Note: Descriptions are shown in the official language in which they were submitted.
CA 02386131 2002-04-02
WO 01/30949 PCT/US00/29295
Detergent Compositions
Field of the Invention
This invention relates to stable particulate components comprising two
reactants
which react with one another on contact with a fluid, in particular a liquid
such as water,
wherein such particles may be exposed to such fluid on storage, before the
reaction is
desired. The invention relates to providing such particulate components in a
stable form,
such that the reaction between the two reactants will substantially not take
place until
desired. The invention also relates to compositions containing such
particulate
components.
The invention particularly relates to effervescence particles which promote
rapid
dissolution for incorporation into compositions which need to dissolve readily
and rapidly
in an aqueous medium. The technology may find application in various fields
such as
cleaning compositions, in particular laundry and dishwashing detergent
compositions
which may be in a granular form or which may have been further processed into
in a
tablet form. The invention relates particularly to laundry detergent
applications.
Background of the Invention
Poor dissolution and dispensing problems are well-known in the detergent
field.
This problem has been exacerbated by recent tendencies to produce higher bulk
density
detergents, such as above 600g/1, to meet the consumer need for lower product
and
packaging volumes and less wastage i.e. higher active cleaning compositions.
The
problem is compounded by the use of detergent formulations which are based not
on
readily soluble phosphate builders, but instead on less soluble alternatives
which
overcome any environmental problems associated with phosphate builders. In
addition,
there is an increased need to promote rapid release of detergents into the
wash water to
provide greatest cleaning performance in short, energy-efficient wash cycles
where the
time of contact of the detergent solution with the items to be washed may be
reduced to a
minimum. Many solutions have been proposed to try to avoid the problems of
poor
dissolution and dispensing.
CA 02386131 2002-04-02
WO 01/30949 PCT/US00/29295
One such solution has been the use of effervescent systems in detergents. For
example, detergent compositions comprising effervescing ingredients are
described in
W098/04687. In W098/04671, effervescence systems for use in detergents are
disclosed
in which in an effort to improve dissolution, acid and alkaline effervescing
reactants
which react on contact with water to produce a gas, are mixed with a
stabilising agent to
produce a substantially anhydrous effervescence particle which has maximum
efficacy on
use in a washing step. Similarly, W098/35011 also discloses particles
comprising sodium
bicarbonate and organic acid reactants which react together and which are
formed into a
particle with a binder. EP-A-918 087 describes co-builder particles for adding
to
detergent compositions, comprising bicarbonate and polycarboxylic acid which
are
formed by roller-compaction and which contain no free moisture. However, the
requirements of providing good storage stability and good end use
effervescence on
contact with the wash liquor are conflicting requirements; the use of
stabilising agents
may prevent or reduce efficacy in the wash conditions as the water contact
with the
effervescing reactants and the resulting reaction rate slows down, so that the
effervescing
and therefore, dissolution aid effect is undesirably reduced. There is
therefore still a need
for effervescence delivery systems for use in such applications which have
good stability
on storage and rapid dissolution and therefore release of effervescence, on
contact with
water on use.
Summary of the Invention
The present inventors have found that surprisingly improved stability on
storage
and maximised efficacy on use can be achieved by careful selection of the
particle sizes
of the reactants in the effervescence particle.
Thus, in accordance with the present invention, there is provided a reactive
particle comprising two particulate reactants which react together on contact
with a
reaction-promoting fluid, the particle number ratio of the first reactant to
the second
reactant (that is the ratio of number of particles of the first reactant to
the second reactant)
is at least 50:1. Preferably, the ratio of the median particle size of the
second reactant to
the first reactant is at least 2:1. Thus, although a larger number of the
relatively larger
particle size reactant may be used, preferably a larger number of the
relatively smaller
particle size reactant are used.
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3
This combination of a large number of relatively smaller particle size
reactant,
and a smaller number of relatively larger particle size components has been
found to lead
to the surprising result that during a process for combining the first and
second reactants
to from the reactive particle, the larger particle size reactant acts as a
"core" which is
effectively surrounded in the reactive particle by the second component. Thus,
the
second component provides a barrier so that a fluid which promotes reaction
between the
two reactants cannot penetrate the barrier layer which acts as a barrier to
moisture ingress
to the interface between the two reactants , so that no reaction between the
first and
second reactants is promoted and storage stability is surprisingly,
significantly improved.
In a preferred aspect of the invention, the particle is an effervescence
particle in
which at least one of each of the first and second reactants are respectively,
an alkaline
source and an acid source, and the fluid is a liquid i.e. water or other
aqueous component.
However, it will be clear to the skilled reader that the principle is more
broadly applicable
to improved stability of any other reactants where they may be exposed to a
fluid (i.e. a
liquid or a gas) which will promote their reaction with one another, prior to
the desired in
use conditions where exposure to the fluid is desirable.
The present invention also relates to detergent compositions comprising such
effervescence particles.
The present invention also relates to washing processes in which a detergent
composition comprising effervescence particles is contacted with water to
provide rapid
dissolution of the detergent composition in the water, and the water
comprising dissolved
detergent composition is then used for washing soiled articles. The invention
is directed
in particular to the washing of soiled household items, particularly
dishwashing and/or
laundry washing applications. The invention is particularly useful for laundry
washing
processes.
Detailed Description of the Invention
Reactive Particle
The reactive particle comprises two particulate reactants which react together
on
contact with a third component, generally a reaction-promoting fluid. The
reaction-
promoting fluid may be either a third reactant which is required for a
reaction between
the first and second reactants, or it may comprise a reaction medium either
which enables
penetration of a third reactant to the reactive particle so that a reaction
takes place, or
WO 01/30949 CA 02386131 2002-04-02 pCT/US00/29295
4
which promotes contact between the first and second reactants so that the
reaction
between the first and second components is enabled or promoted. The invention
is
particularly useful where the fluid is a liquid and in particular where the
fluid is water,
which may come into contact with the reactive particle either in the gaseous
or liquid
phase. In particular the reactive particle may comprise an effervescence
particle where
the first and second reactants react with one another on contact with water to
produce
effervescence. Thus, in this embodiment, at least one of each of the first and
second
reactants comprises an acid source and at least one comprises an alkali
source.
The particle number ratio of the first reactant to the second reactant (that
is the
ratio of number of particles of the first reactant to the second reactant) is
at least 50:1,
preferably at least 100:1, more preferably at least 500:1, or even at least
1000:1 and most
preferably at least 5000:1 or even at least 10000:1.
In addition, the ratio of the median particle size of the second reactant to
the first
reactant is at least 2:1, preferably at least 8:1, more preferably at least
15:1, or at least
20: I or even at least 30:1. Preferably the span of the particle size of each
reactant is no
greater than 3, more preferably no greater than 2, most preferably no greater
than 1.5.
As used herein, the phrase "median particle size" means the geometric mass
median diameter of a set of discrete particles as measured by any standard
mass-based
particle size measurement technique, preferably by dry sieving. As used
herein, the
phrase "geometric standard deviation" or "span" of a particle size
distribution means the
geometric breadth of the best-fitted log-normal function to the above-
mentioned particle
size data which can be accomplished by the ratio of the diameter of the 84.13
percentile
divided by the diameter of the 50''' percentile of the cumulative distribution
(Dg4.,~/D;~);
See Gotoh et al, Powdef- Technology Handbook, pp. 6-11, Marcel Dekker 1997.
Preferably, the mean particle size of the particles is from about 500 microns
to
about 1500 microns, more preferably from about 600 microns to about 1200
microns, and
most preferably from about 700 microns to about 1000 microns. The particle
size
distribution is defined by a relatively tight geometric standard deviation or
"span" so as
not to have too many particles outside of the target size. Accordingly, the
geometric
standard deviation is preferably is from about 1 to about 2, more preferably
is from about
1.0 to about 1.7, even more preferably is from about 1.0 to about 1.4, and
most preferably
is from about 1.0 to about 1.2.
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In particular for preparing an effervescence particle to be used for example,
in a
household or industrial cleaning application, the median particle size of the
second
reactant is preferably greater than 100pm, more preferably greater than 200qm
and most
preferably greater than 300q,m. The particle size of the first reactant is
preferably below
5 SOq.m, more preferably below 25qm and most preferably below lOqm. Where the
reactive particle is an effervescence particle, the first reactant comprises
either the acid
source or the alkali source, but preferably comprises the alkali source, and
the second
reactant preferably comprises acid source.
The first reactant is preferably present in the reactive particles at a level
of from
0.1% to 99% by weight of the total particle, preferably from 3% to 80%, more
preferably
from 10% to 75% and most preferably from 15% to 70%.
