CA2069928A1 - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA2069928A1 CA2069928A1 CA002069928A CA2069928A CA2069928A1 CA 2069928 A1 CA2069928 A1 CA 2069928A1 CA 002069928 A CA002069928 A CA 002069928A CA 2069928 A CA2069928 A CA 2069928A CA 2069928 A1 CA2069928 A1 CA 2069928A1
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- CA
- Canada
- Prior art keywords
- polymer
- viscosity
- liquid detergent
- polymers
- detergent composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3711—Polyacetal carboxylates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A liquid detergent composition comprising a dispersion of lamellar droplets in an aqueous continuous phase and a block copolymer consisting of alternating hydrophobic and hydrophilic groups, wherein the equivalent composition, minus the polymer has a significantly higher viscosity and/or becomes unstable.
Description
~3 uS~
I~ETERGENT 'COMPOSITIONS
- 5 The present invention relates to liquid detergent composlt-o}ls, in ~articular to liquid detergent compo~itions which comprise a dispersion of lamellar droplets in an aqueous continuous phase.
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Lam~lla- dr,plets a~e ?. p2rticular class of surfactant ~; structu~s which, inter alla, are already known from a variety OL ~r~ferPnc7~sl ~.g. H.~.Barnes, 'Det2rgents', Ch.2. in 7~ alters (3d), t~heometry: Industrial ; ~pplications', J. T~7iley & 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 ` 20 abrasive particles. Examples of lamellar structured ;~ liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles-are suspended are disclosed in specifications EP-A-160 342;
~i EP-A-38 101; EP-A-104 452 and also in the aforementioned ~5 US 4 244 340. Others are disclosed in European Patent , Specification EP-A-151 88~, where the lamellar droplet i are call~d 'spherulites'.
The presencs of lamellar droplets in a ~iquid detergent product may be detected by means known to those skilled in the ar~, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and`electron microscopy.
The drople~s consist OI an onion-like configuration of concentric bi-layers of surfactant molecules, between whic~ is trapped water or electrolyte solution (aqueous .
.
phase). Systems in which such droplets are close-pac~ed provide a very desirable combination o~~ physi~al stability and solid-suspending properties with us2rul flow propertias.
s ;~ A problem in formulating det2rg~nt co~posi;: 0l15 GL ;i .
~;~ lamellar phase volume is a possi~la instaailit-i ~n~/3-,-high viscosity of the product. Th~s2 probi2~s ara ,~uïl~
described in our co-pending ou ~pean ~at~n_ ap~ll C2' ion ;~ lO 89201530.6 (EP 346 995).
'";~;
;~ We have now found that the depor.doncy of sta~ilit~
and1or viscosity upon volum2 Lracti~n _~ iO~
influenc d ~y incorporating into a la~ellar dec~org~onc composition a deflocculating polymer consisting of alternating hydrophobic and hydrophilic groups; these polymers have-one of the following general structures:
A~ A--B ~ or B--A-EB--A ~B
: wherein A represents a hydrophobic sroup, B a hydrophilic group and z is an integer which is preferably zero.
Accordingly the present invention relates to a liquid detergent composition comprising a dispe~sion of lamellar droplets in an aqueous continuous phase and a block copolymer consisting of alternating hydropho~ic and hydrophilic moieties, wherein the equivalent composition, minus the polymer has a significantly higher viscosity and/or becomes unstable.
The defIocculating polymer allows, iL desir~d, -'he incorporation of greater amounts of surfactan-ts and/or electrolytes than would otherwise be compatibl2 with the need for a stable, low-viscosity product. It also ~ ' .
:
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allows (if desired) the incorporation of greater amounts of certain other ingredients co whl~n, ~i-cherto, lamellar dispersions have been hlghlv st2bility-sensitive. ~urther details of ~hese ar~ -J.iYen S hereinbelow.
The prPsent invention allows formulation o; staDle, pourable products wherein the volume rraction oE the ~- lamellar ~hase is 0.5- 0.6 or nigner, out ~ith ; 10 combinations or concentratlons o-r i ~groaie.n CS no ,_ possible hitherto. A method of deter~ining the volume fraction of the lamell2r phase is descr bed in our copending european patent applic~-cion o3201~30.o.
~ 15 Generally, it is preferred for t~s compositions OI the ; present invention to have solid-suspending properties (i.e. capable of suspending solid particles).
In practical terms, i.e. as determining product properties, the term 'deflocculating' in respect of the ~ polymer means that the equivalent composition, minus the `~ polymer, has a significantly higher viscosity and/or becomes unstable. It is not intended to embrace polymers which would increase the viscosity but not enhance the stability of the composition. It is also not intended to embrace polymers which would lower the viscosity simply by a dilution effect, i.e. only by adding to the volume of the continuous phase. Nor does it include those polymers which lower viscosity only bè reducing the volume fraction (shrinking) of the làmellar droplets, as ~; disclosed in our UK Patent Application N 8718217 (corresponding to E~ 301 883). Thus, although within the ambit of the present invention, relatively high levels of the deflocculating polymers can be used in tnose systems where a viscosity reduction is brought about;
typically levels as low as from about 0.01% by weight to about 1.0% by weight can be capable of considerably .
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WO91/06622 ~ PCT/EP90/01679 reducing the viscosity at 21 5-1, Preferably the reduction ir1 viscosity at a polymer level of l.0% by weight is moro than 10%, more preferred 20% or more, especial ~7 s~re1red more than 30~.
~ ~speclally pre~erL~d embodim~onts of the present ;~ invenLion ~ibit less phase separation on storage and aYe a 19~er viscosi~ than an equivalent composition withou_ ~n~J o~ the derlocculating polymer. Preferably composit~ons Oe the ~resPnt ~nvention ~ill yield no more han lO~ 3 mOI e pref2rr~d no more than 5 ~, especially proferred no mor~ ~an 2 ~ by volume phase saparation as e~idenced by appearanc~ OI 2 or mora phases when ~tored at 25 C lor 21 days from the time of preparation. The viscosity o~ compositions according to the invention is preferably less than 3.5 Pas, more preferably less than 2.5 Pas and especially not greater than l-,500 mPas at a ;~ shear rate of 21 s-l.
, . , Without being bound by any particular interpretation or theory, the Applicants have hypothesised that the polymers exert their action on the composition by the ~ollowing mechanism~ The hydrophobic group(s) could be incorporated in the outer bi-layer of the lamellar droplets, ls3ving the hydrophilic groups over the outside of the droplets and/or the polymers could be incorporated deeper inside the droplet.
When the hydrophobic groups are incorporated in the outer bilayer of the droplets, this has the effect of decoupling the inter- and intra-droplet forces i.e. the difference between the forces between individual surfactant molecules in adjacent layers within a particular droplet and those bet~een surfactant mole~ 1PS in adjac2nt dropl~:s could become accentuated in that the Iorces between adjacent droplets are rQduced. This will generally rssult in an increased , '' '` ' ` , ., . . .
