Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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A Process and Composition for Deter; ents
Technical Field
The present invention relates to a process for making a detexgent composition
which
is suitable for use in laundry and dish washing methods. The present invention
also
relates to a detergent composition, and, particularly, but not exclusively, to
detergent
compositions made by the process.
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 weight of the filler particles is less than 150 microns. The
filler
particles include salts of citrate, sulphate, (bi-)carbonate and silicates.
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2
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 encapsulated or agglomerated with bicarbonate,
for
reaction with it to generate carbon dioxide.
W092/18596 discloses that improved solubility/dispersion 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.
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EP-A-0 534 525 discloses the use of citric acid with a specified particle size
range of 350 to 1500 microns.
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.
Summary of the Invention
According to one aspect of the present invention there is provided a process
for making a detergent composition comprising: i) making a detergent base
composition comprising a solid acid source which is a member selected from
the group consisting of citric acid, glutaric acid, adipic acid, sodium
hydrogen
sulfate and boric acid; ii) coating the solid acid source with a detergent
surfactant; and iii) further adding an alkaline source and agglomerating said
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4
alkaline source with said acid source; wherein the alkaline source and the
acid
source are capable of reacting together to produce a gas and wherein said
composition contains a source of hydrogen peroxide.
According to another aspect of the present invention there is provided a
detergent composition produced by the process of the present invention.
Detailed Description of the Invention
The detergent composition can be in the form of a powder or a granulate.
In one embodiment of the present invention, such compositions comprise
a base composition containing one or more surfactants, and preferably
a builder. The base composition may be prepared by spray-drying
and dry-mixing/agglomeration. The base composition may also
comprise the particulate alkaline source. Alternatively the alkaline
source may be added as a separate component to the detergent base
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composition, preferably in granular form and delivered by dry-adding. It will
be
appreciated that when the alkaline source is added as a separate component to
the base
composition in order to improve the storage stability of the detergent it is
preferable to
coat the base composition with the nonionic surfactant/acid source mix prior
to the
addition of the alkaline source.
Although any convenient technique could be used for coating the detergent
surfactant,
in an especially preferred embodiment the nonionic surfactant/acid source mix
is
sprayed on to the detergent surfactant. More particularly the acid source is
mixed with
liquid nonionic surfactant and then sprayed on to the particle.
In a preferred embodiment of the present invention the particulate detergent
surfactant of the base composition is different from the nonionic surfactant
with
which it is coated. In an especially preferred embodiment the particulate
detergent
surfactant is not a nonionic surfactant.
In a second embodiment of the present invention, the compositions comprise a
base
composition containing one or more acid source, and preferably a builder. The
base
composition may be prepared by spray-drying and dry-mixing/agglomeration. The
base composition may also comprise the alkaline source material. Alternatively
the
alkaline source may be added as a separate component to the detergent base
composition, preferably in granular form and delivered by dry-adding. It will
be
appreciated that when the alkaline source is added as a separate component to
the base
composition in order to improve the storage stability of the detergent it is
preferable to
coat the base composition with the nonionic surfactant/acid source mix prior
to the
addition of the alkaline source. In another embodiment, the alkaline source
material
coats the base composition.
Although any convenient technique could be used for coating the acid source,
in an
especially preferred embodiment the nonionic surfactant/detergent surfactant
mix is
sprayed on to the detergent surfactant. More particularly the detergent
surfactant is
mixed with liquid nonionic surfactant and then sprayed on to the particle.
In a preferred embodiment of the present invention the detergent surfactant of
the
coating is different from the nonionic surfactant with which it coats the
base. In an
especially preferred embodiment the detergent surfactant is not a nonionic
surfactant.
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It will be appreciated that the detergent composition of the present invention
can be
built up in layers around a base composition. The base composition may
comprise the
acid source or detergent surfactant and/or alkalinity source. The other
components
then coat this base composition. The use of such layers allows the amount of
acid used
to be reduced compared to conventional compositions, whilst still provided
efficient
dispersion of the detergent.
