Note: Descriptions are shown in the official language in which they were submitted.
2 ~ 7
W091~09107 PCT/EP90/01874
LIOUID DETERGENTS
The presen-t invention is concerned with aqueous liquid
detergen~ compositions which contain sufficient
detergent-active material and, optionally, sufficiently
dissolved electrolyL2 to result in a structure of
lamellar droplets dispersed in a continuous aqueous
phas2~ In p3,-~_cular the pres2nt invention relates to
liquia de--_Lgen-c compositions having improved solid
suspending proyerties.
~amella droplets are a particular class of surfactant
. ~ structl'rQs ~.lhiCh, inter 21ia, are already known from a
variety OI references, e.g. H.A.Barnes, 'Detergents',
Ch.2. in ~.~alters tEd), 'Rheo~etry: Industrial
Applications', J. Wiley & Sons, Letchworth 1980.
Such lamellar dispersions are used to endow properties
such as consumer-preferred flow behaviour and/or turbid
appearance. Many are also capable of suspending
particulate solids such as detergency builders or
abrasiv2 particles. ~xamplos of such structured
~ liquids without suspended solids are given in US
; 25 patent 4 244 840, whilst examples where solid particles
are suspended are disclosed in specifications EP-A-160
342; EP-A-38 lOl; EP-A-~04 452 and also in the
aforementioned US 4 244 840. Others are disclosed in
European Patent Specification ~P-A-151 884, where the
lamellar droplet are called 'spherulites'.
The presence or lamellar droplets in a liquid detergent
product may be detected by means known to those skilled
in the art, for example optical techniques, various
rheometrical measurements. X-ray or neutron
diffraction, and electron microscopy.
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W09l/09107 2 ~ 6 9 6 4 ~ PCT/EP90/0187
The droplets consist of an onion-like configuration of
concentric hi-layers of surfactant molecules, between
~hich is trapped water or electrolyte solution (aqueous
phase). Systems in which such droplets are clase-packed
provide a very desirable combination of physical
stability and solid-suspending properties with useful
flow properties.
The VlSCosity and stability of the product depend on
tn~ volume Iraction which is occupied by che droplets.
Genorally sp2a1cing, ~hen the volume fraction is around
O.S, tne droplets are just touching (space-filling).
This allows raasonable stability with an acceptable
visco5 ' ty (say no more than 2.5 Pa.s, preferably no
more than 1 Pa.s at a shear rate of 21s-1). This volume
fraction also endows useful solid-suspending
properties.
., .
A problem in formulating liquid detergent compositions
is to prevent the occurence of flocculation. When
flocculation occurs between the lamellar droplets at a
given volume fraction, the viscosity of the
co-responding product will incr~ase due to the
formation of a network throughout the liquid.
Flocculation may also lead to instability reflected in
phase separation of the product.
:~ .
Another problem in formulating liquid detergent
~ compositions of the lamellar droplet type, i9 that
sometimes these compositions are not fully capable of
stably suspending solid materials, especially when the
volums fraction of lamellar droplets is relatively low,
say less than 0.6 or less than 0.5.
:~
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It has no~.~ been found, that liquid detergent
compositions having improved solid suspending
properties and/or improved stability and/or improved
viscosity can be obtained by carefully controlling the
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~ , WO 91/09107 PCT/EP90/01874
droplet size of the lamellar droplets. In particular an
increase in solid suspending properties can be observed
-especially when thP volume fraction of lamellar
droplets is relatively low, say less than'O.6 or less
than 0.5- if a relatively high fraction of the lamellar
droplets consists of small droplets.
It has baen sugg~sted in ~P 151 884 (Albright and
~ilson~ _o pr2par2 liyuid detaLg2nt products comprising
dispe sed lamellar d-oplecs wner~b~ a ma~or proportion
of -th? d.~plets havs a diameter of 0.2 to 1 micrometer.
It has no~ 2en found that the solid suspending
propertles and~or the stability and/or the viscosity of
liquid detergent compositions comprising relatively
high amounts of lamellar droplets can be favourably
influenced by incorporating therein a deflocculating
polymer.
; 20 Ac~ordingly the present invention relates to a liquid
detergent composition comprising a di-spersion of
lamellar droplets of detergent active materials in an
aqueous continuous ~hase, said composition also
comprising a deflocculating polymer and suspended
particles of solid material, wherein at least one of
the following conditions are fulfilled:
~1) at least 50 ~ of the lamellar droplets have a
diameter of less than 0.45 micrometer;
(2) the detergent composition has a refractive
index for light having a wavelength of 589 nm which is
at least 0.01 above the refractive index of its
corresponding aqueous continuous phase.
Compositions of the invention may satisfy condition
(1), (2) or both conditions as speclfied above. Both
conditions are believed to correspond to liquid
compositions, comprising relatively high numbers of
small particles.
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WO91/09107 2 ~ L~7 PCT/EP90/0187~
The percentage of lamellar droplets having a diameter
of less than 0.45 micrometer can be determined by
making electron microscopy pictures of the liquid
detarg2nt composition at a magni~ication of between
15,000 and 60,000 (preferably about 30,000) and
dPtormining th~ rela-tive number of droplets having a
diametor of less than 0.45 micrometer.