' , ~
. '; ~ ' :, WO91/06622 ~ PCT/~P90/0~67 stability due to less flocculation and a decrease in ~iscos~ty du~ to smaller forces between the droplets resulting in ~r~ater distances ~etween adjacent droplets~
T~h~n t'ne pol~mers are incorporated deeper inside the droplets also 12ss flocculation will occur, resulting in an incrs~sz in ~tahility. The influence of these ~ ~ol~rmer5 ~llt:~in the droplets on the viscosity is : ~ 10 gO~2--.~d ~y ~',Y0 opposite effects: firstly the presence or^ dscoupling polymers will decrease the forces ~etween ~; ad;acent d~o~lets resulting in greater distances between ~-" the dro~le.s, generally resulting in a lower viscosity of tha syiatem; secondly the forces between the layers ~; 15 within the droplets are equally reduced by the presence of the polymers in the droplet, this generally results in an-increase in-the layer thickness, therewith increasing the lamellar volume of the droplets, therewith increasing the viscosity. The net effect of these two opposite effects may result in either a decrease or an increase in the viscosity of the product.
The composition according to the invention may contain only one, or a mixture of deflocculating polymer types.
The term 'polymer types' is used because, in practice, nearly all polymer~samples will have a spectrum of structur~s and mol~cular weights and often impurities.
Thus, any structure of defloccu}ation polymers described in this specification refers to polymers which are~
believed to be effective for deflocculation purposes as defined hereabove. In practice these effective polymers may constitute only part of the polymer sample, provided that the amount of deflocculation polymer in total is suffici2nt to er I eci the desired deflocculation effects.
Furthermore, any structure described herein for an individual polymer type, refers to the structure of the predominating deflocculating polymer species and the ' ' :
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W091/06622 2 ~ ~ ~ 9 ~ 8 PCT/EP90/0l679 ~ molecular weight specified is the weight aYerage ! molecular weight of the defloccul~tlon -ol~mers in tne polymer mixture.
The hydrophilic groups OI the polyme~ aro prsf3rably composed of hydrophillc monomar ~nlcs -iaicn san bo ~ selected from a varlet~ o-f uni~s a~il 2b~ - -or rhr `~ preparation of polymers. Suicablo nyfroo~nilic monom~-r :~ units are for instance described in our coo2nding ~: 10 european patQnt applicati.on Q9~ '530.~. ?~rr,~ ar!v ~: preferred hydrophilic groups ar- polyec~lo~ grou?s preîerably ComprisincJ rom ~ ~o ~0 eL~ n'^ oxic'e groups, polyglycerol, condensacion pO1~2rS OL
polyglycerol and citric acid a~hydrl~e and cond~nsation . 15 polymers of alpha-hydroxy acids or polyzc~tals.
The hydrophobic groups of the polymer are preferably selected from saturated and unsaturated alkyl chains, 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 adjacent hydrophilic groups via an alkoxylene or polyoxyalkylene linkage, ror example a polypropoxy or butyloxy linkage having from 1 to 50 alkoxylene groups. Other suitable hydrophobic groups are polyoxyalkylene groups comprising from 4 to 50 propylene oxide and/or butylene oxide grouDs.
The hydrophilic groups may be linXed to the hydrophobic : groups by any possible chemical link, although the~
~following types of linkages are preferred: -C-O-, -CO-O-or -o-.
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~ 35 :~ :
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WO91/06622 P~T/EP90/01679 In ~pecific the following types of polymers are :~ preferred:
, `I
~ Rl__~2. -OCH2CH ~ 3 ;~ 5 r , (II) Rl--R2t-oc~2cHcH2~ 3--~l g ~, ~, 10 ~ ~ ) .~j (III) ~ R~{-O--I--C--Cl--LO--~--~_l- O__~l .
(IV) Rl__R2 -O--~H- _~3_ R
S-IC-S
S-~-S
H x wherein:
Rl represents a C6_24 alkyl or alkenyl group and/or from z5 4 to 50 propylene oxide or buthylene oxide;
R2 represents -CO- or is absent R3 represents -CO-O- or -O-A is -H, or -CO-CH2-C(OH)CO2Al-CH2-CO2Al, or may be a branching point whereto 0th2r poly glycerol molecules are attached : 35 Al is independently selected from ~ydrog2n, alkalimètals, alkaline earth metals, iammonium and amine bases and Cl_4 alkyl or alkenyl groups.
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-,~ . . . .
.. .
.. . .
: -, - : ~ -.
WO91/06622 ~ 3 PCT/EP90/01679 ~i S is sel2ct~d from -H,-COOA1, -CH(COOA1)2, -(CHOOA1)2H
:~
ana y a~ from ~ to 1,000, pref~orably from 6 to 250.
;~` 5 Prefera~ly compositions according to the present inven~ion havP a pH of loss than 12.5, more prererred less than 11.~. ~ost preferred from 7.0 to 10.5.
- ~0 Fo~ _he ol~ners of fo~mula (I3IV) and their salts, it~`~ is proIerrod ~o have a weight average molecular weight in the r2gion of rrom 500 to 500,000, most preferably from 1,OoO to 250,000, especially rrom 2,000 to 30,000, when measured by GPC using polyacrylate standards or by S.V. measurements. For the purposes of this de~inition, the molecular weights of the standards are measured by the absoluté intrinsic viscosity method described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710-719.
The polymers for use in compositions of the present invention may be prepared in analogy of conventional polymerisation methods, eg condensation reactions.
Those skilled in the art will be capa~le of adapting khese methods for preparing other polymers for use in the present invention.
Generally, the deflocculating polymer will be used at from 0.01% to 5.0% by weight of the composition, mcst ; 30 preferably from 0.1~ to 2.0%.
.~
Although it is possible to form lamellar dispersions of surfactant in water alone, in many cases it is preferred for the aqueous continuous phase to contain ; 35 dissolved electrolyte. As used herein, the term electrolyte means any ionic water-soluble material.
~; However, in lamellar dispersions, not all the :`' . .
,. .
~ : '.-. ' ., " ., ~ .
- .
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,,, ' 2~:J~Q23 ~" ' 9 electrolyte is necessarily dissolved but may be suspend~d as particles of solid because the total electrolyte ~oncentration of the liquid is higher than ~; the so~ lit~t limit of the electrolyte. ~ixturas of electrolytes also may be used, with one or more of the ~ electrolvt~s b ing in the dissolved aqueous phase and -~ one or mors ~eing substantially only in the suspended - solid phase. ~o or more electrolytes may also be dlstributed approximately proportionally, between these tT~o phases. Tn Part, ~his may depend on processing, e.g.
the order of addition of components. On the other hand, the -~erm ~salts ! includes all organic and inorganic materials s~hich may ~e included, other ~han surfactants and wa~er, whether or not they are ionic, and this term encompasses thP sub-set of the electrolytes (water-soluble materials).
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 dispersion.
