Note: Descriptions are shown in the official language in which they were submitted.
CA 02261349 1999-O1-27
WO 98/04668 PCT/US97/12963
A Detereent Composition
Technical Field
The present invention relates to a detergent composition comprising high
levels of
perborate bleach and a tri- or mufti protonic acid and alkali source. The
detergent
compositions are useful for laundry and dish washing methods.
Backr~round 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 as bleach. Such detergents offer
greater
convenience to the consumer. The desire for such concentrated products ensures
that
the amount of filler materials are reduced and packaging materials will,
ultimately, be
disposed of.
Amongst consumers there is also a need for detergents which provide improved
bleachable stain removal. Therefore, in the recent past detergents have been
developed
which contain various types of bleaches, which can be incorporated at high
levels.
Detergents, comprising high levels of bleach can lead to poor solubility
properties,
arising from low rate of dissolution or 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. This poor
dispensing is often caused by gelling of particles, which have high levels of
surfactant
and especially perborate bleach, 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 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.
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2
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.This
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 particulate 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 a problem of the poor dispensing of perborate
bleach
and particularly perborate monohydrate bleach, is the formation of a localized
high
concentratation of bleach, which will contact the fabric. This can lead to
fabric
damage. This problem can especially be encountered with detergent compositions
comprising high levels of perborate (monohydrate) bleach. However, these high
concentrations are often required for an optimum bleachable stain removal.
The problem of poor dispensing may be exacerbated when high levels of
surfactants
are present. High levels of surfactants can lead to problems of solid
detergent
particles remaining in the washing machine and on washed clothes.
The Applicants now have found that this particular problem can be solved or
reduced
when there is provided a tri- or mufti protonic acid, such as a citric acid
and an alkali
source, capable of producing a gas when reaction together. We have found that
the
addition of such an acid and an alkali source to a detergent composition,
containing
perborate bleach, improves the solubility and/or dispersion of the detergent
and the
perborate bleach therein, in the wash water and eliminates or reduces the
problems of
fabric damage by high concentrate bleach remaining in the washing machine and
on
washed clothes.
CA 02261349 2001-12-20
The improved dispensing of the perborate bleach amounts to an overall improved
and
more efficient performance and particularly improved bleachable stain removal.
Furthermore, it has been found that if the detergent compositions also
comprise high
levels of surfactants, such as anionic, cationic and nonionic surfactants,
dispensing of
surfactants can also be improved by the inclusion of these acid and an alkali
sources
(capable of producing a gas when reaction together), whilst the performance of
the
surfactants is maintained. This eliminates or reduces the problems of solid
surfactant
particles remaining in the washing machine and on washed clothes and it helps
to
minimise the formation of high concentrations of insoluble clumps.
Furthermore,
since the surfactants are more efficiently dispensed into the wash water, the
overall
performance of the surfactants is more efficient and an overall improved
cleaning,
stain removal a.nd soil suspending can be achieved.
Summary of the Invention
According to the present invention there is provided a detergent composition
comprising
an anionic surfactant, perborate bleach at a level of at least 13% of a
perborate
component, by weight of the composition, citric acid and an alkali source
wherein said
citric acid and alkali source are capable of reacting together in the presence
of water to
produce a gas and a cationic C6-C~g N-alkyl or alkenyl mono- or bis-
alkoxylated amine
surfactant wherein the weight ratio of anionic surfactant to cationic
surfactant is from
15:1 to 1:1.
Detailed Description of the Invention
Alkali Source
In accordance with the present invention, an alkali source is present in the
detergent
composition such that it has the capacity to react with the acid to produce a
gas.
Preferably this gas is carbon dioxide, and therefore the alkali is a
carbonate, or a
suitable derivative thereof.
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WO 98/04668 PCT/US97/12963
4
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 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.
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 l .b to 2.0 being preferred, and 2.0 ratio
being most
preferred. The silicates may be in the form of either the anhydrous salt or a
hydrated
salt. Sodium silicate with an Si02: Na20 ratio of 2.0 is the most preferred
silicate.
Alkali metal persilicates are also suitable sources of alkali herein.
Other suitable sources will be known to those skilled in the art.
Tri-or multi protonic acid
In accordance with the present invention, a tri- or multi protonic acid is
present in the
detergent composition such that the it is capable of reacting with the source
of alkali
in the presence of water to produce a gas.
The source of acidity may be any suitable tri-protonic or multi-protonic acid
or
mixtures thereof. Preferably, the acid source is a tri-protonic acid, most
preferably
this is a citric acid.
