Note: Descriptions are shown in the official language in which they were submitted.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
BLEACHING DETERGENT COMPOSITIONS
Technical Field
This invention provides specific sanitising compositions and methods for
improved
sanitisation of fabrics.
Backøround to the Invention
Traditionally, hard-surface cleaners contain bleach as cleaning agent and
disinfectant.
They generally contain high levels of chlorine bleach to achieve the required
cleaning and
disinfecting properties.
Research has shown that hydrogen peroxide bleach in laundry and dish washing
detergents also has a disinfecting action and, more recently, detergent
manufacturers have
become interested in the disinfecting properties of these detergents.
Peroxyacid bleach
precursors are also known to provide antimicrobial action.
However, not all bleach systems which have sufficient disinfecting properties
are suitable
for detergents: bleach is not always compatible with other detergent
ingredients, such as
enzymes, or moreover, the levels of bleach required to obtain disinfecting are
too high
and may damage the fabrics.
The inventors found that peroxyacid bleach precursors can be the preferred
bleach species
to deliver sanitisation of fabrics during the wash. They found however that a
problem
with these bleach precursors is that they form the peroxyacid bleach at a
high, alkaline pH
, but that at such a high, alkaline pH the peroxyacid, which is found to be
the active
species which gives the sanitisation benefits, dissociates to the inactive
form, resulting
thus in reduced sanisatation.
Also, a preferred bleaching ingredient in detergents is a percarbonate salt.
The
percarbonate makes the solution very alkaline, which is as set out above not
desirable
when aiming to keep high levels of the active species, i.e. the peroxyacid
itself, and thus
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
2
the antimicrobial performance thereof. Also many builders provide an alkaline
pH in the
wash, which is not desirable when seeking an efficient sanitisation.
Moreover, many detergent ingredients also require high. alkaline pH conditions
in the
wash, which are not compatible with the preferred pH of the wash required to
have a high
level of peroxyacid.
Thus it is difficult to formulate detergents in such a way that preferably
small amounts
peroxyacid bleach precursors provide efficient sanitisation whilst at the same
time
excellent cleaning is achieved.
They inventors have now found a way to provide efficient antimicrobial
performance and
or sanitisation whilst a good cleaning of both bleachable and non-bleachable
stains is
achieved. They found a that when the pH of the detergent in the wash water is
controlled,
namely from 8.8 and 9.9, preferably from 9.0 or even 9.2 to 9.85 or even to
9.8, in
particular achieved by using specific levels of acid and alkaline ingredients
and optionally
buffers, excellent sanitisation and cleaning is obtained, whilst only limited
amounts of
precursor are required, making the compositions more storage stable and safer
to use.
They found that these detergent compositions can then even contain
percarbonate bleach.
The specific compositions of the invention are preferably used to effectively
provide
sanitisation of fabrics or, effectively inactivate micro-organisms, in
particular bacteria
which are difficult to inactivate, such as in particular E. Hirae, but also S.
Aureus, E Coli
and Ps Aeruginosa.
Summary of the invention
The invention relates to laundry or dish washing detergent composition
comprising, at
least 15% by weight of a carbonate source and a bleach system which contains
at least
2.5% by weight of a peroxyacid bleach precursor and a hydrogen peroxide
source, which
may include a salt of a percarbonate and may thus be part of the carbonate
source, and at
least 7% by weight of an acid, preferably an organic acid, more preferably
including a
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
3
organic carboxylic acid, characterised in that a 1 % by weight mixture of the
composition
in demineralised water of a temperature of 20°C obtained after 10
minutes stirring at a
speed of 200rpm, provides a pH from 8.8 to 9.9.
The invention also relates to a method of providing sanitisation during the
wash by use of
a composition of the invention and a method for inactivate E. Hirae, S.
Aureus, E. Coli
and Ps Aeruginosa.
The inventors have also found that, when the laundry and dish washing
compositions of
the invention are for use in automatic laundry methods, improved antimicrobial
performance or sanitisation of the fabrics is achieved when the composition is
delivered
directly into the drum of the washing machine, for example by use of a
dispensing device.
One embodiment of the invention thus relates to a washing method for washing
fabrics
whereby a the composition of the invention is introduced into the drum of a
washing
machine by placing a dispensing device comprising the composition in the drum
prior to
the introduction of wash water.
Detailed Description of the Invention
The composition of the invention is preferably such that a 1 % mixture of the
composition
in demineralised water, at a temperature of 20°C, obtained after 10
minutes stirring at a
speed of 200rpm, provides a pH from 9.0 to 9.85 or even from 9.2 to 9.85 or
even to 9.8,
or even from 9.4 to 9.8. The pH is measured after stirring the mixture, for 10
minutes at a
constant temperature, by any conventional pH measurement method.
With the term ' 1 % mixture' is meant any mixture, dispersion or solution of 1
weight unit
of the composition in 99 weight units of demineralised water, and it is thus
to be
understood that if the composition is not dissolved fully after 10 minutes,
the pH is
measured of such a mixture or dispersion.
When used herein, 'reduction of the activity of the micro-organisms' includes
a reduction
of the activity as defined in the CEN method prEN1276, 1993, (Comite Europeen
de
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
4
Normalisation) and CEN method prEN 1650. The reduction therein is preferably
represented by a reduction of the specific micro-organism or bacteria by at
least 105, more
preferably at least 2x 105, or even 3x 105.
The reduction of the activity of the micro-organisms when used herein includes
the
reduction of any of the processes conducted by the micro-organism, including
secretion
of products but preferably the growth of the micro-organisms.
The invention also provides a method for reduction of the activity of micro-
organisms, or
preferably specific bacteria, comprising the steps of contacting the micro-
organism with
an aqueous liquor comprising the composition of the invention such that the
peroxyacid
provided by the precursor is present at a level of at least 100 ppm in the
liquor, per 106
micro-organisms.
