Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
Detergent Granule
Technical Field
The present invention relates to a detergent granule having a diameter of from
1.0
mm to 4.5 mm, comprising an acid source and an alkali source, which are
suitable
for use in laundry washing and dish washing methods. The invention also
relates to a
process for making the detergent granule.
Background to the Invention
There is a trend amongst commercially available granular detergents
manufacturers
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. However, traditional
detergent
formulations and processes to produce the final detergent powder are not
always
satisfactory or suitable for these detergents, with higher active ingredient
concentration.
Recently, processes have been developed whereby detergent particles or
granules
can be produced in such a manner that each individual granule or particle has
a high
content of active ingredients and high density. Examples of such processes are
agglomerating and extrusion. However, the agglomerated particles or extruded
granules do not always dissolve satisfactory water, due to the increase in
their
density, the high content of various components, which are partially non-water-
soluble, their relatively large particle size (up to 4.Smm).
Therefore, the (high density) detergents, comprising these particles or
granules can
also have poor solubility properties, leading to a low rate of dissolution,
and
moreover the formation of gels, and thus to 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. Namely, gelling of the detergent is often
caused
by gelling of particles or granules, which have high content of detergent
components, especially high levels of surfactants, upon contact with water.
The gel
prevents a proportion of the detergent powder from being solubilized in the
wash
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
2
water which reduces the effectiveness of the powder. This is a particular
problem at
low water pressures and/or at lower washing temperature.
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 dispensability 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.
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, 114,647 discloses a sanitising composition comprising granules of
alkali
metal carbonate and aliphatic carboxylic acid of a particle size 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.
The Applicants have found that the problem of the poor dispensing of detergent
granules of particle size of from 1.0 to 4.5 mm, with a high content of active
ingredients, especially a high content of surfactants and especially those
detergents
with a high density, can be solved or reduced when an acid source and an
alkali
source is included in the detergent granule. We have found that addition of
such an
acid source and an alkali source in the detergent granule, improves the
solubility
and/or dispersion of the active detergent ingredients in the wash water and
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
3
eliminates or reduces the problems of fabric or machine damage by solid
detergent
particles or active ingredients remaining in the washing machine and on washed
clothes. It is believed that the acid reacts rapidly with the alkali in the
wash water to
release the gas. This helps disperse the active detergent ingredients in the
particle in
general and minimise the formation of high concentrations of ingredients and
of
insoluble clumps.
The improved dispensing of the detergent granule and the ingredients thereof
can
amount to an overall improved and more efficient performance.
Furthermore, the detergent or granule residues in the dispensing drawer or
dispensing device are reduced.
All documents cited in the present description are, in relevant part,
incorporated
1 S herein by reference.
Summary of the Invention
According to the present invention there is provided a detergent granule
having a
diameter of 1.0 to 4.5 mm, comprising an acid source and an alkali source,
capable
of reacting together in the presence of water to produce a gas. According to
the
present invention there is also provided a process for making the detergent
granule.
Detailed Description of the Invention
Dete_r;~ent trranule
The detergent granule of the present invention has a diameter of 1.0 mm to 4.5
mm
and comprises an acid source and an alkali source, capable of reacting
together in the
presence of water to produce a gas.
More preferably the diameter size of the granule is from 1.3 mm to 2.8 mm,
more
3 S preferably from 1.3 mm to 2.5 mm, even more preferably from 1.4 mm to 2.1
mm,
most preferably from 1.4 mm to 1.8 mm.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
4
The diameter size as defined herein can be determined by sieving a sample of
the
granules into a number of fractions (typically 5 fractions) on a series of
sieves, with
mazes of various diameter or aperture size. Granules with a diameter above 4.5
mm
will not be used as granules for the present invention. The mean diameter size
of the
granules can be calculated by plotting the weight fractions, obtained by the
sieving,
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 mean diameter size of the granules of the invention should in a highly
preferred
embodiment of the invention be such that no more that 3% of particles are
greater
than 2.Smm, or even 2.1 mm, in diameter and not more than 3% of particles are
less
than l.3mm in diameter.
A process for making the granules will be described below.
Components of the ~ ranule
Acid Source
In accordance with the present invention, an acid source is present in the
detergent
granule, capable of reacting with the source of alkali in the presence of
water to
produce a gas.
