Note: Descriptions are shown in the official language in which they were submitted.
WO91/08280 PCT/EP90/01791
LIOUID DE~ERGENTS ~ f~
The present invention is concerned with aqueous liquid
detergent compositions which contain sufficient
detergent-active material and, optionally, sufficiently
dissolved electrolyte to result in a structure of
lamellar droplets dispersed in a continuous aqueous
phase. In particular the present invention relates to
lamellar structured detergent compositions which
comprise r~latively low levels of water.
Lamellar dropleLs are a par~icular class OL surfactant
struc'ures waich, int~r alia, are already ~nown from a
variety OL references, e.g. ~.A.Barnes, 'Detergents',
Ch.2. in ~.Walters (Ed), 'Rh~ometry: Industrial
Applic~tior.s', J. Wiley & Sons, Letchworth 1980.
Such lamellar dispersions are used to endow properties
such as consumer-preferred flow behaviour and/or turbid
appearance. Many are also capable of suspending
particulate solids such as detergency builders or
abrasive particles. Examples of such structured liquids
without suspended solids are given in US patent 4 244
840, whilst e~amples where solid particles are suspended
are discloced in specifications EP-A-160 342; EP-A-38
101; EP-A-104 452 and also in the aforementioned
US 4 244 840. Others are disclosed in European Patent
Specification EP-A-151 884, where the lamellar droplet
are called 'spherulites'.
The presence of lamellar droplets in a liquid detergent
product may be detected by means known to those skilled
in the art, for example optical techniques, various
rheometrical measurements. X-ray or neutron
diffraction, and electron microscopy.
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WO91/08280 ~ PCT/EP90/01791
,~
The droplets consist of an onion-like configuration of
concentric bi-layers of surfactant molecules, between
which is trapped water or electrolyte solution (aqueous
phase). Systems in which such droplets are close-packed
provide a very desirable combination of physical
stability and solid-suspending properties with useful
~ flow properties.
::
The viscosity and stability of the product depend on
the volume L^raction of the liquid which is occupied by
the dropl~-s Gener211y speaking, when the volume
fraction is around 0.6, Lhe droplets are just touching
(space-filling). This allows reasonable stability with
an accep~able -~iscosi~y (say no ~,o~e than 2.S Pas,
preferably no more than 1 Pas at a shear rate of 2ls~
). This volume frac~ion also endows useful solid-
suspending propertles.
A problem in the formulating of liquid detergent
compositions is to prevent the occurence of
flocculation. When flocculation occurs between the
lamellar droplets at a given volume fraction, the
viscosity of the corresponding product will increase
due to the formation of a network throughout the
liquid. Flocculation may also lead to instability
reflected in phase separation of the product.
.
It has been described in our non-prepublished European
patent appIica~ion 89201530.6 (EP 346 995) to
incorporate deflocculating polymers comprising a
hydrophilic backbone and one or more hydrophobic
sidegroups in lamellar structured aqueous liquid
detergent compositions for increasing the stability
and/or decreasing the viscosity. The use of other
deflocculating polymers in lamellar structured a~ueous
detergent compositions is described in our non-
` prepublished British patent applications 8924479.2,
; 8924478.4 and 8924477.8. Compositions as described in
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W091/08280 PCT/EP90/01791
_~ 3
the above mentioned patent applications compriserelatively high levels, say about 37 % or more of
water.
It has now been recognised that deflocculating polymers
can also be us2d for -che stabilisation and/or viscosity
reduction of lamellar structured aqueous liquid
detergent composiLions comprising relatively low levels
of water.
~: 10
` According1l~ the present inv2ntion relates to a liquid
detergen~ CGmpOsition com?r'sing a dispersion of
lamellar droplets OL deterger.~ astive materlals in an
- aqueo~s continuous phasc, sa d composition somprisins a
defloccula~ing polymer and from 1-~5 % by weight OI
wàter.
It is well-known in the art to formulate liquid
detergent compositions which comprise no or only low
levels of water, these compositions are however
generally not of the lamellar droplet type and
therefore they often do not have the advantages such as
solid suspending properties, robustness, and sometimes
tolerance to electrolyte levels etc 2S may be observed
in lamellar structured detergent compositions; also
' these prior art compositions are often not of
acceptable V15Cosity and/or physical stability.
: . ,
Preferably compositions of the invention are physically
j 30 stable. In the context of the present invention,
~` ~ physical stability for these systems can be defined in
` terms of the maximum phase separation compatible with
most manufacturin~ and retail requirements. That is,
the 'physically stable' compositions will yield no more
' 35 lO %, preferably no more than 5 %, most preferred no
` more than 2% by volume phase separation as evidenced by
appearance of 2 or more separate phases when stored at
25~C for 21 days from the time of preparation. Ideally
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WO9l/08280 ~ PCT/EP90/01791
compositions of the invention yield no visible phase
separation when stored at 25 C for 21 days.
