Note: Descriptions are shown in the official language in which they were submitted.
CA 02261609 1999-O1-27
WO 98/04662 PCTlUS97/12894
A DETERGENT COMPOST1TON COMPRISING AN ACID SOURCE WITH A SPECIFIC PARTICLE
SIZE
Technical Field
The present invention relates to a detergent composition which is suitable for
use in
laundry and dish washing methods. The present invention also relates to a
process for
preparing these detergent powders.
Background to the Invention
There is a trend amongst commercially available granular detergents towards
higher bulk
densities and towards granular detergent compositions which have a higher
content of
detergent active ingredients. Such detergents offer greater convenience to the
consumer
and at the same time reduce the amount of packaging materials which will,
ultimately, be
disposed of.
Many of the prior art attempts to move in this direction have met with
problems of poor
solubility properties arising from low rate of dissolution or the formation of
gels. A
consequence of this in a typical washing process can be poor dispensing of the
product,
either from the dispensing drawer of a washing machine, or from a dosing
device placed
with the laundry inside the machine. This poor dispensing is often caused by
gelling of
particles, which have high levels of surfactant, upon contact with water: The
gel prevents
a proportion of the detergent powder from being solubilized in the wash water
which
reduces the effectiveness of the powder. This is a particular problem at low
water
pressures and/or at lower washing temperatures.
Further, there has been another recent trend towards reducing or eliminating
the use of
phosphate builders, which have generally been replaced with zeolite
(crystalline
aluminosilicate). Detergents containing zeolite builders have been found to be
poorer
dispensers than detergents containing phosphate builders.
EP-A-0 578 871 describes a process which seeks to make a high bulk density
detergent
composition which dissolves rapidly and dispenses effectively. The process
involves
formulating a base powder with a particle size distribution between 150
microns and
1700 microns in combination with additional filler ingredients whereby at
least 20% by
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WO 98104662 PCT/US97/12894
2
weight of the filler particles is less than 150 microns. The filler particles
include salts of
citrate, sulphate, (bi-)carbonate and silicates.
W095/14767 relates to the poor dispensing of high density, non-spray-dried
detergent
powders, and discloses the use of a citric acid salt which has a Rosin Rammler
particle
size of less than 800 microns.
W094/28098 discloses a non-spray-dried detergent powder comprising a
combination of
an ethoxylated primary C8-18 alcohol, an alkali metal aluminosilicate builder
and 5 to 40
wt% of a water-soluble salt of a citric acid.
EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali
metal
percarbonate to improve the dispensing profile and dissolution rate of a
detergent. Citrate
or mixtures of citrate with sulphate or carbonate can be used to coat the
percarbonate
bleach.
EP-A-0 639 639 contains a similar disclosure in this respect.
Other ways to improve dispensing include the use of an effervescence system.
If the
detergent contains an effervescence system then the generation of a gas such
as carbon
dioxide pushes the particles of the detergent apart, and prevents them from
gelling.
The use of effervescence to improve the dispersibility of granular materials
has been
used extensively in pharmaceutical preparations. The most widely used
effervescent
system in this respect is citric acid in combination with bicarbonate. The use
of this
simple effervescent system has also been described for improving the
dispersibility of
pesticidal compositions for controlling water-borne pests, e.g. GB-A-
2,184,946.
US-A-4,414,130 discloses the use of a readily disintegratable builder particle
with a
zeolite-based detergent. It also discloses the use of an effervescence
material to improve
the dissolving and dissolution of the particles. Sodium carbonate or sodium
bicarbonate
may be combined with the zeolite binder mix and the balance of the detergent
may
include citric acid, monosodium phosphate, boric acid or other suitable
acidifying
material, preferably fated or agglomerated with bicarbonate, for reaction with
it to
generate carbon dioxide.
CA 02261609 2001-12-27
W092118596 discloses that improved solubilityldispersion for granular
detergents can be
achieved by admixing sodium carbonate and citric acid in a specified weight
ratio of
from 2:1 to 15:1.
EP-A-0 534 525 discloses the use of citric acid with a specified particle size
range of 350
to 1500 microns.
US -A-5, l 14,647 discloses a sanitising composition comprising granules of
alkali metal
carbonate and aliphatic carboxylic acid of a particle sixe of 150 to 2,000
microns.
EP-A-0 333 223 discloses a bathing preparation comprising fumaric acid having
an
average particle size of 50-500 microns.
We have now found surprisingly that improved dispensing benefits can be
achieved from
using citric acid which has a very specific particle size distribution and
which is very
different from that taught in the prior art. We have also found that
surprisingly good
storage stability is achieved with citric acid of with this same very specific
particle size
distribution; again this is very different from the teaching of the prior art.
The addition of citric acid results in a reduction in alkalinity. Such an
alkaline pH
promotes cleaning, stain removal and soil suspension, there is need to
minimize the level
of citric acid used. Also citric acid is a relatively expensive ingredient
which further
reinforces the need to
keep the level of citric acid very low. We have also surprisingly found that
the present
invention allows low levels of the acid to be satisfactorily used in the
detergent
composition.
CA 02261609 2001-12-27
3a
Summary of the Invention
According to the present invention there is provided a granular detergent
composition
having a bulk density of at least 600 g/1 comprising a branched-chain
alkoxylated
nonionic detergent surfactant, from about 1 % to about 3% by weight of
particulate citric
S acid and an alkaline source, wherein said citric acid and alkaline source
are capable of
reacting together to produce a gas, and wherein about 80% or more of the
citric acid has
a particle size in the range of from about 150 microns to about 710 microns,
with at least
37% by weight of the citric acid having a particle size of about 350 microns
or less.
CA 02261609 2001-12-27
4
We have found that the addition of the acid source in accordance with the
particle size
distribution of the present invention and an alkaline source to a detergent
composition
improves the solubility and/or dispersion of the detergent in the laundering
solution and
eliminates or reduces the problems of solid detergent particles remaining in
the washing
machine and on washed clothes. It is believed that the acid reacts rapidly
with the alkali
in the laundering solution to release the gas. This helps disperse the
detergent and
minimize the formation of insoluble clumps.
Detailed Description of the Invention
The present invention includes a granular detergent composition. Such
compositions
1 S comprise a base composition containing one or more surfactant, and
preferably a builder
material. The base composition may be prepared by spray-drying and dry-'
mixing/agglomeration. The base composition may also comprise the alkaline
source.
Alternatively the particulate acid source and/or alkaline source may be added
as separate
components to the detergent base composition, preferably in a granular form.