In detergent granule, the level of the acid source is preferably of from 0.1 %
to 50%,
more preferably from 0.5% to 25%, even more preferably from 1% to 12%, most
preferably from 1% to 7% by weight of the composition.
Preferably, 80% or more of the acid source 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 source having a particle size of about 350 microns or less. Preferably,
100% of
the acid source has a particle size of no greater than 710 microns.
Alternatively,
greater than about 38%, more preferably 38.7%, of the acid source has a
particle size
of about 350 microns or less.
The particle size of the source of acidity is calculated by sieving a sample
of the
source of acidity on a series of Tyler sieves. For example, a Tyler sieve mesh
100
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
corresponds to an aperture size of 150 microns. The weight fractions thereby
obtained are plotted against the aperture size of the sieves.
The acid source may be any suitable organic, mineral or inorganic acid, or a
5 derivative thereof, or a mixture thereof. The acid source 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, which can improve storage stability.
However, a monohydrate acid source can be useful herein. Organic acids and
their
derivatives are preferred. The acid is preferably water-soluble. Suitable
acids 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.
Source of Alkali
In accordance with the present invention the detergent granule comprises an
alkali
source, which has the capacity to react with the acid source in the presence
of water
to produce a gas. Preferably this gas is carbon dioxide, and therefore the
alkali is a
carbonate, or a suitable derivative thereof.
The detergent granule, preferably comprises 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.
In a preferred embodiment, the alkali 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 may
also be included in the detergent compositions and are also suitable sources
of
carbonate species and are described below in more detail.
Other suitable sources will be known to those skilled in the art.
The alkali 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
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
6
salt. Sodium silicate with an Si02: Na20 ratio of 2.0 is the most preferred
silicate.
Alkali metal persilicates are also suitable sources of alkali herein.
Formation of the granule
The granule of diameter size of 1.0 mm to 4.5 mm can be produced via a variety
of
methods commonly known. Preferred methods are agglomeration, pre-mixing and
spray-on and granulation. The most preferred method for making the granules of
the
invention is extrusion.
Extruded granules can generally be prepared by mixing the various detergent
components, optionally addition of powdered components and/or slip additives,
forcing the obtained mixture by pressure through the extruder holes of the
required
diameter or less, cutting of the extruded paste into extrudates (granules) of
the
required length and rounding the extrudates. WO 91/13678 and WO 91/02047
describe such processes.
In more detail the extruded granules can be made as follows. The various
detergent
granule ingredients can be mixed into one paste. Preferably, the various
detergent
components are pre-mixed in different pastes, preferably two, whereby the acid
source preferably is present in a different pre-mixed past than the alkali
source,
especially when the alkaline source is a carbonate or bicarbonate.
In a highly preferred embodiment, one pre-mixed paste comprises the alkali
source
and anionic surfactant, and additional components such as zeolite, layered
silicate,
bleach activator and cationic surfactant, and one pre-mixed paste comprises
the acid
source and nonionic surfactant. The premixed pastes will then be mixed to form
one
paste.
Optionally, water and additional detergent components, such as slip additives,
bleach, enzymes, bleach activators, stabilisers and soap can be added to the
pre-
mixed paste or pastes or to the paste as a whole, simultaneously with or
shortly after
the mixing process has started. Optionally, the bleach activators) and
enzymes) can
be dry-added to the finished extrudates or granules.
Preferably the obtained paste is coated with a slip material prior to or
simultaneously
with the introduction of the paste in the extruder. Under pressure (20 bar or
more)
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
7
the paste or coated paste is then passed through the holes (of the extruder)
of the
required diameter or less, whereafter the extruded granules are cut in to
granules of
the required length (preferably from 0.8 mm to 4.0 mm, more preferably 1.0 mm
to
3.0 mm, even more preferably from 1.3 mm to 2.5 mm).
The viscosity of the paste should be controlled to avoid cacking of the paste
in the
extruder or during mixing and to avoid the paste from blocking the extruder.
By
constant pressure, the viscosity is best controlled by heating and cooling the
paste
and/ or the extruder.
Optionally, the obtained granules or extrudates are rounded, to obtain round
or
spherical granules.
Preferably, the thus obtained gianules are dusted with a powder, preferably
zeolite,
and dried, to form equally shaped granules, and to avoid agglomeration of the
granules.