The second reactant is preferably present in the reactive particles at a level
of
from 0.1% to 99% by weight of the total, preferably from 20% to 95%, more
preferably
from 30% to 85% and most preferably from 35% to 75% by weight of the
effervescence
particle. For optimum reaction, the weight ratio of the first and second
reactants, in the
reactive particle is preferably substantially stoichiometric, such that there
are
substantially equal moles of reactive groups. Thus, the moles of reactive
group of first
reactant to second reactant are preferably from 5:1 to 1:5, more preferably
from 3:1 to
1:3, more preferably from 3:2 to 2:3 and most preferably from 9:10 to 10:9.
Suitable acid sources include solid organic, mineral or inorganic acids, salts
or
derivatives thereof or mixtures thereof. It may be preferred that the acids
are mono-, bi-
or tri-protonic acids. Such acids include mono- or polycarboxylic acids
preferably citric
acid, adipic acid, glutaric acid, 3-chetoglutaric acid, citramalic acid,
tartaric acid, malefic
acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are
preferably
used in their acidic form. Derivatives also include esters of the acids.
Preferred acids
include citric acid and malic acid. Citric acid is particularly preferred.
Any alkali-source may be used in the reactive particle. Carbonate alkali-
sources
are particularly preferred, for example including carbonate, bicarbonate,
sesquicarbonate
and percarbonate salts, in particular bicarbonate and/or carbonate. Preferred
carbonates to
be used herein include carbonate and hydrogen carbonates which should be
present in the
effervescence particle in a from which can react with the acid-source.
Generally,
therefore, the alkali-source should be water soluble, or of very fine particle
size such that
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a reaction with the acid-source takes place readily on contact of the
effervescence particle
with water. Salts of alkali metals or alkaline earth metals are suitable.
Water-soluble salts
such as salts of potassium, lithium, sodium, and the like are preferred
amongst which
sodium and potassium carbonate are particularly preferred. Suitable
bicarbonates to be
used herein include any alkali metal salt of bicarbonate like lithium, sodium,
potassium
and the like, amongst which sodium and potassium bicarbonate are preferred.
Bicarbonate may be preferred to carbonate, because it is more-weight
effective, i.e., at
parity weight bicarbonate is a larger CO~ "reservoir" than carbonate. However,
overall
detergent formulation requirements may result in the more alkaline pH,
produced by
carbonates, providing a more useful overall detergent formulation, thus the
choice of
carbonate or bicarbonate or mixtures thereof in the effervescence granules may
depend on
the pH desired in the aqueous medium wherein the detergent composition
comprising the
effervescence particles is dissolved. For example where a relatively high pH
is desired in
the aqueous medium (e.g., above pH 9.5) it may be preferred to use carbonate
alone or to
use a combination of carbonate and bicarbonate wherein the level of carbonate
is higher
than the level of bicarbonate, typically in a weight ratio of carbonate to
bicarbonate from
0.1 to 10, more preferably from 1 to 5 and most preferably from I to 2. In one
aspect of
the invention, where the detergent composition comprises bicarbonate alone as
the alkali-
source, preferably the effervescence particle additionally comprises greater
than 6 wt%
citric acid optionally in mixtures with other acid-source components.
Preferably the reactant particle, is substantially anhydrous such that the
overall
moisture content (including both bound i.e. water of crystallisation, and
unbound i.e. free
moisture) is less than 0.5 wt% of the effervescence particle. This is
particularly preferred
where the reaction-promoting fluid is water, or where water promotes contact
of the
reaction-promoting fluid with the reactants. More particularly, where the
effervescence
particle comprises both acid-source and alkali-source, preferably at least the
acid-source
used for forming the effervescence particle has an overall moisture content
less than 0.1
wt%, more preferably less than 0.05 wt% and most preferably less than 0.01
wt%. More
preferably, the alkali-source also has an overall moisture content less than
0.1 wt% ,
more preferably less than 0.05 wt% and most preferably less than 0.01 wt%.
Preferably, the effervescence particles have a particle size such that the
median
particle size is from 0.001 mm to 7 mm, preferably less than 2 mm.
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The bulk density of the effervescence particles is preferably from 500 g/1 to
1200
g/1, more preferably from 700 g/1 to 1100 g/1.
The reactive particles may optionally comprise additional ingredients.
Generally,
the effervescence particles comprise no more than 50 wt% of the particle of
additional
ingredient(s), preferably no more than 35 wt% and more preferably no more than
20% or
10%. It may be particularly preferred to have a highly active particle
comprising no more
than 5 wt% or even no more than 2 wt% of additional ingredients besides the
components
which contribute to the gas production/release. Where the reactive particle is
an
effervescence particle for use in a detergent composition, suitable additional
ingredients
may comprise any of the detergent ingredients which are described below simply
or in
mixtures. Particularly suitable are surfactants or organic or inorganic
builder
components, preferably those which are water soluble such as those described
below.
The reactive particles of the invention may optionally comprise binders or
coatings. Suitable bonding or coating materials are selected from one or
mixtures of
more than one of the binders and coating materials known to those skilled in
the art. In
particular suitable binders include anionic surfactants like C6-C20 alkyl or
alkylaryl
sulphonates or sulphates, preferably C8-C20 aklylbenzene sulphonates,
cellulose
derivatives such as carboxymethylcellulose and homo- or co- polymeric
polycarboxylic
acid or their salts, nonionic surfactants, preferably C 10-C20 alcohol
ethoxylates
containing from 5-100 moles of ethylene oxide per mole of alcohol and more
preferably
the C15-C20 primary alcohol ethoxylates containing from 20-100 moles of
ethylene
oxide per mole of alcohol. Of these tallow alcohol ethoxylated with 25 moles
of ethylene
oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of
alcohol
(TAE50) are preferred. Other preferred binders include the polymeric materials
like
polyvinylpyrrolidones with an average molecular weight of from 12 000 to 700
000 and
polyethylene glycols with an average weight of from 600 to 10 000. Copolymers
of
malefic anhydride with ethylene, methylvinyl ether, methacrylic acid or
acrylic acid are
other examples of polymeric binders. Others binders further include C10-C20
mono and
diglycerol ethers as well as C 10-C20 fatty acids. In the embodiment of the
present
invention where a binder is desired C8-C20 alkylbenzene sulphonates are
particularly
preferred.
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The reactive particles used in the present invention are preferably prepared
by
mixing the reactant components) with any additional ingredients to produce an
intimate
mixture and then submitting the mixture to a granulation step to form
particles. Any
granulation process may be used, however, in order to maintain high active
levels in the
finished reactive particles, the granulation should preferably take place
substantially
without addition of any free moisture to the mixture. Conventional
agglomeration,
extrusion, marumerisation, compaction processes are all suitable. However, a
preferred
agglomeration step comprises a pressure agglomeration step to form an
agglomerate
mixture, followed if necessary by a granulation step in which the agglomerate
is formed
into the reactive particles, such as effervescence particles for use in the
detergent
compositions of the invention.
In the preferred pressure agglomeration process, the substantially dry mixture
comprising the reactants and any optional additional ingredients is exposed to
high
external forces that bring the particles closely together thereby densifying
the bulk mass
of said particles and creating binding mechanisms between the components in
the
mixture. Indeed, pressure agglomeration results in an aggregation mechanism
which is
characterised by the presence of inter-particle bonds between primary solid
effervescent
particles and a structure in which these effervescence particles are still
identifiable and
retain many of their characteristics, e.g. the ability to react together in
presence of water
to deliver carbon dioxide.
The increase of density associated with the preferred processes for making the
reactive particles for use in the present invention, is closely linked to the
pressure applied.
Typically, the bulk density will increase up to 200g/1, preferably from 10 g/1
to 150 g/1,
starting from the density of the mixture comprising the effervescent raw
materials, i.e.,
acid and the carbonate source, and optionally the binder, before having
undergone a
pressure agglomeration.
Pressure agglomeration may be carried out using different processes which can
be
classified by the level of forces applied. A preferred process to be used
herein is roller
compaction. In this process the reactants, preferably the acid-source and the
alkali-source
and any optional additional ingredients after having been mixed together are
forced
between two compaction rolls that applies a pressure to said mixture so that
the rotation
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of the rolls transforms the mixture into a compacted sheet/flake. This
compacted
sheet/flake is then broken up to form reactive i.e. effervescence particles.