Derivatives include a salt or ester of the acid. The source of acidity is
preferably non-
hygroscopic, which can improve storage stability. However, a hydrated and
especially
monohydrate acidic source can be useful herein. The acid is preferably water-
soluble.
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WO 98/04668 PCT/US97/12963
The acid is preferably present at a level 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. The present invention allows the use of levels
as low as
5 about 0.25% to about 5%.
Preferably, 80% or more of the acid has a particle size in the range of from
about 1 SO
microns to about 710 microns, with preferably 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 has a particle size of about 710 microns or less. Alternatively,
greater than
about 38%, more preferably 38.7%, of the particulate acid source has a
particle size of
about 350 microns or less.
The particle size of the acid is calculated by sieving a sample of the source
of acidity
on a series of Tyler sieves. For example, a Tyler seive mesh 100 corresponds
to an
aperature size of 150 microns. The weight fractions thereby obtained are
plotted
against the aperture size of the sieves.
Perborate component
Another essential ingredient of the detergent compositions of the present
invention is
a perborate component, present at a level of at least 13% by weight of the
composition.
More preferably, the perborate is present at a level of from 13% to 40% by
weight,
even more preferably from 15% to 30% by weight and most preferably from 17% to
25% by weight of the compositions.
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 most preferably a sodium perborate in the form of the
monohydrate, of nominal formula NaB02H202. Another highly preferred perborate
bleach is the tetrahydrate, of nominal formula NaB02H202.3H20.
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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.
Preferably, the detergent composition comprises a bleach activator, such as
TAED or
a hydrophobic bleach activator, as described below. Preferably the activator
is present
at a level of from 0.5% to 15%, more preferably from 1.0% to 10%, most
preferably
from 2.0% to 6% by weight of the detergent composition.
Optionally, a bleach catalyst can be present, as described below.
Surfactants
In a highly preferred embodiment of the invention the detergent compositions
comprise one or more surfactants, selected from the group consisting of
anionic,
cationic and nonionic surfactants.
The surfactant or surfactants are preferably present at a level of from 1 % to
60%,
more preferably from 3% to 45%, most preferably from 7% to 35% by weight of
the
detergent composition.
Anionic surfactant
The detergent composition of the present invention preferably comprises one or
more
anionic surfactants. Any anionic surfactant useful for detersive purposes is
suitable.
Examples include salts (including, for example, sodium, potassium, ammonium,
and
substituted ammonium salts such as mono-, di- and triethanolamine salts) of
the
anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic
sulfate
surfactants are preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18
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WO 98/04668 PCTIUS97/12963
7
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6-C 14
diesters), N-acyi 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.
The anionic surfactant can be present at a level of 0.5% to 60%, preferably at
a level
of from 3% to 50%, more preferably of from 5% to 35%, most preferably from 6%
to
20% by weight of the composition.
The ratio of the anionic surfactant to the cationic surfactant is preferably
from 25:1 to
1:3, more preferably from 15:1 to 1:1. most preferably from 10:1 to 1:1.
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
Cg-C22 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
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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
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 1 and 8
carbon
atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a
carboxyl unit connected to a secondary carbon. Preferred secondary soap
surfactants
for use herein are water-soluble members selected from the group consisting of
the
water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-
propyl-
1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps
may also be included as suds suppressors.
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,
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R 1 is a C 1-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 surfactant
Another preferred component of the detergent composition of the invention is a
cationic surfactant, which can be present at a level of from 0.1 % to 30% by
weight of
the detergent composition.
Preferably the cationic surfactant is selected from the group consisting of
cationic
ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis
alkoxylated amine surfactants and mixtures thereof.
The cationic surfactant is preferably present at a level of from 0.1 % to 20%,
more
1 S preferably from 0.4% to 12%, most preferably from 0.5% to 5% by weight of
the
detergent composition.
The ratio of the anionic surfactant to the cationic surfactant is preferably
from 25:1 to
1:3, more preferably from 15:1 to 1:1. most preferably from 10:1 to 1:1.
The ratio of cationic surfactant to nonionic surfactant is preferably from
1:30 to 10:1,
more preferably from 1:20 to 1:1, most preferably from 1:12 to 1:2.
Cationic ester surfactant
The cationic surfactant may comprise a cationic ester surfactant.
If present in the detergent composition of the invention, the cationic ester
surfactant is
preferably present at a level from 0.1 % to 20.0%, more preferably from 0.4%
to 12%,
most preferably from 0.5% to 5.0% by weight of the detergent composition.