Prefera~ly the level of electrolyte is more than 1%, more preferred more than 2%, especially preferred from 5-40% by weight of the composition. Thus, within the ambit of the present invention, a very wide variation in surfactant types and levels is possi~le. The selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure~will be fuIly within the capability of those skilled in the art. Ho~eYer, it can be mentioned that an important sub-class of useful compositions is those where the detergcnt-active material comprises blends of different surfactant cypes. Typical blends useful for fabric washing compositions include those wher2 the primary surfactant(s) comprise nonionic and~or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
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, W091/06622 'J ~ ~ PCT/EP90/01679 ;
In many (but not all) cas2s, rh~ total det~rsent-active material may be pr~s2nt ~7t from ~- to ~0% '~y weigh-t oF the total com~ositlon ~ am,l ' ' - 5m ~~
:
40% and typically ~rom 10% ~o 3C ~y -;;eiv,h~. X0~2~r, one prererred class Oæ compos7~ ions co~?.ri3~s ac 12ast :~ 20%, most prefera~ly ac least .~ , and es?2clally at least 30% of detergent-acti~te mac~ri~l `vas2d on -cne weight or t'n~ to~al co~positlon.
In the case of blends 3f SuiL .act.nts, h~ prccise proportions o. each comonent whi C. ~ ^25'11 t in gUCh stability and viscosity -.~111 dav2nc. o..~ tyv2~s~ and amount(s) of the el~ctrolytes, as is the case ~ith ;~ 15 conventional structurPd liquids.
In the widest definition the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof. For example, they may be chosen from any of the classes, sub-classes and specific materials described in 'Sur~ace Ac~ive Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.II by Schwartz, Perry ~&
Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in 'Tensid-Taschenbuch', ~. ,tache, 2nd Edn., Carl Hanser Verlag, ~unchen & Wien, 1981.
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:; Suitable nonionic surfact~nts include, n particular, the reaction products of compounds having a hydrophobic group and a reacti~e hydrogPn atom, .or -2xampl2 ~; 35 aliphatic alcohols, acids, amides or al~yl phenols with alkylene oxides, especially ethylene oxide, either alone ~: or with propylene oxide. Specific nonionic detergent ~, :
:~ ' , -:
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7 ~n:~
; ~ compounds are al~yl (C6-C18) primary or secondary linear ~ or branched alcohols with ~thylone o~ide, and products `:; made by condensation o~ ethyl.one o~cid2 with the reaction products of p.ropylone o~'d~ 2nd e~n~,71 ~n~liamino. Other so-called nonionic det2rgent compounds include long chain tertiary ~mine oxid~s, long-cilaill certiary phosphine oxides and dlal'{~l sulpnoxld3s.
Sultable anionic surractants a.e usually ,7a'~er-soluble alXal~ me~al sa~rs or orga.nic sulphaLes and - sulphonates having alkyl radicals con~_aining from about 8 to about 2~ car~on a'toms, ~'~2 t '~ al~yl being used to include the al',~yl portion or ~igi~er aoyi .adicai3.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alXyl sulphates, espeoially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow-or-coconut oil, sodium and potassium alkyl ~Cg-C20) benzene sulphonates, particularIy sodium linear secondary alkyl.
tClo-cls) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and -synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher ~C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxids, reaction products;
:` the reaction products of fatty acids such as coconut ; fatty acids esterified wi~h isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine;
alkane monosulphonates such as those derived by reacting alpha-olefins (C8-20) with sodium bisulphite and those derived from reacting pararfins wi-th SO2 and C12 and then hydrolyzing with a base to produce a random sulponate; and olefin sulphonates, which term is usèd to descri~e the material made ~y reacting oleflns, ~' ~; ' .. . . ..
~;
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particularly Clo-C20 alpha-olefins, with S03 and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergent compounds are sodium (Cll-C~5) all{yl ~enzene sulphonates and sodium (C15-Cl8) alkyl sulphates.
, SuitablP surractants also include stabilisingsurfactants pre~erably having a salting out resistance -as defined in our copending ~uropean patent application ~P 328 177- of more than 6.4. some preferred classes of stabilising surfactants are : alkyl amine oxides; alXyl polyalkoxylated carbo~y~ates; alkyl polyalXo~ylated phosphat2s; alXyl polyalXoxylat2d sulpnosuccinates;
dialkyl diphenyloxide disulphonates; and alkyl polysaccharides (sometimes called alkyl polyglucosides or polyglycosides); selected as those which have a æalting out-resistance of at least 6.4.
A wide variety of such stabilising surfactants is known in the art, for example the alkyl polysaccharides described in European patent specification nos.
EP-A-70 074; 70 075; 70 076; 70 077; 75 994; 75 995;
75 996 and 92 355. The use of these materials is especially preferred for environmental reasons.
It is also possible, and sometimes preferred, to include an alkali metal soap of a mono- or di-carboxylic acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used.
~5 Some or all of the electrolyte, or any substantially water-insoluble salt which may be present in - ;ositions of the invention, may have detergency ,, '~' `
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: : -,, W091/06622 ~J~ ~3 9 ?~ PCT/EP90/01679 , .
builder properties. In any event, it is preferred that compositions according to the present invention include d~terg~ncy builder material, some or all of which may be electrolYte. The builder material is any capable of reducing the level of free calcium ions in the wash li~uor and T~ill preferably provide the composition with other ~eneficial properties such as the generation of an alkaline p~, the suspension of soil removed from the fa~ric and the dispersion o~ the fabric softening clay mat2rial ~xamplss o~ phosphorous-containing inorganic detergency buiIders, when present, include th2 water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
: .
In the context of inorganic builders, we prefer to include electrolytes which promote the solubility of ~ ; other electrolytes, for example use of potassium salts - to promote the solubility of sodium salts~ Thereby, the amount of dissolved electrolyte can be increased considerably (crystal dissolution) as described in UR
patent specification GB 1 302 543.
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WO91/06622 ~ J ~ ~ PCT/EP90/01679 Examples of organic detergency builders, when present, include the al~aline me-tal, a~moniu~ and substituted ammonium polyacotatos, carbQxyla!es, polycar~o~l7lat2s, polyacotyl ~ o~ ~s ~ s~1~:~o~2~s.
Speci~ic examples include sodium, pocassium, lithium, ammonium and subs4itut2d ammonium ,al4s of ethylenediaminetet-~acetlc acid, ~ar~ratQ mono succinat~, tartrato di suc~inate, c~oS~ nitrlLicriacetic acid, oxydisuccinjc acid/ melitic acid, benzon~
polycarboxyllc acids and c~t ic ~cid~
` In the contoxt of organic bul.'d er 3, i t iS al30 desirable to incorporato ~ol~rs ~Aich are only ~artly dissolved in the aqu~ous con~inuous phase as described in our ~ patent application ~ 871~215 (cor-~sponding to EP 301 882). This allows a viscosity~reduction (owing 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.
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Also other pol~mers may be incorporated in compositions of the present invention, particularly advantageous the use of polymers as described in EP 301 883.