Possible granules, which do not have the required diameter size of 1.0 mm to
4.5
mm, can be removed from the granule mix by sieving.
A variety of compounds are known to be useful herein as slip additives, as
mentioned above. Preferred slip additives are those compounds which also have
a
secondary detergent function, such as certain anionic and nonionic
surfactants,
polymeric polycarboxylates, polyvinyl alcohols.
A typical agglomeration process involves mixing an effective amount of powder,
comprising the alkali and acid source, with a high active component paste,
especially
high active surfactant, 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 Name). The particle size of the resultant agglomerates is
controlled within specified limits of 1.0 mm to 4.5 mm.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
8
Optionally, additional detergent ingredients can be sprayed-on an agglomerated
particle, having a particle size of just under 1.0 mm to 4.5 mm, to obtain the
granule
of the present invention.
A high active surfactant paste, as mentioned above, comprising a mix of,
typically,
from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight
of surfactant, as described hereinafter. 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.
Additional components of the re anule
The level of the components of the detergent granule can vary, depending on
the
nature of the granule. The additional components can be detergent ingredients
traditionally employed in detergents, such as surfactants, builders, bleaches
bleach
activators, polymeric compounds, soil release polymers, enzymes, perfumes,
suds
suppressors, (lime soap) dispersants, soil suspension and anti-redeposition
agents,
corrosion inhibitors and brightners.
Surfactant
The Ievel of surfactant is preferably from 8% to 60%, more preferably from 10%
to
50%, most preferably from 14% to 30% by weight of the granule.
Preferred surfactant are anionic, nonionic and cationic surfactants and
mixtures
thereof. Preferably, at least one anionic surfactant is present. Preferably,
the anionic
surfactant is a mixture of anionic sulphate surfactant and anionic sulphonate
surfactant, whereof exemples are described below. More preferably one or more
nonionic surfactants and anionic surfactants are present. Optionally,
ampholytic,
amphoteric and zwitterionic surfactants can be present in the particle
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes,
and
species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin
and
Hearing on December 30, 1975. Further examples are given in "Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
9
suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on
March
31, 1981.
Anionic surfactant
The detergent granule in accord with the present invention preferably comprise
one
or more anionic surfactants. Essentially any anionic surfactants useful for
detersive
purposes can be comprised in the detergent composition. These can include
salts
(including, for example, sodium, potassium, ammonium, and substituted ammonium
salts such as mono- di- and triethanolamine salts) of the anionic sulfate,
sulfonate,
carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are
preferred.
The level of anionic surfactant is preferably from 2% to 40%, more preferably
from
4% to 30%, even more preferably from 5% to 25%, most preferably from 6% to 15%
1 S by weight of the granule.
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
C12-C18 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 17 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
3 5 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.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the C 1 p-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 1 S alkyl sulfate which has been
ethoxylated with
5 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.
Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxyiates, 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)-R3 wherein R is
a C~ to C 1 g alkyl group, x is from 1 to 25, Rl 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
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
11
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-I-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 (R 1 ) CH2 COOM, wherein R is a CS-C I ~ 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.
Cationic surfactants
Another preferred surfactant of the invention is one or more cationic
surfactants.
Suitable cationic surfactants include the quaternary ammonium surfactants
selected
from mono C6-C I 6, preferably C6-C 10 N-alkyl or alkenyl ammonium surfactants
wherein the remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups. Another preferred cationic surfactant is an C6-C 1 g
alkyl or
alkenyl ester of an quaternary ammonium alcohol, such as quaternary choline
esters.
The level of cationic surfactant is preferably from 0.2% to 20%, more
preferably
from 0.5% to 15%, even more preferably from I % to 10%, most preferably from 1
to 5% by weight of the granule.
Nonionic surfactant
The detergent granule of the present invention preferably contains a nonionic
surfactant. Essentially any nonionic surfactant can be used herein.
The level of nonionic surfactant is preferably from 1 % to 30%, more
preferably from
2% to 25%, even more preferably from 3% to 15%, most preferably from 4% to 12%
by weight of the granule.
Alkoxylated nonionic surfactant
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
12
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated
and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the
nonionic
condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic
ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates with propylene glycol, and the nonionic ethoxylate condensation
products with propylene oxide/ethylene diamine adducts.
