Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Detergent compositions
Technical Field
The invention relates to detergent compositions in particular, to laundry
detergent
compositions.
Back. round
All detergents for laundry applications contain surfactants and builders.
Generally, most
detergents comprise a base powder, made by spray-drying or by granulation of
builder
components and surfactant components for example, by agglomeration or
extrusion. The
base powder is often further treated with post-treatment steps such as dry-
adding
additional particulate detergent components, spray-on of further liquid
components such
as surfactants, particularly non-ionic surfactants and/or post-dusting steps
using finely
particulate solid materials to reduce caking and stickiness of the solid
detergents
produced.
Environmental pressures have led to the need to produce detergents which are
as efficient
as possible. The trend to use lower amounts of more highly compact detergent
compositions, for example having a density above 600g/I or 650g/1 or above
700g/1 or
even higher, has emphasised the need to ensure full performance of all of the
detergent
components in the wash.
However, solid detergents tend to form lumps or gel upon contact with water.
Lumps of
gelled material may then fall into the sump of a washing machine where they
are not
disturbed mechanically, or because of their method of use in a machine, solid
detergents
do not dissolve, poor delivery of the product from a dispensing drawer of a
washing
machine or from a dispensing device and/or once in the machine itself results.
Poor use
of all of the detergent components is therefore achieved.
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The inventors have found that in order to overcome this problem a combination
of
properties is required. This can be achieved by control of the detergent and
the detergent
making process so that the combinations of different detergent components,
when formed
into particulates for making finished detergent are modified so that the
maximum
performance benefit for each of the detergent components is achieved. This
results in
detergent compositions which have good solubility and minimum gelling and
therefore
maximum delivery of the detergent components to the wash, for example, by
minimising
the interaction of some detergent components and maximising the interaction
between
other detergent components. These benefits lead to good washing performance
and
minimising of any fabric damage due to high localised bleach concentrations.
Summary of the invention
In accordance with the present invention there is provided a solid detergent
composition
comprising from 10-60 wt % of a surfactant system and having a maximum
Residues
Index of 25 and a maximum Secondary Residues Index of 15.
The Residues Index can be calculated in the following way:
1 litre of de-ionised water is placed in a tergitometer (Erweka DT6-R
hereinafter referred
to as the 'Sotax' apparatus) (USP 711 dissolution standard). The Sotax is
fitted with a
perspex lid to prevent evaporation, it is calibrated to a temperature of
5°C with the stirrer
(paddle) set to 200rpm. The paddle has two blades fixed at the central axis
directly
opposite one another so that overall the two blades provide the paddle with a
diameter of
75mm. The paddle is positioned in the centre of the Sotax apparatus with a
distance
between the bottom of the paddle and the bottom of the tergitometer of 25mm.
The
overall height of the paddle blades is 19mm. A wire basket is provided having
side walls
and base formed from 20 mesh (8500 stainless steel wire, a diameter of 25mm
and a
height of 41 mm. The wire basket is filled with a detergent product, the
surface of the
detergent product is levelled off and a non-permeable lid is used to close off
the top of the
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wire basket. The wire basket is then suspended in a stationary position midway
between
the central axis of the Sotax and the side wall, at a height such that the
base of the wire
basket is 7mm above the upper surface of the paddle.
After twelve minutes the wire basket assembly is removed from the Sotax
apparatus and
the residue is removed to a pre-weighed container. The transfer step must be
quantitative;
a rinsing step with de-ionised water is acceptable if needed. The residues are
oven dried
at 70-80°C until no further weight loss is recorded. The dry residue
weight is recorded.
The percentage residue from the basket as a proportion of the mass of the
initial sample of
the detergent composition which was placed into the Sotax is then calculated.
An average
of the percentage residue remaining for two identical samples provides the
Residues
Index number.
The Residues Index for the detergent compositions of the invention must be no
greater
than 25, preferably being no greater than 20, even more preferably being no
greater than
1 S.
The Secondary Residues Index is calculated in the following way:
Using the same apparatus, 800m1 of de-ionised water is charged to the Sotax
apparatus
and the temperature is allowed to equilibrate to 20 °C with a stirrer
speed of 200rpm. 2
grammes of product is then added to the de-ionised water and stirred at a
stirrer speed of
200rpm for 20 minutes. After 20 minutes, the de-ionised water containing the
detergent
sample is filtered through a C70 black fabric circle (from Empirical
Manufacturing
Company) placed in a Buchner funnel with the smooth side of the fabric
uppermost. The
black fabric is removed from the Buchner funnel and placed on a sheet of
paper. The
black fabric is allowed to dry at ambient temperature for 24 hours. Three
replicates are
obtained for each test and an average of the percent residue remaining on the
black fabric
circle as a proportion of the total detergent sample charged to the Sotax, is
calculated.
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The average residues from the three replicates provide the Secondary Resides
Index
number, which must be a maximum of 1 S. Preferably, the maximum Secondary
Residues
Index is 10, even more preferably, the maximum Secondary Residues Index may be
5 or
less.
Builder System
The detergent compositions comprise a builder system which rnay be provided by
one or
mixtures of more than one builder. Water soluble and/or water insoluble
builders may be
used. The builder system generally comprises from 1 to 90 wt % of the
detergent
composition, preferably from 20 to 80 wt % of the composition.
Water-Soluble or Partially Water-Soluble Builders
The builder system in the compositions according to the invention preferably
contains a
water-soluble and/or partially water-soluble builder compound, typically
present at a level
of from 1 % to 80% by weight, preferably in amounts up to SO wt %, or up to
40% or even
35%. Preferably water-soluble builders are present in amounts from at least 3%
or 8%,
but they are preferably present in amounts from 6 to 25 wt%.
The detergent compositions of the invention may comprise phosphate-containing
builder
material, such as tetrasodium pyrophosphate or more preferably anhydrous
sodium
tripolyphosphate. Phosphate builders may be present at a level of from 0.5% to
60%, or
from S% to SO%, or even from 8% to 40% by weight. However, it is generally
preferred
that the compositions are free of phosphate-containing builder material.
Crystalline layered silicates are also suitable partially water-soluble
builders. The
preferred crystalline layered silicate herein has the general formula
NaMSix02x+1.yH20
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wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0
to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-
0164514
and methods for their preparation are disclosed in DE-A-3417649 and DE-A-
3742043.
For the purpose of the present invention, x in the general formula above has a
value of 2,
5 3 or 4 and is preferably 2. M is preferably H, K or Na or mixtures thereof,
preferably Na.
The most preferred material is a-Na2Si205~ ~- Na2Si205 or S-Na2Si205, or
mixtures
thereof, preferably being at least 75% -Na2Si205~ for example available from
Clariant as
NaSKS-6. The crystalline layered silicate material, in particular of the
formula Na2Si205
may optionally comprise other elements such as B, P, S, for example obtained
by
90 processes as described in EP 578986-B.
Partially water-soluble builder is preferably present at a level up to 40%,
more preferably
up to 35%. When present it may be preferred that the composition of the
invention
comprises from 10% to 40%, more preferably from 12% to 35% or even from 15% to
25% by weight of the composition of the partially water-soluble builder.
The water soluble builders include organic carboxylic acids and salts thereof.
Suitable
water-soluble builder compounds include the water soluble monomeric
polycarboxylates,
or their acid forms, homo or copolymeric polycarboxylic acids or their salts
in which the
polycarboxylic acid comprises at least two carboxylic radicals separated from
each other
by not more that two carbon atoms and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance. In addition to these water-soluble builders, polymeric
polycarboxylates
may be present, including homo and copolymers of malefic acid and acrylic acid
and their
salts.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing two
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carboxy groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid,
malic and fumaric acid, as well as the ether carboxylates and the sulfinyl
carboxylates.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates, aconitrates and citraconates as well as succinate derivatives such
as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates
described in British Patent No. 1,389,732, and aminosuccinates described in
Netherlands
Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-
propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed
citrates described in British Patent No. 1,439,000. Preferred polycarboxylates
are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly citrates. The parent acids of the monomeric or oligomeric
polycarboxylate
chelating agents or mixtures thereof with their salts, e.g. citric acid or
citrate/citric acid
mixtures, are also contemplated as useful builder components.
Most preferred may be acetic acid, citric acid, malic acid, and fumaric acid,
or their salts
or mixtures thereof. It may be preferred that mixtures of the salt and acid
form are
present.
The water soluble builder is preferably present at a level up to 40%, more
preferably up to
35%. When present it may be preferred that the composition of the invention
comprises
from 10% to 40%, more preferably from 12% to 35% or even from 15% to 25% by
weight of the composition of the water-soluble builder.
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It may be preferred that the polymeric or oligomeric polycarboxylates are
present at levels
of less than S%, preferably less than 3% or even less than 2% or even 0% by
weight of the
compositions.
Borate builders, as well as builders containing borate-forming materials that
can produce
borate under detergent storage or wash conditions are useful water-soluble
builders
herein.
Other suitable water-soluble builder materials are polymeric polycarboxylic
acids or
polycarboxylates, including the water soluble homo- or co-polymeric
polycarboxylic
acids or their salts in which the polycarboxylic acid comprises at least two
carboxyl
radicals separated from each other by not more than two carbon atoms. Polymers
of the
latter type are disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylates of
MWt 1000-50000, preferably 10000 or even 7000 and copolymers of (poly)acrylate
and
malefic acid or anhydride, such copolymers having preferably a molecular
weight of from
2000 to 100,000, especially 40,000 to 80,000.