Preferably, the composition is such that at least the activity of E. Hirae,
but more
preferably also of S. Aureus, E Coli and Ps Aeruginosa, is reduced by at least
105,
preferably at least 2 x 105 or even 3 x 105, as measured by the above CEN
method.
In particular, the activity reduction is done during a laundering process.
Hereby, the
composition of the invention can be contacted with the specific micro-
organisms in solid
form, but preferably the bleaching agent is present in a liquor in contact
with the micro-
organisms.
The specific micro-organisms, preferably the specific bacteria, can be present
on the
surfaces or fabrics to be cleaned and sanitised, for example on the fabrics to
be cleaned in
a laundry process. The bacteria can also be present in the liquor used for the
cleaning or
sanitisation process or in the equipment used in the process, such as the
washing machine
or dispensing device.
The composition of the invention is particularly useful in inactivating micro-
organisms
having cell walls comprising relatively high levels of peptidoglycan, in
particular gram
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
positive bacteria, which can be present in soils or stains on the fabrics or
surfaces, in
particular in body soils.
The amount of composition required to obtain effective reduction of the
activity of the
specific micro-organisms depends on various factors, such as the amount of
micro-
organisms present, the conditions of the sanitisation or cleaning process,
including the
other compounds present and the temperature of the cleaning process.
In the method of the invention, the liquor used preferably comprises at least
100 ppm of
the peroxyacid per 106 micro-organisms, more preferably at least 200 ppm or
even 250
ppm.
The reduction of the activity of the specific micro-organisms, having a
peptidoglycan-
containing cell walls can be determined by the Petrocci and Clarke method, as
described
in JOAC 1981, but is preferably determined for the purpose of this invention
by the CEN
method prEN1276, 1993 for bacteria and CEN method prEN1650 for yeast.
Such a CEN method involves, for example, the preparation of gram positive
bacterial
inocula conform the CEN method, pages 7 and further, preparation of a solution
comprising the hydrophobic bleaching agent at a level of about 250ppm,
conducting the
test following the CEN method, incubation TSA plates for 24 hours at
36°C;
and subsequently counting of the bacteria colonies on the plates.
This is compared with the results of the reference and the reduction of
bacteria growth is
calculated, for the defined contacting time.
Acids
The composition comprises at least 7% by weight of one or more acids,
preferably an
organic acid, preferably including at lest an organic carboxylic acid. The
exact levels will
depend on the other ingredients of the detergent composition and the
alkalinity thereof, so
that the level of the acid is adjusted to provide the required pH.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
6
Preferably the acid is present at a level of at least 8% by weight of the
composition or
even at least 9% -or even at least 10% by weight of the composition, with as
upper limit a
level of preferably 30% or even 20% by weight of the composition.
Suitable acids to be used herein include materials or which not only help to
provide the
required pH of the formulation, but which also have a secondary function in
the
composition, such as acting as a chelating agent, builder and/ or
effervescence source.
Useful inorganic acids include boric acid, bisulphite salts and bisulphite
salts, preferably
sodium salts thereof.
Preferably, the acid comprises at least an organic carboxylic acid. Such acids
include
mono- or polycarboxylic acids preferably citric acid, adipic acid, glutaric
acid, 3
chetoglutaric acid, citramalic acid, tartaric acid, malefic acid, fumaric
acid, malic acid,
succinic acid, malonic acid but also polymeric or oligomeric polycarboxylic
acids, such
as acrylic acid polymers or malefic acid polymers, or copolymers of malefic
acid and
acrylic acid.
Most preferably the organic carboxylic acid herein comprises at least 7% by
weight of the
composition of malefic acid, malic acid or citric acid, or mixtures thereof.
It may be preferred that mixtures of organic carboxylic acids and inorganic
acids are
used, for example in ratio's of from 1:1 to 10:1 or even from 2:1 to 5:1.
The acid may be present as a separate components or in solid compositions of
the
invention, the acid may be incorporated in a granule together with other
detergent
ingredients. In the latter case, it may be preferred the acid is a a
particulate material
whereof at least 75%, preferably at least 85% or even at least 90% or even at
least 95% or
even at least 99% by volume, has a particle size from 1 to 500 microns and
more
preferably from 1 to 350 microns and it may even be preferred that at least
65% or even
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
7
at least 75% or even at least 85% has a particle size from 1.0 to 250 microns
or even from
1.0 to 150 microns.
These particle sizes can be determined by any method known in the art, in
particular by
laser light scattering or defraction technique, such as with Malvern 2600 or
Sympatec
Helos laser light scattering equipment (or defractometer).
When the acid is present as a separate particle in solid composition of the
invention, the
particle size distribution and mean is preferably similar to particle size
distribution and
mean of the other components of the composition, as described hereinafter.
Salts of inorgnic acids and/ or salts or esters of organic carboxylic acids
may also be
present as additional components, in particular because it may be beneficial
to thus buffer
the composition at the required pH. For example, it may be preferred that the
composition comprises a salt of citric acid, malefic acid, malic acid,
glutaric acid or
tartaric acid or barate salt, or mixtures thereof.
Carbonate source
The compositions of the present invention comprises at least 15% by weight of
a
carbonate source. Preferred carbonate sources include carbonate, bicarbonate
and
percarbonate salts and preferably the carbonate source comprises a mixture of
three salts.
It is to be understood that the percarbonate salt when present, forms part of
both the
carbonate source and the hydrogen peroxide source as defined herein. Thus, in
a
preferred embodiment of the invention, the composition comprises a
percarbonate salt to
provide hydrogen peroxide and carbonate. For example, when the composition
comprises
at least 10% by weight of a percarbonate salt, as hydrogen peroxide source and
carbonate
source, the composition also contains at least 5% by weight of another
carbonate source.