Suitable deflocculating polymers for use in
compositions of the present invention are for instance
described in our copending European patent application
89201530.6 (EP 346 995), polymers as described in this
patent have a hydrophilic backbone and at least one
hydrophobic side chain.
Generally the hydrophilic backbone of the polymer is
predo-..inan_ly l n_ar (_h2 mair. chaln of the backbone
constitu,_s at leas~ 50 ~, preîera,ly more than 75 %,
mcst preîerrod more than 90% by weight of the
backbonej, sui~abie monomer constituenls of the
hydro?hilic bac~bone are for e~ample unsaturated C1_6
acids, ethers, alcohols, aldehydes, ketones or esters,
sugar units, alXoxy units, maleic anhydride and
saturated polyalcohols such as glycerol. Speci~ic
examples of suitable monomer units are acrylic acid,
methacrylic acid, maleic acid, vinyl acetic acid,
glucosides, ethylene oxide and glycerol. The
hydrophilic backbone made from the backbone
- constituents in the absence of hydrophobic side-groups
is relatively water-soluble at ambient temperature and
a pH of between 6.5 and 14.5. Preferably the solubility
is more than lg/l, more preferred more than 5 g/l most
preferred more than 10 g/l.
Preferably the hydrophobic sidegroups are composed of
relatively hydrophobic alkoxy groups for example
butylene oxide and/or propylene oxide and/or alkyl or
alkenyl chains having from 5 to 24 carbon atoms. The
hydrophobic groups may be connected to the hydrophilic
backbone via relatively hydrophilic bonds for example a
poly ethoxy linkage.
~`
WO91/08280 ~CT/EP90/01791
~ ~ $ ~ ~.D ~
Preferred polymers are of the formula:
S H t CH --- - ;-- t~----~ _j __ Q1 ---tQ~ -H
wherein:
Q2 is a molecula,- ea~ity ol ormula ~Ia):
~-H2--CH~C --CH~ f5_ c
CO2A1 J x lCO~A2 CO2A JY ¦ R I
`! R3
.,, 1.
~ 25 (Ia) R~
:~' , z
wherein:
~: Rl represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-
~;. 30 or is absent;
: .
~ R2 represents from l to 50 independently selected
:~ alkyleneoxy groups preferably ethylene oxide or
propylene oxide groups, or is absent, provided that
when R3 is absent and R4 represents hydrogen or
contains no more than ~ carbon atoms, then R2 must
.: contain an alkyleneoxy group preferably more than 5
' alkyleneoxy groups with at least 3 carbon atoms;
.
.
WO91/08280 PCT/EP90/01791
~ 6
R3 represents a phenylene linkage, or is absent;
R4 represents hydrogen or a C1_24 alkyl or C2_24
al~enyl group, with the provisos that
a) when Rl represents -O-Co-, R2 and R3 must be absent
and R4 must ^ontain at least ~ carbon atoms;
b) when R2 is absent, R4 is not hydrogen and when also
R3 is absent, then R~ must contain at least 5 carbon
atoms;
R5 represents n~drogen or a group of formula -CooA4;
R6 represen~s hydrogen or C1_ alkyl; and
Ai, A2, A- and A~ are independently selected from
hydrogen, al~ali metals, al~aline earth metals,
ammonium and amine bases and Cl_4, or (C2H4O)tH wherein
t is from 1-50, and wherein the monomer units may be in
random order.
l is a multifunctional monomer, allowing the branching
of the poly~er, wherein the monomers of the polymer may
be connected to Q1 in any direction, in any order,
therewith possibly resulting in a branched polymer.
Preferably Q1 is trimethyl prop~ane triacrylate (TMPTA),
methylene bisacrylamide or divinyl glycol.
n is at least 1; z and v are 1; and (x + y + p + q + r)
: z is from 4 : 1 to 1,000 : 1, preferably from 6 : 1
to 250 : 1; in which the monomer units may be in random
order; and preferably p and q are~zero and/or r is
zero; most preferàbly p, q, y and r are zero.
R7 and R8 represent -CH3 or -H;
R9 and R10 represent substituent groups such as amino,
amine, amide, sulphonate, sul?hate, phophonate,
phosphate, hyd~roxy, carboxyl and oxide groups,
.