Typical roller compactors for use herein are for example Pharmapaktor L200/SOP
~ commercially available from Hosokawa Bepex GmbH. The process variables
during
the pressure agglomeration step via roller compaction are the distance between
the rolls,
the feed rate, the compaction pressure and the roll speed. A typical feeding
device is a
feed screw. The distance between the rolls is typically from 0.5 cm to 10 cm,
preferably
from 3 to 7 cm, more preferably from 4 to 6 cm. The pressing force is
typically between
20 kN and 120 kN, preferably from 30 kN to 100kN, more preferably from 50 kN
to 100
kN. Typically, the roll speed is between 1 rpm and 180 rpm, preferably from 2
rpm to 50
rpm and more preferably from 2 rpm to 35 rpm. Typically, the feed rate is
between 1 rpm
and 100 rpm, preferably from 5 rpm to 70 rpm, more preferably from 8 rpm to 50
rpm.
Temperature at which compaction is carried out is not critical, typically it
varies from 0°
C to 40 °C.
The sheet/flake produced by the pressure agglomeration process is broken up
into
effervescence particles by any suitable method for reducing the size of the
sheet/flake to
form particles, for example, by cutting, chopping or breaking the sheet/flake
to produce
the required length, and if necessary, by a process to make the particles
rounded i.e. to
obtain round or spherical granules according to the diameter size as defined
herein
before. In the preferred embodiment one way to break up the sheet/flake after
the roller
compaction step is to mill the compacted flake/sheet. Milling may typically be
carried out
with a Flake Crusher FC 2000 commercially available from Hosokawa Bepex GmbH.
Depending on the particle size required for the effervescence particles, the
milled
material may be sieved further. Such a sieving of the effervescence granules
can be
carried out, for example with a commercially available Alpine Airjet Screen ~.
In a preferred process for preparing a reactive particle in which water is a
reaction-promoting fluid, processing takes place under controlled conditions
to minimise
the amount of moisture which can contact the respective reactants as they are
formed into
a reactive particle. The inventors have found that even trace amounts of
moisture can
adversely affect the stability of the reactive particle produced. In
particular, where the
reaction is between the first and second reactants is a self accelerating
reaction, for
example where the reaction between the two reactants produces water as a by-
product,
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this may be particularly important. One particular example of where this
factor is
important is where the particle being produced is an effervescence particle
which is
formed from two reactants which are respectively, acid source and alkali-
source, in
particular such as organic acids (e.g. citric acid) and a carbonate source,
respectively.
5 Thus, in such a preferred process, the first and second reactants are formed
into a
reactive particle such as an effervescence particle in over-dried conditions,
in which
atmospheric moisture is reduced from the processing environment. Generally
this is
achieved by the use of a dehumidifier. Preferably, the Relative Humidity (RH)
is less
than 40%, more preferably less than 30% and most preferably less than 20%.
Preferably,
10 in addition, at least one and preferably both of the reactants as provided
in an over-dried
form for preparing into the reactive particles of the invention. By "over-
dried" is meant
that the reactant is provided in a form which is both dry (i.e. substantially
all of the free
moisture is removed) and in addition, is at least partially anhydrous (so that
at least some
of the bound water, such as water of crystallisation or other water bound to
the structure
of the reactant, has been removed). Thus, preferably, when the first and
second reactants
contact one another preferably one, and more preferably both reactants have an
overall
moisture content (comprising both free and water of crystallisation which can
be
measured to drying at 120°C for 2 hours in a drying oven) is no greater
than 0-1% by
weight, more preferably no greater than 0.05% by weight and most preferably no
greater
than 0.01 %.
Detergent Compositions Comprising an Effervescence Particle
In accordance with the present invention, there is also provided a detergent
composition comprising a detergent matrix and the effervescence particle
described
above. The detergent matrix may be any conventional detergent composition.
Generally,
however, it comprises a pre-formed detergent matrix component comprising
surfactant,
and optional additional detergent ingredients. Preferably on contact of the
effervescence
particle, the eRH of the matrix will be no greater than 25%, more preferably
no greater
than 20% or even no greater than 15% or 12% or even 10%. The eRH is measured
usin<~
a RotronicT"~ Hygroskop DT calibrated according to the manufacturers
instructions as set
out in the Rotronic Hygroskop application leaflet 2/E SpilS dated 3.1.83,
using defined
saturated salt solutions which cover the humidity range to be tested. All
measurements
are taken at 25°C.
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In a preferred aspect of the invention, at least one of the components in the
detergent matrix is over-dried i.e. has been dried to a level such that water
which is bound
to one or more of the detergent ingredients either in the detergent matrix
component or
optional additional detergent ingredients, is removed.
Detergent Matrix Component
The detergent matrix generally comprises a detergent matrix component. Such
component comprises a pre-formed particulate which may be in the form of a
powder,
particle, flake or other solid form, comprising surfactant and optional
additional detergent
ingredients.
The surfactant may be anionic, nonionic, cationic, amphoteric, zwitterionic
or mixtures thereof. Preferred detergent matrix components comprise anionic,
nonionic
and/or cationic surfactants. In particular matrix components which comprise
anionic
surfactant may be particularly useful. Suitable surfactants are described in
more detail
below. The surfactant content of a pre-formed matrix component is preferably
from 5 to
80 % by weight of the matrix component. Amounts of surfactants above 10 or
even
above 30% may be preferred. Amounts of surfactant below 70% or even below 50%
may
be preferred.
The detergent matrix component generally also contains a solid material which
may be filler such as sulphates, in particular sodium sulphate, but more
preferably
comprises at least one detergent ingredient, in particular, builder or
alkalinity
components, or mixtures of such components. Suitable examples include
phosphate,
aluminosilicate, crystalline layered silicates, sodium carbonate or amorphous
silicates.
These materials are described below in more detail. For example, each of these
components individually, or in mixtures may be present in amounts above 5%,
preferably
above 10% or even above 20% by weight of the content of the pre-formed matrix
component. Particularly preferred builder components are sodium carbonate
and/or
zeolite. Zeolite A and zeolite MAP are both suitable.
A pre-formed matrix component preferably also comprises an organic builder
such as a poly carboxylic acid and/or salt such as citric acid, tartaric acid,
malic acid,
succinic acid and their salts or a polymeric polycarboxylate such as polymers
based on
acrylic acids or malefic acids or co-polymers thereof. Such components are
generally
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12
present in the matrix component at levels below 15 wt %, preferably below 10
wt % of
the matrix component.
Other preferred ingredients in the pre-formed matrix component are chelants
such
as phosphonate chelants NTA, DTPA and succinic acid derivative chelants, as
described
below. These components are preferably present in a pre-formed particulate
component
in amounts below 5 wt % or even below 2 wt % of the matrix component.
The detergent matrix may comprise one or more pre-formed detergent matrix
components. Suitable pre-formed components may have been formed by spray-
drying,
agglomeration, marumerisation, extrusion or compaction, all of which methods
for
combining detergent ingredients are well-known in the art. Particularly
preferred pre-
formed matrix components are powders obtained from spray-drying processes,
agglomerates and extrudates. Spray-dried powders are particularly useful.
Detergent
matrix components made according to at least one low shear mixing step, for
example in
a fluidised bed, for example by fluid bed agglomeration are also preferred.
Suitable spray-drying processes for forming such pre-formed detergent matrix
components are described for example in EP-A-763594 or EP-A-437888. Suitable
processes for forming detergent matrix components which are agglomerates are
described
for example in W093/25378, EP-A-367339, EP-A-420317 or EP-A-506184. Suitable
moderate to low shear mixers may be for example a Lodige KM (trademark)
(Ploughshare) moderate speed mixer, or mixer made by Fukae, Draes, Schugi or
similar
brand mixers which mix with only moderate to low shear. The Lodige KM
(ploughshare)
moderate speed mixer which is a preferred mixer for use in the present
invention
comprises a horizontal hollow static cylinder having a centrally mounted
rotating shaft
around which several plough-shaped blades are attached. Preferably, the shaft
rotates at a
speed of from about 15 rpm to about 140 rpm, more preferably from about 80 rpm
to
about 120 rpm. The grinding or pulverizing is accomplished by cutters,
generally smaller
in size than the rotating shaft, which preferably operate at about 3600 rpm.
Other mixers
similar in nature which are suitable for use in the process include the Lodige
Ploughshare
TM mixer and the Drais~ K-T 160 mixer. Generally, in the processes of the
present
invention, the shear will be no greater than the shear produced by a Lodige KM
mixer
with the tip speed of the ploughs below 10 m/s, or even below 8m/s or even
lower.
11
In a preferred aspect of the
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Preferably, the mean residence time of the various starting detergent
ingredients
in the low or moderate speed mixer is preferably in range from about 0.1
minutes to about
15 minutes, most preferably the residence time is about 0.5 to about S
minutes. In this
way, the density of the resulting detergent agglomerates is at the desired
level.
Other suitable mixers for use in the present invention are low or very low
shear
mixers such as rotating bowl agglomerators, drum agglomerators, pan
agglomerators and
fluid bed agglomerators.