The cationic ester surfactant is preferably a water dispersible compound
having
surfactant properties comprising at least one ester (i.e. -COO-) linkage and
at least one
cationically charged group.
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Suitable cationic ester surfactants, including choline ester surfactants, have
for
example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are
separated
5 from each other in the surfactant molecule by a spacer group consisting of a
chain
comprising at least three atoms (i.e. of three atoms chain length), preferably
from
three to eight atoms, more preferably from three to five atoms, most
preferably three
atoms. The atoms forming the spacer group chain are selected from the group
consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with
the
10 proviso that any nitrogen or oxygen atom in said chain connects only with
carbon
atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e.
peroxide), -
N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for
example -
CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the
spacer group chain comprises only carbon atoms, most preferably the chain is a
1 S hydrocarbyl chain.
Preferred cationic ester surfactants are those having the formula:
RZ
RS
R1O _ (CH)n0 (X)u - ( C H 2 )m (y)v (C H 2 )t _ N ~ R3 M_
b
a
R4
wherein Rl is a CS-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-
.
N+(R.6R~Rg)(CH2)S; X and Y, independently, are selected from the group
consisting
of COO, OCO, O. CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at
least one of X or fir' is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4,
R6, R~, and Rg are independently selected from the group consisting of alkyl,
alkenyl,
hydroxyalkyl and hydroxy-alkenyl groups having from 1 to 4 carbon atoms and
alkaryl groups; and RS is independently H or a C1-C3 alkyl group; wherein the
values
of m, n, s and t independently lie in the range of from 0 to 8, the value of b
lies in the
range from 0 to 20, and the values of a, a and v independently are either 0 or
1 with
the proviso that at least one of a or v must be l; and wherein M is a counter
anion.
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Preferably M is selected from the group consisting of halide, methyl sulfate,
sulfate,
and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
In a preferred aspect, the cationic ester surfactant is selected from those
having the formula:
R2
R5
Rq O (CH)n0 (X) - (CH2)m - N ~ R3 M_
b
a
R4
wherein R1 is a CS-C31 linear or branched alkyl, alkenyl or alkaryl chain; X
is
selected from the group consisting of COO, OCO, OCOO, OCONH and NHCOO;
R2, R3, and R4 are independently selected from the group consisting of alkyl
and
hydroxyalkyl groups having from 1 to 4 carbon atoms; and RS is independently H
or a
Cl-C3 alkyl group; wherein the value of n lies in the range of from 0 to 8,
the value of
b lies in the range from 0 to 20, the value of a is either 0 or l, and the
value of m is
from3to8.
More preferably R2, R3 and R4 are independently selected from a C 1-C4 alkyl
group
and a C1-C4 hydroxyalkyl group. In one preferred aspect at least one,
preferably only
one, of R2, R3 and R4 is a hydroxyalkyl group. The hydroxyalkyl preferably has
from
1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2
carbon
atoms. In another preferred aspect at least one of R2, R3 and R4 is a C2-C3
alkyl
group, more preferably two C2-C3 alkyl groups are present.
In a preferred aspect two of R2, R3 and R4 and the nitrogen of the
cationically
charged group from part of a ring structure. Preferably, the ring structure
contains
another nitrogen atom or more preferably, an oxygen atom, or mixtures thereof.
Preferably, the ring structure contains 5 to 8 atoms, most preferably 6 atoms.
CA 02261349 2001-12-20
12
1n a highly preferred aspect two of R2, R3 and R4 and the nitrogen of the
cationically
charged group from part of a morpholino ring structure or a substituted
morpholino
ring structure. Highly preferred cationic ester surfactants of this type are
the esters
having the formula:
R5
R O I M_
(CH)~O (X) (CHZ)m--N p
b
a R9
wherein R1 is a CS-C31 linear or branched alkyl, alkenyl or alkaryi chain; X
is
selected from the group consisting of COO, OCO, OCOO, OC~ONH and NHCOO; Rg
is selected from the group consisting of alkyl, alkenyl, hydroxyalkyl and
hydroxy-
alkenyl groups having from 1 to 4 carbon atoms and alkaryl groups; and RS is
independently H or a C 1-C3 alkyl group; wherein the value of n lies in the
range of
from 0 to 8, the value of b lies in the range from 0 to 20, the value of a is
either 0 or 1,
and the value of m is from 3 to 8.
