Note: Descriptions are shown in the official language in which they were submitted.
12~7~
The present invention relates to novel, aqueous-based,
parboil, fluid detergent compositions
DEFINITIONS
The term "builder" is sometimes used loosely in the detergent
art to include any non-surfactant whose presence in a detergent
formulation enhances the cleaning effect of the formulation. More
usually, however, the term is restricted to those typical
"builders", which are primarily useful as a means of preventing or
ameliorating the adverse effects on washing of calcium and magnesium
ions e.g. by chelation, sequestering, precipitation or absorption of
the ions, and secondarily as a source of alkalinity and buffering.
The term "Builder" is used herein in the latter sense, and refers to
additives which ameliorate the aforesaid adverse effects to a
substantial extent. It includes sodium or potassium tripolyphosphate
and other phosphate and condensed phosphate salts such as sodium or
potassium orthophosphates, pyrophosphates, metaphosphates or
tetraphosphate, as well as phosphonates such as acetodiphosphonates,
amino iris ethylene phosphonates and ethylenediamine tetramethylene
phosphonates. It also includes alkali metal carbonates, zealots and
such organic sequestrants as salts of nitrilotriacetic acid, citric
acid and ethylene Damon tetracetic acid, polymeric polycarboxylic
acids such as polyacrylates and malefic android based copolymers.
For the avoidance of doubt, "Builder" is used herein to
include water soluble alkali metal silicates such as sodium silicate,
but excludes additives such as carboxymethyl cellulose, or polyvinyl
pyrrolidone whose function is primarily that of soil suspending or
~nti-redeposition agent
"Electrolyte" is used herein in relation to a component of a
liquid detergent composition to denote those non-surface active,
water soluble, ionic compounds which dissociate at least partially
in aqueous solution to provide ions, and which tend to lower the
volubility or muzzler concentration in the composition of the
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1227719
surfactants present in such solutions by a salting out"
effect. It includes water soluble dissociable, inorganic
salts such as, for example alkali metal or ammonium chlorides,
nitrates, phosphates, carbonates, silicates, perorates and
polyphosphates, and also certain water soluble organic salts
whichdesolubilise or "salt out" surfactants. It doesn't include
salts of cations which form water insoluble precipitates with the
surfactants present, or salts which tend to give unaccept-
able crystallization when the composition is stored.
"Hydrotrope" is used herein in relation to a component ox d
liquid detergent composition to denote any water soluble compound
which tends to increase the volubility in the composition of the
surfactants present. Typical Hydrotropes include urea and the alkali
metal or ammonium salts of the lower alkyd Bunsen sulphonic acids
such as sodium Tulane sulphonate and sodium zillion sulphonate.
Whether a given compound is an Electrolyte or a Hydrotrope may in
some cases depend upon which surfactants are present in the
particular quit detergent composition
As use herein "Soap" means an at least sparingly water soluble
salt of a natural or synthetic aliphatic monocarboxylic acid, which
salt has surfactant properties. The term includes sodium, potassium,
lithium. ammonium and alkanolamine salts of Cog 22 natural and
synthetic fatty acids, including Starkey, palmitic, oleic, linoleic,
ricinoleic, bunk and dodecanoic acids, resin acids and branched
chain monocarboxylic acids.
The "Usual Minor Ingredients" includes those ingredients other
than Water, Active Ingredients, Builders and Electrolytes which may be
included in laundry detergent compositions, typically in proportions
up to 5X. and which are compatible in the relevant Formulation with a
parboil, chemically stable Non-sedimenting composition. The term
includes anti redeposition agents, perfumes, dyes, optical brightening
agents, Hydrotropes, solvents, buffers, bleaches, corrosion
inhibitors, antioxidant, preservatives, scale inhibitors,
humectants, enzymes and their stabilizers, bleach activators, and
the like.
,~;
3 SLY
As used herein "Functional Ingredients" means ingredients
which are required to provide a beneficial effect in the wash liquor
and includes ingredients which contribute to the washing
effectiveness of the composition e.g. surfactants, builders,
bleaches, optical brighteners, buffers, enzymes and anti-
redeposition agents, and also anti-corrosives but excludes water,
solvents, dyes, perfume, Hydrotropes, sodium chloride, sodium
sulfite, solubilisers and stabilizers whose sole function is to
impart stability, fluidity or other desirable characteristics to a
concentrated formulation.
"Payload", means the percentage of Functional Ingredients based
on the total weight of the composition.
"Active Ingredients", means surface active materials.
All references herein to "Centrifuging", unless stated to the
contrary, are to be construed as referring to centrifuging at 25C
for 17 hours at 800 times normal gravitational force.
The expression "Separable Phase" is used herein to denote
phases which are separable from the mixture to form a distinct
layer upon Centrifuging. A single Separable Phase may comprise two
or more thermodynamically distinct phases, which are not separable
from each other on Centrifuging as in, for example, a stable
emulsion.
"Dispersed" is used herein to describe a phase which is
discontinuously distributed as discrete particles or droplets in at
least one other phase. "Co-continuous" describes two or more
inte~pene~r~ti~g-phases aye of which I s sinuously through a
common volume, or else is formed of discreet elements which interact
to form a continuous matrix tending to maintain the position and
orientation of each element in relation to the matrix when the
system is at rest. "Interspersed" describes two or more phases
which are either Co-continuous or of which one or more is Dispersed
in the other or others.
'
PA 12277~9
References to solid phases are to substances actually present
in the composition in the solid state at ambient temperature, and
including any water of crystallization or hydration unless the
context requires otherwise. References to solids include references
to microcrystalline and cryptocrystalline solids, i.e. solids whose
crystals are not directly observed by optical microscopy but whose
presence can only be inferred. A "Solid Layer" is a solid, pasty or
nonoperable gelatinous layer formed on Centrifuging.
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"Total Water" refers to water present as liquid water in a
predominantly aqueous phase, together with any other water in the
composition, e.g. water of crystallization or hydration or water
dissolved or otherwise present in any predominantly non-aqueous
phase. "Dry Weight" refers to residual weight after removal of
Total Water and also of any solvent which
has a boiling point below 110C.
The term "Formulation" is used to describe the combination of
ingredients which make up the Dry Weight of a composition. Thus the
same Formulation may be exemplified by a number of compositions,
differing in their Percentage Dry Weight.
All references herein to viscosities unless otherwise stated are
to the viscosity as measured on a cup and bob viscometer at 25C
after two minutes running using a 20 mm internal diameter flat
bottomed cup, 92 my long, and a 13.7 mm diameter bob, 44 mm long, with
conical ends having 45 horizontal angle, and 4mm diameter spindle,
rotating at 350 rum. The tip of the bob was 23mm from the base of the
cup This corresponds to Contrives "Roommate 30" viscometer using
measuring system C at speed setting 30. These conditions are us-
suitable for measuring viscosities greater than 12 Pascal Seconds at
which partial loss of contact between the bob and the sample may arise.
NPourable" as used herein means having a viscosity of less than
11.5 Pascal Seconds.
Pull" phase denotes a fluid, isotropic, muzzler solution of
surfactant in water, which occurs at concentrations between
the critical muzzler concentration and the first lyotropic mesophase,
wherein the surfactant molecules aggregate to form spherical or rod
shaped muzzles.
"G" phase refers to a liquid crystal phase of the type, also
known in the literature as "neat phase" or "lamellar phase" in which
the surfactant molecules are arranged in parallel layers of indefinite
extent separated by layers of water or an aqueous solution. The
layers may be bowlers or interdigited layers of surfactant. The "G"
phase for any given surfactant or surfactant mixture normally exists
in a narrow range of concentrations. Pure "G" phases can normally be
identified by examination of a sample under a polarizing microscope,
between crossed polarizers. Characteristic
i227719
textures are observed in accordance with the classic
paper by Receiver, JOCKS Vol. 31 P628 (1954) or in J. Killed and
Interracial Science, Vol. 30 No. I, P.500 (1969).
"Yield Points" whenever referred to herein are as measured on
an RML Series II "DEER" Remoter at 25C.
All percentages, unless otherwise stated, are by weight, based
upon the total weight of the composition.
References herein to "sedimentation" include references to
upward as well as downward separation of solid particles. "Non-
sedimenting" means not undergoing significant visible separation of
phases after three months at room temperature under normal earth
gravity. Separation of up to of the volume of the composition Jo
fDnm a clear aqueous phase external thereto, or up to 2% by volume
of a Solid Layer is not considered significant for the purposes of
this definition.
TECHNICAL BACKGROUND
Liquid detergents have hitherto been used mainly for light
duty applications such as dish washing. The market for heavy duty
detergents, e.g. laundry detergents, has been dominated by powders,
due to the difficulty of getting an effective amount of surfactant
and in particular of Builder into a stable liquid formulation. Such
liquids should in theory be cheaper than powder detergents since
they would avoid the need to dry and would in many instances replace
the sulfite filler conventionally used in powder detergents with
water. They also offer the possibilities of greater convenience and
more rapid dissolution in wash water than powder. Attempts to
provide solutions of the Functional Ingredients have been relatively
unsuccessful commercially. One reason for this lack of success has
been that the most commonly used and cost effective Functional
Ingredients, e.g. sodium tripolyphosphate and sodium dodecyl Bunsen
sulphonate, are insufficiently soluble in aqueous formulations
potassium pyrophosphate and amine salts of the Active Ingredients
which are more soluble have been tried as alternatives but have not
been found cost effective.
I.
6 1227719
Unbolt liquid detergents containing high levels of surfactant
have been marketed for laundry use, but are unsuitable for hard water
areas and have enjoyed only limited success.
A different approach is to attempt to suspend the excess
Builder as a solid in the liquid solution of surfactant. The
problem however has been to stabilize the system to maintain the
Builder in suspension and prevent sedimentation. This has in the
sty r~q~ir~d r~la~iY~]y s~phisti~d~ed formula ins prPven~ing
realization of the potential cost saving, and relatively low
concentrations of solid Builder, giving limited washing
effectiveness. This approach has been conditioned by certain
assumptions: that the detergent should as far as possible be in
solution; that the amount of suspended solid should be minimized to
avoid difficulties in stabilizing the suspension against
sedimentation; and that special thickeners or stabilizers were
essential to prevent sedimentation.
The products hitherto introduced commercially have suffered
from certain serious drawbacks. In particular, the individual
compositions have been proved highly sensitive to relatively small
variations in Formulation and manufacturing procedure. Departure
from a particular composition, optimized within fairly narrow
limits, generally results in instability and diminished shelf life.
The formulator has therefore been restricted to particular
ingredients and proportions, which have not included many of the
most effective combinations of surfactants and Builder for laundry
purposes.
because no general adequate theoretical explanation for the
stability of such systems has been proposed, It has not proved
possible to predict which compositions will be stable and which
unstable, or how to set about stabilizing any given surfactant
Builder combination which may be desired for reasons of washing
effectiveness or cost. Each composition has had to be discovered by
trial and error, and little flexibility has existed for adapting the
individual compositions to special requirements.
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12277~ 9
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Moreover, in general, the Payload has been undesirably low. In
addition, the proportion of Builder to Active Ingredient has generally
been less than is preferred for optimum washing, and expensive
ingredients, not usually required in powder formulations, have often
been needed to increase the amount of Functional Ingredient in
solution, and to inhibit sedimentation of the suspended solid.
INTRODUCTION TO THE INVENTION
We have now discovered that by observing certain conditions
it is possible to formulate Non-sedimenting, Parboil, fluid,
aqueous based detergent compositions which have novel structural
features and which can employ as surfactant virtually any surfactant
or surfactant combination which is useful in laundry applications, in
desired optimum proportions with any of the commonly used detergent
Builders. In general, compositions of our invention can be obtained,
which contain substantially higher Payloads at effective Builder to
surfactant ratio than have hitherto been attainable.
Preferred embodiments of our invention exhibit at least some
of the following advantages compared with products marketed
hitherto: Higher Payload; increased Builder to surfactant ratio;
improved stability; lower cost due to use of cheaper ingredients and
ease of production; satisfactory mobility; Improved washing
performance; "non-drip" characteristics, permitting the compositions to
be added to the compartments of washing machines designed to operate
with powders, without premature release; a consistency suitable for
automatic dispensing; and the flexibility to select optimum surfactant
combinations for the requirements of any particular market.
We have found that in general, contrary to what had been
assumed in the art, the higher the amount of undissolved material
the more stable the composition. We have discovered, in particular,
that the lower the proportion of the Active Ingredients dissolved in
the liquid aqueous phase, and the higher the proportion present as a
Interspersed structure of solid or lamellar phase, the more readily
can a Non-sedimenting, Parboil product be obtained at high Payloads.
- 8 1227719
We have further discovered that most surfactants commonly used in
powder detergents can have a stabilizing effect on aqueous suspensions
of Functional Ingredients, when present in certain novel structured
states in the composition, which may, at high Payloads, be sufficient
to stabilize the composition without the presence of special
stabilizers, not otherwise required for the formulation. We have also
discovered that surfactants can be constrained to form an open three
dimensional structure conferring stability on aqueous suspensions, by
the presence of Electrolytes and by controlling the conditions
of mixing. We have discovered that by applying the above principles it
us possible to formulate laundry detergents as thixotropic gels having
a matrix of hydrated solid or liquid crystal surfactant which may
contain suspended particles of solid Builder, which have particular
advantages over conventional detergent suspensions.
THE PRIOR ART
The prior art on liquid detergents is extremely voluminous.
However, for the purpose of this invention the numerous references to
light duty liquids and to unbolt or built Lear Lockwood laundry
detergents in which all ingredients are present in solution may be
disregarded. The Builder level in each case is substantially less
than desirable.
Recent general summaries of the current state of the art include
JOCKS (April 1981) POW - "Heavy Duty Laundry Detergents" which
includes a review of the typical commercially available liquid
formulations, and "Recent Changes in Laundry Detergents" by Rutkowski,
published in 1981 by Marcel Decker Inc. in the Surfactant Science
Serves.
The two principle avenues of approach to the problem of
formulating fully built liquid detergents, have been to emulsify a
surfactant in an aqueous solution of Builder or to suspend a solid
builder in an aqueous solution or emulsion of surfactant.
12Z~77~
The Conner approach is exemplified by U.S.P.3235505,
U.S.P.3346503, U.S.P.3351557, U.S.P.3509059, U.S.P.3574122,
U.S.P.3328309 and Canadian Patent 917031. In each of these patents
an aqueous solution of a water soluble builder is sufficiently
concentrated to salt out the surfactant (usually a liquid non-ionic
type) and the latter is dispersed in the aqueous medium as colloidal
droplets, with the aid of various emulsifiers. In each case the
system is a clear emulsion, which generally, contains relatively low
levels of Builder, and which is undesirably expensive due to the
cost of using soluble Builders.