The essential, and optional, ingredients of the present invention will now be
described
below in detail.
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 anionics, nonionics, zwitterionics, ampholytics,
amphoteric,
cationics and mixtures thereof. Preferably the surfactant is anionic, nonionic
or a
mixture thereof. When the composition contains more than one surfactant the
additional surfactant is preferably present at a level of from 0.1 % to SO%,
more
preferably from 1% to 40%, most preferably from 5% to 30% by weight ofthe
total
surfactant present. Where present, ampholytic, amphoteric and zwitterionic
surfactants
are generally used in combiantion with one or more anionic and/or nonionic
surfactants.
Anionic surfactant
The surfactant system may include an anionic surfactant. Essentially any
anionic
surfactants useful for detersive purposes are suitable. These can include
salts
(including, for example, sodium, potassium, ammonium, and substituted ammonium
salts such as mono-, dl- 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 18
T
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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-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 10-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates
and the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the C 10-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a
C 11-C 1 g, most preferably C 11-C 15 alkyl sulfate which has been ethoxylated
with
from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
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 CS-
C20
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or
secondary
alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfonates, and
any mixtures thereof.
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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-(CHR1-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 l 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-
propyi-
1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps
may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(R1) CH2 COOM, wherein R is a CS-Cl~ linear or branched alkyl or alkenyl
group,
R1 is a C1-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.
Alkoxylated nonionic surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated
and propoxylated nonionic surfactants are preferred.
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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.
Nonionic alkoxvlated alcohol surfactant
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.
Nonionic nolvhvdroxv fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl,
more
preferably C 1 or C2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R2
is a CS-C31
hydrocarbyl, preferably straight-chain CS-C 1 g alkyl or alkenyl, more
preferably
straight-chain Cg-C 17 alkyl or alkenyl, most preferably straight-chain C 11-C
17 alkyl
or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyi having a
linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an
alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z
preferably
will be derived from a reducing sugar in a reductive amination reaction; more
preferably Z is a glycityl.
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, C1-C4
alkyl,
C1-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
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Nonionic alkvlpolysaccharide 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.
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 1 p-C 1 g
alkyl
dimethylamine oxide, and C10-18 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
_____ _ _ __ _
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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 R l is typical ly C 1-C3 alkyl, and R2
is a C 1-
CS hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
Complex betaine surfactants are also suitable for use herein.
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.
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 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.
Preferred water dispersible cationic ester surfactants are the choline esters
having the
formula:
O IHs
Ri-C-O-CH2CH2-N'-CH3 M-
CH3
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wherein R1 is a C11-C19 linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl
choline ester
quaternary methylammonium halides (R1=C17 alkyl), palmitoyl choline ester
quaternary methylammonium halides (R1=C15 alkyl), myristoyl choline ester
quaternary methylammonium halides (Rl=C13 alkyl), lauroyl choline ester
methylammonium halides (R1=C 11 alkyl), cocoyl choline ester quaternary
methylammonium halides (R 1=C 11 _C 13 alkyl), tallowyl choline ester
quaternary
methyiammonium halides (R1=C15_C17 alkyl), and any mixtures thereof.
B. Source of Alkali
In accordance with the present invention, an alkalinity system may be 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 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 include other components, such as is a silicate.
Suitable
silicates include the water soluble sodium silicates with an Si02: Na20 ratio
of from
____ T __... _ _ ___ _____..__ ___.
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1~
1.0 to 2.8, with ratios of from 1.6 to 2.0 being prefer ed. 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+l.yH~O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from
0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-
A-
0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-
A-3742043. Herein, x in the general formula above preferably has a value of ?.
3 or 4
and is preferably 2. The most preferred material is 8-Na~Si~05, available from
TM
Hoechst AG as NaSKS-6.
C. Nonionic surfactant
This component may be one or more of the nonionic surfactants described above
under A.
The nonionic surfactant is preferably in a liquid form. In one embodiment it
is mixed
with the acid source for application to the surfactant of the base
composition. In
another embodiment it is mixed with the surfactant for application to the base
composition. The nonionic surfactant may be melted prior to mixing. In an
especially
preferred embodiment, the nonionic surfactant is a separate layer around the
base
composition.