The detergent composition of the present invention comprises three essential
ingredients:
detergent surfactant, an acid source and an alkali source. These and optional
ingredients,
and processes for making the detergents, are described in detail below.
A. Detergent Surfactant
This ingredient is preferably present in an amount of from 1 % to 90%,
preferably 3% to
70%, more preferably 5% to 40%, even more preferably 10% to 30%, most
preferably
12% to 25% by weight of the detergent composition. Preferably the detergent is
selected
from avionics, nonionics, zwitterionics, ampholytics, amphoteric, cationics
and mixtures
thereof. Preferably the surfactant is anionic, nonionic or a mixtwe thereof.
When the
composition contains more than one surfactant the additional surfactant is
preferably
present at a level of from 0. I % to 50%, more preferably from 1 % to 40%,
most
preferably from 5% to 30% by weight of the total surfactant present. Where
present,
ampholytic, amphoteric and zwitterionic surfactants are generally used in
combination
with one or more anionic and/or nonionic surfactants.
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WO 98/04662 PCT/fJS97/12894
Anionic surfactant
The surfactant system may include an anionic surfactant. Essentially any
anionic
5 surfactants useful for detersive purposes are suitable. 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 surfactants are preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 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 surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, the CS-C 1 ~ acyl-N-(C 1-C4 alkyl)
and -N-(C 1-
C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
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.
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WO 98/04662 PCT/US97/12894
6
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed
in PCT
Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
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 polycarboxyiic acids, alkyl
glycerol
sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates,
and any
mixtures thereof.
Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),
especially
certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to C 1 g alkyl group, x ranges from O to 10, and
the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is
0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy
polycarboxylate
surfactants include those having the formula RO-(CHRI-CHR2-O)x-R3 wherein R is
a
C6 to C 1 g alkyl group, x is from 1 to 25, R1 and R2 are selected from the
group
consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid
radical, and mixtures thereof, and R3 is selected from the group consisting of
hydrogen,
substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms,
and
mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a
carboxyl unit connected to a secondary carbon. Preferred secondary soap
surfactants for
use herein are water-soluble members selected from the group consisting of the
water-
soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-
1-
nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain
soaps may
also be included as suds suppressors.
CA 02261609 2001-12-27
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(R1 ) CH2 COOM, wherein R is a CS-C1 ~ linear or branched alkyl or alkenyl
group, R1
is a CI-C4 alkyl group and M is an alkali metal ion. Preferred examples are
the myristyl
and oleoyl methyl sarcosinates in the form of their sodium salts.
Cationic ester surfactant
The surfactant system may include a cationic ester surfactant. That is, a
preferably water
dispersible compound having surfactant properties comprising at least one
ester (ie -
COO-) linkage and at least one canonically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have
for example
I S been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
Preferred cationic ester surfactants are those having the formula:
R2
RI - (CH)n0 (X)u - ( C H 2 )m (Y)v (C H 2 )t - N -R3 M
b
a
R4
wherein RI is a CS-C31 linear or branched alkyl, alkenyl or alkaryl chain or
M~.N+(R6R~Rg)(CH2)S; X and Y, independently, are selected from the group
consisiting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO
wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2,
R3, R4, R6, R~, and Rg are independently selected from the group consisting of
alkyl,
alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4
carbon
atoms; and RS is independently H or a C1-C3 alkyl group; wherein the values of
m, n, s
and t independently lie in the range of from 0 to 8, the value of b lies in
the range from 0
to 20, and the values of a, a and v independently are either 0 or I with the
proviso that at
least one of a or v must be l; and wherein M is a counter anion.
Preferably R2,R3 and R4 are independently selected from CH3 and -CH2CH20H.
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8
Preferably M is selected from the group consisting of halide, methyl sulfate,
sulfate, and
nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
Preferred water dispersible cationic ester surfactants are the choline esters
having the
formula:
O CH3
R1-C-O-CH2CH2-N~ CH3 M'
CH3
wherein R 1 is a C 11-C 19 linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl
choline ester
quaternary methylammonium halides (R1=C1~ alkyl), palmitoyl choline ester
quaternary
methylammonium halides (R1=C15 alkyl), myristoyi choline ester quaternary
methylammonium halides (R1=C13 alkyl), lauroyl choline ester methylammonium
halides (R1=C11 alkyl), cocoyl choline ester quaternary methylammonium halides
(R1=Cl 1-C13 alkyl), tallowyl choline ester quaternary methylammonium halides
(R1=C 15-C 1 ~ alkyl), and any mixtures thereof.
The particularly preferred choline esters, given above, may be prepared by the
direct
esterification of a fatty acid of the desired chain length with
dimethylaminoethanol, in the
presence of an acid catalyst. The reaction product is then quaternized with a
methyl
halide, preferably in the presence of a solvent such as ethanol, propylene
glycol or
preferably a fatty alcohol ethoxylate such as C 10-C 1 g fatty alcohol
ethoxylate having a
degree of ethoxylation of from 3 to 50 ethoxy groups per mole forming the
desired
cationic material. They may also be prepared by the direct esterification of a
long chain
fatty acid of the desired chain length together with 2-haloethanol, in the
presence of an
acid catalyst material. The reaction product is then quaternized with
trimethylamine,
forming the desired cationic material.
Other suitable cationic ester surfactants have the structural formulas below,
wherein d
may be from 0 to 20.
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O CH3
R -O-~-( CH )-C-O-CH CH -N~ C
1 2 d 2 2 I H3
CH3
CH3 O O CH3
M CH3-N ~ CH2-CH2-O-C-( CH2 ) a C-O-CH2-CH2-N~ CH3M -
CH3 CH3
In a preferred aspect the cationic ester surfactant is hydrolysable under the
conditions of a
laundry wash method.
Alkoxvlated 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
ethoxylatedlpropoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates
with propylene glycol, and the nonionic ethoxylate condensation products with
propylene
oxide/ethylene diamine adducts.
Nonionic alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from I 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.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR I Z wherein : R 1 is H, C 1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy
propyl, ethoxy, propoxy, or a mixture thereof, preferable CI-C4 alkyl, more
preferably
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WO 98104662 PCT/US97/12894
C 1 or C2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R2 is a CS-C31
hydrocarbyl,
preferably straight-chain CS-C 1 g alkyl or alkenyi, more preferably straight-
chain Cg-C17
alkyl or alkenyl, most preferably straight-chain C 11-C 17 alkyl or alkenyl,
or mixture
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at
5 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.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula:
R6CON(R7)2
wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17
carbon
atoms and each R7 is selected from the group consisting of hydrogen, Cl-C4
alkyl, C1-
C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from 6
to 30
carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing
from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glYcosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to
18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The
glycosyl is
preferably derived from glucose.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and
the alkyl amphocarboxylic acids.