Pr~f2rably at least 50 '4 or the lamellar droplets have
a diam_~er of less than 0.3~ micrometer, more preferred
less -tnan 0.25 micrometer, most preferred less than
0.15 mlc~ometar, especially preferred less than 0.10 or
0.07 mic~omot2r.
The refractive index of the liquid detergent
composition can for example be determined as follows:
light having a wavelength of 589 nm is passed through a
thin layer (preferably about 1 mm) of liquid detergent
composition. The angle of incidence and the angle of
refraction are measured, whereafter the refractive
index can be caloulated by using the Snellius equation.
Another, pre~er~ed method to determine the refractive
index is by using internal reflection measurements, for
e~ample by using a Atago digital refractometer RX-
; 1000. The use of internal reflection measurements is
; especially advantageous ~or determining the refractive
index f or opaque systems.
The refractive index of the corresponding aqueous phase
can be measured by isolating the aqueous phase from the
detergent composition (e.g by (ultra-) centrifugation)
or by separate preparation of a composition, whereby
the-insoluble insredients are only added to their
solubility limit and the dispersed phases are omitted.
Applicants believe that a liquid detergent composition
comprising relatively low levels of small particles
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~ WO91/09107 PCT/~P90/01874
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will generally have a lower re~ractive index than a
corr,osponding composition, wherein relatively high
levels of small particles are present. The reason for
this may be the following: in measuring the refractive
index OI a system, droplets being significantly larger
than the wavQlength of the measuring light will cause
the scatiering or incident lignt, but will not
contribu-te to lts Lefracti~e ~ower. Cal~ulations using
~ the ~ie sca-t-c2ring thaor~ CCIIL 1rm this.
.' 10
Thererore, -n20rQtic2ll~, an aqueous composition, ~hich
only comprises lamellar droplets navir.g a particle size
significant~ rabo-~e the ~iavelength of the llght, will
have a e,^racti~2 indox which is slose to the
refractive index of the aqueous base of the product.
Detergent compositions comprlsing particles having a
size comparable or smaller than the wavelength of the
light, will be optically more dense than compositions
without these particles. Therefore, for a given
composition, an increase in refractive index is a sign
of the presence of relatively small particles in the
~ product.
; Preferably the refractive index of the total
composition is more than 0.02 above the refractive
index of the corresponding aqueous phase, more
preferred from 0.03 to 0.20, most praferred from 0.04
to 0.15 especially preferred between 0.05 and 0.10.
Compositions of the invention can be obtained by any
method for preparing liquid detergent compositions. The
man skilled-in the art will ~e able to select the
components and their levels in order to allow the
formation of a lamellar droplet structure. Also the
skilled man will be able to adapt the formulation
andtor the processing conditions thereof, such that
relatively high levels of small droplets are made.
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WO91/09107 ~ PCT/EP90/018
A particularly advantageous method of preparing
rela~ive high levels of small lamellar droplets is the
use of high shear in preparing the compositions of the
invention. Thls can for example be accomplished by
using a high shear device in a recirculation loop
duriny prapara~ion of the liquid or by applying high
sh~ar a-Cter tho preparation of the liquid. Preferred
snear rates a~ more than l,000 s-l, more prefered from
2,000 to l50,000, especiaily preîerred from 4,000 to
l5,000. T~.es2 shear conditions are especially suitable
ror separace r2circulation loops. For high shear
mixln~, gonerallv the average shear will be more than
l0, __ e~am?le from 15 to 200 s-l, more preferred 20
to lO0 5 l
Accordingly the present invention also relates to a
liquid detergent composition comprising a dispersion of
lamellar droplets of detergent active materials in an
aqueous continuous phase, said composition comprising a
deflocculating polymer and said composition being
obtainable by a process comprising the step of mixing
the de~ergant active materials in water (optionally in
the presence of other ingredients of the composition)
at a relatively high shear rate and/or by applying
relatively high shear to the finished composition.
Preferably compositions obtainable by this method
comprise suspended particles of solid material. In the
context of the present invention the term suspended
solid material refers to any solid material that is not
-completely- soluble in the composition. Examples of
matzrials that are usually present in the form of
suspended solids are fluorescers, (partially) insoluble
builder materials such as STP or zeolites etc, silicon
antifoam materials, bleach particles such as perborate
bleaches and softener particles. Preferably the level
of suspended solid materials is from O.Ol to 50 %, most
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~~ WO91/09107 PCT/EP90/01874
2 ~
preferred 1 to 40 % by weight.
It has been found that the stability and/or the
viscosity and/or the solid suspending properties of
compositions of the invention can favourably be
influenced by incorporating therein a deflocculating
~` polymer. The incorporation of derlocculating polymers
is esp_cially useful for stabilising lamellar liquid
detergent compositions, Tihereirl the pnase volume of cne
lamellar droplets is relatively low, say less than 0.5~
or even less than 0.50 or o L~9 . ~5pecially advantageous
is the use of deflocculating polymers in compositions
having a lam211ar pnaso ~olum9 O:e ~re~ 0~0 to 0.48.