Nonionic alkoxylated 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
1 S secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred
are the condensation products of alcohols having an alkyl group containing
from $ to
carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxv fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : R1 is H, CI-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl,
more
preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is
a CS-
C31 hydrocarbyl, preferably straight-chain CS-C 19 alkyl or alkenyl, more
preferably
straight-chain Cg-C 1 ~ alkyl or alkenyl, most preferably straight-chain C11-C
1 ~ alkyl
or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a
linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an
alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z
preferably will be derived from a reducing sugar in a reductive amination
reaction;
more preferably Z is a glycityl.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula:
R6CON(R~)2 wherein R6 is an alkyl group containing from 7 to 21, preferably
from
9 to 17 carbon atoms and each R~ is selected from the group consisting of
hydrogen,
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
13
C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of
from
1 to 3.
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~
1 S 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.
Optional surfactants
AmQhoteric surfactant
Optional amphoteric surfactants for use in the detergent granule include the
amine
oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from
8 to
26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2
to 3
carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3;
and each
RS is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene
oxide
group containing from 1 to 3 ethylene oxide groups. Preferred are C 10-C 1 g
alkyl
dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, lnc., Dayton, NJ.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
14
Zwitterionic surfactant
Optionally, zwitterionic surfactants can be incorporated into the detergent
granule.
S 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-Clg hydrocarbyl group, each Rl is typically C1-C3 alkyl, and
R2
is a C 1-C 5 hydrocarbyl group. Preferred betaines are C 12-18 dimethyl-
ammonio
hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
Water-soluble builder compound
The detergent granule of the present invention can 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
granule.
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
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
acid, tartronic acid and 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.
5 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described
in British Patent No. 1,387,447.
10 Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed
in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing sulfo substituents include the sulfosuccinate derivatives disclosed
in
British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448,
and
15 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.
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 granuleof the present invention may contain a partially soluble
or
insoluble builder compound, typically present at a level of from 1% to 80% by
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
16
weight, preferably from 10% to 70% by weight, most preferably from 20% to 60%
weight of the granule.
Examples of largely water insoluble builders include the sodium
aiuminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)yJ.
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)12J. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106J~ 276 H20.
Preferred crystalline layered silicates for use herein have the general
formula
NaMSix02x+I .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-
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 2,
3 or
4 and is preferably 2. The most preferred material is 8-Na2Si205, available
from
Hoechst AG as NaSKS-6.
Perhydrate bleach components
Perborate component
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
17
A preferred perhydrate bleach for use in the detergent granule of the present
invention is a perborate component.
The perborate is preferably present at a level of from 1 % to 40% by weight,
more
preferably from 6% to 25% by weight, most preferably from 13% to 20% by weight
of the granule.
The perborate is preferably in the form of a salt, normally in the form of the
alkali
metal, preferably sodium salt.
The perborate bleach is preferably a sodium perborate in the form of the
monohydrate or tetrahydrate, respectively of nominal formula NaB02H202 and
NaB02H202.3H20.
The perborate bleach may be included as the crystalline solid without
additional
protection. However, preferred executions of certain granular compositions
utilize a
coated form of the perborate bleach 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.
Other perhydrate bleaches are for example a metal percarbonates, particularly
sodium percarbonate. 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 optinal inorganic perhydrate salt of
use
in the detergent granules herein.
Organic perox~acid bleaching system
A preferred feature of detergent granules 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, such as the perborate bleach
of the
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
18
claimed invention. 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.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in
a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors may be represented as
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 at 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 granule.
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-836988,
864798,
1147871, 2143231 and EP-A-0170386.
Leavinggrouns
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
3 S bleaching composition.
SUBSTITUTE SHEET (RULE 26)
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
19
Preferred L groups are selected from the group consisting of:
Y R3 RaY
-O ~ , -O ~ Y , and -O
O O
-N-C-R~ -N N -N-C-CH-R4
' ~ ~ R3 Y ,
Y
R3 Y
-O-C H=C-C H=C HZ -O-C H=C-C H=C H2
IO ,
O C H -O Y O
If ~ 2 ~ ~ ~NR4
-O-C-R~ -N~C,NR4 , -NBC/ ,
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 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.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
The preferred soiubiiizing groups are -SO, M+, -CO -M+. -S04 M+, -N+(R')4X
and O<--N(R')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
5 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.