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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 S, 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 C 10-18
acylamido
alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions hereof.
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.
Betaine and sultaine surfactants are exemplary zwitterionic surfactants for
use herein.
Suitable betaines are those compounds having the formula R(R')2N~R2C00-
wherein R
is a C6-C 1 g hydrocarbyl group, each R1 is typically C 1-C3 alkyl, and R2 is
a C 1-CS
hydrocarbyl group. Preferred betaines are C 12-18 dimethyl-ammonio hexanoate
and the
C10-lg acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
Cationic surfactants
Additional cationic surfactants can also be used in the detergent compositions
herein.
Suitable cationic surfactants include the quaternary ammonium surfactants
selected from
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.
B. Source of Alkali
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In accordance with the present invention, the alkalinity system is present in
the detergent
composition such that it has the capacity to react with the source of acidity
to produce a
gas. Preferably this gas is carbon dioxide, and therefore the alkali is a
carbonate, or a
suitable derivative thereof.
The detergent composition of the present invention preferably contains from
about 2% to
about 75%, preferably from about 5% to about 60%, most preferably from about
10% to
about 30% by weight of the alkali source. When the alkali source is present in
an
agglomerated detergent particle, the agglomerate preferably contains from
about 10% to
about 60% of the alkali source.
In a preferred embodiment, the alkalinity source is a carbonate. Examples of
preferred
carbonates are the alkaline earth and alkali metal carbonates, including
sodium
carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with
ultra-fine
calcium carbonate such as are disclosed in German Patent Application No.
2,321,001
published on November 15, 1973. Alkali metal percarbonate salts are also
suitable
sources of carbonate species and are described in more detail in the section
'inorganic
perhydrate salts' herein.
Other suitable sources will be known to those skilled in the art.
The alkalinity source may also comprise other components, such as a silicate.
Suitable
silicates include the water soluble sodium silicates with an Si02: Na20 ratio
of from 1.0
to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being
most preferred.
The silicates may be in the form of either the anhydrous salt or a hydrated
salt. Sodium
silicate with an Si02: Na20 ratio of 2.0 is the most preferred silicate.
Alkali metal
persilicates are also suitable sources of silicate herein.
Preferred crystalline layered silicates for use herein have the general
formula
NaMSix02x+1.YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0
to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-
O 164514
and methods for their preparation are disclosed in DE-A-3417649 and DE-A-
3742043.
Herein, x in the general formula above preferably has a value of 2, 3 or 4 and
is
CA 02261609 2001-12-27
13
preferably 2. The most preferred material is 8-Na2Si205, available from
Hoechst AG as
TM .
NaSKS-6.
C. Source of Acidity
S
In accordance with the present invention, the source of acidity is present in
the detergent
composition such that the it is capable of reacting with the sowce of alkali
to produce a
gas.
The particle size of the sowce of acidity is calculated by sieving a sample of
the sowce
of acidity on a series of Tyler sieves. For example, a Tyler sieve mesh 100
corresponds to
an aperatwe size of 150 microns. The weight fractions thereby obtained are
plotted
against the aperture size of the sieves.
The sowce of acidity is preferably present at a level of about to about 15% by
weight of
the composition. Preferably up to about 10%, more preferably up to about 7% by
weight.
As previously mentioned it is advantageous to use as little of the sowce of
acidity as
possible, we have found that the present invention allows the use of levels as
low as
about 0.25% to about 5%. In a preferred embodiment of the present invention
the sowce
of acidity is present in the range of about 1% to about 3%, most preferably
about 3% by
weight of the composition.
In accordance with the present invention, 80% or more of the acid sowce has a
particle
size in the range of from about 150 microns to about 710 microns, with at
least about
37% by weight of the acid sowce having a particle size of about 350 microns or
less. In a
preferred embodiment 100% of the acid source has a particle size of about 710
microns
or less, but this is not essential provided the aforementioned criteria are
fulfilled. In
another preferred embodiment of the present invention, greater than about 38%,
more
preferably 38.7%, of the particulate acid sowce has a particle size of about
350 microns
or less.
The source of acidity may be any suitable organic, mineral or inorganic acid,
or a
derivative thereof, or a mixture thereof. The sowce of acidity may be a mono-,
bi- or tri-
protonic acid. Preferred derivatives include a salt or ester of the acid. The
source of
acidity is preferably non-hygroscopic, in order to improve storage stability.
Organic acids
and their derivatives are preferred. The acid is preferably water-soluble.
Suitable acids
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14
include citric, glutaric, succinic or adipic acid, monosodium phosphate,
sodium hydrogen
sulfate, boric acid, or a salt or an ester thereof. Citric acid is especially
preferred.
Additional detereent components
The detergent compositions of the invention may also contain additional
detergent
components. The precise nature of these additional components, and levels of
incorporation thereof will depend on the physical form of the composition, and
the
precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional
detergent
components selected from additional surfactants, bleaches, builders, organic
polymeric
compounds, enzymes, suds suppressers, lime soap dispersants, soil suspension
and anti-
redeposition agents and corrosion inhibitors.
Water-soluble builder compound
The detergent compositions of the present invention preferably contain a water-
soluble
builder compound, typically present at a level of from 1 % to 80% by weight,
preferably
from 10% to 70% by weight, most preferably from 20% to 60% by weight of the
composition.
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,
phosphates, and
mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric 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
CA 02261609 2001-12-27
fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates, aconitrates and citraconates as well as succinate derivatives such
as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates
described in British Patent No. 1,3$9,732, and aminosuccinates described in
CA 973771 and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
10 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
15 hydroxycarboxylates containing up to three carboxy groups per molecule,
more
particularly citrates.
The parent acids of the monomeric or oligomeric poiycarboxylate 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 materiais that
can produce
borate under detergent storage or wash conditions are useful water-soluble
builders
herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium polymeta/phosphate in which the degree of polymerization ranges from
about 6
to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound
The detergent compositions of the present invention may contain a partially
soluble or
insoluble builder compound, typically present at a level of from 1 % to 80% by
weight,
CA 02261609 1999-O1-27
WO 98/04662 PCT/US97/12894
16
preferably from 10% to 70% by weight, most preferably from 20% to 60% weight
of the
composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. xH20
wherein z and y are at least 6; the molar ratio of z to y is from 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 occurnng materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosiiicate 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.