Fluid bed agglomerators are particularly preferred. Typical fluidised bed
agglomerators are operated at a superficial air velocity of from 0.4 to 4 m/s,
either under
positive or negative pressure. Inlet air temperatures generally range from -10
or 5°C up
to 250°C. However inlet air temperatures are generally below
200°C, or even below
150°C. Suitable processes are described for example in W098/58046 or
W099/03964.
Suitable processes for forming detergent matrix components by extrusion are
described
for example in W091/02047.
The detergent matrix may comprise only one pre-formed component as described
or it may comprise a mixture of components, for example mixtures of different
spray
dried powders or of different agglomerates etc or mixtures of combinations of
agglomerates, spray dried powders and/or extrudates etc. as described above.
Particularly preferred detergent matrix components are spray dried powders.
Additional Detergent Ingredients
As described above, the detergent matrix will comprise surfactant and may
comprise one or more additional detergent ingredients. These may comprise
detergent
raw materials or may be pre-formed particulates made by processing at least
one
detergent ingredient with other ingredients which may be active or inactive in
the
detergent, to form a solid particulate. Where the particulate components are
detergent
raw materials, any particulate detergent ingredient is suitable. These may be
solid
surfactants or soaps, or water soluble or dispersible polymeric materials,
enzymes,
bleaching components such as bleach activators or bleach salts such as peroxy
salts.
Surfactants and additional detergent ingredients are discussed in more detail
below.
Any of the ingredients listed below may be added either as individual solid
particulates or
as pre-formed particulates or via the detergent matrix component. These
additional
WO 01/30949 CA 02386131 2002-04-02 pCT~S00/29295
14
detergent ingredients must be incorporated into the detergent matrix if
needed, having
undergone a drying step. The final detergent matrix preferably has an eRH
below 30%.
Detergent Ingredients
Surfactant
Suitable surfactants for use in the invention are anionic, nonionic,
ampholytic, and
zwitterionic classes 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.
Preferably, the detergent compositions of the present invention and
compositions
comprising such particles comprises an additional anionic surfactant.
Essentially any
anionic surfactants useful for detersive purposes can be comprised in the
detergent
composition. These can include salts (including, for example, sodium,
potassium,
ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine
salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate
surfactants. Anionic
sulfate and sulfonate surfactants are preferred.
The anionic surfactants may be present in the detergent matrix component in
amounts below 25 wt % or even below 20 wt % but in a final detergent
composition
comprising the particle, is preferably present at a level of from 0.1 % to
60%, more
preferably from 1 to 40%, most preferably from 5% to 30% by weight.
Other anionic surfactants include the anionic carboxylate surfactants such as
alkyl
ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl
carboxyls")
such as 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. Other suitable anionic surfactants are the
alkali metal
sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a CS-C17 linear or
branched alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali
metal ion.
Other anionic surfactants include 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)
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diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14
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.
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, the CS-C 1 ~ acyl-N-(C 1-C4 alkyl)
and -N-(C 1-
C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
10 herein). Alkyl sulfate surfactants are preferably selected from the linear
and branched
primary C 10-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched
chain alkyl
sulfates and the C 12-C 14 linear chain alkyl sulfates. Alkyl ethoxysulfate
surfactants are
preferably selected from the group consisting of the C 10-C 1 g alkyl sulfates
which have
been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule.
More
15 preferably, the alkyl ethoxysulfate surfactant is a C 11-C 1 g, most
preferably C 11-C 15
alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1
to S, moles
of ethylene oxide per molecule.
Preferred surfactant combinations are mixtures of the preferred alkyl sulfate
and/
or sulfonate and alkyl ethoxysulfate surfactants optionally with cationic
surfactant. Such
mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or
secondary
alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfonates, and any
mixtures thereof.
Essentially any alkoxylated nonionic surfactant or mixture is suitable herein.
The
ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic
condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic
ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates
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16
with propylene glycol, and the nonionic ethoxylate condensation products with
propylene
oxide/ethylene diamine adducts.
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene oxide, particularly ethylene oxide and/or propylene oxide, are
particularly
suitable for use herein. Particularly preferred are the condensation products
of straight or
branched, primary or secondary alcohols having an alkyl group containing from
6 to 22
carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy
ethyl,
2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4
alkyl; and R2
is a C5-C31 hydrocarbyl; 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.
Suitable alkylpolysaccharides for use herein are 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. Preferred alkylpolyglycosides have
the
formula:
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
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.
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
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WO 01/30949 PCT/US00/29295
17
each RS is an alkyl or hydroxyalkyl group containing from 1 to 3, or a
polyethylene oxide
group containing from 1 to 3 ethylene oxide groups. Preferred are C I p-C 1 g
alkyl
dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.
Zwitterionic surfactants can also be incorporated into the detergent
compositions
in accord with the invention. These surfactants can be broadly described as
derivatives of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary amines,
or derivatives of quaternary ammonium, quaternary phosphonium or tertiary
sulfonium
compounds. Betaines such as C12-18 dimethyl-ammonio hexanoate and the C10-18
acylamidopropane (or ethane) dimethyl (or diethyl) betaines and sultaine
surfactants are
exemplary zwitterionic surfactants for use herein.
Suitable cationic surfactants to be used herein include the quaternary
ammonium
surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C16,
preferably C6-C 1 p N-alkyl or alkenyl ammonium surfactants wherein the
remaining N
positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Preferred are
also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Cationic ester surfactants such as choline ester surfactants, have for example
been
disclosed in US Patents No.s 4228042, 4239660 and 4260529 are also suitable as
are
cationic mono-alkoxylated amine surfactants preferably of the general formula
I:
R ((CHz)z-a~O-sH
N+ X'~
CH3 CH3
wherein Rl is C I p~-6.1,g hydro y1 and mixtures thereof, especially C 10-C 14
alkyl,
preferably C 1 p ansl-c:12 alkyl, a is any convenient anion to provide charge
balance,
preferably chloride or bromide.
The levels of the cationic mono-alkoxylated amine surfactants in the detergent
compositions of the invention are generally from 0.1 % to 20%, preferably from
0.2% to
7%, most preferably from 0.3% to 3.0% by weight.
Cationic bis-alkoxylated amine surfactant such as
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WO 01/30949 PCT/US00/29295
18
+/CH2CH20H
N X
CH / \CHZCH20H
3
are also useful, wherein R 1 is C 10-C 1 g hydrocarbyl and mixtures thereof,
preferably
C 10~ C 12 ~ C 14 alkyl and mixtures thereof. X is any convenient anion to
provide charge
balance, preferably chloride.
Bleach Activator
The detergent compositions of the invention preferably comprise a bleach
activator, preferably comprising an organic peroxyacid bleach precursor. It
may be
preferred that the composition comprises at least two peroxy acid bleach
precursors,
preferably at least one hydrophobic peroxyacid bleach precursor and at least
one
hydrophilic peroxy acid bleach precursor, as defined herein. The production of
the
organic peroxyacid occurs then by an in situ reaction of the precursor with a
source of
hydrogen peroxide. The bleach activator may alternatively, or in addition
comprise a
preformed peroxy acid bleach. Preferably, the bleach activator is present as a
separate,
admixed particle.
Preferably, any bleach activator is present in a particulate component having
an
average particle size, by weight, of from 600 microns to 1400 microns,
preferably from
700 microns to 1100 microns. It may be preferred that at least 80%, preferably
at least
90% or even at least 95 % or even substantially 100% of the component or
components
comprising the bleach activator have a particle size of from 300 microns to
1700 microns,
preferably from 425 microns to 1400 microns. Preferred hydrophobic peroxy acid
bleach
precursor preferably comprise a compound having an oxy-benzene sulphonate
group,
preferably NOBS, DOBS, LOBS and/ or NACA-OBS. Preferred hydrophilic peroxy
acid
bleach precursors preferably comprises TAED.
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 X-C(O)-L where L is a leaving group and X is
essentially any functionality, such that on perhydroloysis the structure of
the peroxyacid
produced is
CA 02386131 2002-04-02
WO 01/30949 PCT/US00/29295
19
O
X-C-OOH
For the purpose of the invention, hydrophobic peroxyacid bleach precursors
produce a peroxy acid of the formula above wherein X is a group comprising at
least 6
carbon atoms and a hydrophilic peroxyacid bleach precursor produces a
peroxyacid
bleach of the formula above wherein X is a group comprising 1 to 5 carbon
atoms. 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-C-R -N N -N-C-CH-R
R3 Y ,
I
1o Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O Y O
4 1 -NCH2-C NR4 -N~ /NR4
_O-C-R wC/ w
II O
O
R3 O Y
O-C=CHR4 , and -N-S-CH-R4
R3 O
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
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R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be
substituted by
essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03 M+, -C02 M+, -S04 M+, -N+(R3)4X
5 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 activator and X is an anion which provides solubility to the bleach
activator.
