflocculating polymers

Info

Publication number: CA2069647A1
Application number: CA002069647A
Authority: CA
Inventors: Cornelis J. Buytenhek; Mansur S. Mohammadi; Johannes C. Van De Pas; Frederik J. Schepers; Caecilia H. E. Van Lingen
Original assignee: Individual
Current assignee: Unilever PLC
Priority date: 1989-12-07
Filing date: 1990-11-07
Publication date: 1991-06-08
Also published as: DE69009775T2; WO1991009107A1; NO922242D0; EP0504155B1; EP0504155A1; ES2055452T3; NO179678C; NO179678B; DE69009775D1; GB8927729D0; NO922242L

Abstract

A liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition also comprising suspended particles of solid material and a deflocculating polymer, wherein the composition comprises relatively high amounts of small lamellar droplets.

Description

2 ~ 7 W091~09107 PCT/EP90/01874 LIOUID DETERGENTS

The presen-t invention is concerned with aqueous liquid detergen~ compositions which contain sufficient detergent-active material and, optionally, sufficiently dissolved electrolyL2 to result in a structure of lamellar droplets dispersed in a continuous aqueous phas2~ In p3,-~_cular the pres2nt invention relates to liquia de--_Lgen-c compositions having improved solid suspending proyerties.

~amella droplets are a particular class of surfactant . ~ structl'rQs ~.lhiCh, inter 21ia, are already known from a variety OI references, e.g. H.A.Barnes, 'Detergents', Ch.2. in ~.~alters tEd), 'Rheo~etry: Industrial Applications', J. Wiley & Sons, Letchworth 1980.

Such lamellar dispersions are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending particulate solids such as detergency builders or abrasiv2 particles. ~xamplos of such structured ~ liquids without suspended solids are given in US
; 25 patent 4 244 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342; EP-A-38 lOl; EP-A-~04 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification ~P-A-151 884, where the lamellar droplet are called 'spherulites'.

The presence or 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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W09l/09107 2 ~ 6 9 6 4 ~ PCT/EP90/0187 The droplets consist of an onion-like configuration of concentric hi-layers of surfactant molecules, between ~hich is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are clase-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.

The VlSCosity and stability of the product depend on tn~ volume Iraction which is occupied by che droplets.
Genorally sp2a1cing, ~hen the volume fraction is around O.S, tne droplets are just touching (space-filling).
This allows raasonable stability with an acceptable visco5 ' ty (say no more than 2.5 Pa.s, preferably no more than 1 Pa.s at a shear rate of 21s-1). This volume fraction also endows useful solid-suspending properties.
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A problem in formulating 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 co-responding product will incr~ase 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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Another problem in formulating liquid detergent ~ compositions of the lamellar droplet type, i9 that sometimes these compositions are not fully capable of stably suspending solid materials, especially when the volums fraction of lamellar droplets is relatively low, say less than 0.6 or less than 0.5.
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It has no~.~ been found, that liquid detergent compositions having improved solid suspending properties and/or improved stability and/or improved viscosity can be obtained by carefully controlling the ` ,; . , , 2~9~
~ , WO 91/09107 PCT/EP90/01874 droplet size of the lamellar droplets. In particular an increase in solid suspending properties can be observed -especially when thP volume fraction of lamellar droplets is relatively low, say less than'O.6 or less than 0.5- if a relatively high fraction of the lamellar droplets consists of small droplets.

It has baen sugg~sted in ~P 151 884 (Albright and ~ilson~ _o pr2par2 liyuid detaLg2nt products comprising dispe sed lamellar d-oplecs wner~b~ a ma~or proportion of -th? d.~plets havs a diameter of 0.2 to 1 micrometer.

It has no~ 2en found that the solid suspending propertles and~or the stability and/or the viscosity of liquid detergent compositions comprising relatively high amounts of lamellar droplets can be favourably influenced by incorporating therein a deflocculating polymer.

; 20 Ac~ordingly the present invention relates to a liquid detergent composition comprising a di-spersion of lamellar droplets of detergent active materials in an aqueous continuous ~hase, said composition also comprising a deflocculating polymer and suspended particles of solid material, wherein at least one of the following conditions are fulfilled:
~1) at least 50 ~ of the lamellar droplets have a diameter of less than 0.45 micrometer;
(2) the detergent composition has a refractive index for light having a wavelength of 589 nm which is at least 0.01 above the refractive index of its corresponding aqueous continuous phase.

Compositions of the invention may satisfy condition (1), (2) or both conditions as speclfied above. Both conditions are believed to correspond to liquid compositions, comprising relatively high numbers of small particles.

