Note: Descriptions are shown in the official language in which they were submitted.
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
Detergent Compositions and Methods for Cleaning
Field of the Invention
This invention relates to detergent compositions and methods for cleaning
which
provide most effective cleaning results with least physical washing being
needed. The
technology may find application in various cleaning compositions, in
particular laundry
and dish-washing detergent compositions which may be in a fluid, such as
granular,
liquid or flowable gel or paste form or which may have undergone additional
processing
steps to be in a tablet form. The invention relates particularly to laundry
detergent
applications. The invention particularly relates to cleaning applications
which require
hand washing by the user.
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, or detergent tablets 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 particular, in applications where washing is carried out by hand, it is
beneficial
to wait until the detergent composition has at least partially dissolved in
the aqueous
solution so that the cleaning properties of the active detergent ingredients
can begin to
take effect. In this way, the chemical cleaning which takes place, as the soil
begins to be
broken down can at least partially replace the need for intensive mechanical
cleaning by
the user. However, the user will tend to commence washing as soon as the
detergent is
added to water so that chemical cleaning performance is not maximised at the
time of
commencement of the washing action by the user. Machine-washing processes will
also
reduce energy consumption if the chemical cleaning has begun to take effect at
the time
the mechanical cleaning (e.g. agitation) has commenced.
WO 01/30954 CA 02386338 2002-04-03 pCT~S00/29238
2
Many suggestions have been made in an effort to increase the rate of
dissolution
and dispensing of detergents in aqueous solutions in an effort to overcome
this problem.
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, in fact, 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 can 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.
Furthermore, washing processes are still commenced by the end users before
detergent active components have entered into the aqueous wash solution. The
present
inventors have now provided a washing process in which an audible signal is
produced by
the detergent composition to indicate to the user when the detergent
composition is at
least partially dissolved in the wash water, indicating that mechanical
cleaning can begin.
This washing process thereby maximises the efficiency of the cleaning process
by
ensuring that the chemical cleaning begins prior to the mechanical cleaning
applied by
the user.
Summary of the Invention
In accordance with the present invention there is now provided a method for
washing soiled articles comprising obtaining a detergent composition
comprising a signal
component, adding the detergent composition to water, and commencing
mechanical
cleaning of the soiled articles characterised in that on addition of the
detergent
composition to the water a signal is produced which indicates at least partial
dissolution
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
of the detergent composition in the wash water. Preferably the signal lasts
for a duration
which indicates when the chemical cleaning by the at least partially dissolved
detergent
composition has commenced so that the user is directed to commence mechanical
cleaning when the signal is completed. By "mechanical cleaning" herein is
meant any of
the conventional mechanical methods for cleaning, such as agitation, contact
with jets of
liquid or gas to mechanically remove soil and/or abrasion. Preferably the
signal is
audible. Preferably the signal is produced by an effervescence system. This is
found to
be particularly beneficial as the effervescence may also contribute to
mechanical
cleaning.
In accordance with a further aspect of the invention, there is also provided a
detergent composition comprising a signal component such that on contact of
the
detergent composition with water, a signal is produced. Preferably the signal
is audible.
Preferably the signal component comprises an effervescence system such that on
contact
with water effervescence is released which is audible to the user. Preferably
the duration
of the signal corresponds with time taken for the detergent composition to at
least
partially dissolve in the washing water so that the user waits for the
substantial
completion of the signal before commencing the mechanical washing step.
In accordance with a further aspect of the invention there is also provided
use of a
signal component in a detergent composition to generate a signal which
provides an
indicator of dissolution of the detergent composition. Preferably the signal
is an audible
signal.
Detailed Description of the Invention
The detergent compositions of the invention comprise a signal component such
that on contact with water, a signal is produced which provides an indicator
of the at least
partial dissolution of the detergent composition. Preferably the signal
component
produces an audible signal. Preferably the audible signal is produced by an
effervescence
system; preferred effervescence systems comprise an acid-source and an alkali-
source
which react with one another on contact with water. In a particularly
preferred
embodiment of the invention, the effervescence system comprises an
effervescence
particle. The audible signal produced by the signal component is preferably at
a noise
level of at least 42dB, more preferably at least 45dB and most preferably at
least SOdB for
at least part of its duration. Preferably, the noise level generated by the
audible signal is
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
4
at least 3dB greater than the average ambient background noise level as
measured over a
five minute measurement period for background noise. Preferably the noise
level will be
at least SdB greater than ambient background noise, more preferably at least l
OdB greater
than ambient background noise. A suitable apparatus for measuring noise levels
is a
CEL SoundTrack dB21 apparatus, (Model CEL-480 Version 1.8) from CEL
Instruments
Ltd using a microphone and run on Broadband SLM mode with the frequency
weighting
for RMS set at A and the frequency rating for peak set at Z. A measurement
range of 20-
90 dB is generally suitable.