.., Although it is possible to incorporate minor amounts of hydrotropes such as lower alcohols-(e.g. ethanol) or al~anolamines (e.g. triethanolamine), in order to ensure integrity of the lamellar dispersion we prefer that the compositions of the present invention are substantially ~ free from hydrotropes. By hydrotrope is meant any water ;; soluble agent which tends to enhance the solubility of surfactants in aqueous solution.
Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for :
~.
, ~ ' ' ' :
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,~, . , S;~ ) f3 WO91/06622 PCT/EP90/01679 ,y example lather boosters such as al~anolamides, particularly the monoethanolamides dQrlved rrom palm kernel fatty acids and ~oconut Fa~,~y acids, fabric softeners such as clays, amine~ r7rr~ ?mine oxides, lather depressants, o~ygen-releasing bleaching agents such as sodium per~oratQ and sodium pe-cal~onaze, ~eracid bleach precursors, chlorin2- 21s2sing blr~a~hlng ag~nts such as trichloroisocyanuric acid, lno~ ganic salts such as sodium sulphate, and, usuall~-presenc in very minor amounts, fluo e55Qnt a~9~s, per~ eg~ enzymes such as proteases, amylases and li pases ! includ1ng Lipolase (Trade ~ark) æ~c ~OVO), germicldces and colourants.
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Amongst these optional ingr~dients, as mentioned previously, are agents ~o which lamallar dispersions without deflocculating polymer are highly stability-sensitive and by virtue of the present invention, can be incorporated in higher, more useful amounts. These agents cause a problem because they tend to promote flocculation of the lamellar droplets. Examples of such agents are fluorescers like Blankophor RKH, Tinopal LMS, and ~inopal ~MS-X and Blankophor BBM as well as metal chelating agents, especially of the phosphonate type, for example the Dequest range sold by Monsanto.
Compositions of the invention may be prepared in analogy to conventional methods ~or the preparation of liquid detergent compositions. A preferred method of preparing compositions of the present invention involves the~
addition of the water-soluble electrolyte -if any- to water, followed by the addition of any water-insoluble material such as aluminosilicat2s, followed by the :. .
polymer ingredients and finally the surfactant ingredients. Another prererred method o F preparing a composition of the present invencion involves the addition of the surfactant ingredients to water at ambient temperaturo, followed by the addition of the ., , ' ..
, , ~ .
: ~.
:
iJ3 ~ 3 WO91/06622 PCT/EP90/01679 :
- pol~mer inyredients, and the cooling of the mixture to below 30 c, wharea~ter the remaining ingredients arP
added. ~inally, if necessary, the pH of the composition may be adjus~2d, 2.g. by the addition of small quantitias of caustic materials.
The inv~ntion will now be illustrated ~y ~ay of the following Examples. In all Examples, unless stated to the cont;^ary, all percentages are by weight.
A. Base formulations Table l Composition of basic formulation i.e without deflocculating polymers.
Inqredient : Basic formulation l 2 Na Dobs 26.1 26.3 Synperonic A7 lO.5 lO.6 Na citrate lO.9 8.8 water 52.5 54.3 ; polymer weights additional to basic formulation Raw material Specification Na Dobs Na Dodecyl Benzene sulphonate Synperonic A7 . C12_15 ethoxylated alcohol, 7EO, ex ICI.
`',' ' .
.
. .
~ , .
. .:.
.... .
, .
WO9l/06622 ~ PCT/EP90/01679 Basic Polymer Product EX~MPLE com~osition Tv~e x ~ stabilitY visc *
Reference 2 -- -- -- unstable 1600 1 2 I1) 7 1.0 stable 1440 : 2 2 I1) 7 Z.0 stable 1230 3 2 I1) 14 0.5 stable 1470 4 2 I1) 14 1.0 stable 1160 2 I1) 23 1.0 stable 1110 ) polymers of formula I as described above, ~herein is -C11H23, ~2 is -CO- and R3 is -CO-O-.
*) ~iscosity in mPas at 21 s-1.
: 15 Basic Polymer Product EXAMPLE ComDosition TyPe x % stability visc *
Reference 1 -- -- -- unstable 1380 6 1~ II1) 25 2.0 stable 520 1) polymers of formula II as described above, wherein . is -Cl1H23, R2 is -C0- ,R3 is -O-, A is -H and the poiyglycerol is branched.
*~ Yisco~.3ity in mPas at 21 s-l.
~ .
:' :~ .
-.~
:
., ~ , . . . - ", , . :
. , - . , . ~ :, , .
- 5 The present invention relates to liquid detergent composlt-o}ls, in ~articular to liquid detergent compo~itions which comprise a dispersion of lamellar droplets in an aqueous continuous phase.
~-:
Lam~lla- dr,plets a~e ?. p2rticular class of surfactant ~; structu~s which, inter alla, are already known from a variety OL ~r~ferPnc7~sl ~.g. H.~.Barnes, 'Det2rgents', Ch.2. in 7~ alters (3d), t~heometry: Industrial ; ~pplications', J. T~7iley & 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 ` 20 abrasive particles. Examples of lamellar structured ;~ liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles-are suspended are disclosed in specifications EP-A-160 342;
~i EP-A-38 101; EP-A-104 452 and also in the aforementioned ~5 US 4 244 340. Others are disclosed in European Patent , Specification EP-A-151 88~, where the lamellar droplet i are call~d 'spherulites'.
The presencs of lamellar droplets in a ~iquid detergent product may be detected by means known to those skilled in the ar~, for example optical techniques, various rheometrical measurements. X-ray or neutron diffraction, and`electron microscopy.
The drople~s consist OI an onion-like configuration of concentric bi-layers of surfactant molecules, between whic~ is trapped water or electrolyte solution (aqueous .
.
phase). Systems in which such droplets are close-pac~ed provide a very desirable combination o~~ physi~al stability and solid-suspending properties with us2rul flow propertias.
s ;~ A problem in formulating det2rg~nt co~posi;: 0l15 GL ;i .
~;~ lamellar phase volume is a possi~la instaailit-i ~n~/3-,-high viscosity of the product. Th~s2 probi2~s ara ,~uïl~
described in our co-pending ou ~pean ~at~n_ ap~ll C2' ion ;~ lO 89201530.6 (EP 346 995).
'";~;
;~ We have now found that the depor.doncy of sta~ilit~
and1or viscosity upon volum2 Lracti~n _~ iO~
influenc d ~y incorporating into a la~ellar dec~org~onc composition a deflocculating polymer consisting of alternating hydrophobic and hydrophilic groups; these polymers have-one of the following general structures:
A~ A--B ~ or B--A-EB--A ~B
: wherein A represents a hydrophobic sroup, B a hydrophilic group and z is an integer which is preferably zero.
Accordingly the present invention relates to a liquid detergent composition comprising a dispe~sion of lamellar droplets in an aqueous continuous phase and a block copolymer consisting of alternating hydropho~ic and hydrophilic moieties, wherein the equivalent composition, minus the polymer has a significantly higher viscosity and/or becomes unstable.