In a preferred embodiment of the invention, the water-soluble or partially
insoluble
builder, and in particular, crystalline layered silicate when present, is at
least partially, for
example at least 50 wt % present, in an intimate mixture with a surfactant,
preferably an
anionic surfactant.
It has also been found that when the highly water-soluble carboxylate- or
carboxylic acid-
containing compounds are present in an intimate mixture with one or more of
the
surfactants and optionally other ingredients, the rate of dissolution of the
intimate mixture
and also of the surfactants and other ingredients is increased. Thus, overall
a faster
delivery of the surfactants and other ingredients can be achieved.
Thus, a preferred particulate component in the detergent compositions of the
invention
herein may comprise an intimate mixture of preferably from 25% to 75% by
weight, more
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preferably from 35% to 68%, even more preferably from 45% to 62% by weight of
the
component of a of a crystalline layered silicate or water-soluble builder and
from 25% to
75% by weight, more preferably from 32% to 62% by weight more preferably from
38%
to 48% by weight of the component of an anionic surfactant.
Such a particulate component preferably comprises less than 10% by weight of
free
moisture, preferably Iess than 5%, or even less than 3% or even less than 2%
by weight.
The free moisture content as used herein, can be determined by placing 5 grams
of the
particulate component in a petri dish and placing this petri dish in a
convection oven at
50°C for 2 hours, and subsequently measuring the weight loss, due to
water evaporation
The anionic surfactant preferably comprises from 50% to 100% by weight,
preferably
from 60% or even 75% to 100% of the anionic surfactant of a sulphonate
surfactant
preferably an alkyl benzene sulphonate surfactant, as described below. As much
as 50
by weight or more based on the total amount of anionic surfactant in the
detergent
composition is preferably incorporated into such a particulate component.
Preferably such a particulate component is present in the detergent
composition in
amounts of from 0.5 to 60 wt %, preferably from 3% to 50%, more preferably
from 5% to
45%, even more preferably at a level of at least 7% by weight of the
composition.
Preferably, the weight ratio of the crystalline layered silicate and/or one or
more water-
soluble builders to the anionic surfactant in the intimate mixture is from 4:5
to 7:3, more
preferably from 1:1 to 2:1, most preferably from 5:4 to 3:2.
Such a component may also comprise additional ingredients, for example in
amounts of
from 0% to 25%, generally no greater than 20% or even 15% by weight of the
particulate
component. The precise nature of these additional ingredients, and levels of
incorporation
thereof will depend on the application of the component or compositions and
the physical
form of the components and the compositions. It may be preferred that the
particulate
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composition comprises less than 15% or even less 10% or even 5% by weight of
the
granulate of non-ionic ethoxylated alcohol surfactant, preferably less than
15%, or even
less than 10% or even Iess than 5% of any non-ionic surfactant.
It may be preferred that the particulate composition comprises less than 10%
by weight,
preferably less than 5% by weight of an aluminosilicate material. If any
aluminosilicate
material is present, it may be preferred that the particulate composition is
dusted with the
aluminosilicate material.
The particulate component may comprise polymeric binder material, although it
is
preferred to use as little binder material as possible. It may be preferred
that the intimate
mixture comprises less than 25%, preferably less than 10%, more preferably
less than S%
by weight, most preferably 0% by weight of ethylene oxide polymers.
The particulate component preferably has a weight average particle size of at
least SO
microns, preferably from 150 microns to 1500 microns, or more preferably 80%
by
weight of the particles has an particle size of more than 300 microns (80% by
weight on
Tyler sieve mesh 48) and less than 10% by weight of the particles has a
particle size of
more than 1180 microns or even 710 microns (on Tyler mesh sieve24).
Preferably, the density of the particulate component is from 380g/litre to
1500gr/litre, or
more preferably from S00 g/litre to 1200 g/litre, more preferably from 550
g/litre to
900g/litre.
The particulate component can be present in the detergent compositions of the
invention
as a separate particle, or it may be further mixed with other detergent
ingredients,
including by further agglomeration, compaction, tabletting or extrusion.
Such an intimate mixture or particulate component may be prepared by any well-
known
method for forming such detergent particulates e.g. agglomeration, spray-
drying, roll
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compaction and/or extrusion or combinations of these process steps. Such
processes may
optionally be followed by a drying step or a dusting step and/or a spray-on
step. The
granulate produced is then preferably mixed with the other detergent
ingredients.
5 The crystalline layered silicate and/or highly water-soluble builder may
also be in an
intimate mixture with other materials, including one or more of the water-
soluble builders
or polymeric compounds such as acrylic and/ or malefic acid polymers,
inorganic acids or
salts, including carbonates and sulphates, or small levels of other silicate
material,
including amorphous silicate, meta silicates, and aluminosilicates, as
described herein.
It may be preferred that part or even all of the water-soluble builder, in
particular,
monomeric or oligomeric (poly)carboxylic acid or salt thereof is in the form
of a separate
particle, whereby it may be preferred that the average particle size of this
builder material
is then preferably less than 150 microns, or even less than 100 microns. It
may be
preferred that part of the water-soluble or partially water-soluble builder is
used as dusting
agent, to reduce the caking of the product when necessary.
In particular, when small amounts of insoluble builder are present in the
compositions a
polycarboxylate polymer, such as polymer and copolymer of malefic anhydride or
acid and
(poly)acrylic acid and their salts may be incorporated at a level of from 0.5%
to 1 S%,
preferably from 1 % to 12% or even from 2% to 8% by weight of the composition.
Hereby, it may be preferred that the water-insoluble builder and the polymer
are not in an
intimate mixture with one another.
The inventors have also found that when a polymeric polycarboxylate is
present, it may
be preferred that the polymer is comprised in an intimate mixture with other
detergent
components, preferably in a spray-dried particle, which is prepared by first
mixing a
carbonate salt and the polymer and then addition and intimately mixing of
other
ingredients.
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Insoluble Builders
The compositions of the invention may contain an insoluble builder compound.
Generally these are present in amounts no more than 30 wt% based on the
detergent
composition as a whole, preferably no greater than 25 wt %.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. xH20
wherein z and y are at least 6; the molar ratio of z to y is from I .0 to 0.5
and x is at least 5,
preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate material
are in hydrated form and are preferably crystalline, containing from 10% to
28%, more
preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurnng materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS
and mixtures thereof. Zeolite A has the formula:
Na I2 [A102) 12 (Si02)12)~ xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106~~ 276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder. Zeolite MAP
is
described in EP 384070A (Llnilever). It is defined as an alkali metal
aluminosilicate of the zeolite P type having a silicon to aluminium ratio not
greater
than 1.33, preferably within the range from 0.9 to 1.33 and more preferably
within
the range of from 0.9 to I .2. Of particular interest is zeolite MAP having a
silicon
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to aluminium ratio not greater than 1.15 and, more particularly, not greater
than
1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size,
expressed as a ds0 value of from 1.0 to 10.0 micrometres, more preferably from
2.0
to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres. The ds0 value
indicates that 50% by weight of the particles have a diameter smaller than
that
figure. The particle size may, in particular be determined by conventional
analytical
techniques such as microscopic determination using a scanning electron
microscope
or by means of a laser granulometer. Other methods of establishing ds0 values
are
disclosed in EP 384070A.
Water insoluble-builders, in particular aluminosilicates, have been found to
contribute to
the problems of poor overall use of components of detergent compositions.
Therefore,
their incorporation into detergent compositions is generally at low levels, or
requires
specific processing to enable maximum efficiency of all the detergent
ingredients in a
detergent composition.
Thus, in one embodiment of the invention, aluminosilicate builder is
preferably present in
amounts below 9 wt %, preferably below 6 wt % or 4 wt %. It may even be
preferred that
substantially no water-insoluble builder is present. Preferably a detergent
composition
will contain low levels of amorphous silicates, for example less than 5 wt %
of the
composition of amorphous sodium silicate, most preferably less than 2 wt %.
In a preferred aspect the detergent composition preferably comprises a builder
system
which comprises less than 30% or even less than 20% or even less than 10% by
weight of
water insoluble builder, whereby in the preferred embodiments the balance of
the builder
system are the water-soluble builders and/ or partially water soluble
builders.
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When present, the aluminosilicate may be contained in a component containing
other
detergent ingredients, such as surfactants for example, in a detergent
agglomerate,
extrudate or a blown powder. It may even be preferred that substantially no
aluminosilicate is present as a separate (dry-added) particulate ingredient.
Also, preferably less than 3% or even less than 1.5% or even less than 0.8% by
weight of
amorphous silicate is present. When present, the amorphous silicate is
preferably
contained in a component containing other detergent ingredients, such as
surfactant for
example, in a detergent agglomerate, extrudate or a blown powder. It may be
preferred
that substantially no amorphous silicate is present as separate particulate
ingredient.
As described above, detergent compositions of the invention preferably
comprise at least
one particulate component containing an intimate mixture of one or more of the
water
soluble or partially water soluble builders and one or more surfactants.
Preferably, at
least two of such particulate components are present in the detergent
composition.
In a further embodiment of the invention, if it is desired to incorporate
insoluble builder,
particularly aluminosilicates in amounts of, for example, S wt % or more where
the
compositions also comprise anionic surfactant for example, in amounts of S wt
% or
more, the detergent composition is preferably such that there are at least two
detergent (n)
components (i) in the composition and the degree of mixing (M) or the anionic
surfactant
and aluminosilicate builder is from 0 to 0.7 where
and
a is the fraction of the anionic surfactant of the composition comprised in
the component
(i);
~ is the fraction of the aluminosilicate of the composition comprised in
component (i).