Preferably the effervescence system is designed so that the duration of the
signal
corresponds to the length of time needed for the detergent active ingredients
to at least
partially dissolve in the wash water so that in the preferred method of the
invention, on
completion of the audible signal, the mechanical washing process commences. By
duration of the signal it is intended to refer to the time delay between
contact of the
detergent composition comprising the signal component with the wash water and
completion of the signal. The audible signal may either commence immediately
during
this time or there may be an initial delay before the signal is produced.
Preferably the
audible signal has a duration of at least 5 seconds, more preferably at least
10 seconds or
even at least 30 seconds or 1 minute.
Effervescence System
The effervescence system comprises one or more effervescence components such
that on contact of the effervescence system with water, effervescence is
produced. This
effervescence may be as a result of gas trapped in the matrix of the
effervescence system
being released when the particle contacts water, or more usually, is the
result of a reaction
which takes place between two or more reactants present in the effervescence
system
which, on contact with water react with one another to produce a gas. Where
the
effervescence is produced by reaction of two or more reactants, preferably,
the reactants
are provided by an acid-source and an alkali-source.
Acid-Source
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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
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.
Alkali-Source
Any alkali-source may be used in the effervescence system. 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 system in a form which can react with
the acid-
source. Generally, therefore, the alkali-source should be water soluble, or of
very fine
particle size such that 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 systems 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 1 to 2.
Preferably, the detergent composition will comprise at least O.Swt% total
effervescence components, more preferably at least 1 wt% total effervescence
components and most preferably at lesat Swt% or even at least 10 or 20 wt%
based on the
weight of the detergent composition, of total effervescence components.
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
6
The delivery of the effervescence via an effervescence particle can be
particularly
useful in the present invention because adjustment of the parameters described
below
enable the duration of the audible signal to be tailored to the needs of the
detergent
composition. This will be clear to the person skilled in the art. Thus, for
example for
slower dissolving detergent compositions, an effervescence particle comprising
a greater
proportion of non-effervescent components such as binder or other optional
ingredients,
which slows dissolution, or a higher compaction pressure may be used to ensure
that the
signal is delivered either more slowly or after a delay period on contact with
the wash
water, so that the signal stops after a longer time span from contact of the
detergent
composition with the water.
Effervescence Particle
Where the effervescence system comprises the preferred effervescence particle,
suitable acid-sources and alkali-sources are as set out above. The acid-source
is
preferably present in the effervescence particle 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 carbonate source is preferably present in
the
effervescence 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.
It may be preferred for the number ratio of the alkali-source to the acid-
source
(that is the ratio of number of particles of the alkali-source to the acid-
source) to be 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 alkali-source to the
acid-
source is preferably at least 2:1, preferably at least 8:1, more preferably at
least 15:1, or at
least 20:1 or even at least 30:1. Preferably the span of the particle size of
each of the
acid-source and the alkali-source 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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
7
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
(D84,,3/Dso)~
See Gotoh et al, Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997.
Preferably, the mediann particle size of the effervescence 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.
In particular for preparing an effervescence particle to be used in the
detergent
compositions of the invention, the median particle size of the acid-source is
preferably
greater than 100~m, more preferably greater than 200~m and most preferably
greater
than 300gm. The median particle size of the alkali-source is preferably below
SO~m,
more preferably below 25pm and most preferably below lOqm.
In the effervescence particle, the molar ratio of the reactive groups on the
alkali-
source and the reactive groups of the acid-source is preferably substantially
stoichiometric, such that there are substantially equal moles of reactive
groups. Thus, the
molar ratio of reactive groups of acid-source to reactive groups of alkali-
source is
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.