The defIocculating polymer allows, iL desir~d, -'he incorporation of greater amounts of surfactan-ts and/or electrolytes than would otherwise be compatibl2 with the need for a stable, low-viscosity product. It also ~ ' .
:
.
' ~ ~ u;J Jl 2 ~
allows (if desired) the incorporation of greater amounts of certain other ingredients co whl~n, ~i-cherto, lamellar dispersions have been hlghlv st2bility-sensitive. ~urther details of ~hese ar~ -J.iYen S hereinbelow.
The prPsent invention allows formulation o; staDle, pourable products wherein the volume rraction oE the ~- lamellar ~hase is 0.5- 0.6 or nigner, out ~ith ; 10 combinations or concentratlons o-r i ~groaie.n CS no ,_ possible hitherto. A method of deter~ining the volume fraction of the lamell2r phase is descr bed in our copending european patent applic~-cion o3201~30.o.
~ 15 Generally, it is preferred for t~s compositions OI the ; present invention to have solid-suspending properties (i.e. capable of suspending solid particles).
In practical terms, i.e. as determining product properties, the term 'deflocculating' in respect of the ~ polymer means that the equivalent composition, minus the `~ polymer, has a significantly higher viscosity and/or becomes unstable. It is not intended to embrace polymers which would increase the viscosity but not enhance the stability of the composition. It is also not intended to embrace polymers which would lower the viscosity simply by a dilution effect, i.e. only by adding to the volume of the continuous phase. Nor does it include those polymers which lower viscosity only bè reducing the volume fraction (shrinking) of the làmellar droplets, as ~; disclosed in our UK Patent Application N 8718217 (corresponding to E~ 301 883). Thus, although within the ambit of the present invention, relatively high levels of the deflocculating polymers can be used in tnose systems where a viscosity reduction is brought about;
typically levels as low as from about 0.01% by weight to about 1.0% by weight can be capable of considerably .
,`
WO91/06622 ~ PCT/EP90/01679 reducing the viscosity at 21 5-1, Preferably the reduction ir1 viscosity at a polymer level of l.0% by weight is moro than 10%, more preferred 20% or more, especial ~7 s~re1red more than 30~.
~ ~speclally pre~erL~d embodim~onts of the present ;~ invenLion ~ibit less phase separation on storage and aYe a 19~er viscosi~ than an equivalent composition withou_ ~n~J o~ the derlocculating polymer. Preferably composit~ons Oe the ~resPnt ~nvention ~ill yield no more han lO~ 3 mOI e pref2rr~d no more than 5 ~, especially proferred no mor~ ~an 2 ~ by volume phase saparation as e~idenced by appearanc~ OI 2 or mora phases when ~tored at 25 C lor 21 days from the time of preparation. The viscosity o~ compositions according to the invention is preferably less than 3.5 Pas, more preferably less than 2.5 Pas and especially not greater than l-,500 mPas at a ;~ shear rate of 21 s-l.
, . , Without being bound by any particular interpretation or theory, the Applicants have hypothesised that the polymers exert their action on the composition by the ~ollowing mechanism~ The hydrophobic group(s) could be incorporated in the outer bi-layer of the lamellar droplets, ls3ving the hydrophilic groups over the outside of the droplets and/or the polymers could be incorporated deeper inside the droplet.
When the hydrophobic groups are incorporated in the outer bilayer of the droplets, this has the effect of decoupling the inter- and intra-droplet forces i.e. the difference between the forces between individual surfactant molecules in adjacent layers within a particular droplet and those bet~een surfactant mole~ 1PS in adjac2nt dropl~:s could become accentuated in that the Iorces between adjacent droplets are rQduced. This will generally rssult in an increased , '' '` ' ` , ., . . .
' , ~
. '; ~ ' :, WO91/06622 ~ PCT/~P90/0~67 stability due to less flocculation and a decrease in ~iscos~ty du~ to smaller forces between the droplets resulting in ~r~ater distances ~etween adjacent droplets~
T~h~n t'ne pol~mers are incorporated deeper inside the droplets also 12ss flocculation will occur, resulting in an incrs~sz in ~tahility. The influence of these ~ ~ol~rmer5 ~llt:~in the droplets on the viscosity is : ~ 10 gO~2--.~d ~y ~',Y0 opposite effects: firstly the presence or^ dscoupling polymers will decrease the forces ~etween ~; ad;acent d~o~lets resulting in greater distances between ~-" the dro~le.s, generally resulting in a lower viscosity of tha syiatem; secondly the forces between the layers ~; 15 within the droplets are equally reduced by the presence of the polymers in the droplet, this generally results in an-increase in-the layer thickness, therewith increasing the lamellar volume of the droplets, therewith increasing the viscosity. The net effect of these two opposite effects may result in either a decrease or an increase in the viscosity of the product.
The composition according to the invention may contain only one, or a mixture of deflocculating polymer types.
The term 'polymer types' is used because, in practice, nearly all polymer~samples will have a spectrum of structur~s and mol~cular weights and often impurities.
Thus, any structure of defloccu}ation polymers described in this specification refers to polymers which are~
believed to be effective for deflocculation purposes as defined hereabove. In practice these effective polymers may constitute only part of the polymer sample, provided that the amount of deflocculation polymer in total is suffici2nt to er I eci the desired deflocculation effects.
Furthermore, any structure described herein for an individual polymer type, refers to the structure of the predominating deflocculating polymer species and the ' ' :
, . .
W091/06622 2 ~ ~ ~ 9 ~ 8 PCT/EP90/0l679 ~ molecular weight specified is the weight aYerage ! molecular weight of the defloccul~tlon -ol~mers in tne polymer mixture.
The hydrophilic groups OI the polyme~ aro prsf3rably composed of hydrophillc monomar ~nlcs -iaicn san bo ~ selected from a varlet~ o-f uni~s a~il 2b~ - -or rhr `~ preparation of polymers. Suicablo nyfroo~nilic monom~-r :~ units are for instance described in our coo2nding ~: 10 european patQnt applicati.on Q9~ '530.~. ?~rr,~ ar!v ~: preferred hydrophilic groups ar- polyec~lo~ grou?s preîerably ComprisincJ rom ~ ~o ~0 eL~ n'^ oxic'e groups, polyglycerol, condensacion pO1~2rS OL
polyglycerol and citric acid a~hydrl~e and cond~nsation . 15 polymers of alpha-hydroxy acids or polyzc~tals.
The hydrophobic groups of the polymer are preferably selected from saturated and unsaturated alkyl chains, 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 adjacent hydrophilic groups via an alkoxylene or polyoxyalkylene linkage, ror example a polypropoxy or butyloxy linkage having from 1 to 50 alkoxylene groups. Other suitable hydrophobic groups are polyoxyalkylene groups comprising from 4 to 50 propylene oxide and/or butylene oxide grouDs.