The alternative approach is exemplified by BY 855893,
B.P.948617, B.P.943271, B.P.2028365 E.P.38101, Australian P.522983,
US 4018720 U.S.P.3232878, U.S.P.3075922 and U.S.P.2920045. The
formulations described in these patents separate, on Centrifuging,
into a Solid Layer comprising the majority of the sparingly soluble
Builder and an aqueous layer containing at least the majority of the
Active Ingredients. Commercial products corresponding to the example
of two of these patents have been marketed recently inAustralla
and Europe The stability of these compositions is generally highly
sensitive to minor variations in Formulation. Most require
expensive additives which are not Functional Ingredients.
EN 0079646, published after the filing date of the present
application, but clowning a priority date of Thea November, 1981,
describes and claims compositions containing a "salting out
electrolyte" and an "auxiliary electrolyte". The latter is "an
electrolyte of high lyotropic number" (i.e. a Hydrotrope as herein
defined) whereas the "salting out electrolyte" corresponds to an
Electrolyte as herein defined. Thus the earlier filed application
describes the use of Hydrotropes to counteract the salting out effect
of Electrolyte. The "auxiliary electrolytes described are all
expensive non-Functional additives which are required in substantial
concentrate onto
pa 1227719
A different approach is to suspend solid builder in an an hydrous
liquid non-ionic surfactant, e.g. BY 1600981. Such systems are costly,
restrictive with regard to choice of surfactant and give
unsatisfactory rinsing properties.
Several patents describe emulsions in which the Builder is in
the dispersed phase of an emulsion rather than in suspension.
U~SoP~4057506 describes the preparation of clear emulsions of sodium
tripo1yphosphate, and U.S.P.4107067 describes inverse emulsions in
which an aqueous solution of Builder is dispersed in a liquid crystal
surfac~ant system.
o- 12277~9
Reference may also be made to the numerous patents relating to
hard surface cleaners, in which an abrasive is suspended usually in an
aqueous solution of surfactant, e.g. U.S.P.3281367 and U.S.P.3813349.
U.S.P.3956158 describes suspensions of abrasive in a gel system of
interlocking fires of e.g. asbestos or soap. However, the low levels
of surfactant, absence of Builder and presence of high concentrations
of abrasive, generally preclude these patents from being of any
assistance in the formulating of laundry detergents.
Powder detergents are normally prepared by spray drying aqueous
slurries, which may superficially resemble liquid detergent
formulations, but which are not required to be stable to storage, and
which, are prepared and handled at elevated temperatures. Such
slurries are generally not Parboil at ambient temperature. Patents
describing the preparation and spray drying of such slurry
intermediates include U.S.P.3639288 and W. German OWLS 1567656.
Other publications of possible interest are:
Australian patent 507431, which describes suspensions of
Builder on aqueous surfactant, stabilized with sodium carboxymethyl
cellulose or clay as a thickening agent. However, the levels of
junctional Ingredients, and in particular of builder, in the
formulations exemplified, are not sufficient for a fully acceptable
commercial product;
U.S.P.3039971 describes a detergent paste containing the Builder
in solution;
Fry Patent 2839651 describes suspensions of zealot Builders on
non ionic surfactant systems; the compositions are, however, stiff
pastes rather than Parboil rids.
AWAKES. Symposium series No. 194 "Silicates in Detergents"
describes the effect of silicates on liquid detergents.
It will be understood that each of the foregoing patent
references was selected from the very extensive prior art, and
relevant aspects highlighted with the aid of hindsight, using our
knowledge of the invention as a guide to such selection and
highlighting. The
~227719
ordinary man skilled in the art at the time of our first
claimed priority, and without foreknowledge of the applicant's
invention, would not necessarily have selected those
patents as being particularity significant or those
aspects as being of special interest or relevance.
The foregoing summary does not therefore represent
the overall picture of the art possessed by the ordinary
skilled man. We believe that the latter has generally
held the view, either that fully built liquid detergents
containing sparingly soluble Builders were unattainable,
or that progress towards such formulations would be by
suspending the Builder in aqueous solutions of the surfactant,
earlier, alternative approaches having failed.
THE INVENTION
According to one embodiment, our invention
provides a Parboil, Non-sedimenting, aqueous based detergent
composition containing surfactant and solid Builder,
having at least 25% by weight Payload and comprising a
first predominantly aqueous liquid phase, containing
dissolved Electrolyte, at least one Dispersed solid phase
comprising said Builder, and at least one other phase,
comprising more than 25% of the total surfactant, separable
from at least said first phase by Centrifuging at 800
times normal Earth gravity for 17 hours at 25 C.
According to a second embodiment, our invention
provides a Parboil, Non-sedimenting, aqueous based detergent
composition, comprising water, at least 5% by weight of
surfactant and at least 16% by weight of Builder, which,
on Centrifuging at 800 times normal Earth gravity for 17 hours
at 25C, provides a predominantly aqueous liquid layer
containing dissolved Electrolyte and one or more other
layers, said one or more other layers containing at least
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12 - 1227719
a proportion of said Builder as a solid and at least 25%
of said surfactant.
According to a third embodiment, our invention
provides a Parboil, Non-sedimenting, aqueous based detergent
composition having at least 25% by weight Payload, said
composition comprising at least three phases including a
first predominantly aqueous, liquid phase containing
dissolved Electrolyte, a second phase Interspersed with
said first phase at least partially separable therefrom,
by Centrifuging and comprising at least a substantial
proportion of the surfactant, having an organic lamellar
structural component, and a third phase at least partially
separable from said first phase by centrifuging and comprising
solid particles of Builder Dispersed in said first and
second phases.
According to a fourth embodiment, our invention
provides a Parboil, Non-sedimenting, fluid detergent
having a Payload of at least 25% by weight and comprising
at least one, predominantly aqueous, liquid phase and one
or more other phases at least partially separable from
said at least one predominantly aqueous phase by centrifuging,
at least one of which one other phases comprises a matrix
I: of solid surfactant hydrate which is Interspersed with
: said at least one predominantly aqueous liquid phase to
form a thixotropic gel; and at least one of which one or
more other phases comprises particles of solid Builder
suspended in said composition.
According to a fifth embodiment, our invention
provides a Non-sedimenting Parboil fluid detergent
composition comprising at least one, predominantly aqueous,
liquid phase; at least one liquid crystal phase containing
surfactant and Interspersed with said at least one
predominantly aqueous liquid phase, and at least partially
separable therefrom by Centrifuging; and at lease one
phase comprising particles of solid Builder suspended in
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said composition and at least partially separable from
said at least one predominantly aqueous, liquid phase by
Centrifuging. Preferably the liquid crystal phase is a
"G" phase.
According to a sixth embodiment, our invention
provides a Non-sedimenting, Parboil, fluid, built detergent
composition containing water, surfactant at least partially
present as spheroids or vessicles formed from one or more
shells of surfactant, particles of solid Builder suspended
in said composition and dissolved Electrolyte, said composition
having a Payload of at least 35% and comprising at least
one predominantly aqueous liquid, phase and one or more
other phases, at least partially separable from said at
least one predominantly aqueous liquid phase by Centrifuging
for 17 hours at 800G or 25C; at least one of said one or
more other phases comprising at least part of said surfactant.
Said shells of surfactant may optionally be separated by
shells of water or aqueous solution. Said vessicles may
contain a predominantly aqueous liquid phase, and/or one
or more spherical or rod shaped surfactant muzzles and/or
one or more particles of solid Builder and said Active
Ingredient preferably comprises a substantially linear
alkyd Bunsen sulphonate.
According to a seventh embodiment, the invention
provides a Non-sedimenting, Parboil, fluid, detergent
composition comprising a first predominantly aqueous,
liquid, phase containing less than 60% of the total weight
of surfactants in the composition, and one or more other
phases Interspersed therewith and at least partially
separable therefrom by Centrifuging, at least one of said
other phases containing anionic and/or non ionic Active
Ingredients and at least one of said other phases containing
solid Builder.
According to a further embodiment, our invention
provides a Non-sedimenting, Parboil, fluid detergent
2X7719
14
composition comprising at least one predominantly aqueous
Separable Phase containing dissolved Electrolyte and
substantially saturated with respect to each of at least
one surfactant, capable of forming a solid hydrate or
liquid crystal phase, and at least one Builder; at least
one Separable Phase containing said surfactant as solid
hydrate or liquid crystal, Interspersed with said predominantly
aqueous Separable Phase, at least one Separable Phase
comprising solid particles of Builder suspended in said
composition, said particles having a size below the threshold
at which sedimentation would occur; said composition
containing a crystal growth inhibitor sufficient to maintain
the size of said particles below said threshold, and an
agglomeration inhibitor sufficient substantially to prevent
agglomeration of said particles. Preferably the Dry
Weight content in said further embodiment is greater than
35% by weight of the composition and the ratio of Builder
to Active Ingredients is greater than 1:1.
According to another embodiment, the present
invention provides a Non-sedimenting, Parboil, fluid
detergent composition having a Pay Load of greater than
25% which, on Centrifuging, is separable into a single
liquid layer containing dissolved Electrolyte and a said
Layer containing Builder and at least 25~ of the total
weight of surfactant, as a lamellar hydrated solid.
In one specific embodiment of the invention,
there is provided a Non-sedimenting, Parboil, fluid
detergent composition having a Payload of from 30 to 75%
and comprising water; from 15-60% Dry Weight of Active
Ingredients based on the Dry Weight of the composition,
said Active Ingredients consisting at least predominantly
of anionic sulfated or sulphonated surfactant, and from
20 to 80% based on the Dry Weight of the composition, of a
Builder, at least partly present as solid particles suspended
in said composition; the Payload being above the minimum
'`
- aye 1227719
value at which the composition is Non-sedementing and
below the maximum value at which the composition is Parboil,
and the composition containing at least sufficient of a
dissolved Electrolyte to exhibit increased Viscosity on
recovery after exposure to high shear stress.
In another specific embodiment of the invention,
there is provided a Non-sedimenting, Parboil, fluid,
detergent composition having a Payload of from 20 to 60%
and comprising water; from 10 to 55% Dry Weight of Active
Ingredients based on the Dry Weight of the composition,
said Active Ingredients consisting at least predominantly
of Soap; and from 20 to 80%, based on the Dry Weight of
the composition of a Builder at least partly present as
solid particles suspended in said composition; the Payload
being above the minimum value at which the composition is
Non-sedimenting and below the maximum value at which the
composition is Parboil; and the composition containing
sufficient Electrolyte to form a lamellar or vesicular
organic structural component.
In more detail, our invention provides Non-
sedementing, Parboil, fluid detergent composition comprising
Active Ingredients and Dispersed solid Builder said composition
comprising a predominantly aqueous liquid Separable Phase
preferably containing less than 75% by wt. of the Active
Ingredient all of which compositions exhibit at least
some, but not necessarily all, of the following characteristics:
They are-thixotropic; they comprise at least one predominantly
aqueous liquid phase and one or more other phases separable
from said predominantly aqueous liquid phase by Centrifuging
and containing Active Ingredient present in at least one
of said one or more other phases, and a Builder, present
in at
.
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:
~.227719
least one of said one or more other phases, said one or more other
phases being Interspersed with the predominantly aqueous phase; they
are gels; they comprise a continuous, at least predominantly aqueous
Separable Phase, containing dissolved Electrolyte, a solid or liquid
crystal Separable Phase containing a substantial proportion of the
Active Ingredient, Interspersed with said at least predominantly
aqueous phase, and a Dispersed solid phase consisting at least
predominantly of Builder; They have an organic lamellar component;
said lamellar component comprises layers of surfactant and aqueous
solution; said layers repeat at intervals of 20 to 65 Angstrom; said
one or more other phases are at least predominantly non-aqueous; the
compositions have a high Payload of Functional Ingredients, typically
greater than 20X by weight, e.g. 25 to 75X, more usually at least 30X
preferably at least 35X most preferably at least 40X by weight; they
contain a high ratio of Builder to Active Ingredient e.g. greater than
1:1 preferably 1.2:1 to 4:1; they contain more than 5 and preferably
more than 8X by weight of Active Ingredients; the predominantly
aqueous phase contains a concentration of lose than SO preferably
less than 8X, e.g. less than 2X, typically, in the case of non ionic
surfactant or alkyd Bunsen sulphonates, less than OX by weight
dissolved Active Ingredients; the proportion by weight of Active
Ingredient in the predominantly aqueous phase to total Active
Ingredient in the composition is less than 1:1.5, preferably less
than 1:2, e.g. less than 1:4; the at least one predominantly aqueous
liquid phase contains sufficient Electrolyte to provide a
concentration of at least 0.8 preferably at least 1.2 e.g. 2.0 to
4.5 gram tans per lithe of total alkali metal and/or ammonium cations;
the compositions contain at least 15X by weight, preferably more
than 20X by weight of Builder; the Builder is at least predominantly
sodium tripolyphosphate; the Builder comprises a minor proportion of
alkali metal silicate, preferably sodium silicate; the bulk Viscosity
of the composition is between 0.1 and 10 Pascal seconds, preferably
between 0.5 and 5 Pascal seconds; the composition has a Yield Point
preferably of at least 0.2, e.g. at least 0.5, preferably less than 20
e.g. 1 to 15 Newtons/sq.m; a phase containing Builder comprises solid
particles having a maximum particle size below the limit at which the
particles tend to sediment; the particles have, adsorbed on their
surfaces at least one crystal growth inhibitor sufficient to maintain
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1 6 122'7719
the solid particles below the limit at which the particles tend to
sediment; the composition contains an agglomeration inhibitor
sufficient to prevent flocculation or coagulation of the solid
particles.
CLASSIFICATION BY CENTRIFUGING
Aqueous based liquid laundry detergents containing suspended
solid builder can, in general, conveniently be classified by
Centrifuging as herein before defined.
Three principal types of laundry liquid having a continuous
aqueous phase and dispersed solid are distinguishable, which will be
hereinafter referred to as Group I, Group II and Grow p III
suspensions.
The first Group of laundry suspensions is characteristic of the
prior art discussed above which relates to suspensions of solid
Builder in aqueous solutions or emulsions of surfactant, On
Centrifuging as defined herein, Group I compositions separate into a
Solid Layer consisting essentially of Builder, and a viscous liquid
layer comprising water and surfactant. Formulation factors tending to
form Group 1 compositions include the use of the more water soluble
surfactants, such as alkyd ether sulfites, the presence of solubilising
agents such as Hydrotropes and water miscible organic solvents,
relatively low levels of Electrolyte and relatively low Pay Loads. Group
1 compositions normally display at least some of the following typical
properties. The bulk Viscosity of the composition is determined by,
and is similar to, the Viscosity of the aqueous liquid layer. The
aqueous layer typically has a viscosity of from 0.1-1.0 Pascal seconds.
Viscosities of the compositions are generally also under 1 Pascal second,
e.g. 0.3 to 0.6 Pascal seconds. The compositions usually have Yield
Points of less than 0.4, often less than 0.1 Newtons m -2. This implies
a relatively unstructured composition. This is confirmed by neutron
scattering and x-ray diffraction studies and by electron microscopy.
Subjection to high shear rate renders many Group I compositions unstable.
Group II is essentially distinguished from Group I in that at
least a substantial proportion of the surfactant is present in a
Separable Phase, which is distinct from the predominantly aqueous
liquid phase containing the Electrolyte. This Group is distinguished
from Group III in that at least a substantial portion of the surfactant
separates on Centrifuging as a liquid or liquid crystal layer.