Preferably, M is an alkali metal, ammonium or substituted ammonium canon, with
sodium and potassium being most preferred, and X is a halide, hydroxide,
methylsulfate
10 or acetate anion.
Peroxyacid bleach precursor compounds are preferably incorporated in final
detergent compositions at a level of from 0.5% to 30% by weight, more
preferably from
1% to 15% by weight, most preferably from 1.5% to 10% by weight. The ratio of
hydrophilic to hydrophobic bleach precursors, when present, is preferably from
10:1 to
15 1:10, more preferably from 5;1 to 1:5 or even from 3:1 to 1:3. 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-
1586789.
20 Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and
EP-A-
0170386.
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-
,N,N 1N 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 I ,
2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
prefewed as
hydrophilic peroxy acid bleach precursor. Other preferred alkyl percarboxylic
acid
precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-
NOBS),
WO 01/30949 CA 02386131 2002-04-02 pCT~S00/29295
21
sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate
(ABS)
and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including those of the following general formulae:
R~ CNR2CL R~ NCR2CL
I
O R5 O or R5 O O
wherein Rl is an aryl or alkaryl group with from about 1 to about 14 carbon
atoms, R2 is
an alkylene, arylene, and alkarylene group containing from about 1 to 14
carbon atoms,
and RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon
atoms and L can
be essentially any leaving group. R1 preferably contains from about 6 to 12
carbon
atoms. R2 preferably contains from about 4 to 8 carbon atoms. R1 may be
straight chain
or branched alkyl, substituted aryl or alkylaryl containing branching,
substitution, or both
and may be sourced from either synthetic sources or natural sources including
for
example, tallow fat. Analogous structural variations are permissible for R2.
R2 can
include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen,
sulphur and other
typical substituent groups or organic compounds. RS is preferably H or methyl.
R1 and
RS should not contain more than 18 carbon atoms total. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386. It can be
preferred that
Rl and RS forms together with the nitrogen and carbon atom a ring structure.
Preferred examples of bleach precursors of this type include amide substituted
peroxyacid precursor compounds selected from (6-octanamido-
caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and
the
highly preferred (6-nonanamidocaproyl)oxy benzene sulfonate, and mixtures
thereof as
described in EP-A-0170386.
Perbenzoic acid precursor compounds which provide perbenzoic acid on
perhydrolysis benzoxazin organic peroxyacid precursors, as disclosed for
example in EP-
A-332294 and EP-A-482807 and cationic peroxyacid precursor compounds which
produce cationic peroxyacids on perhydrolysis are also suitable.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015; 4.988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528;
U.K.
WO 01/30949 CA 02386131 2002-04-02 pCT/US00/29295
22
1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of
preferred cationic peroxyacid precursors are described in UK Patent
Application No.
9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and
08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams,
and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic
peroxyacid
precursors of the N-acylated caprolactam class include the trialkyl ammonium
methylene
benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
The particles or compositions of the present invention 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 0.1% to 15% by weight, more
preferably
from 1 % to 10% by weight. A preferred class of organic peroxyacid compounds
are the
amide substituted compounds as 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.
Peroxide Source
Inorganic perhydrate salts are a preferred source of peroxide. Preferably
these
salts are present at a level of from 0.01% to 50% by weight, more preferably
of from
0.5% to 30% by weight of the composition.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persilicate salts. Generally these materials are
prepared by
crystallisation or fluidised bed processes. The inorganic perhydrate salts are
normally the
alkali metal salts. The inorganic perhydrate salt may be included as the
crystalline solid
without additional protection. For certain perhydrate salts however, the
preferred
executions of such granular compositions utilize a coated form of the material
which
provides better storage stability for the perhydrate salt in the granular
product. Suitable
coatings comprise inorganic salts such as alkali metal silicate, carbonate or
borate salts or
mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
Sodium
perborate is a preferred perhydrate salt and can be in the form of the
monohydrate of
WO 01/30949 CA 02386131 2002-04-02 pCT~S00/29295
23
nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20. Alkali metal
percarbonates, particularly sodium percarbonate are preferred perhydrates
herein. Sodium
percarbonate is an addition compound having a formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid. Potassium
peroxymonopersulfate is another inorganic perhydrate salt of use in the
detergent
compositions herein.
Chelants
As used herein, chelants refers to detergent ingredients 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. Chelants are generally present in the
detergent
matrix component and/or as dry added additional detergent ingredients so that
they are
present in the final detergent composition at total levels 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 or component.
Suitable chelants include organic phosphonates, such as the amino alkylene
poly
(alkylene phosphonates), alkali metal ethane I-hydroxy disphosphonates and
nitrilo
trimethylene phosphonates, preferably, 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 chelants 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, and iminodiacetic acid derivatives such as 2-
hydroxyethyl
diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 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-
516,102 are also suitable herein. The [3-alanine-N,N'-diacetic acid, aspartic
acid-N,N'-
diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid
sequestrants
described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable
amino
WO 01/30949 CA 02386131 2002-04-02 pCT/US00/29295
24
based sequestrants. EP-A-510,331 describes suitable sequestrants derived from
collagen,
keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid
sequestrant.
Dipicolinic acid 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. In particular the chelating agents comprising a amino or
amine group
can be bleach-sensitive and are suitable in the compositions of the invention.
Water-Soluble Builder Compound
The detergent compositions herein preferably contain a water-soluble builder
compound, typically present in the detergent compositions at a level of from 1
% to 80%
by weight, preferably from 10% to 60%, most preferably from 15% to 40% by
weight.
One preferred detergent composition of the invention comprises phosphate-
containing builder material, preferably present at a level of from 0.5% to
60%, more
preferably from 5% to 50%, more preferably from 8% to 40% by weight. Suitable
examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates,
sodium, potassium and ammonium pyrophosphate, sodium and potassium and
ammonium pyrophosphate, sodium and potassium orthophosphate, sodium
polymeta/phosphate in which the degree of polymerization ranges from about 6
to 21, and
salts of phytic acid. The phosphate-containing builder material preferably
comprises
tetrasodium pyrophosphate or even more preferably anhydrous sodium
tripolyphosphate.
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, borates, 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. Suitable carboxylates containing one carboxy
group
include the water soluble salts of lactic acid, glycolic acid and ether
derivatives thereof.
Polycarboxylates containing two carboxy groups include the water-soluble salts
of
CA 02386131 2002-04-02
WO 01/30949 PCT/US00/29295
succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid,
diglycolic acid,
tartaric acid, tartronic acid and fumaric acid, as well as the ether
carboxylates and the
sulfmyl carboxylates. Polycarboxylates or their acids containing three carboxy
groups
include, in particular, water-soluble citrates, aconitrates and citraconates
as well as
5 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. The most preferred polycarboxylic acid
containing three
10 carboxy groups is citric acid, preferably present at a level of from 0.1 %
to 15%, more
preferably from 0.5% to 8% by weight.
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
15 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 hydroxy-carboxylates containing up to three carboxy
groups per
molecule, particularly citrates.
20 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. 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.
25 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 polyamino compounds are also useful herein
including
WO 01/30949 CA 02386131 2002-04-02 pCT/US00/29295
26
those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-
305283
and EP-A-351629.
Partially Soluble or Insoluble Builder Compound
The compositions of the invention may contain a partially soluble or insoluble
builder compound present in the detergent matrix component and/or the optional
additional ingredients. Where present, typically they will be present in the
detergent
compositions in a total amount of from 0.5% to 60% by weight, preferably from
5% to
50% by weight, most preferably from 8% to 40% weight. Examples of largely
water
insoluble builders include the sodium aluminosilicates. As mentioned above, it
may be
preferred in one embodiment of the invention, that only small amounts of
alumino silicate
builder are present.
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 1.0 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 occurring 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 12 [A102) 12 (Si02)12]. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)86(Si02)106]~ 276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder. The
zeolite MAP may be present in amounts from 1 to 80%, more preferably from 15
to
40 wt%. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an
alkali metal alumino-silicate 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 1.2. Of particular interest is
zeolite
MAP having a silicon to aluminium ratio not greater than 1.15 and, more
particularly, not greater than 1.07. In a preferred aspect the zeolite MAP
detergent
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27
builder has a particle size, expressed as a median particle size d50 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 d50 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, described herein. Other methods of establishing d50 values are
disclosed in EP 384070A.