Oreanic peroxyacid bleaching system
A preferred feature of detergent compositions of the invention is an organic
peroxyacid
bleaching system. In one preferred execution the bleaching system contains a
hydrogen
peroxide source and an organic peroxyacid bleach precursor compound. The
production
of the organic peroxyacid occurs by an in situ reaction of the precursor with
a source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate
bleaches. In an alternative preferred execution a preformed organic peroxyacid
is
incorporated directly into the composition. Compositions containing mixtures
of a
hydrogen peroxide source and organic peroxyacid precursor in combination with
a
preformed organic peroxyacid are also envisaged.
Inor anic perhydrate bleaches
CA 02261609 2001-12-27
17
Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These
salts are
normally incorporated in the form of the alkali metal, preferably sodium salt
at a level of
from I % to 40% by weight, more preferably from 2% to 30% by weight and most
preferably from 5% to 25% by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate,
persulfate and persilicate salts. The inorganic perhydrate salts are normally
the alkali
metal salts. The inorganic perhydrate salt may be included as the crystalline
solid
without additional protection. For certain perhydrate salts however, the
preferred
executions of such granular compositions utilize a coated form of the material
which
provides better storage stability for the perhydrate salt in the granular
product. Suitable
coatings comprise inorganic salts such as alkali metal silicate, carbonate or
boratC 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 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.
Peroxvacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
rnay 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
CA 02261609 2001-12-27
18
O
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a Ievel
of from
0.5% to 20% by weight, more preferably from 1 % to 15% by weight, most
preferably
from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
1586789. Suitable esters are disclosed in GB-A-83698$, 864798, 1147871,
2143231 and
EP-A-O 170386.
Leaving_groups
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 ~ Y , and -O
O 1 O
-N-C-R -N N -N-C-CH-R'°
' ~ ~ R3 Y ,
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
CA 02261609 1999-O1-27
WO 98/04662 PCT/US97112894
19
O C H -C Y O
-O-C-R~ -N~ jNR4 , -N~ /NR4
C C
II II
O O
3
R 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 $ 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 -SO -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.
Alkvl percarbox~ic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
,N,N1N1 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.
CA 02261609 2001-12-27
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
5 Amide substituted alkyl~eroxyacid precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ -C-N-R2-C L R~ N-C-R2-C-L
10 OI RS
or R O O
wherein Rl 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. Amide substituted
bleach
15 activator compounds of this type are described in EP-A-0170386.
Perbenzoic acidprecursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable
20 O-acylated perbenzoic acid precursor compounds include the substituted and
unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of
sorbitol,
glucose, and all saccharides with benzoylating agents, and those of the imide
type
including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-
benzoyl
substituted areas. Suitable imidazole type perbenzoic acid precursors include
N-benzoyl
imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing
perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoy! taurine
and benzoyl
pyroglutamic acid.
Cationic peroxvacid nrecwsors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
CA 02261609 2001-12-27
21
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part
of a suitable peroxyacid precursor compound with a positively charged
functional group,
such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl
ammonium group. Cationic peroxyacid precursors are typically present in the
solid
S detergent compositions as a salt with a suitable anion, such as a halide
ion.
The peroxyacid precursor compound to be so canonically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as
described
hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl
percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter.
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 yip
95/29160
and US Patent Nos. 5,6$6,015; 5,460,747; 5,578,136 and 5,584,888.
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.
Benzoxazin organic neroxyacid precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example
in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
CA 02261609 2001-12-27
22
O
i1
CEO
I
N C_'R~
wherein R 1 is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed organic peroxvacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic
peroxyacid , typically at a level of from 1 % to 1 S% by weight, more
preferably from 1
to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
R~ -C -N-R2- C-OOH R~ -N- C- R2--C-OOH
O R5 O or R O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
aikylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS is
H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide
substituted
organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc
acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach catalyst
The compositions optionally contain a transition metal containing bleach
catalyst. One
suitable type of bleach catalyst is a catalyst system comprising a heavy metal
canon of
defined bleach catalytic activity, such as copper, iron or manganese cations,
an auxiliary
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WO 98/04662 PCT/US97/12894
23
metal cation having little or no bleach catalytic activity, such as zinc or
aluminum
cations, and a sequestrant having defined stability constants for the
catalytic and
auxiliary metal cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof. Such
catalysts are 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(I,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-
OAc)2(I,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4-(C104)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-
I5 1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and
mixtures
thereof.
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. Other
examples
include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands,
including N4MnIII(u_O)2MnIVN4)+and [Bipy2MnIII(u_p)2MnIVbipY2J-(C104)3~
Further suitable bleach catalysts are described, for example, in European
patent
application 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
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
cations and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
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WO 98/04662 PCT/US97/12894
24
Heaw metal ion sequestrant
The detergent compositions of the invention preferably contain as an optional
component
a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant
herein
components which act to sequester (chelate) heavy metal ions. These components
may
also have calcium and magnesium chelation capacity, but preferentially they
show
selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 20%,
preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most
preferably
from 0.5% to 5% 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.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine
pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric
acid, 2-
hydroxypropylenediamine disuccinic acid or any salts thereof. Especially
preferred is
ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline
earth metal,
ammonium, or substituted ammonium salts thereof, or mixtures 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 j3-
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 02261609 2001-12-27
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.
E me
10 Another preferred ingredient useful in the detergent compositions is one or
more
additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, esterases, cellulases,
pectinases,
15 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
trademarks Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S
20 (Denmark), those sold under the trademarks Maxatase, Maxacal and Maxapem by
Gist-
Brocades, those sold by Genencor International, and those sold under the
trademarks
Opticiean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated
into
the compositions in accordance with the invention at a level of from 0.0001 %
to 4%
active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a special
strain of B
licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred
commercially
available amylases include for example, those sold under the trademark
Rapidase by
Gist-Brocades, and those sold under the trademarks Tetmamyl and BAN by Novo
Industries A/S. Amylase enzyme may be incorporated into the composition in
accordance with the invention at a level of from 0.0001 % to 2% active enzyme
by weight
of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001 % to
2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001
% to
0.5% by weight of the compositions.
CA 02261609 2001-12-27
26
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 pseudoalcalig,enes or Pseudomas fluorescens. Lipase from
chemically or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is
derived from Pseudomonas pseudoalcaligenes, which is described in Granted
European
Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanu ig nosa and expressing the gene in AsperQillus orlrza, 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 mark Lipolase. This
lipase is
also described in U.S. Patent 4,810,4I4, Huge-Jensen et al, issued March 7,
1989.
