Note: Descriptions are shown in the official language in which they were submitted.
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STRUCTURED LIQUID DETERGENT COMPOSITION
FIELD OF THE INVENTION
The present invention is concerned with aqueous liquid
detergent compositions of the kind which contain sufficient
detergent-active material and, optionally, sufficiently
dissolved electrolyte to result in a lamellar structure.
BACf~:GROUND OF THE INVENTION
Conventially, aqueous liquid detergent compositions may be
structured in one of- two different ways to endow consumer-
preferred flow behavuour and/or turbid appearance and/or of
suspending particulate solids such as detergency builders
or abrasive particles.
The first way is to employ an "external structurant" such
as a gum or polymer t=hickener. The second way is to form a
lamellar phase "internal structure" from the surfactants)
and water, the latter usually containing d-issolved
electrolyte.
Lamellar phases are <3 particular class of surfactant
structures which, inter alia, are already known from a
variety of references, e.g. H.A. Barnes, 'Detergents', Ch.2
in K.Walters (Ed), Rheometry: Lndustrial Applications', J.
Wiley & Sons, Letchworth 1980.
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Lamellar phases can themselves be considered as divided
into the sub-classes planar lamellar phases and lamellar
droplets. Products can contain exclusively planar lamellar
phases or exclusively lamellar droplets or the two forms
can co-exist in the same product.
The presence of lamellar phase~> 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.
Lamellar 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.
Examples of internally structured liquids containing a
dispersion of lamel.lar droplets but 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: 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 droplets are called 'spherulites'.
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There are also known examples of products containing planar
lamellas phases which may be extensive throughout the
liquid or distributed as discrete layers interspersed with
an aqueous continuous phase. Planar lamellas phases are
generally less wel.l_ suited to combine suspending solid
material with preferred flow properties than are lamellas
droplets, but they are nevertheless eminently suitable for
thickening the product or endowing it with other consumer-
preferred properties.
Lamellas phases cause the resultant liquid product to be
turbid (i.e. cloudy). In order to produce certain visually
pleasing effects in aqueous liquid products there is a need
to produce a lamellas-structured detergent liquid which is
substantially clear (i.e. substantially transparent).
Products with a microstructure consisting of predominantly
planar lamellas phasE:s are usually less turbid than
products with a microstructure of lamellas droplets.
However, these produ.c:ts have usually an inhomogeneous
appearance and are not substantially clear, so that
visually, they do not: have a pleasing appearance.
Furthermore, in the~~e planar lamellas products, it is often
difficult to incorporate sufficient functional
electrolytes, e.g. ~~uilder or buffer electrolyte, while
maintaining clarity. Until now, it has only been possible
to produce commercially viable liquid detergents which are
substantially clear by use of external structurants in
intrinsically isotropic liquids, such as disclosed in GB-A-
1 303 810.
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SUI~1ARY OF THE INVENTION
A first aspect of the present invention provides an aqueous
detergent composition. having a physical form selected from
the group consisting of liquids, pourable gels and non-
pourable gels, said composition comprising surfactant and
water, which composition is structured with a lamellar
phase formed of at least some of the surfactant and at
least some of the water, the composition being
substantially clear at 25°C.
One means of providing the clarity afforded by the first
aspect of the present invention is when the lamellar phase
is in the form of lamellar droplets and a deflocculating
polymer is incorporated in a composition which is already
colloidal.ly stable, even in the absence of the
deflocculating polymer. Thus <~ second aspect of the
present invention provides an aqueous detergent composition
having a physical form selected from the group consisting
of liquids, pourab:le gels and non-pourable gels, said
composition comprising a dispersion of lamellar droplets in
an aqueous continuous phase, the composition further
comprising deflocculating polymer, which composition at
25°C in the absence c>f the deflocculating polymer does not
have a substantially higher viscosity and is colloidally
stable.
Another means of providing the clarity afforded by the
first aspect of the present invention is also when the
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lamellar phase is in the form of lamellar droplets whereby
a significant size fraction of the droplets is below a
critical value. Thus, a third aspect of the present
invention provides an aqueous detergent composition having
5 a physical form selected from the group consisting of
liquids, pourable gels and non--pourable gels, said
composition comprising a dispersion of lamellar droplets in
an aqueous continuc:~us phase, wherein the D", go of the
lamellar droplets is less than '~ micrometers. D~,9o = 900
of the volume of all. droplets having a diameter smaller
than stated.
The clarity as provided by the .first aspect of the present
invention can also be provided by substantially matching
the refractive index of the larnellar phase and that of the
aqueous phase. Thus, a fourth aspect of the present
invention provides an aqueous detergent composition having
a physical form selected from the group consisting of
liquids, pourable gels and non--pourable gels, said
composition comprising a lamellar phase and an aqueous
continuous phase, wherein the difference between the
refractive index of the lamellar phase and the refractive
index of the aqueous continuous phase is such that the
composition has an optical transmissivity of at least 5o as
defined hereafter.
In the fourth aspect of the invention, the refractive
indices of the lamellar and aqueous phases can each be
adjusted by means which will be described in more detail
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hereinbelow. However, one advantageous manner of adjusting
the refractive index of the aqueous phase is to increase it
by dissolving a sugar therein. Although it is known to
incorporate small am~~unts of non-sugar polyols (e. g.
glycerol or sorbitol) in aqueous liquid detergents, for the
purpose of enzyme st~~blilisation, use of sugars, such as
those having a six membered ring structure, particularly
for purposes of achieving clarity, is new. Thus, a fifth
aspect of the present invention provides an aqueous
detergent composition having a physical. form selected from
the group consisting of liquids, pourable gels and non-
pourable gels, said composition comprising a lamellar phase
and an aqueous phase, which aqueous phase has a sugar
dissolved therein.
Applicants may also claim any composition simultaneously
exhibiting the features of any two or more aspects of the
present invention.
DETAILED DESCRIPTION OF THE INVENTION
Product Form
Compositions according to any aspect of the present
invention have a physical form which may be that of a
liquid, a pourable gel or a non-pourable gel. These forms
are conveniently characterised by the product viscosity. In
these definitions, and unless indicated explicitly to the
contrary, throughout this specification, all stated
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viscosities are those measured at a shear rate of 21 s-1
and at a temperature of 25°C.
Compositions according to any aspect of the present
invention which are 1_iquids, preferably have a viscosity of
no more than 1,500 rr~Pa.s, more preferably no more than
1,000 mPa.s, still more preferably, no more than 500 mPa.s.
Compositions according to any aspect of the present
invention which are pourable gels, preferably have a
viscosity of at least: 1,500 mPa.s but no more than 6,000
mPa.s, more preferah~l_y no more than 4,000 mPa.s, still more
preferably no more than 3,000 mPa.s and especially no more
than 2,000 mPa.s.
Compositions according to any aspect of the present
invention which are non-pourable gels, preferably have a
viscosity of at least 6,000 mPa.s but no more than 12,000
mPa.s, more preferat~ly no more than 10,000 mPa.s, still
more preferably no more than 8,000 mPa.s and especially no
more than 7,000 mPa.:~.
Clarity
The first aspect of t=he present invention requires the
composition to be substantially clear. Preferably, this
means that the composition as an optical transmissivity of
at least 50, most preferably 100, still more preferably
250, especially >50°,, through a path length of lcm at 25°C.
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These measurements m.ay be obtained using a Perkin Elmer
UV/VIS Spectrometer Lambda 12 or a Brinkman PC801
Colorimeter at a wavE:length of 520nm, using water as the
1000 standard.
The clarity of the compositions according to the first (or
any other) aspect of- the present invention does not
preclude the composition being coloured, e.g, by addition
of a dye, provided that it does not detract substantially
from clarity. Morecv-er, an opacifier could be included to
reduce clarity if .rec.~uired to appeal to the consumer. In
that case the definition of clarity applied to the
composition according to any aspect of the invention will
apply to the base (ectuivalent) composition without the
opacifier.
Other Visible Solids.
As already mentioned, structuring can be used to suspend
particulate solids such as detergency builder or abrasive
particles. Normally, these are so small as to simply give
the composition a cloudy appearance. However, in
compositions according to any aspect of the present
invention, a relatively small number of large particles of
functional material; could be suspended to give a pleasing
visual effect without affecting the clarity of the bulk of
the liquid.
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However, i.t is also possible to suspend within compositions
of any aspect of the present invention, particles or
speckles, purely for their visual effect. These particles,
may be coloured. Su~~h particles or speckles may for
example be chosen fr~~m any of those previously known in
liquid detergent pro~~ucts, albeit not in substantialy clear
internally structured liquids.
An example of such speckles in externally structured
liquids is described in GB-A-1 303 810 which discloses a
pourable cleaning or rinsing aqueous detergent compositions
in which a visually distinct component is incorporated in
the form of particl.e;s of at least 500mm in diameter. These
particles comprise an agent having a useful effect in the
wash, encapsulated i~~ an inert carrier such as wax or
gelatin. In order to keep the particles in suspension, the
composition comprises a suspending aid such as a gum or a
clay.
An example of a (non-clear) internally structured liquid
which contains visible particles or speckles is disclosed
in GB-A-2 194 793. 'The visible particles contain a carrier
material such as sodium tripolyphosphate and/or a bentonite
clay, plus a pigment. Preferably, these speckles have an
average particle size of from 1 to 1000mm (most preferably
no more than 100mm), and constitute from 0.5a to 15o by
weight of the composition, most preferably from to to 50.