More preferably R2, R3 and R4 are independently selected from a C1-C4 alkyl
group
and a C 1-C4 hydroxyalkyl group. In one preferred aspect at least one,
preferably only
one, of R2, R3 and R4 is a hydroxyalkyl group. The hydroxyalkyl preferably has
from
1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2
carbon
atoms.1n another preferred aspect at least one of R2, R3 and R~ is a C2-C3
alkyl
group, more preferably two C2-C3 alkyl groups are present.
Highly preferred water dispersible cationic ester surfactants are the esters
having the
formula:
CH3
R~ -C-O-(CH2)rn-N+-CH3 M'
CH3
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where m is from 1 to 4, preferably 2 or 3 and wherein R I is a C I I -C 19
linear or
branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl
choline ester
quaternary methylammonium halides (RI=CIA alkyl), palmitoyl choline ester
quaternary methylammonium halides (Rl=CI5 alkyl), myristoyl choline ester
quaternary methylammonium halides (R I=C 13 alkyl), lauroyl choline ester
methylammonium halides (RI=CI I alkyl), cocoyl choline ester quaternary
methylammonium halides (R 1=C I I _C 13 alkyl), tallowyl choline ester
quaternary
methylammonium halides (RI=C15_CI~ alkyl), and any mixtures thereof.
Other suitable cationic ester surfactants have the structural formulas below,
wherein d
may be from 0 to 20.
IS
O CH3
R -O-~-( CH )-C-O-CH CH -N~ CH M
1 2 d 2 2 ' 3
CH3
CH3 O O CH3
M CH3-N ~ CH2-CH2-O-C-( CHz ) a C-O-CH2-CH2-N~ CH3M
CH3 CH3
In a preferred aspect the cationic ester surfactant is hydrolysable under the
conditions
of a laundry wash method.
The particularly preferred choline esters, given above, may be prepared by the
direct
esterification of a fatty acid of the desired chain length with
dimethylaminoethanol, in
the presence of an acid catalyst. The reaction product is then quaternized
with a
methyl halide, preferably in the presence of a solvent such as ethanol, water,
propylene glycol or preferably a fatty alcohol ethoxylate such as C I 0-C 1 g
fatty
alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy
groups per
mole forming the desired cationic material. They may also be prepared by the
direct
esterification of a long chain fatty acid of the desired chain length together
with 2-
haloethanol, in the presence of an acid catalyst material. The reaction
product is then
quaternized with trimethylamine, forming the desired cationic material.
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14
Cationic mono-alkoxylated amine surfactants
The cationic surfactant of the present invention can contain a cationic mono-
alkoxylated amine surfactant, which has the general formula:
Rl /ApR4
~N+ X_
R2~ ~R3
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to
about
11 carbon atoms; R2 and R3 are each independently alkyl groups containing from
one
to about three carbon atoms, preferably methyl; R4 is selected from hydrogen
(preferred), methyl and ethyl, X- is an anion such as chloride, bromide,
methylsulfate,
sulfate, or the like, to provide electrical neutrality; A is selected from C1-
C4 alkoxy,
especially ethoxy (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; and
p is
from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.
Highly preferred cationic mono-alkoxylated amine surfactants for use herein
are of the
formula
R1\ /(CH2CH20)i-S H
\N+ XO
CH3/ \CH3
wherein R 1 is C6-C 1 g hydrocarbyl and mixtures thereof, preferably C6-C 14,
especially C6-C 11 alkyl, preferably Cg and C 10 alkyl, and X is any
convenient anion
to provide charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (E0) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr
and/or i-Pr units.
_____T _~-...._ ____._ ___...,..__._...~._
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When used in granular detergent compositions cationic mono-alkoxylated amine
surfactants wherein the hydrocarbyl substituent R1 is C6-C11, especially C10,
are
preferred, because they enhance the rate of dissolution of laundry granules,
especially
under cold water conditions, as compared with the higher chain length
materials.
S
The levels of the cationic mono-alkoxylated amine surfactants used in
detergent
compositions of the invention can range from 0.1% to 20%, more preferably from
0.4% to 12%, most preferably from 0.5% to 5.0% by weight of the composition.