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WO91/09107 2 ~ L~7 PCT/EP90/0187~

The percentage of lamellar droplets having a diameter of less than 0.45 micrometer can be determined by making electron microscopy pictures of the liquid detarg2nt composition at a magni~ication of between 15,000 and 60,000 (preferably about 30,000) and dPtormining th~ rela-tive number of droplets having a diametor of less than 0.45 micrometer.

Pr~f2rably at least 50 '4 or the lamellar droplets have a diam_~er of less than 0.3~ micrometer, more preferred less -tnan 0.25 micrometer, most preferred less than 0.15 mlc~ometar, especially preferred less than 0.10 or 0.07 mic~omot2r.
The refractive index of the liquid detergent composition can for example be determined as follows:
light having a wavelength of 589 nm is passed through a thin layer (preferably about 1 mm) of liquid detergent composition. The angle of incidence and the angle of refraction are measured, whereafter the refractive index can be caloulated by using the Snellius equation.
Another, pre~er~ed method to determine the refractive index is by using internal reflection measurements, for e~ample by using a Atago digital refractometer RX-; 1000. The use of internal reflection measurements is ; especially advantageous ~or determining the refractive index f or opaque systems.

The refractive index of the corresponding aqueous phase can be measured by isolating the aqueous phase from the detergent composition (e.g by (ultra-) centrifugation) or by separate preparation of a composition, whereby the-insoluble insredients are only added to their solubility limit and the dispersed phases are omitted.

Applicants believe that a liquid detergent composition comprising relatively low levels of small particles .~ .
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2~69~7 ~ WO91/09107 PCT/~P90/01874 , .

will generally have a lower re~ractive index than a corr,osponding composition, wherein relatively high levels of small particles are present. The reason for this may be the following: in measuring the refractive index OI a system, droplets being significantly larger than the wavQlength of the measuring light will cause the scatiering or incident lignt, but will not contribu-te to lts Lefracti~e ~ower. Cal~ulations using ~ the ~ie sca-t-c2ring thaor~ CCIIL 1rm this.
.' 10 Thererore, -n20rQtic2ll~, an aqueous composition, ~hich only comprises lamellar droplets navir.g a particle size significant~ rabo-~e the ~iavelength of the llght, will have a e,^racti~2 indox which is slose to the refractive index of the aqueous base of the product.
Detergent compositions comprlsing particles having a size comparable or smaller than the wavelength of the light, will be optically more dense than compositions without these particles. Therefore, for a given composition, an increase in refractive index is a sign of the presence of relatively small particles in the ~ product.

; Preferably the refractive index of the total composition is more than 0.02 above the refractive index of the corresponding aqueous phase, more preferred from 0.03 to 0.20, most praferred from 0.04 to 0.15 especially preferred between 0.05 and 0.10.

Compositions of the invention can be obtained by any method for preparing liquid detergent compositions. The man skilled-in the art will ~e able to select the components and their levels in order to allow the formation of a lamellar droplet structure. Also the skilled man will be able to adapt the formulation andtor the processing conditions thereof, such that relatively high levels of small droplets are made.
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WO91/09107 ~ PCT/EP90/018 A particularly advantageous method of preparing rela~ive high levels of small lamellar droplets is the use of high shear in preparing the compositions of the invention. Thls can for example be accomplished by using a high shear device in a recirculation loop duriny prapara~ion of the liquid or by applying high sh~ar a-Cter tho preparation of the liquid. Preferred snear rates a~ more than l,000 s-l, more prefered from 2,000 to l50,000, especiaily preîerred from 4,000 to l5,000. T~.es2 shear conditions are especially suitable ror separace r2circulation loops. For high shear mixln~, gonerallv the average shear will be more than l0, __ e~am?le from 15 to 200 s-l, more preferred 20 to lO0 5 l Accordingly the present invention also relates to a liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition comprising a deflocculating polymer and said composition being obtainable by a process comprising the step of mixing the de~ergant active materials in water (optionally in the presence of other ingredients of the composition) at a relatively high shear rate and/or by applying relatively high shear to the finished composition.

Preferably compositions obtainable by this method comprise suspended particles of solid material. In the context of the present invention the term suspended solid material refers to any solid material that is not -completely- soluble in the composition. Examples of matzrials that are usually present in the form of suspended solids are fluorescers, (partially) insoluble builder materials such as STP or zeolites etc, silicon antifoam materials, bleach particles such as perborate bleaches and softener particles. Preferably the level of suspended solid materials is from O.Ol to 50 %, most ~: . "

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~~ WO91/09107 PCT/EP90/01874 2 ~

preferred 1 to 40 % by weight.