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GB-A-2 247 028 describes a lamellar structured aqueous
detergent liquid whic~:h is also not substantially clear but
in which are dispersE=d particles or droplets of a sparingly
water-soluble or sub:wtantially water-insoluble dye.
5
It is also possible to utilise coloured speckles or
particles of a kind previously proposed for dispersion in a
non-aqueous detergent= liquid. 'these are described in EP-0
635 569, according to which the speckles as particles
10 comprising a carrier material such as a bleach, builder,
clay, abrasive, enzyme or biopol.ymer with a dye or pigment
associated thereto. 'These particles must have a D(3,2)
average particle sizE~ of from 50mm to less than 500mm
A more recent (unpub:L.ished) proposal in the field of
internally structured liquids is for an aqueous liquid
detergent composition which are not substantially clear but
which comprise a structured lamellar phase comprising
surfactant, the lame_Llar phase being capable of suspending
particulate solids and being dispersed in a continuous
phase, and coloured ~~articles suspended by said lamellar
phase, wherein the coloured particles comprise a polymer
shell in which is contained a core material, the coloured
particles further comprising a colourant.
According to this unpublished proposal, the colourant of
the coloured particlc~.s may be contained in the shell and/or
the core. The colou:r~ant may comprise a dye and/or a
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pigment material anc~ (as appropriate) may be admixed with,
dispersed in and/or
dissolved in the core material and/or the polymer shell
material . When co1_ourant is included in the core (whether
or not also in the ~>hell), the amount of colourant i.s
preferably from 0.07. to 2%, more preferably from O.lo to
to by weight of the t=otal of colourant plus core material.
When colourant is additionally or alternatively part of the
shell, then it prefEarably is included at from 0.010 to 9%
by weight of the total of colourant plus shell, more
preferably from 0.1« to to by weight.
The core material preferably constitutes from loo to 99%,
more preferably from 30o to 98o by weight of the coloured
particles.
The polymer shell may comprise any polymer which is
substantially insoluble in the rest of the composition,
preferred examples of suitable polymers include poly
oxymethylene melamine urea (PMMU), polyamides , cell.ulosic
polymers , poly vinyl alcohol (PVA) , Polyurethane and
carrageen (i.e. 3, 6--anhydro-d-galactan, which is a
polysaccharide) ,amongst others .
Suitable core materials include diethylphthalate, alginate,
and paraffin oil.
The D(3,2) average c~:iameter of the coloured particles is
from 250 to 2,500 mp_crons, more preferably from 300 to
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2,200 microns and most preferably from 350 to 2,000
microns.
For optimum dispersion within the body of the liquid
detergent composition, it is preferred that the average
density of the coloured particles is between + 350, more
preferably + 300 or + 2.50, still more preferably + 200, yet
more preferably + 1.8 ~ and most: + 150 of the density of the
composition without the coloured particles.
Another means of enhancing the visual appearance of
compositions according to any aspect of the present
invention is to incorporate encapsulates of functional
materials, e.g. enzymes, which encapsulates may or may not
be coloured. However, they wil_1 normally be large enough
to be distinctly visible so that the bulk of the liquid
between the particles still appears substantially clear.
Enzyme encapsulates
Suitable enzyme encapsulates of the kind mentioned
above are intended to effectively protect the enzyme
from the adverse effect of UV radiation. Therefore it
is essential that t:he enzyme is adequately contained in
the encapsulate to prevent any significant leaking of
the enzyme into the liquid detergent composition during
storage i.e. preferably less th<~n 50%, more preferably
less than 400, most preferably .Less than 300 of the
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encapsulated enzyme leaks into the liquid detergent
composition while being stored for 4 weeks at 37°C.
The enzyme encapsulate may contain polymeric material,
but this is not a limiting condition. If polymers are
present in the capsules, at least part of the polymeric
material should not ~~issolve iru the liquid detergent,
whereas they disperse or dissolve upon dilution.
Examples of syntheti~~ polymeric: materials are:
- polyvinyl alcohol. (PVA) of different molecular weight and
degrees of hydrolysis, which is defined as a homopolymer or
copolymer in which vinyl acetate is a starting monomer unit
and in which most or all or the acetate moieties are
subsequently hydrolysed to alcohol moieties.( e.g. Airvol
range from Air Products, Mowiol. range from Hoechst)
- polyamide (obtained via reaction between a diamine with a
dicarboxylic acid)
- polyester (obtained via reaction between a diol and a
dicarboxylic acid)
- polyurea
- polyurethane
- epoxy resin
Other examples of natural polymers include:
- methyl cellulose (e. g. Methocal A15LV ex Dow Chemical)
- hydroxypropylcellulose (e.g. Klucel L or Klucel G ex
Aqualon)
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- hydroxypropylmethy:Lcellulose
- carrageenan (kappa or iota forms) (various types ex FMC)
- alginate (e. g. Manucol DM or DH ex Kelco).
- gellan gum (e. g. Kc=_lcogel ex Kelco)
- gelatine
Further reference: Encyclopaedia of polymers and thickeners
for cosmetics, vol. :L08, May 1993, 95-135.
If polymers are present in the capsules, they can be
present as a small solid grains, either dispersed
throughout the partic;:Le or preferentially located in part
of the capsules, for example in the outside layer of the
capsule. The polymer: can also be present as hydrated
particles, which can either be dispersed throughout the
particle or located in a part of the capsule. Polymers can
also be present in tree core of the capsules, in the form of
an onion ring inside the capsule or as a shell around the
core.
The enzyme capsules can also contain hydrophobic or fatty
materials. Examples of this are:
- Paraffins (preferab.ly petroleum jelly)
- Triglycerides
- Fatty acids
- Fatty alcohols
- Mixtures of fatty acid and fatty acid soaps
- Esters (e. g. ceto stearyl stearatej
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If the capsules contain hydrophobic materials they should
protect the enzyme against moisture. The hydrophobic
material should envelope the enzyme solid particles or
droplets which are present in the capsule.
5
The capsules can contain also other ingredients:
- density modifiers, e.g. sucrose
- structurants, e.g. silica, oz- zeolite
10 - fillers, e.g. talc:, bentonite
- scavengers, e.g., ammonium sulphate
- plasticizers
- anti-agglomeration or layering agents
- releasing agents
Thus, in one preferred embodiment the enzyme encapsulate
may comprise polymeric material. Preferably, the enzyme
encapsulate comprise polymeric materials selected from the
group consisting of polyvinylalcohol, polyamide, polyester,
polyurea, polyurethane, epoxyresin, methylcellulose,
hydroxypropylcellul.ose, hydroxypropylmethylcellulose,
carrageenan, alginate, gellan gum, gelatine and mixtures
thereof.
Examples of enzyme encapsulates can be found in WO-
93/07263, EP-A-585295, EP-A-356239, US-A-5 281 356, US-A-5
281 355 and GB-A-2 186 884.
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The enzyme encapsulates have a D (3,2) average diameter
between 30 and 5000 microns, preferably between 200 and
3000 microns, most F~referably between 500 and 2500 microns.
The particle shape c.an vary from irregular to spherical; in
the preferred form they should be close to spherical, but
this should not be limiting.
The enzyme encapsulates have an enzyme encapsulates
density.- as measured in the detergent solution - of
between 700 and 2500 kg/m3, more preferably between 800 and
2000 kg/m3 and most preferably between 900 and 1500 kg/m3.
The enzyme can be distributed homogeneously throughout the
particle (matrix capsule), be Located in the core of the
capsule (core-shell capsule) o:r be present in any other
confined zone in the capsule, e.g. in an onion-ring shaped
zone.
The enzyme can be present in the capsules in solid form, as
small particles, which can comprise pure protein or
optionally a mixture of protein and other materials
(optionally in a matrix with other components). The enzyme
can also be present i.n the capsule in the form of small
droplets of an enzyme solution, or as mixture of solid and
liquid (slurry).
The enzyme encapsulate may comprise any detergent enzymes
including protease lipase, amylase, peroxidase, cellulase
or a mixture thereof.
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Examples of. protease are commercially available types such
as AlcalaseTM, DurazymTM, RelaseTM, SavinaseTM ex Novo
Nordisk and OptimaseT~', Puraf.ect TM , ProperaseTM ex Genencor
International.
Examples of lipase ar_e LipolaseTM ex Novo Nordisk and
LipomaxTM ex Genencor International.
Examples of cellulase are CelluzymeTM and CarezymeTM ex Novo
Nordisk, and C:lazinaseTM ex Genencor International.
Examples of amylase are TermamylTM ex Novo Nordisk and
MaxamylTM ex Genencor International.
Preferably the enzyme is a protease.
When the enzyme is a protease, the protein content is
preferably in the rarxge between 0.1 and 20%, more
preferably between 0.5o and 100, most preferably between to
and 5o.
When the enzyme is a protease, the enzyme activity is from
100 GU/mg and 20000 GU/mg, more preferably between 500 and
10000 GU/mg, most preferably between 1000 and 5000 GU/mg.
Deflocculatina Polvmer
In accordance with the second aspect of the present
invention, the clarity may be achieved by (when the
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lamellar phase comprises lamellar droplets) incorporating a
deflocculatinc~ polymer.