;
Suitable deflocculating polymers for use in
compositions of the present invention are for instance
described in our copending European patent application
89201530.6 (EP 346 995), polymers as described in this
` patent have a hydrophilic backbone and at least one
hydrophobic side chain. Generally the hydrophilic
backbone of the polymer is predominantly linear ( the
main chain of the backbone constitutes at least 50 %,
preferably more than 75 %, most prPf2rred more than 90
by weight of the backbone), suitable monomer
constituents of the hydrophilic backbone are for
~ example unsaturated Cl_6 acids, ethers, alcohols,
; aldehydes, ketones or esters, sugar units, alkoxy
units, maleic anhydride and saturated polyalcohols such
as glycerol. Examples of suitable monomer units are
~30 acrylic acid, methacrylic acid, maleic acid, vinyl
acetic acid, glucosides, ethylene oxide and glycerol.
The hydrophilic backbone made from the backbone
constituents in the absence of hydrophobic side-groups
is relatively water-soluble at ambient temperature and
a pH of between 6.0 and 14Ø Preferably thP solubility
is more than lg/l, more preferred more than 5 g/l most
preferred more than 10 g/l.
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WO91/09107 2 0 ~ PCT/EP90/0187
Preferably the hydrophobic sidegroups are composed of
relatively hydrophobic alkoxy groups for example
butylPne oxid~ and/or propylene oxide and/or alkyl or
alXenyl chains haviny ~rom 5 to 24 carbon atoms. The
hydropho~lc groups may b2 connected to the hydrophilic
bac~bone via relatiYely hydrophllic bonds for example a
poly ethoxy linkage.
.
Pre~L.-;2d polymeLa a_- oî the formula:
H -CH2--- JH2---~ tQ1~---{-Q23 1
wherein:
Q2 ia a mo~2cula. en'ity of formula (I2?:
J l
CO2Al x CO2A2 Co2A3 y R 1l
-~ 30 R
.', . I
13
. . . I
(Ia) R4
;
z
wherein:
.. ~. . .
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:
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-i WO91/09107 2 ~ 6 ~ ~ ~ 7 PCT/EP90/01874
1 represents -CO-O-, -O-, -O-CO-, -CH2-, -CO-NH-
or is absent;
R2 represents from 1 to 50 indapendently selected
; alkyleneo~y groups preferably ethylene oxide or
propylene oxide groups, or is abs2nt , provided that
when R3 is abs2n~ and ~4 r 2prasents hydrog2n or
contains no more than ~ car~on a-to-,ns, t~en ~ must
contain an alkyleneoxy group prz,~Pra~ly mora chan 5
alkyleneo~y groups with ak least 3 carbon aJcoms;
R3 reprPsents a han~flQne l~n~age, or is absent;
R4 represents hydrogen or a C1_24 alkyl or C2_24
alkenyl group, with the provisos that
a) when R1 represents -O-CO-I R2 and R3 must be
absent and R4 must contain at least 5 carbon
atoms;
b) when R2 is absent, R4 is not hydrogen and
when also R3 is absentl then R4 must contain
at least 5 carbon atoms î
: R5 represents hydrogen or a group of formula -CooA4;
R6 represents hydrogen or C1_4 alkyl; and
. A1l A2l A3 and A4 are independently selected from
~ hydrogenl alkali metalsl alXaline earth metals,
: ~ 30 ammonium and amine bases and C1_4, or (C2H4O)tH wherein
- t is from 1-50, and wherein the monomer units may be in.
random order.
:: Q1 is a multifunctional monomer, allowing thP branching
of the polymer/ wherein the monomars of the polymer may
be connected to Q1 in any direction/ in any order/
therewith possibly resulting in a branched polymer.
Preferably Ql is trimethyl propane triacrylate (TMPTA)
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WO91/09107 ~9~ ~ PCT/EP90/0187
methylena bisacrylamide or divinyl glycol.
n is at least 1; z and v are 1; and (x + y + p + q + r)
: z is from 4 : 1 to 1,OOO : 1, preferably from 6 : 1
to 250 ~ 1, in which the monomer units may be in random
ordPr; and preferably either p and q are zero, or r 1s
zero; especially preferably p,q,y and r are zero.
R7 a~d ~8 r~preseilc -c~3 or
R9 and ~10 r-p-resen' subs~lL~ent groups such as amino,
amine, amide, sulphonate, sulphate, phophonate,
; . phosp'r.at~. hydro~, sar~o~yl and o~.ide g_-oups,
pre.2_ably Lhey a-3 sel2cted IrOm -S03~a, -CO-O-C2H4-
OS03Na, -CO-O-NH-C(CH3)2-S03Na, -CO-NH2, -O-CO-CH3, -
OH;
Preferably polymers for use in compositions of the
` invention which are of relatively high pH (say 10 or
more) are subst~ntially free of hydrolysable groups
such as carbonyl groups for increased polymer stability
at high pH values. Particularly preferred polymers for
use in high pH compositions of the invention comprise
hydrophilic ~acX~ones constitu~ed by acid groups such
as acrylic acid and at least one hydrophobic side chain
~ which is constituted of from 5 to 75 relatively water-
insoluble alkoxy groups such as propoxy units
optionally linked to the hydrophylic backbone via an -
. poly-alkoxy linkage constituted of from 1-10 relatively
watersoluble alkoxy groups such as ethoxy units.