The hydrophilic groups may be linXed to the hydrophobic : groups by any possible chemical link, although the~
~following types of linkages are preferred: -C-O-, -CO-O-or -o-.
.' ~
~ 35 :~ :
~ . .
. "
~:
` :`. ? ~ 2 ~
WO91/06622 P~T/EP90/01679 In ~pecific the following types of polymers are :~ preferred:
, `I
~ Rl__~2. -OCH2CH ~ 3 ;~ 5 r , (II) Rl--R2t-oc~2cHcH2~ 3--~l g ~, ~, 10 ~ ~ ) .~j (III) ~ R~{-O--I--C--Cl--LO--~--~_l- O__~l .
(IV) Rl__R2 -O--~H- _~3_ R
S-IC-S
S-~-S
H x wherein:
Rl represents a C6_24 alkyl or alkenyl group and/or from z5 4 to 50 propylene oxide or buthylene oxide;
R2 represents -CO- or is absent R3 represents -CO-O- or -O-A is -H, or -CO-CH2-C(OH)CO2Al-CH2-CO2Al, or may be a branching point whereto 0th2r poly glycerol molecules are attached : 35 Al is independently selected from ~ydrog2n, alkalimètals, alkaline earth metals, iammonium and amine bases and Cl_4 alkyl or alkenyl groups.
.' .
-,~ . . . .
.. .
.. . .
: -, - : ~ -.
WO91/06622 ~ 3 PCT/EP90/01679 ~i S is sel2ct~d from -H,-COOA1, -CH(COOA1)2, -(CHOOA1)2H
:~
ana y a~ from ~ to 1,000, pref~orably from 6 to 250.
;~` 5 Prefera~ly compositions according to the present inven~ion havP a pH of loss than 12.5, more prererred less than 11.~. ~ost preferred from 7.0 to 10.5.
- ~0 Fo~ _he ol~ners of fo~mula (I3IV) and their salts, it~`~ is proIerrod ~o have a weight average molecular weight in the r2gion of rrom 500 to 500,000, most preferably from 1,OoO to 250,000, especially rrom 2,000 to 30,000, when measured by GPC using polyacrylate standards or by S.V. measurements. For the purposes of this de~inition, the molecular weights of the standards are measured by the absoluté intrinsic viscosity method described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710-719.
The polymers for use in compositions of the present invention may be prepared in analogy of conventional polymerisation methods, eg condensation reactions.
Those skilled in the art will be capa~le of adapting khese methods for preparing other polymers for use in the present invention.
Generally, the deflocculating polymer will be used at from 0.01% to 5.0% by weight of the composition, mcst ; 30 preferably from 0.1~ to 2.0%.
.~
Although it is possible to form lamellar dispersions of surfactant in water alone, in many cases it is preferred for the aqueous continuous phase to contain ; 35 dissolved electrolyte. As used herein, the term electrolyte means any ionic water-soluble material.
~; However, in lamellar dispersions, not all the :`' . .
,. .
~ : '.-. ' ., " ., ~ .
- .
:
,,, ' 2~:J~Q23 ~" ' 9 electrolyte is necessarily dissolved but may be suspend~d as particles of solid because the total electrolyte ~oncentration of the liquid is higher than ~; the so~ lit~t limit of the electrolyte. ~ixturas of electrolytes also may be used, with one or more of the ~ electrolvt~s b ing in the dissolved aqueous phase and -~ one or mors ~eing substantially only in the suspended - solid phase. ~o or more electrolytes may also be dlstributed approximately proportionally, between these tT~o phases. Tn Part, ~his may depend on processing, e.g.
the order of addition of components. On the other hand, the -~erm ~salts ! includes all organic and inorganic materials s~hich may ~e included, other ~han surfactants and wa~er, whether or not they are ionic, and this term encompasses thP sub-set of the electrolytes (water-soluble materials).
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 dispersion.
Prefera~ly the level of electrolyte is more than 1%, more preferred more than 2%, especially preferred from 5-40% by weight of the composition. Thus, within the ambit of the present invention, a very wide variation in surfactant types and levels is possi~le. The selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure~will be fuIly within the capability of those skilled in the art. Ho~eYer, it can be mentioned that an important sub-class of useful compositions is those where the detergcnt-active material comprises blends of different surfactant cypes. Typical blends useful for fabric washing compositions include those wher2 the primary surfactant(s) comprise nonionic and~or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
.
,' ~
, ~ , . . .
, W091/06622 'J ~ ~ PCT/EP90/01679 ;
In many (but not all) cas2s, rh~ total det~rsent-active material may be pr~s2nt ~7t from ~- to ~0% '~y weigh-t oF the total com~ositlon ~ am,l ' ' - 5m ~~
:
40% and typically ~rom 10% ~o 3C ~y -;;eiv,h~. X0~2~r, one prererred class Oæ compos7~ ions co~?.ri3~s ac 12ast :~ 20%, most prefera~ly ac least .~ , and es?2clally at least 30% of detergent-acti~te mac~ri~l `vas2d on -cne weight or t'n~ to~al co~positlon.
In the case of blends 3f SuiL .act.nts, h~ prccise proportions o. each comonent whi C. ~ ^25'11 t in gUCh stability and viscosity -.~111 dav2nc. o..~ tyv2~s~ and amount(s) of the el~ctrolytes, as is the case ~ith ;~ 15 conventional structurPd liquids.
In the widest definition the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof. For example, they may be chosen from any of the classes, sub-classes and specific materials described in 'Sur~ace Ac~ive Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.II by Schwartz, Perry ~&
Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in 'Tensid-Taschenbuch', ~. ,tache, 2nd Edn., Carl Hanser Verlag, ~unchen & Wien, 1981.
. . .~
.:
:; Suitable nonionic surfact~nts include, n particular, the reaction products of compounds having a hydrophobic group and a reacti~e hydrogPn atom, .or -2xampl2 ~; 35 aliphatic alcohols, acids, amides or al~yl phenols with alkylene oxides, especially ethylene oxide, either alone ~: or with propylene oxide. Specific nonionic detergent ~, :
:~ ' , -:
.
.
7 ~n:~
; ~ compounds are al~yl (C6-C18) primary or secondary linear ~ or branched alcohols with ~thylone o~ide, and products `:; made by condensation o~ ethyl.one o~cid2 with the reaction products of p.ropylone o~'d~ 2nd e~n~,71 ~n~liamino. Other so-called nonionic det2rgent compounds include long chain tertiary ~mine oxid~s, long-cilaill certiary phosphine oxides and dlal'{~l sulpnoxld3s.