D. Source of Acidity
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 source
of alkali
to produce a gas.
The source of acidity is preferably present at a level of up to about 15% by
weight of
the composition. Preferably up to about 10%, more preferably up to about 7% by
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14
weight. As previously mentioned it is advantageous to use as little of the
source 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 source of acidity is present in the range of about 1% to about
3%, most
preferably about 3% by weight of the composition. Further when the acid source
is
particulate at least about 25% of the acid source preferably has a particle
size below
about 350 microns. The particle size may be calculated using a Tyler sieve.
The source of acidity may be any suitable organic, mineral or inorganic acid,
or a
derivative thereof, or a mixture thereof. The source 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 nonhygroscopic, in order to improve storage stability.
Organic
acids and their derivatives are preferred. The acid is preferably water-
soluble. Suitable
acids include citric, glutaric, succinic or adipic acid, monosodium phosphate,
sodiumhydrogensulfate, boric acid, or a salt or an ester thereof. Citric acid
is
especially preferred.
Other suitable sources will be known to those skilled in the art.
Additional detergent 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,
CA 02261348 2002-O1-04
l~
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 fumaric acid, as well as the ether carboxylatcs and the sulfinyl
carboxylates.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates. aconitrates and citraconates.as well as succinate derivatives such
as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732. and
aminosuccinates
described in CA 973,771, and the oxypolycarboxylate materials
such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1.387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,?.2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and I ,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent
Nos. 1.398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the
sulfonated
pyrolysed citrates described in British Patent No. 1,439,000. Preferred
polycarboxylates are hydroxycarboxylates containing up to three carboxy groups
per
molecule. more particularly citrates.
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WO 98/04671 PCT/LTS97/12964 - -
16
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can
produce borate under detergent storage or wash conditions are useful water-
soluble
builders herein.
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, 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[(A1~2)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
__ ._ _ _ . _ ___ ._ ___ ~ ___ ._._.~_ ____
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WO 98/04671 _ PCT/US97/12964
17
wherein x is from 20 to 30, especially 27. Zeoiite X has the formula Nag6
[(A102)g6(Si02)106~~ 276 H20.
Organic peroxyacid bleachin,~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.
Inoreanic perhydrate bleaches
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 1 % 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
borate salts or mixtures thereof, or organic materials such as waxes, oils, or
fatty
soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of the
monohydrate of nominal formula NaB02H202 or the tetrahydrate
NaB02H202.3H20.
CA 02261348 2002-O1-04
18
Alkali metal percarbonates. particularly sodium percarbonate are preferred
perhydrates herein. Sodium percarbonate is an addition compound having a
formula
corresponding to 2Na~C0~.3H~0~, 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 peroxvacid. 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
Peroxyacid bleach precursor compounds are preferably incorporated ai a level
of from
0.5% to 20% by weight, more preferably from 1 % to 15% by weight, most
preferably
from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or
O-acyl groups. which precursors can be selected from a wide range of classes.
Suitabie classes include anhydrides, esters, imides, lactams and acylated
derivatives of
imidazoles and oximes. Examples of useful materials within these classes are
disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988,
864798,
1147871. 2143231 and EP-A-0170386.
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WO 98/04671 PCT/US97/12964 -
19
Leavin Qrou~s
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis reaction to occur within the optimum time frame (e.g., a wash
cycle).
However, if L is too reactive, this activator will be difficult to stabilize
for use in a
bleaching composition.
Preferred L groups are selected from the group consisting of:
Y R3 RsY
-O ~ , -O ~ Y , and -O
O O
-N-C-R~ - i1
-N N N-C-CH-R4
Rs ' ~ ' R3 Y ,
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O O Y O
C H2-C ~--C w
_p-C-R~ -N\C/NRa -N"\C/NR4
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 8 carbon atoms,
R4 is H
or R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be
substituted
by essentially any functional group including, for example alkyl, hydroxy,
alkoxy,
halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
CA 02261348 2002-O1-04
The preferred3 olubilizing groups are -SO~-M+, -C02-Mr, -S04-M~. -N+(R')4X-
and O<--N(R )3 and most preferably -SO~-M and -CO.,-M wherein R' 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
canon, with sodium and potassium being most preferred, and X is a halide,
hydroxide,
methylsulfate or acetate anion.