In order to achieve particularly good detergent delivery, it is preferred that
M is from 0 to
0.6, or even from 0 to 0.5.
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In such an embodiment of the invention, the detergent composition herein
comprises at
least two mufti-ingredient (i.e. no more than 95 wt % of a single ingredient
in each
component) components which comprise an anionic surfactant or an
aluminosilicate or
mixtures thereof, whereby if mixtures of aluminosilicate and the surfactant
are present in
one or more of the components, the degree of mixture M is less than 0.7, as
defined by the
formula. Thus, each component comprises part or all of the aluminosilicate,
all or part of
the anionic surfactant or mixtures thereof, provided that M is from 0 to 0.7.
The components together comprise the aluminosilicate builder at a level of
least 5% by
weight of the composition of and the anionic surfactant at a level of at least
5% by weight
of the composition. Preferably, the components comprise the aluminosilicate at
a level of
at least 7%, or more preferably at least 10% or even 15% by weight of the
composition.
Depending on the precise formulation of the composition and the conditions of
use, the
compositions of the invention can even comprise higher levels of
aluminosilicate, such as
more than 20% or even more than 25%, whilst still providing an improved
delivery of the
detergent to the wash.
Preferably at least 7% or more preferably at least 10% or even at leastl2% by
weight of
the composition of anionic surfactant is present in the components. Depending
on the
precise formulation of the composition and the conditions of use, it may be
preferred to
have levels of anionic surfactants of I 8% by weight of the composition or
more.
Such components are prepared as described above: by any granulation method
such as
agglomeration, co-compaction, spray-drying or extrusion.
Effervescence System
Any effervescence system known in the art can be used in the detergent
compositions of
the invention. A preferred effervescence system for incorporation in the
particle of the
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invention, comprises an acid source, capable of reacting with an alkali source
in the
presence of water to produce a gas.
Preferably, where the effervescence system comprises two or more reactants,
these will
be provided in an intimate mixture as an effervescence component. Most
preferably, the
effervescence component comprises an intimate mixture of substantially
anhydrous
stabilising agent with acid and alkaline reactants.
The acid source component may be any organic, mineral or inorganic acid, or a
derivative
10 thereof, or a mixture thereof. Preferably the acid source component
comprises an organic
acid. The acid source is preferably substantially anhydrous or non-hygroscopic
and the
acid is preferably water-soluble. It may be preferred that the acid source is
overdried.
Suitable acid source components include citric, malic, malefic, fiunaric,
aspartic, glutaric,
tartaric succinic or adipic acid, monosodium phosphate, boric acid, or
derivative thereof.
15 Citric acid, malefic or malic acid are especially preferred.
Most preferably, the acid source provides acidic compounds which have an
average
particle size in the range of from about 75 microns to 1180 microns, more
preferably from
150 microns to about 710 microns, calculated by sieving a sample of the source
of acidity
on a series of Tyler sieves.
As discussed above, the effervescence system preferably comprises an alkali
source,
however, for the purpose of the invention, it should be understood that the
alkali source
may be part of the effervescence particle or can be part of the cleaning
composition
comprising the particle, or can be present in the washing liquor, whereto the
particle or
the cleaning composition is added.
Any alkali source which has the capacity to react with the acid source to
produce a gas
may be present in the particle, which may be any gas known in the art,
including nitrogen
oxygen and carbondioxide gas. Preferred can be perhydrate bleaches, including
perborate,
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16
and silicate material. The alkali source is preferably substantially anhydrous
or non-
hydroscopic. It may be preferred that the alkali source is overdried.
Preferably this gas is carbon dioxide, and therefore the alkali source is a
preferably a
source of carbonate, which can be any source of carbonate known in the art. In
a preferred
embodiment, the carbonate source is a carbonate salt. Examples of preferred
carbonates
are the alkaline earth and alkali metal carbonates, including sodium or
potassium
carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with
ultra-fine
calcium carbonate such as are disclosed in German Patent Application No.
2,321,001
published on November 15, 1973. Alkali metal percarbonate salts are also
suitable
sources of carbonate species, which may be present combined with one or more
other
carbonate sources.
The carbonate and bicarbonate preferably have an amorphous structure. The
carbonate
and/ or bicarbonates may be coated with coating materials. It can be preferred
that the
particles of carbonate and bicarbonate can have a mean particle size of 75
microns or
preferably 150pm or greater, more preferably of 250p,m or greater, preferably
500p,m or
greater. It may be preferred that the carbonate salt is such that fewer than
20% (by weight)
of the particles have a particle size below 500p,m, calculated by sieving a
sample of the
carbonate or bicarbonate on a series of Tyler sieves. Alternatively or in
addition to the
previous carbonate salt, it may be preferred that the fewer than 60% or even
25% of the
particles have a particle size below 150~m, whilst fewer than 5% has a
particle size of
more than 1.18 mm, more preferably fewer than 20% have a particle size of more
than
212 p,m, calculated by sieving a sample of the carbonate or bicarbonate on a
series of
Tyler sieves.
The molecular ratio of the acid source to the alkali source present in the
particle core is
preferably from 50:1 to 1:50, more preferably from 20:1 to 1:20 more
preferably from
10:1 to 1:10, more preferably from 5:1 to 1:3, more preferably from 3:1 to
1:2, more
preferably from 2:1 to 1:2.
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17
Stabilisin~LAgentnt
The preferred stabilising agents are substantially anhydrous stabilising
agent. The
stabilising agent can comprise one or more components. It can be preferred
that the
stabilising agent comprises compounds which are, at least partially, water-
soluble.
Preferably, the stabilising agent is solid under normal storage conditions,
e.g. the
component preferably has a melting point above 30°C, more preferably
above 45°C, or
even more preferably above 50°C and it may be preferred that the
stabilising agent is such
that it readily forms a melt above 80°C.
Preferably, the stabilising agent comprises one or more components, selected
from the
group comprising alkoxylated alcohols, including polyethylene and/or propylene
glycols,
and alkoxylated alcoholamides, including ethanolamides, alkoxylated ethanol
amides,
alkoxylated fatty acid amides or ethanolamides and specific non-ionic
surfactants,
including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants and
specific
alkylpolysaccharides surfactant, and mixtures of any of these compounds, as
described
herein.
Preferably, one or more of the components comprised in the stabilising agent
are a
detergent active which can contribute to the cleaning performance of the
particle or the
cleaning composition comprising the particle. Highly preferred substantially
anhydrous
components suitable in the stabilising agent of the particle of the invention,
are one or
more non-ionic surfactant, selected from the group of non-ionic alkoxylated
surfactants,
including alkoxylated alcohol surfactants, polyhydroxyfattyacid amide
surfactants, fatty
acid amide surfactants, alkoxylated fatty acid amides, alkyl esters of fatty
acids and
alkylpolysaccharide surfactants, and mixtures thereof, as described herein
after.
In a highly preferred aspect of the invention, the stabilising agent comprises
a mixture of
polyhydroxy fatty acid amides and/ or polyethylene glycols, and/ or
alkoxylated fatty acid
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1$
amides and/ or condensation products of aliphatic alcohols with from 1 to 15,
or more
preferably 11, moles of alkylene oxide, as described in more detail below in
the
description of suitable surfactants. When present, the ratio of the
polyhydroxy fatty acid
amides to the condensation products of aliphatic alcohols is preferably from
20:1 to 1:20,
more preferably from 10:1 to 1:10, more preferably from 8:1 to 1:8, more
preferably from
6:1 to 1:6, most preferably from 2:1 to 1:3. When present, the ratio of the
polyhydroxy
fatty acid amides to the polyethylene glycol is preferably from 20:1 to 1:8,
more
preferably from 15:1 to 1:3, more preferably from 12:1 to 1:1, more preferably
from 10:1
to 1:1. When present, the ratio of the polyhydroxy fatty acid amides to the
alkoxylated
fatty acid amides is preferably from 20:1 to 1:20, more preferably ftom 15:1
to 1:10, more
preferably from 10:1 to 1:10.
Surfactants suitable for use in the Detergent Composition
The detergent compositions of the invention can contain one or more
surfactants selected
from anionic, cationic, ampholytic, amphoteric and zwitterionic surfactants or
nonionic
surfactants as described below, and mixtures thereof.
A typical listing of these surfactants, is given in U.S.P. 3,929,678 issued to
Laughlin and
Heuring on December 30, 1975. Further examples are given in "Surface Active
Agents
and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of
suitable cationic
surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
Some
examples are given below.
Anionic Surfactant
Any anionic surfactant can be incorporated in the compositions of the
invention.
The anionic surfactant herein preferably comprises at least a sulphate
surfactant and/ or a
sulphonate surfactant or mixtures thereof. It may be preferred that the
anionic surfactant
comprises only alkyl sulphonate surfactant or optionally combined with fatty
acids or
soap salts thereof. Alternatively, it may be preferred that the composition
comprises only
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19
akly sulphate surfactant, but hereby it is preferred that at least a mid-chain
branched alkyl
surfactant is present or at least two alkyl surfactants are present.
Depending on the precise formulation of the composition and the use thereof,
it may be
preferred that the compositions herein comprise a particulate component, as
descriebd
above, preferably in the form of a flake of an alkyl sulfate or sulphonate
surfactant,
preferably an alkyl benzene sulphonate, present at a concentration of from 8S%
to 9S% of
the particle or flake, the balance being an sulfate salt and moisture, the
particle or flake
being admixed to the other detergent components) or ingredients.