According to the specification of EP-A-346 995, the
dependency of stability and/or viscosity upon volume
fraction is favourably influenced by incorporating into the
lamellar dispersion, a deflocculating polymer comprising a
hydrophilic backbone and one oz- more hydrophobic side-
chains.
The theory of function of these deflocculating polymers is
that the hydrophobic chains arE= anchored in the outer
bilayer of the lamell.ar droplet. The hydrophilic part is
extended outwards. 'these hydrophilic 'brushes' are
responsible for the steric stabilisation of the droplets,
provided that the 'brushes' exceed a certain length. For
surfactant blends in common use, the optimum length of the
polymer hydrophobic chain, in order to be anchored into the
bilayer is in the order of C1z - Cls, about the length of
the surfactants in the droplet.
Thus, it is already well known to incorporate
deflocculating polymers in aqueous liquid detergents which
are structured with :l_amellar droplet dispersions. However,
in these conventiona.7_ compositions, the polymer is
incorporated in a base composition (i.e. the same
composition without t:he polymer) which is already stable
and pourable. EP-A- 346 995 defines, in practical terms,
the conventional def7_occulating effect as that of a polymer
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in a stable and pour,able composition whereby the equivalent
composition minus the deflocculating polymer, has a
significantly higher viscosity and/or becomes unstable.
In contrast, compositions according to the second aspect of
the present invention are such that the equivalent
composition at 25°C, without deflocculating polymer does
not have a significantly higher viscosity and is stable.
Preferably, the term "does not have significantly higher
viscosity" means that a shear rate of 21s-1, the difference
in viscosity is no more than 500 mPa.s, preferably no more
than 250 mPa.s.
Preferably, the term "stable" means that the composition
yields no more than 2o by volume visible phase separation
when stored at 25°C for 21 days from the time of
preparation, more preferably less than 0.1% by volume
visible phase separation when stored at 25°C for 90 days
from the time of preparation. Compositions according to
the present invention in any aspect are preferably "stable"
according to these definitions.
Thus, when any composition according to the present
invention comprises deflocculating polymer this may
comprise one or more deflocculating polymer materials
according to EP-A 346 995 and/or as recited hereinbelow.
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Generally, the amount: of material of deflocculating polymer
in a composition according to any aspect of the invention
will be from O.Olo to 5.0o by weight in the composition,
most preferably from 0.1~ to 2.Oo.
5
For example, EP-A-438 215 discloses preparation of acrylic
acid telomers with a functional terminal group, using a
secondary alcohol ch~iin transfer agent which may, for
example be a C6 - C1~ monofunctional secondary alcohol.
10 These materials are described as detergent additives, in
particular sequestrarnt:s or anti-precipitants. The
materials are produced using polymerisation initiators such
as ditertiary butyl peroxide. In the description of
various different poC>sible initiators, there is mentioned
15 lauryl peroxide.
Some specific kinds of deflocculating polymers which
contain only one hydrophobic moiety and which is attached
to an end position of'. a hydrophilic chain, are disclosed in
20 EP-A-623 670.
Various sub-types are described for the deflocculating
polymers in EP-A-623 670. However, many of those actually
exemplified are thio~_ polyacrylates, that is to say,
materials formed by polymerisation of acrylic acid in the
presence of a hydrophobic chain transfer agent having from
five to twenty five c<~rbon atoms and a terminal-SH group,
in a radical polymerusation process. Analagous materials
having a thia linkagE: between the hydrophilic and
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hydrophobic parts of the molecule are disclosed in US-A-5
489 395, US-A-5 489 397 and EP-A-691 399.
Another class of suitable deflocculating polymers comprises
oligomers or polyme r, of formu.La (I) as disclosed in our
unpublished international patent application WO 98/55576
Qi - X~. - ~.i - Z - W ( I )
wherein Q~- represents a hydrophobic moiety, -X1- and -Y1-
are independently Eeach absent o:r represent a suitable
linking group, -Z- represents a hydrophilic chain; and
-W represents hydrogen or a group of formula -Y2-Xz-Q2, each
of -X2,-YZ and -QZ being independently selected from the
values for X1, Y1 and Q1 as hereinbefore defined.
Preferably Q1 represE~nts an optionally substituted C5 - C3o
alkyl, C5-C3o alkenyl or C5-C3o aralkyl group, or a
hydrophobic monomer- residue, such as from lauryl
methacrylate or a hydrophobically modified TEMPO (2,2,6,6-
tetramethylpiperdinyl-1-oxy) moiety. Alkyl, alkenyl or
aralkyl groups most preferably have from 8 to 18 carbon
atoms and are preferably straight-chained or have only
limited branching. Preferably, X1 is absent or represents
a group of formula (-CHz-)n where n is 1 or 2 or X1 is
phenyl. Preferably,
Y1 is absent or represents a carbonyl group, an ester
linkage, a hydroxy C1._5 alkyl group or a silyl group of
formula (-SiRlR2) , where R1 and RZ independently represent
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-CH3 or-CZHS; or else Y~ is a thia-, aza-, carboxy- (i.e.
ester), carboxy-aza-, phosphoryl-, phosphonyl- or
phosphinyl- linkage, but then with the proviso that W is
not hydrogen.
The group -Z- is preferably a linear, branched or slightly
crosslinked molecular composition containing one or more
types of relatively hydrophilic. monomer units. Preferably
the hydrophilic monomers themselves are sufficiently water
soluble to form at least a to by weight solution when
dissolved in water. The only limitations to the structure
of -Z- are that the resultant polymer of formula (I) must
be suitable for incorporation in an active-structured
aqueous liquid detergent composition and that a polymer
corresponding to the hydrophilic. moiety alone, i.e. H-Z-H
is relatively soluble in water, in that the solubility in
water at ambient temperature and at a pH of 3.0 to 12.5 is
preferably more than 1 g/1, more preferred more than 5 g/1,
most preferred more l~han 10 g/1..
Preferably the group -Z- is predominantly linear; more
preferably the main chain of the backbone constitutes at
least 50o by weight, preferably more than 75%, most
preferred more than '~Oo by weight of the backbone.
The group -Z- is generally composed of monomer units, which
can be selected from a variety of units available for the
preparation of polymers.
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Examples of types of monomer units for inclusion alone or
in combination in -~;- are:
(i) Unsaturated C1-C~ acids, ethers, alcohols, aldehydes,
ketones or esters. Preferably these monomer units are
mono-unsaturated. Examples of suitable monomers are
acrylic acid, methac:rylic acid, malefic acid, crotonic acid,
itaconic acid, aconit:ic acid, citraconic acid, vinyl-methyl
ether, vinyl sulphonate, vinylalcohol obtained by the
hydrolysis of vinyl ~icetate, acrolein, alkenyl alcohol and
vinyl acetic acid. The corresponding salts, e.g. alkali
metal salts such as t:he sodium salt, are also included.
(ii) Cyclic units, either being unsaturated or comprising
other groups capable of forming inter-monomer linkages. In
linking these monomers the ring-structure of the monomers
may either be kept intact, or the ring structure may be
disrupted to form the backbone structure. Examples of
cyclic monomer units are sugar units, for instance
saccharides and glucosides; alkoxy units such as ethylene
oxide and hydroxy prapylene oxide; and malefic anhydride.
(iii) Other units, for example glycerol, polyalkylene
oxides) or unsaturated polyalcohol(s) .
Each of the above mentioned monomer units for inclusion in
-Z- may be substituted with groups such as amino, ammonium,
amide, sulphonate, sulphate, phosphonate, phosphate,
hydroxy, carboxyl and oxide groups.
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The group -Z- is preferably composed of one or two monomer
types but also possible is the use of three or more
different monomer types in one hydrophilic backbone.
Examples of preferred hydrophilic backbones are:
homopolymers of acrylic acid, copolymers of acrylic acid
and malefic acid, poly (2-hydroxy ethyl acrylate),
polysaccharides, cellulose ethers, polyglycerols,
polyacrylamides, polyvinylalcohol/polyvinylether
copolymers, poly sodium vinyl sulphonate, poly 2-sulphato
ethyl methacrylate, polyacrylamido methyl propane
sulphonate and copolymers of acrylic acid and trimethylol
propane triacrylate.
Optionally, the group -Z- may also contain small amounts of
relatively hydrophobic units, e.g. those derived from
polymers having a solubility of less than 1g/1 in water,
provided that the ov~~ral1 solubility of the hydrophilic
polymer backbone still satisfies the solubility
requirements as specified hereabove. Examples of
relatively water insoluble polymers are polyvinyl acetate,
polymethyl methacrylate, polyethyl acrylate, polyethylene,
polypropylene, polysi~;yrene, polybutylene oxide,
polypropylene oxide and polyhydroxy propyl acetate.
Preferred sub-classes of the oligomers or polymers of
formula (I) (hereina:Eter referred to as "materials of the
invention"), include :respectively, those where W is
hydrogen, those where W is -Y2-Xz-Q2, some or all of XZ' YZ
and QZ respectively differing from X1, Y1 and Q1 and those
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where W is -Y'-XZ-Q2, Xz, YZ and Q2 each being the same as
X1, Y1 and Q1.
If W is hydrogen, there is only a single hydrophobic moiety
5 attached to one end of the hydrophilic moiety. Such
materials are ideally suited as deflocculating materials.