The level of carbonate sources will depend on the nature of the detergent.
Also, if
percarbonate salt is used as hydrogen peroxide source, reduced levels of other
carbonate
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
sources may only be needed. Preferably, the composition comprises a mixture of
carbonate sources, preferably including a carbonate salt, bicarbonate salt and
percarbonate salt. Then, the composition comprises preferably at least 5% by
weight of a
carbonate salt, at least 2% by weight of a bicarbonate slat and at least 8% by
weight of a
percarbonate salt, more preferably at least 7% by weight of a carbonate salt ,
at least 4%
by weight of a bicarbonate salt and at least 15% by weight of a percarbonate
salt.
Suitable carbonates sources to be used herein include carbonate and hydrogen
carbonate
or bicarbonate of earthalkali or alkali metals and sodium and potassium salts.
The
inventors found that it may be particularly useful to include a bicarbonate
salt into the
compositions, because it has been found that the bicarbonate salt provides a
buffered pH
at around the pH value needed to form the peroxyacids from the precursors, for
example
of TAED as described hereinafter.
In a preferred embodiment of the invention, the composition comprises at least
1%,
preferably a at least 2% or even at least 4% by weight of the composition of
an alkali or
earth alkali salt of bicarbonate, preferably sodium bicarbonate. This salt may
be present
up to any level, preferably up to 20% by weight of the composition, more
preferably up to
15% or even up to 10% by weight of the composition.
The carbonate, bicarbonate and percarbonate salts herein my be present as
separate
particulate components or may be incorporated in detergent granules together
with other
detergent ingredients.
The carbonate and bicarbonate material, when present in other detergent
granules, may
preferably have a volume median particle size from 1 to 500 microns, whereby
preferably
at least 60%, preferably at least 70% or even at least 80% or even at least
90% by
volume, has a particle size of from 0.5 to 1180 microns. More preferably, the
carbonate or
bicarbonate salts has a volume median particle size of 10 to 375, whereby
preferably at
least 60 %, or even at least 70% or even at least 80% or even at least 90% by
volume,
has a particle size of from 1 to 850 microns; or even preferably a volume
median particle
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
9
size from 10 to 250 microns, whereby preferably at least 60 %, preferably at
least 70% or
even at least 80% or even at least 90% by volume, has a particle size of from
5 to 425
microns.
It may be preferred that the required particle size of the carbonate and/ or
bicarbonate salt
is obtained by grinding a larger particle size material, optionally followed
by selecting the
material with the required particle size by any suitable method.
Preferably, the carbonate source is incorporated in the composition in such a
manner that
it is capable to react with the acid to provide effervescing upon contact with
water.
Hydrogen peroxide source
The compositions of the invention comprise a hydrogen peroxide source.
Preferably, this
is a persalt such a salts of percarbonate, perborate, perphosphate,
peroxymonopersulfate
and persilicate salts. The inorganic perhydrate salts are normally the alkali
metal salts.
The alkali metal salt of percarbonate, perborate, or mixtures thereof, are the
preferred
inorganic perhydrate salts for use herein. Preferred perborate is sodium
perborate in the
form of the monohydrate or tetrahydrate, respectively of nominal formula
NaB02H202
and NaB02H202.3H20. Other suitable oxygen bleaches include persulphates,
particularly potassium persulphate K2S2Og and sodium persulphate Na2S20g.
Highly preferred is an alkali metal salt of percarbonate, preferably sodium
percarbonate,
which then forms also part of the carbonate source, described above.
Typically, the compositions in the present invention comprise from 5% to 50%
by weight
of the total composition of a hydrogen peroxide source, preferably from 10% to
45% and
more preferably from 15% to 35% by weight or even form 17% or even 19% to 30%
or
even to 25% by weight of the composition.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
The persalts may be coated by any coating material, preferably comprising a
sulphate salt,
such as magnesium sulphate or preferably sodium sulphate, carbonate or
bicarbonate salt
or mixtures thereof.
5 Preferred persalts and methods for making it are described in for example
W097/35951, W096/14388, W097/19890, W094/02568, EP891417-A, EP681557A.
Bleach~recursors
The granular compositions herein comprise a peroxyacid bleach precursor.
Preferably, the
10 peroxyacid bleach precursor is present at a level of from 3% to 10% or even
3.5% to 8%
or even 4% to 6% by weight of the composition.
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is
O
X-C-OOH
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
11
1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871,
2143231 and
EP-A-01703 86.
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 R3Y
-O , -O ~ Y , and -O
O O
II - ~ II -R4
-N-C R -N N -N-C-CH
Rs ~ ~ , R3 Y ,
I
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O Y O
O CHZ-C 4 -N~ ~NR4
-~C-R1 -Nw /NR wC/
O , O
R3 O Y
-N-S-C H-R4
-O-C=CHR4 , and
R3 O
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
12
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 canon which provides solubility to
the bleach
activator and X is an anion which provides solubility to the bleach activator.
Preferably,
M is an alkali metal, ammonium or substituted ammonium cation, with sodium and
potassium being most preferred, and X is a halide, hydroxide, methylsulfate or
acetate
anion.
Preferred examples of such compounds are tetracetyl ethylene diamine, (TAED),
sodium
3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, nonylamide of peroxyadipic
acid and
n-nonanoyloxybenzenesulphonate (NOBS), -decanoyloyloxybenzenesulphonate,
dodecanoyloxybenzenesulphonate and acetyl triethyl citrate (ATC),
Phenolsulphonate
Ester of N-nonanoyl-6-aminocaproic acid, aliphatic diacyl peroxide (DAP)
having the
general formula R-C(O)-O-O-(O)C-Rl, wherein R and R1 can be the same or
different
and are linear or branched aliphatic groups having from 6 to 20 carbon atoms.