10 AIkyl percarboxylic 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 1 N 1 tetra acetylated alkylene diamines wherein the alkylene group
contains
from 1 to 6 carbon atoms, particularly those compounds in which the alkyiene
group
contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is
particularly preferred.
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.
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
C If ~ II (I
R5 O or RS O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group containing from 1 to 14 carbon atoms, and RS is H or an alkyl group
SUBSTITUTE SHEET (RULE 26)
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
21
containing 1 to 10 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,precursors
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.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
22
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK
Patent
Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650,
08/298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred
cationic peroxyacid precursors of the N-acylated caprolactam class include the
trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium
methylene alkyl caprolactams.
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
II
CEO
I
wherein R1 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 15% by weight, more
preferably from 1 % to 10% by weight of the granule.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the following general formulae:
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
23
R~-C -N-R2-C-OOH
IO
or
R~ -N-C-R2-C-OOH
II
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-01703 86.
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.
Heaw metal ion seauestrant
The granule of the present 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 granule.
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.
SUBSTITUTE SHEET (RULE 26)
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
24
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
~i-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-
N-
monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-
509,382
are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes
suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859
describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid
and 2-
phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-
disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Enzyme
Another preferred ingredient useful in the detergent granules of the invention
is one
or more additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, esterases, cellulases,
pectinases,
lactases and peroxidases conventionally incorporated into detergent
compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem
by Gist-Brocades, those sold by Genencor International, and those sold under
the
tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
incorporated into the compositions in accordance with the invention at a level
of
5 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
10 tradename Rapidase by Gist-Brocades, and those sold under the tradename
Termamyl 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 granule.
i 5 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 granule.
The lipase may be fungal or bacterial in origin being obtained, for example,
from a
20 lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp.
including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from
chemically or genetically modified mutants of these strains are also useful
herein. A
preferred lipase is derived from Pseudomonas pseudoalcali enes, which is
described
in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanu~inosa and expressing the gene in Asner illus oryza, as host, as described
in
European Patent Application, EP-A-0258 068, which is commercially available
from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This
lipase
is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7,
1989.
Or anic polymeric compound
Organic polymeric compounds are preferred additional components of the
granule,
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
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
26
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 granules
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 granule.
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
1 S 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, 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.
Another organic compound, which is a preferred clay dispersant/ anti-
redeposition
agent, for use herein, can be the ethoxylated cationic monoamines and diamines
of
the formula:
CA 02284187 1999-09-10
WO 98/42811 27 PCT/IB9$/00357
CH3 CH3
X -~ OCH CH ) N+- CH - CH CH N+- CH
2 2 n ~ 2 2 ~ 2)a b f 2CH20 ~ X
(CH2CH20~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C1-C4
alkyl
or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to
20,
preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0;
for
cationic monoamines (b=0), n is at least 16, with a typical range of from 20
to 35;
for cationic diamines (b=1), n is at least about 12 with a typical range of
from about
12 to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-
011965 and US 4,659,802 and US 4,664,848.
Suds suppressing system
The detergent granules, 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 granule.
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
SUBSTITUTE SHEET (RULE 26~
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
28
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 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 1:0.9 to 1:1.1, at a level of from 0.5% to
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
29
10%, preferably 1 % to 10% by weight; a particularly preferred silicone
glycol rake copolymer of this type is DC0544, commercially available from
DOW Corning under the tradename DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C 18
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 carrier
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 softening system
The granule 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 Nos. 3,862,058, 3,948,790, 3,954,632 and
4,062,647. European Patents Nos. 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.
Polvmeric dye transfer inhibitine a ents
The detergent granules 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-vinylpyrroiidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
a) Polyamine N-oxide~olymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
P
I
()
R
wherein P is a polymerisable unit, and
O O O
10 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 part of these groups.