: ED
17 1227719
Group II is not represented in the prior art, but is typical of
those laundry detergents of our invention which are prepared from non-
ionic or some mixed nonionic/anionic surfactants as the major
constituent of the Active Ingredients. Group II compositions typically
show a three layer separation on Centrifuging, giving a non-viscous
liquid aqueous layer (e.g. less than 0.1 Pascal seconds, usually less
than 0.02 Pascal seconds), which contains Electrolyte but little or no
surfactant, a viscous liquid layer which usually contains a major
proportion of the Active Ingredients and a Solid Layer consisting
predominantly of Builder.
Group II compositions have, typically, a very low Yield Point on
being first prepared but become more gel like on aging. The
Viscosity of the composition is usually between 1 and 1.5 Pascal
seconds. The compositions of this type show evidence of lamellar
structure in X-ray and neutron diffraction experiments and by electron
microscopy. Most Centrifuged Group II compositions have the liquid
or liquid crystal surfactant layer uppermost, but we do not exclude
compositions in which the aqueous Electrolyte layer is uppermost or
in which there are two or more Solid Layers distinguishable from each
other, at least one of which may sediment upwardly, in relation to
either or both liquid layers on Centrifuging.
The essential distinction of Group III from the other Groups is
that at least a substantial DroPortinn of the surfactant Centrifuges
into a Solid Layer.
Group III compositions may Centrifuge into more than one Solid
,
Layer. Normally both surfactant and Builder sediment downwardly on
Centrifuging and the two solid phases are intermixed.
However some Group III compositions may provide an upwardly
sedimentary surfactant phase or more than one surfactant phase at
least one of which may sediment upwardly. It us also possible for
some or all of the Builder to sediment upwardly.
The third Group of laundry liquids is typical of those
compositions of the present invention prepared from those surfactants
which are more sparingly soluble in the aqueous phase, especially
anionic surfactants such as sodium alkyd Bunsen sulphonates, alkyd
:,~
I
-I.
Jo I
,
::
1227719
18
sulfites, carboxylic ester sulphonates and many soaps, as well as
mixtures of such surfactants with minor proportions of non-ionic
surfactant. Group III compositions typically separate on Centrifuging
into two layers. The first of which is a non-viscous aqueous layer
(e.g. less than OWE Pascal seconds, and usually less than 0.02 Pascal
seconds) containing dissolved Electrolyte and little or no surfactant,
and the second is a Solid Layer comprising Builder and surfactant.
The theological properties of Group III, typically, show the
strongest evidence for structure. The Viscosity of the suspension is
substantially greater than that of the aqueous layer, e.g. typically
1.2 to 2 Pascal seconds. The compositions generally have a fairly
high Yield Point, e.g. greater than I Newton my and a very short
recovery lime after subjection to shear stresses in excess of the
Yield Point, e.g. usually 20 to 100 minutes. On recovery after
subjection to high shear stresses many Group III compositions
exhibit increased viscosity and greater stability.
There is gradual progression from Group I to Group III with some
compositions having some properties characteristic of one group and some
characteristic of another. Soap based compositions of our invention, for
example, may skew, in addition to a liquid layer and a Solid Layer, a
small amount of a third layer which is liquid, on Centrifuging but
have theological properties characteristic of Group III.
Compositions of Group I are sometimes unstable but may be
converted into stable Group II or III compositions of the invention
by addition of sufficient Electrolyte and/or by increasing Pay Load.
Most Group I compositions may be converted into Group II or III if
sufficient Electrolyte is added. Similarly, addition of more
Electrolyte may convert Group II compositions into Group III.
Conversely, Group III and Group II can generally be converted to
Group I, by addition of Hydrotrope.
,
CLASSIFICATION BY DIFFRACTION AND MICROSCOPY
Compositions of our invention and of the prior art, have been
examined by x-ray and neutron diffraction and by electron microscopy.
Samples for neutron diffraction studies were prepared using
deuterium oxide in place of water. Water was kept to a minimum,
, :
,, ,., ,, .
1 9 122'7719
although some ingredients, normally added as aqueous solutions (e.g.
sodium silicate), or as hydrates, were not available in a deuterated
form.
Deuterium oxide based compositions were examined on the Harley
small angle Neutron Scattering Spectrometer. Both deuterium oxide
based and aqueous samples were also examined using a small angle x-ray
diffractometer. Aqueous samples were freeze fracture etched, coated
with gold or gold/paladium and studied under the Lancaster University
Low Temperature Scanning Electron Microscope. Competitive commercial
compositions, which are not, of course, available in a deuterated
form, could not be examined by neutron scattering.
As in the case of Centrifuging, the three techniques described
above all provide an indication of three broad categories of liquid
detergent suspension, which appear to correspond generally to the
Group I, Group II and Group III compositions, described under
"Classification by Centrifuging".
The first category of composition, which included, generally
those compositions belonging typically to Grow p I, was characterized
under both neutron and x-ray analysis by high levels of small angle
scattering and an absence of discrete peaks, corresponding to regular,
repeating, structural features. Some çom~ositions showed broad
indistinct shoulders or humps, others a smooth continuum.
Small angle scattering is scattering very close to the line of
the incident beam and is usually dominated by scattering from dilute
dispersions of in homogeneities in the composition. The shoulders or
humps observed with some Group I çom~ositions additionally show a form
and angular displacement typical of concentrated muzzler solutions of
surfactant ill phase).
Under the electron microscope typical Group l compositions
gave a largely featureless granular texture with crystals of Builder
distributed apparently at random. These results were consistent with
the hypothesis based on their theological properties that typical
Group I compositions are relatively unstructured and lacking
detectable lamellar features. However some members of Group I showed
Jo evidence under the electron microscope of spherical structures of
approximately 5 microns diameter.
A very different type of pattern was obtained from typical Group
I I compositions. These showed relatively low levels of small angle
scattering near the incident beam, a peak typical of concentrated
I",
,
I 1227719
muzzler solution ill phase) and a sharply defined peak or peaks
corresponding to a well defined lamellar structure. The positions of
the latter peaks were in a simple numerical ratio, with first, second
and, sometimes, third order peaks usually distinguishable. The peaks
were evidence of relatively broadly spaced lamely (36-60 Angstrom).
Under the electron microscope lamellar structures were visible. In
some instances spheroidal structures could also be observed e.g. of
approximately 1 micron diameter.
Typical Group III compositions gave relatively narrow and
intense small angle scattering, together with distinct peaks
indicative of a lamellar structure. The peaks were broader than in
the case of typical Group II compositions, and second and third order
peaks were not always separately distinguishable. In general
the displacement of the peaks indicated a lamellar structure with the
lamely more closely spaced than in the case of typical Group II
compositions (e.g. 26-36 Angstrom). Lamellar structures were clearly
visible under the electron microscope.
PROPOSED STRUCTURE
We believe that the foregoing properties can most readily be
explained by the hypothesis that our invention embodies a novel
' structure of matter in which solid Builder is suspended in a structured
Jo arrangement of solid surfactant hydrate, and/or of "G" phase surfactant
in association with an Lo phase muzzler solution.
Preferred embodiments of our invention and in particular, Group
Jo III compositions, are believed to comprise parboil gel systems in which
there may be two or more Co-continuous or Interspersed phases. The
properties of the Group III compositions can be explained on the basis
that they are th1xotropic gels comprising a relatively weak three
dimensional network of solid surfactant hydrate Interspersed with a
relatively non viscous aqueous phase which contains dissolved
Electrolyte, but little or no surfactant. The network prevents
sedimentation of the network-fonming solids, and any suspended discrete
particles. The network forming solids may be present as platelets,
sheets of indefinite extent, or fires or alternatively, as asymmetric
particles joined into or interacting to provide, a random mesh, which
is Interspersed with the liquid. The structure is sufficiently stable to
inhibit or prevent precipitation on storage and will also limit the
extent of spreading of the gel on a hori20ntal surface, however the
Jo
`~:
`:
--` Al 1227719
structure is weak enough to permit the compositions to be poured or
pumped. The solid structure is composed at least predominantly of
surfactant hydrate e.g. sodium alkyd Bunsen sulphonate or alkyd
sulfite. Thus no other stabilizing agent is required over that required
in the end-use of the composition. Such gels may, in particular,
exhibit a clay-like structure, sometimes referred to as a "house of
cards" structure, with a matrix of plate shaped crystals orientated at
random and enclosing substantial interstices, which accommodate the
particles of builder. The solid surfactant may, in some instances be
associated with, or at least partially replaced by "G" phase surfactant.
In the case of Group II compositions there may be four
thermodynamically distinct phases of which only three are Separable
Phases under the conditions herein defined.
The phases detected by diffraction comprise a lamellar phase,
which is probably a "G" phase, but possibly in some instances
surfactant hydrate or a mixture thereof with "G" phase, and
predominantly aqueous "Lo" muzzler solution, together with the
solid Builder. There is also a predominantly aqueous solution
containing Electrolyte but less than 75X particularly 50~, usually
less than 40X, more usually less than 20X preferably less than 10~
more preferably less than I e.g. less than 2X of the total weight of
Active Ingredients.
The Builder is suspended in a system which may comprise a
network of "6" phase and/or spheroids or vessicles, which may have an
onion like structure, or outer shell, formed from successive layers of
surfactant, and which may contain at least one of the predominantly
aqueous phases, e.g. the Electrolyte solution, or more probably the
"Lo" muzzler solution. At least one of the predominantly aqueous
phases is the continuous phase. Evidence for the presence of
vessicles is provided by microscopy in the case of the compositions
containing olefin and paraffin sulphonates.
SURFACTANTS
The compositions of our invention preferably contain at least 5X by
weight of surfactants. Preferably the surfactant constitutes from 7
to 35~ by weight of the composition, e.g. 10 to 20X by weight.
22 1227~1~
The surfactant may for example consist substantially of an at
least sparingly water-soluble, salt of sulphonic or moo esterified
sulfuric acids e.g. an alkylbenzene sulphonate, alkyd sulfite, alkyd
ether sulfite, olef~n sulphonate, Al Kane sulphonate, alkylphenpl
sulfite, alkylphen~l ether sulfite, alkylethanolamide sulfite,
alkylethanolamide ether sulfite, or alpha sulfa fatty acid or its
esters each having at least one alkyd or alkenyl group with from 8
to 22, more usually 10 to 20, aliphatic carbon atoms. Said alkyd or
alkenyl groups are preferably straight chain primary groups but may
optionally be secondary, or branched chain groups. The expression
"ether" here~nbefore refers to polyoxyethylene, polyoxypropylene,
glycerol and mixed polyoxyethylene-oxy propylene or mixed glycerol-
oxyethylene or glyceryl-oxy propylene groups, typically containing
from 1 to 20 oxyalkylene groups. For example, the sulphonated or
sulfated surfactant may be sodium dodecyl Bunsen sulphonate,
potassium hexadecyl Bunsen sulphonate, sodium dodecyl dim ethyl
Bunsen sulphonate, sodium laurel sulfite, sodium tallow sulfite,
potassium oilily sulfite, ammonlum laurel monoethoxy sulfite, or
monoethanolamine Seattle 10 mole ethoxylate sulfite.
Other anionic surfactants useful according to the present
invention include fatty alkyd sulphosuccinates, fatty alkyd ether
sulphosucc~nates, fatty alkyd sulphosuccinamates, fatty alkyd ether
sulphosuccinamates, azalea sarcosinates, azalea towards, iseth~onates,
Soaps such as struts, palpitates, resonates, owlets, linoleates,
and alkyd ether carboxylates. Anionic phosphate esters may also be
used. In each case the anionic surfactant typically contains at least
one aliphatic hydrocarbon chain having from 8 to 22 preferably 10 to
20 carbon atoms, and, in the case of ethers one or more glycerol
and/or from 1 to 20 ethyleneoxy and or propyleneoxy groups.
- 23 - 1227719
Certain anionic surfactants, such as olef~n sulphonates and
paraffin sulphonates are commercially available only in a form
which contains some disulphonates formed as by-products of the
normal methods of industrial manufacture. The latter tend to
syllables the surfactant in the manner of a Hydrotope. However, the
olef~n and paraffin sulphonates readily form stable compositeness
which, on centrifuging, contain a minor portion of the total
surfactant in the aqueous phase, and which show evidence of spheroidal
structures. These composlt~ons are valuable, novel, laundry
detergents and which accordingly constitute a particular aspect of the
present ~nventlon.
Preferred anionic surfactants are sodium salts. Other salts of
commercial interest include those of potassium, lithium, calcium,
magnesium, ammonlum, monoethanolamlne, d~ethanolamlne, trlethanolamine
and alkyd amlnes contaln~ng up to seven al~phat~c carbon atoms.
The surfactant may optionally contain or consist of nonion~c
surfactants. The nonlonlc surfactant may be e.g. a C10_22
alkanolamlde of a moo or dip lower alkanolamlne, such as
coconut monoethanolamlde. Other non~onlc surfactants which may
opt~onal1y be present, include ethoxylated alcohols, ethoxylated
carboxyl~c acids, ethoxylated amlnes, ethoxylated alkylolamides,
ethoxylated alkylphenols, ethoxylated glycerol esters, ethoxylated
sorbltan esters, ethoxylated phosphate esters, and the propoxylated or
ethoxylated and propoxylated analogies of all the aforesaid
ethoxylated nonlon~cs, all having a C8_22 alkyd or alkenyl group and
up to 20 ethyleneoxy and/or propyleneoxy groups, or any other non ionic
surfactant which has hitherto been incorporated in powder or llqu~d
detergent composlt~ons e.g. amine oxides. The latter typically have
at least one C8_22, preferably C10_20 alkyd or alkenyl group and
up to two lower (e.g. Clue, preferably Clue) alkyd groups.
I'
- 24 - i227719
The preferred nonionics for our invention are for example
those having an HUB range of 7-18 e.g. 12-15.
Certain of our detergents may contain cat ionic surfactants,
and especially cat ionic fabric softeners usually as a minor
proportion of the total active material. Cat ionic fabric softeners
of value in the invention include qua ternary amine having two long
chain (e-g- C12_22 typically C16_2~ alkyd or alkenyl groups and
ether two short chain (e.g. C1_4) alkyd groups, or one short
chain and one bouncily group. They also include median and
quaternised imidazolines having two long chain ilkyl or alkenyl
groups, and amid amine and quaternised amino amine having two
long chain alkyd or alkenyl groups. The quaternised softeners are
all usually salts of anions which impart a measure of water
sealability such as format, acetate, lactate, tart rate, chloride,
methosulphate, ethosulphate, sulfite or nitrate. Compositions of
our invention having fabric softener character may contain smectite
clays.
Compositions of our invention may also contain amphoteric
surfactant, which may be Included typically in surfactants having
cat ionic fabric softener, but may also be included, usually as a
minor component of the Active Ingredients, In any of the other
detergent types discussed above.
Amphoteric surfactants include buttons, sulphobetaines and
phosphobetaines formed by reacting a suitable tertiary nitrogen
compound having a long chain alkyd or alkenyl group with the
appropriate reagent such as chloroacetic acid or propane sultan.