Dyes, Perfumes, Enzymes, Optical Brighteners
A preferred ingredient of the compositions herein are dyes and dyed particles
or
speckles, which can be bleach-sensitive. The dye as used herein can be a dye
stuff or an
aqueous or nonaqueous solution of a dye stuff. It may be preferred that the
dye is an
aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing
of the
detergent particles or speckles, preferably such that levels of dye solution
are obtained up
to 2% by weight of the dyed particle, or more preferably up to 0.5% by weight,
as
described above. The dye may also be mixed with a non-aqueous carrier
material, such
as non-aquous liquid materials including nonionic surfactants. Optionally, the
dye also
comprising other ingredients such as organic binder materials, which may also
be a non-
aqueous liquid. The dyestuff can be any suitable dyestuff. Specific examples
of suitable
dyestuffs include E 104 - food yellow 13 (quinoline yellow), E 1 I 0 - food
yellow 3 (sunset
yellow FCF), E131 - food blue 5 (patent blue V), Ultra Marine blue (trade
name), E133 -
food blue 2 (brilliant blue FCF), E140 - natural green 3 (chlorophyll and
chlorphyllins),
E 141 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs
may be
Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name).
Another preferred ingredient of the compositions of the invention is a perfume
or
perfume composition. Any perfume composition can be used herein. The perfumes
may
also be encapsulated. Preferred perfumes containing at least one component
with a low
molecular weight volatile component , e.g. having a molecular weight of from
150 to 450
or preferably 350. Preferably, the perfume component comprises an oxygen-
containing
functional group. Preferred functional groups are aldehyde, ketone, alcohol or
ether
functional groups or mixtures thereof.
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Another highly preferred ingredient useful in the particles or compositions
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.
Preferred commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by
Gist-
Brocades, those sold by Genencor International, and those sold under the
tradename
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated
into
the compositions in accordance with the invention at a level of from 0.0001 %
to 4%
active enzyme by weight of the composition. Preferred amylases include, for
example, a
-amylases described in more detail in GB-1,269,839 (Novo). Preferred
commercially
available amylases include for example, those sold under the tradename
Rapidase by
Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by
Novo Industries A/S. Highly preferred amylase enzymes maybe those described in
PCT/
US 9703635, and in W095/26397 and W096/23873. Amylase enzyme may be
incorporated into the composition in accordance with the invention at a level
of from
0.0001% to 2% active enzyme by weight. Lipolytic enzyme may be present at
levels of
active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 %
to 1 % by
weight, most preferably from 0.001 % to 0.5% by weight. The lipase may be
fungal or
bacterial in origin being obtained, for example, from a lipase producing
strain of
Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas
pseudoalcali e~ nes or Pseudomas fluorescens. Lipase from chemically or
genetically
modified mutants of these strains are also useful herein. A preferred lipase
is derived
from Pseudomonas pseudoalcaligenes, which is described in Granted European
Patent,
EP-B-0218272. Another preferred lipase herein is obtained by cloning the gene
from
Humicola lanu_i~OSa and expressing the gene in Asper ig llus o za, as host, as
described
in European Patent Application, EP-A-0258 068, which is commercially available
from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This
lipase is
also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7,
1989.
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29
The compositions herein also preferably contain from about 0.005% to 5% by
weight of certain types of hydrophilic optical brighteners, as mentioned
above. Examples
are Tinopal-LTNPA-GXTM and Tinopal-CBS-XTM by Ciba-Geigy Corporation. Others
include Tinopal SBM-GXTM, Tinopal-DMS-XTM and Tinopal AMS-GXTM by Ciba Geigy
Corporation.
Photo-Bleaching Agent
Photo-bleaching agents are preferred ingredients of the compositions or
components
herein. Preferred photo-bleaching agent herein comprise a compounds having a
porphin
or porphyrin structure. Porphin and porphyrin, in the literature, are used as
synonyms,
but conventionally porphin stands for the simplest porphyrin without any
substituents;
wherein porphyrin is a sub-class of porphin. The references to porphin in this
application
will include porphyrin. The porphin structures preferably comprise a metal
element or
cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si
or Ga, or
more preferably A1 , most preferably Zn. It can be preferred that the photo-
bleaching
compound or component is substituted with substituents selected from alkyl
groups such
as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as
pyridyl, pyridyl-
N-oxide, phenyl, naphthyl and anthracyl moieties. The photo-bleaching compound
or
component can have solubilizing groups as substituents. Alternatively, or in
addition
hereto the photo-bleaching agent can comprise a polymeric component capable of
solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI or co-
polymers thereof or mixtures thereof. Highly preferred photo-bleaching
compounds are
compounds having a phthalo-cyanine structure, which preferably have the metal
elements
or cations described above.
The phthalocyanines can be substituted for example the phthalocyanine
structures
which are substituted at one or more of the 1-4, 6, 8-1 l, 13, 15-18, 20, 22-
25, 27 atom
positions.
Organic Polymeric Ingredients
Organic polymeric compounds are preferred additional herein and are preferably
present as components of any particulate component such as the detergent
matrix
component where they may act as binders. By organic polymeric compound it is
meant
herein essentially any polymeric organic compound commonly used as
dispersants, and
anti-redeposition and soil suspension agents in detergent compositions,
including any of
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the high molecular weight organic polymeric compounds described as clay
flocculating
agents herein, including quaternised ethoxylated (poly) amine clay-soil
removal/ anti-
redeposition agent in accord with the invention. Organic polymeric compound is
typically incorporated in the detergent compositions of the invention at a
level of from
5 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10%
by
weight of the compositions or component. 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
10 compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
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
15 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.60/051517. 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)nN+-CH2CH2-(-CH2)a -N+-_ CH2CH20 )n X
(CH2CH20 ~ X (CH2CH20 )n X
wherein X is a nonionic 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-Ol 1965
and US 4,659,802 and US 4,664,848.
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31
Polymeric dye transfer inhibiting agents when present are generally in amounts
from 0.01% to 10 %, preferably from 0.05% to 0.5% and 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.
Polymeric soil release agents, hereinafter "SRA", can optionally be employed
in the
present components or compositions. If utilized, SRAs will generally be used
in amounts
from 0.01 % to 10.0%, typically from 0.1 % to 5%, preferably from 0.2% to 3.0%
by
weight. 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 SRAs are for example as described in U.S. 4,968,451, November 6, 1990
to J.J. Scheibel and E.P. Gosselink. Other SRAs include the nonionic end-
capped 1,2-
propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December
8, 1987
to Gosselink et al. 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; the
nonionic-
capped block polyester oligomeric compounds of U.S. 4,702,857, October 27,
1987 to
Gosselink; and the anionic, especially sulfoaroyl, end-capped terephthalate
esters of U.S.
4,877,896, October 31, 1989 to Maldonado, Gosselink et al. SRAs 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 Cl-C4
alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December
28, 1976
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32
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 SRAs include those described in U.S. 4,201,824, Violland
et
al. and U.S. 4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al., and U.S.
4,201,824,
Violland et al.
Suds Suppressing_S~stem
The detergent compositions herein, in particular when formulated for use in
machine washing compositions, may comprise a suds suppressing system present
at a
level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from
0.05%
to 3% by weight of the composition or component. Suitable suds suppressing
systems for
use herein may comprise essentially any known antifoam compound, including,
for
example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds or
soap.
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
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
"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. Other
suitable antifoam compounds include the monocarboxylic fatty acids and soluble
salts
thereof as described in US Patent 2,954,347, issued September 27, 1960 to
Wayne St.
John. Other suitable antifoam compounds include, for example, high molecular
weight
fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols,
aliphatic C 1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such
as tri- to
hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as
products of
cyanuric chloride with two or three moles of a primary or secondary amine
containing 1
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33
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 antifoam compound, preferably
comprising in combination polydimethyl siloxane, at a level of from 50% to
99%,
preferably 75% to 95% by weight of the silicone antifoam compound; and silica,
at a
level of from 1% to SO%, preferably 5% 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 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% such as DC0544, commercially available from DOW Corning,
and
an inert carrier fluid compound, most preferably comprising a C 16-C 1 g
ethoxylated
alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at
a level of 5 to
80%, preferably 10 to 70% by weight.
A highly preferred particulate suds suppressing system is described in EP-A-
0210731. EP-A-0210721 discloses other preferred particulate suds suppressing
systems.
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.
Other optional ingredients suitable for inclusion in the compositions of the
invention include colours and filler salts, with sodium sulfate being a
preferred filler salt.
Highly preferred compositions contain from about 2% to about 10% by weight of
an organic acid, preferably citric acid. Also, preferably combined with a
carbonate salt,
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.
The detergent compositions can include as an additional component a chlorine-
based bleach. However, since the detergent compositions of the invention are
solid, most
liquid chlorine-based bleaching will not be suitable for these detergent
compositions and
only granular or powder chlorine-based bleaches will be suitable.