-
WO91/08280 ~2~r~ PCT/EP90/01791
preferably they are selected from -SO3Na, CO-O-C2H4-
OSO3Na, -CO-O-NH-C(CH3)2-SO3Na, -CO-NH2, -O-CO-C~3, -
OH;
Preferably polymers for use in compositions which are
of relatively high pH (say 10 or more) are
substantially free of hydrolysable groups such as
carbonyl groups for increased polymer stability at high
pH values. Particularly prefe red polymers for use in
high pH compositions comprise hydrophilic backbones
constituted by acid groups s~ch 2S acrylic acid and at
least one hydrophobic side chain ~hich is c5ns tituted
of from 5 to 75 relatively w2cer-insoluDle al~.o~y
; groups such as propo~:y unit, op~ional~y lin~.ed to the
hydrophylic backbone via an poly-al,;o~y iin~age
constituted of from l-10 relatively watersoluble alkoxy
groups such as ethoxy units.
.,,
Other preferred polymers for use in compositions of the
; invention are described in our copending Brithish
patent applications 8924479.2, 8924478.4 and 8924477.6.
Of the polymers described in those patent applications,
especial-ly the use of polymers in accordance with
British patent application 8924478.4 is preferred. These
~, polymers are constituted of nonionic monomers and ionic
monomers, wherein the ionic monomers are from 0.1 to 50
% by weight of the polymer.
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WO91/08280 PCT/EP90/01791
Especially preferred polymers of this type are of the
formula: .~
S ~HC~2- lc~2l ~
~o ~ P ~ (II)
pjC I ~n
j~:
wherein: x, z and n are as above;
R3 and R4 represent hydrogen or Cl_4 alkyl;
- R2 represents -CO-O-, -O-, -O-CO-,
-CH2-, -CO-NH-, or is absent;
: _ Rl represents -C3H6-N+-(CH3)3(Cl-),
~`,!' -C2H4-OSO3 (Na+), -SO3 (Na+),
-C2H4 N+(CH3)3 Cl , -C2H4 N (C2H6)3 Cl
' -CH2 N+ (CH3)3 Cl , -C~2 N (C2H5)3 Cl or
; 25 benzyl-SO3 (Na+);
:~l - Ra is CH2, C2H4, C3H6 or is absent;
~' - Rb represents form l to 50 independently
., selected alkylene:oxide groups, preferably
ethylene oxide groups or is absent;
: 30 - Rc represents -OH or -H;
and wherein if R2,Ra and Rb are absent, then Rc is not
-H-
~ ~ .
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WO91/08280 PCT/EP90/01791
Other preferred polymers have the formula:
5 R5 16 ~ 13 4
CH - CH / \ CH - C~
HC _ CH HC _c _ ~ HC_c _ CH jHC - O H
~ l CIH _ O 1~ i:2~ ~2
(III)
_ 15
I Wherein:
-- X = Xl + X2
- x,z and n are as defined above
_ R1 represents -CH2O- or -O-;
- R2 represents -CH2COO~Na+, -C3H6ON+(CH3)3Cl or C3H6
N~ (CH3)3 Cl
- R3 and R4 represents -OH, CH2OH, -O(C3H6O)p-H,
i -CH2-O(C3H6O)p-H or -OCH2COO Na+,
-O-C3H6ON+(CH3)3Cl- or -0- C3~5 N~ (C~3)3 Cl-
- R5 represents ~OH, -NH-CO-CH3 or -O(C3H6O)p-H
- R6 represents -OH,-CH2OH, -CH~-OCH3,~-O(C3H6O)p-H or
-CH2-O-(c3H6O)p-H
- p is from 1 -.10.
Preferably polymers for use in compositions have a
: molecular weight (as determined as in our co-pending
european patent application 89201530.6 (EP 346 995) of
~; between 500 and 100,000, more preferred from 1,000 to
~:~ 20,000, especially preferred from 1,500 to 10,000.
Polymers for use in compositions of the invention may
for example be prepared by using conventional aqueous
polymerisation procedures, suitable methods are for
example described in the above mentioned co-pending
'
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WO91/08280 ~ir~ ~ PCT/EP90/01791
european patent application. Another suitable method for
the preparation of defloc~ulating polymers is described
in example I.
Compositions according to the invention comprise from
1-35 % by weight o wa~er, prererably rrom ~-32 %, more
. preferred from lO-27 %, most preferred from 12-23 %.
Gene-,-ally the deiloccula~ing poly~er will be used at
from O.Ol to 5 ~ by weight of the composition, more
lO pre-^erabl1 ~r~m 0' to 3.~ ?, especially preferred from
0.2~ ~o 2.0 -;.
~ . .
Preferably, composi~ions o~ ~h~ invention have a pH of
~ between ~ and l~, more preferred between 6 and 12
: 15 especial~y pre~ red from 7 to ll.
. :, - ,
Compositions of the invention preferably have a
viscosity of less than 2,000 mPas at 21 s-l, more
; preferred less than 1,500 mPas, most preferred less than
l,000 mPas, especially preferred between lO0 and 750
mPas at 21 s-l.