It has been found that the stability and/or the viscosity and/or the solid suspending properties of compositions of the invention can favourably be influenced by incorporating therein a deflocculating ~` polymer. The incorporation of derlocculating polymers is esp_cially useful for stabilising lamellar liquid detergent compositions, Tihereirl the pnase volume of cne lamellar droplets is relatively low, say less than 0.5~
or even less than 0.50 or o L~9 . ~5pecially advantageous is the use of deflocculating polymers in compositions having a lam211ar pnaso ~olum9 O:e ~re~ 0~0 to 0.48.
;

Suitable deflocculating polymers for use in compositions of the present invention are for instance described in our copending European patent application 89201530.6 (EP 346 995), polymers as described in this ` patent have a hydrophilic backbone and at least one hydrophobic side chain. Generally the hydrophilic backbone of the polymer is predominantly linear ( the main chain of the backbone constitutes at least 50 %, preferably more than 75 %, most prPf2rred more than 90 by weight of the backbone), suitable monomer constituents of the hydrophilic backbone are for ~ example unsaturated Cl_6 acids, ethers, alcohols, ; aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol. Examples of suitable monomer units are ~30 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 6.0 and 14Ø Preferably thP solubility is more than lg/l, more preferred more than 5 g/l most preferred more than 10 g/l.

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. , WO91/09107 2 0 ~ PCT/EP90/0187 Preferably the hydrophobic sidegroups are composed of relatively hydrophobic alkoxy groups for example butylPne oxid~ and/or propylene oxide and/or alkyl or alXenyl chains haviny ~rom 5 to 24 carbon atoms. The hydropho~lc groups may b2 connected to the hydrophilic bac~bone via relatiYely hydrophllic bonds for example a poly ethoxy linkage.
.
Pre~L.-;2d polymeLa a_- oî the formula:

H -CH2--- JH2---~ tQ1~---{-Q23 1 wherein:

Q2 ia a mo~2cula. en'ity of formula (I2?:

J l CO2Al x CO2A2 Co2A3 y R 1l -~ 30 R

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(Ia) R4 ;
z wherein:

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-i WO91/09107 2 ~ 6 ~ ~ ~ 7 PCT/EP90/01874 1 represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-or is absent;

R2 represents from 1 to 50 indapendently selected ; alkyleneo~y groups preferably ethylene oxide or propylene oxide groups, or is abs2nt , provided that when R3 is abs2n~ and ~4 r 2prasents hydrog2n or contains no more than ~ car~on a-to-,ns, t~en ~ must contain an alkyleneoxy group prz,~Pra~ly mora chan 5 alkyleneo~y groups with ak least 3 carbon aJcoms;

R3 reprPsents a han~flQne l~n~age, 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-I R2 and R3 must be absent and R4 must contain at least 5 carbon atoms;
b) when R2 is absent, R4 is not hydrogen and when also R3 is absentl then R4 must contain at least 5 carbon atoms î

: R5 represents hydrogen or a group of formula -CooA4;
R6 represents hydrogen or C1_4 alkyl; and . A1l A2l A3 and A4 are independently selected from ~ hydrogenl alkali metalsl alXaline earth metals, : ~ 30 ammonium and amine bases and C1_4, 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 thP branching of the polymer/ wherein the monomars of the polymer may be connected to Q1 in any direction/ in any order/
therewith possibly resulting in a branched polymer.
Preferably Ql is trimethyl propane triacrylate (TMPTA) .
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WO91/09107 ~9~ ~ PCT/EP90/0187 methylena 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,OOO : 1, preferably from 6 : 1 to 250 ~ 1, in which the monomer units may be in random ordPr; and preferably either p and q are zero, or r 1s zero; especially preferably p,q,y and r are zero.

R7 a~d ~8 r~preseilc -c~3 or R9 and ~10 r-p-resen' subs~lL~ent groups such as amino, amine, amide, sulphonate, sulphate, phophonate, ; . phosp'r.at~. hydro~, sar~o~yl and o~.ide g_-oups, pre.2_ably Lhey a-3 sel2cted IrOm -S03~a, -CO-O-C2H4-OS03Na, -CO-O-NH-C(CH3)2-S03Na, -CO-NH2, -O-CO-CH3, -OH;
Preferably polymers for use in compositions of the ` invention which are of relatively high pH (say 10 or more) are subst~ntially free of hydrolysable groups such as carbonyl groups for increased polymer stability at high pH values. Particularly preferred polymers for use in high pH compositions of the invention comprise hydrophilic ~acX~ones constitu~ed by acid groups such as acrylic acid and at least one hydrophobic side chain ~ which is constituted of from 5 to 75 relatively water-insoluble alkoxy groups such as propoxy units optionally linked to the hydrophylic backbone via an -. poly-alkoxy linkage constituted of from 1-10 relatively watersoluble alkoxy groups such as ethoxy units.
-~ Other preferred polymers for use in compositions of the invention are described in our copending patent British applications 8924479.2, 8924478.4 and 8~24477.6. Of .: the polymers described in those patent applications, ~: 35 especially the use of polymers in accordance with 8924478.4 is preferred. These polymers are constituted of nonionic monomers and ionic monomers, wherein the ionic monomer is from 0.1 to 50 % hy welght of the .
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. WO91/09107 2 ~ ~ 9 ~ ~ 7 PCT/EP90/01874 polymerO Especially preferred polymers of this type are of the formula:
~, CH2 H t.~ ~H