Also particularly preferred are N-acyl caprolactam selected from the group
consisting of
substituted or unsubstituted benzoyl caprolactam, octanyl caprolactam,
nonanoyl
caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam,
formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl
caprolactam
pentanoyl caprolactam.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
13
Examples of other unable compounds are disclosed in British Patent GB 1 586
769 , GB
2 143 231, US 4 818 425 and US 4 259 201.
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ C-N--R2C-L R~ NCR2CL
i
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing
1 to 10
carbon atoms and L can be essentially any leaving group, preferably a
oxybenzene
sulfonate. Amide substituted bleach activator compounds of this type are
described in EP-
A-0170386. Nonanamido caproyl oxybenzene sulfonate, preferably in the form of
the
sodium salt, NACA-OBS, is a preferred precursor of this type.
A highly preferred bleach precursor herein is TAED, NACA-OBS, DOBS and/ or
NOBS. The compositions herein may comprise mixtures of said bleach activators,
because it has been found that this may result in improved sanitisation.
Highly preferred
is a mixture of TAED and a precursor selected from NOBS, DOBS or NACA-OBS. It
has
been found that further improved sanitisation is achieved when such mixed
precursor
systems are used, in particular when the ratio of TAED to NOBS, DOBS or NACA-
OBS
is from 1:2 to 2:1.
The precursor may be in the form of a separate detergent granule, which may be
coated,
or in the form of a detergent granule comprising also other detergent actives.
It
preferably is present in the form of a particulate component having a similar
particle size
distribution and mean particle size as the other detergent particles.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
14
The inventors also found that it can be beneficial when the precursor and
hydrogen
peroxide source are present intimately mixed with one another, for example in
a granule.
This mixture or granule is preferably being substantially free of organic
acids.
It should be understood that for the purpose of the invention, the peroxy acid
formed of
the precursor is not part of the acid component of the composition of the
invention.
Laundr~and Dish Washing Method
Machine laundry methods herein typically comprise treating soiled laundry or
dishes with
an aqueous wash solution in a washing machine having dissolved or dispensed
therein an
effective amount of a detergent in accord with the invention. In particular
laundry
washing methods are envisaged herein. For example, an effective amount of the
laundry
detergent composition for laundry washing is normally meant from lOg 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. Dosage is dependent upon the particular conditions
such as
water hardness and degree of soiling of the soiled laundry.
The reduction of the activity of the micro-organisms present in the wash and
on the soiled
fabrics preferably takes place during a washing method, preferably a automatic
or hand
laundry, at low temperatures up to 60°C or even up to 45°C or
even around 30°C.
The detergent composition may be dispensed for example, from the drawer
dispenser of a
washing machine or may be sprinkled over the soiled laundry placed in the
machine.
In one highly preferred use aspect a dispensing device is employed in the
washing
method, to introduced the composition of the invention directly in the drum of
the wash.
It has been found that improved sanitisation is then achieved.
Any dispensing device can be sued, including preferred dispensing devices for
use with
the composition of the invention have been described in the following patents;
GB-B-2,
WO 01/16279 cA o23a2~22 2002-02-22 pCT/US00/23964
157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346,
W094/ 115 62.
Detergent compositions
5 The compositions of the present invention can be prepared with different
bulk densities,
preferably being from 300 to 1200 g/1, preferably from 500 to 1100 g/1 or even
SSOg/1 to
900g/1. These compositions are preferably solid compositions, preferably solid
laundry
detergents, which can be made by a variety of methods well known in the art,
including
dry-mixing, spray drying, extrusion, roller compaction, agglomeration and
combinations
10 thereof. The solid compositions may have any form, preferably granular or
in the form of
a tablet or bar.
It may be preferred that the composition is made by mixing all or part of the
granules,
including those made by agglomeration or spray-drying, and subsequently adding
a
15 binder and mixing or agglomerating the granules and binder to form the,
preferably
agglomerated detergent granules. These may be of the required particle size or
they may
be sieved to obtain particles of the required size.
In a highly preferred embodiment, the acid, or part thereof, and the carbonate
source or
part thereof, are present in an intimate mixture with one another, preferably
in a granule,
which means for the purpose of the invention that the acid and carbonate
source are
preferably homogeneously mixed. For optimum effervescence in aqueous medium
the
weight ratio of acid to carbonate source in the intimate mixture or the
effervescent
granule is preferably from 0.1 to 10, preferably from 0.5 to 2.5 and more
preferably from
1 to 2.
The acid is preferably present in such a granule at a level of from 5% to 85%
by weight
of the total granule, preferably from 10% to 75%, more preferably from 15% to
60% and
most preferably from 10% to 50%.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
16
The carbonate source is preferably present in such a granule at a level of
from 5% to 90%
by weight of the total, preferably from 10% to 80%, more preferably from 20%
to 75%
and most preferably from 30% to 65%.
The granule is preferably substantially free of water, i.e. no water has been
added or
present other than the moisture of the raw materials themselves. Typically,
the level of
water is below 5% by weight of the total intimate mixture or granule,
preferably below
3% and more preferably below 1.5%.
It may be preferred that a desiccant is present in the intimate mixture or the
granule, such
as overdried inorganic and organic salts, anhydrous salts, in particular
overdried silicates
and aluminosilicates, anhydrous silicates and/ or sulphate salts.
The granules are preferably obtainable by a process comprising a granulation
step,
preferably comprising the step of dry-powder compaction or pressure
agglomeration.