Alkyl~ercarboxylic 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.N I N I tetra acerylated alkylene diamines wherein the alkylene group
contains from
1 to 6 carbon atoms, particularly those compounds in which the alkvlene group
contains I. 2 and 6 carbon atoms. Tetraacetvl ethylene diamine (TAED) is
particularly
preferred.
Other preferred alkyl percarboxvlic acid precursors include sodium 3.~.~-tri-
methyl
hexanoyloxybenzene sulfonate (iso-HOBS ), sodium nonanovloxvbenzene sutfonate
(HOBS), sodium acetoxybenzene sulfonate IABS) and pentaacety! glucose.
Amide substituted alkyl peroxyacid 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
II I n I fl
O R5 O or RS O O
wherein R 1 is an alkyl group with from 1 to 14 carbon atoms, R~ is an
alkylene group
containing from 1 to 14 carbon atoms. and R~ is H or an alkyl group containing
1 to
CA 02261348 1999-O1-27
WO 98104671 _ PCT/US97/12964
21
carbon atoms and L can be essentially any leaving group. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386.
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted and
unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of
sorbitol, glucose, and all saccharides with benzoylating agents, and those of
the imide
type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-
benzoyl substituted areas. Suitable imidazole type perbenzoic acid precursors
include
N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-
containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl
taurine and benzoyl pyroglutamic acid.
Cationic peroxyacid~recursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
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 detergent compositions as a salt with a suitable anion, such as a halide
ion.
The peroxyacid precursor compound to be so cationically 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; S,I27,852; 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.
CA 02261348 2002-O1-04
'17
Examples of preferred cationic peroxyacid precursors are described in
WO 95/29160 and US Patent Nos. 5,686,015; 5,460,747; 5,578,136 and
5,584,888.
Suitable cationic peroxyacid precursors include any of the ammonium or aikvl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated '
caprolactams, and monobenzoyltetraacetyl glucose ben2oyl 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 peroxyacid 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:
O
i1
C~O
I
,C-R~
N
wherein R1 is H, alkyl, alkaryl, aryl. or arylalkyl.
Preformed orr~anic~eroxyacid
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 15% 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
II I II ! 11 II
O R5 O or R5 O O
CA 02261348 1999-O1-27
WO 98/04671 - PCT/US97/12964
23
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS
is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
Amide
substituted organic peroxyacid compounds of this type are described in EP-A-
0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and
diperbrassylic
acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
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
cation of
defined bleach catalytic activity, such as copper, iron or manganese cations,
an
auxiliary 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(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-(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-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)
CA 02261348 1999-O1-27
WO 98/04671 PCT/US97/12964 - -
24
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_O)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).
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.
T _ ____ _.._.__ ______._ _. _._ ~.~
CA 02261348 1999-O1-27
WO 98/04671 PCT/US97/12964 - -
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 ~3
-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-
monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-
509,382 are
also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes
suitabie 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
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, ceilulases,
pectinases,
CA 02261348 2002-O1-04
26
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 (Denmark), those sold under the trademarks Maxatase, Maxacal and Ma~capem
by
Gist-Brocades, those sold by Genencor International, and those sold under the
trademarks Opticlean and Optimase by Solvay Enzymes. Protease enryme 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 trademark Termamvl 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.
The lipase may be fungal or bacterial in origin being obtained. for example,
from a
lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp.
including Pseudomonas pseudoalcalieenes 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 Asper illus oryza, as host, as
described in
European Patent Application. EP-A-0258 068, which is commercially available
from
Novo Industri AIS, Bagsvaerd. Denmark. under the trade mark Lipolase. This
lipase
is also described in U.S. Patent 4,810,414: Huge-Jensen et al, issued March 7,
1989.