Rlb X Rl (Il) RC n ; 15 ~

wherein: x, z and n are as above;
- R3 and R4 represent hydrogen or Cl_4 alkyl;
- R2 represents -CO-O-! -O-, -O-CO-, -CH2-, -CO-NH-, or is absent;
_ R1 represents -C3H6-N~-(CX3)3(Cl-), -C2H4-OSO3 (Na+), -SO3~(Na+), -C2H4 N+(CH3)3 Cl , -C2H4 ~ (C2~6)3 Cl ~
-CH2 N+ (CH3)3 Cl , -CH2 N (C2H6)3 Cl or benzyl-SO3~ Na+;
;~ : - Ra is CH2, C2H4, C3H6 or is absent;
- Rb represents from 1 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 ~~
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WO91/09107 PCT/EP90/018-~

Other preferred polymers have the formula:

R5 ~5 R R3 R4 I ~ HOl CH HC--3 ~ IC ~ '~ CrI HC-- ~--H
I fX o 1I f~ 1~ I 1~ o I

l~ R 6 ~ 1~ 5 ~ 9 1 1 ~1 zJ

(III) ~ .
Wherein:
- x = xl + x2 - x,z and n are as defined above ; _ R1 represents -CH2O- or -O-;
- R2 repres~nts ~CX2COO Na-~, -C3H6~(CH3)3C1 or -C3H6ON+(CH3)3cl - R3 and R4 represents -OH, CH2OH, -O(C3H6O)p-H, . -CH2-O(C3H6O)p-H or -OCH2COO~Na+, -O-C3H6ON+(CH3)3Ci- or -O-C3H6N+(CH3)3Cl-;~ - R5 represents -OH, -NH-CO-CH3 or -O(C3H6O)p-H
:~ - R6 represents -OH,-CH2OH, -CH2-OCH3, -O(C3H6O)p-H or :~ - 30 -CH2-O-(C3H6O)p-H
1¦~ - p is from 1 - 10.
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~ Preferably polymers for use in compositions have a : molesular ~.~eight (as determin2d as in our co-pending european patent application 89201530.6) of betw2en 500 ~ and 100,000, more-preferred rrom 1,000 to 50,000, I especially preferred from 2,000 to 20,000 most : preferred from 4,000 to 15,000. Polymers for use in ~'.; .
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~ WO91/09107 2 0 ~ 9 6 4 ~ PCT/EP90/01874 compositions of the invention may for example be prepared by using conventional aqueous polymerisation procedures, suitable methods are for e~ample described in the above mentioned co-pending european patent application.
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Generally the deflocculating polymer will be used at from O.Ol to 5 % by weight of the composition, more preferably from 0.1 to 3.0, especially pre~erred ~rom 0.25 to 3.0 %, most pref2rr~d f-om 0.5 'co 2 5 ~.

Without being bound by any particular inter?r~tatlon or theory, the Applicants have hypothesized ~;~at t~e polymers exert their action on the composition by the following mechanism. ~he hydrophobic side-chain(s) or ionic groups could be incorporated in or onto the outer bi-layer of the droplets, leaving the hydrophilic or nonionic backbone over the outside of the droplets and/or the polymers could be incorporated deeper inside the droplet.
:
When the hydrophobic or side chains or ionic groups are incorporated in or onto the outer bilayer o~ the ` droplets, this has the effect of decoupling the inter-;~i 25 and intra-droplet forces i.e. the difference between the forces between individual surfactant molecules in adjacent layers within a particular droplet and those between surfactant molecules in adjacent droplets could become accentuated in that the attractive forces between adjacent droplets are reduced. This will generally result in an increased stability due to less - ~ flocculation and a decrease in viscosity due to smaller attractive forces between the droplets resulting in greater distances between adjacent droplets.
The polymers can also be incorporated deeper inside the droplets, then possibly also less flocculation will occur, resulting in an increase in stability. The : ~ s W O 9t/09tO7 2 ~ ~ ~ 6 '17 PC~r/EP9010187'~i influenc~ of these polymers within the droplets on the viscosity is governed by two opposita effects : firstly the presence of deflocculacing polymers will decr2ase the attractive forces between adj2c~nt droplets resulting in greater distances ~ecween the drople-ts, generally resultin~ in a lower viscosity of the system secondly the a~'ctraccive ~orces becween -cne layers within the dropl2ts a,e ecEllally ~-edmced b~ th~ pr^sence of the polymers in th2 droo1~ hl s ~enecally resulc in an increase in ch2 la~r tnic'cn2ss ~ there~ h increasing the la~.nellar vol-a-~Ale- o~ _:~o dropioLs~
therewith increasing che viscosicy. The net effect of these two opposits eff^cts may r~sult 'n e~thor a decrease or an increzs~ ln th2 V' SC5S'L LY OL th~
product.