-~ Other preferred polymers for use in compositions of the invention are described in our copending patent British
applications 8924479.2, 8924478.4 and 8~24477.6. Of
.: the polymers described in those patent applications,
~: 35 especially the use of polymers in accordance with
8924478.4 is preferred. These polymers are constituted
of nonionic monomers and ionic monomers, wherein the
ionic monomer is from 0.1 to 50 % hy welght of the
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11
polymerO Especially preferred polymers of this type are
of the formula:
~, CH2 H t.~ ~H
Rlb X Rl (Il)
RC n
; 15 ~
wherein: x, z and n are as above;
- R3 and R4 represent hydrogen or Cl_4 alkyl;
- R2 represents -CO-O-! -O-, -O-CO-,
-CH2-, -CO-NH-, or is absent;
_ R1 represents -C3H6-N~-(CX3)3(Cl-),
-C2H4-OSO3 (Na+), -SO3~(Na+),
-C2H4 N+(CH3)3 Cl , -C2H4 ~ (C2~6)3 Cl ~
-CH2 N+ (CH3)3 Cl , -CH2 N (C2H6)3 Cl or
benzyl-SO3~ Na+;
;~ : - Ra is CH2, C2H4, C3H6 or is absent;
- Rb represents from 1 to 50 independently
- . . selected alkylene oxide groups, preferably
: ethylene oxide groups or is absent;
` ~ 30 - Rc represents -OH or -H;
and wherein if R2,Ra and Rb are absent, then Rc is not
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WO91/09107 PCT/EP90/018-~
12
Other preferred polymers have the formula:
R5 ~5 R R3 R4
I ~ HOl CH HC--3 ~ IC ~ '~ CrI HC-- ~--H
I fX o 1I f~ 1~ I 1~ o I
l~ R 6 ~ 1~ 5 ~ 9 1 1 ~1 zJ
(III)
~ .
Wherein:
- x = xl + x2
- x,z and n are as defined above
; _ R1 represents -CH2O- or -O-;
- R2 repres~nts ~CX2COO Na-~, -C3H6~(CH3)3C1 or
-C3H6ON+(CH3)3cl
- R3 and R4 represents -OH, CH2OH, -O(C3H6O)p-H,
. -CH2-O(C3H6O)p-H or -OCH2COO~Na+,
-O-C3H6ON+(CH3)3Ci- or -O-C3H6N+(CH3)3Cl-
;~ - R5 represents -OH, -NH-CO-CH3 or -O(C3H6O)p-H
:~ - R6 represents -OH,-CH2OH, -CH2-OCH3, -O(C3H6O)p-H or
:~ - 30 -CH2-O-(C3H6O)p-H
1¦~ - p is from 1 - 10.
.,
:
~ Preferably polymers for use in compositions have a
: molesular ~.~eight (as determin2d as in our co-pending
european patent application 89201530.6) of betw2en 500
~ and 100,000, more-preferred rrom 1,000 to 50,000,
I especially preferred from 2,000 to 20,000 most
: preferred from 4,000 to 15,000. Polymers for use in
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compositions of the invention may for example be
prepared by using conventional aqueous polymerisation
procedures, suitable methods are for e~ample described
in the above mentioned co-pending european patent
application.
,, .
Generally the deflocculating polymer will be used at
from O.Ol to 5 % by weight of the composition, more
preferably from 0.1 to 3.0, especially pre~erred ~rom
0.25 to 3.0 %, most pref2rr~d f-om 0.5 'co 2 5 ~.
Without being bound by any particular inter?r~tatlon or
theory, the Applicants have hypothesized ~;~at t~e
polymers exert their action on the composition by the
following mechanism. ~he hydrophobic side-chain(s) or
ionic groups could be incorporated in or onto the outer
bi-layer of the droplets, leaving the hydrophilic or
nonionic backbone over the outside of the droplets
and/or the polymers could be incorporated deeper inside
the droplet.
:
When the hydrophobic or side chains or ionic groups are
incorporated in or onto the outer bilayer o~ the
` droplets, this has the effect of decoupling the inter-
;~i 25 and intra-droplet forces i.e. the difference between
the forces between individual surfactant molecules in
adjacent layers within a particular droplet and those
between surfactant molecules in adjacent droplets could
become accentuated in that the attractive forces
between adjacent droplets are reduced. This will
generally result in an increased stability due to less
- ~ flocculation and a decrease in viscosity due to smaller
attractive forces between the droplets resulting in
greater distances between adjacent droplets.
The polymers can also be incorporated deeper inside the
droplets, then possibly also less flocculation will
occur, resulting in an increase in stability. The
: ~ s
W O 9t/09tO7 2 ~ ~ ~ 6 '17 PC~r/EP9010187'~i
14
influenc~ of these polymers within the droplets on the
viscosity is governed by two opposita effects : firstly
the presence of deflocculacing polymers will decr2ase
the attractive forces between adj2c~nt droplets
resulting in greater distances ~ecween the drople-ts,
generally resultin~ in a lower viscosity of the system
secondly the a~'ctraccive ~orces becween -cne layers
within the dropl2ts a,e ecEllally ~-edmced b~ th~ pr^sence
of the polymers in th2 droo1~ hl s ~enecally resulc
in an increase in ch2 la~r tnic'cn2ss ~ there~ h
increasing the la~.nellar vol-a-~Ale- o~ _:~o dropioLs~
therewith increasing che viscosicy. The net effect of
these two opposits eff^cts may r~sult 'n e~thor a
decrease or an increzs~ ln th2 V' SC5S'L LY OL th~
product.