Other possible anionic surfactants include the isethionates such as the acyl
isethionates,
N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6 C 1 ~
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
Depending on the precise formulation of the composition and the use thereof,
it may be
preferred that the compositions herein comprise a component which contains
high levels
of an alkyl sulphate or sulphonate surfactant or mixtures thereof, preferably
an alkyl
benzene sulphonate, intimately mixed with an sulphate salt and moisture. For
example,
such a component comprising from 8S% to 9S% of one an anionic sulphate or
sulphonate
surfactant and from 1 S% to S% sulphate salt and moisture. Such a component
may be in
the form f a flake, which can be admixed or dry-added to the other components
of the
detergent composition herein.
Anionic Sulphonate Surfactant
The anionic sulphonate surfactants in accordance with the invention include
the salts of
CS-C2p linear or branched alkylbenzene sulphonates, alkyl ester sulphonates,
C6-C22
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primary or secondary alkane sulphonates, C6-C24 olefin sulphonates,
sulphonated
polycarboxylic acids, and any mixtures thereof.
Highly preferred is a C 12-C 16 linear alkylbenzene sulphonate. Preferred
salts are sodium
5 and potassium salts.
The alkyl ester sulphonated surfactant are also suitable for the invention,
preferably those
of formula
10 R1 - CH(S03M) - (A)x- C(O) - OR2
wherein R1 is a C6-C22 hydrocarbyl, R2 is a C1-C6 alkyl, A is a C6-C22
alkylene,
alkenylene, x is 0 or 1, and M is a cation. The counterion M is preferably
sodium,
potassium or ammonium.
The alkyl ester sulphonated surfactant is preferably a a-sulpho alkyl ester of
the formula
above, whereby thus x is 0. Preferably, R' is an alkyl or alkenyl group of
from 10 to 22,
preferably 16 C atoms and x is preferably 0. Rz is preferably ethyl or more
preferably
methyl.
It can be preferred that the R1 of the ester is derived from unsaturated fatty
acids, with
preferably 1, 2 or 3 double bonds. It can also be preferred that R' of the
ester is derived
from a natural occurring fatty acid, preferably palmic acid or stearic acid or
mixtures
thereof.
Anionic Alkyl Sulphate Surfactant
The anionic sulphate surfactant herein include the linear and branched primary
and
secondary alkyl sulphates and disulphates, alkyl ethoxysulphates having an
average
ethoxylation number of 3 or below, fatty oleoyl glycerol sulphates, alkyl
phenol ethylene
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21
oxide ether sulphates, the CS-C 1 ~ acyl-N-(C 1-C4 alkyl) and -N-(C 1-CZ
hydroxyalkyl)
glucamine sulphates, and sulphates of alkylpolysaccharides.
Primary alkyl sulphate surfactants are preferably selected from the linear and
branched
primary C 10-C 1 g alkyl sulphates, more preferably the C 11-C 15 linear or
branched chain
alkyl sulphates, or more preferably the C 12-C 14 linear chain alkyl
sulphates.
Preferred secondary alkyl sulphate surfactant are of the formula
R3-CH(S04M)-R"
wherein R3 is a Cg CZOhydrocycarbyl, R' is a hydrocycarbyl and M is a cation.
Alkyl ethoxy sulphate surfactants are preferably selected from the group
consisting of the
C 10-C 1 g alkyl sulphates which have been ethoxylated with from 0.5 to 3
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulphate
surfactant is a
C 11-C 1 g, most preferably C 11-C 15 alkyl sulphate which has been
ethoxylated with from
0.5 to 3, preferably from 1 to 3, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulphate and alkyl ethoxysulphate surfactants. Preferred salts are sodium and
potassium
salts.
Mid-chain branched anionic surfactants
Preferred mid-chain branched primary alkyl sulfate surfactants for use herein
are of the
formula
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22
R R1 R2
CH3CH2(CH2~,CH(CH2~CH(CH2h,CH(CH2)ZOS03M
These surfactants have a linear primary alkyl sulfate chain backbone (i.e.,
the longest
linear carbon chain which includes the sulfated carbon atom) which preferably
comprises
from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise
preferably a total of at least 14 and preferably no more than 20, carbon
atoms. In the
surfactant system comprising more than one of these sulfate surfactants, the
average total
number of carbon atoms for the branched primary alkyl moieties is preferably
within the
range of from greater than 14.5 to about 17.5. Thus, the surfactant system
preferably
comprises at least one branched primary alkyl sulfate surfactant compound
having a
longest linear carbon chain of not less than 12 carbon atoms or not more than
19 carbon
atoms, and the total number of carbon atoms including branching must be at
least 14, and
further the average total number of carbon atoms for the branched primary
alkyl moiety is
within the range of greater than 14.5 to about 17.5.
R, R1, and R2 are each independently selected from hydrogen and C1-C3 alkyl
group
(preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and
most
preferably methyl), provided R, R1, and R2 are not all hydrogen. Further, when
z is 1, at
least R or R1 is not hydrogen.
M is hydrogen or a salt forming cation depending upon the method of synthesis.
w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer
from 0 to 13; z is
an integer of at least 1; and w + x + y + z is an integer from 8 to 14.
A preferred mid-chain branched primary alkyl sulfate surfactant is, a C 16
total carbon
primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and
having 1, 2,
or 3 branching units (i.e., R, R1 and/or R2) of in total 3 carbon atoms,
(whereby thus the
total number of carbon atoms is at least 16). Preferred branching units can be
one propyl
branching unit or three methyl branching units.
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23
Another preferred surfactant are branched primary alkyl sulfates having the
formula
RI R2
I I
CH3CH2(CH2)xCH(CH2)yCH(CH2)zOS03M
wherein the total number of carbon atoms, including branching, is from 1 S to
18, and
when more than one of these sulfates is present, the average total number of
carbon
atoms in the branched primary alkyl moieties having the above formula is
within the
range of greater than 14.5 to about 17.5; RI and R2 are each independently
hydrogen or
C1-C3 alkyl; M is a water soluble cation; x is from 0 to I l; y is from 0 to
11; z is at least
2; and x + y + z is from 9 to 13; provided R1 and R2 are not both hydrogen.
Dianionic Surfactants
The dianionic surfactants are also useful anionic surfactants for the present
invention, in
particular those of formula
AX'-M+
R
~(B)Z-Y_-M+
where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether,
ester, amine or
amide group of chain length C 1 to C2g, preferably C3 to C24, most preferably
Cg to C20,
or hydrogen; A nad B are independently selected from alkylene, alkenylene,
(poly)
alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain
length C 1
to C2g preferably C 1 to C5, most preferably C I or C2, or a covalent bond,
and preferably
A and B in total contain at least 2 atoms; A, B, and R in total contain from 4
to about 31
carbon atoms; X and Y are anionic groups selected from the group comprising
carboxylate, and preferably sulfate and sulfonate, z is 0 or preferably 1; and
M is a
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24
cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an
alkali or
alkaline earth metal ion.
The most preferred dianionic surfactant has the formula as above where R is an
alkyl
group of chain length from C 1 p to C 1 g, A and B are independently C 1 or
C2, both X and
Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.
Preferred dianionic surfactants herein include:
(a) 3 Bisulphate compounds, preferably 1,3 C7-C23 (i.e., the total number of
carbons
in the molecule) straight or branched chain alkyl or alkenyl disulphates, more
preferably having the formula:
~OS03'M+
R
~OSO 3 M +
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C4 to about C 2p;
(b) 1,4 Bisulphate compounds, preferably 1,4 C8-C22 straight or branched chain
alkyl or alkenyl disulphates, more preferably having the formula:
25
R OS03 ' M +
OS03 M+
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C4 to about C 1 g; preferred R are selected from octanyl, nonanyl,
decyl, dodecyl,
tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and
(c) 1,5 Bisulphate compounds, preferably 1,5 C9-C23 straight or branched chain
alkyl or alkenyl disulphates; more preferably having the formula:
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OSO 3 ~ M +
R
OS03 M+
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C4 to about C I g.
5
It can be preferred that the dianionic surfactants of the invention are
alkoxylated dianionic
surfactants.
The alkoxylated dianionic surfactants of the invention comprise a structural
skeleton of at
10 least five carbon atoms, to which two anionic substituent groups spaced at
least three
atoms apart are attached. At least one of said anionic substituent groups is
an alkoxy-
linked sulphate or sulphonate group. Said structural skeleton can for example
comprise
any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl,
alkaryl, ether, ester,
amine and amide groups. Preferred alkoxy moieties are ethoxy, propoxy, and
15 combinations thereof.
The structural skeleton preferably comprises from S to 32, preferably 7 to 28,
most
preferably I2 to 24 atoms. Preferably the structural skeleton comprises only
carbon-
containing groups and more preferably comprises only hydrocarbyl groups. Most
20 preferably the structural skeleton comprises only straight or branched
chain alkyl groups.
The structural skeleton is preferably branched. Preferably at least 10 % by
weight of the
structural skeleton is branched and the branches are preferably from 1 to S,
more
preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not
including the
25 sulphate or sulphonate group attached to the branching).