Preferred compositions according to the invention are physically stable and have a relatively low viscosity.
Preferably a corresponding composition minus the def}occulating polymer is less stable andlor has a higher viscosity.

In the cont2xL OL L~1e PL ~s2nL ~ }~i~Lion, physical stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requlrements. That is, the 'stable' compositions will-yield no more 10 %, preferably no more than 5 %, most preferred no mor~
than 2% by volume phase`separation as evidenced by - 30 appearance of 2 or more separate phases when stored at 25C for 21 days from the time of preparation.

Preferably, compositions of the invention have a pH
between 6 and 14, more pref2rr2d from 6.5 to 13, especially preferred from 7 to 12.
:, , Compositions of the invention preferably have a viscosity of less than 2,500 mPa.s at 21 s-1, more - ~ ~
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~- r~, WO 91/09107 ~ ? O ~ 9 ~ ~ 7 PCT/EP90/01874 preferred less than 1,S00 mPa.s, most preferred less than 1,000 mPa.s, especially preferred between 100 and 750 mPa.s at 21 s-1. Also preferably the viscosity at a shear rate of 10-4 s-l is at least 10,000 mPa.s, more preferred more than loO,000, especially prefer.2d mor~
than 1,000,000, most preferred more than 10,000,000 mPa.s.

Compositions of the invention also compris2 det~rgent active materials, preferably at a leval of from 1 LO
70% by weight of the composition, mor2 preI2rr2d a level of 5 to 40 % by weight, most preferr~d from 1~ LO
35 % by weight.

In the case of blends of surfactants, the precise proportions of each component which will result in lamellar structures will depend on the type(s) and amount(s~ of the electrolytes, as is the case with ~ conventional structured liquids.
`- 20 In the widest definition the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof. For example, they may be chosen from any of~the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol.I, by Schwartz ~`Perry, Interscience 1949 and 'Surface Active Agents' Vol.II by Schwart~, Perry &
.
30~ Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in 'Tensid-Taschenbuch', H.Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wisn, 1981.
Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example wo 91~09107 2 ~ S ~ PCT/EP90/0l87~

aliphatic alcohols, acids, amides or alXyl ph~nols with alkylene oxides, especially ethylene oxide, either alone or with propylene o.~ide. Specific nonionic detergent compounds are alkyl (C6-C18) primary or secondary linear or ~ranched alcohols T~tith ethylene oxide, and products made bv condensa-tlon of ~thylene oxide T~ith ~he reacJcion products OL propyll~ne oxide and ethylenediamine~ Oth~r so-c~113d nonionic d~tergent compounds includ2 lon2j cnaiil ~c~rtiGl~-y amine o~ldes, long-cnain tertiary pnospnin_ o~id~s and dial.cyl sulphoxides.
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Prefera~ly the le~lel of nonionlc surfactan. matorlals is from 1 -40 % by T~'7'~ght ~r the c3mposltl-n~ ~~vre preferred from 2-20 %.

~iCompositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials. Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing fr_m about 3 ~o about ~2 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (Cg-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C1O-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols deriYed from petroleum; sodium coconut oil fatty monoglycPride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene WO91/09107 - 2 0 ~ 9 6 ~ 7 PCT/EP90/01874 oxide, particularly ethylene oxide, reaction products;
the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine;
alkane monosulphonates such as those derived by reacting alpha-olefins (C8~20) with sodium bisulpllit2 and those d2rived from r2acting paraffins with SO2 and Cl2 and then hydrolyzing with a base to produce a ; 10 random sulphonate; and olefin sulphonates, ~hich term is used to describe the material made by r2acting olefins, particularly C10-C20 alpha-olefins, with SG3 and th~n neutralizing and hydrolyzing the reaction product. The pref~rred anionic detergent compounds ar~
sodium (C11-C15) alkyl benzene sulphonates and sodium ~ (C16-C18) alkyl sulphates.

; Generally the level of the above mentioned non-soap anionic surfactant materials is from 1-25 % by weight of the composition, more preferred from 2 to 15 %.