~ Compositions of the invention also comprise detergent
j acti~ mate_izls, preferably at a level of from l to 70
by weight of the composition, more preferred a level of
30 to 65 % by weight, especially preferred from 40 to 60
~ by weight, most preferred from ~5 to 55 ~.
In the case of blends of surfactants, the precise
proportions of each component which will result in
lamellar structures will depend on the type(s) and
~ ; amount(s) of the electrolytes, as is the case with
: conventional structured liquids.
. 35 In the widest definition the detergent-active material
in general, may comprise one or more surfactants, and
may be selected from anionis, cationic, nonionic,
zwitterionic and amphoteric species, and (provided
WO9l/08280 ~'r~3~ PCT/EP90/01791
. . .
11
mutually compatible) mixtures thereof. For example, they
may be chosen from any of the classes, sub-classes and
specific materials described in 'Surface Active Agents'
Vol.I, by Schwartz & Perry, Interscience 1949 and
'Surface Active Agents' Vol.II by Schwartz, Perry &
Berch (Interscience 1958), in the currenc edition of
"McCutcheon's Emulsifiers & Detergents" published by the
~cCutcheon division of Manufacturing Confoction~rS
Company or in 'Tensid-Taschenbuch', H.Stache, 2nd Edn.,
Carl Hanser Verlag, Munchen & Wien, l9~1.
Suitable nonionic surfactants include, in parricu~ar,
the reaction products of compound, having a h~dro~;^oDic
group and a reactive hydrogen atom, ror e~ample
aliphatic alcohols, acids, amides or alkvl phenols with
alkylene oxides, especially ethylene oxide, either alone
or with propylene oxide. Specific nonionic detergent
compounds are alkyl (C6-C18) primary or secondary linear
or branched alcohols wlth ethylene oxide, and products
made by condensation of ethylene oxide with the reaction
products of propylene oxide and ethylenediamine. Other
so-called nonionic detergent compounds include long
chain tertiary amine oxides, long-chain tertiary
phospine o~ides and dialkyl sulpho~ides.
Preferably the level of nonionic surfactants is from 2
~ ~ to 50 % by weight of the composition, more preferably
; from 10 to 45 ~ by weight of the composition, morepreferred from ll to 40 %, especially preferred from 12
to 35 %.
Compositions of the present invention may contain
synthetic anionic surfactan' ingredients, which are
preferably present in combination with the above
mentioned nonionic materials. Suitable anionic
` surfactants are usually water-soluble al~ali metal salts
of organic sulphates and sulphonates having alkyl
radicals containing from about 8 to about 22 carbon
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WO91/08280 ~ PCT/EP90/01791
12
atoms, the term alkyl being used to include the alkyl
portion of higher acyl radicals. Examples of suitable
; synthetic anionic detergent compounds are sodium and
potassium alkyl sulphates, especially those o~tained by
sulphating higher (C~-C18) alcohols produced, for
example, from tallow or coconut oil, sodium and
potassium alkyl (Cg-C20) benzene sulphonates,
particularly sodiur~ linear secondary alkyl (C10-Cl5)
benzene sulphonates; sodium alkyl glyceryl ether
sulphates, especlally chos~ et`ners of the higher
alcohols d-~ived ~_om tGll~ or _oconu_ oil and
synthetic aicohols de- ved -rom pe~:-oleum; sodium
coconut oil fatty ~?noglyce~ide sulphates and
sulphonates; sodiu~ and po~~ssium sal~s of sulphuric
acid esters of higher (Cg~C18) ~at~v alcohol-alkylene
oxide, particularly ethylene oxide, reaction products;
- the reaction products of falty acids such as coconut
fatty acids esterified with isethionic acid and
neutralized with sodium hydroxide; sodium and
potassium salts of fatty acid amides of methyl taurine;
alkane monosulphonates such as those derived by reacting
; alpha-olefins ~C8-20) with sodium bisulphite and those
derived from reacting paraffins with SO2 and Cl2 and
then hydrolyzin with a ba~e to produce a random
sulphonate; and olefin sulphonates, which term is used
to describe the material made by reacting olefins,
particularly C10-C20 alpha-olefins, with S03 and then
neutralizing and hydrolyzing the reactlon product. The
preferred anionic detergent compounds are sodium
(C11-C15) alkyl benzene sulphonates and sodium (C16-
C18) alkyl sulphates.
Preferably the level of nor.-soap anionic surfactants is
from 2 to 40 % by weight o, the composition, more
preferred from 5 to 37 %, ..,ost preferred from 7 to 35 %
by weight of the composition.
.