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 effervescence 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. More
particularly,
where the effervescence component comprises both acid-source and alkali-
source,
preferably at least the acid-source used for forming the effervescence
particle has an
CA 02386338 2002-04-03
WO 01/30954 PCT/CTS00/29238
8
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 0.5 or less than 0.1 wt%, more preferably less than
0.05 wt%
and most preferably less than 0.01 wt%.
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 effervescence 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.
Suitable
additional ingredients may comprise any detergent ingredients which are
described
below. Particularly suitable are surfactants or organic or inorganic builder
components,
preferably those which are water soluble such as those described below.
Although not preferred for the reasons given above, optional binders or
coating
agents may be incorporated into the effervescence particles. Suitable
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 C 10-
C20 mono and diglycerol ethers as well as C 10-C20 fatty acids. In the
embodiment of the
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
9
present invention where a binder is desired C8-C20 alkylbenzene sulphonates
are
particularly preferred.
The effervescence particles used in the present invention are preferably
prepared
by mixing the effervescence components) which contribute to gas
production/release,
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 effervescence
particles,
the granulation should preferably take place substantially without addition of
any free
moisture to the mixture. 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 effervescence
particles for
use in the detergent compositions of the invention. In the preferred pressure
agglomeration process, the substantially dry mixture comprising the
effervescence
components 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
effervescence 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 effervescence components, 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
WO 01/30954 CA 02386338 2002-04-03 pCT~S00/29238
rotation of the rolls transforms the mixture into a compacted sheet/flake.
This
compacted sheet/flake is then broken up to form effervescence particles.
Typical roller compactors for use herein are for example Pharmapaktor L200/SOP
~ commercially available from Hosokawa Bepex GmbH. The process variables
during
5 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
kN and 120 kN, preferably from 30 kN to 100kN, more preferably from 50 kN to
100
10 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.
15 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
20 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 200~ 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 dry effervescent
granules can be
carried out, for example with a commercially available Alpine Airjet Screen ~.
Detergent Matrix
In addition to the signal component, the detergent compositions according to
the
invention comprise a detergent matrix which includes all of the other
detergent
ingredients. Generally, the detergent matrix comprises at least one pre-formed
detergent
matrix component which comprises surfactant, and optional additional detergent
ingredients. Preferably the detergent matrix has eRH no greater than 30%.
Preferably the
eRH is no greater than 25%, more preferably no greater than 20% or even no
greater than
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
11
15% or 12% or even 10%. The eRH can be measured using a RotronicTM Hygroskop
DT
calibrated according to the manufacturers instructions as set out in the
Rotronic
Hygroskop application leaflet 2/E Spi/S dated 3.1.83, using defined saturated
salt
solutions which cover the humidity range to be tested. All measurements are
taken at
25°C. In addition, preferably the detergent matrix has a free moisture
content of no
greater than 2wt%, preferably no greater than 1 wt%, and even more preferably
no greater
than 0.5 or 0.1 or 0.05 wt%. This low free moisture content may be achieved by
drying
one or more than one, or all of the components in the detergent matrix. Thus
the
detergent matrix component and one or more optional additional ingredients may
be pre-
mixed before drying or may be dried after mixing. Additional detergent matrix
component and/or optional additional ingredients may then be combined with
these pre-
dried components without an additional drying step. In accordance with a
further
preferred aspect of the invention, at least one of the components in the
detergent matrix
(either a detergent matrix component or an additional optional detergent
ingredient) 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.
In accordance with a further preferred aspect of the invention, the detergent
composition comprises an effervescence system and a low density detergent
matrix
component having a bulk density below 400g/1.
Detergent Matrix Component
The detergent matrix 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 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% by wt or even above 20 wt% or above 30 wt%, based on the total
weight of
the detergent matrix component, may be preferred. Amounts of surfactant below
70% or
even below 50% may be preferred.
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
12
The detergent matrix component generally also comprises a solid material which
may be filler such as sulphates, in particular sodium sulphate, but more
preferably the
detergent matrix component 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
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 optical
brighteners or 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
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
13
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~ h-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.
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 5
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 using a fluid bed agglomerator 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.
In order to
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
14
obtain a detergent matrix having the desired low eRH, the detergent matrix
component or
mixture thereof, will have undergone drying to provide the required low
moisture content.