CA 02261348 1999-O1-27
WO 98/04671 PCTlUS97/12964 -
27
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 1 % 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.
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, hydroxypropyimethylcellulose and
hydroxyethylcellulose.
CA 02261348 1999-O1-27
WO 98/04671 . PCT/US97/12964
28
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 suppressing system
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 I O%, 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 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.
_. _ ..._. _ __.._
r
CA 02261348 2002-O1-04
?9
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 dl- to tetra alkyldiamine chlortriazines formed as products
of
cyanuric 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
(l) 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 silicalsilicone antifoam compound is incorporated at a level of
from 5%
to SO%. preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to 1:1.1. at a level of from 0.5% to 10%,
preferably I% to 10% by weight; a particularly preferred silicone glycol rake
copolymer of this tyt~e is DC0544, commercially available from DOW
Corning under the trademark DC0544;
( c) an inert carrier fluid compound, most preferably comprising a C I 6-C ~ g
ethoxylated alcohol with a degree of ethoxylation of from 5 to S0, 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 carrier material
having a
melting point in the range 50°C to 85°C. wherein the organic
carrier material
CA 02261348 2002-O1-04
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 softenine 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 inhibitine aeents
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,
polyvinylpyrrolidonepoiymers or combinations thereof.
a~ Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
P
(I)
R
wherein P is a polvmerisable unit, and
CA 02261348 2002-O1-04
Jl
O O O
II II II
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
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 pan of these groups.
The N-O group can be represented by the following general
structures
O
1
O
(R 1 ) x -N-(R2)y
(R3)z or N_(R1)x
wherein R,, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x oriand 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,
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, pvrrolidine, 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 poiyamine N-oxides having the general formula (I) wherein R is
an
aromatic.heterocyclic or alicyclic groups wherein the nitrogen of the N-O
functional
CA 02261348 2002-O1-04
group is part of said R group. Examples of these classes are polyamine oxides
wherein
R is a heterocyclic compound such as pyrridine, pyn;ole, imidazole and
derivatives
thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation.
The
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 1000,000.
b) Copolymers of N-vinvipvrrolidone and N-vinvIimidazole
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-vinylpyrrolidone from 1 to 0.?.
c) Poivvinvlnvrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone
("PVP")
having an average molecular weight of from 2,500 to 400,000. Suitable
polyvinyipyrrolidones 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 h-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 (SP Corporation. Other suitable
polyvinylpyrrolidones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinvloxazolidone
The detergent compositions heiein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average
molecular weight of from ?,500 to 400,000.
CA 02261348 2002-O1-04
33
a 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
S%
by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural
formula:
Ri R,_
--N H H N
N OON C C O N-.~O N
/ N H H N
R, S03M S03M R
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R~ 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.
Vl-'hen in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M
is a
canon such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-
s-triazine-2-yl)amino]-?,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the trademark Tinopal-LTNPA-
GX
by Ciba-Geigy Corporation. Tinopal-LINPA-GX is the preferred hydrophilic
optical
brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-I~'-2-
methylamino
and M is a canon such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(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 Tinopal SBM-GX by Ciba-Geigy Corporation.
CA 02261348 2002-O1-04
~4
When in the above formula, R1 is anilino, R~ is morphilino and M is a cation
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)aminoJ2.2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially marketed under the trademark Tinopal AMS-GX by Ciba Geigy
Corporation.
Cationic fabric softenins a ents
Cationic fabric softening agents can also be incorporated into compositions in
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 S 14 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5%
to 1 S% by weight. normally from 1 % to 5% by weight.
Other optional ingredients
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
Fonn of the compositions
The compositions in accordance with the invention can take a variety of
physical
forms including granular, tablet, and bar forms. The compositions are
particularly the
so-called concentrated granular detergent compositions adapted to be added to
a
washing machine by means of a dispensing device placed in the machine drum
with
the soiled fabric load.