The N-O group can be represented by the following general
structures
O
1
O
(R1) x-N-(R2)Y
~(R )
3 z or N-(R1)x
wherein R1, R2, 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
SUBSTITUTE SHEET (RULE 26)
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
31
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 pyrndine, 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 part of said R group. Examples of these classes are polyamine oxides
wherein R is a heterocyclic compound such as pyrridine, pyrrole, 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-vinylpyrrolidone and N-vinvlimidazole
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
0.2.
cwvinylnyrrolidone
The detergent granules herein may also utilize polyvinylpyrrolidone ("PVP")
having
an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are commercially valuable 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-15 is also available from ISP Corporation. Other suitable
polyvinylpyrrolidones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98100357
32
d) Polyvinyloxazolidone
The detergent granules 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 granules 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 granules 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 OOlj O C C O NOON
ON H H N O
R2 S03M S03M Rt
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 cation 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'-stilbenedisuifonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
tradename
CA 02284187 1999-09-10
WO 98/42811 PCTlIB98/00357
33
Tinopal-LINPA-GX by Ciba-Geigy Corporation. Tinopal-LJNPA-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-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-
6-(N-2-hydroxyethyi-N-methylamino)-s-triazine-2-yl)amino]2,2'-
stilbenedisulfonic
acid disodium salt. This particular brightener species is commercially
marketed
under the tradename Tinopal 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-aniIino-6-morphilino-s-triazine-2-
yl)aminoJ2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species
is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98100357
34
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into the detergent
granules.
Suitable cationic fabric softening agents include the water insoluble tertiary
amines
or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011
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 ingredients
Other optional ingredients suitable for inclusion in the particle and the
detergent
compositions include perfiunes, colours and filler salts, with sodium chloride
and
1 S sulfate being a preferred filler salt.
Densi
The bulk density of granules is typically of at least 650 g/litre, more
preferably from
850 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 overFll 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.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
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.
Laundry washine 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 granules in accord with the
10 invention. By an effective amount of the detergent granules it is meant
from 40g to
3008 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.
1 S 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
20 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
25 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.
30 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
35 providing transient localised high concentrations of product in the drum of
the
washing machine at this stage of the wash cycle.
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
36
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.
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
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 arrangement to prevent egress of
wetted,
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 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, OOI 1501, 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.
Packagin~for the compositions
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
37
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. A preferred packaging execution is
described
in European Application No. 94921505.7.
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 C14-C15 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 C12-15 branched primary alcohol condensed
with an
average of 3 moles of ethylene oxide
C25E5 . A C 12-1 S branched primary alcohol condensed
with an
average of 5 moles of ethylene oxide
CEQ : RICOOCH2CH2.N+(CH3)3 with R1 = C11-C13
QAS . R2.N+(CH3)2(C2I-i4OH) 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 1 g 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~ 27H20 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
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
38
Carbonate : Anhydrous sodium carbonate with a particle
size
between 200 p,m and 900~tm
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size
distribution between 400p.m and 1200p,m
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
particle size distribution between 425~m
and 850~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid,
average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
Protease : Proteolytic enzyme of activity 4KNPU/g
sold by
NOVO Industries A/S under the tradename
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 tradename
Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g
sold by
NOVO Industries A/S under the tradename
Termamyl 60T
Lipase . Lipolytic enzyme of activity 100kLU/g
sold by
NOVO Industries A/S under the tradename
Lipolase
Endolase . Endoglunase enzyme of activity 3000 CEVU/g
sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
PB 1 : Anhydrous sodium perborate monohydrate
bleach of
nominal formula NaB02.H202
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03.3H202
NOBS . Nonanoyloxybenzene sulfonate in the form
of the
sodium salt.
TAED : Tetraacetylethylenediamine
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
39
DTPMP : Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under
the
Trade name 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'-his(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
SR.P 1 : Sulfobenzoyl end capped esters with
oxyethylene
oxy and terephtaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
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.