Examples of suitable tertiary nitrogen containing compounds include:
tertiary amine having one or two long chain alkyd or alkenyl groups,
optionally a bouncily group and any other substituent such as a short
chain alkyd group; ~midazoline having one or two long chain alkyd or
alkenyl groups and amidoamines having one or two long chain alkyd or
alkenyl groups.
I
- us - i227719
Those skilled on the detergent art will appreciate that the
spool if c surfactant types described above are only exemplary of the
commoner surfactants suitable for use according to the invention.
Any surfactant capable of performing a useful function in the wash
liquor may be included. A fuller description of the principal types
of surfactant which are c N erc~ally available is given in "Surface
Active Agents and Detergents by Schwartz Perry and Bench.
BUILDERS
The Budder, on preferred corposlt~ons of our invention us
believed to be normally present, at least portly, as discrete
solid crystall~tes suspended on the compost on The crystall~tes
typically have a size of up to 60 erg 5 to 50 microns.
We have found that Formulations contaln~ng sodium
tr1polyphosphate as Builder, or at least a major proportion of
sodium trtpolyphosphate on admixture with other Builders, exhibit
stability and mobility over a wider range of Dry White
than corresponding Formulations with other Builders. Such
h rmulatlons are therefore preferred. Our ~nvent~on, however, also
provides compositeness comprising other Budders such as potassium
tr1polyphosphate, carbonates, zealots, n1tr~10 tr~acetates,
citrates, metaphosphates, pyrophosphates, phosphonates, ETA and/or
polycarboxylates, optionally but preferably, on admixture with
trlpolyphosphate. Orthophosphates may be present, preferably as
minor components on admixture with trlpolyphosphate, as may alkali
metal slates
The last mentioned are particularly preferred and constitute
a feature of our preferred embodiments since they perform several
valuable functions. They provide the free alkal~nlty desirable to
I` saponify fats on the soul, they ~nhlb~t corrosion of aluminum
surfaces on washing machines and they have an effect as Builders.
In addtt~on, they are effective as Electrolytes to Halt out
Active Ingredients from the predominantly aqueous liquid phase
thereby reducing the proportion of Active Ingredient in solution and
mprov1ng the stability and fluidity of the composition.
- 26 -
227719
Accordingly, ye prefer that compositions of our invention should
contain at least I and up to 12.3X by weight of the composition
preferably at least 2X and up to 10X, most preferably more than 3X
and up to 6.5% e.g. 3.5 to 5% of alkali metal silicate, preferably
sodium silicate measured as Sue based on the total weight of
composition.
Typically, the silicate used to prepare the above compositions
has an NATO : Sue ratio of from 1:1 to 1:2 or 1:1.5 to 1:1.8.
It will however be appreciated that any ratio of Noah (or other
base) to S~02, or even s~licic acid could be used to provide the
silicate in the compos1t~on, and any necessary additional alkalinity
provided by addtt~on of another base such as sodium carbonate or
hydroxide. Formulations not intended for use in washing machines
do not require silicates provided that there is an alternative
source of alkalinity.
The Builder normally constitutes at least 15~ by eight of the
compositions, preferably at least 20X. We prefer that the ratio of
Builder to surfactant us greater than 1:1 preferably 1.2:1 to 5:1.
ELECTROLYTE
The concentration of dissolved organic material and more
particularly of Active Ingredients on the predominantly aqueous,
liquid phase us preferably maintained at a low level. This may be
achieved by selecting, so far as possible, surfactants which are
sparingly soluble in the predominantly aqueous phase, and keeping to
a minimum the amount of any more soluble surfactant which us desired
for the part ular end use. For a given surfactant system and
Payload, we have found that it is generally possible to stabilize
the system in accordance with an embodiment of our invention by
including in the at least one predominantly aqueous phase a
sufficient quantity of Electrolyte.
27 1Z27719
An effect of the Electrolyte is to limit the volubility of
Active Ingredient in the at least one predominantly aqueous phase,
thereby increasing the proportion of surfactant available to provide
a solid, or liquid crystal, matrix which stabilizes the compositions
of w r invention. A further effect of the Electrolyte is to raise
the transition temperature of the "G" phase to solid for the
surfactant. One consequence of raising the phase transition
temperature is to raise the minimum temperature above which the
surfactant forms a liquid or liquid crystal phase. Hence
surfactants which in the presence of water are normally liquid
crystals or aqueous muzzler solutions at ambient temperature may
be constrained by the presence of Electrolyte to form solid matrices
or "G" phases.
Preferably, the proportion of Electrolyte dissolved in the at
least one predominantly aqueous phase is sufficient to provide a
concentration of at least 0.8 preferably at least 1.2 erg 2.0 to 4.5
gram ions per lithe of alkali metal alkaline earth metal and/or
ammonium cations. The stability of the system may be further
improved by ensuring so far as possible that the anions required in
the composition are provided by salts which have a common cation,
preferably sodium. Thus, for example, the preferred Builder is
sodium tripolyphosphate, the preferred anionic surfactants are
sodium salts of sulfated or sulphonated anionic surfactants and any
anti-redeposition agent, e.g. carboxymethyl cellulose, or alkali,
e.g. silicate or carbonate are also preferably present as the sodium
salts. Sodium chloride, sodium sulfite or other soluble inorganic
sodium salts may be added to increase the electrolyte concentration
and minimize the concentration of Active Ingredients in the
predominantly aqueous liquid phase. The preferred electrolyte,
however, is sodium silicate. Alkaline earth metals are only
normally present when the Active Ingredients comprise surfactants,
such as olefin sulphonates or non-ionics which are tolerant of their
presence. Sodium sulfite in concentrations above about 3% may tend
to give unacceptable crystallization when the composition is stored.
It is possible, alternatively, but less preferably to choose
salts of potassium, ammonium, lower amine, alkanolamines or even
mixed cations.
I.
I`: D
.
28 1 2 2 7 7 1 9
We prefer that at least two thirds of the weight of the
Functional Ingredients should be in a phase separable from the at
least one predominantly aqueous liquid phase, preferably at least
75%, e.g. at least 80~.
The concentration of Active Ingredient in the predominantly
aqueous liquid Separable Phase is generally less than 10~ by weight,
of said Separable Phase, preferably less than 7% by weight, more
preferably less than 5% by weight e.g. less than 2%. Many of our
most effective formulations have a concentration of less than 1%
Active Ingredient in the predominantly aqueous liquid Separable
Phase e.g. less than 0.5%.
The concentration of solids in the predominantly aqueous
liquid Separable Phase may be determined by separating a sample of
the aqueous liquid, e.g. by Centrifuging to form an aqueous
liquid layer and evaporating the separated layer to constant
weight at 110C.
STABILIZING SUSPENDED SOLID
The particle size of any solid phase should be less than that
which would give rise to sedimentation. The critical maximum limit
to particle size will vary according to the density of the
particles and the density of the continuous phase and the yield
; point of the composition.
'~'~'-''~
Jo ....... .
- 29 - 1227719
Compositions of our invention preferably contain a particle
growth inhibitor. The particle growth inhibitor is believed to
function by adsorption onto the faces of suspended crystallizes of
sparingly soluble solids preventing deposition of further solid
thereon from the saturated solution in the predominantly aqueous
liquid phase. Typical particle growth inhibitors include sulphonated
aromatic compounds. Thus for example, a sodium alkyd Bunsen
sulphonate such as sodium dodecyl Bunsen sulphonate when present as
a surfactant is itself a particle growth inhibitor and may be
sufficient to maintain particles of, for example, builder in the
desired size range without additional stabilizers. Similarly, lower
alkyd Bunsen sulphonate salts such as sodium xytene sulphonate or
sodium Tulane sulphonate have stabilislng activity, as well as
being conventionally added to liquid detergents as Hydrotropes. In
our invention, however, the presence of the lower alkyd Bunsen
sulphonates is less preferred. Sulphonated naphthalenes especially
methyl naphthalene sulphonates are effective crystal growth
inhibitors. They are not, however, normal ingredients of detergent
compositions and therefore on cost grounds they are not preferred.
Other particle growth inhibitors include water voluble
polysaccharide derivatives such as sodium carboxymethyl cellulose,
which is frequently included in detergent compositions as a soil
anti-redeposition agent. We, therefore prefer that it should be
present in minor amounts in compositions according to our invention,
sufficient to perform its normal functions in detergent compositions
and to assist in stabilizing the suspension, but preferably not
sufficient to increase so substantially the viscosity of the
predominantly aqueous liquid phase as to impair the pour ability of
the composition.
Another group of particle growth inhibitors which may
optionally be included in compositions according to our invention
are the sulphonated aromatic dyes, especially the sulphonated
aromatic optical brightening agents, which are sometimes included in
powder formulations.
r-
~X;~717~9
-- 30 --
Typical examples include Boyce (4-phenyl-1,2,3-triazol-2-
yl-2,2'-stilbene disulphonate salts and 4,4'-diphenylvinylene-2,2'-
biphenyl disulphonate salts. Such particle growth inhibitors may
be included instead of, or more usually in addition toSfor example,
a sulphonated surfactant.
Other effective particle growth inhibitors include
lignosulphonates and C6_18 Al Kane sulphonate surfactants, which
latter compounds may also be present as part of the surfactant
content of the composition.
The presence of an agglomeration inhibitor is also preferred.
The agglomeration inhibitor for use according to our invention may
also conveniently be sodium carboxymethyl cellulose. It is
preferred that the composition should include an effective
agglomeration inhibitor which is chemically distinct from the
particle growth inhibitor, despite the fact that, for example,
sodium carboxymethyl cellulose, is capable of performing either
function. It is sometimes preferred, when preparing the detergent
composition to add the crystal growth inhibitor to the composition
prowar to the agglomeration inhibitor, and to add the agglomeration
inhibitor subsequent to the solid phase, so that the crystal growth
inhibitor is first adsorbed onto the solid particles to inhibit
growth thereof and the agglomeration Inhibitor is subsequently
introduced to inhibit agglomeration of the coated particles.
Other agglomeration inhibitors which may less preferably be
used include polyacrylates and other polycarboxylates, polyvinyl
pyrrolidone, car boxy methyl starch and lignosulphonates.
The concentration of the crystal growth inhibitor and
agglomeration inhibitor can be widely varied according to the
proportion of solid particles and the nature of the dispersed solid
as well as the nature of the compound used as the inhibitor and
227719
- 31 -
whether that compound is fulfilling an additional function in the
composition. For example, the preferred proportions of alkyd
Bunsen sulphonate are as set out herein before in considering the
proportion of surfactant. The preferred proportions of sodium
car boxy methyl cellulose are up to 2.5~ by weight of the composition
preferably 0.5 to I by weight e.g. 1 to I although substantially
higher proportions up to 3 or even I are not excluded provided they
are consistent in the particular formulation with a parboil
composition. The sulphonated optical brighteners may typically be
present in proportions of 0.05 to lo by weight e.g. 0.1 to 0.3X
although higher proportions e.g. up to I may less preferably be
present in suitable compositions.
ALKALINITY
The compositions or our invention are preferably alkaline,
being desirably buffered with an alkaline buffer adapted to provide
a pi above 8 erg above 9 most preferably above 10 in a wash liquor
containing the composition diluted to 0.5X Dry Weight. They
preferably have sufficient free alkalinity to require from 0.4 to 12
mls. preferably 3 to 10 mls of N/10 Hal to reduce the pi of 100 mls.
of a dilute solution of the composition containing 0.5~ Dry Weight,
to 9, although compositions having higher alkalinity may also be
commercially acceptable. In general lower alkalinities are less
acceptable in commercial practice, although not excluded from the
scope of our invention.
The alkaline buffer is preferably sodium trlpolyphosphate and
the alkalinity preferably provided at least in part by sodium
silicate. Other less preferred alkaline buffers include sodium
carbonate.
SOLUBI~ISERS
hitherto, liquid detergent compositions have commonly
contained substantial concentrations of Hydrotropes and/or organic
water miscible hydroxylic solvents such as methanol, ethanol,
isopropanol, glycol, glycerol, polyethylene glycol and polypropylene
glycol. Such additives are often necessary to stabilize Group I
formulations. However, in Group II and III formulations of the
present invention, they may have a destabilizing effect which often
requires the addition of extra amounts of Electrolyte to maintain
stability. they are, moreover costly and not Functional
r
- 32 - 122'7~19
Ingredients. They may, however, in certain circumstances, promote
Pour ability. We do not therefore totally exclude them from all
compositions of our invention, but we prefer that their presence be
limited to the minimum required to ensure adequate Pour ability.
If not so required we prefer that they be absent.
PAYLOAD
Selection of the appropriate Payload is generally important to
obtain desired stability and Pour ability. Optimum Payload may vary
considerably from one type of Formulation to another. Generally
speaking it has not been found possible to guarantee Non-sedimenting
compositions below about 35X by weight Payload, although some types
of Formulation can be obtained in a Non-sedimebting form below 30X
Payload, and sometimes as low as 25X Payload. In particular we have
obtained Soap based Formulations at concentrations below 25X Pay
Load erg 24%. We do not exclude the possibility of making such
Formulations at Pay Loads down to 20%.
Prior art references to stable compositions at low Payloads
have either been limited to particular Formulations using special
stabilizers, or have not provided sufficiently stable suspensions
to satisfy normal commercial criteria.
For any given Formulation according to our invention a range
of Payloads can be identified within which the composition is both
stable and parboil. Generally below this range, sedimentation
occurs and above the range the Formulation is too viscous. The
acceptable ran g may be routinely determined for any given
Formulation by preparing the suspension using the minimum water
required to maintain a storable composition, diluting a number of
samples to progressively higher dilutions, and observing the samples
for signs of sedimentation over a suitable period. For some
Formulations the acceptable range of Payloads may extend from 30X or
35% to 60 or even 70X by weight for others it may be much narrower,
e.g. 40 to 45X by weight.
If no stable Parboil range can be determined by the above
methods, the Formulation should be modified according to the
teaching herein e.g. by the addition of more sodium silicate
solution or other Electrolyte.
- 33 - 12277~9
Typically Group III formulations show an increase in yield point
with increasing Pay Load. The minimum stable Pay Load for such
typical Group III formulations usually corresponds to a yield Point
of about 10-12 degrees/cm2.
PREPARATION
Compositions of our invention can, in many instances be
readily prepared by normal stirring together of the ingredients.
However, some Formulations according to the invention are not fully
stable unless the composition us subjected to more prolonged or
vigorous mixing. In some extreme cases the solid content of product
may require comminution in the presence of the liquid phase. The
use of a killed mill for the latter is not excluded, but is not
generally necessary. In some instances mixing under high shear rate
provides products of high viscosity.
The order and conditions of mixing the ingredients are often
important in preparing a stable structured mixture according to our
invention. Thus a system comprising: water, sodium dodecylbenzene
sulphonate, coconut monoethanolamide, sodium tri?olyphosphate,
sodium silicate, sodium carboxymethyl cellulose and optical
brightener at 45X Dry Weight was unstable when the compounds were
mixed in the order described above, but when mixed with the coconut
monoethanolamide and sodium tripolyphosphate added as the last of
the Functional Ingredients, a stable composition was formed.