CA 02261348 1999-O1-27
WO 98/04671 PCT/US97/12964 - -
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 O.lSmm 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 S00 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 1.6°C and 10°C.
Surfactant agglomerate particles
CA 02261348 2002-O1-04
36
The surfactant system herein is preferably present in granular compositions in
the
form of surfactant agglomerate particles, which may take the form of flakes,
prilIs,
marumes, 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 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 Mark).
In one embodiment, a high active surfactant paste comprising (l) typically
from 50%
by weight to 95% by weight, preferably 70% by weight to 85% by weight of
surfactant and (ii) optionally the alkaline source 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 another embodiment.
the paste comprises the acid source.
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 S% by weight of the alkaline source,
preferably (bi-) carbonate or percarbonate. The carbonate material is either
dry-added
or delivered via agglomerates.
In one embodiment, the citric acid is introduced by mixing it with the
nonionic
surfactant followed by spray-on. In another embodiment, the detergent
surfactant is
introduced by mixing it with nonionic surfactant followed by spray-on.
Optional
ingredients may also be applied by spraying them as a molten liquid on to
solid
components of the composition.
Laundry washings method
CA 02261348 1999-O1-27
WO 98/04671 PCT/US97/12964 -
37
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, 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
CA 02261348 2002-O1-04
38
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.
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 to the bag sufficient
product for
one washing cycle in a washing process. A portion of the washing meditun 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 wetted, undissolved, product,
this
arrangement typically comprising radiallv 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 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.
Packa ing for the compositions
Commercially marketed executions of the bleaching compositions can be packaged
in
any suitable container including those constructed from paper, cardboard,
plastic
materials and any suitable laminates.
Abbreviations used in following Examples
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WO 98/04671 _ PCT/US97/12964 -
39
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 C 1 x-C 1 y 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 C 12-15 branched primary alcohol condensed
with an
average of 3 moles of ethylene oxide
C25E5 . A C 12-15 branched primary alcohol condensed
with an
average of 5 moles of ethylene oxide
CEQ : R1COOCH2CH2.N+(CH3)3 with R1 = C11-C13
QAS . R2.N+(CH3)2(C2H4OH) with R2 = C 12 -
C 14
Soap . Sodium linear alkyl carboxylate derived
from an
80/20 mixture of tallow and coconut oils.
TFAA : C 16-C 18 alkyl N-methyl glucamide
TPKFA . C 12-C 14 topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
Zeolite A Hydrated Sodium Aluminosilicate of formula
:
Nal2(A102Si02)12~ 22H20 having a primary
particle
size in the range from 0.1 to 10 micrometers
NaSKS-6 . Crystalline layered silicate of formula
8 -Na2Si205
Citric acid Anhydrous citric acid
.
Carbonate Anhydrous sodium carbonate with a particle
: size
between 200 ~m and 900p,m
Bicarbonate Anhydrous sodium bicarbonate with a particle
: size
distribution between 400~m and 1200~sm
Silicate : Amorphous Sodium Silicate (Si02:Na20; 2.0
ratio)
Sodium sulfateAnhydrous sodium sulfate
:
Citrate : Tri-sodium citrate dehydrate of activity
86.4% with a
particle size distribution between 425P.m
and 850Pm
CA 02261348 2002-O1-04
MA/AA : Copolymer of 1:4 maleic/acrylic acid. average
molecular weight about 70.000.
CMC : Sodium carboxymethyl cellulose
Protease : Proteolytic enzyme of activity 4KNPUig sold by
NOVO Industries A/S under the trademark Savinase
Alcalase : Proteolytic enzyme of activity 3AUlg sold by
NOVO Industries A/S
Cellulase : Celluiytic enzyme of activity 1000 CEVU/g sold
by NOVO Industries A/S under the trademark
C arezvme
Amylase : Amylolvtic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the trademark
Termamyl 60T
Lipase : Lipolvtic enzyme of activity 100kLU/g sold by
NOVO Industries A/S under the trademark
Lipolase
Endoiase : Endoglunase enzyme of activity 3000 CEVU/g
sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB0~.3H~O.H~02
PB 1 : Anhydrous sodium perborate monohydrate bleach of
nominal formula NaB02.H202
Percarbonate : Sodium Percarbonate of nominal formula
2Na~C03.3H~0~
NOBS : Nonanovloxvbectzene sulfonate in the form of the
sodium salt.