Preferred compositions according to the invention are
physically stable and have a relatively low viscosity.
Preferably a corresponding composition minus the
def}occulating polymer is less stable andlor has a
higher viscosity.
In the cont2xL OL L~1e PL ~s2nL ~ }~i~Lion, physical
stability for these systems can be defined in terms of
the maximum separation compatible with most
manufacturing and retail requlrements. That is, the
'stable' compositions will-yield no more 10 %,
preferably no more than 5 %, most preferred no mor~
than 2% by volume phase`separation as evidenced by - 30 appearance of 2 or more separate phases when stored at
25C for 21 days from the time of preparation.
Preferably, compositions of the invention have a pH
between 6 and 14, more pref2rr2d from 6.5 to 13,
especially preferred from 7 to 12.
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Compositions of the invention preferably have a
viscosity of less than 2,500 mPa.s at 21 s-1, more
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preferred less than 1,S00 mPa.s, most preferred less
than 1,000 mPa.s, especially preferred between 100 and
750 mPa.s at 21 s-1. Also preferably the viscosity at a
shear rate of 10-4 s-l is at least 10,000 mPa.s, more
preferred more than loO,000, especially prefer.2d mor~
than 1,000,000, most preferred more than 10,000,000
mPa.s.
Compositions of the invention also compris2 det~rgent
active materials, preferably at a leval of from 1 LO
70% by weight of the composition, mor2 preI2rr2d a
level of 5 to 40 % by weight, most preferr~d from 1~ LO
35 % by weight.
In the case of blends of surfactants, the precise
proportions of each component which will result in
lamellar structures will depend on the type(s) and
amount(s~ of the electrolytes, as is the case with
~ conventional structured liquids.
`- 20
In the widest definition the detergent-active material
in general, may comprise one or more surfactants, and
may be selected from anionic, cationic, nonionic,
zwitterionic and amphoteric species, and (provided
mutually compatible) mixtures thereof. For example,
they may be chosen from any of~the classes, sub-classes
and specific materials described in 'Surface Active
Agents' Vol.I, by Schwartz ~`Perry, Interscience 1949
and 'Surface Active Agents' Vol.II by Schwart~, Perry &
.
30~ Berch (Interscience 1958), in the current edition of
"McCutcheon's Emulsifiers & Detergents" published by
the McCutcheon division of Manufacturing Confectioners
Company or in 'Tensid-Taschenbuch', H.Stache, 2nd Edn.,
Carl Hanser Verlag, Munchen & Wisn, 1981.
Suitable nonionic surfactants include, in particular,
the reaction products of compounds having a hydrophobic
group and a reactive hydrogen atom, for example
wo 91~09107 2 ~ S ~ PCT/EP90/0l87~
aliphatic alcohols, acids, amides or alXyl ph~nols with
alkylene oxides, especially ethylene oxide, either
alone or with propylene o.~ide. Specific nonionic
detergent compounds are alkyl (C6-C18) primary or
secondary linear or ~ranched alcohols T~tith ethylene
oxide, and products made bv condensa-tlon of ~thylene
oxide T~ith ~he reacJcion products OL propyll~ne oxide and
ethylenediamine~ Oth~r so-c~113d nonionic d~tergent
compounds includ2 lon2j cnaiil ~c~rtiGl~-y amine o~ldes,
long-cnain tertiary pnospnin_ o~id~s and dial.cyl
sulphoxides.
., .
Prefera~ly the le~lel of nonionlc surfactan. matorlals
is from 1 -40 % by T~'7'~ght ~r the c3mposltl-n~ ~~vre
preferred from 2-20 %.
~iCompositions of the present invention may contain
synthetic anionic surfactant ingredients, which are
preferably present in combination with the above
mentioned nonionic materials. Suitable anionic
surfactants are usually water-soluble alkali metal
salts of organic sulphates and sulphonates having alkyl
radicals containing fr_m about 3 ~o about ~2 carbon
atoms, the term alkyl being used to include the alkyl
portion of higher acyl radicals. Examples of suitable
synthetic anionic detergent compounds are sodium and
potassium alkyl sulphates, especially those obtained by
sulphating higher (C8-C18) alcohols produced, for
example, from tallow or coconut oil, sodium and
potassium alkyl (Cg-C20) benzene sulphonates,
particularly sodium linear secondary alkyl (C1O-C15)
benzene sulphonates; sodium alkyl glyceryl ether
sulphates, especially those ethers of the higher
alcohols derived from tallow or coconut oil and
synthetic alcohols deriYed from petroleum; sodium
coconut oil fatty monoglycPride sulphates and
sulphonates; sodium and potassium salts of sulphuric
acid esters of higher (C8-C18) fatty alcohol-alkylene
WO91/09107 - 2 0 ~ 9 6 ~ 7 PCT/EP90/01874
oxide, particularly ethylene oxide, reaction products;
the reaction products of fatty acids such as coconut
fatty acids esterified with isethionic acid and
neutralized with sodium hydroxide; sodium and
potassium salts of fatty acid amides of methyl taurine;
alkane monosulphonates such as those derived by
reacting alpha-olefins (C8~20) with sodium bisulpllit2
and those d2rived from r2acting paraffins with SO2 and
Cl2 and then hydrolyzing with a base to produce a
; 10 random sulphonate; and olefin sulphonates, ~hich term
is used to describe the material made by r2acting
olefins, particularly C10-C20 alpha-olefins, with SG3
and th~n neutralizing and hydrolyzing the reaction
product. The pref~rred anionic detergent compounds ar~
sodium (C11-C15) alkyl benzene sulphonates and sodium
~ (C16-C18) alkyl sulphates.