A method of preparation that we have found generally suitable
for preparing stable mixtures from those Formulations which are
capable of providing them, is to mix the Active Ingredients or their
hydrates, in a concentrated form, with concentrated (e.g. 30 to 60X,
preferably 45-50X) aqueous silicate solution, or alternatively, a
concentrated solution of any other non-surfactant electrolyte
required in the Formulation. Other ingredients are then added
including any anti-redeposition agents, optical brightening agents
and foaming agents. The Builder, when not required to provide the
initial Electrolyte solution, may be added last. During mixing
just sufficient water is added at each addition to maintain the
composition rid and homogeneous. When all the Functional
'
- 34 - l X 2 7~7~Lg
Ingredients are pro en, the mixture is diluted to provide the
required Pay Load. Typically, mixing is carried out at ambient
temperature where consistent with adequate dispersion, certain
ingredients, e.g. non-ionic surfactants such as coconut
monoethanolamide require gentle warming e.g. 40 for adequate
dispersion. Thus degree of warming may generally be achieved by the
heat of hydration of sodium tripolyphosphate. To ensure sufficient
warming we prefer to add the tripolyphosphate in the an hydrous form
containing a sufficiently high proportion of the high temperature
rise modification commonly called "Phase I". The foregoing
procedure is only one of several methods that may be satisfactorily
used for all or most of the compositions of out invention. Some
formulations are more sensitive to the order and temperature of
mixing than others.
FORMULATION TYPOS
Typically, our Formulations may most conveniently be one of
the following types; (A) A non soap anionic type in which the Active
Ingredient preferably consists at least predominantly of sulfated
or sulphonated anionic surfactant, optionally with a minor
proportion of non-ionic surfactant; IBM A Soap based detergent
wherein the Active Ingredient consists of or comprises a substantial
proportion of Soap, preferably a major proportion, together
optionally with non-ionic, and/or sulfated or sulphonated anionic
surfactant; (C) A Non-ionic type in which the Active Ingredient
consists, at least predominantly of non-ionic surfactant, optionally
with minor proportions of anionic surfactant, soap, cat ionic fabric
softener and/or amphoteric surfactant.
The foregoing types are not an exhaustive list of Formulation
types of our invention which includes other types not listed
separately above.
Considering the different types of Formulation according to
our invention in more detail, we particularly distinguish, among
type "A", high foaming sulfite or sulphonate type formulations and
low foaming type "A" formulations.
-` 12X771 9
High roaming type "A' Formulations may typically be based on
sodium C10-14 straight or branched chain alkyd Bunsen sulphonate,
alone or in admixture with a C10-18 alkyd sulfite and/or C10-20
alkyd 1-10 mole ether sulfite. Small amounts (e.g. up to I of the
weight of the compositions) of Soap may be present to aid rinsing of
the fabric. Non ionic foam boosters and stabilizers, such as C12 18
azalea (e.g. coconut) monoethanolam;de or diethanolamide or their
ethoxylates, ethoxylated alkyd phenol, fatty alcohols or their
ethoxylates may optionally be present as foam boosters or
stabilizers, usually in~roportions up to about 6% of the Dry Weight
I the composition.
The sodium alkyd Bunsen sulphonate may be totally or
partially replaced, in the above Formulations by other sulphonated
surfactants including fatty alkyd zillion or Tulane sulphonates, or
by eye. alkyd ether sulfites (preferably) or alkyd sulfites,
paraffin sulphonates and olefin sulphonates, sulphocarboxylate~, and
their esters and asides, including sulphosuccinates and
sulphosuccindmates~ alkyd phenol ether sulfites, fatty azalea
monoethanolamide ether sulfites or mixtures thereof.
According to a specific embodiment, therefore, our
invention provides a Non-sedimenting, Parboil, detergent
composition having a Payload of from 30 to 75% and
comprising water; from 15 to 60% Dry Weight of Active
Ingredients based on the Dry Weight of the composition,
preferably at least partly present as a lamellar or
vessicu1ar phase, said Active Ingredients consisting at
least predominantly of anionic sulfated or sulphonated
surfactant; and from 20 to 80% Dry Weight of Builder
based on the Dry Weight of the composition at least
partly present as solid particles suspended in said
composition, the Payload being above the minimum value
at which the composition is Non-sedimenting and below
the maximum value at which the composition is Parboil;
the composition optionally containing up to 20% by Dry
Weight of the composition of non ionic foaming gent
and/or foam stabilizer and up to 6% by Dry Weight of the
composition of Soap; and the composition containing at
12Z'77~9
AYE
least sufficient of a dissolved Electrolyte (which may
optionally comprise a dissolved portion of the Builder )
to exhibit increased Viscosity on recovery after exposure
to high shear stress.
Preferably the sulfated or sulphonated anionic surfactant
consists substantially of alkyd Bunsen sulphonate preferably sodium
alkyd Bunsen sulphonate, e.g. C110-14 alkyd Bunsen sulphonate.
The proportion of alkyd Bunsen sulphonate in the absence of foam
boosters is preferably from 20 to 60% e.g. 30 to 55 of the Dry
Weight of the composition.
;
- 36 - 1Z27~19
Alternatively, the anionic surfactant may comprise a mixture
of alkyd Bunsen sulphonate, and alkyd sulfite and/or alkyd ether
sulfite and/or alkyd phenol ether sulfite in weight proportions
of e.g. from 1:5 to 5:1 typically 1:2 to 2:1 preferably 1:1.5 to
1.5:1 e.g. 1:1. In the latter case the total anionic surfactant is
preferably from 15 to 50~ e.g. 20 to 40~ of the Dry Weight of the
compositions, in the absence of foam booster.
The alkyd sulfite, and/or alkyd ether sulfite for use in
admixture with the alkyd Bunsen sulphonate typically has an average
of from 0 to 5 ethyleneoxy groups per sulfite group e.g. 1 to 2
groups.
In an alternative type "A" Formulation the anionic surfactant
consists substantially of alkyd sulfite and/or, alkyd ether
sulfite. The total concentration of Active Ingredients in the
absence of foam booster is preferably from 15 to 50~ of the Dry
Weight of the composition. Typically the Active Ingredients comprise
an average of from 0 to 5 e.g. 0.5 to 3 ethyleneoxy groups per
molecule of sulfated surfactant. The fatty alkyd chain length is
preferably from 10 to 20C, higher chain lengths being preferred with
higher ethylene-oxy content.
The foregoing types may be varied by substituting for all or
part of the anionic active content, any of the sulfated or
sulphonated anionic surfactant classes herein before specified.
Soap may be added to any of the foregoing detergent
Formulations as an aid to rinsing the fabric. Soap is preferably
present for this purpose in concentrations of from 0 to 6%
preferably 0.1 to I e.g. 0.5 to I by Dry Weight of the
composition. The amount of Soap is preferably less than 25~ of the
total sulfated and sulphonated surfactant, to avoid foam
suppression; typically less than 10%.
12;~7719
Foam boosters and/or stabilizers may be incorporated in any of
the foregoing types of high foam anionic detergent. The foam
boosters or stabilizers are typically C10_18 alkyd non ionic
surfactants such as coconut monoethanolamide or diethanolamide or
their ethoxylates, alkyd phenol ethoxylates, fatty alcohols or their
ethoxylates or fatty acid ethoxylates. The foam booster
and/or stabilizer is added typically in proportions up to 20X of
the Dry Weight of the composition e.g. 0.1 to I preferably 0.5 to
I The presence of foam booster and/or stabilizer may permit a
reduction of total concentration of Active Ingredients in a high
foam product. Typically, compositions comprising alkyd Bunsen
sulphonate with a foam booster and/or stabilizer will contain from
15 to 40~ of alkyd Bunsen sulfite based on the weight of the
composition preferably 20 to 36~ e.g. 25% with from 2 to I e.g. 4X
of nonion~c surfactant, the lower proportions of anionic surfactant
being preferred with higher proportions of non ionic surfactant and
vice versa. The other sulfated or sulphonated anionic surfactant
Formulations discussed above may be similarly reduced in active
concentration by inclusion of foam boosters and/or stabilizers.
The Builder is preferably sodium tripolyphosphate, optionally
but preferably with a minor proportion of soluble silicate although
the alternative Builders herein before described may be employed
instead, as may mixed builders. The proportion of Builder in
type "A" formulations is usually at least 30X of the Dry Weight of
the composition, preferably from 35~ to 85~ e.g. 40 to 80~. builder
proportions in the range 50 to 70~ of Dry Weight are particularly
preferred. The Builder to Active Ingredients ratio should desirably
be greater than 1:1 preferably from 1.2:1 to 4:1 e.g. from 1.5:1 to
3:1.
Low foaming type "A" Formulations are generally dependent upon
the presence of lower proportions of sulfated or sulphonated
anionic surfactant than on the high foam types together with higher,
but still minor, proportions of Soap, and/or the addition of non-
ionic, silicone, or phosphate ester foam depressants.
- 38 - lX~7719
Our invention therefore provides, according to a second
specific embodiment, a Non-sedimenting Parboil rid, aqueous
based detergent composition, comprising an at least predominantly
aqueous phase containing Electrolyte in solution, and suspended
particles of Builder, said composition comprising from 15 to 50~
based on Dry Weight of Active Ingredient , at least 30~ of Builder
based on Dry Weight, a ratio of Builder to Active Ingredient
greater than 1:1, and optionally the Usual Minor Ingredients,
whereon the surfactant comprises from 15 to 50~ based on the Dry
weight of the composition of sulfated and/or sulphonated anionic
surfactant and an effective amount of at least one foam depressant.
;
Preferably, the foam depressant is selected from Soap, in a
proportion of from 20 to 60X based on the weight of sulfated or
sulphonated anionic surfactant, C16_20 alkyd non ionic foam
depressant in a proportion of up to 10X of the Dry Weight of the
composition, C16_20 alkyd phosphate ester in a proportion of up to
lox of the Dry Weight of the composition and silicone anti foams.
The function of Soap as a foam depressant is dependent on the
proportion of Soap to sulfated or sulphonated anionic surfactant.
Proportions of 10X or less are not effective as foam depressants but
are useful as rinse aids in high foaming detergent compositions.
Foam depressant action requires a minimum proportion of about 20X
of soap based on the sulfated and/or sulphonated surfactant. If
the proportion of soap to sulphated/sulphonated surfactant in a type
"A" detergent is above about 60X by weight, the foam depressant
action us reduced. Preferably, the proportion of Soap is from 25
to 50X e.g. 30 to 45~ of the weight of sulphated/sulphonated
surfactant.
Low foaming type "A" surfactants may contain, in addition to,
or instead of soap, a non ionic foam depressant. This may, for
example, be a C16_22 azalea monoethanolamide e.g. rape
monoethanolamide, a C16_22 a~kyl phenol ethoxylate, ~16 22
- 39 - 1 X~7 7 1 9
alcohol ethoxylate or C16_22 fatty acid ethoxylate.
Alternatively, or additionally, the composition may contain an
alkali metal moo and/or do C16 22 alkyd phosphate ester. The
non ionic or phosphate ester foam depressant is typically present in
the Formulation in a proportion of up to 10X, preferably 2 to 8X
e.g. 3 to 4% based on Dry Weight.
Silicone anti foams may also be used, as or as part of, the
foam depressant. The effective concentration of these last in the
formulation is generally substantially lower than in the case of the
other foam depressants discussed above. Typically, it is less than
2X, preferably less than 0.1%, usually 0.01 to ~.05X e.g. 0.02X of
the Dry Weight of the formulation.
Type "A" formulations preferably contain the Usual Minor
Ingredients. Certain fabric softness, such as clays, Jay be included,
however cat ionic fabric softeners are not normally effective in
anionic based Formulations, but may sometimes be included in
specially formulated systems.
The type "B" Formulations of our invention comprise Soap as
the principal active component. They may additionally contain minor
amounts of non ionic or other anionic surfactants.
The typical percentage Dry Weight of type "B" Formulations may
be rather lower than type "A", e.g. 25 to 60X, preferably 29 to 45X.
The total proportion of Active Ingredients is usually between 10
and 60X, preferably 15 to 40X e.g. 20 to 30X of the Dry Weight of
the composition. Builder proportions are typically 30 to 80X
of Dry Weight. In general the mobility of type "B" Formulation can
be improved by including sufficient water soluble inorganic
electrolyte, especially sodium silicate, in the Formulation.
High foam Soap Formulations may typically contain Active
Ingredient consisting substantially of Soap, optionally with a minor
proportion of a non ionic foam booster and/or stabilizer as described
in relation to type "A" Formulations, and/or with sulfated anionic
booster such alkyd ether sulfite or alkyd ether sulphosuccinate.
i2277i9
Low foam type B Formulations may contain a lower concentration
of Soap together with minor proportions of sulfated and or
sulphonated anionic surfactant, non ionic or phosphate ester foam
depressants and/or silicone anti foams.
The relationship between sulfated and/or sulphonated anyone
surfactants and Soap in a type "B" low foam formulation is the
converse of that in a type "A" low foam formulation. In a type I
fonmulatian, the sulfated and/or sulphonated anionic surfactant
acts as foam suppressant when present in a proportion of from about
20 to about 60~ of the weight of the Soap.
The non ionic, phosphate ester and silicone foam depressant are
conveniently, substantially as described in relation to type "A"
detergents.
"Type "B" detergents may contain any of the Usual Minor
Ingredients. As in the case of type A Formulations, cat ionic Annie
softness are not normally included, but other fabric softeners may
be present.
Our invention therefore, provides, in accordance
with a specific embodiment, a Non-sedimenting, Parboil,
fluid, detergent composition having a Payload of from 20
to 60% and comprising water; from 10 to 55% Dry Weight
of Active Ingredients based on the Dry Weight of the
composition, said Active Ingredients consisting at least
predominantly of Soap; and from 20 to 80%, based on the
Dry Weight of the composition of a Builder at least
partly present as solid particles suspended in said
composition; the Payload being above the minimum value
at which the composition is Non-sedimenting and below
the maximum value at which the composition is Parboil;
and the composition containing sufficient Electrolyte to
form a lamellar or vesicular organic structural component.
I
~.~
` ` 41 i22~719
Non ionic based detergents of type "C" represent a partaker
important aspect of the present invention. There has been a trend
towards the use of non-ion~c surfactants in 1 sundry detergents
because of the increasing proportion of man-made fire in the average
wash. Non-ionics are particularly suitable for cleaning man-made
fires. However, no commercially acceptable, fully built nonionic
liquid detergent formulation has yet been marketed.
Even in the detergent powder field, the choice and level
of non-ionic surfactant has been restricted. Many of the detergent
Formulations of our invention here~nbefore described have been
designed to give stable, Parboil, rid detergent compositions
having a washing performance equivalent to existing types of powder
Formulation, or to compositions which could readily be formulated as
powders. However, It has not hitherto been possible to formulate
certain types of potentially desirable non ionic based detergents
satisfactorily, even as powders. Thus is because "solid"
compositions containing sufficiently high proportions of the desired
non ionic surfactant often form sticky powders which do not flow
freely and may give rise to packaging and storage problems. Such
surfactants have therefore had to be restricted to below
optimum proportions of detergent powders or to low Pay Load,
dilute, or light duty, liquid compositions.