TAED : Tetraacetvlethvlenediamine
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)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : l.l-hydroxyethane diphosphonic acid
CA 02261348 2002-O1-04
41
PAD : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrrolidone
and
vinylimidazole
SR.P 1 : Sulfobenzoyl end capped esters with
oxyethylene
oxy and terephthaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene
terephthalate)
short block polymer
Silicone antifoamPolydimethylsiloxane 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 1
The following detergent formulations, according to the present invention were
prepared.
B C
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
TAS 2.0 - _
CEQ 1.5 3.0 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.p
DTPMP ( 0.4 0.4 0.2
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WO 98/04671 _ PCT/IJS97/12964 -
42
Spray On
Citric acid 2.5 2.0 S.0
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 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
Example 2
The following nil bleach-containing detergent formulations of particular use
in the
washing of colored clothing, according to the present invention were prepared:
D E
Blown Powder
Zeolite A 15.0 -
Sodium sulfate - -
LAS 3.0 -
CEQ - 1.3
DTPMP 0.4 -
CMC 0.4 -
MA/AA 4.0 -
Agglomerates
T ____. _ ._ ___
CA 02261348 1999-O1-27
WO 98!04671 PCT/ITS97/12964
43
C45AS - 11.0
LAS 6.0
TAS 3.0 -
Silicate 4.0 -
Zeolite A 10.0 13.0
CMC - 0.5
M~~ - 2.0
Carbonate 9.0 7,p
Spray On
Citric acid 4.0 3.0
Perfume 0.3 0.5
C45E7 4.0 4.0
C25E3 2.0 2.0
Dry additives
M~~ - ' 3.0
NaSKS-6 - 12.0
Citrate 10.0 8.0
Bicarbonate 7.0 5.0
Carbonate 8.0 7.0
PVPVIlPVNO 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 5.0
Dry additives
Sodium sulfate 0.0 0.0
Balance (Moisture and Miscellaneous)100.0 100.0
Density (g/litre) 700 700
Example 3
The following detergent formulations, according to the present invention were
prepared:
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WO 98/04671 PCT/US97/12964 -
44
E F G
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
Silicate - 1.0 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
Citric acid 2.5 2.5 2.0
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 - 6.1 4.5
PB 1 1.0 5.0 6.0
Sodium sulfate - 6.0 -
Balance (Moisture 100 100 100
and
Miscellaneous)
Example 4
The following high density and bleach-containing detergent formulations,
according
to the present invention were prepared:
_.__.-... T _. ___.._.._..v..-..~ .__.__ .
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WO 98/04671 - PCT/L1S97/i2964
H I
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
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
Citric acid 2.0 3.0
Perfume 0.3 0.3
C45E7 2.0 2.0
C25E3 2.0 -
Dry additives
Citrate 5.0 2.0
Bicarbonate - -
Carbonate 8.0 10.0
TAED 6.0 5.0
PB 1 14.0 10.0
Polyethylene oxide of MW - 0.2
5,000,000
Bentonite clay - 10.0
Protease 1.0 1.0
Lipase 0.4 0.4
Amylase 0.6 0.6
Cellulase 0.6 0.6
Silicone antifoam S.0 5.0
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WO 98/04671 - PCT/ITS97/12964
46
Dry additives
Sodium sulfate 0.0 0.0
Balance (Moisture and 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850
Example 5
The following high density detergent formulations, according to the present
invention
were prepared:
J K
Agglomerate
C45AS 11.0 14.0
CEQ 3.0 -
Zeolite A I5.0 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
Citric acid 1.5 2.0
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 I3.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
- _._._ __...~. - -
CA 02261348 1999-O1-27
WO 98104671 - PCT/US97/12964
47
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