Organic polymeric compound
Organic polymeric compounds are preferred additional components of the
detergent
compositions in accord with the invention, and are preferably present as
components of
any particulate components where they may act such as to bind the particulate
component together. 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.
Organic polymeric compound is typically incorporated in the detergent
compositions of
the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%,
most
preferably from I % to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids or their salts in which the polycarboxylic
acid
comprises at least two carboxyl radicals separated from each other by not more
than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples
of such salts are polyacrylates of MWt 2000-5000 and their copolymers with
malefic
anhydride, such copolymers having a molecular weight of from 20,000 to
100,000,
especially 40,000 to 80,000.
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WO 98/04662 PCT/US97/12894
27
The polyamino compounds are useful herein including those derived from
aspartic acid
such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent
compositions herein include cellulose derivatives such as methylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose and
hydroxyethylcellulose.
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 suppressingsystem
The detergent compositions of the invention, when formulated for use in
machine
washing compositions, preferably comprise a suds suppressing system present at
a level
of from 0.01 % to 15%, preferably from 0.05% to 10%, most preferably from 0.1
% to 5%
by weight of the composition.
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.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a
detergent composition, particularly in the presence of agitation of that
solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component.
Such silicone antifoam compounds also typically contain a silica component.
The term
"silicone" as used herein, and in general throughout the industry, encompasses
a variety
of relatively high molecular weight polymers containing siloxane units and
hydrocarbyl
CA 02261609 1999-O1-27
WO 98/04662 PCT/US97/12894
28
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. These materials are described in US Patent 2,954,347, issued
September
27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof,
for use
as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal
salts such as
sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic
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
1 S chloride with two or three moles of a primary or secondary amine
containing 1 to 24
carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-
alkali metal
(e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to
95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1% to 50%, preferably 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;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from I :0.9 to I :1.1, at a level of from 0.5% to
10%,
preferably I % to 10% by weight; a particularly preferred silicone glycol rake
CA 02261609 2001-12-27
29
copolymer of this type is DC0544, commercially available from DOW Corning
under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C I8
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to
15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731
and comprises a silicone antifoam compound and an organic cattier material
having a
melting point in the range 50°C to 85°C, wherein the organic
carrier material comprises a
monoester of glycerol and a fatty acid having a carbon chain containing from
12 to 20
carbon atoms. EP-A-0210721 discloses other preferred particulate suds
suppressing
systems wherein the organic carrier material is a fatty acid or alcohol having
a carbon
chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a
melting point
of from 45°C to 80°C.
Clay softenin,~~ system
The detergent compositions may contain a clay softening system comprising a
clay
mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite
clays are
disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and
4,062,647.
European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter
and
Gamble Company describe suitable organic polymeric clay flocculating agents.
Polymeric dye transfer inhibiting agents
The detergent compositions herein may also comprise from 0,01% to 10 %,
preferably
from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
a~ Polvamine N-oxide polymers
CA 02261609 2001-12-27
Polyamine N-oxide polymers suitable for use herein contain units having the
following
structure formula
P
(I)
5 R
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C, -O-, -S-, -N-; x is O o~ 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or aIicyclic
groups or any
combination thereof whereto the nitrogen of the N-O group can be attached or
wherein
the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general
structures
O
O
(R1) x _ ~ -(R2)Y
(R3)z or = N-(R~)x
wherein R~, Rz, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups
or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the
nitrogen of the N-
O group can be attached or wherein the nitrogen of the N-O group forms part of
these
groups. The N-O group can be part of the polymerisable unit (P) or can be
attached to the
polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable
unit comprise polyamine N-oxides wherein R is selected from aliphatic,
aromatic,
CA 02261609 2001-12-27
31
alicyclic or heterocyclic groups. One class of said polyamine N-oxides
comprises the
group of polyamine N-oxides wherein the nitrogen of the N-O group forms part
of the R-
group. Preferred polyamine N-oxides are those wherein R is a heterocyclic
group such
as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine
and
derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O
group is
attached to the polymerisable unit. A preferred class of these polyamine N-
oxides
comprises the polyamine N-oxides having the general formula (I) wherein R is
an
aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O
functional
group is pari of said R group. Examples of these classes are polyamine oxides
wherein R
is a heterocyclic compound such as pyridine, pyrrole, imidazole and
derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation.
The
I S degree of polymerisation is not critical provided the material has the
desired water-
solubility and dye-suspending power. Typically, the average molecular weight
is within
the range of 500 to I 000,000.
b~ Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone
having an
average molecular weight range of from 5,000 to 50,000. The preferred
copolymers have
a molar ratio of N-vinylimidazole to N-vinylpynolidone from 1 to 0.2.
c~ Polyvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone
("PVP") having
an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones
are commercially vailable from ISP Corporation, New York, NY and Montreal,
Canada
under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-
30
(average molecular weight of 40,000), PVP K-60 (average molecular weight of
160,000),
and PVP K-90 (average molecular weight of 360,000). PVP K-IS is also available
from
ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially
available
from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) PolvvinYloxazolidone
CA 02261609 2001-12-27
32
The detergent compositions herein may also utilize polyvinyloxazolidones as
polymeric
dye transfer inhibiting agents. Said polyvinyloxazolidones have an average
molecular
. weight of from 2,500 to 400,000.
e) Polyvinylimidazole
The detergent compositions herein may also utilize polyvinylimidazole as
polymeric dye
transfer inhibiting agent. Said polyvinylimidazoles preferably have an average
molecular
weight of from 2,500 to 400,000.
Optical brightener
The detergent compositions herein also optionally contain from about 0.005% to
5% by
weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
Ri R2
N H H N
N N C C T1 N
~."'N H H N
R2 S03M S03M Ri
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming canon such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a cation
such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-
2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener
species is commercially marketed under the trademark Tinopal-UNPA-GX by Ciba-
Geigy Corporation. Tinopal-LJNPA-GX is the preferred hydrophilic optical
brightener
' useful in the detergent compositions herein.
CA 02261609 2001-12-27
33
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and
M is a canon such as sodium, the brightener is 4,4'-bis[(4-anilino-b-(N-2-
hydroxyethyl-
N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium
salt. This
particular brightener species is commercially marketed under the trademark
Tinopai
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-rnorphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This pariicular brightener species is
commercially
marketed under the trademark Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into compositions in
1 S accordance with the present invention. Suitable cationic fabric softening
agents include
the water insoluble tertiary amines or dilong chain amide materials as
disclosed in GB-A=
1 514 27b and EP-B-0 OI 1 340.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5% to
15% by weight, normally from 1 % to 5% by weight.