Our invention therefore provides, according to a preferred
specific embodiment, a Non-sedimenting, Parboil, fluid, aqueous
based, detergent composition having a Payload of from
30% to 75% and comprising water; from 10% to 50% Dry
Weight of Active Ingredients, based on the Dry Weight of
the composition, said Active Ingredients consisting, at
least predominantly, of non-ionic surfactant, preferably
having an HUB of from 10 to 18; sufficient Electrolyte
to form an organic lamellar or vesicular structural
component; and from 30% to 80%, based on the Dry Weight
of the composition, of Builder, at least partially
present as suspended solid particles; the Payload being
above the minimum level at which the composition is
Non-sedimenting and below the maximum at which it is
Parboil.
Jo ,
122'7719
4 1 A
Preferably the surfactant is present as a hydrated solid or
liquid crystal Separable Phase.
Any of the non ionic surfactants herein before described or any
mixture thereof may be used according to this embodiment of the
invention. Preferably, the surfactant comprises a C alkyd
group, usually straight chain, although branched chain and/or
unsaturated hydrocarbon groups are not excluded. Preferably, the
non ionic surfactants present have an average HUB of 12 to 15.
The preferred non ionic surfactant in Type C Formulations is
fatty alcohol ethoxylate.
_ 42 - 1 Z 2 7 7 1 9
For high foam type "C" Formulations, we prefer C12 16 alkyd
nonionics having 8 to 20 ethylenoxy groups, alkyd phenol ethoxylate
having 6-12 aliphatic carbon atoms and 8 to 20 ethyleneoxy groups
together optionally with a minor proportion e.g. 0 to 20~ of the Dry
Weight of the composition of anionic surfactant preferably sulfated
and/or sulphonated anionic e.g. alkyd Bunsen sulphonate, alkyd
sulphate,alkyl ether sulfite, paraffin sulphonate, olefin
sulphonate or any of the other sulfated or sulphonated surfactants
described above, but not including substantial amounts of any foam
depressant. The Formulation may however include a non ionic foam
booster and/or stabilizer such as C10_18 azalea m~noethanolamide
typically in proportions as described above in relation to type "A"
Formulations. Preferably the non-ionic Active ingredients together
have an HUB of 12-15.
Low foam non10nic compositions according to our invention are
especially preferred. They preferably comprise 10 to 40% based on
Dry Weight of the compoSlt~n of C12-18 alkyd 5 to
ethyleneoxy, non ionic surfactants such as fatty alcohol ethoxylates,
fatty acid ethoxylates or alkyd phenol ethoxylates, having a
preferred HUB of 12 to 15. They optionally contain a minor
proportion, e.g. up to 10~ by weight of the composition of any of
the anionic sulfated and/or sulphonated surfactants herein before
described in relation to type luau detergents, and they contain a
foam depressant such as a moo, dip or trialkyl phosphate ester or
silicone foam depressant, as discussed herein before in the context
of low foaming type aye detergents.
Type "C" Formulations may contain any of the Usual Minor
Ingredients.
In particular, non ionic based detergents of our invention may
incorporate cat ionic fabric softeners. The cat ionic fabric
softeners may be added to type "C" Formulations, in
_ 43 _ 122~7~L9
a weight proportion based on the non ionic surfactant of from 1:1.5
to 1:4 preferably 1:2 to 1:3. The cat ionic fabric softeners are
cat ionic surfactants having two long chain alkyd or alkenyl groups,
typically two Clue alkyd or alkenyl groups, preferably two
tallowyl groups. Examples include do C12_20 alkyd do (lower, e-g-
Clue, alkyd) ammonium salts, e.g. do tallowyl dim ethyl ammonium
chloride, Dick alkyd) benzalkonium salts e.g. ditallowyl
methyl bouncily ammonium chloride, do C16_20 alkyd amino
idazolines and do Clue azalea amino amine or quaternised amino
ammonias, e.g. bus (tallow amino ethyl) am~onium salts.
Formulations containing cat ionic fabric softeners preferably
do not contain sulfated or sulphonated anionic surfactants or
soaps. They may however contain minor proportions of anionic
phosphate ester surfactants e.g. up to I by weight of the
composition preferably up to 2X. They may additionally or
alternatively contain minor proportions leg. up to 3X, preferably 1
to I by weight of amphoteric surfactants such as buttons and
sulphobetaines. They may also contain smectite clays, and the Usual
Minor Ingredients.
Minor Ingredients
Compositions of the invention may contain the Usual Minor
Ingredients. Principal of these are anti redeposition agents,
optical brightening agents and bleaches.
The most commonly used anti redeposition agent in making
f`
44 1Z27719
detergents us sodium carboxymethyl cellulose (SCMC), and we prefer
that this be present in compositions of this invention e.g. in
conventional amounts e.g. greater than 0.1 but less than 5X, and
more usually between 0.2 and 4X, especially 0.5 to 2X preferably 0.7
to 1.5X. Generally speaking SCMC is effective at concentrations of
about 1X and we prefer not to exceed the normal effective
concentrations very substantially, since SCMC in greater amounts can
raise the viscosity of a liquid composition very considerably. At
the higher limits discussed above e.g. 4-5~ of SCMC, many
Formulations cannot be obtained in a Parboil form at high Payloads.
Alternative antlredeposition and/or soil releasing agents
include methyl cellulose, polyvinylpyrrolidone, carboxymethyl starch
and similar posy electrolytes, all of which may be used in place of
SCMC, as may other water soluble salts of carboxymethyl cellulose.
Optical Brighteners (Oboes) are optional, but preferred,
ingredients of the compositions of our invention. Unlike some prior
art formulations, our compositions are not dependent on Oboes for
stability and we are therefore free to select any convenient and
cost effective OVA, or to omit them altogether. We have found that
any of She fluorescent dyes hitherto recommended for use as Oboes in
liquid detergents may be employed, as may many dyes normally
suitable for use in powder detergents. The OVA may be present in
conventional amounts. However we have found that Oboes in some
liquid detergents (e.g. type C formulations) tend to be slightly
less efficient than in powder detergents and therefore may prefer
to add them in slightly higher concentrations relative to the
Formulation than is normal with powders. Typically concentrations
of OVA between 0.05 and 0.5X are sufficient e.g. 0.075 to 0.3X
typically 0.1 to 0.2S. Lower concentrations could be used but are
unlikely to be effective, while higher concentrations, while we do
not exclude them, are unlikely to prove cost effective and may, in
some instances give rise to problems of computability.
Typical examples of Oboes which may be used in the present
invention include : ethoxylated l, 2-(benzimidazolyl) ethylene; 2-
styrylnaphthtl,2d-]oxazole; Boyce' methyl-2-benzoxazolyl)
ethylene;disodium-4,4'-bis(6-methylethanolamine-3-anilino-11,3,5-
triazin-2"-yl)-2,2'-stilbene sulphonate; N-(2-hydroxyethyl-4,4'-bis
/ - -
i227719
(benzimidazolyl)stilbene; tetrasodium Boyce ~4U-bis(2''-
hydroxyethyl)-amino-6"~3"-sulphophenyl) amino-1", 3", treason"-
ye amino]-2,2'-stilbenedisulphonate; disodium-4-(6"-
sulphonaphthotl',2'-d]triazol-2-yl)-2-stllbenesulpfount; dtsodium
Boyce~4"-(2"'-hydroxyethoxy)-6"-amino-1",3",~"-triazin--yule
amino] 2,2'-stilbenedisulphonate; 4-methyl-7-dimethyl aminocoumarin;
and alkoxylated 4,4'-bis-(benzimidazolyl) stilbene.
Bleaches may optionally be incorporated in liquid detergent
compositions of our invention subject to chemical stability and
compatibility. Encapsulated bleaches may form part of the suspended
solid.
The action of proxy bleaches in compositions of our invention
may be enhanced by the presence of bleach activators such as twitter
acutely ethylenediamine, in effective amounts.
Photoactive bleaches such as zinc or aluminum sulphonated
phthalocyanin, may be present,
Perfumes and colorings are conventionally present in laundry
detergents in amounts up to 1 or 2%, and may similarly be present in
compositions of our invention. Provided normal care is used in
selecting additives which are compatible with the Formulation, they
do not affect the performance of the present invention.
Proteolytic and amylolitic enzymes may optionally be present
in conventional amounts, together optionally with enzyme stabilizers
and carriers. Encapsulated enzymes may be suspended.
Other Minor Ingredients include germicides such as
formaldehyde , pacifiers such as vinyl latex emulsion and
anticorrosives such as benzotriazole.
46
1227719
Compositions ox our invention are, in general, s~itabte for
laundry use and our invention provides a method of washing clothes
by agitating them in a wash liquor containing any composition of the
invention as described herein. Low foam compositions herein
described are on particular of use in automatic washing machines.
rho compositions may also be used in the washing of dishes, or the
gleaning of hard surfaces, the low foam products being particularly
suitable for use on dish washing machines. These uses constitute a
further aspect of the ~nvent~on.
Compositions of our invention may, generally, be used for
washing clothes on bullying water, or for washing at medium or cool
temperatures, e.g. 50 to 80C, especially 55 to 68C, or 20 to
50C especially 30 to 40C, respectively. Typically the
composlt~ons may be added to the wash water at concentrations of
between 0.05 and 3Z Dry Weight based on the wash water preferably
0.1 to I more usually 0.3 to 1Z e.g. 0.4 to 0.8Z.
47 1227719
The invention will be illustrated by the following examples:
wherein all figures relate to by wt. based on total composition,
unless otherwise stated.
Compositions of the Various Feed stocks Materials
1. Sodium Clue linear alkyd Bunsen sulphonate
For all formulations the alkyd Bunsen sulphonate used was the
sodium salt of the largely para-sulphonated "Do bane" JO material.
(Do bane us a Registered Trade Mark).
The composition is as follows:-
Coo Oil C12 C13 C14 C15
13.0 27.0 27.0 19.0 11.0 1.0
This composition refers only to the alkyd chain length.
2. Coconut Monoethanolamide
Has the following composition:-
RCO(NHCH2CH20H)
where R Is as follows:-
C5 0.5X
C7 6.5X
Cog 6.0X
C11 49.5X
clue 19. So
C15 8.5X
Starkey C17 2.0X
Oleic C17 6.0X
Linoleic C17 1.5
48 ill 7 I
3. Sodium alpha olefin sulphonate
This material is the sodium salt of sulphonated C16~C18olefin having the following approximate composition.
55.0~ C16 Terminal olefin
45.0% C18 Terminal olefin
4. C12-C18 Alcohol + 8 moles Ethylene Oxide
This material is an average 8 mole ethylene oxide condensate
of an alcohol of the following composition:-
C1~ 3.0
C12 57.0
C14 20.0~
C16 9.0%
C18 11.0~
5. Sodium C14_17 n-Alkane Sulphonate
This material was prepared by neutralizing sulphonated
C14-C17 normal paraffins with sodium hydroxide and contained
10X disulphonatPs based on total Active Ingredients.
6. Sodium C12-C1~ Sulfite
-
This refers to the sodium salt of a sulfated fatty alcohol
having the following composition:-
C10 3.0X
C12 57-0
C14 20.0
C16 9.0~
C18 11 . OX
49 12277~9
7. Sodium Tripolyphosphate
This material was added as an hydrous Nope containing
30~ Phase I.
8. Sodium Silicate
This material is added to Formulations as a viscous aqueous
solution containing 47X solids with a Noah ratio of 1:1.6.
9. Optical Brightener
The optical brightening agent for Examples 51 to 66 was the
disodium salt of 4;4'- ~di(styryl-2-sulphonic acid)] biphenyl which
us marketed under the trademark "TIN OPAL C8S-X ". The optical
brightener for Examples 1 to 50 was a mixture of the aforesaid
Optical brightener with the disodium salt of 4'4'- do
chlorostyryl-3-sulphonic Acadia biphenyl which mixture is marketed
under the trademark "TIN OPAL ATS-X".
Note
All alcohols and their ethylene oxide adduces referred to are
straight chained and primary.
All the examples were prepared by adding the surfactant,
usually as hydrated solid, to a 47~ solution of the silicate. The
other ingredients were then added in the order shown in the tables
reading from top to bottom, except that the principal Builder was
added last. At each stage, a small addition of water was made,
whenever it was required in order to maintain a fluid homogeneous
system. Finally, the composition was diluted to the desired
percentage Dry Weight. The entire preparation was carried out as
close as possible to ambient temperature consistent with adequate
dispersion of the ingredients. In the case of examples 20,21,22
and 23, a concentrated aqueous solution of the electrolyte (i.e.
sodium sulfite, sodium chloride, sodium carbonate and potassium
carbonate respectively) was used in place of the solution of
silicate in the above procedure. In some instances, especially with
relatively high melting non-ionic surfactants, such as coconut
monoethanolamide, gentle warming e.g. to about 40C was required
to ensure complete dispersion. In all the Examples on which sodium
tripolyphosphate was used in substantial amounts this temperature
was achieved by the heat of hydration without external heating.
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I 12Z7719
Ego 33 Ego 34
Components
_ _
Sodium C10-C14 linear 12.0 13.1
alkylbenzene sulphonate
.