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WO9l/08280 PCT/EP90/01791
13
Preferably the weight ratio of the above mentioned
synthetic anionic surfactant materials to the nonionic
surfactant materials is be~ween lO :1 and 1:10, more
preferred between 5:1 and 1:5, especially preferred from
3:1 to 1:3.
.~ .
It is also possible, and sometimes preferred, to
- include an alkali metal soap of a mono- or di-carbo~ylic
acid, especially a soap of an acid having from 12 to 1
carbon atoms, for example oleic acid, ricinoleic acid,
alk(en)yl succinates e.g. dodecyl succinate and ^atty
acids derived from castor oil, rapeseed oil, groundnu-~
oil,coconut oil, palmkernel oil or mixtures th2reo.. 'rh~
sodium or potassium soaps of these acids can
advantageously be used. Preferably the level of s02p in
cbmpositions of the invention i5 from 1-40 % by weignt
of the composition, more preferred from 2-20 ~, most
preferred from 5 to 15 %.
~ .
Also possible is the use of salting out resistant active
materials such as for example described in EP 328 177,
especially the use of alkyl poly glycoside surfactants
such as for example disclosed in EP 70 074. Also alkyl
mono glucosides may be used.
The compositions optionally also contain electrolyte
in an amount sufficient to bring about lamellar
structuring of the detergent-active material. Preferably
.
the compositions contain from-1% to 60%, especially from
10 to 45~ of a salting-out electrolyte. Salting-out
electrolyte has the meaning ascribed to in specification
~; ! EP-A-79 646,that is salting-out electrolytes have a
lytropic number of less than 9.5. Optionally, some
salting-in electrolyte (as defined in the la~ter
specification) may also be included.
In any event, it is preferred that compositions
according to the present invention include detergency
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WO91/08280 ~'rq~ PCT/EP90/01791
.
14
builder material, some or all of which may be
electrolyte. In this context it sr.ould be noted that
some detergent active materials such as for example
soaps, also have builder properties.
Examples of phosphorous-contalning inorganic
detergency builders include the water-soluble salts,
especially alXali met.~l2y opr.osprla_ea, o thophospha.ea,
polyphosphates and phosphonates. Specific examples of
inorganic phospha~e bulld~, in~'ul~ 50dium and
potassium tripolyphcsphat2a, ~ho,;vl.a _s and
hexametaphosphates. ?hosphon2_e se~-~es~ran-c buildera may
also be useà. ~or many reasons, i-._luding en-~ironmen~al
reasons it is howe~er prerer~ed to r~nimise the amount
of phosphate builders.
Examples of non-phosphorus-containing inorganic
detergency builders, when present, include water-soluble
alkali metal carbonates, bicarbonates, silicates and
crystalline and amorphous aluminosilicates. Specific
examples include sodium carbonate (with or without
calcite seeds), potassium carbonate, sodium and
potassium bicarbonates, silicates and zeolites.
In the context of inorganic builders, we prefer to
include electrolytes which promote the solubility of
other electrolytes, for example use of potassium salts
to promote the solubility of $odium salts. Thereby, the
amount of dissolved electrolyte can be increased
considerably (crystal dissolution) as described in UK
patent specification GB l 302 543.
Examples of organic detergen-y builders, when present,
include the al~aline metal, ammonium and substituted
ammonium polyacetates, carboxylates, polycarboxylates,
polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodiu.." potassium, lithium,
ammonium and substituted ammonium salts of
;, ..
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~ W~91/08280 F~ PCT/EP90/01791
: :
ethylenediaminetetraacetic acid, nitrilitriacetic
acid, oxydisuccinic acid, melitic acid, benzene
; polycarboxylic acids, CMOS, tartrate mono succinate,
tartrate di succinate and citric acid.
In the context of organic builders, it is also desirable
to incorporate polymers which are only partly dissolved,
in the aqueous continuous phase as described in EP
301.882. This allows a viscosity reduction (due to the
polymer which is dissolved) whilst incorporating a
sufficiently high amount to achieve a secondary benefi_,
especially building, because the part which is not
- dissolved does not bring about the instability that
would occur iL substantially all were dissolved. Typica
amounts are from 0.5 to 4.5~ by weight.
- It is further possible to include in the compositions of
the present invention, alternatively, or in addition to
the partly dissolved polymer, yet another polymer which
is substantially totally soluble in the aqueous phase
and has an electrolyte résistance of more than 5 grams
sodium nitrilotriacetate in l00ml of a 5% by weight
aqueous solution of the polymer, said second polymer
~also having a vapour pressure in 20~ aqueous solution,
equal to or less than the vapour pressure of a reference
2% by weight or greater aqueous solution of polyethylene
glycol having an average molecular weight of 6000; said
second polymer having a molecular weight of at least
l000. Use of such polymers is generally described in our
EP 301,883. Typical levels are from 0.5 to 4.5% by
weight.