Alternatively, a
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34
chlorine based bleach can be added to the detergent composition by the user at
the
beginning or during the washing process. The chlorine-based bleach is such
that a
hypochlorite species is formed in aqueous solution. The hypochlorite ion is
chemically
represented by the formula OCI-. Those bleaching agents which yield a
hypochlorite
species in aqueous solution include alkali metal and alkaline earth metal
hypochlorites,
hypochlorite addition products, chloramines, chlorimines, chloramides, and
chlorimides.
Specific examples include sodium hypochlorite, potassium hypochlorite,
monobasic
calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium
phosphate
dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate
sodium
dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-S,S-
dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine
B
and Dichloramine B. A preferred bleaching agent for use in the compositions of
the
instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture
thereof. A
preferred chlorine-based bleach can be Triclosan (trade name).
Most of the above-described hypochlorite-yielding bleaching agents are
available
in solid or concentrated form and are dissolved in water during preparation of
the
compositions of the instant invention. Some of the above materials are
available as
aqueous solutions.
Laundry Washing Method
Machine laundry methods herein typically comprise treating soiled laundry with
an aqueous wash solution in a washing machine having dissolved or dispensed
therein an
effective amount of a machine laundry detergent composition in accord with the
invention. By an effective amount of the detergent composition it is meant
from l Og to
300g of product dissolved or dispersed in a wash solution of volume from 5 to
65 litres,
as are typical product dosages and wash solution volumes commonly employed in
conventional machine laundry methods. Preferred washing machines may be the so-
called low-fill machines.
In a preferred use aspect the composition is formulated such that it is
suitable for
hard-surface cleaning or hand washing. In another preferred aspect the
detergent
composition is a pre-treatment or soaking composition, to be used to pre-treat
or soak
soiled and stained fabrics.
EXAMPLES
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The following examples are presented for illustrative purposes only and are
not to
be construed as limiting the scope of the appended claims in any way.
Abbreviations used in the Examples
In the detergent compositions, the abbreviated component identifications have
the
5 following
meanings:
LAS : Sodium linear C11-13 alkyl benzene sulfonate
TAS :Sodium tallow alkyl sulfate
CxyAS : Sodium C 1 x - C 1 y alkyl sulfate
Branched :branched sodium alkyl sulfate as described in W099/19454
AS
10 C46SAS :Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS : Sodium C 1 x-C 1 y alkyl sulfate condensed with
z moles of ethylene oxide
CxyEz :Clx-Cly predominantly linear primary alcohol condensed
with an
average of z moles of ethylene oxide
QAS : R2.N+(CH3)2(C2H40H) with R2 = C 12 - C 14
15 QAS 1 :R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11
APA :C8 - C10 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
20 CFAA :C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA :C 16-C 18 alkyl N-methyl glucamide
TPKFA :C 12-C 14 topped whole cut fatty acids
STPP :Anhydrous sodium tripolyphosphate
TSPP :Tetrasodium pyrophosphate
25 Zeolite :Hydrated sodium aluminosilicate of formula
Nal2(AlO2Si02)12.27H20
A
having a primary particle size in the range from
0.1 to 10 micrometers
(weight expressed on an anhydrous basis)
NaSKS-6 :Crystalline layered silicate of formula d- Na2Si2O5
Citric :Anhydrous citric acid
acid
30 Borate :Sodium borate
Carbonate :Anydrous sodium carbonate: particle size 200gm
to 900gm
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36
Bicarbonate :Anhydrous sodium bicarbonate with a particle size distribution
between
400pm and 1200~m
Silicate :Amorphous sodium silicate (Si02:Na20 = 2.0:1 )
Sulfate :Anhydrous sodium sulfate
Mg sulfate :Anhydrous magnesium sulfate
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 m. wt. about 70,000
MA/AA (1) :Copolymer of 4:6 maleic/acrylic acid, average m. wt. 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
Lipase :Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Lipolase
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 enzyme, sold
by
NOVO Industries A/S
PB4 :Sodium perborate tetrahydrate of nominal formula NaB02.3H2 O.H2O2-
PB1 :Anhydrous sodium perborate bleach of nominal formula NaB02.H 2O2
Percarbonate :Sodium percarbonate of nominal formula 2Na2C03.3H2O2
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NOBS :Nonanoyloxybenzene sulfonate in the form of the sodium salt
NAC-OBS :(6-nonamidocaproyl) oxybenzene sulfonate
TAED :Tetraacetylethylenediamine
DTPA :Diethylene triamine pentaacetic acid
DTPMP :Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename bequest 2060
EDDS :Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer sodium salt.
Photoactivated
bleach : Sulfonated zinc phthlocyanine encapsulated in bleach ( 1 ) dextrin-
sol.pol.
Photoactivated
bleach :Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin
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
m. wt. of 60,000
PVNO :Polyvinylpyridine N-oxide polymer, with an av.
m. wt. of 50,000
PVPVI :Copol of polyvinylpyrolidone and vinylimidazole
(av. m wt of 20,000)
QEA :bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H50)-
(C2H4 O))n, wherein n = from 20 to 30
SRP 1 :Anionically end capped poly esters
SRP 2 :Diethoxylated poly (1, 2 propylene terephthalate)
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 said foam controller
to said dispersing agent of 10:1 to 100:1
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Opacifier :Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft
under the tradename Lytron 621
Wax :Paraffin wax
HMEO :Hexamethylenediamine tetra(ethylene oxide)24
Example 1: Preparation of Effervescence Particle
A 2 kg batch of citric acid and sodium carbonate having a composition of 64wt%
citric acid/36 wt% sodium carbonate was prepared by mixing in a Hosokawa
Mikron
'Nautamix' DBY-SR rotating screw mixer for five minutes at a speed setting of
9(maximum): 1280 g anhydrous citric acid ex Citrique Belge (Fine Granular
Grade:
16/40) having a particle size of from 200-400~m and 720g anhydrous Sodium
Carbonate(Light Soda Ash ex Brunner Mond) pre-milled using a Hosokawa Mikron
Air-
Classifying Mill(ACM 15) to a median particle size of Sqm. The mixture was
then
compacted in a Bepex Compaction Unit (Roll 200mm Diameter, SOmm Width): the
pre-
mixed powders were poured into the feed-hopper above the compacting rolls. The
feed-
hopper has a vertical screw which feeds the powder into the rolls. The force
applied to
push these two rolls together known as compaction force was adjusted to 80kN
by
adjusting the feed-screw speed. The compacted material was collected in the
form of
broken and unbroken corrugated sheets which were then milled in a Hosokawa
Bepex
F200 Flake Breaker at speed setting I . This equipment consists of a Rolling
Cage with a
1000qm Screen.
The material produced by the Flake breaker was then placed on a Vibrating
Sieving device( Retsch model AST200) with sieve size of 355~tm. The material
retained
on the screen was the desired finished particle (effervescence particle A in
the table
below) with median particle size 620~m, and the fines were removed for
recycle.
The process is repeated using the following mixtures of components in the
quantities (respective amounts are given in wt% based on the effervescence
particle)
given in table I, to make alternative effervescence particles B-E.
Table 1
EffervescenceB C D E
Particle
Citric acid ~ 40 ~ 10 55 -
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Malic acid 20 30 - 35
Tartaric acid- - - 15
Sodium 25 70 - 40
carbonate
Sodium 1 S - 45 10
bicarbonate
These effervescence particles are then incorporated into detergent
compositions as set out
in Examples 2 to 6.
Example 2
A spray dried granule, having the composition set out in example 3 below,
produced by
forming an aqueous slurry which is then formed into particulates in a spray-
drying tower
is then mixed with, 5 wt% TAED, 1 wt% suds suppressor, 7.5 wt% sodium
carbonate and
2.5 wt% sodium sulphate, as additional detergent ingredients in an Eirich
mixer. An
aqueous solution of PEG-4000 (35% by weight solids) is then sprayed onto the
mixture,
which is allowed to granulate for 5 minutes. The resultant product is screened
to collect
particles between 300 and 1200 microns. 10 wt% sodium percarbonate, 0.5 wt%
perfume
and 1 wt% enzymes (comprising a mixture of prills comprising amylase,
cellulase,
protease and lipase) are then dry added and mixed. The mixture produced has an
eRH of
59%. 10 wt% effervescence particles of any of formulations A to E or mixtures
of these
are then added to this mixture in a Nautamix conical mixer and subsequently
packed into
detergent cartons.
Example 3
A spray dried granule is produced on a counter-current spray drying tower with
an air
inlet temperature of 300°C. Agglomerates and other admixes (see Table
2) are mixed
with the spray dried granule in a batch rotating drum mixer. The detergent
matrix has an
eRH of 38°~0. The effervescence particle A is then added, and the
product is then packed
into detergent cartons. Further examples of detergent compositions according
to the
invention may be prepared by the use of effervescence particles B to E or
mixtures of any
of the particles A to E.