If W is a group -Y'-Xz-Q~ then there is a respective
hydrophobic group at either end of the hydrophobic moiety.
Such materials may be employed for deliberate bridging of
10 lamellar droplets, e.g. to increase viscosity.
Of course, as mentioned above, often deflocculation is
needed to inhibit viscosity increase at high volume
fractions so that in principle, bridging can be .
15 undesirable. However', the bridging materials having a pair
of hydrophobic groups (W riot hydrogen) are within the ambit
of the present invention. For example, a predetermined
blend of materials of the invention may be used, comprising
one deflocculating material to control stability and one
20 bridging material to increase viscosity in a controlled
fashion.
The bridging material has, on average, more than one
hydrophobic (Q1/Qz) c~r_oups per molecule and preferably two
25 or more such hydrophobic groups. As a consequence the
molecular weight (Mw) of the bridging material is larger
than (x.Mi + Mo), preferably larger than (x.Mi + 2Mo) and
more preferably larger than 2(x.Mi + Mo), with x being the
molecular ratio between hydrophilic monomers and
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hydrophobic monome.r~~, Mi being the average molecular weight
of the hydrophilic groups and Mo the average molecular
weight of the hydrophobic groups.
The bridging polymer is preferably prepared using
conventional aqueous polymerisation procedures, but
employing a process wherein the polymerisation is carried
out in the presence of a suitable cosolvent and wherein the
ratio of water to cc',olvent is carefully monitored so as to
keep the polymer as i.t forms in a sufficiently mobile
condition and to prevent unwanted homopolymerisation and
precipitation of the polymer from the hydrophobic monomer.
The process of the invention provides a product which is
stable and clear and which exhibits no gelling or product
separation on standing. Suitable cosolvents are selected
from the group consisting of isopropanol, n-propanol,
acetone, lower (C1 t~~ C4) alcohols, esters and ketones and
wherein the water to cosolvent ratio is smaller than 1.5,
more preferably less than 1.0, more preferably less than
0.75, and especially less than 0.5.
The use of a better defined mixture of a deflocculating
material and of a bridging material allows a degree of
control of rheology n.ot possib:Le with the "cocktail" of
polymers resulting from the process of EP-A-346 995.
Nevertheless, it should be appreciated that any method of
forming either the deflocculating (W=H) or bridging (W= -
Yz_Xz-Qz) oligomers or polymers of formula (I) will not form
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1000 pure materials. However, sample oligomers or polymers
according to the present invention will have a high weight
percentage of oligome r or polymer species having a
structure of formula (I), although not necessarily all of
that percentage will have the same structure of formula
(I). Thus, a preferred sample or batch of oligomer and/or
polymer material the present invention may have at least
50o by weight o.f its total of oligomers and/or polymers
having the general formula (I) as defined in claim l, or
optionally, of any preferred sub-class of polymers or
oligomers of formula (I) as defined in the description or
any other claim. ''his weight percentage is more
preferably, in ascending order of preference, at least 650,
700, 750, 800, 850 or 90o by weight of the total batch or
sample.
Lamellar Droplets
The second and third aspects of the present invention apply
to the subset of compositions whereby the lamellar phase
comprises lamellar droplets.
The third aspect of the present invention relies on the
finding of being able to produce clarity by limiting the
size of a significant fraction of the lamellar droplets,
i.e. so that their D",9o is less than 2 microns, more
preferably less than 1.0 microns, e.g. less than 0.5
microns, still more preferably less than 0.2 microns, yet
more preferably less than 0.1 microns and especially less
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than 0.05 microns. 'The D~,9o of the droplets is defined as
90% of the volume o:E all droplets having a diameter smaller
than that indicated. The actual value of D~,9q for a given
sample may be determined by making electron microscopy
pictures of the liquid detergent composition at a
magnification of bei~ween 15,000 and 60,000 (preferably
about 30,000) and determining the relative number of
droplets of each diameter and calculating from the obtained
cumulative diameter .size distribution the cumulative volume
size distribution or by laser light scattering particle
sizers such as the Malvern Mastersizer.
The D~,9o of the draplets can be brought to below the
critical value, for example by incorporating deflocculating
polymer in accordance with the second aspect of the present
invention, or by using as part of the surfactant blend, so-
called stabilising :>urfactants as disclosed in EP-A-328
177. Other ways of producing small lamellar droplets of
the defined size include processing routes where high shear
conditions are used to apply high fluid stresses. This
will be explained in more detail hereinbelow in the section
relating to processing.
Refractive Index
The fourth aspect of the present invention requires the
refractive index of the lamellar phase and that of the
aqueous phase to be substantially matched in such a way
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that the composition has an optical transmissivity of at
least 5%.
The refractive index of the lamellar phase (nlam) can be
calculated by using 'the refractive index of each component
(nk) in the lamellar phase and the volume fraction (Vk~Vlam)
by which that componE=nt is present in the lamellar phase
using:
1 n 2 ~1
nlam - 1 * ~ _ nk - 1
~2 + 2 lam ~ 2 vk
lam k-1 'nk + 2
The refractive index of the liquid detergent composition as
a whole can for examp:Le be determined as follows. Light
having a wavelength o.f 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 calculated by using the Snellius equation. Another,
preferred method to determine the refractive index is by
using internal reflection measurements, for example by
using an Atago digital refractometer RX-1000 or a
Bellingham and Stanley refractometer RFM91. The use of
internal reflection measurements is especially advantageous
for determining the refractive index for opaque systems.
The refractive index of the corresponding aqueous phase can
be measured by isolat::ing the aqueous phase from the
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detergent composition (e.g. by (ultra-) centrifugation) or
by separate preparation of a composition, whereby the
insoluble ingredient; are only added to their solubility
limit and the disper:~ad phases are omitted.
5
Preferably, the difference between the refractive index of
the lamellar phase and the aqueous phase is no greater than
0.02, more preferably no greater than 0.01, still more
preferably no greater than 0.005 and especially no greater
10 than 0.002.
To achieve substantia_L refractive index matching, the
refractive index of t;he aqueous phase can be increased
and/or the refractive index of the lamellar phase can be
15 decreased.
The refractive index of the aqueous phase may be increased
by dissolving therein materials. However, often the added
materials which resu7_ts in a refractive index increase,
20 affect the physical stability of the system, like
electrolyte or hydrot:rope. Other relatively low molecular
weight materials may not significantly affect the stability
or viscosity of the composition, although there will be
some effect because being an additional component of the
25 aqueous phase, it wi~_1 inevitably affect the volume
fraction of the lame~_lar phase and/or the viscosity of the
aqueous phase. Often these components are neutral non-
electrolytic materials of relatively low molecular weight.
Especially useful to increase the refractive index of the
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aqueous phase without negative effects on the properties of
the total system, is a sugar (as required by the fifth
aspect of the present invention) since such a material is
both effective and has relatively low cost.
However, in general, water soluble non-electrolyte
materials for i.ncre~~sing the refractive index of the
aqueous phase may b~~ selected from sugars and cellulose
derivatives contai.n.ing one or more hydrophilic substituents
to make them water ;soluble.
Suitable sugars include mono saccharides such as glucose
and fructose, disacc:harides such as saccharose, sucrose,
lactose, maltose anc~ cellobiose. Glucose syrups can also
be employed. These contain mixtures of mono, di and
polysaccharides. Preferably the mono and disaccharide
fractions of the carbohydrate mix should be at least 50%.
As mentioned above, it is already known to use non-sugar
polyols such as glycerol or sorbitol, in minor amounts in
aqueous liquid detergents, for enzyme stabilisation. Such
materials may also be employed in the compositions
according to the present invention for refractive index
matching but the amounts will be higher than for enzyme
stabilisation, e.g, as specified hereinbelow.
Also useful for refractive index matching, although less
preferred, are polysaccharides such as water soluble gums,
e.g. guar gum, xantl~an gum, arabic gum and tragacanth,
because these ingredients increase the viscosity of the
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total system when added in appreciable amounts for
refractive index matching.
A further class of useful materials to increase the
refractive index of the aqueou~> phase are polyols, such as
glycerol and polyethylene glycol.
The amount of water aoluble non-electrolyte material in the
composition will be ~~hosen as that required to effect the
substantial refracti~~e index matching. However the minimum
will amount typically/ be 2.50, preferably 50, especially
10%, by weight of thc~ total composition. The maximum
amount of water soluble non-electrolyte material is
typically 50%, preferably 40%, especially 30o by weight of
the total compositlOll. If it is desired to specify a
particular range of i~hese amounts, any specified minimum
value may be paired with any specified maximum.
Detergent Active Material
The refractive index of the lamellar phase may be reduced
by choosing an appropriate surfactant or blend of
surfactants. One su=Ltable approach is to substantially
exclude aralkyl surfactants such as alkyl benzene
sulphonates, i.e the total of aralkyl surfactants should be
less than 300, preferably less than 100, more preferably
less than 50, and especially less than to by weight of the
total surfactants (including any soap). Most preferably,
such aralkyl surfactants are completely absent.
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To formulate a surfactant blend suitable for forming a
lamellar phase without using aralkyl materials, one may,
for example, employ ~~ blend of primary and/or secondary
alkane sulphate or sulphonate material together with one or
more nonionic surfactants.