Preferably the total level of non-soap builder material
is from 5-40 ~ by weight of the composition, more
preferred from 5 to 35 ~ by weight of the composition.
Especially preferred is the use of from 5-25 ~ by
weight of the composition of a soluble organic builder
material. Especially preferred is the use of a soluble
.~ .
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. :
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. . . .
- '
.
WO91/08280 ~ir~ PCT/EP90/01791
16
builder materials such as citrate builders. The level of
such builders is preferably from 2 to 40 ~ by weight of
the compostion, more preferred from 7.5 to 30 %,
especially preferred from lO to 25 ~, most preferred
from 12.5 to 22.5%.
Apart from the ingredients already mentioned, a number
of optional ingredients may also be prGsent, for
example lather boosters such as alkanolamides,
particularly the monoethanolamides der1Jed from ~alm
kernel fatty acids and _~conut ~atty acids, -- -!b-i~
softeners such as clays, amii1es and am:Lne oxides ~ latne~
depressants, o~yyen-releasiny bleac:nlny agenrs such as
sodium perborate and sodium percarbona~e, peracid bieach
precursors, chlorine-releasing bieaching agents such as
;; trichloroisocyanuric acid, inorgani_ salts such as
sod1um sulphate, and, usually present in very minor
amounts, fluorescent agents, perfumes, enzymes such as
proteases, amylases and lipases (including Lipolase
(Trade Mark) ex Novo), anti-redeposition agents,
germicides and colourants.
Compositions of the invention may be prepared by any
conver~tional method for the preparation of liquid
detergent compositions. A preferred method involves the
dispersing of the electrolyte ingredient together with
the minor ingredients except for the temperature
sensitive ingredients -if any- in water of elevated
temperaturej followed by the addition of the builder
material and the detergent active materlals which are
optionally premixed under stirring and finally cooling
the mixture and adding any temperature sensitive minor
ingredients such as enzymes perfumes etc. The
defloccculating polymer may advantageously be added just
before or after the detergent active materials.
, .
In use the detergent compositions of the invention will
be diluted with wash water to form a wash liquor for
:, .
W091/0~280 ~ PCT/~P9OtO1791.
: 17
instance for use in a washing machine. The
concentration of liquid detergent composition in the
wash liquor is preferably from O.l to lO ~, more
preferred from O.l to 3% by weight.
The invention wiIl now be illustrated by way of the
following Examples.
.
,
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,
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.
-
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WO91/08280 ~ r~ PCT/EP9~/01791
18
EXAMPLE I
Preparation of deflocculatina ~olymer
A suitable method of preparing deflocculatiny polymersis the preparation of a 'backbone' polymer CollG~ed by
a reaction thereof with one or more side groups.
Polymers comprising a hydrophilic backboIie and one or
more hydrophobic side groups ~as for exam?lQ dsscribed
; lO in our co-pending European patent z~plicz'ion
89201530.6) can be prepared by this m-~_hoa 3'~ r-~ctincj ;
hydrophilic 'backbone' polymer wi~.rl 5ne or `QO-~
hydrophobic moieties. Polymers comprisins nonionic
monomers and ionic monomers (as for e~ample describe~l in
our co-pénding British patent applica ion 892~7~.~) can
; be prepared by this method~by reacting a nonionic
'backbone' polymer with one or more ionic groups.
An example of a suitable reaction between the backbone
polymer and the side groups is an esterification
reaction wherein acid- or hydroxy groups of the backbone
polymer are esterified with hydroxy- or acid groups of
the side groups.
If the backbone polymer is hydrophilic, two situations
can be distinguished. Firstly, the backbone polymer may
comprise carboxylic acid groups which may be esterified
with hydrophobic moieties such as fatty alcohols, fatty
glycerol ethers, fatty di-hydroxy alcohols, alkoxylated
fatty alcohols and alkyl polyglycosides. In this
situation, the backbone polymer is preferably free of
`~ ~ carboxylic acid anhydride groups. Alternatively the
backbone may comprise alcohol groups which may be
esterified with hydrophobic moieties comprising acid
groups such as fatty acids and fatty ethers
carboxylates.
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WO91/~8280 ~ .~.~8 PCT/EP90/01791
19
Preferably at least 50 % of the backbone monomers
comprise reactive groups, allowing the esterification,
more preferred more than 75 % of the monomers comprise
reactive groups, most preferred more than 9O %. The
reason for this is that the esterification reaction is
an equilibrium reaction, and under normal conditions a
small amount -say about 0.2-lO %- of the backbone
reactive groups will be esterified. If the polymer
'bac~bone' contains relative high amounts of reactive
groups, these relative low amounts of side groups are
sufficient to provide deflocculating polymers. ~re~erred
clrcumstances for the esterification reaction are high
concentrations of backbone polymers, relative high
concent~ations of the side-group moieties and a
~ 15 relatively low pH.