Other optional inrtredients
Other optional ingredients suitable for inclusion in the compositions of the
invention
include perfumes, colours and filler salts, with sodium sulfate being a
preferred filler salt.
pH of the compositions
The present compositions preferably have a pH measured as a 1 % solution in
distilled
water of at least 10.0, preferably from 10.0 to 12.5, most preferably from
10.5 to 12Ø
Fo~rn of the compositions
The compositions in accordance with the invention can take a variety of
physical forms
including granular, tablet, bar and liquid forms. The compositions are
particularly the so-
called concentrated granular detergent compositions adapted to be added to a
washing
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WO 98/04662 PCT/L1S97/12894 -
34
machine by means of a dispensing device placed in the machine drum with the
soiled
fabric load.
The mean particle size of the base composition of granular compositions in
accordance
with the invention should preferably be such that no more that 5% of particles
are greater
than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm
in
diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the
composition into a number of fractions (typically 5 fractions) on a series of
Tyler sieves.
The weight fractions thereby obtained are plotted against the aperture size of
the sieves.
The mean particle size is taken to be the aperture size through which 50% by
weight of
the sample would pass.
The bulk density of granular detergent compositions in accordance with the
present
invention typically have a bulk density of at least 600 g/litre, more
preferably from 650
g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel
and cup
device consisting of a conical funnel moulded rigidly on a base and provided
with a flap
valve at its lower extremity to allow the contents of the funnel to be emptied
into an
axially aligned cylindrical cup disposed below the funnel. The funnel is 130
mm high
and has internal diameters of 130 mm and 40 mm at its respective upper and
lower
extremities. It is mounted so that the lower extremity is 140 mm above the
upper
surface of the base. The cup has an overall height of 90 mm, an internal
height of 87
mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring,
the flap
valve is opened and powder allowed to overfill the cup. The filled cup is
removed from
the frame and excess powder removed from the cup by passing a straight edged
implement eg; a knife, across its upper edge. The filled cup is then weighed
and the
value obtained for the weight of powder doubled to provide a bulk density in
g/litre.
Replicate measurements are made as required.
The composition is preferably soluble in cold or cool water, i.e. the
composition readily
dissolves/disperses in water at a temperature between about 0°C and
32.2°C, preferably
between about i.6°C and 10°C.
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WO 98/04662 PCT/US97/12894
Surfactant agglomerate particles
The surfactant system herein is preferably present in granular compositions in
the form
of surfactant agglomerate particles, which may take the form of flakes,
prills, marumes,
5 noodles, ribbons, but preferably take the form of granules. The most
preferred way to
process the particles is by agglomerating powders (e.g. aluminosilicate,
carbonate) with
high active surfactant pastes and to control the particle size of the
resultant agglomerates
within specified limits. Such a process involves mixing an effective amount of
powder
with a high active surfactant paste in one or more agglomerators such as a pan
10 agglomerator, a Z-blade mixer or more preferably an in-line mixer such as
those
manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad,
Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1,
Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer
is used,
such as a Lodige CB (Trade Name).
A high active surfactant paste comprising from 50% by weight to 95% by weight,
preferably 70% by weight to 85% by weight of surfactant is typically used. The
paste
may be pumped into the agglomerator at a temperature high enough to maintain a
pumpable viscosity, but low enough to avoid degradation of the anionic
surfactants used.
An operating temperature of the paste of 50°C to 80°C is
typical.
In an especially preferred embodiment of the present invention, the detergent
composition has a density of greater than about 600 g/1 and is in the form of
powder or a
granulate containing more than about 5% by weight of of the alkali, preferably
(bi-
)carbonate or percarbonate. The carbonate material is either dry-added or
delivered via
agglomerates. The addition of the acid, preferably citric acid, (up to 10%)
may be
introduced into the product as a dry-add, or via a separate particle.
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 40g to
300g of product dissolved or dispersed in a wash solution of volume from 5 to
65 litres,
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WO 98/04662 PCT/US97/12894 -
36
as are typical product dosages and wash solution volumes commonly employed in
conventional machine laundry methods.
In a preferred use aspect a dispensing device is employed in the washing
method. The
dispensing device is charged with the detergent product, and is used to
introduce the
product directly into the drum of the washing machine before the commencement
of the
wash cycle. Its volume capacity should be such as to be able to contain
sufficient
detergent product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement of the
wash cycle of the washing machine water is introduced into the drum and the
drum
periodically rotates. The design of the dispensing device should be such that
it permits
containment of the dry detergent product but then allows release of this
product during
the wash cycle in response to its agitation as the drum rotates and also as a
result of its
contact with the wash water.
To allow for release of the detergent product during the wash the device may
possess a
number of openings through which the product may pass. Alternatively, the
device may
be made of a material which is permeable to liquid but impermeable to the
solid product,
which will allow release of dissolved product. Preferably, the detergent
product will be
rapidly released at the start of the wash cycle thereby providing transient
localised high
concentrations of product in the drum of the washing machine at this stage of
the wash
cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container
integrity is maintained in both the dry state and during the wash cycle.
Especially
preferred dispensing devices for use with the composition of the invention
have been
described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-
0201376,
EP-A-0288345 and EP-A-0288346. An article by J.Bland published in
Manufacturing
Chemist, November 1989, pages 41-46 also describes especially preferred
dispensing
devices for use with granular laundry products which are of a type commonly
know as
the "granulette". Another preferred dispensing device for use with the
compositions of
this invention is disclosed in PCT Patent Application No. W094/11562.
T______. - - -_ __ _ _. ~ . -
CA 02261609 2001-12-27
37
Especially preferred dispensing devices are disclosed in European Patent
Application
Publication Nos. 0343069 & 0343070. The latter Application discloses a device
comprising a flexible sheath in the form of a bag extending from a support
ring defining
an orifice, the orifice being adapted to admit Lo the bag sufficient product
for one
S washing cycle in a washing process. A portion of the washing medium flows
through the
orifice into the bag, dissolves the product, and the solution then passes
outwardly
through the orifice into the washing medium. The support ring is provided with
a
masking arrangemnt to prevent egress of weried, undissolved, product, this
arrangement
typically comprising radially extending walls extending from a central boss in
a spoked
wheel configuration, or a similar structure in which the walls have a helical
form.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch.