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Table 2
Snray dried Granule 50%
Spray dried granule composition % Weight of Total
5 Feed
LAS 10.4
Tallow Alkyl Sulphate 1.6
EDDS 0.4
Brightener 15 0.1
10 Magnesium sulphate 0.7
Sokalan CPS 2.5
HEDP 0.3
Sodium carbonate 8.4
Sodium sulphate 23.5
15 Zeolite A 40.0
(water, perfume, etc.) 12007
Misc. _ _
100.0
Anionic surfactant agglomerate 10%
20 Agglomerate composition % Weight of Total
Feed
C45 alkyl ethoxylate sulfate (E0 0.6) 29.1
Zeolite A 45.0
Sodium carbonate 15.1
25 Polyethylene glycol (MW 4000) 1.3
Misc. (water, perfume, etc.) 955
100.0
Percarbonate 10%
TAED 5%
30 Effervesence granule 10%
Minors 15%
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Example 4
Example 3 is repeated except that the spray dried granule is dried at the
higher tower inlet
temperature of 350°C and some of the bound moisture is removed. In this
case the
detergent matrix eRH was 24%.
Example 5
The detergent matrix of example 3 is reproduced and to it is added 5% of
overdried
zeolite in a Nautamix conical mixer. (Overdried zeolite is a Zeolite A which
has had more
than half of the water of crystallisation removed by additional drying). The
resulting
detergent matrix has an eRH of 12%. 10% of effervesence particle B is then
added to this
matrix and the product packed into detergent cartons. Alternative examples can
be
prepared by the use of any of effervescence particles B to E or mixtures of
any of
particles A to E.
Example 6
Spray dried particles, agglomerates and builder agglomerates of the
formulation
described in Tables 3A and 3B below are fed first into a Lodige KMT"~ 600
mixer at 660
kg, with the drum rotation at 100 RPM and cutter speed at 3600RPM. The
resulting
mixture is fed into a fluid bed dryer. Optionally an aqueous solution of PEG-
4000 (30%
by weight solids) is sprayed onto the mixture in the first of three stages in
the fluid bed
dryer. The resulting product is screened to collect the particles in the range
of about 600
to about 1100. The fines are recycled to the Lodige KM and the large particles
are
ground and recycled to the fluid bed dryer. The dry-add detergent components
and spray-
on from the tables below are then added. The detergent matrix eRI-~ was
typically around
14%.
'TACT L' Z A
The following compositions are in accordance with the invention.
B C E F G H I
S ra -dried Granules
AS 10.010.0 15.0 5.0 8.0 10.0
TAS 1.0
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BAS 5.0 8.0
C45AS 1.0 1.0 2.0
C45AE3S 1.0
QAS 1.0 1.0
TPA, HEDP and/or 0.3 0.3 0.5 0.3
DDS
gS04 0.5 0.5 0.1
Sodium citrate 3.0 5.0
Sodium carbonate 10.0 7.0 15.0 10.0 10.0
Sodium sulphate S.0 5.0 5.0 3.0
Sodium silicate 2.0
1.6R
eolite A 16.0 18.0 20.0 20.0
SKS-6 3.0 5.0
A/AA or AA 1.0 2.0 11.0 2.0
EG 4000 2.0 1.0 1.0
QEA 1.0 1.0
rightener 0.05 0.05 0.05 0.05
Silicone oil 0.01 0.01 0.01 0.01
lomerate
LAS 2.0 2.0
MBAS 1.0
C45AS 2.0
E3 1.0 0.5
Carbonate 1.0 1.0 1.0
Sodium citrate 5.0
CFAA
Citric acid .0 1.0 1.0
QEA 2.0 .0 1.0
SRP 1.0 1.0 0.2
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iZeolite A 15.06.0 15.0 16.0
Sodium silicate
EG .0
wilder A lomerates
SKS-6 6.0 6.0 3.0 7.0 10.0
AS .0 5.0 5.0 3.0 10.0 12.0
-add articulate
com onents
ffervescence Particle8.0 10.0 12.0 .0 .0
ffervescence Particle 10.0
ffervescence Particle .0
C
ffervescence Particle 8.0
Effervescence 2.0
Pauticle
QEA 0.2 0.5
ACAOB S 3.0 1.5 2.5
OBS 3.0 3.0 5.0
AED 2.5 1.5 .5 6.5 1.5
BAS 8.0 8.0 .0
LAS (flake) 10.0 10.0 8.0
S ra -on
rightener 0.2 0.2 0.3 0.1 0.2 0.1 0.6
ye 0.3 0.05 0.1
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AE7 0.5 0.7
I
erfume 0.8 0.5 0.5
-add
Citrate 0.0 .0 5.0 15.0 5.0
ercarbonate 15.0 3.0 6.0 10.0 18.05.0
erborate 6.0 18.0
hotobleach 0.02 0.02 0.02 0.1 0.05 0.3 0.03
nzymes (cellulase,1.3 0.3 0.5 0.5 0.8 .0 0.5 0.160.2
amylase, protease,
lipase)
Carbonate 0.0 10.0 5.0 8.0 10.05.0
erfume (encapsulated)0.6 0.5 0.5 0.3 0.5 0.2 0.1 0.6
Suds suppressor 1.0 0.6 0.3 0.10 0.5 1.0 0.3 1.2
Soap 0.5 0.2 0.3 3.0 0.5 0.3
Citric acid 6.0 6.0 5.0
yed carbonate 0.5 0.5 1.0 2.0 0.5 0.5 0.5 1.0
(blue,
green)
SKS-6 .0 6.0
fillers up to
100%
TABLE 3 B
The following compositions are in accordance with the invention.
B C E F G H I
S ra -Dried Granules
AS 10.0 10.0 16.0 5.0 5.0 10.0
TAS 1.0
BAS 5.0 5.0
C45AS 1.0 2.0 2.0
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C45AE3S 1.0
QAS 1.0 1.0
TPA, HEDP and/or 0.3 0.3 0.3 0.3
DDS
gS04 0.5 0.4 0.1
Sodium citrate 10.0 12.0 17.0 3.0 5.0
Sodium carbonate 1 8.0 15.0 10.0
S.0
Sodium sulphate 5.0 5.0 5.0 3.0
Sodium silicate 2.0
1.6R
eolite A 2.0
SKS-6 3.0 5.0
A/AA or AA 1.0 2.0 10.0 .0
EG 4000 2.0 1.0 1.0
QEA 1.0 1.0
rightener 0.05 0.05 0.05 0.05
Silicone oil 0.01 0.01 0.01 0.01
lomerate
AS .0 2.0
BAS 1.0
C45AS .0
E3 1.0 0.5
Carbonate .0 1.0 1.0 1.0
Sodium citrate 5.0
CFAA
Citric acid .0 1.0 1.0
QEA .0 2.0 1.0
SRP 1.0 1.0 0.2
eolite A 15.0 26.0 15.0 16.0
Sodium silicate
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46
EG 4.0
uilder A lomerate
SKS-6 6.0 5.0 6.0 3.0 7.0 10.0
AS .0 5.0 5.0 3.0 10.012.0
-add articulate
com onents
ffervescence Particle8.0 .0 .0 2.0 2.0 .0
ffervescence Particle 10.0
ffervescence Particle 8.0
QEA 0.2 0.5
ACAOBS 3.0 1.5 2.5
OBS 3.0 3.0 5.0
AED 2.5 1.5 2.5 6.5 1.5
BAS 8.0 8.0 .0
AS (flake) 8.0
S ra -on
rightener 0.2 0.2 0.3 0.1 0.2 0.1 0.6
ye 0.3 0.05 0.1
E7 0.5 0.7
erfume 0.8 0.5 0.5
-add
Citrate .0 3.0 .0 5.0 15.0 5.0
ercarbonate 15.0 3.0 6.0 10.0 18.05.0
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47
erborate 6.0 18.0
hotobleach 0.02 0.02 0.02 0.1 0.05 0.3 0.03
nzymes (cellulase,1.5 0.3 0.5 0.5 0.8 .0 0.5 0.16 0.2
amylase, protease,
lipase)
Carbonate 5.0 8.0 10.0 5.0
erfume (encapsulated)0.6 0.5 0.5 0.3 0.5 0.2 0.1 0.6
Suds suppressor 1.0 0.6 0.3 0.100.5 1.0 0.3 1.2
Soap 0.5 0.2 0.3 3.0 0.5 0.3
Citric acid 6.0 6.0 5.0
yed carbonate 0.5 0.5 .0 0.5 0.5 0.5 1.0
(blue,
green)
SKS-6 .0 6.0
fillers up to
100%