A preferred alkoxylated dianionic surfactant has the formula
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26
A-(EO/PO)n X - M +
R--C
B-(EO/PO~ Y M +
where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether,
ester, amine or
amide group of chain length C1 to C2g, preferably C3 to C24, most preferably
Cg to C20,
or hydrogen; A and B are independently selected from, optionally substituted,
alkyl and
alkenyl group of chain length C 1 to C2g, preferably C 1 to C5, most
preferably C 1 or C2,
or a covalent bond; EO/PO are alkoxy moieties selected from ethoxy, propoxy,
and mixed
ethoxy/propoxy groups, wherein n and m are independently within the range of
from
about 0 to about 10, with at least m or n being at least 1; A and B in total
contain at least 2
atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y
are anionic
groups selected from the group consisting of sulphate and sulphonate, provided
that at
least one of X or Y is a sulfate group; and M is a cationic moiety, preferably
a substituted
or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.
The most preferred alkoxylated dianionic surfactant has the formula as above
where R is
an alkyl group of chain length from C 10 to C 1 g, A and B are independently C
1 or C2, n
and m are both 1, both X and Y are sulfate groups, and M is a potassium,
ammonium, or a
sodium ion.
Preferred alkoxylated dianionic surfactants herein include:
ethoxylated and/or propoxylated disulphate compounds, preferably C 10-C24
straight or
branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates,
more
preferably having the formulae:
(EO/PO)n OS03 M + R +
R ~(EO/PO)n OS03 M
(EO/PO)m OSO 3 - M + (EO/PO)m OSO 3 - M +
and
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27
wherein R is a straight or branched chain alkyl or alkenyl group of chain
length from
about C6 to about C 1 g; EO/PO are alkoxy moieties selected from ethoxy,
propoxy, and
mixed ethoxy/propoxy groups; and n and m are independently within the range of
from
about 0 to about 10 (preferably from about 0 to about 5), with at least m or n
being 1.
Anionic Carboxylate Surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),
especially
certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to C 18 alkyl group, x ranges from O to 10, and
the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is 0
is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate
surfactants
include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to Clg
alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
consisting of
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted or
unsubstituteds.hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl
unit connected to a secondary carbon. Preferred secondary soap surfactants for
use herein
are water-soluble members selected from the group consisting of the water-
soluble salts
of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic
acid, 2-
butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps may also be included as suds suppressors.
Alkali Metal Sarcosinate Surfactant
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28
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(Rl) CH2 COOM, wherein R is a CS-C17 linear or branched alkyl or alkenyl
group, Rl is
a Cl-C4 alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and
oleoyl methyl sarcosinates in the form of their sodium salts.
Non-ionic Alkoxylated Surfactants
When non-ionic surfactants are present, it may be preferred that the
components of the
compositors herein are free of sprayed-on non-ionic alkoxylated alcohol
surfactants. It has
been found that hereby the delivery of the composition to the washing water
can be
improved and the caking of the product can be reduced. It may be preferred
that the
composition comprises a non-ionic surfactant which is solid at temperatures
below 30°C
or even 40°C, preferably present in an intimate mixture with other
ingredients.
Essentially any alkoxylated non-ionic surfactants can also be comprised in the
detergent
compositions of the invention. The ethoxylated and propoxylated non-ionic
surfactants
are preferred. Preferred alkoxylated surfactants can be selected from the
classes of the
non-ionic condensates of alkyl phenols, non-ionic ethoxylated alcohols, non-
ionic
ethoxylated/propoxylated fatty alcohols, non-ionic ethoxylate/propoxylate
condensates
with propylene glycol, and the non-ionic ethoxylate condensation products with
propylene oxide/ethylene diamine adducts.
Highly preferred are non-ionic alkoxylated alcohol surfactants, being the
condensation
products of aliphatic alcohols with from 1 to 75 moles of alkylene oxide, in
particular
about 50 or from 1 to 15 moles, preferably to 11 moles, particularly ethylene
oxide and/or
propylene oxide, are highly preferred non-ionic surfactant comprised in the
anhydrous
component of the particles of the invention. The alkyl chain of the aliphatic
alcohol can
either be straight or branched, primary or secondary, and generally contains
from 6 to 22
carbon atoms. Particularly preferred are the condensation products of alcohols
having an
alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and in
particular
3 or 5 moles, of ethylene oxide per mole of alcohol.
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Non-ionic Polyhydroxy Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides are highly preferred non-ionic surfactants for
use in the
invention , in particular those having the structural formula R2CONR1Z wherein
: R1 is
H, C 1 _ 1 g, preferably C ~-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, ethoxy,
propoxy, or a mixture thereof, preferable C 1-C4 alkyl, more preferably C 1 or
C2 alkyl,
most preferably C 1 alkyl (i.e., methyl); and R2 is a CS-C31 hydrocarbyl,
preferably
straight-chain CS-Clg or C~-C19 alkyl or alkenyl, more preferably straight-
chain Cg-C17
alkyl or alkenyl, most preferably straight-chain C 11-C 1 ~ alkyl or alkenyl,
or mixture
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at
least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably
ethoxylated or propoxylated) thereof. Z preferably will be derived from a
reducing sugar
in a reductive amination reaction; more preferably Z is a glycityl.
A highly preferred non-ionic polyhydroxy fatty acid amide surfactant for use
herein is a
C 12-C 14 ~ a C 15-C 17 ~~or C 16-C 18 alkyl N-methyl glucamide.
It may be particularly that mixtures of a C 12-C 18 alkyl N-methyl glucamide
and a
condensation product of an alcohol having an alkyl group containing from 8 to
20 carbon
atoms with from 2 to 9 moles and in particular 3 or 5 moles, of ethylene oxide
per mole of
alcohol.
The polyhydroxy fatty acid amide can be prepared by any suitable process. One
particularly preferred process is described in detail in WO 9206984.
Non-ionic Fattv Acid Amide Surfactant
Fatty acid amide surfactants or alkoxylated fatty acid amides include those
having the
formula: R6CON(R7) (R8 ) wherein R6 is an alkyl group containing from 7 to 21,
preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R7 ~d R8 are
each
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individually selected from the group consisting of hydrogen, C 1-C4 alkyl, C 1-
C4
hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 11,
preferably 1 to 7,
more preferably form 1-5, whereby it may be preferred that R7 is different to
R8~ one
having x being 1 or 2, one having x being from 3 to 11 or preferably 5.
5
Non-ionic Alkyl Esters of Fattv Acid Surfactant
Alkyl esters of fatty acids include those having the formula: R9C00(R10)
wherein R9 is
an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even
11 to 13
carbon atoms and R 10 is a C 1-C4 alkyl, C 1-C4 hydroxyalkyl, or -(C2H40)xH,
where x is
10 in the range of from 1 to 11, preferably 1 to 7, more preferably form 1-5,
whereby it may
be preferred that R10 is a methyl or ethyl group.
Non-ionic Alkylpo~saccharide Surfactant
Alkylpolysaccharides can also be comprised in the anhydrous material of the
particle of
15 the invention, such as those disclosed in U.S. Patent 4,565,647, Llenado,
issued January
21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and
a
polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3
to 10
saccharide units.
20 Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
25 hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to
18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The
glycosyl is
preferably derived from glucose.
Cationic Surfactant
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31
Another preferred component of the compositions of the invention is a cationic
surfactant,
which is preferably be present at a level of from 0.1 % to 60% by weight of
the
composition, more preferably from 0.4% to 20%, most preferably from 0.5% to 5%
by
weight of the composition.
When present, the ratio of the anionic surfactant to the cationic surfactant
is preferably
from 25:1 to 1:3, more preferably from 15:1 to 1:1. most preferably from 10:1
to 1:1 The
ratio of cationic surfactant to the stabilising agent is preferably from 1:30
to 20:1, more
preferably from 1:20 to 10:1.
Preferably the cationic surfactant is selected from the group consisting of
cationic ester
surfactants, cationic mono-alkoxylated amine surfactants, cationic bis-
alkoxylated amine
surfactants and mixtures thereof.
Cationic Mono-Alkoxylated Amine Surfactants
The optional cationic mono-alkoxylated amine surfactant for use herein, has
the general
formula:
Rl /ApRa
~N+ X_
R2~ ~R3
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to
about 11
carbon atoms; R2 and R3 are each independently alkyl groups containing from
one to
about three carbon atoms, preferably methyl; R4 is selected from hydrogen
(preferred},
methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate,
sulphate, or the
like, to provide electrical neutrality; A is selected from C1-C4 alkoxy,
especially ethoxy
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32
(i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; and p is from 1 to
about 30,
preferably 1 to about 15, most preferably 1 to about 8.
Highly preferred cationic mono-alkoxylated amine surfactants for use herein
are of the
formula
~(CH2CH20)~_SH
/N \ XO
CH3/ CH3
wherein R1 is C6-C 1 g hydrocarbyl and mixtures thereof, preferably C6-C 1 q.,
especially
C6-C 11 alkyl, preferably Cg and C 10 alkyl, and X is any convenient anion to
provide
charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr
and/or
i-Pr units.