:
;~ An especially preferred embodiment of a process for
preparing the polymers is the reaction of a backbone
polymer with hydrophobic or ionic moieties, wherein the
hydrophobic or ionic moiety has surfactant properties.
An example of such a reaction is the esterification of a
carboxylic acid group containing backbone with
alkoxylated nonionic surfactant materials. The use of
surfactant materials as the source for the side-groups
of the polymer has the advantage that this allows the
in-situ preparation of deflocculating polymers, the
polymer can be formed in the presence of an excess of
surfactant materials under acid conditions; the part of
the reactive surfactant materials that do not react with
the backbone in the equilibrium reaction will be
present as detergent active materials in the final
" detergent composition. This method avoids the waste of
starting materials and also allows the preparation of
the polymer at a late stage of the product formulation:
~,~ 35 in some cases, especially when low pH products are
- concerned, the deflocculating polymer may be formed 'in-
situ' in a composition containing all or a significant
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WO91/08280 ` PCT/EP90/0179l
part of the ingredients of the final detergent
composition.
Preferably the formation of the polymer takes place in a
composition comprising the detergent active materials or
the final detergent composition, but at a relati-~ely 1GW
pH, say less than 6.0, more preferred less than 4.0,
most preferred less than 2Ø The low pH can
advantageously be provided by the presence of par' of
all of the anionic surfactants in non-neu~_ali'sed ,_ ~,..
The reaclion may then be stopped Dy :neucrcllising ChG
anionic surfactants, for example by th2 addi~is~ c an
amount of NaOH and or KOH.
lS METHOD A
.
; The following compositions were made by mixing the
ingredients in the order listed
Composition A B
% wt
water 50.5 50-5
~ Marlon AS-3 2) 21 21
Synperonic A7 9 9
Polymer backbone1) 1.5 1.5-
NaOH 3.0 3.0
NaCitrate 15 15
30 1) Sokolan PA50 ~ex BASF), polyacrylate polymer of
MW = lOK (PAA standards).
2) Dodecyl benzene sulphonic acid (EX Hils)
Composition A was made by mixing the ingredients in the
~- 35 order listed under stirring. Composition B was made by
the same method, but the product was stored for 5 days
at 52C at a pH of about 0 after the addition of the
polymer backbone.
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WO91/08280 ~ PC~/EP90/01791
. 21
Composition A was unstable (24% phase separation) and
had a viscosity of 740 mPas at 2ls~l.
Composition B was stable (no phase separation) and had a
viscosity of 1320 mPas at 2ls~l.
It is believed that the increased stability of
: composition B can be explained by an esterification
reaction between the polymer backbone and the
Synperonic A7 component whereby a deflocculating
polymer is formed.
. METHOD B
.
The fol.l.owlng com?ositions were made by mi~ing the
ingredients in the listed order. After addition of the
~; water the product was stored for a variable time period
at 20~C and 60DC at a pH of 0.3.
~,' .
Composition C
~, 20 % wt
Marlon AS3 15.6
LES 2.l
25 SyperoniG A7 4.2
Sokolan CP~ 3.5
. Water 63.3
Na-citrate 9.5
NaOH l.9 to pH ~.2
In a first set of tests the intermadiate product was
. . stored at 20C. The product which was not stored but
~ .
immediately further processed was unstable and had a
`~ viscosity of 600 mPas at 21 5-1. A storage period of 3
: 35 days gave a stable product having a.viscosity of 50 mPas
at 21 s~l; 6 days storage gave a viscosity of 150 mPas
. and a stable product; after l0 days storage the final
~, product was still stable and had a viscosity of 320 mPas
at 21 s~l.
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WO91/08280 ~ PCT/EP90/01791
22
When storing the intermediate at 60C, similar results
were obtained. Unstable, highly viscous (about 600mPas)
products were obtained without storage~or after a short
period of storage. With 2 hours of storage the ~iscosity
was 30 mPas; 3 hours storage gave a viscosity of 50
mPas; 8 hours storage gave a viscosity of l90 mPas,
these three products were stable.
Again it is believed that the increase instability and 2
decrease in viscosity can be explained by a reaction
between the So~olan CP5 polymer bac',;bone and the
Synperonic A7 material whereby a deflocculatiny pol~er
is formed. The occurence of deflocculation in
composition B is nicely illustrated in the attached
Micrographs l,2~
Photograph l is an electron-mieroseopy micrograph of a
flocculated lamellar dispension, in accordance to
Example I, Method A, Composition A.
Photograph 2 is an eleetron-microscopy micrograph of a
defloceulated lamellar dispension, in accordance to
Examp'e I, Method A, Composition ~.