Such drying may be provided in any conventional drying step, or may be the
result of
more thorough drying than is conventional using the usual processing route.
For
example, in the spray drying process the spray drying tower may be operated at
higher air
inlet temperatures for example from 300°C to 350°C or even
400°C. Alternatively, an
extra drying step may be provided in which the agglomerates/spray dried
powders/extrudates etc are dried by any convenient means. Suitable examples
include
drying ovens and fluidised bed dryers. For example, in a drying oven, the
detergent
matrix powder may be passed through such a drying oven on a conveyor or other
convenient means. Preferably the free moisture in the detergent matrix
component will
be dried to below 1 wt%, more preferably below 0.5 wt%, or even below 0.1 or
0.05 wt%
of the detergent matrix component. There is not necessarily a direct
correlation between
the free moisture content of the detergent matrix component and the eRH, so
the eRH for
a particular detergent matrix must be measured in order to ensure the
appropriate eRH is
achieved. In a particularly preferred aspect of the invention, the detergent
matrix
component is over-dried (i.e. at least some of the bound water which is
naturally
associated with one or more of the chemical constituents of the component is
at least
partially removed). Particularly preferred detergent matrix components are
spray dried
powders.
In particular in detergent compositions which comprise the effervescence
system
in the form of effervescence particles, the incorporation of a low density
surfactant-
containing detergent matrix component surprisingly promotes effervescence of
the
detergent , and in particular promotes both the initial effervescence and the
duration of
the effervescence. This can be particularly advantageous as it enables lower
amounts of
effervescence particle to be used in the detergent compositions of the
invention to achieve
the same effervescence effect. The low density detergent matrix component
preferably has a bulk density of at least 100g/1, more preferably at least
120g/1.
Preferably the bulk density is below 350g/1 or even below 300g/1 or 250g/1.
The median
particle size of the low bulk density detergent matrix component is preferably
at least 50
Vim, more preferably at least 75~m and most preferably at least 100~m.
Generally, the
WO 01/30954 CA 02386338 2002-04-03 PCT/US00/29238
median particle size will be below SOO~m, preferably below 450p,m and even
below 400
or 350pm.
Preferably the surfactant content in the low density detergent matrix
component is
at least 20 wt%, more preferably at least 25wt% and most preferably at least
30 wt%
5 based on the total weight of the detergent matrix component. Any of the
surfactants
described below are suitable, preferred are any suds-generating surfactants.
Anionic
and/or nonionic surfactants are particularly preferred. Cationic surfactants
which have
good foaming properties may also be preferred. As for the other detergent
matrix
components described, the low density detergent matrix component preferably
comprises
10 additional ingredients which may be fillers such as sulphate or more
preferably comprises
additional detergent ingredients as described below. Particularly preferred
additional
ingredients are alkali metal carbonates, preferably sodium carbonate,
silicates which may
be either amorphous or crystalline, zeolites, brighteners and polymeric
materials such as
acrylate polymers which may be either homo or copolymers, for example
copolymers of
15 acrylic and malefic acids are particularly preferred.
Preferably the low density detergent matrix component is incorporated into the
detergent compositions of the invention in amounts greater than 0.1 wt% based
on the
total weight of the detergent composition, more preferably in amounts greater
than 2 wt%
or even greater than 5 wt% or 10 wt%. Generally, the detergent compositions of
the
invention will contain no more than 20 wt% of the low density detergent matrix
component, preferably no more than 15 wt%, or even no more than 10 wt% based
on the
total weight of detergent composition. Preferably the weight ratio of
effervescence
components to the low density detergent matrix component is from 10:1 to 1:10,
preferably being from 5:1 to 1:3 and most preferably from 3:1 to 1:2.
The low density detergent matrix component can be prepared by any of the
methods for making the detergent matrix component as described above as long
as they
permit a sufficiently low density to be achieved. Spray drying processes and
fluid bed
agglomeration processes are particularly suitable. Spray drying processes are
particularly
preferred.
Additional Detergent Ingredients
As described above, the detergent matrix may comprise one or more additional
detergent ingredients. These may comprise detergent raw materials or may be
pre-formed
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
16
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 to the
detergent
compositions claimed either as individual solid particulates or as pre-formed
particulates
or via a detergent matrix component. These additional detergent ingredients
may be
incorporated into the detergent matrix if needed, having undergone a drying
step.