; Generally the level of the above mentioned non-soap
anionic surfactant materials is from 1-25 % by weight
of the composition, more preferred from 2 to 15 %.
` It is also possible, and sometimes preferred, to
include an alkali metal soap of a mono- or d~-
carboxylic acid, especially a soap of an acid having
from 12 to 18 carbon atoms, for example oleic acid,
ricinoleic acid, alke(ny)l succinate for example
dodecyl succinate, and fatty acids derived from castor
oil, rapeseed oil, groundnut oil,~oconut oil,
palmXernel oil or mixtures thereof. The sodium or
potassium soaps of these acids can be used. Preferably
the level of soap in compositions of the invention is
fr 1-35 ~ by weight of the composition, more
pr ~rred from 5-25 %.
Also possible is the use of salting out resistant
active materials for example those described in EP 328
177, especially the use of alkyl poly glycoside
surfactants for example those disclosed in EP 70 074.
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WO91/09107 ~ 0~ 7 PCT/E~90/0187-~:
18
Also alkyl mono glucoside.s may be used.
The compositions op-cionally also contain electrolyte
in an amount sufficient to bring about lamellar
structuring of the detergonc-ac-ci~/e marerial.
Preferably the compositions contain from l~ to 60%,
especially from l0 ~o ~5% oî a sal-'i.lg-out al_ct olyte.
Salting-out electrolyt2 has the meaning ascr~bed to ln
specification EP-A-79 6~S, that is 5a:! sg ou-
eleccrolytes have a 11OtLOP1C nu.n e-- OL 1 ~.aSS :han ~. 3.
Optionally, some salting-in ~ ctrol~r~ (as de~i.n~d in
the latt2r specirication) may a'so bz included.
In any eventt it~is pr~ferred thak compositions
; 15 according to the present invencion include dPtergency
builder material, some or all of which may be
electrolyte. In this context it should be noted that
some detergent active materials such as for example
soaps, also ha~e builder properties.
Examples of phosphorous-containing inorganic
detergency builders include the water-soluble salts,
especi2lly a1kali metal pyrophosphates,
~ orthophosphates, polyphosphates and phosphonates.
; 25 Specific examples of inorganic phosphate builders
include sodium and potassium tripolyphosphates,
phosphates and hexametaphosphates. Phosphonate
sequestrant builders may also be used. Sometimes it is
however preferred to minimise the amount of phosphate
; 30 builders
~. .
~ . .
Examples of non-phosphorus-con-aining inorganic
detergency builders, when present, include
water-soluble alkali metal carbonates, bicarbonates,
silicates and crystalline and amorphous
~- aluminosilicates. Specific examples include sodium
carbonate (with or without calcite seeds), potassium
carbonate, sodium and potassium bicarbonates, silicates
.
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2 a ~ 7
~-~ WO91/09107 PCT/EP90/01874
; , . .. . .
19
and æeolites.
In the context of inorganic builders, we prefer to
include electrolytes which promote the solubility of
other electrolytes, for example use of potassium salts
to promote the solubility of sodium salts. Thereby, the
-~ amount of dissolved electrolyte can be increased
considerably (crystal dissolution) as described in ~K
patent specification GB l 302 543.
Examples of organic detergency builders, when present,
include the alkaline metal, ammonium and substituted
ammonium polyacetates, carbo~ylates, polycarboxylates,
polyacetyl carboxylates and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium,
ammonium and substituted ammonium salts of
ethylenediaminetetraacetic acid, nitrilitriacetic
acid, oxydisuccinic acid, melitic acid, benzene
polycarboxylic acids, CMOS, tartrate mono succinate,
tartrate di succinate and citric acid. Citric acids or
` salts thereof are preferred builder materials for use
~ in compositions of the invention.
:'
In the context of organic builders, it is aIso
desirable to incorporate polymers which are only partly
dissolved, in the aqueous continuous phase as described
~; in EP 301.882. This allows a viscosity reduction (due
to the polymer which is dissolved) whilst incorporating
a sufficiently high amount to achieve a secondary
benefit, especially building, because the part which is
not dissolved does not bring about the instability that
would occur if substantially all were dissolved.
Typical amounts are from 0.5 to 4.5% by weight.
It is further possible to include in the compositions
of the present invention, alternatively, or in addition
to the partly dissolved polymer, yet another polymer
which is substantially totally soluble in the aqueous
WO91/09107 ~ 7 PCT/EP90/OIX7 ;
phase and has an electrolyte resistance of morQ than 5
grams sodium nitrilotriacetate in lOOml of a 5~ by
weight aqueous solution of the polymer, said second
polymer also having a vapour pressure in 20~ aqueous
solution, equal to Or less than the vapour pressure OL
a reference 2% by weight or gr ater aqueous solution o~
polyethylene glycol having an averay3 ~ol-cular ~eighk
of 6000; said second polymer ha~ing ~ mOlQCll~ ar ~"~igh~
of at least loO0. Use of such pol~,i.ers ls ~ena-~lly
described in our EP 301,883. ;~ypical le~J!~ia are L-Om
0.5 to 4.5~ by weight.