` It is also possible, and sometimes preferred, to include an alkali metal soap of a mono- or d~-carboxylic acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, alke(ny)l succinate for example dodecyl succinate, and fatty acids derived from castor oil, rapeseed oil, groundnut oil,~oconut oil, palmXernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used. Preferably the level of soap in compositions of the invention is fr 1-35 ~ by weight of the composition, more pr ~rred from 5-25 %.

Also possible is the use of salting out resistant active materials for example those described in EP 328 177, especially the use of alkyl poly glycoside surfactants for example those disclosed in EP 70 074.
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WO91/09107 ~ 0~ 7 PCT/E~90/0187-~:

Also alkyl mono glucoside.s may be used.

The compositions op-cionally also contain electrolyte in an amount sufficient to bring about lamellar structuring of the detergonc-ac-ci~/e marerial.
Preferably the compositions contain from l~ to 60%, especially from l0 ~o ~5% oî a sal-'i.lg-out al_ct olyte.
Salting-out electrolyt2 has the meaning ascr~bed to ln specification EP-A-79 6~S, that is 5a:! sg ou-eleccrolytes have a 11OtLOP1C nu.n e-- OL 1 ~.aSS :han ~. 3.
Optionally, some salting-in ~ ctrol~r~ (as de~i.n~d in the latt2r specirication) may a'so bz included.

In any eventt it~is pr~ferred thak compositions ; 15 according to the present invencion include dPtergency builder material, some or all of which may be electrolyte. In this context it should be noted that some detergent active materials such as for example soaps, also ha~e builder properties.
Examples of phosphorous-containing inorganic detergency builders include the water-soluble salts, especi2lly a1kali metal pyrophosphates, ~ orthophosphates, polyphosphates and phosphonates.
; 25 Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. Sometimes it is however preferred to minimise the amount of phosphate ; 30 builders ~. .
~ . .
Examples of non-phosphorus-con-aining 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 .
-, 2 a ~ 7 ~-~ WO91/09107 PCT/EP90/01874 ; , . .. . .

and æeolites.

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

Examples of organic detergency builders, when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carbo~ylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid. Citric acids or ` salts thereof are preferred builder materials for use ~ in compositions of the invention.
:' In the context of organic builders, it is aIso desirable to incorporate polymers which are only partly dissolved, in the aqueous continuous phase as described ~; in EP 301.882. This allows a viscosity reduction (due to the polymer which is dissolved) whilst incorporating a sufficiently high amount to achieve a secondary benefit, especially building, because the part which is not dissolved does not bring about the instability that would occur if substantially all were dissolved.
Typical amounts are from 0.5 to 4.5% by weight.

It is further possible to include in the compositions of the present invention, alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous WO91/09107 ~ 7 PCT/EP90/OIX7 ;

phase and has an electrolyte resistance of morQ than 5 grams sodium nitrilotriacetate in lOOml 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 OL
a reference 2% by weight or gr ater aqueous solution o~
polyethylene glycol having an averay3 ~ol-cular ~eighk of 6000; said second polymer ha~ing ~ mOlQCll~ ar ~"~igh~
of at least loO0. Use of such pol~,i.ers ls ~ena-~lly described in our EP 301,883. ;~ypical le~J!~ia are L-Om 0.5 to 4.5~ by weight.
, Preferably the level of non-soap bu.lld2 matQ~ial is from 5-40 % by weight of the composition, mOrQ
preferred from 5 to 25 % by weight of the composi-tion.

Apart from the ingredients already mentioned, a number - of optional ingredients may also be present, for example lather boosters such as alkanolamides, ` particularly the ~onoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen releasing bleaching agents such as sodium perborate and sodium perca-~ona'_, p2raci~
bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually pr~Qsent in very minor amounts, fluorescent agents, per~umes, enzymes such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo), enzyme sta~ilisers, anti-~ 30 redeposition agents, germicides and colourants.

Compositions of the invention may be prepared ~y any conventional method for the preparation of liquid detergent compositions, although.the use of high shear conditions is preferred~ A preferred method ~nvolYes the dispersing of the electrolyte ingredient ( iI
present) together with the minor ingredienks except for the temperature sensitive ingredients -if any- in water . ' .
. ~ . . .
,,' . . : .

`- W091/09107 2 0 ~ 7 PCT/EP~0/0187 of elevated temperature, followed by the addition of the builder material- if any-, the detergent active material under stirring and thereafter cooling the mixture and adding any temperature sensitive minor - 5 ingredients such as enzymes perfumes etc. The deflocculating polymer may for example be added after the electrolyte ingredient or as the final ingredient.
It is sometimes pref~rable that the deflocculating polymers are added prior to the formation of the lamellar structure. Alternatively part of th2 pol~rler ~- may be added prior to the formation of the lamellar structure and the remaining part of the polymer is add~d as the final ingrPdient. Also it is sometimes pr~ferred to add all or a major part of the polymer as ` 15 the final ingredient.
~, .
;~ In use the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine. The concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 %, more preferred from 0.1 to 3% by weight.