Cationic Bis-Alkoxylated Amine Surfactant
The cationic bis-alkoxylated amine surfactant for use herein, has the general
formula:
R\ / ApR3
\N+ X
2o R2/ \A~qR4
wherein Rl is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11,
most
preferably from about 8 to about 10 carbon atoms; R2 is an alkyl group
containing from
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33
one to three carbon atoms, preferably methyl; R3 and R4 can vary independently
and are
selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as
chloride,
bromide, methylsulfate, sulphate, or the like, sufficient to provide
electrical neutrality. A
and A' can vary independently and are each selected from C 1-C4 alkoxy,
especially
ethoxy, (i.e., -CH2CH20-}, propoxy, butoxy and mixtures thereof; p is from 1
to about
30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about
4, and most
preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
R\ CH2CH20H
N+~ XO
CH3/ \CH2CH20H
wherein R1 is C6-Clg hydrocarbyl and mixtures thereof, preferably C6, Cg, C10,
C12
C 1 ~ alkyl and mixtures thereof. X is any convenient anion to provide charge
balance,
preferably chloride. With reference to the general cationic bis-alkoxylated
amine
structure noted above, since in a preferred compound Rl is derived from
(coconut) C12-
C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each
monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include
compounds of the
formula:
t
R~ ~(CH2CH20)pH
N+ X-
R2~ ~(CH2CH20)qH
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wherein RI is C6-C I g hydrocarbyl, preferably C6-C 14 alkyl, independently p
is I to
about 3 and q is 1 to about 3, R2 is CI-C3 alkyl, preferably methyl, and X is
an anion,
especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20)
units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20] and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr}, or mixtures of EO and/or Pr
and/or
i-Pr units.
Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the
alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
from 0 to 5, preferably from 0 to 3; and each RS is an alkyl or hydroxyalkyl
group
containing from 1 to 3, or a polyethylene oxide group containing from I to 3
ethylene
oxide groups. Preferred are C 10-C I g alkyl dimethylamine oxide, and C 10-18
acylamido
alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the particle of the
invention or the
compositions containing the particle of the invention. These surfactants can
be broadly
described as derivatives of secondary and tertiary amines, derivatives of
heterocyclic
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secondary and tertiary amines, or derivatives of quaternary ammonium,
quaternary
phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants
are
exemplary zwitterionic surfactants for use herein.
5 Suitable betaines are those compounds having the formula R(R')ZN+R2C00-
wherein R
is a C6-C1 g hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R2 is a
C1-CS
hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
Additional Deter ent Ingredients
The detergent composition of the invention can comprise any additional
detersive actives
or ingredients known in the art. The precise nature of these additional
components, and
levels of incorporation thereof will depend on the physical form of the
composition, and
the precise nature of the washing operation for which it is to be used.
Other preferred ingredients comprise a perfume, brightener or dye or mixtures
thereof,
which may be sprayed onto the particular component herein.
The compositions of the invention preferably contain one or more additional
detergent
components selected from surfactants, bleaches, builders, chelants,
(additional) alkalinity
sources, organic polymeric compounds, enzymes, brightners, suds suppressors,
lime soap
dispersants, soil suspension and anti-redeposition agents and corrosion
inhibitors.
Heavy metal ion seguestrant
Heavy metal ion sequestrant are also useful additional ingredients herein. By
heavy metal
ion sequestrant it is meant herein components which act to sequester (chelate)
heavy
metal ions. These components may also have calcium and magnesium chelation
capacity,
but preferentially they show selectivity to binding heavy metal ions such as
iron,
manganese and copper.
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Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 10%,
preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most
preferably
from 0.3% to 2% by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine tetra
(methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane
diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenediamine
disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine
disuccinic
acid or any salts thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid, described
in EP-A-31?,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl
sulfonic
acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid
sequestrants
described in EP-A-S 16,102 are also suitable herein. The ~3-alanine-N,N'-
diacetic acid,
aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and
iminodisucciruc
acid sequestrants described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-S 10,331
describes suitable sequestrants derived from collagen, keratin or casein. EP-A-
528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic
acid
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37
and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-
N,N'-disuccinic acid (GADS}, ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-
N,N'-
disuccinic acid (EDDS} and 1,1 hydroxyethane diphosphonic acid or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof.
Perhydrate Bleaches
Preferably the detergent compositions of the invention comprise oxygen bleach,
preferably comprising a hydrogen peroxide source and a bleach precursor or
activator.
Since the present invention improves product delivery to the wash, it
increases bleach
efficiency and reduces the risk of fabric damage by bleaches present in the
detergent.
A preferred source of hydrogen peroxide is a perhydrate bleach, such as metal
perborates,
more preferably metal percarbonates, particularly the sodium salts. Perborate
can be mono
or tetra hydrated. Sodium percarbonate has the formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid.
In particular the percarbonate salts are preferably coated. Suitable coating
agent are
known in the art, and include silicates, magnesium salts and carbonates salts.
Potassium peroxymonopersulfate, sodium per is another optional inorganic
perhydrate
salt of use in the detergent compositions herein.
Oreanic Peroxyacid Bleachine System
A preferred feature of the composition herein is an organic peroxyacid
bleaching system.
In one preferred execution the bleaching system contains a hydrogen peroxide
source and
an organic peroxyacid bleach precursor compound. The production of the organic
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38
peroxyacid occurs by an in situ reaction of the precursor with a source of
hydrogen
peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate
bleaches,
such as the perborate bleach of the claimed invention. In an alternative
preferred
execution a preformed organic peroxyacid is incorporated directly into the
composition.
Compositions containing mixtures of a hydrogen peroxide source and organic
peroxyacid
precursor in combination with a preformed organic peroxyacid are also
envisaged.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as
O
;i
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is
O
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of from
0.5% to 20% by weight, more preferably from 1% to 15% by weight, most
preferably
from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
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39
1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871,
2143231 and
EP-A-0170386.
Leaving Grouvs
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis
reaction to occur within the optimum time frame (e.g., a wash cycle). However,
if L is too
reactive, this activator will be difficult to stabilize for use in a bleaching
composition.
Preferred L groups are selected from the group consisting of
Y R3 RsY
-O ~ , -O ~ Y , and -O
-N-~-R1 O
- ~ -N-C-CH-R4
R3 Y ,
I
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O CH O Y O
-O-C-R~ -N 2 ~NR4 -N~C~NR4
~C.'i ' ~C~ '
' II II
O O
3
R O Y
I 4 II I
-O-C=CHR , and -N-S-CH-R4
R3 ~
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and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to
14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4
is H or
R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be
substituted by
essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen,
5 amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03-M+, -C02-M+, -S04-M+, -N+(R3)4X-
and
O<--N(R3)3 and most preferably -S03-M+ and -C02-M+ wherein R3 is an alkyl
chain
containing from 1 to 4 carbon atoms, M is a canon which provides solubility to
the bleach
10 activator and X is an anion which provides solubility to the bleach
activator. Preferably,
M is an alkali metal, ammonium or substituted ammonium cation, with sodium and
potassium being most preferred, and X is a halide, hydroxide, methylsulfate or
acetate
anion.
15 Alkvl PercarboxYlic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
20 ,N,N 1 N 1 tetra acetylated alkylene diamines wherein the alkylene group
contains from 1
to 6 carbon atoms, particularly those compounds in which the alkylene group
contains 1,
2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred. The
TAED is preferably not present in the agglomerated particle of the present
invention, but
preferably present in the detergent composition, comprising the particle.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS), sodium acetoxybenzene sulfonate (ABS} and pentaacetyl glucose.
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Amide Substituted Plkvl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ --C--N-R2--CL R~ -N-C-R2-C-L
O R O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing
I to 10
carbon atoms and L can be essentially any leaving group. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386.
Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable
O-acylated perbenzoic acid precursor compounds include the substituted and
unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of
sorbitol,
glucose, and all saccharides with benzoylating agents, and those of the imide
type
including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-
benzoyl
substituted areas. Suitable imidazole type perbenzoic acid precursors include
N-benzoyl
imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing
perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine
and benzoyl
pyroglutamic acid.
Preformed Organic Perox acid
The detergent composition may contain, in addition to, or as an alternative
to, an organic
peroxyacid bleach precursor compound, a preformed organic peroxyacid ,
typically at a
level of from 1 % to I 5% by weight, more preferably from 1 % to 10% by weight
of the
composition.
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A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
R~ -CN-R2-C-OOH R~ -NC-R2C-OOH
O R5 ~ ~ 5 ~~ i
or R O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS is
H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide
substituted
organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc
acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid are also suitable herein.
E me
Another preferred ingredient useful herein is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, cellulases, endolases,
esterases,
pectinases, lactases and peroxidases conventionally incorporated into
detergent
compositions. Suitable enzymes are discussed in US Patents 3,519,570 and
3,533,139.
Oreanic Polymeric Compound
Organic polymeric compounds are preferred additional components of the
compositions
herein.
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By organic polymeric compound it is meant herein essentially any polymeric
organic
compound commonly used as binder, dispersants, and anti-redeposition and soil
suspension agents in detergent compositions, including any of the high
molecular weight
organic polymeric compounds described as clay flocculating agents herein,
including
quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition
agent.
Organic polymeric compound is typically incorporated in the detergent
compositions of
the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%,
most
preferably from 0.5% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids or their salts in which the polycarboxylic
acid
comprises at least two carboxyl radicals separated from each other by not more
than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of
such salts are polyacrylates of MWt 1000-5000 and their copolymers with
malefic
anhydride, such copolymers having a molecular weight of from 2000 to 100,000,
especially 40,000 to 80,000.
The polyarnino compounds are useful herein including those derived from
aspartic acid
such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
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Further useful organic polymeric compounds are the polyethylene glycols,
particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000 and most
preferably about 4000.
Highly preferred polymeric components herein are cotton and non-cotton soil
release
polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent
5,415,807,
Gosselink et al., and in particular according to US application no.60/OS 1517.