In the following Examples all levels are quoted as % by weight of the
composition:
Example 1
The following laundry detergent granules A to F were prepared in accord with
the
invention:
A B C D E F
TAS 8.5 3.5 5.5 8.0 6.8 7.5
LAS 6.0 7.0 6.2 8.0 6.8 7.0
C25E3 4.4 6.7 6.5 5.8 6.0 5.4
citrate 1.0 0.5 - 0.7 0.4 0,g
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
Zeolite A 18. 18. I 26.0 15.0 24.0 10.5
I
Carbonate 9.0 12.0 13.0 17.0 8.5 7.0
Citric acid 3.4 1.4 I.4 0.5 5.0 0.8
Silicate 8.1 S.I 6.1 12.0 15.0 18.0
Sodium sulfate1.0 - 2.0 2.4 - -
PB1 9.0 10.0 9.0 12.0 8.0 13.0
PB4 5.5 7.0 I.5 4.5 3.5 2.5
TAED 0.3 0.2 - 0.5 0.5 0. S
HEDP 4.3 5.3 1.5 0.6 1.8 0.4
MA/AA 0.2 0.2 2.5 0.9 1.1 0.2
CMC 1.0 0.4 0.5 0.2 1.2 1.6
amylase 0.3 0.4 0.6 1.1 1.0 0.1
cellulase - 0.3 0.5 - 0.2 -
lipase 1.0 2.0 0.5 3.0 2.5
protease 0.3 0.3 0.3 0.3 0.3 0.3
Perfume 0.5 0.2 0.3 0.2 0.5 0.5
Silicone
antifoam
Misc/minors
to
100%
850 850 850 850 850 850
Densi in litre
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
41
Example 2
The following laundry detergent granules G to L were prepared in accord with
the
invention:
G H I J K L
Paste I
TAS 4.5 - 5.5 8.0 6.8 7.6
LAS 8.0 12.0 6.2 8.0 6.8 7.0
citric acid 2.0 4.0 7.0 0.5 0.8 1.0
citrate 1.0 0.5 - 0.7 0.4 0.8
Zeolite A 18.1 18.1 26.0 15.0 24.0 10.0
HEDP 0.3 0.2 0.9 - 0.5 -
MA/AA 4.3 5.0 6.5 5.8 3.0 -
CMC 0.2 0.4 0.9 1.0 2.5 3.0
Paste II
C25E3 5.5 3.5 7.5 8.7 4.5 2.0
Carbonate 6.9 15.3 17.9 21.0 11.0 13.0
Silicate 3.4 1.4 1.4 4.5. 5.0 3.0
Sodium sulfate 8.1 5.1 6.1 12.0 15.0 18.0
additives
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
42
PB1 1.0 - 2.0 2.4 -
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone antifoam0.5 0.2 0.3 0.2 0.5 0.5
PB4 9.0 10.0 3.0 12.0 5.0 13.0
d added
amylase 1.0 0.4 0.5 0.2 - -
cellulase 0.3 0.4 0.6 1.1 1.0 -
lipase - 0.3 0.5 - 0.2 -
protease . 1.0 2.0 0.5 3.0 2.5
TAED S.5 7.0 1.5 4.5 3.5 8.5
Misc/minors to
100%
Density in g/litre850 850 850 850 850 650
I I 1
Example 3
The following granular laundry detergent compositions were prepared in accord
with the invention:
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
43
M N p
LAS 5.61 4.76 7.5 8.5
TAS 1.86 1.57 3.5 1.4
C45AS 2.24 3.89 2.2 3.5
C25AE3S 0.76 1.18 1.1 1.1
C45E7 - 5.0 4.0 -
C25E3 5.5 - - 3.0
CEQ 2.0 2.0 -
QAS _ _ _ 1.0
STPP _ _ - _
Zeolite A 19.5 19.5 19.5 16.5
NaSKS-6/citric acid 10.6 10.6 10.6 10.6
(79:21 )
Carbonate 21.4 21.4 16.4 18.2
Bicarbonate 2.0 2.0 2.0 -
Silicate - - - 3.0
Sodium sulfate - 14.3 - -
PB4 13.7 15.0 14.0 17.5
TAED 3.1 - 4.2 -
CA 02284187 1999-09-10
WO 98/42811 PCT/IB98/00357
44
DETPMP 0.2 0.2 0.2 0.2
HEDP 0.3 0.3 0.3 0.3
Protease 0.85 0.85 0.85 0.85
Lipase 0.15 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28 0.28
Amylase 0.1 0.1 0.1 -.1
MA/AA 1.6 1.6 1.6 1.6
CMC 0.4 0.4 0.4 0.4
Photoactivated bleach 27 ppm 27 ppm 27 ppm 27 pp
(ppm)
Brightener 1 0.19 0.19 0.19 0.19
Brightener 2 0.04 0.04 0.04 0.04
Perfume 0.3 0.3 0.3 0.3
Silicone antifoam 2.4 2.4 2.4 2.4
Citric acid 1.5 3.5 4.0 4.5
Minors/misc to 100%