,
Preferably the level of non-soap bu.lld2 matQ~ial is
from 5-40 % by weight of the composition, mOrQ
preferred from 5 to 25 % by weight of the composi-tion.
Apart from the ingredients already mentioned, a number
- of optional ingredients may also be present, for
example lather boosters such as alkanolamides,
` particularly the ~onoethanolamides derived from palm
kernel fatty acids and coconut fatty acids, lather
depressants, oxygen releasing bleaching agents such as
sodium perborate and sodium perca-~ona'_, p2raci~
bleach precursors, chlorine-releasing bleaching agents
such as trichloroisocyanuric acid, inorganic salts such
as sodium sulphate, and, usually pr~Qsent in very minor
amounts, fluorescent agents, per~umes, enzymes such as
proteases, amylases and lipases (including Lipolase
(Trade Mark) ex Novo), enzyme sta~ilisers, anti-
~ 30 redeposition agents, germicides and colourants.
Compositions of the invention may be prepared ~y any
conventional method for the preparation of liquid
detergent compositions, although.the use of high shear
conditions is preferred~ A preferred method ~nvolYes
the dispersing of the electrolyte ingredient ( iI
present) together with the minor ingredienks except for
the temperature sensitive ingredients -if any- in water
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`- W091/09107 2 0 ~ 7 PCT/EP~0/0187
21
of elevated temperature, followed by the addition of
the builder material- if any-, the detergent active
material under stirring and thereafter cooling the
mixture and adding any temperature sensitive minor
- 5 ingredients such as enzymes perfumes etc. The
deflocculating polymer may for example be added after
the electrolyte ingredient or as the final ingredient.
It is sometimes pref~rable that the deflocculating
polymers are added prior to the formation of the
lamellar structure. Alternatively part of th2 pol~rler
~- may be added prior to the formation of the lamellar
structure and the remaining part of the polymer is
add~d as the final ingrPdient. Also it is sometimes
pr~ferred to add all or a major part of the polymer as
` 15 the final ingredient.
~, .
;~ In use the detergent compositions of the invention will
be diluted with wash water to form a wash liquor for
instance for use in a washing machine. The
concentration of liquid detergent composition in the
wash liquor is preferably from 0.1 to 10 %, more
preferred from 0.1 to 3% by weight.
The invention will now be illustrated by way of the
following Examples.
.
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W091/09107 PCT/EP90/0187 ~~
2 ~
22
EXAMPLE I
For illustrating the correlation between the size of
the lamellar droplets and the increase in the
. refractive index, the following compositions ( ~hich are
free from suspended solids) were made by mixing the
citrate and NaOH (in an amount sui.'icia~ o i1~u';ralisP
the LAS-acid) into water of ~0 C, fol lo~:~e~ 'my t'ne
addition of the d~flocculating ~ol~rime~ an~ . T~
10 LAS-acid an~ the Synperonic A7 ar2 adced a~ a ?re;ni,~ as
the final ingredients. The samples conca1niiîg 2 ~ cr $
of deflocculating polymer wer2 divide~ i-n ~wo pa~s
one of the parts being subjected ~o ni~h shear
conditions (70,000 s~l) using an Ultra T11rra~,
Of all the samples the refractive index ror 589 nm
light was measured using the Atago digital
refractometer RX-lOOO. ~he lamellar droplet size of the
unsheared samples was measured from electron microscopy
20 pictures at a magnification of 15,000 x.
. FORMULATION wt ~arts A B C _ D E
NaLA 2) <--~ 3.3------->
Synperonic A7 <--~ -lO.O------->
Na-citrate 2aq <--------16.7-------j
Water ~--------50-0------->
polymerl) - 0.5 l.O 2.0 4.0
, .
1) deflocculating polymer of formula A-ll of
EP 346 995.
2) derived from Marlon AS3
.
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2~96~
WO91/09107 PCT/EP90/01874
. 23
The following results were obtained:
sample ~RI-~ _ lamellar droplets2)
~ no high shear high shear ~m
:~ 5
A o.ooo -- __3)
; B 0.0106 -- 0.12
.: .
C 0.0154 -- 0.09
D 0.0229 0.0360 0.06
E 0.0338 0.0447 0.04
~,~ l) dif~er nce between ReIractive index (nD25) and
refractlve index of isolated continuous aqueous phase.
2) 50 % of the droplets have a diameter of less than
the value indicated (no high shear).
3) impossible to measure due to strong I locculation.
These results indioate that the decreasé of lamellar
droplet size correlates to an increase of refractive
index and that high shear conditions can advantageously
be used for obtaining a decrease of the lamellar dropet `
size.
- .
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~ ' ' ' .
,~ .
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WO91/09107 PCr/EP~0/0187'~
2~96~
24
EXAMPLE II
The following compositions were made by mi,cing the
borax and the citrate in water of 50 C, followed by
the addition o-E the zeolite mat~rial and cn2
deflocculating polymer. The LAS and the Synperonic A7
ars added as a pre-mix, whereby the ~S is added in
acid form. The LAS-acid is neutralised with ?TaOH.