While all binding mechanisms can occur in pressure agglomeration, adhesion
forces
between the solid particles, i.e., between the acid, carbonate source and
optionally the
binder if present, play an especially important role. This is because pressure
agglomeration, especially high pressure agglomeration, is an essentially dry
process that
forms new entities (i.e., dry effervescent granules) from solid particles
(i.e., the acid,
bicarbonate, carbonate source and optionally the binder) by applying external
forces to
densify a more or less defined bulk mass or volume and create binding
mechanisms
between the solid particles providing strength to the new entity, i.e. the
high external
force applied brings the solid particles closely together.
The effervescent granules may optionally comprise a binder or a mixture
thereof.
Typically, the granules comprise up to 50 % by weight of the total granule of
a binder or
a mixture thereof, preferably up to 35% and more preferably up to 20%.
Suitable binders
to use herein are those known to those skilled in the art and 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
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
17
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 C10-C20 fatty acids.
The effervescent granules may have any particle size, the preferred particle
size
depending on the application and the component of the granule.
The inventors have found that it can be beneficial for the sanitisation and
cleaning
performance that the acid herein is separated from the precursor and
preferably any other
bleach components present including any hydrogen peroxide source, including
percarbonate salt, if present. Thus, the effervescing granules described
above, preferably
comprise no percarbonate salt as carbonate source, but preferably comprise
carbonate
salts and/ or bicarbonate salts.
In a preferred embodiment, the composition preferably comprises granules
whereof at
least 60%, more preferably at least 80% by weight have an average particle
size, by
weight, of from 400 microns to 1400 microns, preferably from 500 microns to
1100
microns or even 750 to 1000 microns. It may be preferred that the compositions
comprises less than 20% or even less than 10% or even less than 5% by weight
of
particulate components of a particle size of less than 300 microns, or even
less than 425
microns or even less than 600 microns; it may also be preferred the
composition comprise
less than 20% or even less thanl0% or even less than 5% by weight of the
composition,
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
18
of particulate components of a particle size of more than 1700 microns, or
even more than
1400 microns or even more than 1180 microns.
Thus, the compositions may comprise different granular components, which each
have
the above particle size requirements, and thus have a similar particle size
distribution and
mean particle size.
The inventors found that improved sanitisation is achieved when the
composition
contains perfumes or perfume components with a high fabric substantivity. It
is believed
that this is due to the perfume oils which remain on the surface of the washed
fabric and
which can thus provide sanitisation during the subsequent use of the fabric.
Such preferred perfume granules of encapsulated perfume oils are described in
co-
pending European patent application 98870137.1. Preferred levels of perfume
granules
will depend on the level of perfume oils therein, but generally the level is
from about 0.05
to 8% or even 0.5% to 5% or even 0.8% to 3% by weight of the composition.
Moreover,
preferably the composition also comprises perfume components which are not in
the form
of encapsulated perfume oil granules, but preferably in the form of perfume
components
sprayed onto the detergent granules of the composition.
The compositions herein preferably contain one or more additional detergent
components
selected from surfactants, bleach catalysts, additional builders, additional
organic
polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil
suspension
and anti-redeposition agents soil releasing agents, brightners, photobleaching
agents and
additional corrosion inhibitors.
30
It is to be understood that the levels of detergent ingredients are to be
chosen such that the
pH of 1 % by weight of composition in demineralised water is as defined above.
For
example, it may be preferred that when crystalline layered silicates or
amorphous silicates
are used, the level thereof is up to about 12% by weight or even up to 10% by
weight.
Surfactant
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
19
The detergent compositions herein preferably contain one or more surfactants.
The
surfactant may comprise any surfactant known in the art selected from anionic,
nonionic,
cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures
thereof.
It should be understood that for the purpose of the invention the detergent
composition
may comprise surfactant which is not present in the intimate mixture with the
crystalline
layered silicate, but present in the other detergent components.
Anionic Surfactant
The compositions in accord with the present invention preferably comprise an
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.
Highly preferred are surfactants systems comprising a sulfonate and a sulfate
surfactant,
preferably a linear or branched alkyl benzene sulfonate and alkyl
ethoxylsulfates, as
described herein, preferably combined with a cationic surfactants as described
herein.
Highly preferred herein are anionic sulfonate surfactants. Particularly
suitable for use
herein include the salts of CS-C2p linear or branched alkylbenzene sulfonates,
but also
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. Most
preferred are
C9-C,4 linear alkyl benzene sulfonates.
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-(Cl-C4 alkyl) and -N-
(Cl-C2
hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as
the
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
5 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
C10-C1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles
of
10 ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a C11-
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.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
15 sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such
mixtures have been
disclosed in PCT Patent Application No. WO 93/18124.
Highly preferred herein, in particular for providing an improved surfactant
performance,
are alkyl chain, mid-chain branched surfactant compounds of the formula
R R1 R2
CH3CH2(CH2)wCH(CH2)xCH(CH2)yCH(CH2)z
wherein the total number of carbon atoms in the branched primary alkyl moiety
of this
formula (including the R, R1, and R2 branching) is from 13 to 19; R, R1, and
R2 are each
independently selected from hydrogen and C1-C3 alkyl (preferably methyl),
provided R,
R1, and R2 are not all hydrogen and, when z is 0, at least R or R1 is not
hydrogen; w is an
integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to
13; z is an
integer from 0 to 13; and w + x + y + z is from 7 to 13.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
21
The most preferred mid-chain branched surfactants compounds for use in the
detergent
compositions herein are mid-chain branched primary alkyl sulfonate and, even
more
preferably, sulfate surfactants. It should be understood that for the purpose
of the
invention, it may be preferred that the surfactant system comprises a mixture
of two or
more mid-chain branched primary alkyl sulfate or sulphonate surfactants.