The bag may be of fibrous construction coated with a water impermeable
protective
material so as to retain the contents, such as is disclosed in European
published Patent
I 5 Application No. 0018678. Alternatively it may be formed of a water-
insoluble synthetic
polymeric material provided with an edge seal or closure designed to rupture
in aqueous
media as disclosed in European published Patent Application Nos. 0011500,
0011501,
0011502, and 0011968. A convenient form of water frangible closure comprises a
water
soluble adhesive disposed along and sealing one edge of a pouch formed of a
water
impermeable polymeric film such as polyethylene or polypropylene.
Packaging for the compositions
Commercially marketed executions of the bleaching compositions can be packaged
in
any suitabie container including those constructed from paper, cardboard,
plastic
materials and any suitable laminates.
Example 1 - Comparative Performance Testing
The following experiments illustrate the benefits of using a formulation of
the present
invention, in which the source of acidity has the specified particle size
distribution. More
particularly we found that the formulation of the present invention showed a
significant
improvement at least in terms of the dispensing profile under stressed
conditions (i.e. low
water pressure and temperature) compared to the same fonmulation without the
source of
acidity having the particle size distribution of the present invention.
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WO 98/04662 PCT/US97/12894
38
Test Protocol
A Hotpoint automatic washing machine was employed, and a 2 minute
20°C cycle
selected. 150 g of detergent dispensed via the dispenser drawer was used. The
water
flow rate into the machine was set at 2.01/minute.
The results are shown below in Table 1.
Table I
Detergent Detergent DensityCitric Acid % Detergent
(approi.)(g/1) Level Residue in
(weight %) Dispenser Drawer
STDI
Formulation 730 - 40% 8%
I
" 850 - 57% 6%
" 850 0.8% 50% 4%
" 850 1.5% 39% 3%
" 850 2.0% 29% 1%
Formulation 850 - 50% 4%
II
" 850 0.8% 41% 14%
" 850 1.5% 39% 6%
" 850 2.0% 27% 4%
1 Standard Deviation
The data shown in Table 1 was generated using a citric acid material with the
particle
size distribution shown in Table 2.
Ta 1e 2
Particle Size of Citric Particle Size Distribution
Acidl
> 710 microns 6.0%
425 - 710 microns 41.7%
355 - 425 microns 14.6%
SUBSTITUTE SHEET (RULE 26)
CA 02261609 2001-12-27
39
250 - 355 microns2 25.3%
150 - 250 microns 11.1
< 150 microns 1,3%
'Citric acid, monohydrate, fine granular, supplier Citrique Belge Ltd.
The fraction with a particle size of greater than 355 microns was found to be
62.2%
(STD 0.4%, 2 replicates). The estimated fraction with a particle size greater
than 350
microns is 61.3%.
Abbreviations used in following_Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
LAS : Sodium linear C 12 alkyl benzene sulfonate
TAS . Sodium tallow alkyl sulfate
C45AS . Sodium C 14-C 15 linear alkyl sulfate
CxyEzS : Sodium Clx-Cly branched alkyl sulfate condensed
with z
moles of ethylene oxide
C45E7 : A C14-15 Predominantly linear primary alcohol
condensed with an average of 7 moles of ethylene
oxide
C25E3 . A C12-15 b~ched primary alcohol condensed
with an
average of 3 moles of ethylene oxide
C25E5 : A C12-15 b~ched primary alcohol condensed
with an
average of 5 moles of ethylene oxide
CEQ . R1 COOCH2CH2.N+(CH3)3 with R 1 = C 11-C
13
QAS . R2.N+(CH3~(C2H40H) with R2 = C 12 - C 14
Soap : Sodium linear alkyl carboxyiate derived
from an
80/20 mixture of tallow and coeonut oils.
TFAA : C 16-C 1 g alkyl N-methyl glucamide
TPKFA . C12-C14 topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12~ 2~1"I20 having a primary
particle size
in the range from 0.1 to 10 micrometers
NaSKS-6 : Crystalline layered silicate of formula
CA 02261609 2001-12-27
8 -Na2Si205
Citric acid . Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a panicle size
between
200 pm and 900~m
5 Bicarbonate : Anhydrous sodium bicarbonate with a particle size
distribution between 400pm and 1200pm
Silicate : Amorphous Sodium Silicate (Si02:Na20; 2.0 ratio)
Sodium sulfate Anhydrous sodium sulfate
.
Citrate : Tri-sodium citrate dihydrate of activity 86.4% with
a
10 particle size distribution between 425pm and 850
m
MA/AA : p
Copolymer of I :4 maleic/acrylic acid, average
molecular weight about 70,000.
CMC . Sodium carboxymethyl cellulose
Protease . Proteolytic enzyme of activity 4KNPU/g sold by
15 NOVO Industries A/S under the trademark Savinase
Alcalase : Proteolytic enzyme of activity 3AU/g sold by
NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold
by NOVO Industries A/S under the trademark
20 Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the trademark
Termamyl 60T
Lipase . Lipolytic enzyme of activity I OOkLU/g sold by
25
NOVO Industries A/S under the trademark
Lipolase
Endolase . Endoglunase enzyme of activity 3000 CEVU/g
sold by NOVO Industries AIS
PB4 : Sodium perborate tetrahydrate of nominal formula
30 NaB02.3H20.H202
PB 1 : Anhydrous sodium perborate monohydrate bleach of
nominal formula NaB02.H202
Percarbonate Sodium Percarbonate of nominal formula
:
2Na2C03.3H202
35 NOBS . Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
CA 02261609 2001-12-27
41
TAED : Tetraacetylethylenediamine
DTPMP : Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under
the
Trade mark bequest 2060
Photoactivated . Sulfonated Zinc Phthlocyanine encapsulated
in bleach
dextrin soluble polymer
Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyi
Brightener 2 . Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP . 1,1-hydroxyethane diphosphonic acid
PVNO : Polyvinylpyridine N-oxide
PVPVI . Copolymer of polyvinylpyrolidone and
vinylimidazole
SRP 1 : Sulfobenzoyl end capped esters with
oxyethylene
oxy and terephthaloyl backbone
SRP 2 . Diethoxyiated poly (1, 2 propylene terephthalate)
short block polymer
Silicone antifoam : Polydimethylsiloxane foam controller
with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller
to said
dispersing agent of 10:1 to 100:1.
Alkalinity . % weight equivalent of NaOH, as obtained
using the
alkalinity release test method described
herein.