Finally the glycerol is added and ths mi~ctll-e -s
cooled. Composi'ion B was pr2pared suc~ na'; 53 '; o~
the lamellar droplets nad a diameter or 0.l~ ~icromo~-c_r
or less. The number OI droplets was determin2d ~y using
x30,000 electron microscopy pictures.
INGREDIENT %twt) A B
NaLAS 18.4
Synperonic A7 ll.5
Glycerol 5.5
~; Borax 3.8
Na-citrate 7.7
Zeolite (Wessalith P) 16.4
deflocculating polymer -- l.0
water balance
polymer A44 as described in EP 89201530.6 (EP ~46 995)
Compositions A and B were liquid detergent compostions
comprising a dispersion of lamellar droplets.
Composition A was a flocculated highly viscous system
which was unstable and had poor suspending properties,
the zeolite particles were not stably suspended and
formed a sediment upon storage at 25 C. Composition B
` defloculated and well poorable and had good suspending
properties, the zeolite was stably suspended in the
system. This example illustrates that small lamellar
droplets in combination with deflocculating polymers
~`~ can provide increased stability.
,
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-~ WO91/09107 PCT/EPg0/018~4
Example III
The following formulations each were made by two
- methods: formulations A1-D1 were made by mixing the
MaOH, borax, citrate and glycerol in water of 50 C,
rollowed by the addition of the deflocculating polymer
and a premix of the LAS, Fatty acid and the Synperonic
A7. Formulations A2-D2 were of the same composition as
A1-D1 except that they were prepared by mixiny the
Glycorol, Borax, NaOH and citrate in water of 50 C
rollow2d ~y the addition of the active premix and
finally adding the deflocculating polymer.
Forumulation (% wt~ A B C D
L~S acid (Marlon As3) <--------10.3--------->
Synperonic A7 <~ -16.0~ -->
Fatty acid2) <--------10.0---------~
Na-citrate 2aq <-~ -10.0~ -->
Glycerol <---------5.0--------->
Borax <-~-~ ~~3-5~~~~~~-~~>
NaOH <--- -----6.0--------->
Polymerl) 0.18 0.36 0.72 1.06
Water <-~ --balance------>
1) Polymer A-11 of EP 346 995 (deflocculating polymer
of formula I, wherein q, p and r are 0, v=l, x=25,
Y=0r R1 is - CO - 0 -, R2 is absent R3 is absent, R4 is
. -C12H25, R5 is -H, R6 is -CH3 and A1 is Na. The
molecular weight of the polymer is about 3.5 X).
2) 60/40 mixture of Priolene 6902 and Prifac 7904.
: For each of the formulations the Delta-RI (difference
between refractive index of product and refractive
index OI continuous phase of composition minus
deflocculating polymer) was measured as well as the
physical stability upon storage for 21 days at 25 C.
The following results were obtained:
:
: .
WO9l/09107 ~ PCT/EP90/0187
26
FORM~LATION Delta RI s ~hase separation
A1 0.0179 7 %
A2 0.0299 0 ~s
B1 0.0164 7 ~5
B2 0.0298 o %
C1 0.0179 5 ~s
C2 0.0289 o s
D1 0.0179 3 ~
D2 0.0289 o s
Comparativel)O.001 35 ,i
:
~ ~ 1) composicion without deflocculating polrmer.
,
This example clearly indicates that an incr~ased
~ stability can be obtained by adding a deflocculating
:~ polymer to a formulation. The stability increase is
~; . especially pronounced in systems having a high
Delta-RIO
~ .
.
,: .
::
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,. ~ ,
.. ~ . .
.
: :
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... .
:;
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-~
--~
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.~ . WO91/09107 ~ PCr/EP90/01874
27
Example IV
The following compositions were made as in example II
INGREDIENT (%wt) A B c D E F
Na~as <~ -18.4---------->
Synperonic A7 <~ -11.5---------->
~a-citrate ?aq <------------6.7----------~
Glycerol <------------5.5-~
: Borax <------------3.8---------->
10 ~eoli_~ (.1essalithP)<-----------16.4---------->
water <-----~-----37.7---------->
; pol~ymer1) -- 0.5 1.0 1.5 2.0 2.5
1) pol~mer A-11 of EP 346 9~5, percentage on top of the
formulation.
~ ' .
;~ The physical properties of the formulation were as
follows: -
COMPviscositv_L~ stability2~ _ deltaRI3
: A 3,550 ~ 4) 0.0051
B 600 5) not measurable
C 570 5) 0.0043
D 700 5) 0.0050
E 820 6) 0.0245
F 1,290 6) 0.0331
1) viscosity.at 21 5-l at ambient temperature
2) after staorage fro 3 weeks at ambient temperature
: 3) di~ference between refractive index of product an
~ refractive index of isolated aqueosu phase
:~ 4) strongly flocculated, highly unstable
- 5) partly deflocculated, unstable, zeolite
~: sedimentation
6) deflocculated, stable, no zeolite sedimentation
These examples illustratP that small lamellar droplets
as evidenced by a relatively hig deltaRI can provide
increased stability and less zeolite sedimentation.
. ' '
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