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WO91/08280 PCT/EP90/01791
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METHOD C
The following composition were made by mixing the
ingredients in the lister order.
Ingredients % wt D E F
water 31.7 26.7 16.7
Sokalan CP5 2.7 2.4 1.8
Marlon AS 3 5.8 4.8 2.8
L~S (~7~) 8.9 8.9 8.9
Synperonic A7 2.0 1.7 1.0
Premix 1) 6.7 13.4 26.7
Citric acid 1.5 1.5 1.5
Glvcerol 8.0 8.0 8.0
Borax 5.7 . 5-7 5-7
Na O H (to pHg) 1.8 1.8 1.8
Zeolite A4 25 25 25
.'~ .
) The premixes were of the following composition:
Ingredients ~ wt D E F
Water 5.0 10.0 20.0
Sokalan CP5 0.3 0.6 1.2
Marlon AS3 1.0 2.0 4.0
Synperonic A7 0.~. 0.8 1.5
The premixes were mixed and stored for 120 hours at a pH
of 0.3.
.
Product D was just unstable, whereas products E and F
are perfectly stable, having viscosities of 640 and 1750
~; mPas at 21 S-l. Since products D-F were made of the same
:::` starting materials, it is believed that the differences
as observed are due to the fact that in compositions E
and F more esterification of the polymer has taken
pla e, the=ewith resulting in an increas~ in stabiliby.
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WO91/08280 '2~ PCT/EP90/01791
24
EXAMPLE II
The following compositions were made by dissol~ing the
citrate material together with the minor ingredients in
water of 50 C, followed by the addition of the
glycerol, borax, the deflocculating polymer and the
detergent active materials under stirring and finally
cooling the mixture.
INGREDIENT A B C D E G H
; ~ detergent base1) 44 47 49 52 545~ 63
sodium cilrate 12 12 12 12 12 1212
glycerol 5 5 5 5 5 5 5
borax 3.5 3.5 3.5 3.5 3.5 3.53.
minors2) 0.5 0.5 0.5 0.5 0.5 0.
polymer3)
water 34 31 29 26 24 2015
~'
20 1) mixture of Synperonic A7, Na-Las and Oleate soap in
weight ratios of 1:3:1.
2) 0.2% fluorescer (Tinopal), 0.3 % perfume.
3) polymer All disclosed in P 89201530.6 (EP 346 995)
(deflocculating polymer of formula I, wherein q, p
and r are 0, v=l, x=25, y=0, R1 is - CO - O -, R2 is
- absent R3 is absent, R4 is - C12H25, R5 is -H, R6 is
; - CH3 and A1 is Na. The molecular weight of the
polymer is about 3.5 K).
Compositions A-H were stable pourable liquid detergent
compositions comprising a dispersion of lamellar
droplets of detergent active material in an aqueous
phase. This example illustrates that stable aqueous
liquid detergent compositions can be obtained comprising
water levels of less than 35 ~.
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WO91/08280 ~ PCT/EP90/01791
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EXAMPLE III
The following composition was made by mixing the
ingredien-ts in the listed order:
Ingredient (wt %)
Water 32.7
Na-citrate 9.9
citric acid 2.2
CaCl2 0.2
Glycerol 4.3
Na-perborat2 l.2
Na-metaborate 3.2
NaLas 30.2
Synperonic A7 13.0
Deflocculating polymerl) l.0
Dequest 2060S 0.5
Tinopal CBS-X O.l
Silicon oil (DB 30) 0.3
Alcalase 0.9
Perfume 0.3
l~ poly~2r as in examplé II.
The product was stable (no visible phase separation) and
had a pH of 9.0 and a viscosity of 710 at 21 s-l. A
corresponding composition minus the deflocculating
polymer is unstable (more than lO % phase separation
after storage for 21 days at 25~C).
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WO91/08280 PCr/EP90/0179l
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26
EXAMPLE IV
The following compositions were made by mixing the
ingredients in,the order listed:
INGRDIENT (wt %) A B
water 27.0 29.0
KOH -- 4.6
NaOH 2.3 --
Na Citrate 2aq 10.0 15.0
:~ Glycerol 2.0 2.0
Borax 1.5 2.0
Zeolite 4A 25.0 --
Synperonic A7 12.0 18.0
: Priolene 6902 3.6 5.4
Prifac 7904 2.4 3.6
Dobanic 113 12.0 18.0
: - . Polymer 1) 1.0 1.0
Savinase 0.6 0.6
~ . 20 Amylase 0.2 0.2
; Tinopal CBS-X 0.2 0.2
Perfume 0.4 0.4
1) Polymers 25 in Example II
Both compositions were stable pourable liquid detergent
compositions.
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