Coconut monoethanolamide 1.6 1.7
Sodium Tripolyphosphate 28.0 30.7
Sodium silicate 6.4 7.0
Sodium zillion sulphonate - 5.5
Sodium carboxymethyl 1.6 1.7
cellulose
Optical brightening - 0.18
agent
Detergent Enzymes 0.07
(Espresso urea 8.0)
Water to 100 to 100
i227719
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Ego 48
Components (a) (b) (c) Ego 49
Sodium C10-14 linear alkylbenzene8.5 9.0 10.0 3.6
sulphonate
Fifteen moles ethoxylate - - ^ 7.1
of C16-C18 alcohol
Sodium salt of a 50:50 mixed 1.7 1.8 2.0
moo and do C16-18 alkyd phosphate
Sodium trlpolyphosphate 25.5 27.0 29.0 24.9
Sodium silicate 5.1 5.4 6.0 3.6
Sodium carboxymethyl cellulose 1.4 1.4 1.6 0.7
Optical brightening agent 0.17 0.18 0.20 0.14
Silicone defamer - - - 0.02
Water to loo to loo to loo to 100
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~2Z7719
Of the Examples, 1 and 2 represent a basic type A Formulation, 3
and 4 a type A formulation with SCMC and optical brightener, I,
(b) and (c) represent a type A Formulation at three different Pay
Loads, 6 and 7 demonstrate that neither SCMC nor optical brightener
is essential to obtain a Non-sedimenting Formulation; 8 contains
anticorrosive and perfume; 9 (a) and (b) illustrate a high Builder to
Active ratio Formulation (3:1) at two Pay Loads, aye and (b)
illustrate a relatively low Builder to Active Formulation at two Pay
Loads; 11 corresponds to a Non-sedimenting Formulation obtained by
centrifuging the Formulation of Example 9 at low Payload for only
three hours and decanting the supernatent liquor; 12 illustrates the
effect of relatively high SCMC levels; 13 to 19 illustrate Type A
Formulations with various anionic surfactants; 20 is a
comparative example illustrating an inoperative concern-
traction of sulfite; 21 to 24 illustrate
various Electrolytes, and 25 is a Formulation in which sodium
tripclyphosphate is the sole Electrolyte; 26 to 31 illustrate various
Builders and mixtures thereof; 32 is a high Builder to Active
Formulation; 33 is an enzyme Formulation; 34 contains Hydrotrope; 35
has a triethanolamine salt of the surfactant; 36 to 38 illustrate
olef~n sulphonate and 39 to 42 paraffin sulphonate Formulations, on
each case with successively increased Electrolyte; 43 to 46
illustrate type B formulations, 43 at three Pay Loads and 44 to 46
with increasing Electrolyte; 47 corresponds to Type B Formulation
obtained after centrifuging 43 at low Pay Load for only three hours;
48 and 49 illustrate low foam Type A and C Formulations respectively;
50 to 54 illustrate various Type C Formulations; 55 is a Type C Form-
elation with cat ionic fabric softener; 56 illustrates a branched
chain alkyd Bunsen sulphonate, 57 coconut diethanolamide and 58 a
non ionic free formulation; 59 and 60 illustrate the use of
phosphonate builders; 61 to 62 relate to formulations particularly
adapted to different parts of the North American market, being
respectively phosphate free and high phosphate; 63 to 66 are
formulations adapted to the needs of certain Asian markets.
122~7719
6~/65
The comparative example represents a commercial
Formulation currently being marketed in Australia which
corresponds to Australian Patent 522,983. The material
as purchased was tested, except for the neutron scattering
results which were carried out on samples prepared in
accordance with the example of the patent to match the
commercial Formulation as analyzed and using deuterium
oxide instead of water. The composition, by analysis,
was:
Sodium C10-14 linear ~lkylbenzene sulphonatP 12
Sodium salt of three mole ethoxylate of 3
C12-15 alcohol sulfite
Sodium tr~polyphosphate 15
Sodium carbonate 2.5
Optical brightener (Tin opal LAMS) 0.5
Sodium carboxymethyl cellulose 1.0
Water to 100
3. Example Test Ryes _ s
The foregoing examples were subjected to various tests, the
results of which are tabulated:
Note The Phases separated from the centrifuge test are numbered from
the bottom (i.e. the densest layer) upwards.
12Z7719
- 66 -
Examples 1 2
1. Centrifuge Test Results
No. of Phases Separated 1 2 1 2
_ . , _
i i . Description Opaque clear Opaque clear
solid/paste thin solid/paste thin
l squid liquid
iii. Proportion I _ 80.9 19.1
iv. Surfactant content (~) _ ~0.1
v. Loss on Drying at 110 C (X) _ 74.8
vi. Y;scosity (Pays) at 20 CC 0.01
2. Classification (croup) III III
_ by C~ifuging
3. Viscosity (Pays)
4. Yield Point (DYnestcm 2) _
5. Neutron Diffraction Results
i. Muzzler scattering
__
Ida No. of other peaks
b Description -
c Structural repeat distance (A)
iii. Suggester Structure
6. Zoo Diffraction Results
i. Muzzler Scattering
Ida No. of o'er peaks
b Description
c Stn~ral repeat distance (A)
iii. Suggested Stmcture
7. Electron Microscopy Results
i. Co~resDondin~ Figure Nun.
' i i Doherty -
8. Mobility Parboil Parboil
9. Stability No sedimentation Corey No sedimentation
12 ninths at ambient Corey 12 ninths at
laboratory sorters ~nbient laborabD~y
tourer
1227~i9
- 67 -
Expels 3 4 _ I
1.
i. 1 2 1 2 1 _ I
i i. Opaque clear Opaque clear Opaque clear
solid/paste thin solid/paste thin solid paste thin
l issue d l icky d i d
iv. - _ _ _ - 0.1
v. - 77.3
vi - _ _ - 0.01
2. III _ III III
3. _ _ 1.70
4. _ 12
5. _
¦ Present- Norway
Ida _ I one
b ¦ name
c ¦ 33.4 A
iii. ¦ Lapel far drayed solid
I See FIG l
6. 1
i.
Ida
C
iii.
7.
i.
ii.
8. Curable Curable Readily parboil
9. No sedimentation over No sedimentation No sedimentation over
12 nonwhites at ambient aver 12 norTths at 12 nuns at ambientliberal t~peratures ambient t~perat~re I-
I' .
~2Z7719
\
- 68 -
Examples I I _ 6
1.
i. 1 2 1 2 ` 1 2
i i . Opaque clear Opaque clear Opus clear
solid/paste thin solid/paste thin solid/paste thin
liquid l squid l squid
iii. 81.7 18.3 86 14X
iv. C0.1 0.1
v. 75.7 74X
TV 0.01 O 01
2 III III III
3. 2.60 4.8~ 4.58
4. 36 178
5.
i. Preser~t-nan~
Ida two
b Nan, broad
O O
c 34.9 A, 26.7 A
iii. 2 Discrete lonelier
structures
6.
i. Present
Ida one
b nay
c 31 A
iii. on ageirg tire Jo lonelier
strokers have urged
7.
i. FIG 12
ii. Littler Features
8. Curable Viscous but Parable Parable
9. No sedimentation won No sedimentation No sedimentation outer
12 no at ancient also won 12 ninths at 12 ninths at ancient
3 no s at 0 and 37C ambient top. up.
7~19
- 69 -
ExanDles 7 8 I
1.
i. 1 2 1 2 1 2
_
i i . Opaque clear Opus clear Opaque clear
solid/paste thin solid/paste thin solid/paste thin
liquid liquid liquid
Jo; .
iv, -
v. -
TV --
.
2 III III III
3. 3.04 2.84 1 4.00
4 . .
5.
i. . _
Ida
c
iii.
_
6.
i.
Ida
iii.
7.
i
i;.
8. Parboil Curable Curable
9. No sedimentation over No sedimentation No sedimentation over
12 ninths at ambient won 12 ninths at 12 n~r~ths at ambient
Taipei. arrant top.
12Z7~19
- 70 -
Exiles jib) aye , 10(b)
1 1 2 1 2 1 2
i i . Opaque clear Opus clear Opaque clear
solid/paste thin solid/paste thin solid/paste thin
liquid liquid liquid
.
i l i . - -
iv. - _ _
v. -- _ _ _
Vi. _ _
2. III _ _ III III
3. 8.75 3.85 8.00
4.
5.
1. .
Ida
b
c .
. iii.
6.
i. -
aye -
iii. .
_
7.
I., .
ii.
8. Yiscaus but parable Curable viscous jut parboil
9. No sedimentation aver No sedimentation No sedimentation won 12 north at ambient over 12 Nanette at 12 ninths at arrant
I- Anita ten. top.
g
lo 9
- 71 -
Exam pi en 11 12 13
I - .
i. l 2 1 2 1 2
. .
i i. Opaque clear Opaque clear Opaque clear
solid/paste thin solid/paste thin solid/paste thin
l icky d l icky d l icky d
jjj. _ _ _
i v. - _
y. _ _
ye _ _
2. III ¦ III III
3. 2.48 1 0.93 1 _
4. - I _ 48
5. 1
i. I
Ida
b
c I .
iii. I
6-;.
Ida
b
c
iii.
I
ii. ' .
8. Parboil Readily curable Visuals but Curable
9. No sedimentation won No sedimentation No sedimentation over
12 ninths at ancient over 12 ninths at 12 ninths at ambientto ambient to. top.
-" ~2277~9
- 72 -
ales 14 15 16
i. 1 2 1 2 1 2 3
ii. Opaque clear Opaque clear Opaque clear solid
solid/paste thin solid/paste thin solid/paste yin
1 squid liquid l squid
iii.92.4~ (w/w) 7.6X _ _ 72 (vol/vol)12 16
iv - 1.7X _ 0.3
v I 7X _ _ 76.3
Vi. - 0.01 _ _
2. III III III
3. 1.95 3.00 2.97
4. _ _
5.
i. ..
Ida
C
iii-
I
Ida
C
jig.
Jo i-
I: ii-
8. Curable Viscous but parable Parboil
9. No se~inentation aver No sedin~ntation clef No sedimentation over
12 ninths at ambient 6 n~n~6 at ambient 6 ninths at ambient
top. top. up.
Jo
12277~1 9
- 73 -
Examples 17 18 19
1. l
i. 1 2 1 2 1 2
ii. Opaque clear Opaque clear Opaque clear
solid/paste thin solid/paste ~nsc~s solid/paste thin
liquid liquid liquid
iii i I (vilely) 10 Ox
iv. 7.9 _ _ _ 74.7X
v. 72.1 _ - _ - O.OlX
TV _ _--
Z. III III III
3. 5.15 6.46 2.20
4. _ 4 36
5.
Present includes Peak
Ida one
b very Norway
c AYE
iii. Mueller + 'I" Phi
(see FIG 2)
6.
i- very broad
Ida two
O
b nary at SOAR broad at AYE
c 50 A
iii. Muzzler 'I" Phi
7.
i.
ii.
8. Viscous but parboil Viscous but parboil Curable
9. No sedimentation over No sedimentation over No sedimentation over
10 ninths at ancient 6 ninths at ancient 6 ninths at ambient
--up. up. I-
`
.
12277~
74
Examples
20 (Comparative) 21 22
1.
ii. Opaque Clear Opaque clear Opaque clear
solid/paste thin solid/ thin solid/ thin
iii. liquid P 78 22 paste fig id
iv. - ~0.1 - - ~0.1 _ 0.4
v. _ 74. , _ 79.6 _ 79.1
vi. _ 0.0 . - 0.01 - 0.01
III III III
3 2.60 4.28 2.48 ~~-`~ Jo
4.
5 .
i Present
Ida one
sharp
AYE
iii. lamellar hydrated
solid
(see Fugue)
6.
i. Present
Ida one
. lo her hydrated
solid
7.
i.
ii
8. Parboil Viscous but Parboil
I Parboil .
9. Unstable,un- No sedimentation No sedimental
acceptable over 12 months lion over 12
crystallize- at ambient temp. months at
lion also 3 months ambient temp.
at 0 & 37C also 3 months
at 0 & 37C
~%277~
- 75 -
Examples 23 aye 24(b)
1.
i. 1 2 1 2 1 2
i i . Opaque clear Opaque clear Opaque clear
solid/paste thin solidlpaste thin solid past thin
1 idea liquid 1 iqùid
__
iii. 30 _ _ _ ..
iv. - < 0.1 - 0.1 - < 0.1
v. ;1~.4 _ I - 82.9
Vi. - 0.01 - 0.01 - 0.0
2. III III III
3. 3.21 0.88 1.87
4 _ _
I:
I-
Ida
b
c
iii.
6.
i. .
Ida
c
iii.
7. ;.
it
8. Curable ¦ Readily Curable Curable
9. No sedimentation over No sedimentation over No sanitation over
12 n~r~ths at aTbie~Tt 3 ninths at Anita 12 n~rths at ambient
top. also 3 ninths at up. up.
O and awoke
122771 9
- 76 -
Examples 24~c) 25 26
i. 1 2 1 2 1 2
ii. Opaque clear Opaque clear Opaque clear
solid/paste thin solid/pastethin solid/paste flown
liquid liquid livid
;. _ _ (vo1/vol )40 1 - -
iv - 0.1 - ~0.1
v. - ED - 84.6
Vi. - 0.~31 - 0.01
2. III III III
3. 2.38 I . 1.9g
5.
i. Present- nary
_
Ida one
b sharp
c __ 34.5 A
iii. lamellar drayed solid
(see FIG 4)
6.
i. Present
Ida one
b Sharp
c 33 A
iii. Lalellar Hydrated solid
.
7.
i. _
ii.
.
8. Parable Parable Parboil
9. No sedimentation over No sedinentat70n over No sedimentation o'er
12 nones at arbie~t 9 ninths at ambient 6 ninths at arrant
ten. Tut. up.
or
. to
--`` i227~
- 77 -
lies 27 28 29
En 1- - .
i. 1 2 1 2 3 1 2
ii. Opaque clear Opaque clear solid Opaque clear
solid/paste thin solid/paste thin solid/paste thin
1 ill; d 1 iqlid l it d
_ 2D(vol/vol) I 45 74 26
iv. - _ 0.8
v. - _ 58.5
Vi. - - .
2. III III III
3. 1.31 6.91 8.46
4. _ _
i. _
Ida
b
iii.
6.
I.
Ida
c . . .
iii.
7. ;.
ii.
8. Readily Parboil Viscous but parboil Viscous but parboil
9. No sedin~n~ation aver No sedime~ation aver No sedimentation won
2 no s at ambient 9 ninths at into 3 nDrTths at ambient
tell. up. slop.
I 9
- 78 -
Examples 30 _ 31 32
i. 1 2 3 1 2 1 2
ii. Opaque . clear solid Opaque clear Opaque clear solid/paste thin solid/paste thin solid past thin
Lyle l it d l icky d
Volvo I 33 _ 87 13
MY- _ _ __ I
I. 0.01
2. III III III
3. 3 11 0 33 6.50
5. _
I.
Ida
b
_ _
ill.
6.
I . _
Ida , .
b
c
iii.
7.
i.
ii. . .
8. Curable Readily Plrable Yip sets jut pourab to
........................... ....... ....
9. No sedimentation over No sedimentation over No sedimentation over
1 ninths at arrant 2 ninths at Anita 12 n~rths at ambient
t31p. top. I-
227719
- 79 -
Exiles 33 34 35
1.
i. 1 2 1 2 _ 1 2
i i. Opaque clear Opaque cloy Opaque clear
solid/paste thin solid/paste thin solid/paste yin
liquid liquid livid
lit 83 O 72 28 _ _
TV. 0.1 _ 27
v. - _ _ 45
vi. - 0.01 _ 0.3
2. III III III
3. 2.~3 7.0 1.10
4 _ 3
i.
ii pa _
c
iii.
6.
Ida
b
c
iii.'
7.
i.
ii. .
8. Curable ¦ Discos but pcur~le Readily Parboil
9. No sedime1ltation over No sedimentation over No sedi~ntation Corey
12 ninths at alDient 9 nD~ths at ancient 4 nollths at ambient
I- up. Snoopy.
1~277~
- 80 -
lies 36 37 38
Jo . _
1.
i. 1 2 1 2 1 2 3
ii. Opaque coal Opaque cluck Opaque clear visuals
solid/paste viscous solid/paste viscous solidlpaste thin liquid
Lydia lulled livid
iii. 75~vol/vol) 25 35(vol/vol) 15
TV. - 16.7 - 15.0 _ _
v - 65 5 59.3
TV 1 0.5
.