Examples of suitable alkane sulph(on)ates are sodium and
potassium alkyl sulpl-~ates, especially those obtained by
sulphonating higher (Ce-C1~), primary or secondary alcohols
produced, for examplf~, from tallow or coconut oil.
Suitable nonionic suofactants include, in particular, the
reaction products of compounds having a hydrophobic group
and reactive hydrogen atom, for example aliphatic alcohols,
acids, amides 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 with ethylene oxide,
and products
made by condensation of ethylene oxide with the reaction
products of propylene oxide and ethylenediamine. Other so-
called nonionic dete~__°gent compounds include long chain
tertiary amine oxides, long-chain tertiary phosphine oxides
and dialkyl sulphoxides.
Preferably, the weight ratio at the total alkane
sulph(on)ate materia~~ to the total nonionic material is
from 90:10 to 10:90, more preferably from 80:20 to 50:50.
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Another suitable surfactant blend for this purpose
comprises one or more soaps with one or more nonionic
surfactants.
Suitable soaps include alkali metal soaps of long chain
mono- or dicarboxylic: acids for example one having from 12
to 18 carbon atoms. Typical acids of this kind are oleic
acid, ricinoleic acid and fatty acids derived from castor
oil, rapeseed oil, groundnut oil, coconut oil, palm kernel
oil or mixtures thereof. The sodium or potassium soaps of
these acids can be used.
Suitable nonionic surfactants to blend with the soap are
mentioned above. Preferably, the weight ratio of the total
soap to the total nonionic material is from 60:40 to 90:10,
more preferably from 70:30 to 80:20.
In other preferred compositions, part or all of the
detergent active material is a stabilising surfactant,
which has an average alkyl chain length greater then ~ C-
atoms, and which has a salting out resistance, greater
than, or equal. to 6.4. These stabilising surfactants are
disclosed in EP-A-328 177. Examples of these materials are
alkyl polyalkoxylated phosphates, alkyl polyalkoxylated
sulphosuccinates; dialkyl diphenyloxide disulphonates;
alkyl polysaccharides and mixtures thereof. The advantage
of these surfactants is that they are surfactants with a
relatively low refractive index and these surfactants tend
to decrease the droplet size of the Iamellar droplets.
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Both effects have a positive effect on the clarity of the
systems.
However, aside from any desire to formulate the surfactant
5 content to reduce t:he refractive index of the lamellar
phase, in the widest sense, the detergent-active material
in the composition, in general, may comprise one or more
surfactants, and may be selected from anionic, cationic,
nonionic, zwitterionic and amphoteric species, and
10 (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, l, by Schwartz & Perry, Interscience 1949 and
'Surface Active Agents' vol. II by Schwartz, Perry & Berch
15 (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, Mi.inchen & Wien, 1981.
In many (but not all) cases, the total detergent-active
material may be present at from 2o to 60o by weight of the
total composition, for example from 5% to 40% and typically
from 10% to 30% by weight. However, one preferred class of
compositions comprises at least 150, most preferably at
least 25% and especially at least 300 of detergent-active
material based on the weight of the total composition. In
the case of blends of surfactants, the precise proportions
of each component which will result in such stability and
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36
viscosity will depend on the types) and amounts) of the
electrolytes, as is the case with conventional structured
liquids.
S Common anionic surfa~~tants are usually water-soluble alkali
metal salts of organic sulphates and sulphonates having
alkyl radicals containing from about 8 to 22 carbon atoms,
the term alkyl being used to include the alkyl portion of
higher acyl radicals.
Aside from anionic surfactants already mentioned with
regard to refractive :index control, where appropriate, one
may still employ conventional sodium and potassium alkyl
(C9-C2o) benzene sulphonates, particularly sodium linear
secondary alkyl (Clo-415) 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. Other suitable
anionics include sodium coconut oil fatty monoglyceride
sulphates and sulphonates; sodium and potassium salts of
sulphuric acid ester: of higher (C6-C1$) fatty alcohol-
alkylene oxide, particularly ethylene oxide, reaction
products; the reaction products of fatty acids such as
coconut fatty acids c:sterified with isethionic acid and
neutralised with sodium hydroxide; sodium and potassium
salts of fatty acid amides of methyl taurine; alkane
monosulphonates such as those derived by reacting alpha-
olefins (Ca_ZO) with sodium bisulphate and those derived
from reacting paraffi.ns with SOZ and C1z and then
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hydrolyzing with a :base to produce a random sulphonate; and
olefin sulphonates, which term is used to describe the
material made by reacting olefins, particularly Clo-C2o
alpha-olefins, with S03 and then neutralising and
hydrolyzing the rea~~tion product.
G7 -. ~ r. ,-
Preferably the amount of water in the composition is from 5
to 950, more preferred from 25 to 750, most preferred from
30 to 500. Especia_Lly preferred less than 45% by weight.
Electrolyte
Although it is possilale to form lamellar dispersions of
surfactant in water alone, in many cases it is preferred
for the aqueous coni:.inuous phase to contain dissolved
electrolyte. As used herein, the term electrolyte means
any ionic water-soluble material. However, in lamellar
dispersions, not. a.11 the electrolyte is necessarily
dissolved but may be suspended as particles of solid
because the total electrolyte concentration of the liquid
is higher than the solubility limit of the electrolyte.
Mixtures of electrolytes also may be used, with one or more
of the electrolytes being in the dissolved aqueous phase
and one or more being substantially only in the suspended
solid phase. Two or more electrolytes may also be
distributed approximately proportionally, between these two
phases. In part, this may depend on processing, e.g. the
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order of addition of components. On the other hand, the
terms 'salts' includes all organic and inorganic materials
which may be included, other than surfactants and water,
whether or not they are ionic, and this term encompasses
the sub-set of the electrolytes (water-soluble materials).
However, there is a limit to the size and amount of non-
dissolved (i.e. suspended) electrolytes in these
formulation which is consistent with the objective of
clarity. The amount of small particles which are not
vis-ible as separate entities should be so low that ~he bulk
of the liquid remains substantially clear in accordance
with the definition of the first aspect of the present
invention. The amounts of relatively large particles (i.e.
visible as separate entities) should be such that they have
. a pleasing visual effect like the aforementioned "visible
solids" .
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. Thus, within
the ambit of the present invention, a very wide variation
in surfactant types and levels is possible. The selection
of surfactant types and their proportions, in order to
obtain a stable liquid with the required structure will be
fully within the capability of those skilled in the art.
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Preferably, the compositions contain from 1% to 60%,
especially from 10 to 95% of a salting-out electrolyte.
Salting-out electrolyte has the meaning ascribed to in
specification EP-A-79 646. Optionally, some salting-in
electrolyte (as defined in the latter specification) may
also be included, provided if of a kind and in an amount
compatible with the other components and the composition is
still in accordance with the definition of the invention
claimed herein. Some or all of the electrolyte (whether
salting-in oz salting-out), or_ any substantially water-
insoluble salt which may be present, may have detergency
builder properties. In any event, it is preferred that
compositions according to the present invention include
detergency builder :material, some or a1.1 of which may be
electrolyte. The builder material is any capable of
reducing the level of free calcium ions in the wash liquor
and will preferably provide the composition with other
beneficial properties such as the generation of an alkaline
pH, the suspension of soil removed from the fabric and the
dispersion of the fabric softening clay material.
Detergency Builder
As already mentione~~, water soluble inorganic detergency
builders (if dissolved in the aqueous phase) are
electrolytes but any solid material above the solubility
limit will normally be suspended by the lamellar phase.
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Examples of phosphorous-containing inorganic detergency
builders, when present, include the water-soluble salts,
especially alkali metal pyrophosphates, orthophosphates,
polyphosphates and phosphonates. Specific examples of
5 inorganic phosphate builders include sodium and potassium
tripolyphosphates, phosphates and hexametaphosphates.
Phosphonate sequesi~zant builders may also be used.
Examples of non-phosphorous-containing inorganic detergency
10 builders, when present, include water-soluble alkali metal
carbonates, bicarbonates, silicates and crystalline and
amorphous aluminosili.cates. Specific examples include
sodium carbonate (wit.h or without calcite seeds), potassium
carbonate, sodium and potassium bicarbonates, silicates and
15 zeolites, although there are restrictions with respect to
the amount and volume fraction of solid particles which can
be added while retaining substantial clarity.
In the context of inorganic builders, we prefer to include
20 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 UK patent
25 specification GB 1 302 543.
Examples of organic detergency builders, when present,
include the alkaline metal, ammonium and substituted
ammonium polyacetat:es, carboxy:Lates, polycarboxylates,
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91
polyacetyl carboxylates, carboxymethyloxysuccinates,
carboxymethyloxymalonates, ethylene diamine-N,N-disuccinic
acid salts, polyepo};ysuccinates, oxydiacetates, triethylene
tetramine hexa-acetic acid salts, N-alkyl imino diacetates
or dipropionates, a1_pha sulpho- fatty acid salts,
dipicolinic acid salts, oxidised polysaccharides,
polyhydroxysulphonat:es and mixtures thereof.
Specific examples include sodium, potassium, lithium,
ammonium and subst:it:uted ammonium salts of ethylenediamino-
tetraacetic acid, nitrilo-triacetic acid, oxydisuccinic
acid, melitic acid, benzene polycarboxylic acids and citric
acid, tartrate mono succinate and tartrate di succinate.