Whether a drying step is needed depends upon the form and level of
incorporation of the
individual additional ingredient materials and the eRH which they and the
detergent
matrix component and other ingredients provide in the overall detergent
matrix. In
accordance with the first embodiment of the invention, the final detergent
matrix must
have 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 particles and detergent compositions of the present invention
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
WO 01/30954 CA 02386338 2002-04-03 pCT~S00/29238
17
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-C 1 ~ 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 1 g
monoesters)
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-C1~ acyl-N-(C1-C4 alkyl)
and -N-(C1
C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
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
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 5, moles
of ethylene oxide per molecule.
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
18
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 C5-
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
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, Cl-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
WO 01/30954 CA 02386338 2002-04-03 pCT~S00/29238
19
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
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 10-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-C 16,
preferably C6-C 10 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
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
cationic mono-alkoxylated amine surfactants preferably of the general formula
I:
R WH2~2-4W 1-SH
N+ Xe
CH3 CH3
5 wherein R1 is C 10-C 1 g hydrocarbyl and mixtures thereof, especially C 10-C
14 alkyl,
preferably C 10 and C 12 alkyl, and X 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
10 7%, most preferably from 0.3% to 3.0% by weight.
Cationic bis-alkoxylated amine surfactant such as
\ +/CH2CH20H
N X
CH / \CH2CH20H
3
are also useful, wherein R 1 is C 10-C 1 g hydrocarbyl and mixtures thereof,
preferably
C 10~ C 12~ C 14 alkyd mixturesthereof. X is any convenient anion to provide
charge
15 balance, preferably-~c~Ioride~
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,
20 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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
21
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
O
I~
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
4
-N-C-R - ~ -N-C-CH-R
R3 , R3 Y ,
I
Y
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
22
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 ~C~
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
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
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 cation 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 cation,
with
sodium and potassium being most preferred, and X is a halide, hydroxide,
methylsulfate
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
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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
23
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.
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 1,
2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred as
hydrophilic peroxy acid bleach precursor. Other preferred alkyl percarboxylic
acid
precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-
NOBS),
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:
R1 CNR2C~ R1 N_.__C__ _R2_C__- ~
O R5 O or R5 O O
wherein R1 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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
24
activator compounds of this type are described in EP-A-0170386. It can be
preferred that
R1 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.
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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
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,
5 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
10 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
nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20. Alkali metal
15 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.
20 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
25 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 1-hydroxy disphosphonates and
nitrilo
trimethylene phosphonates, preferably, diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
26
tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane diphosphonic acid and 1,l 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
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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
27
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
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
sulfinyl carboxylates. Polycarboxylates or their acids containing three
carboxy groups
include, in particular, water-soluble citrates, aconitrates and citraconates
as well as
succinate derivatives such as the carboxymethyloxysuccinates described in
British Patent
No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732,
and
aminosuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in
British Patent No. 1,387,447. The most preferred polycarboxylic acid
containing three
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
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.
CA 02386338 2002-04-03
WO 01/30954 PCT/LTS00/29238
28
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.
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
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:
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
29
Na 12 [A102) 12 (Si02)12~. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106~~ 276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder. 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
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 110 - food
yellow 3 (sunset
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
yellow FCF), E131 - food blue S (patent blue V), Ultra Marine blue (trade
name), E133
food blue 2 (brilliant blue FCF), E 140 - natural green 3 (chlorophyll and
chlorphyllins),
E141 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs
may be
Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name).
5 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 1
SO to 450
or preferably 350. Preferably, the perfume component comprises an oxygen-
containing
10 functional group. Preferred functional groups are aldehyde, ketone, alcohol
or ether
functional groups or mixtures thereof.
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,
15 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
20 (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
25 -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
30 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
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
31
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 eg 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 pseudoalcali~e~, which is described in Granted European
Patent,
EP-B-0218272. Another preferred lipase herein is obtained by cloning the gene
from
Humicola lanuginosa and expressing the gene in As~ergillus oryza, 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.