10 Cationic bis-alkoxylated amine surfactant
The cationic surfactant of the invention can be a cationic bis-alkoxylated
amine
surfactant, which has the general formula:
R\ /ApR3
\N+ X
R2~ ~A,qRa
wherein R 1 is an alkyl or alkenyi moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about i6 carbon atoms, more preferably 6 to about 1 l,
most
preferably from about 8 to about 10 carbon atoms; R2 is an alkyl group
containing
from one to three carbon atoms, preferably methyl; R3 and R4 can vary
independently
and are selected from hydrogen (preferred), methyl and ethyl, X- is an anion
such as
chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide
electrical
neutrality. A and A' can vary independently and are each selected from C1-C4
alkoxy,
especially ethoxy, (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; p
is
from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30,
preferably 1
to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
R\ +/CH2CHZOH
N X
CH3/ 'CHZCH20H
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WO 98/04668 PCT/~TS97/12963
16
wherein R1 is C6-C I g hydrocarbyl and mixtures thereof, preferably Cg, Cg, C
10,
C 12~ C 14 alkyl and mixtures thereof. X is any convenient anion to provide
charge
balance, preferably chloride. With reference to the general cationic bis-
alkoxylated
amine structure noted above, since in a preferred compound R1 is derived from
(coconut) C 12-C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and
A'qR4 are
each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include
compounds of
the formula:
R~ /(CH2CH~0)pH
N+ X-
RZ'~ ~(CH2CH20)qH
wherein R I is C6-C I g hydrocarbyl, preferably C6-C I4 alkyl, independently p
is 1 to
about 3 and q is 1 to about 3, R2 is CI-C3 alkyl, preferably methyl, and X is
an anion,
especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (E0) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20]
and [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO
and/or Pr
and/or i-Pr units.
When used in granular detergent compositions in accord with the invention,
cationic
bis alkoxylated amine surfactants wherein the hydrocarbyl substituent RI is C6-
CI I,
especially Cg or CIO, are preferred cationic surfactants, because they enhance
the rate
of dissolution of laundry granules, especially under cold water conditions, as
compared with the higher chain length materials.
The levels of the cationic bis-alkoxylated amine surfactants used in detergent
compositions of the invention can range from 0.1 % to 20%, preferably from
0.4% to
I2%, most preferably from 0.5% to about 5.0%, by weight of the detergent
composition.
Alkoxylated nonionic surfactant
_ ._ .._. _..... ____.___.. _. ..____._._
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WO 98/04668 PCT/US97/12963
17
Another preferred surfactant in accord with the detergent composition of the
invention
is a nonionic surfactant present at a level of from 0.1 % to 40%, more
preferably from
0.2% to 20% by weight, most preferably from 0.5% to 5% by weight of the
detergent
composition.
S
The ratio of cationic surfactant to nonionic surfactant is preferably from
1:30 to 10:1,
more preferably from 1:20 to 1:1, most preferably from 1:12 to 1:2.
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
secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred
are the condensation products of alcohols having an alkyl group containing
from 8 to
20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula 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 alkenyi, 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 polyhydroxyhydrocarbyl having a
linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an
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18
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.
A preferred nonionic polyhydroxy fatty acid amide surfactant for use herein is
a C 15-
C 17 alkyl N-methyl glucamide. The ratio of polyhydroxy fatty acid amide to
cationic
ester surfactant is preferably between 1:1 to 1:8, more preferably 1:2.5. It
has been
found that such surfactant systems are able to reduce 'lime soap' formation
and
deposition of encrustation on the fabric.
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, C 1-C4
alkyl,
C 1-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic alk~polvsaccharide 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
carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing from 1.3 to 10 saccharide units.
25 Preferred alkylpolyglycosides have the fonmula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
30 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.
Additional detergent components
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19
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 surfactants, additional bleaches, builders, organic
polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil
suspension and anti-redeposition agents and corrosion inhibitors.
Additional surfactant
The detergent compositions of the invention cancontainsone or more surfactants
selected from ampholytic, amphoteric and zwitterionic surfactants and mixtures
thereof.
A typical listing of 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 suitable cationic
surfactants is given
in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
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 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.
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A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
5
Zwitterionic surfactants can also be incorporated into the detergent
compositions or
components thereof in accord with the invention. These surfactants can be
broadly
described as derivatives of secondary and tertiary amines, derivatives of
heterocyclic
secondary and tertiary amines, or derivatives of quaternary ammonium,
quaternary
I O 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 1 is typically C 1-C3 alkyl, and R2
is a C 1-
15 CS hydrocarbyl group. Preferred betaines are C12_18 dimethyl-ammonio
hexanoate
and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
Complex betaine surfactants are also suitable for use herein.