In the context of organic builders, it is also desirable to
incorporate polymers which are only partly dissolved in the
aqueous continuous ~~hase. This allows a viscosity
reduction (owing to t:he 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 ~>ubstantially all were dissolved). As
for inorganic builders, the same restrictions apply with
respect to the amour..t: and volume fraction of non-dissolved
polymer phase which can be added while retaining
substantial clarity.
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Other Polymers
Examples of partly dissolved polymers include many of the
polymer and co-polymer salts already known as detergency
builders. For example, may be used (including building and
non-building polymers) polyethylene glycols, polyacrylates,
polyma:Leates, polysugars, polysugarsulphonates and co-
polymers of any of these. Preferably, the partly dissolved
polymer comprises a c.o-polymer which includes an alkali
metal salt of a polyacrylic, polymethacrylic or malefic acid
or anhydrides Preferably, compositions with these co-
polymers have a pH of above 8.0 In general, the amount of
viscosity-reducing polymer can vary widely according to the
formulation of the rest of the composition. However,
typical amounts are from 0.5 to 4.5o 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 resistance of more than 5 grams sodium
nitrilotriacetate in 100 ml of a 5o by weight aqueous
solution of the polymer, said second polymer also having a
vapour pressure in 20o aqueous solution, equal or less than
the vapour pressure of a reference 2o by weight or greater
aqueous solution of polyethylene glycol having an average
molecular weight of 6,000; said second polymer having a
molecular weight of at least 1,000.
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The incorporation of the soluble polymer permits
formulation with improved stability at the same viscosity
(relative to the composition without the soluble polymer)
or lower viscosity with the same stability. The soluble
polymer can also reduce viscosity drift, even when it also
brings about a viscosity reduction. Here, improved
stability and lower viscosity mean over and above any such
effects brought about by the deflocculating polymer.
It is especially preferred to incorporate the soluble
polymer with a partly dissolved polymer which has a large
insoluble component. That is because although the building
capacity of the part:Ly dissolved polymer will be good
(since relatively high quantities can be stably
incorporated), the viscosity reduction will not be optimum
(since little will bc~ dissolved). Thus, the soluble
polymer can usefully function to reduce the viscosity
further, to an ideal level.
The soluble polymer can, for example, be incorporated at
from 0.05 to 20% by weight, although usually from 0.1 to
loo by weight of the 'total composition is sufficient, and
especially from 0.2 to 3.5 - 4.5o by weight. It has been
found that the presence of deflocculating polymer increase
the tolerance for higher levels of soluble polymer without
stability problems. A large number of different polymers
may be used as such <~ soluble polymer, provided the
electrolyte resistance and vapour pressure requirements are
met. The former is measured as the amount of sodium
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nitrolotriacetate (NaNTA) solution necessary to reach the
cloud point of 100 m7_ of a 5o w/w solution of the polymer
in water at 25°C, with the system adjusted to neutral pH,
i.e. about 7. This is preferably effected using sodium
hydroxide. Most preferably, the electrolyte resistance is
g NaNTA, especial~.y 15g. The latter indicates a vapour
pressure low enough t:o have sufficient water binding
capability, as generally explained in the applicants'
specification GB-A-2 ()53 249. Preferably, the measurement
10 is effected with a rEeference solution at loo by weight
aqueous concentration, especially 180.
Typical classes of pc>lymers which may be used as the
soluble polymer, provided they meet the above requirements,
include polyethylene glycols, Dextran, Dextran sulphonates,
polyacrylates and pol.yacrylate/maleic acid co-polymers.
The soluble polymer must have an average molecular weight
of at least 1,000 but. a minimum average molecular weight of
2,000 is preferred.
The use of partly soluble and the use of soluble polymers
as referred to above in detergent compositions is described
in our European patent specifications
EP-A-301 882 and EP-A--301 883.
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
Hydrotropes
Although it is possible to incorporate minor amounts of
hydrotropes such as lower alcohols (e.g. ethanol) or
5 alkanolamines (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 hydrotrope:~. By hydrotrope is meant any water
soluble agent which tends to enhance the solubility of
10 surfactants in aqueous solution.
Other Optional Ingredients
Apart from the ingredients already mentioned, a number of
15 optional ingredients may also be present. Enzymes,
optionally together with enzyme stabilises may be
incorporated. Enzymes in encapsulated form, as a visually
distinct suspended component have already been mentioned
hereinbefore.
Other optional ingredients include lather booster such as
alkanolamides, particularly the monoethanolamides derived
from palm kernel fatty acids and coconut fatty acids,
fabric softeners such as clays, amines and amine oxides;
lather depressants, oxygen-releasing bleaching agents such
as sodium perborate and sodium percarbonate; peracid bleach
precursors, chlorine-releasing bleaching agents such as
trichloroisocyanuric acid, inorganic salts such as sodium
sulphate, and, usually present in very minor amounts,
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
46
fluorescent agents, perfumes, germicides and colourants,
oily-soil release polymers, such as Poly Ethylene
Terephthalate - Poly Oxy Ethylene Terephtalates or (partly)
sulphonate versions thereof (including Permalose and
Aquaperle (Trademarks) ex. ICI, Gerol and Repe-0-Tex
(Trademarks) ex. Rhone-Poulenc and Sokalan HP22 (Trademark)
ex. BASF); anti-rede~>osition agents, such as sodium carboxy
methyl cellulose; ant.:i-dye transfer agents, such as PVP,
PVI and co-polymers thereof.
Amongst these optional ingredients, as mentioned
previously, are agents to which lamellar dispersions
without deflocculatir~g 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 in the absence of deflocculating polymer
because they tend to promote flocculation of the lamellar
droplets. Examples of such agents are soluble polymers,
soluble builders such as succinate builders, fluorescers
like Blankophor RKH, Tinopal LMS, and Tinopal DMS-X and
Blankophor BBH as well as metal chelating agents,
especially of the phosphonate type, for example the bequest
range sold by Monsanto.
Processing
Compositions of the invention may be prepared by any
conventional method for the preparation of liquids
detergent compositions. A preferred method involves the
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
47
dispersing of the e7.ectrolyte ingredient (if present)
together with the minor ingredients except for the
temperature sensitive ingredients (if any) in water of
elevated temperature, followed by the addition of the
builder mate vial (if'- any), the detergent active material
under stirring and thereafter cooling the mixture and
adding any temperature sensitive minor ingredients such as
enzymes, perfumes etc. The deflocculating polymer (where
used) may for examplE: be added after the electrolyte
ingredient or as the final ingredient.
The manner of preparation and of treatment post processing
can materially influence the optical transmittance and
clarity of the compo-sition produced. In particular the use
of high shear conditions (preferably at least 10,000s-1) to
apply high fluid stresses and facilitate the production of
small lamellar droplets is preferred for the second and
third aspects of the invention. The high shear conditions
(where ~~shear" refers to deformation rates involving either
or both shear or extensional deformations) can be applied
during the preparation, for example during the formation of
lamellar droplets stage.
Thus, a sixth aspect of the present invention provides a
process for preparing a composition according to any one or
more aspects (but especially the second and or third
aspects) of the present invention, the process comprising
mixing at least some of the ingredients of the composition
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
4 f3
at a shear rate of at= least 10,OOOs-1 and then admixing the
resultant composition with any remaining ingredients.
High fluid stresses and consequent smaller lamellar
droplets created by application of high shear during the
preparation ar_e enhanced by employing mixes of higher
viscosity. To this end, it is preferable to add the sugar
component (if present:) prior to the surfactants in order to
thicken the mix at the point of formation of the lamellar
droplets. However, due regard has to be given to the
chemical sensitivity of the sugar. For example pH
sensitive sugars such as fructose should not be exposed to
extremes of pH during the preparation.
Higher viscosity mixes can also be generated by withholding
some of the process water in order to apply the high shear
step to a concentrate of the final product followed by a
dilution step, for example as part of the process described
in the specification of patent application WO 96/20270.
Alternatively the high shear conditions can be applied to
the final composition after preparaton. High shear may be
applied by a static device, for example a shear valve such
as a Saunders diaphragm valve. Preferably it is applied by
a dynamic device such as a dynamic mill. Examples of such
devices include those manufactured by Silverson, Fryma or
Janke & Kunkel and that described in the specification of
patent application W'O 96/20270. Preferably the shear
device should be located in line in order to minimise
aeration of the composition which would detract from the
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
99
optical transmittance and clarity. In the event that the
composition becomes substantially aerated a de-aeration
step, such as centrifugation, can be incorporated into the
preparation.
The following examples are intended to further illustrate
the invention and are not intended to limit the invention
in any way:
All percentages, unless indicated otherwise, are intended
to be percentages by weight.
All numerical ranges in this specification and claims are
intended to be modified by the term about.
Finally, where the term comprising is used in the
specification or claims, it is not intended to exclude any
terms, steps or features not specifically recited.
EXAMPLES
The invention will now be illustrated by way of the
following Examples, in all Examples, unless stated to the
contrary, all percentages are by weight.
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
Ingredient , by weight
(if not otherwise
stated)
Comparitive Ex. Ex. 2 Ex.