Preferred mid-chain branched primary alkyl_sulfate surfactants are of the
formula
R R1 R2
CH3CH2(CH2)~,~CH(CH2)xCH(CH2)yCH(CH2)z0 S03M
These surfactants have a linear primary alkyl sulfate chain backbone (i.e.,
the longest
linear carbon chain which includes the sulfated carbon atom) which preferably
comprises
from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise
preferably a total of at least 14 and preferably no more than 20, carbon
atoms. In the
surfactant system comprising more than one of these sulfate surfactants, the
average total
number of carbon atoms for the branched primary alkyl moieties is preferably
within the
range of from greater than 14.5 to about 17.5. Thus, the surfactant system
preferably
comprises at least one branched primary alkyl sulfate surfactant compound
having a
longest linear carbon chain of not less than 12 carbon atoms or not more than
19 carbon
atoms, and the total number of carbon atoms including branching must be at
least 14, and
further the average total number of carbon atoms for the branched primary
alkyl moiety is
within the range of greater than 14.5 to about 17.5.
R, R1, and R2 are each independently selected from hydrogen and C1-C3 alkyl
group
(preferably hydrogen or C 1-C2 alkyl, more preferably hydrogen or methyl, and
most
preferably methyl), provided R, R1, and R2 are not all hydrogen. Further, when
z is 1, at
least R or R1 is not hydrogen.
Preferred mono-methyl branched primary alkyl sulfates are selected from the
group
consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-
methyl
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
22
pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol
sulfate, 8-
methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl
pentadecanol
sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-
methyl
pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol
sulfate, 5-
methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol
sulfate,
8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl
hexadecanol
sulfate, 11-methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-
methyl
hexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof.
Preferred di-methyl branched primary alkyl sulfates are selected from the
group
consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol
sulfate, 2,5-
methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl
tetradecanol
sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate,
2,10-methyl
tetradecanol sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyl
tetradecanol sulfate,
2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl
pentadecanol sulfate, 2,6-methyl pentadecanol sulfate, 2,7-methyl pentadecanol
sulfate,
2,8-methyl pentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methyl
pentadecanol sulfate, 2,11-methyl pentadecanol sulfate, 2,12-methyl
pentadecanol sulfate,
2,13-methyl pentadecanol sulfate, and mixtures thereof.
AlkoxYlated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are 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.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
23
Nonionic surfactant can be present in the detergent compositions. It may be
preferred that
the level of ethoxylated nonionic surfactants in the intimate mixture are
below 10% by
weight of the mixture, preferably even 5% by weight.
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are suitable for
use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or
secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred are
the condensation products of alcohols having an alkyl group containing from 8
to 20
carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Cationic Surfactants
Suitable cationic surfactants to be used herein include the quaternary
ammonium
surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C 16,
preferably Cg-CI4 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.
Another suitable group of cationic surfactants which can be used in the
detergent compositions or components thereof herein are cationic ester
surfactants.
The cationic ester surfactant is a, preferably water dispersible, compound
having
surfactant properties comprising at least one ester (i.e. -COO-) linkage and
at least one
cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have
for example
been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
24
Bleach Catalyst
The composition herein can contain a transition metal containing bleach
catalyst.
One suitable type of bleach catalyst is disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in U.S.
Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include
MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4-(CI04)2, MnIIIMnIV4(u_O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)3, and mixtures thereof. Others are described in
European
patent application publication no. 549,272. Other ligands suitable for use
herein include
1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-
methyl-
1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and
mixtures
thereof.
The bleach catalysts useful herein may also be selected as appropriate for the
present
invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612
and U.S. Pat.
5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese
(IV)
complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3_(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a water-
soluble complex of manganese (III), and/or (IV) with a ligand which is a non-
carboxylate
polyhydroxy compound having at least three consecutive C-OH groups. Preferred
ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, meso-
erythritol, meso-inositol, lactose, and mixtures thereof.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition metals,
including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands
are of the
formula:
R2 R3
5 R1 _N-C_B_C-N_R4
wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring.
Said ring can further be substituted. B is a bridging group selected from O,
S. CRSR6,
10 NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups,
including
substituted or unsubstituted groups. Preferred ligands include pyridine,
pyridazine,
pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally,
said rings may
be substituted with substituents such as alkyl, aryl, alkoxy, halide, and
nitro. Particularly
preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts
include Co, Cu,
15 Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred
catalysts
include Co(2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt
(II),
trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)202C104, Bis-
(2,2'-
bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II)
perchlorate, and
mixtures thereof.
Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-
dentate
ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2]-
(C104)3.
Other bleach catalysts are described, for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
26
application, publication no. 224,952, (absorbed manganese on aluminosilicate
catalyst),
U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium
salt),
U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex
catalyst),
German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191
(transition metal-containing salts), U.S. 4,430,243 (chelants with manganese
canons and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
Builder material
In addition to the organic carboxylic acids, which may act as builders, and
the carbonate
salts, which may act as builders, the detergent compositions of the invention
preferably
comprise additional water-soluble and/ or water insoluble builder material.
Preferred are
silicates, aluminosilicates, crystalline layered silicates and phosphate
salts.
The compositions may for example comprise phosphate-containing builder
material,
preferably comprises tetrasodium pyrophosphate or even more preferably
anhydrous
sodium tripolyphosphate, present at a level of from 0.5% to 60%, more
preferably from
5% to 50%, more preferably from 8% to 40.
Suitable water-soluble builder compounds include the water soluble
(poly)carboxylate
salts and borates. The carboxylate or polycarboxylate builder can be momomeric
or
oligomeric in type although monomeric polycarboxylates are generally preferred
for
reasons of cost and performance.