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

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, W091/09107 PCT/EP90/0187 ~~
2 ~

EXAMPLE I

For illustrating the correlation between the size of the lamellar droplets and the increase in the . refractive index, the following compositions ( ~hich are free from suspended solids) were made by mixing the citrate and NaOH (in an amount sui.'icia~ o i1~u';ralisP
the LAS-acid) into water of ~0 C, fol lo~:~e~ 'my t'ne addition of the d~flocculating ~ol~rime~ an~ . T~
10 LAS-acid an~ the Synperonic A7 ar2 adced a~ a ?re;ni,~ as the final ingredients. The samples conca1niiîg 2 ~ cr $
of deflocculating polymer wer2 divide~ i-n ~wo pa~s one of the parts being subjected ~o ni~h shear conditions (70,000 s~l) using an Ultra T11rra~, Of all the samples the refractive index ror 589 nm light was measured using the Atago digital refractometer RX-lOOO. ~he lamellar droplet size of the unsheared samples was measured from electron microscopy 20 pictures at a magnification of 15,000 x.

. FORMULATION wt ~arts A B C _ D E
NaLA 2) <--~ 3.3------->
Synperonic A7 <--~ -lO.O------->
Na-citrate 2aq <--------16.7-------j Water ~--------50-0------->
polymerl) - 0.5 l.O 2.0 4.0 , .
1) deflocculating polymer of formula A-ll of EP 346 995.
2) derived from Marlon AS3 .

~ . , ,~

2~96~

. 23 The following results were obtained:

sample ~RI-~ _ lamellar droplets2) ~ no high shear high shear ~m :~ 5 A o.ooo -- __3) ; B 0.0106 -- 0.12 .: .
C 0.0154 -- 0.09 D 0.0229 0.0360 0.06 E 0.0338 0.0447 0.04 ~,~ l) dif~er nce between ReIractive index (nD25) and refractlve index of isolated continuous aqueous phase.
2) 50 % of the droplets have a diameter of less than the value indicated (no high shear).

3) impossible to measure due to strong I locculation.

These results indioate that the decreasé of lamellar droplet size correlates to an increase of refractive index and that high shear conditions can advantageously be used for obtaining a decrease of the lamellar dropet `
size.
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WO91/09107 PCr/EP~0/0187'~
2~96~

EXAMPLE II

The following compositions were made by mi,cing the borax and the citrate in water of 50 C, followed by the addition o-E the zeolite mat~rial and cn2 deflocculating polymer. The LAS and the Synperonic A7 ars added as a pre-mix, whereby the ~S is added in acid form. The LAS-acid is neutralised with ?TaOH.
Finally the glycerol is added and ths mi~ctll-e -s cooled. Composi'ion B was pr2pared suc~ na'; 53 '; o~
the lamellar droplets nad a diameter or 0.l~ ~icromo~-c_r or less. The number OI droplets was determin2d ~y using x30,000 electron microscopy pictures.

INGREDIENT %twt) A B
NaLAS 18.4 Synperonic A7 ll.5 Glycerol 5.5 ~; Borax 3.8 Na-citrate 7.7 Zeolite (Wessalith P) 16.4 deflocculating polymer -- l.0 water balance polymer A44 as described in EP 89201530.6 (EP ~46 995) Compositions A and B were liquid detergent compostions comprising a dispersion of lamellar droplets.
Composition A was a flocculated highly viscous system which was unstable and had poor suspending properties, the zeolite particles were not stably suspended and formed a sediment upon storage at 25 C. Composition B
` defloculated and well poorable and had good suspending properties, the zeolite was stably suspended in the system. This example illustrates that small lamellar droplets in combination with deflocculating polymers ~`~ can provide increased stability.
, '' :-:;, , .' ' 2 0 ~ 9 6 ~ r~
-~ WO91/09107 PCT/EPg0/018~4 Example III
The following formulations each were made by two - methods: formulations A1-D1 were made by mixing the MaOH, borax, citrate and glycerol in water of 50 C, rollowed by the addition of the deflocculating polymer and a premix of the LAS, Fatty acid and the Synperonic A7. Formulations A2-D2 were of the same composition as A1-D1 except that they were prepared by mixiny the Glycorol, Borax, NaOH and citrate in water of 50 C
rollow2d ~y the addition of the active premix and finally adding the deflocculating polymer.