Another organic compound, which is a preferred clay dispersant/ anti-
redeposition agent,
for use herein, can be the ethoxylated cationic monoamines and diamines of the
formula:
CH3 CH3
X --~ OCH2CH2)n __ N+ ~ CH2 _- CH2 _(_ CH2)a _ -N+ _~ CH2CH20 ~ X
b
(CH2CH20 ~ X (CH2CH20 y X
wherein X is a non-ionic group selected from the group consisting of H, C 1-C4
alkyl or
hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20,
preferably
from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for
cationic
monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for
cationic
diamines (b=1), n is at least about 12 with a typical range of from about 12
to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-011965
and US 4,659,802 and US 4,664,848.
Suds Suppressing System
T'he detergent compositions of the invention, when formulated for use in
machine
washing compositions, may comprise a suds suppressing system present at a
level of from
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0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3%
by
weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
5 antifoam compound, including, for example silicone antifoam compounds and 2-
alkyl
alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a detergent
10 composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component.
Such silicone antifoam compounds also typically contain a silica component.
The term
15 "silicone" as used herein, and in general throughout the industry,
encompasses a variety of
relatively high molecular weight polymers containing siloxane units and
hydrocarbyl
group of various types. Preferred silicone antifoam compounds are the
siloxanes,
particularly the polydimethylsiloxanes having trimethylsilyl end blocking
units.
20 Other suitable antifoam compounds include the monocarboxylic fatty acids
and soluble
salts thereof. These materials are described in US Patent 2,954,347, issued
September 27,
1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for
use as
suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably 12
to 18 carbon atoms. Suitable salts include the alkali metal salts such as
sodium,
25 potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic
Clg-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to
hexa-
30 alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as
products of cyanuric
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46
chloride with two or three moles of a primary or secondary amine containing 1
to 24
carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-
alkali metal
(e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75% to 95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1 % to 50%, preferably S% to 25% by
weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from
5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%,
preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake
copolymer of this type is DC0544, commercially available from DOW Corning
under the tradename DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C 18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to
15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
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A highly preferred particulate suds suppressing system is described in EP-A-
0210731 and
comprises a silicone antifoam compound and an organic carrier material having
a melting
point in the range 50°C to 85°C, wherein the organic Garner
material comprises a
monoester of glycerol and a fatty acid having a carbon chain containing from
12 to 20
carbon atoms. EP-A-0210721 discloses other preferred particulate suds
suppressing
systems wherein the organic carrier material is a fatty acid or alcohol having
a carbon
chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a
melting point of
from 45°C to 80°C.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane
or
mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and
polycarboxylic
polymers, such as copolymers of laic and acrylic acid.
Polymeric Dye Transfer Inhibiting Aeents
The compositions herein may also comprise from 0.01 % to 10 %, preferably from
0.05%
to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers
can be
cross-linked polymers.
Optical Brightener
The compositions herein also optionally contain from about 0.005% to 5% by
weight of
certain types of hydrophilic optical brighteners, as known in the art.
Polymeric Soil Release Agent
Polymeric soil release agents, hereinafter "SRA", can optionally be employed
in the
present compositions. If utilized, SRA's will generally comprise from 0.01% to
10.0%,
typically from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of the
compositions.
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Preferred SRA's typically have hydrophilic segments to hydrophilize the
surface of
hydrophobic fibers such as polyester and nylon, and hydrophobic segments to
deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This can
enable stains occurring subsequent to treatment with the SRA to be more easily
cleaned in
later washing procedures.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by
processes
involving at least one transesterification/oligomerization, often with a metal
catalyst such
as a titanium(IV) alkoxide. Such esters may be made using additional monomers
capable
of being incorporated into the ester structure through one, two, three, four
or more
positions, without, of course, forming a densely crosslinked overall
structure.
Suitable SRA's include a sulfonated product of a substantially linear ester
oligomer
comprised of an oligomeric ester backbone of terephthaIoyl and oxyalkyleneoxy
repeat
units and allyl-derived sulfonated terminal moieties covalently attached to
the backbone,
for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel
and E.P.
Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl
alcohol; (b)
reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-
propylene glycol
("PG") in a two-stage transesterification/oligomerization procedure; and (c)
reacting the
product of (b) with sodium metabisulfite in water. Other SRA's include the non-
ionic
end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
4,711,730,
December 8, 1987 to Gosselink et al., for example those produced by
transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT,
PG and
poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and
fully-
anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to
Gosselink,
such as oligomers from ethylene glycol ("EG"}, PG, DMT and Na-3,6-dioxa-8-
hydroxyoctanesulfonate; the non-ionic-capped block polyester oligomeric
compounds of
U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT,
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methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or
PG,
Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially
sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31,
1989 to
Maldonado, Gosselink et al., the latter being typical of SRA's useful in both
laundry and
fabric conditioning products, an example being an ester composition made from
m-
sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably
further
comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or
propylene
terephthalate with polyethylene oxide or polypropylene oxide terephthalate,
see U.S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975;
cellulosic
derivatives such as the hydroxyether cellulosic polymers available as METHOCEL
from
Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
4,000,093,
December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an
average
degree of substitution (methyl) per anhydroglucose unit from about 1.6 to
about 2.3 and a
solution viscosity of from about 80 to about 120 centipoise measured at
20°C as a 2%
aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE
SM200, which are the trade names of methyl cellulose ethers manufactured by
Shin-etsu
Kagaku Kogyo KK.
Additional classes of SRA's include: (I) non-ionic terephthalates using
diisocyanate
coupling agents to link polymeric ester structures, see U.S. 4,201,824,
Violland et al. and
U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups
made by
adding trimellitic anhydride to known SRA's to convert terminal hydroxyl
groups to
trimellitate esters. With the proper selection of catalyst, the trimellitic
anhydride forms
linkages to the terminals of the polymer through an ester of the isolated
carboxylic acid of
trimellitic anhydride rather than by opening of the anhydride linkage. Either
non-ionic or
anionic SRA's may be used as starting materials as long as they have hydroxyl
terminal
groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes
include:
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(III) anionic terephthalate-based SRA's of the urethane-linked variety, see
U.S. 4,201,824,
Violland et al.;
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Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of the
invention
include perfumes, speckles, colours ar dyes, filler salts, with sodium
sulphate being a
preferred filler salt. Also, minor amounts (e.g., less than about 20% by
weight) of
neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme
stabilizing
agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and
dyes, such as
those described in US Patent 4,285,841 to Barrat et al., issued August 25,
1981 (herein
incorporated by reference), can be present. Highly preferred are encapsulated
perfumes,
preferably comprising a starch encapsulte.
In the compositions of the invention, it may be preferred that when dyes and/
or perfumes
are sprayed onto the another component, the component does not comprise spray-
on non-
ionic alkoxylated alcohol surfactant.
Form of the Compositions
The composition of the invention thereof can be made via a variety of methods
involving
the mixing of ingredients, including dry-mixing, compaction such as
agglomerating,
extrusion, tabletting, or spray-drying of the various compounds comprised in
the
detergent component, or mixtures of these techniques, whereby the components
herein
also can be made by for example compaction, including extrusion and
agglomerating, or
spray-drying.
The compositions herein can take a variety of physical solid forms including
forms such
as tablet, flake, pastille and bar, and preferably the composition is in the
form of granules
or a tablet.
The compositions in accordance with the present invention can also be used in
or in
combination with bleach additive compositions, for example comprising chlorine
bleach.
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The compositions preferably have a density of more than 350 gr/litre, more
preferably
more than 450 gr/litre or even more than 570 gr/litre.
Below are some examples of detergent compositions according to the invention.
Abbreviations used in Examples
In the detergent compositions exemplified below, the abbreviated component
identifications have the following meanings:
LAS : Sodium linear C11-13 alkyl benzene sulfonate
LAS (I) . Flake containing sodium linear C11-13 alkyl benzene
sulfonate (90%) and sodium sulphate and moisture
LAS(II) : Potassium linear C11-13 alkyl benzene sulfonate
MES . a-sulpho methylester of C,g fatty acid
TAS . Sodium tallow alkyl sulphate
CxyAS . Sodium C 1 x - C 1 y alkyl sulphate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulphate
CxyEzS . Sodium C 1 x-C 1 y alkyl sulphate condensed with z moles
of ethylene oxide
CxyEz . C 1 x-C 1 y predominantly linear primary alcohol condensed
with an average of z moles of ethylene oxide
QAS : R2.N+(CH3)2(C2H4OH) with R2 = C 12 - C 14
QAS 1 : R2.N+(CH3)2(C2H4OH) with R2 = Cg - C11
SADS . Sodium C,4-C2z alkyl disulfate of formula 2-(R).C4 H,.-1,4-
(S04-)2 where R = C,~C,s
SADE2S : Sodium C,4-CZZ alkyl disulfate of formula 2-(R).C4 H,.-1,4-
(S04-)z where R = C,o-CAB, condensed with z moles of
ethylene oxide
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APA : Cg - C I0 amido propyl dimethyl amine
Soap . Sodium linear alkyl carboxylate derived from
an 80/20
mixture of tallow and coconut fatty acids
STS : Sodium toluene sulphonate
CFAA : C 12-C I 4 (coco) alkyl N-methyl glucamide
TFAA : C 16-C 18 alkyl N-methyl glucamide
TPKFA : C 16-C I 8 topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
Zeolite A . Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12~2~H20 having a primary particle
size
in the range from 0.1 to 10 micrometers (weight
expressed
on an anhydrous basis)
NaSKS-6 (I) : Crystalline layered silicate of formula 8-
Na2Si205 of
~ 5 weight average particle size of 18 microns
and at least 90%
by weight being of particle size of below 65.6
microns.