It may be preferred that the(poly)carboxylates andl or polymeric or oligomeric
(poly)carboxylates are present at levels of less than 5%, preferably less than
3% or even
less than 2% or even 0% by weight of the compositions.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
27
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. xH20
wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5
and x is at least
5, preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate
material are in hydrated form and are preferably crystalline, containing from
10% to 28%,
more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS
and mixtures thereof. Zeolite A has the formula:
Na 12 [A102) 12 (Si02)12]. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106]~ 276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder. 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.
The compositions herein may also comprise additional silicate material,
including
amorphous silicate material, meta-silicates, preferably at least crystalline
layered
silicate material such as sold under the trade name SKS-6. The silicate
material is
preferably present at a level of less than 20% by weight of the compositions,
preferably less than 15% by weight or even less than 10% by weight.
Heavy metal ion sequestrant
Heavy metal ion sequestrant are also useful additional ingredients herein. By
heavy
metal ion sequestrant it is meant herein components which act to sequester
(chelate)
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
28
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.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 10%,
preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most
preferably
from 0.3% to 2% by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine tetra
(methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane
diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenediamine
disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine
disuccinic
acid or any salts thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid, described
in EP-A-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.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
29
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.
Enzyme
Another preferred ingredient useful herein is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, cellulases, endolases,
esterases,
pectinases, lactases and peroxidases conventionally incorporated into
detergent
compositions. Suitable enzymes are discussed in US Patents 3,519,570 and
3,533,139.
Preferred commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by
Gist-
Brocades, those sold by Genencor International, and those sold under the
tradename
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated
into
the compositions in accordance with the invention at a level of from 0.0001%
to 4%
active enzyme by weight of the composition.
Additional Organic Polymeric Compound
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
Additional organic polymeric compounds, not being the carboxylic acids herein,
are
preferred additional components of the compositions herein or the agglomerates
herein,
where they may act such as to bind the agglomerate components together.
5 By organic polymeric compound it is meant herein essentially any polymeric
organic
compound commonly used as binder, dispersants, and anti-redeposition and soil
suspension agents in detergent compositions, including any of the high
molecular weight
organic polymeric compounds described as clay flocculating agents herein,
including
quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition
agent in accord
10 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.
Organic polymeric compounds suitable for incorporation in the detergent
compositions
herein include cellulose derivatives such as methylcellulose, sodium
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
Highly preferred is also - or amide-modified carboxymethyl cellulose and - or
amide-
modified celluloses, or derivatives thereof
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.
Suds Suppressin System
The detergent compositions of the invention, when formulated for use in
machine
washing compositions, may comprise a suds suppressing system present at a
level of from
0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3%
by
weight of the composition.
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
31
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.
Clay softening agents
The composition herein may be a detergent which provides softening through the
wash.
Preferred may be that the composition comprises a clay softening agent, and
preferably
also a flocculating agent.
Specific examples of suitable smectite clays include those selected from the
classes of the
montmorillonites, hectorites, volchonskoites, nontronites, saponites and
sauconites,
particularly those having an alkali or alkaline earth metal ion within the
crystal lattice
structure. Sodium or calcium montmorillonite are particularly preferred.
Preferred are
bentonite clays.
Preferred as clay flocculating agents herein are organic polymeric materials
having an
average weight of from 100,000 to 10,000,000, preferably from 150,000 to
5,000,000,
more preferably from 200,000 to 2,000,000.
Suitable organic polymeric materials comprise homopolymers or copolymers
containing
monomeric units selected from alkylene oxide, particularly ethylene oxide,
acrylamide,
acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine.
Homopolymers of, on
particular, ethylene oxide, but also acrylamide and acrylic acid are
preferred.
European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter
and
Gamble Company describe preferred organic polymeric clay flocculating agents
for use
herein.
Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of the
invention
include perfumes, such as the encapsultyed perfumes described above,
brightners,
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
32
speckles, including colours or dyes, filler salts, with sodium sulfate being a
preferred
filler salt.
Also, minor amounts (e.g., less than about 20% by weight) of neutralizing
agents,
additional 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.
Abbreviations used in the examples
LAS : Sodium linear C11-13 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
CxyAS : Sodium C 1 x - C 1 y alkyl sulfate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS : Sodium C 1 x-C 1 y alkyl sulfate condensed with z moles of ethylene
oxide
CxyEz : 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 : R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of
tallow and coconut fatty acids
STS : Sodium toluene sulphonate
STPP : Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(AlO2Si02)12.27H20 having a primary particle
size in the
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
33
range from 0.1 to 10 micrometers (weight expressed on an
anhydrous basis)
NaSKS-6 : Crystalline layered silicate of formula d- Na2Si2O5
average particle size of 25 microns
Carbonate : Anydrous sodium carbonate
Bicarbonate : Anhydrous sodium bicarbonate
Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1)
Sulfate : Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
Citrate : Tri-sodium citrate dihydrate
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight
about 70,000
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 or
proteolytic enzyme, having 4% by weight of active enzyme, as
described in WO 95/10591, sold by Genencor Int. Inc.
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 or
lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Lipolase Ultra
PB4 : Particle containing sodium perborate tetrahydrate of nominal
formula NaB02.3H2 O, the particles having a weight average
particle size of 950 microns, 85% particles having a particle size of
from 850 microns to 950 microns
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
34
PB 1 : Particle containing anhydrous sodium perborate bleach of nominal
formula NaB02.H 202, the particles having a weight average
particle size of 800 microns, 85% particles having a particle size of
from 750 microns to 950 microns
Percarbonate : Particle containing sodium percarbonate of nominal formula
2Na2C03.3H2O2, the particles having a weight average particle
size of 550 to 850 microns, 5% or less having a particle size of less
than 300 microns and 7% or less having a particle size of more
than 1180 microns
NOBS : Particle comprising nonanoyloxybenzene sulfonate in the form of
the sodium salt, the particles having a weight average particle size
of 550 microns to 900 microns
NAC-OBS : Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate,
the particles having a weight average particle size of from S50
microns to 900 microns
TAED I : Particle containing tetraacetylethylenediamine, the particles having
a weight average particle size of from 550 microns to 900 microns
DTPA : Diethylene triamine pentaacetic acid
DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename bequest 2060
Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach ( 1 )
dextrin
soluble polymer
Photoactivated : Sulfonated alumino phthlocyanine encapsulated in bleach (2)
dextrin soluble polymer
Brightener : Disodium 4,4'-bis(2-sulphostyryl)biphenyl or Disodium 4,4'-bis(4-
anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-
disulfonate
EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of
its sodium salt.