In the following Examples all levels are quoted as % by weight of the
composition:
Example 2
The following granular laundry detergent compositions A and B of bulk density
750
g/litre were prepared in accord with the invention:
A B
LAS 5.61 4.76
TAS 1.86 1.57
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42
C45AS 2.24 3.89
C25AE3S 0.76 1.18
C45E7 - 5.0
C25E3 5.5 -
CEQ 2.0 2.0
STPP _ -
Zeolite A 19.5 19.5
NaSKS-6/citric acid 10.6 10.6
(79:21 )
Carbonate 21.4 21.4
Bicarbonate 2.0 2.0
Silicate - _
Sodium sulfate - 14.3
PB4 12.7 -
TAED 3.1 -
DETPMP 0.2 0.2
HEDP 0.3 0.3
Protease 0.85 0.85
Lipase 0.15 0.15
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43
Cellulase 0.28 0.28
Amylase 0.1 0.1
MA/AA 1.6 1.6
CMC 0.4 0.4
Photoactivated bleach 27 ppm 27 ppm
(ppm)
Brightener 1 0.19 0.19
Brightener 2 0.04 0.04
Perfume 0.3 0.3
Silicone antifoam 2.4 2.4
Citric acid 1.5 2.0
Minors/misc to 100%
Example 3
The following detergent formulations, according to the present invention were
prepared,
where C is a phosphorus-containing detergent composition, D is a zeolite-
containing
detergent composition and E is a compact detergent composition:
C D E
Blown Powder
STPP 14.0 - 14.0
Zeolite A - 20.0 -
C45AS 9.0 6.0 8.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 9.0
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WO 98/04662 PCT/US97/12894
44
TAS 2.0 - -
CEQ 1.5 3.U 3.5
Silicate 7.0 8.0 8.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 26.0 23.0 25.0
PB4 18.0 18.0 10
PB 1 4.0 4.0 0
TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.25 0.30 0.15
Dry mixed sodium sulfate3.0 3.0 S.0
Citric acid 2.5 2.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
Example 4
The following nil bleach-containing detergent formulations of particular use
in the
washing of colored clothing, according to the present invention were prepared:
F G
Blown Powder
Zeolite A 15.0 -
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Sodium sulfate - -
LAS 3.0 -
CEQ 2.0 I .3
DTPMP 0.4
CMC 0.4 -
MA/AA 4.0 -
Agglomerates
C45AS - 11.0
LAS 6.0
TAS 3.0 -
Silicate 4.0 -
Zeolite A 10.0 13.0
CMC - 0.5
MA/AA - 2.0
Carbonate 9.0 7.0
Spray On
Perfume 0.3 0.5
C45E7 4.0 4.0
C25E3 2.0 2.0
Dry additives
MA/AA - 3.0
NaSKS-6 - 12.0
Citric acid 4.0 3.0
Citrate 10.0 8.0
Bicarbonate 7.0 5.0
Carbonate 8.0 7.0
PVPVI/PVNO 0.5 0.5
Alcalase 0.5 0.9
Lipase 0.4 0.4
Amylase 0.6 0.6
Cellulase 0.6 0.6
Silicone antifoam 5.0 S.0
Dry additives
Sodium sulfate 0.0 0.0
Balance (Moisture and Miscellaneous)100.0 100.0
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Density (g/litre) 700 700
Example 5
The following detergent formulations, according to the present invention were
prepared:
H I J K
LAS 12.0 12.0 12.0 10.0
QAS 0.7 1.0 - 0_7
TFAA - 1.0 - _
C25E5/C45E7 - 2.0 - 0.5
C45E3 S - 2.5 -
CEQ 2.0 1.5 1.0 1.0
STPP 30.0 18.0 1 S.0 -
Silicate 9.0 7.0 10.0
Carbonate 15.0 10.5 I5.0 25.0
Bicarbonate - 10. 5 -
DTPMP 0.7 1.0 - -
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 - -
Photoactivated70ppm 45ppm - lOppm
bleach (ppm)
Brightener 0.2 0.2 0.08 0.2
i
PB 1 ~ 6.0 2.0 - -
NOBS 2.0 1.0 - -
Citric acid 3.5 5.0 3.0 2.0
Balance (Moisture100 100 100 100
and
Miscellaneous)
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Example 6
The following detergent formulations, according to the present invention were
prepared:
L M N
Blown Powder
Zeolite A 10.0 15.0 6.0
Sodium sulfate 19.0 5.0 7.0
MA/AA 3.0 3.0 6.0
LAS 10.0 8.0 10.0
C45AS 4.0 5.0 7.0
CEQ 2.0 2.0 2.0
Silicate - I.0 7.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 28.0 26.0 20.0
DTPMP - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS - 6. I 4.5
PB 1 1.0 5.0 6.0
Sodium sulfate - 6.0 -
Citric acid 2.5 2.5 2.0
Balance (Moisture 100 100 100
and
Miscellaneous)
Example 7
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The following high density and bleach-containing detergent formulations,
according to
the present invention were prepared:
O P
Blown Powder
Zeolite A 15.0 15.0
Sodim sulfate 0.0 0.0
LAS 3.0 3.0
QAS - 1.5
CEQ 2.0 2.0
DTPMP 0.4 0.4
CMC 0.4 0.4
MA/AA 4.0 2.0
Agglomerates
LAS 4.0 4.0
TAS 2.0 1.0
Silicate 3.0 4.0
Zeolite A 8.0 8.0
Carbonate 8.0 6.0
Spray On
Perfume 0.3 0.3
C45E7 2.0 2.0
C25E3 2.0 _
Dry additives
Citric acid 2.0 3.0
Citrate 5.0 2.0
Bicarbonate - _
Carbonate 8.0 10.0
TAED 6.0 5.0
PB1 14.0 10.0
Polyethylene oxide of MW ~ - 0.2
5,000,000
Bentonite clay - 10.0
Protease. I.0 1.0
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Lipase 0.4 0.4
Amylase 0.6 0.6
Cellulase 0.6 0.6
Silicone antifoam 5.0 5.0
Dry additives
Sodium sulfate 0.0 0.0
Balance (Moisture and 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850
Example 8
The following high density detergent formulations, according to the present
invention
were prepared:
Q R
Agglomerate
C45AS 11.0 14.0
CEQ 3.0 3.5
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
Citric acid 1.5 2.0
HEDP 0.5 0.3
SKS 6 I3.0 10.0
Citrate 3.0 1.0
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TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Amylase 0.6 0.6
Silicone antifoam 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2 -
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