Sultable anionic surractants a.e usually ,7a'~er-soluble alXal~ me~al sa~rs or orga.nic sulphaLes and - sulphonates having alkyl radicals con~_aining from about 8 to about 2~ car~on a'toms, ~'~2 t '~ al~yl being used to include the al',~yl portion or ~igi~er aoyi .adicai3.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alXyl sulphates, espeoially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow-or-coconut oil, sodium and potassium alkyl ~Cg-C20) benzene sulphonates, particularIy sodium linear secondary alkyl.
tClo-cls) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and -synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher ~C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxids, reaction products;
:` the reaction products of fatty acids such as coconut ; fatty acids esterified wi~h isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine;
alkane monosulphonates such as those derived by reacting alpha-olefins (C8-20) with sodium bisulphite and those derived from reacting pararfins wi-th SO2 and C12 and then hydrolyzing with a base to produce a random sulponate; and olefin sulphonates, which term is usèd to descri~e the material made ~y reacting oleflns, ~' ~; ' .. . . ..
~;
: .
: .
:~ .
particularly Clo-C20 alpha-olefins, with S03 and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergent compounds are sodium (Cll-C~5) all{yl ~enzene sulphonates and sodium (C15-Cl8) alkyl sulphates.
, SuitablP surractants also include stabilisingsurfactants pre~erably having a salting out resistance -as defined in our copending ~uropean patent application ~P 328 177- of more than 6.4. some preferred classes of stabilising surfactants are : alkyl amine oxides; alXyl polyalkoxylated carbo~y~ates; alkyl polyalXo~ylated phosphat2s; alXyl polyalXoxylat2d sulpnosuccinates;
dialkyl diphenyloxide disulphonates; and alkyl polysaccharides (sometimes called alkyl polyglucosides or polyglycosides); selected as those which have a æalting out-resistance of at least 6.4.
A wide variety of such stabilising surfactants is known in the art, for example the alkyl polysaccharides described in European patent specification nos.
EP-A-70 074; 70 075; 70 076; 70 077; 75 994; 75 995;
75 996 and 92 355. The use of these materials is especially preferred for environmental reasons.
It is also possible, and sometimes preferred, to include an alkali metal soap of a mono- or di-carboxylic acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used.
~5 Some or all of the electrolyte, or any substantially water-insoluble salt which may be present in - ;ositions of the invention, may have detergency ,, '~' `
.
, -:
: - .
, .- . ,:
, ; :
: : -,, W091/06622 ~J~ ~3 9 ?~ PCT/EP90/01679 , .
builder properties. In any event, it is preferred that compositions according to the present invention include d~terg~ncy builder material, some or all of which may be electrolYte. The builder material is any capable of reducing the level of free calcium ions in the wash li~uor and T~ill preferably provide the composition with other ~eneficial properties such as the generation of an alkaline p~, the suspension of soil removed from the fa~ric and the dispersion o~ the fabric softening clay mat2rial ~xamplss o~ phosphorous-containing inorganic detergency buiIders, when present, include th2 water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
: .
In the context of inorganic builders, we prefer to include electrolytes which promote the solubility of ~ ; other electrolytes, for example use of potassium salts - to promote the solubility of sodium salts~ Thereby, the amount of dissolved electrolyte can be increased considerably (crystal dissolution) as described in UR
patent specification GB 1 302 543.
~ .
:
- ,. . - . . - .
, :
WO91/06622 ~ J ~ ~ PCT/EP90/01679 Examples of organic detergency builders, when present, include the al~aline me-tal, a~moniu~ and substituted ammonium polyacotatos, carbQxyla!es, polycar~o~l7lat2s, polyacotyl ~ o~ ~s ~ s~1~:~o~2~s.
Speci~ic examples include sodium, pocassium, lithium, ammonium and subs4itut2d ammonium ,al4s of ethylenediaminetet-~acetlc acid, ~ar~ratQ mono succinat~, tartrato di suc~inate, c~oS~ nitrlLicriacetic acid, oxydisuccinjc acid/ melitic acid, benzon~
polycarboxyllc acids and c~t ic ~cid~
` In the contoxt of organic bul.'d er 3, i t iS al30 desirable to incorporato ~ol~rs ~Aich are only ~artly dissolved in the aqu~ous con~inuous phase as described in our ~ patent application ~ 871~215 (cor-~sponding to EP 301 882). This allows a viscosity~reduction (owing 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.
., .
, .
Also other pol~mers may be incorporated in compositions of the present invention, particularly advantageous the use of polymers as described in EP 301 883.
.., Although it is possible to incorporate minor amounts of hydrotropes such as lower alcohols-(e.g. ethanol) or al~anolamines (e.g. triethanolamine), in order to ensure integrity of the lamellar dispersion we prefer that the compositions of the present invention are substantially ~ free from hydrotropes. By hydrotrope is meant any water ;; soluble agent which tends to enhance the solubility of surfactants in aqueous solution.
Apart from the ingredients already mentioned, a number of optional ingredients may also be present, for :
~.
, ~ ' ' ' :
.
,~, . , S;~ ) f3 WO91/06622 PCT/EP90/01679 ,y example lather boosters such as al~anolamides, particularly the monoethanolamides dQrlved rrom palm kernel fatty acids and ~oconut Fa~,~y acids, fabric softeners such as clays, amine~ r7rr~ ?mine oxides, lather depressants, o~ygen-releasing bleaching agents such as sodium per~oratQ and sodium pe-cal~onaze, ~eracid bleach precursors, chlorin2- 21s2sing blr~a~hlng ag~nts such as trichloroisocyanuric acid, lno~ ganic salts such as sodium sulphate, and, usuall~-presenc in very minor amounts, fluo e55Qnt a~9~s, per~ eg~ enzymes such as proteases, amylases and li pases ! includ1ng Lipolase (Trade ~ark) æ~c ~OVO), germicldces and colourants.
.
Amongst these optional ingr~dients, as mentioned previously, are agents ~o which lamallar dispersions without deflocculating polymer are highly stability-sensitive and by virtue of the present invention, can be incorporated in higher, more useful amounts. These agents cause a problem because they tend to promote flocculation of the lamellar droplets. Examples of such agents are fluorescers like Blankophor RKH, Tinopal LMS, and ~inopal ~MS-X and Blankophor BBM as well as metal chelating agents, especially of the phosphonate type, for example the Dequest range sold by Monsanto.
Compositions of the invention may be prepared in analogy to conventional methods ~or the preparation of liquid detergent compositions. A preferred method of preparing compositions of the present invention involves the~
addition of the water-soluble electrolyte -if any- to water, followed by the addition of any water-insoluble material such as aluminosilicat2s, followed by the :. .
polymer ingredients and finally the surfactant ingredients. Another prererred method o F preparing a composition of the present invencion involves the addition of the surfactant ingredients to water at ambient temperaturo, followed by the addition of the ., , ' ..
, , ~ .
: ~.
:
iJ3 ~ 3 WO91/06622 PCT/EP90/01679 :
- pol~mer inyredients, and the cooling of the mixture to below 30 c, wharea~ter the remaining ingredients arP
added. ~inally, if necessary, the pH of the composition may be adjus~2d, 2.g. by the addition of small quantitias of caustic materials.
The inv~ntion will now be illustrated ~y ~ay of the following Examples. In all Examples, unless stated to the cont;^ary, all percentages are by weight.