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-UNPA-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
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
32
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
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
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
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
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:
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
33
~H3 ~H3
X ~ OCH2CH2)n N+CH2 CH2 -~ CH2)a b N+CH2CH20 ~ X
(CH2CH20 ~ X (CH2CH20 ~- X
wherein X is a nonionic group selected from the group consisting of H, C1-C4
alkyl or
hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20,
preferably
from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for
cationic
monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for
cationic
diamines (b=1 ), n is at least about 12 with a typical range of from about 12
to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-011965
and US 4,659,802 and US 4,664,848.
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. I % 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.
WO 01/30954 CA 02386338 2002-04-03 pCT~S00/29238
34
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 C1-C4
alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December
28, 1976
to Nicol, et al.; and the methyl cellulose ethers having an average degree of
substitution
(methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution
viscosity of
from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous
solution. Such
materials are available as METOLOSE SM 100 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 System
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.
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
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
5 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.
10 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
15 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
20 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
25 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-
30 0210731. EP-A-0210721 discloses other preferred particulate suds
suppressing systems.
WO 01/30954 CA 02386338 2002-04-03 pCT/LTS00/29238
36
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
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-5,5-
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
WO 01/30954 CA 02386338 2002-04-03 PCT/US00/29238
37
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
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 iu the Examples
In the detergent compositions, the abbreviated component identifications have
the
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 AS :branched sodium alkyl sulfate as described in W099/19454
C46SAS :Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS :Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide
CxyEz : C 1 x-C 1 y predominantly linear primary alcohol condensed with an
average of z moles of ethylene oxide
QAS : R2.N+(CH3)2(C2H40H) with R2 = C12 - C14
QAS 1 :R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11
APA :C8 - C10 amido propyl dimethyl amine
WO 01/30954 CA 02386338 2002-04-03 pCT/L1S00/29238
38
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of tallow
and coconut fatty acids
STS :Sodium toluene sulphonate
CFAA :C12-C14 (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
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
Borate :Sodium borate
Carbonate :Anydrous sodium carbonate: particle size 200gm
to 900~m
Bicarbonate:Anhydrous sodium bicarbonate with a particle size
distribution between
400pm and 1200pm
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 425gm and 850pm
MA/AA :Copolymer of 1:4 maleic/acrylic acid, average m.
wt. about 70,000
MA/AA ( :Copolymer of 4:6 maleic/acrylic acid, average m.
1 ) 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 :Proteolytic enzyme, having 4% by weight of active
I enzyme, as described
in WO 95/10591, sold by Genencor Int. Inc.
WO 01/30954 CA 02386338 2002-04-03 pCT~S00/29238
39
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-
PB 1 :Anhydrous sodium perborate bleach of nominal formula NaB02.H 2O2
Percarbonate :Sodium percarbonate of nominal formula 2Na2C03.3H2O2
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 phosphonatej, 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.x-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)
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
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
5 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
10 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
15 to said dispersing agent of 10:1 to 100:1
Opacifier :Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft
under the tradename Lytron 621
Wax :Paraffin wax
HMEO :Hexamethylenediamine tetra(ethylene oxide)24
20 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-5R rotating screw mixer for five minutes at a speed setting of
9(maximum): 1280 g anhydrous citric acid ex Citrique Belge (Fine Granular
Grade:
25 16/40) having a particle size of from 200-400pm 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 Spm. 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-
30 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
WO 01/30954 CA 02386338 2002-04-03 pCT/LTS00/29238
41
broken and unbroken corrugated sheets which were then milled in a Hosokawa
Bepex
F200 Flake Breaker at speed setting 1. This equipment consists of a Rolling
Cage with a
1000pm Screen.
The material produced by the Flake breaker was then placed on a Vibrating
Sieving device( Retsch model AST200) with sieve size of 355~m. 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 1, to make alternative effervescence particles B-E.
Table 1
EffervescenceB C D E
Particle
Citric acid 40 10 55 -
Malic acid 20 30 - 35
Tartaric acid- - - 15
Sodium 25 70 - 40
carbonate
Sodium 15 - 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
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
42
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%. 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.