NaSKS-6 (II) : Crystalline layered silicate of formula 8-
Na2Si205 of
weight average particle size of 18 microns
and at least 90%
by weight being of particle size of below 42.1
microns.
Citric acid . Anhydrous citric acid
Borate : Sodium borate
Carbonate : Anydrous sodium carbonate with a particle
size between
200~m and 900pm
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size
distribution between 400~m and 1200pm
Silicate . Amorphous sodium silicate (Si02:Na20 = 2.0:1
)
Sulphate : Anhydrous sodium sulphate
Mg sulphate . Anhydrous magnesium sulphate
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Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a
particle size distribution between 425pm and
850pm
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular
weight about 70,000
MA/AA (1) : Copolymer of 4:6 maleic/acrylic acid, average
molecular
weight about 10,000
AA . Sodium polyacrylate polymer of average molecular
weight
4,500
CMC : Sodium carboxymethyl cellulose
Cellulose ether Methyl cellulose ether with a degree of polymerization
: of
650 available from Shin Etsu Chemicals
Protease : Proteolytic enzyme, having 3.3% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Savinase
Protease I : Proteolytic enzyme, having 4% by weight of
active
enzyme, as described in WO 95/10591, sold
by Genencor
Int. Inc.
Alcalase . Proteolytic enzyme, having 5.3% by weight
of active
enzyme, sold by NOVO Industries A/S
Cellulase . Cellulytic enzyme, having 0.23% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Carezyme
Amylase : Amylolytic enzyme, having 1.6% by weight of
active
enzyme, sold by NOVO Industries A/S under
the
tradename Termamyl 120T
Amylase II : Amylolytic enzyme, as disclosed in PCT/ US9703635
Lipase : Lipolytic enzyme, having 2.0% by weight of
active
enzyme, sold by NOVO Industries A/S under
the
tradename Lipolase
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Lipase ( 1 ) : Lipolytic enzyme, having 2.0% by weight of
active
enzyme, sold by NOVO Industries A/S under the
tradename Lipolase Ultra
Endolase : Endoglucanase enzyme, having 1.5% by weight
of active
5 enzyme, sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
PB 1 . Anhydrous sodium perborate bleach of nominal
formula
NaB02.H202
10 Percarbonate : Sodium percarbonate of nominal formula
2Na2C03.3H202
DOBS : Decanoyl oxybenzene sulfonate in the form of
the sodium
salt
DPDA : Diperoxydodecanedioc acid
15 NOBS . Nonanoyloxybenzene sulfonate in the form of
the sodium
salt
NACA-OBS : (6-nonamidocaproyl) oxybenzene sulfonate
LOBS : Dodecanoyloxybenzene sulfonate in the form
of the
sodium salt
20 DOBS : Decanoyloxybenzene sulfonate in the form of
the
sodium salt
DOBA . Decanoyl oxybenzoic acid
TAED : Tetraacetylethylenediamine
DTPA : Diethylene triamine pentaacetic acid
25 DTPMP : Diethylene triamine penta (methylene phosphonate),
marketed by Monsanto under the Tradename bequest
2060
EDDS . Ethylenediamine-N,N'-disuccinic acid, (S,S)
isomer in the
form of its sodium salt.
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Photoactivated bleach: Sulfonated zinc phthlocyanine encapsulated
in or carried
by soluble polymer or sulfonated alumino
phthlocyanine
encapsulated in or carried by soluble
polymer
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-
yl)amino) stilbene-2:2'-disulfonate
HEDP . 1,1-hydroxyethane diphosphonic acid
PEGx : Polyethylene glycol, with a molecular
weight of x
(typically 4,000)
PEO : Polyethylene oxide, with an average molecular
weight of
50,000
TEPAE : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidosole, with an average molecular
weight of
20,000
PVP : Polyvinylpyrolidone polymer, with an average
molecular
weight of 60,000
PVNO . Polyvinylpyridine N-oxide polymer, with
an average
molecular weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an average molecular weight of 20,000
QEA . bis((C2HS0)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2HS0)-(C2H40))n, wherein n = from 20 to 30
SRP 1 : Anionically end capped poly esters
SRP 2 . Diethoxylated poly (1, 2 propylene terephtalate) short
block polymer
PEI : Polyethyleneimine with an average molecular weight of
1800 and an average ethoxylation degree of 7 ethyleneoxy
residues per nitrogen
Silicone antifoam . Polydimethylsiloxane foam controller with siloxane-
oxyalkylene copolymer as dispersing agent with a ratio of
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said foam controller to said dispersing agent of 10:1 to
100:1
Opacifier : Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron 621
Wax . Paraffin wax
Example 1
A detergent composition was formed comprising blown powder, an agglomerate
comprising crystalline layered silicate and anionic surfactant, an
effervescent particle and
dry-mixed bleach activator particle, sodium percarbonate, sodium citrate and
suds
supressor.
The individual particulates were prepared and dry-mixed together with gentle
mixing e.g.
in a Nautamixer for a period of at least 4 minutes.
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Preparation of the Blown Powder
The composition of the final blown powder was as follows:-
Ingredient % in Blown Powder
Sodium Linear Alkyl Sulphonate (LAS) 20
Copolymer of Acrylic/Maleic Acid 5
Sodium Sulphate 16
Sodium Carbonate 31
Sodium Citrate 20
Water g
The blown powder was prepared by a standard spray drying process. The above
ingredients were mixed into a slurry with water. The aqueous slurry may be
prepared by
a batch or continuous process. In this case, a batch mixer, or "crutcher" was
used in which
the various detergent components were dissolved in, or slurried with, water to
provide a
slurry containing 35% water. The water content my be varied from about 20% to
about
60% by weight of water, preferably it is about from about 30% to about 40% by
weight
water. In this example the order of addition of the ingredients to water to
form the
aqueous slurry was as listed above in the final composition of the blown
powder. The
aqueous slurry was then pumped at high pressure through atomising nozzles into
a spray-
drying tower where excess water was driven off, producing a flowable powder
product
(blown powder). Fines were screened out through a mesh.
Preparation of Crystalline layered silicate/Anionic Surfactant Particle
An agglomerate comprising 70% SKS6 and 30% LAS was prepared by a conventional
agglomeration process.
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Preparation of the Effervescent Particle
Particles were prepared having the following composition:
In~ red diem Composition
Malic Acid 44
Sodium Bicarbonate 40
Sodium Carbonate 16
The particle was made via a roller compaction process. The raw materials in
the
proportions indicated above, were fed at a press force of 80kN into a
Pharmapaktor
L200/50 P roller, set up with concave smooth rolls with a 0.3mm axial
corrugation
installed. The flakes produced were then compacted using a Flake Crusher FC
200 with a
mesh size selected to produce the required particle size. The product was
screened to
remove the fines.
These three components were mixed with the additional dry-added ingredients
listed
below, in the proportions given below, to form a detergent composition
according to the
invention.
In redient % in Deter;~ent Composition
Spray Dried 42
Bleach Activator 3
Sodium Percarbonate 15
Sodium Citrate 10
SKS6/LAS granulate 10
Suds supressor particle 4
(95% PEG, 5% silicone
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Effervescent Particle 16
Example 2
Further examples of detergent compositions of the invention are given as
formulations A-
D in the table below which also indicates the method of preparation of the
examples.
A B C D
Blown powder
LAS 10.0 10.0 5.0 8.0
TAS - 1.0 - 1.0
MBAS - - _ _
C45AS _ _ - -
C45AE3S
QAS - _
DTPA, HEDP and/or0.3 0.3 0.3 0.3
EDDS
MgS04 0.5 0.4 0.5 0.5
Sodium citrate 10.0 12.0 - -
Sodium carbonate15.0 8.0 10.0 7.0
Sodium sulphate 5.0 5.0 5.0 5.0
Sodium silicate - - - -
1.6R
Zeolite A - - 16.0 18.0
SKS-6 - - - _
MA/AA or AA 1.0 2.0 1.0 2.0
PEG 4000 - 2.0 - 2.0
QEA 1.0 - 1.0 -
Brightener 0.05 0.05 0.05 0.05
Silicone oil 0.01 0.01 0.01 0.01
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Agglomerates
SKS-6 6.0 S.0 6.0 8.0
LAS 4.0 S.0 4.0 S.0
Drv-add particulate
components
Malefic acid/ 8.0 10.0 8.0 10.0
carbonate/bicarbonate
(40:20:40)
QEA - - _
NACAOBS 3.0 - 3.0 -
NOBS - 3.0 - 3.0
TAED 2.S - 2.S -
MBAS - - _
LAS (I) S.0 3.0 10.0 10.0
Spray
Brightener 0.2 0.2 0.2 0.2.
Dye - - _ _
C24AES - - - _
Perfume - - - _
Citrate 4.0 - -
Percarbonate 1 3.0 1 3.0
S.0 S.0
Perborate - - - _
Photobleach 0.02 0.02 0.02 0.02
Enzymes (cellulase,1.S 0.3 1.3 0.3
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amylase, protease,
lipase)
Carbonate - - 0.0 10.0
Perfume 0.6 0.5 0.6 0.5
(encapsulated)
Suds suppressor 1.0 0.6 1.0 0.6
Soap 0.5 0.2 0.5 0.2
Citric acid - - -
Dyed carboanate 0.5 0.5 0.5 0.5
(blue, green)
SKS-6 - - -
Fillers up to
100%