HEDP : l , l -hydroxyethane diphosphonic acid
PEGx : Polyethylene glycol, with a molecular weight of x (typically 4,000)
CA 02382722 2002-02-22
WO 01/16279 PCT/US00/23964
PEO : Polyethylene oxide, with an average molecular
weight of 50,000
TEPAE : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidosole, with an average molecular
weight of 20,000
pVp : Polyvinylpyrolidone polymer, with an average molecular
weight of
5 60,000
PVNO : Polyvinylpyridine N-oxide polymer, with an average
molecular
weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an
average molecular weight of 20,000
10 QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-(C2H4 O))n, wherein n = from 20 to 30
SRp : Anionically end capped poly esters
Silicone antifoam : Polydimethylsiloxane foam controller with siloxane
15 or suds suppresser oxyalkylene copolymer as dispersing agent with a ratio
of said
foam controller to said dispersing agent of 10:1 to 100:1
WO 01/16279 cA o23a2~22 2002-02-22 pCT/US00/23964
36
In the following examples all levels are quoted as % by weight of the
composition:
TABLE I
The following compositions are in accordance with the invention and have pH in
the wash, as measured by the method defined herein, of around 9.4 -9.85:
C E F G
S ra -dried
Granules
AS 8.0 10.0 15.0 5.0 5.0 10.0
AS 1.0 0.5 0.5
BAS .0 5.0
C45AS 1.0 5.0 .0
C45AE3S 1.0 1.0
QAS 1.0 1.0 1.0 1.0
TPA, HEDP .3 .3 0.5 .3 0.4
andlor EDDS
gS04 0.5 .5 .l .1 .1
Sodium .0 7.0 5.0 .0 3.0
carbonate
Sodium 5.0 3.0
sulphate
Sodium 0.3 .0
silicate
1.6R
STPP 16.0
eolite A 16. 18.0 0.0 0. 10.
0 0
SKS-6 8.0 5.0
A/AA or 1.0 .0 ~0
EG 4000 .0 1.0
W~ X1/16279 CA 02382722 2002-02-22
PCT/US00/23964
37
QEA 1.0 1.0 1.0
rightener 0.0 0.05 0.05 .0
5 5
Silicone 0.0 0.01 0.01 0.01
oil 1
lomerate
AS 0.5 .5 .8
AS 3.0 6.0 .0 8.0
BAS .0 1.0 14.0 8.0
C45AS .0 .0
C45AE3 1.0 1.0 0.5 1.0
Carbonate 1.0 6.0 7.0 S.0 .0
Sodium citrate.0 5.0
Citric acid .0 9.0
QEA .0 1.0 1.0
SRP 1.0 .2
eolite A .0 0. 15. 18. 15.0 5.0
0
Sodium 0.5 0.5
silicate
EG
A/AA or .0 .0 1.0 1.0 .8
uilder
lomerates
SKS-6 3.0 7.0
6.0
AS .0 3.0 6.0
WO 01/16279 CA 02382722 2002-02-22 pCT/US00/23964
38
-add
articulate
com onents
ffervescence10. 15.0 15.0 12.0 .0 15. 12.0
granule of 0 0
carbonate/
icarbonate/cit
is acid 1:1:1
Sodium .0 2.0 .0 .0 7.0 8.0 3.0 .0 5.0
icarbonate
Sodium 3.0 .0 .0 5.0
carbonate
OBS 3.0 3.0 .5 5.0
AED .5 .0 6.0 .0 5.0 .5 S.0
ACA-OB S .5 .5
Citric acid 5.0 5.0 3.0 8.0 10. 7.0 7.0 10.0
aleic acid 10. 10.0
0
Citrate .0 .0
ercarbonate 1 6.0 6.0 0. 14. 0. 10.0 16.0
S.
0 0 18.
B 1 and/ 6.0 10. 18.0
or
B4 0
hotobleach 0.0 0.02 0.02 0.1 0.0 0.3 0.0
5 3
W~ O1/1C)279 CA 02382722 2002-02-22
PCT/US00/23964
39
nzymes 1.3 0.5 0.2 0.8 2.0 0.8 1.0 0.2 0.7
(amylase,
rotease,
lipase)
erfume 0.5 0.5 0.3 0.8 0.2 0.5 1.0 .0
(encapsulated)
Suds 1.0 0.6 0.3 0.1 .5 1.0 0.3 1.2 .5 0.9
suppressor 0
Soap 0.5 0.2 0.3 3.0 0.5 0.3
SKS-6 .0 6.0
entonite 8.0 10.
clay
0
yed 0.5 0.5 1.0 .0 0.5 0.5 .5 1.0 1.0
carbonate
(blue, green)
S ra -on
rightener 0.2 .2 0.3 .1 .2 0.1 .6 .3
ye 0.3 .0 0.1
5
C25AE5 0.5 0.7
erfume 1.0 0.5 1.1 0.8 0.5 0.3 0.5 0.8 .5 1.0
0.3
otal balanced
0 100%