2. III III II
3 3.7~ 6.36 3.74
4 Tao Tao Tao
5. very broad with surfer-
i. ionized Peak
Ida one
b Nan
c 61 A
i ii. mice far phase +
'I" Phase (see FIG 6)
6.
Present
Ida two`
b sharp, sharp
c 57 38 A
i ii . mice far phi +
'I" Phase
7.
FIX 13
i i . Lyle far features sot
concentric structures
8. Discs Tut parboil Viscous but Parboil Parboil
9. No sedimentation over No Sydney on over No sedimentation over
6 ninths at ambient 9 ninths at ancient 9 n~rrths at aye en
top. spy
i~27~1~
- 81 -
Ex~nples 39 40 4
1.
i. 1 2 1 2 1 2 3
i i . opaque clear Opaque clear Opaque Opaque
solid/paste vies solid/p~ste viscous solid/paste Lydia
liquid liquid Lydia solid
iii.66 34 77 23
iv. - 12 10 4.4
v. 6B - 61 - 58.1
TV - 0.15 - 0.1~ 0.07
2. III III III
3. 3.10 2.87 3.21
4 0.5 0.5 0.
5.
i. Print very broad
i a aye
b broad
O
c 31 A
i ii. Mice far + 'I" Phase
(see FIX 5)
6.
i. Pent very broad
Ida one
b sharp
c 28.5 A
iii. Muzzler + 'I" Phase
7.
FITS 14 and lo
.
i i. Laurel far art
spheroidal fablers
8. Parable Parable Curable
9. No sanitation per No sedimentation over No sedimentation per
12 ninths at aFDient 9 Tenths at ambient 6 rorlths at ambient
top. top. pi
,
1227719
- 82 -
Ex~Tples 42 aye 43(b)
2 _ 3 1 1 2 1 2
ii. Opaque thin Opaque Opaque~isc~s Opt e clear
solid/paste liquid soiled solid/paste clear solid/paste thin
solid livid l squid_
j j j 8.0 _ 42.0
iv. - - 3.0
y 91 .4
I. -
2. III III III
3. 4.10 0.73 - 0.97
4. 4 1 -
5. 1
i.
Ida ¦ I
c
iii.
6.
i.
aye
b
c
iii.
7. .
i. _
ii.
8. Viscous hut curable YiscQ~s jut curable Yiscals hut parable
9. No sedimentation per No s~rentation over No sedimentation over
4 runts at arrant 12 ninths at ambient 12 months at ambient
top. to. tsp.
~-<,~
..~
1227~19
- 83 -
Expel en 43 ( c ) 44 45
i. l_ 2 1 2 3 1 2 3
ii. Opaque clear Opaque clear Clear Opaquely clear clear
solid/paste viscous solid/pas~e yin viscous solid/paste thin viscous
liquid liquid liquid liquid liquid
iii. _ ~Otv/v) 60 10
iv. . .
v
2 III II II
3. 1.72 1.19 2.74
4.
5.
i.
Ida
b
c
ii. I
I. I I
i
Ida ¦
b
c
iii. I
7.
ii.
8. Viscous but parable viscous but parboil Discs jut curable
g. No sedimentation No sedin~ntation Corey No sedinen~ation over
o'er 12 nuns at 9 errs at Ahab en 9 nuns at Aruba en
arrbient top. sty. up.
12Z7719
- 84 -
E lies 46 47 aye
x~r,p
1. i I
i. 1 2 I 1 2 1 1 _ 2
i;. Opaque clear clear Opaque clear Opaque clear
solid/ thin viscous solid/paste viscous solid/paste thin
paste liquid liquid liquid liquid
iii. 40(v/v) 50 10 1 1 7~.0 Z
iv. ! - I_ owl
v. I ! I)
vi. . I 1 0.01
2 If ¦ III ! III
3 2.48 1 11.0 1 1.58
5. I I
i. I I _
Ida
c ' I
iii.
6.
i
Ida
iii. .
7.
I.
ii.
8. ViscaJs but parable viscous but parable Readily curable
9. No sedimentation aver No sedin~r~,,ation tuner No sedi~en~tion per
9 months at ambient 4 n~ths at ambient 6 ninths at Burr
top top. tarp.
~227~19
- 85 -
E lo 48(b) 48(c) 49
,
i. 1 2 1 2 l 2 3
ii. Opaque clear Opaquely clear Opaque clear
solid/paste thin solid/past~thin solid/paste thin solid
livid liquid Lund
_.
it 83 ED 82 18.0 31.9(v/v) 23.4 44.7
iv. - / 0.1 - 0.1 - KIWI 29.6
y 79 - 76.6 - 67.1 Do
vi - O 01 0.01 0.01
.
2 III III III
3. 2.31 3.65 5.95
.
5.
i.
it .
b .
c _
it
,
6.
i ,
isle
b
c .
iii.
7. -
i.
ii.
8. Curable Parboil Eli Schulz hut parable
9. No citation over No sedin~ntation over No sedi~en~.,ation over
12 ninths at ambient 12 months at arrant 12 nuns at await.
to up. I-
i22~77~ 9
- 86 -
Expels aye 50(b) 50(c)
1.
i. 1 2 1 2 _ 1 2
i i. Opaque clear Opaque clear Opaque clear
solidlpaste thin solid/past_ thin solid/paste thin
l icky d l icky d _ l icky d
it 76 24 77.5 _22.5
iv. <0.1 < 0.1 _ C 0.1
v. 81 79.7 78~
vi. < 0.01 < 0.01 0.01
2. III III III
3. OBOE I 3.89
I
5 -
i . Very small
_
ii pa one
b _
O
.. Muzzler + "G" phase
ill. (no" predominates)
see FIG 7
6.-
i. very small
Ida two
b Nay at AYE, & AYE
c 54 A
iii. phase + same Mueller
7.
i.
ii. .
_
8. Readily curable ¦ Curable Y;SOQ1S Tut parboil
- I
9. No sedimentation aver No sedimentation won No sedimentation over
12 ninths at ambient 12 no at ambient 12 months at art
top. tsp. stop.
l~Z7~9
- 87 -
ales 51 52 53
i. 1 2 3 1 2 3 1 1 2 3
ii. Opaque clear clear Opaque clear cloudy Opaque clear waxy
solid thin oily solid thin viscous solid thin solid
paste liquid layer paste liquid Lockwood") paste liquid
iii. S9(v/v) 39 2 45(v/v) 19 36 36(v/v) 30 34
iv. 0.2 49 0.1 31.5
v. 72 48 82
vi. < 0.01 > 1.0 0.01
2 II II III
3 11.40 4.42 1.42
4. ~0.5
-5.
i . nar~/str~ng Norwalk
Ida one one
b broad Norway
c 54.2 A 56.1 A
iii. Muzzler + 'I" Phase 'I" Phase
See FIG 9 see FIG 8
6.
i. Nan
Ida two
b Norway at AYE & AYE
c 51 A
iii. nlicellar 'I" Phase
7.
i. FIG 16
ii. . Larellar features
I:
8. viscous but curable viscous but parboil Yisca~sbut parboil
9. No sedimentation over No sedinlentation over No sedimentation over
12 ninths at ambient o ninths at ambient 4 n~ntks at Anita
tell. tarp. top.
i22~7~ I
- 88 -
Exile en 54 55 56
1.' .' ..
i. 1 2 3 1 2 3 1 2
i i. Opaque clear my opaque clear waxy Opaque clear
solid/ thin solid solid/ thin solid solid/ -thin
paste 1 icky d paste 1 icky d paste 1 i gut d
iii 43(v/v) 19 3~3 qO(v/v) 27 33 76 24
iv. ~0.1 32.9 0.2 0.05
.
v 71.6 51.5 82.2
_
vi I 0.01
2 III III III
3. 1.~0 1.86 2.43
4. I _
5. .
i.
flab
iii.
6.
I. .
Ida
b
iii.
.
7.
i.
Jo I I
8. Parboil ¦ Puerilely ¦ curable
9. No sedimentation over No sedimentation over No sedimentation
4 months at ambient 3 months at ambient over 1 month at
temp. temp. laboratory ambient
temp.
~2~7~9
- 89 -
lies 57 _ 58 59
1. `
i. 1 2 1 2 1 1 2
ii. Opaque clear Opaque clear Opaque clear
solid/paste thin solid past thin solid/paste Tony
liquid liquid likelihood
jjj. 82.5 _ 17.5 1 6~.9 35.1 1 77 0 _ 23.0
iv. 0.02 1 _ 0 3 0.4
_
vi. ! -
2. III III III
3. 1.8 2.1 2.9
4. _
I. -
i.
Ida
b
iii.
.
6.
i.
Ida I -
.. I
c ,
iii.
7. 1 l
i. _ I I .
ii. I I
8. Curable Curable j Parable
9. No sedimentation won No sedimentation over ¦ Jo sedi~enta~icn over
1 ninth at laboratory 1 north at laboratory nth at laboratory
Anita to ancient top. 'into up.
~227~L9
- 90 -
En 1 en 60 6 1 62
lineup
i. 1 2 1 1 2 3 1 2
i i. Opaque clear Opaque clear Cpaq~ Opaque clear
solid/ thin solid/ yin solid solid,' viscous
waste 1 icky d paste 1 icky d paste paste 1 icky d
r
iii 73~0 27~0 1 5~v/v) 45 1 95~0 5~0
iv. 0.1 1 005 _ 1 26.2 _
v.
vi.
2. III I III I III
I 2~2 8~1 6~0
5.
i.
Ida
b
`
...
111.
6.
i.
Ida
c I I .
iii.
I 1 1
ii. ! . I
8. Parable ¦ YiscaJs it curable ¦ ViscQls it curable
9. No sedin~ntation over ¦ #o sedimentation aver lo sedinenta~ion over
1 month at laboratory ! 1 ninth at laboratory 1 n~ntn at laboratory
into top tent t3np. ambient sty.
~2;~7~
- 91 -
Examples 63 64 US
1. i 1
i. 1 2 1 1 2 1 1 2 3
ii. Opaque Clue Opaque Clay Opaquely clear Solid/
solid/ viscous solid/ viscous idea/ thin paste
paste _ l squid paste l ibid paste liquid
iii. 42.8 57.2 51.0 49.0 10(v/v) 40
iv. 21.3 22.5 0.01
TV.
Vi-
2. III III III
3 3.26 5.~0 0.75
5.
i.
ii pa
b
c
iii.
6.
Ida
c
iii.
7.
Parable ¦ Curable ¦ Readily parable
9. No sedimentation over No sedimentation over No sedimentation
1 into at laboratory ! 1 ninth at laboratory per 1 north at
attenuate to. ! ancient t3Tp. laboratory into
t top.
- 92 ^ ~2~:77~9
_ Example 66
1.
i 1 2
iiOpaque solid paste Clear thin liquid
iii 64.0 36.0
_
iv 0.2
v
vi
2. III
3. 0.56
4.
5.
ii a
b
c
I
a
b
c
iii
7.
i
8. Readily Parboil
9. No sedimentation over
1 nth at laboratory
ambient temperatures
Comparative i227719
1. Example
i. 1 2
_ . Opaque solid viscous
. liquid
24 76
i`/. 17.3
v. i 77.0
vi, 0.26
I
2.
1 '
3.
0.3
4. 4
5' I very broad with
. superimposed peaks
ii, a I None
b _
c _ ,
iii, gone. muzzler dis~er~cn
ye TIC I
i, I very wide
ii. a I one
b small
_
c t AYE
iii, kink. muzzler dispersion
7.
See FIG 17
Spheroidal features
_
8. ¦ Readily Parboil
No sedimentation over IT
. outs at laboratory
ambient temperature
Ye
, 1 .
94
1227719
Certain of the foregoing examples were tested for washing
performance as follows:-
Series 1
Representative high foaming formulations were each compared with a standard powder formulation in machine washing tests on two
different standard soiled fabric samples.
Example Cotton Polyester/Cotton Conditions
31 95Z 100X ) Temp. 50C
90X 70X ) Water 300 Pam calcium
carbonate
16 lox lox Time 30 miss.
33 95X lox Cone. = Equivalent effective
Wash
Powder 100~ 100X Solids
Standard
The term "Effective Wash Solids" refers to the sum of the Active
Ingredient and Builder. The powder standard was used at 6gm/l and
the Examples adjusted to give the same X Effective Wash Solids in
the wash Liquor.
Series 2
Representative formulations of both high and low foaming types were
tested against equal wt. dosage at three temperatures.
122771.9
Cotton Polyester/Cotton
Example Effective 40 60 85+ 40 60 85+
Wash Solids
43 (c) 93 75 100 95 75 85 50
36 66 85 85 100 80 95 75
50 (c) 93 110 110 95 180 200 200
Powder 100 100 100 100 lob 100 100
Standard
onditions: Tempt 40, 60 and 85C+
Water 300 Pam hardness
Time 30 miss.
Cone. 6 gel (as received)
96 1227719
Series 3
In this series low foaming non-ionic based examples were tested
against the powder standard.
Example Effective Cotton Polyester/
Wash Solids Cotton
52 70 110~ 100~ Conditions
53 66 105X 90X Temp...... awoke
54 61 115~120% Water 300 Pam hardness
Time 30 miss
Cone.
powder 6 gm/1
examples 11gm/1
Standard
Series 4
Two low foam non-ionic formulations were tested on naturally
soiled fabric (15 successive washes with natural soiling)
Conditions: Temperature 50C
-
Water 300 Pam hardness (wash and rinse)
Wash time 30 miss
Fabric 65 : 35 white polyester cotton
Concentration EQUAL WEIGHT i.e. 6 gel
97
1227~719
Results:
Example
52 = 100~ Sty ) optical whitener efficiency
54 = 75X Sty
52 = 95-100~ ) Soil Removal and
54 = 9~-100~ ) Deposition efficiency
The two examples were also compared against the three liquid
laundry products which have performed best in our tests out of all
those available commercially in Europe at the date of testing.
Both examples gave superior washing performance to all three
commercial products.
Drawings
Figures 1 to 11 of the drawings are neutron scattering spectra
illustrative of the different Groups herein before described. All
were prepared, using deuterium oxide based analogs of certain
examples of the invention and of the two comparative examples, on
the Harley small angle neutron scattering spectrometer at a
wavelength of 6.00 Angstrom.
In the drawing, is given by the formula:
4~1 sin 6
where is the angle of scattering and is the wavelength
it angstroms. is equal to or where D is the lattice
spacing in angstroms. I is the normalized neutron intensity.
The Figures correspond to the following examples:
98 1 2 2 7 7 1 9
Fix Example
l I
2 18
3 21
4 25
39
6 36
7 SO
8 53
9 52
A (comparative)
11 8 (comparative)
The Figure 12 to 18 are electron micro graphs prepared on the
Lancaster University low temperature scanning electron microscope
using freeze fracture etched samples, as follows:
Fig Example Magnification
12 I x2,000
13 36 x3,000
14 41 x2,000
41 x3,000
16 53 x3,000
17 Commercial Product corresponding to 'A' x2,000
18 Commercial Product corresponding to 'B' x3,000
Figs 17 and 18 relate to the æ tubal commercial products as
purchased.
'`' 'I