T..L1.. '1
dray dried Granule SO%
Spray dried granule composition % Weight of Total Feed
LAS 10.4
Tallow Alkyl Sulphate 1.6
EDDS 0.4
Brightener 15 0.1
Magnesium sulphate 0.7
Sokalan CPS 2.5
HEDP 0.3
Sodium carbonate 8.4
Sodium sulphate 23.5
Zeolite A 40.0
Misc. (water, perfume, etc.) 12.07
100.0
Anionic surfactant agglomerate 10%
Agglomerate composition % Weight of Total Feed
C45 alkyl ethoxylate sulfate (E0 0.6) 29.1
Zeolite A 45.0
Sodium carbonate 15.1
Polyethylene glycol (MW 4000) 1.3
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
43
Misc. (water, perfume, etc.) ~_5
100.0
Percarbonate 10%
TAED 5%
Effervesence Qranule 10%
Minors 15%
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 eRI4 was
typically around
14%.
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
44
TABLE 3 A
The following compositions are in accordance with the invention.
C F G
S ra -dried Granules
AS 1 0.0 0.0 15.0 5.0 8.0 10.0
1
AS 1.0
BAS 5.0 8.0
C45AS 1.0 1.0 2.0
C45AE3S 1.0
QAS 1.0 1.0
TPA, HEDP andlor 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 10.010.0
Sodium sulphate 5.0 5.0 5.0 3.0
Sodium silicate .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 .0 11.0 .0
EG 4000 .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
WO 01/30954 CA 02386338 2002-04-03 PCT~JS00/2923g
Carbonate 1.0 1.0 1.0
Sodium citrate 5.0
CFAA
Citric acid .0 1.0 1.0
QEA .0 .0 1.0
SRP 1.0 1.0 0.2
eolite A 15.0 6.0 15.0 16.0
Sodium silicate
EG .0
udder 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
ffervescence Particle .0
QEA 0.2 0.5
ACAOBS 3.0 1.5 .5
OBS 3.0 3.0 5.0
AED .5 1.5 .5 6.5 1.5
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
46
BAS 8.0 8.0 .0
AS (flake) 10.0 10.0 8.0
S ra -on
rightener .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 0.0 .0 5.0 15.0 5.0
ercarbonate 15.0 3.0 6.0 10.0 18.0 S.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 0.16 0.2
amylase, protease,
lipase)
Carbonate 0.0 10.0 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 0.10 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 III B
The following compositions are in accordance with the invention.
CA 02386338 2002-04-03
WO 01/30954 PCT/US00/29238
47
C F G
S ra -Dried Granules
AS 1 0.0 0.0 16.0 .0 .0 0.0
1 5 5 1
AS 1 .0
BAS 5.0 5.0
C45AS 1.0 2.0 .0
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 15.0 8.0 15.0 10.0
Sodium sulphate 5.0 5.0 5.0 3.0
Sodium silicate .0
1.6R
eolite A .0
SKS-6 3.0 5.0
A/AA or AA 1.0 .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 .0
BAS 1.0
C45AS .0
E3 1.0 0.5
Carbonate .0 1.0 1.0 1.0
Sodium citrate 5.0
WO 01/30954 CA 02386338 2002-04-03 pCT/US00/29238
48
CFAA
Citric acid .0 1.0 1.0
QEA .0 .0 1.0
SRP 1.0 1.0 0.2
eolite A 15.0 6.0 15.0 16.0
Sodium silicate
EG 4.0
udder A lomerate
SKS-6 6.0 5.0 6.0 3.0 7.0 10.0
AS .0 5.0 5.0 3.0 10.0 12.0
-add articulate
com onents
ffervescence Particle8.0 .0 .0 .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 .5 1.5 2.5 6.5 1.5
BAS 8.0 8.0 .0
LAS (flake) 8.0
S ra -on
rightener 0.2 0.2 0.3 0.1 0.2 0.1 0.6
ye 0.3 0.050.1
W~ 01/30954 CA 02386338 2002-04-03 pCT~S00/29238
49
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 18.0 5.0
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. 0.5 0.5 1.0
(blue, S
reen)
SKS-6 .0 6.0
fillers up to
100%
Noise data was obtained for the examples of the invention and it was found
that
using levels of effervescence particle A as low as 1 wt% based on the weight
of the
detergent composition, the noise level rose to approximately 49 dB and that
for use of
levels of effervescence particle A at 10 wt% based on the weight of the
detergent
composition, the noise level rose to as high as SSdB.