1 3
example
Nonionic, 3..0 3.0 3.0 3.0
Synperonic A7
Oleic acid, 7"() 7.0 7.0 7.0
Priolene 6907
NaOH, to pH ~ 9.0 0.99 0.99 0.99 0.99
STP _ 12__.5 12.5 12.5 12.5
Deflocculating 1.0
polymer (1)
Water up to 100 up up to up to
to
1000 100% 100
-
Saccharose g added 20 90 20
on top
Stability _OP;_ OK OK OK
Viscosity 150 E 320 340 690
(mPa.s at 21 s-1)
Optical 0.2 12 96 66
transmissivity
(~)
at 520nm
These examples show:
- sample without deflocculating polymer is stable
- addition of sugar increases the clarity
5 - on addition of deflocculating polymer more clarity is
obtained
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
51
0
0
r O
~o W
0 o m 0 0
x N C1 o x ao av
W r M O r-1r-t~ Q O l''7f-1
~o
O
O
r-1
i
O
O O OO O O N
~ O ~ O
W r M O r-1~ --i O ~ a1
O
dp
.-1 O
O
-ri
N
~1
r-I
O
R. " ~ ~ i~
~ r
E Og0 00 O N
b
O . N
x ~
U rrr~ o ~ p ~ o
N
N
m i
O
O toO a--i
' o~
O 00 ', O O aD
O O
- I
3 W r II,~~ ~ v O vo ~o O
r1 o ~ ~
1r
JJ I
O
I
~ v ~ O
O 'o ~
c ~ ow
G O N ~~ o O
O ~, o
x '~ ~ tooo W n
W W r O l ~ N O to lD
I M r-~ ,-a -1
i
i
A I
tT -rl O
-.~ J-~ O N
N -ri ~ ri
N
~
3 to
~ .>a
~ W ' O ~
. oo + + ~r o
' .~ t
ro o 00 m o ,-i
0 -
o . .. R. G o
x . i
ow U r o~ ~ D <r o n
N c~ '
!
r
N
+~
U .,
I
.,1
C .-i -
O o O .-,v~
i O, .-itn .-.
N
N oo CI' I .~1 V~
~ y ~ p O ~ ~
I t ~ t O
-.-i +~ +~ .~ C s~
c~ x +-~ . N r0 U
; ~
a I GL v ro nt ~ s~ -.-~
~ o
C ' .1--W-1 V7 O 7,~, J-~
N ~'i O +~ N
I'~
!
U
,, O rt1~ O N W -.~~n ~-
--1 ~ +3 1-~U N f>)-.iN --I
.,-.~ 'O T3 -ri
~
.,~
'a ~ W U N O .-Icn rtf
U ~ ~ tn ~
'~
C
N ! .1O !a ..C~ -.1O U O
r0' 'LJ'O ~
O
i x U .-iv U U .C7U -.-iav
I TJ T3 rtf
"--I
o' cn'~ oa~~ w .,~a ~ rov, v
~ ..-. ro ro w ..,
c ~', roE-~roa~ ro ro ~ +~-.~oa
o r-, ~ ~
a zm z o ;~ ~n ts,cn5 o o
~, -- ~.~ow -- ~-
z
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
52
These examples show:
- sample without- deflocculat.ing polymer is stable
- addition of sugar increases the clarity
- on addition of deflocculating polymer (much) more
clarity is obtained
- effect is not restricted to saccharose
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
~3
N
.-t O
O O O l0 O O O
x . . . ,~. Q, O x !'~ (~'1
O
W tf1f-1N O .-~,--aa ~a O vW fl
.-i
r1
O
n-1 O .1-~
d
O O O l0 O O O
~. (~ O x 07 rl
O
W uW~o N O r-t.-i ~ N O v tf~
.-I
1
O
N '- O
~
r-i O 1
~
da
O O O l57 O O O 00
x . . . ,~
O '.Gri
W tW'~1N O .-t.-i ~ O ~ 00
-rl
3 ~ O
f .-i o +~
a
o o o ~o o 0
!
x . . . . r;
~
W m m N O ~ ~ ~ O N
O
+~
O c~
r-1 O -IJ
ow
O O O lD O O N
C~ O x .--i
O
-rlW u-1(~1N O ,~ ~ N O N t!7
+~ N
'
b ~ ow
!
CT -rl ~ O
~
'..I.1-i O
'~~
N ~
N
I
3 sa
.-i
i
,
ro ! o
a,
~
,
.L7~ O O t0 O N
ro I
~ O
o . . ,-~ a, ~ b,
x .
w U u~ro o ~ 7 p ,-i o
v N
I ~ O ~
r- t +
, ~
U
, -r1 +J .-1
FG
;
O
o x +~ ~ N 5
-- G
p, ro a~ -~I
~i ,--, ~ o
~
C ~ ,--I cn a,>, tn
- - O +~ N
v 'OU O ~ O ~ 1~ u7
C; ro u7
~
-~a~ -,-I-.-I 1~ U 1a -.-I-.-W-1
O S-a 'L3 -rl
I
O
'L7, U , U ro ~ ~ ro
G N N ~ ~
~i
~,
R,
s roO . O i~ 1: -.iO U
a~ ~ T1 c
! r7
O ro
~
I .-~ x .-i N t) .C~U -rl
C~ TJ ro G
U --
CT 1 (nG O 0.iW +~ U roU7 +~
c~ u'1 rl ro W ro
~ .-~ -.
C7
~
~CO ro E-~O ro ro ~ ~ p,
>,j O rl S-I
P~ ~ ow
rt I
-7Z Z tnCa 3 u~ u~' O
vl,, oo C1, M ~- i-~
r.~ cn ~-
C7
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
54
Ingredient ~ by weight
(if not otherwise
.stated)
Compar:iti.veEx. 13
example
_ _
LAS-acid '> . 0 5 . 0
_ _
Nonionic, 3.0 3.0
Synperonic
A7
APG, ?.0 2.0
Glucopon 600CS_
NaOH, to pH 0.61. 0.61
~
Na-citrate. 12.5 12.5 .
2aq _
Deflocculating 1.0
polymer (1)
Water up to 100$ up to
_ 100$
Saccharose, 4D
~ added on _
top
Stability OK _ OK
Viscosity _ 590
200
(mPa.s at 21
s-1)
Optical 0.13 16
transmissivity
at 520nm
Ingredient part~~
by weight
..__ (~.f
not otherwise
state.d)
Ex. l. Ex. 15
4
LAS-acid _ 14.1
_
9.9 _
LES 15 10
NaOH _ 1.72
1.15 _
Na-citrate. 2aq _ 17.1
17.1
Deflocculating 0.25 ~ 0.25
polymer (2)
Water up to up to 7.00
100
Stability OK OK
Viscosity 6170 ~ 6980
(mPa.s at 21 s-1)_
__
Optical 35 10
transmissivity
at 520nm
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
Raw materials
LAS-acid approx C12 alkyl benzene sulphonic
5 acid, ex Hu:ls
LES Sodium lauryl ether (approx. 3 ethylene
oxide) sulfate,
Manro Bes 70 ex Hickson Manro
10 Synperonic A7 C13-15 alcohol, ethoxylated with 7 EO
groups, ex ICi
Oleate friolene 6907, ex Unichema
15 APG Alkyl PolyGlucoside, Glucopon 600CS ex
Henkel
STP Sodium Tri (Poly) Phosphate, Thermphos
NW, ex Knapsack
20 or Sodium Tri (Poly) Phosphate, Rodia-
phos HPA-3.5, ex Rhone Poulenc
Na-citrate.2aq Sodium citrate ex Merck
25 Deflocculating
polymer (1) Polymer A11 from EP 346,995, ex
National Starch
Deflocculating
30 polymer (2) Marchon XB 16, ex Albright & Wilson
Saccharose ex Cooperatieve Suiker
Maatschappi.j, The Netherlands
35 Fructose ex Merck
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
56
The following examp_Les all. illustrate the beneficial
influence of applying shear to generate transparency. In
examples A and B shear was applied to final product using a
Silverson LN4 dynam«c mill on maximum setting for 10
minutes. Samples were then centrifuged to remove air.
Examples 16-19 - various concentrations of glucose +
Silverson. Shear rate approximately 50,000 sec-1.
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
57
o do cn ao .-,
'
rM m . o o tn .v o
x ro
v
~n . o . 0 o vx o r
0 v
~f
W ~ rM r r-1~ l~ 11 Y~O G d f-i
, m ~
~
I
N N ow rtl N
N .1 O ~ S-f
b O. o
~
l1n ~9 O -i -~ Ul
v ~
~ rtI rM <n O
o-.I .. . o . 0 0 ox o
x ~
U +~ rM o ,~,-~ am n zO G
N ~
I
~o o d~ m ~o m
-C~
rM m O O cn .f.~ M
td
Q7
x ~ O O O Nx O O .
O N
fN
W ,~ r~M c~ ~-f~ a a~ ?O t~ ~r .-f
~f ~
~
I ( -O
ro v ~ v
~-I o
a ,~
~
. v ~o o ~ m
-b
rM ca o +~ ov a
rt3 N
N
O -ri o O O O',~O O
x N N
N
U +~ rM c~ ~ .-i ~ v~ zO G ~ C
N ~
~
i
~o O ow tn ao
'O
rM m . o o v~ -a . o~
ro
v
x ~ -- . o . 0 o vx o o
0 v
s~
W ~ rM o ,-i.-m .f M ?~O ~ M o
.-i ~
~
W Ly
~
c~ N ~w
f., o
.-I
d
G1 ~ o f
~ w o .--a m
O. N y
~ ~
~ r0 rM ca o ~ ~o ~
a rt1 to
~ x N
O
-. O O o Oa4O O
' ' N N
Sa
U -a rM o ,-i.~ N M zo 1~ ~ G
v ~
~
I
m o ea m m d.