A. Base formulations Table l Composition of basic formulation i.e without deflocculating polymers.
Inqredient : Basic formulation l 2 Na Dobs 26.1 26.3 Synperonic A7 lO.5 lO.6 Na citrate lO.9 8.8 water 52.5 54.3 ; polymer weights additional to basic formulation Raw material Specification Na Dobs Na Dodecyl Benzene sulphonate Synperonic A7 . C12_15 ethoxylated alcohol, 7EO, ex ICI.
`',' ' .
.
. .
~ , .
. .:.
.... .
, .
WO9l/06622 ~ PCT/EP90/01679 Basic Polymer Product EX~MPLE com~osition Tv~e x ~ stabilitY visc *
Reference 2 -- -- -- unstable 1600 1 2 I1) 7 1.0 stable 1440 : 2 2 I1) 7 Z.0 stable 1230 3 2 I1) 14 0.5 stable 1470 4 2 I1) 14 1.0 stable 1160 2 I1) 23 1.0 stable 1110 ) polymers of formula I as described above, ~herein is -C11H23, ~2 is -CO- and R3 is -CO-O-.
*) ~iscosity in mPas at 21 s-1.
: 15 Basic Polymer Product EXAMPLE ComDosition TyPe x % stability visc *
Reference 1 -- -- -- unstable 1380 6 1~ II1) 25 2.0 stable 520 1) polymers of formula II as described above, wherein . is -Cl1H23, R2 is -C0- ,R3 is -O-, A is -H and the poiyglycerol is branched.
*~ Yisco~.3ity in mPas at 21 s-l.
~ .
:' :~ .
-.~
:
., ~ , . . . - ", , . :
. , - . , . ~ :, , .
Claims (6)
1. A liquid detergent composition comprising a dispersion of lamallar droplets in an aqueous continuous phase and a block copolymer consisting of alternating hydrophobic and hydrophilic groups, wherein the equivalent composition, minus the polymer has a significantly higher viscosity and/or becomes unstable.
2. A liquid detergent composition according to claim 1, wherein the polymer is of the formula I, II, III or IV as described hereinbefore.
3. A liquid detergent composition according to claim 1 or 2 comprising from 0.01 to 5.0% by weight o*
the composition of the polymer.
the composition of the polymer.
4. A liquid detergent composition according to claim 1 containing at least 1% by weight of electrolyte.
5. A liquid detergent composition according to claim 1 containing from 2-60% by weight of detergent active materials.
6. A liquid detergent composition according co claim 1, whereby the viscosity at 21s-1 is at least 10%
less than the viscosity of an equivalent composition minus the block copolymer.
less than the viscosity of an equivalent composition minus the block copolymer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8924479.2 | 1989-10-31 | ||
GB898924479A GB8924479D0 (en) | 1989-10-31 | 1989-10-31 | Detergent compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2069928A1 true CA2069928A1 (en) | 1991-05-01 |
Family
ID=10665458
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002069928A Abandoned CA2069928A1 (en) | 1989-10-31 | 1990-10-05 | Detergent compositions |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0498806B1 (en) |
CA (1) | CA2069928A1 (en) |
DE (1) | DE69010215T2 (en) |
ES (1) | ES2055447T3 (en) |
GB (1) | GB8924479D0 (en) |
NO (1) | NO180203C (en) |
WO (1) | WO1991006622A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4237337A1 (en) * | 1992-11-05 | 1994-05-11 | Basf Ag | Block copolyacetals, process for their preparation and their use in detergents and cleaners |
SK53294A3 (en) | 1993-05-07 | 1995-04-12 | Albright & Wilson | Concentrated aqueous mixture containing surface active matter and its use |
GB9309475D0 (en) * | 1993-05-07 | 1993-06-23 | Albright & Wilson | Concentrated aqueous based surfactant compositions |
ATE229064T1 (en) * | 1994-09-30 | 2002-12-15 | Procter & Gamble | BLOCK COPOLYMERS FOR IMPROVED VISCOSITY STABILITY IN CONCENTRATED FABRIC SOFTENERS |
US5595968A (en) * | 1995-05-23 | 1997-01-21 | Basf Corporation | Polymeric dispersants for soda ash based detergent slurries |
US5733861A (en) * | 1995-05-23 | 1998-03-31 | Basf Corporation | Hydrophilic copolymers for reducing the viscosity of detergent slurries |
US5618782A (en) * | 1995-05-23 | 1997-04-08 | Basf Corporation | Hydrophilic copolymers for reducing the viscosity of detergent slurries |
EP0776965A3 (en) | 1995-11-30 | 1999-02-03 | Unilever N.V. | Polymer compositions |
US6194364B1 (en) | 1996-09-23 | 2001-02-27 | The Procter & Gamble Company | Liquid personal cleansing compositions which contain soluble oils and soluble synthetic surfactants |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0222557B1 (en) * | 1985-10-31 | 1993-10-13 | The Procter & Gamble Company | Liquid detergent composition |
DE3541535A1 (en) * | 1985-11-25 | 1987-05-27 | Henkel Kgaa | USE OF POLYGLYCOLDIALKYLETHERS AS VISCOSITY REGULATORS FOR AQUEOUS ANION ANTI-SOLUTIONS |
GB8718215D0 (en) * | 1987-07-31 | 1987-09-09 | Unilever Plc | Liquid detergent compositions |
GB8718217D0 (en) * | 1987-07-31 | 1987-09-09 | Unilever Plc | Liquid detergent compositions |
GB8813978D0 (en) * | 1988-06-13 | 1988-07-20 | Unilever Plc | Liquid detergents |
-
1989
- 1989-10-31 GB GB898924479A patent/GB8924479D0/en active Pending
-
1990
- 1990-10-05 ES ES90914713T patent/ES2055447T3/en not_active Expired - Lifetime
- 1990-10-05 CA CA002069928A patent/CA2069928A1/en not_active Abandoned
- 1990-10-05 WO PCT/EP1990/001679 patent/WO1991006622A1/en active IP Right Grant
- 1990-10-05 DE DE69010215T patent/DE69010215T2/en not_active Expired - Fee Related
- 1990-10-05 EP EP90914713A patent/EP0498806B1/en not_active Expired - Lifetime
-
1992
- 1992-04-29 NO NO921685A patent/NO180203C/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE69010215D1 (en) | 1994-07-28 |
NO180203C (en) | 1997-03-05 |
NO921685L (en) | 1992-06-29 |
EP0498806B1 (en) | 1994-06-22 |
EP0498806A1 (en) | 1992-08-19 |
NO921685D0 (en) | 1992-04-29 |
WO1991006622A1 (en) | 1991-05-16 |
ES2055447T3 (en) | 1994-08-16 |
DE69010215T2 (en) | 1994-10-13 |
NO180203B (en) | 1996-11-25 |
GB8924479D0 (en) | 1989-12-20 |
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Legal Events
Date | Code | Title | Description |
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FZDE | Discontinued |