Forumulation (% wt~ A B C D
L~S acid (Marlon As3) <--------10.3--------->
Synperonic A7 <~ -16.0~ -->
Fatty acid2) <--------10.0---------~
Na-citrate 2aq <-~ -10.0~ -->
Glycerol <---------5.0--------->
Borax <-~-~ ~~3-5~~~~~~-~~>
NaOH <--- -----6.0--------->
Polymerl) 0.18 0.36 0.72 1.06 Water <-~ --balance------>

1) Polymer A-11 of EP 346 995 (deflocculating polymer of formula I, wherein q, p and r are 0, v=l, x=25, Y=0r R1 is - CO - 0 -, R2 is absent R3 is absent, R4 is . -C12H25, R5 is -H, R6 is -CH3 and A1 is Na. The molecular weight of the polymer is about 3.5 X).
2) 60/40 mixture of Priolene 6902 and Prifac 7904.
: For each of the formulations the Delta-RI (difference between refractive index of product and refractive index OI continuous phase of composition minus deflocculating polymer) was measured as well as the physical stability upon storage for 21 days at 25 C.

The following results were obtained:

:

: .
WO9l/09107 ~ PCT/EP90/0187 FORM~LATION Delta RI s ~hase separation A1 0.0179 7 %
A2 0.0299 0 ~s B1 0.0164 7 ~5 B2 0.0298 o %
C1 0.0179 5 ~s C2 0.0289 o s D1 0.0179 3 ~
D2 0.0289 o s Comparativel)O.001 35 ,i :
~ ~ 1) composicion without deflocculating polrmer.
, This example clearly indicates that an incr~ased ~ stability can be obtained by adding a deflocculating :~ polymer to a formulation. The stability increase is ~; . especially pronounced in systems having a high Delta-RIO

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, ' .~ . WO91/09107 ~ PCr/EP90/01874 Example IV
The following compositions were made as in example II

INGREDIENT (%wt) A B c D E F
Na~as <~ -18.4---------->
Synperonic A7 <~ -11.5---------->
~a-citrate ?aq <------------6.7----------~
Glycerol <------------5.5-~
: Borax <------------3.8---------->
10 ~eoli_~ (.1essalithP)<-----------16.4---------->
water <-----~-----37.7---------->
; pol~ymer1) -- 0.5 1.0 1.5 2.0 2.5 1) pol~mer A-11 of EP 346 9~5, percentage on top of the formulation.
~ ' .
;~ The physical properties of the formulation were as follows: -COMPviscositv_L~ stability2~ _ deltaRI3 : A 3,550 ~ 4) 0.0051 B 600 5) not measurable C 570 5) 0.0043 D 700 5) 0.0050 E 820 6) 0.0245 F 1,290 6) 0.0331 1) viscosity.at 21 5-l at ambient temperature 2) after staorage fro 3 weeks at ambient temperature : 3) di~ference between refractive index of product an ~ refractive index of isolated aqueosu phase :~ 4) strongly flocculated, highly unstable - 5) partly deflocculated, unstable, zeolite ~: sedimentation 6) deflocculated, stable, no zeolite sedimentation These examples illustratP that small lamellar droplets as evidenced by a relatively hig deltaRI can provide increased stability and less zeolite sedimentation.

. ' ' , ,, ~

Claims

WO 91/09107 PCT/EP90/0187?

28

1. A liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition also comprising a deflocculating polymer and suspended particles of solid material, wherein at least one of the following conditions are fulfilled:
(1)at least 50 % of the lamellar droplets have a diameter of less than 0.45 micrometer;
(2)the detergent composition has 2 refractive index for light having a wavelength of 589 nm which is at least 0.01 above the refractive index of its corresponding aqueous continuous phase.

2. A liquid detergent composition comprising a dispersion of lamellar droplets of detergent active materials in an aqueous continuous phase, said composition comprising a deflocculating polymer and said composition being obtainable by a process comprising the step of mixing the detergent active materials in water (optionally in the presence of other ingredients of the composition) at a relatively high shear rate and/or by applying relatively high shear to the finished product.

3. Composition according to claim 2, comprising suspended particles of solid materials.

4. Composition acccording to claim I or II, wherein the deflocculating polymer is of the formula I,II or III as specified hereabove.

5. Composition acccording to claim 1 or 2 having a lamellar phase volume of less than 0.55.

6. Composition according to claim 1 or 2 yielding less than 10 % by volume phase separation as evidences by appearance of 2 or more separate phases when stored at 25 °C for 21 days from the time of preparation.

7. Composition according to claim 1 or 2 having a viscosity at 21 s-1 of less than 2,500 mPa.s.

8. Composition according to claim 1 or 2 comprising 1-70 % by weight of detergent active materials, 1-60 % by weight of salting out electrolytes and 0.01 to 5 % by weight of deflocculating polymers.