W
rM ca o o tn ~ . ,-,
~ c~
v
x r o O o Nx O r
o N
>~
O W .-n rM O r1.-i .1.~N Y~O ~ N .--f
.-1 ~
~
-r-I
3 I
N to v
v S-t O
r-1
.~ t0 O. I
C1n 1D O r-i (/7
N ~ '~
5 ro rM ao o
N
o .~, .. . o . 0 0 ox o .
x ~
~
U ~ rM o ~ ,--iN N zO >~ N c
v ~
~
o
I
~0 0 oa cn 00 0~
't3
-'~ rM m o o tn a..~ . r,
rd
ry
x ~ . . o . 0 o vx o ~
- 0 v
s~
w ~ 'M o ,--f,-f f .-y.o ~ -f '-,
~ ~
.-a ~
x a
-r-II w
v ~s v
3 s~ ~ o
'o ~
u "
~
>, . v ~ o ~
. ~ rM oo . o T3 , u~
ta O ~
N ~ P rt1
t0 W
~
. o -.~ . . o . 0 0 ox o
+~ x v
sa
ow U +~ rM o .-~,-f N -I zO 1~ ,-m n
m a~ ~
~ ~
t G O
r -.-f ~ ,-,
I '>~ .t-i N D
~
+~ !! m O, N ~ t~ ~I
U
C F . 1W-i O ? W, U7
N G~ .y~
N ~'L3 U O N ~ +~+m0 of
.-I-1 -I aJ i-1U N b.i.-I .-1
r-i S-a O --i
X
'U ' U C ~ U ~ v.-itn N
O O O t11
N
O t0 O ~ -.-IO 1.1 O 1-f-.1O U O
G ~ 'O tn
r-i
1-iI -~ :x U .-I N U rt1C7U -~i Ov
t0 N T3 r0 C
--
CT !n C O I W al ~ vt(fUI +~
.4 .-i f6 (1ml t0
f0 --~
c o ro m v ra .--I.ca ..-, o.
o o ~ s~
z I wo
.a 2 T z f~ :~ C~ crWn ;~ O D
fj r I1 ow -- a
v of v
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
58
Examples 20-22 different sugars + Silverson (shear rate ca
50,000 sec-1). This further illustrates the benefits of
shearing and also .il.lustrates the benefit of higher mono-
and di-saccharide cc>ntents in commercial 'glucose' syrups.
It also demonstrates that shearing in the absence of sugar
addition (partial refractive index matching) is not
sufficient.
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99109377
59
v
ap v v
N O S'I Sa
N O
tDG .-1 U1 N fn
~ r M co o ~n +~ .aJ
b it
x o o o v x o N o
~ v v
W r M O .-ir-~JJ i.(~~ O G N S~
~-' ~
'U 'O 't3
N N
l1 S-1 S-1
-
ro on ~o as ro
v
s., o c v v v
.-I
rt o o a~
a,
p, y o c~ ~ b
-.~
rd r M oo o In!~ +~ +.~ +~
a.~
o o o o v v 0 0 0
x r~
U r M o f-~~ W n ~ v7 C ~ S~
N sa
o~
-1 O
N O
lDC> rl ~f1 111
r M OD O U7 O N
x O. ~ o v x ~n o .
W r M O r-i~-i~ u> >-O ~ -I .-i
-.1
l~
ro
v
sa o
rl
b o
p,
na W o o --i
N r M ao.0 0 0 0~
o o 0 0 o x ~o
x
U r~M o ~a~I +~ ~n z o ~ N
v
b
v
ro
+~0 0
tnN O
lQQ r-1 O v-1
v r M OD O U7 O O
m X ' O O O N x r M
-~IW r M O ~~ + n ~ O ~o ~ .-i
3
to i
N N
x D ,
O +~
k op
y W.l O
r-1
O 10 O
GL
(l, l0O -i
~
r M ~ ~ ~ r ao
W O O O O O x
x
.~U - ri o .-~~ ~ ~n z o ~ ~ ~r
W
v
x
tr-.~
Ts
v
3 ~ 0
.-
1
~
7,p, toO N N N t
~ ~1
.L1~ r r7 00 o >~ s~ G ~n o o +.~
c0 rt
~
daU r M o n~-I+~z z z O r
N
4'
U
--I Ca C d
_
~ m
b O~ GL G1 'O 7,
N
r ~ ~ ~ ?n
~
p r
l
s
-I
o x +.~ ~n N 5
ro 'o
v p .ro G G ~n
vz
0 0 . >, >, m
+~
N 'i~U O r0~ v v ~ ~ t~
m rtS
-~-I -.-1-.av-~1.1U ~ a7 cO 'L3-.i-~ ~
1a C3 'd 'b -~I
T7 U G t~U ~ O O v .-itn i0
N N N -~ u1
N b O -O 1-IO a-~ U sa-~IO U O
w~ 'C)'~ ~ v
S-I I -.~x U.-iN U U ~ ~U17 U -~I
r 'O 'D O N C
b ~ cns~ o iw .u~ ~ ~ , m ~n a~
I ~-I rtr~o ~ v w ~
c~
o m rov ro.-,s" c~ .c~ -.~ci.
~n o o ~ s~
-az z zca . c-~r~: - cnv> > o o
i i i N I a ~ ~ ~ ow -- ~
i ~
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
# Cerestar 01411 - of the solids content, 3o is
monosaccharide (dextrose), 12o disaccharide (maltose) and
85% tri- and poly sa~~charides
5 ## Cerestar 01632 - of the solids content, 38% is
monosaccharide (dext:rose), 37o disaccharide (maltose) and
25o tri- and poly sa~~charides
Examples 23-26 other shearing devices. This demonstrates
10 that the benefits of shearing are not confined to the
Silverson.
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
61
b
U
O
m ~n
ro ro
o O O
N O O
10 O e-i .-1 O
f~M <CS O (>7 Ir).yJ
x O O O Nro NO oo O
W f~M <W -Irl +~N ~U YnC N 1~
'b TJ
N N
~
U
v
~
ow ro ro
~n o
N O O
lflO ~ .-1
f~M CD O r-~(n U71~ (~- ~1
p . O . Ort1 vO O
W r M o ,~,~ +~rn ~U ~C of C
O N
~
', U ~ la
m m
ro ro
~
c o N N
N O~ O
lD O r-1Ln .-i
~
r~M CO . O ~ M fn (!).1~ O 1~
x . . . p . O . p~ro NO O
W t~M O ,-a.-t W ~r >.U ?~G ~ G
I
I
I
~
U N
T3 O
N
N i-~
ti7
ro
roM O, O N
O
LiN O O
'i O
In l~ O r-I O N
O
C'M CO O In. (~1~ M M
x . . p . O',~O OOO NO
tnW I~M f7 .-i.-1 .!J'~, ~a ~1~ 00 rl
N 00
3
S.aN
O
-rl U
.1+~ O Tl 'O
~ '
o ro ow m a~ a~
a~
N O S-a 1..1
ri
" ro
c1
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r M c4 o ~no ~n+~ r aJ
ro ro
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CA 02355059 2001-06-13
WO 00/36079 PC'f/EP99/09377
62
~ Device in Example 23 is an example of the dynamic mixer
described in patent application WO 96/20270. This is a
cavity transfer m_~xer modified by axial movement of the
rotor with respect to the stator. This has the function
of allowing combination of significant shear and
extensional flow i=_ields by arranging the cavities such
that the cross-sectional area for flow of the liquid
successively increases and decreases by a factor of at
least S through tree apparatus. Results for Cl represent
averages of diffez-ent machine operating conditions.
~ Examples 24-26 are examples generated via a static
shearing device. This is the Model "A" Sonolator,
manufactured by Sonic Corporation. Compositions were
pumped at backpre~>;~ures ca 150 bar through a circular
nozzle (orifice) of diameter 0.032 cm2 at 30°C.
~ The second comparative example shows lower level of shear
providing insufficient increase in transmittivity.
CA 02355059 2001-06-13
WO 00/36079 PCT/EP99/09377
63
Example 27: pourable gel.
Ingredient ! o by weight (if
stated) not
otherwise
Comparative Ex. 27
example
LAS-aci_d_ 14.8 _ 14.8
Neodol 1-5 __ 22.23 __ 22.23
NaOH ' 6.6 6.6
-_:; _
KOH 3.4 _ 3.4
..
-
to pH _ ~ g . 4 ~ 8 . 4
_
Citric acid .laq _ 13.1 _ 13.1.
x'
Deflocculatinq X 4.0 4.0
polymer (Narlex
DC1)
Water to 1000 to l.OOo
Fructose 0 60
added on top _
Stability Yes Yes
Viscosity 450 4730
(mPa.s at 21 s-1)
j ~
~
Optical ~0. 5.5
transmissivity (o) 06
The foregoing description and Examples illustrate selected
embodiments of the ~~resent invention. In light thereof,
various modifications will be suggested to one skilled in
the art, all of which are within the spirit and purview of
this invention.