Water-soluble builder compound
The detergent compositions of the present invention preferably contain a water-
soluble builder compound, typically present at a level of from 1 % to 80% by
weight,
preferably from 10% to 70% by weight, most preferably from 20% to 60% by
weight
of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or
their salts in which the polycarboxylic acid comprises at least two carboxylic
radicals
separated from each other by not more that two carbon atoms, borates,
phosphates,
and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
CA 02261349 2001-12-20
2I
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 fiunaric acid, as well as the ether carboxylates and the sulfinyl
carboxylates.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates, aconitrates and citraconates as well as succinate derivatives such
as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, 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, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the
sulfonated
pyrolysed citrates described in British Patent No. 1,439,000. Preferred
polycarboxylates are hydroxycarboxylates containing up to three carboxy groups
per
molecule, more particularly citrates.
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 polymetalphosphate in which the degree of polymerization ranges from
about
6 to 21, and salts of phytic acid.
Parllal1u 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
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WO 98/04668 PCT/US97/12963
22
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[(A102)z(Si02)y].
xH20 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to
0.5 and x
is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate material are in hydrated form and are preferably crystalline,
containing from 10% to 28%, more preferably from 18% to 22% water in bound
form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS
and mixtures thereof. Zeolite A has the formula
Na 12 [A102) 12 (Si02)12]~ X20
wherein x is from 20 to 30, especially 27. Zeoiite X has the formula Nag6
[(A102)g6(Si02)106]~ 276 H20.
Preferred crystalline layered silicates for use herein have the general
formula
NaMSix02x+1.yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from
0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-
A-
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.
Additional perhvdrate bleaches
Additional to the perborate bleach, a metal percarbonates, particularly sodium
percarbonate can be an optinal perhydrates herein. Sodium percarbonate is an
addition
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WO 98/04668 PCT/L1S97/12963
23
compound having a formula corresponding to 2Na2C03.3H202, and is available
commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optinal inorganic
perhydrate
salt of use in the detergent compositions herein.
Organic_peroxvacid bleaching s s
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, such as the perborate bleach
of the
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
30
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
E)
X-C-OOH
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WO 98!04668 PCT/US97/12963
24
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 compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or
O-acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated
derivatives of
imidazoles and oximes. Examples of useful materials within these classes are
disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988,
864798,
1147871, 2143231 and EP-A-0170386.
Leaving rg ouDs
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~ II
-N N -N-C-CH-R
' ~ ~ R3 Y ,
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
_,_.__ _~.___
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WO 98/04668 PCT/US97/12963
O C H -O Y C
~NR
_O-C-R~ -NwC/NRa _NwC/ a
II II
O O
3
R O Y
-O-C=CHRa , and -N-S-CH-Ra
R3 O
and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group
containing from 1
5 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.
10 The preferre 3solubilizing groups are -S03-M+, -C02-M+, -S04-M+, -N3 (R3)4X-
and O<--N(R )3 and most preferably -S03-M and -C02-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
15 cation, with sodium and potassium being most preferred, and X is a halide,
hydroxide,
methylsulfate or acetate anion.
Alkyl nercarboxvlic acid bleach precursors
20 AIkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxyIic precursor compounds of the imide type include
the N-
,N,N 1 N I tetra acetylated alkylene diamines wherein the alkylene group
contains from
25 1 to 6 carbon atoms, particularly those compounds in which the alkylene
group
contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is
particularly
preferred.
CA 02261349 2001-12-20
26
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 neroxyacid~precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including those of the following general formulae:
R1 ~__ C-N__R2~C_-L R1 _~N-C-R2-.C-L
O~ R b
or R O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing
1 to
10 carbon atoms and L can be essentially any leaving group. Amide substituted
bleach
activator compounds of this type are described in EP-A-017038b.
Perbenzoic acid precursor
Perbenzoic acid precwsor 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 benzimidazoie. Other useful N-acyl group-
containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl
taurine and benzoyl pyroglutamic acid.
Cationic oeroxvacid~recursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
CA 02261349 2001-12-20
27
Typically, cationic peroxyacid precwsors 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 precwsor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precwsor compound as
described
hereinbefore. Alternatively, the peroxyacid precwsor compound may be an alkyl
percarboxylic acid precwsor compound or an amide substituted alkyl peroxyacid
precwsor as described hereinafter.
Cationic peroxyacid precwsors 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 precwsors are described in WO
95/29160
and U.S. 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 alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred
cationic peroxyacid precwsors of the N-acylated caprolactam class include the
trialkyl
ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene
alkyl caprolactams.
Benzoxazin organic peroxyacid precwsors
Also suitable are precwsor compounds of the benzoxazin-type, as disclosed for
example in EP-A-332,294 and EP-A-482,807, particularly those having the
formula:
CA 02261349 2001-12-20
28
O
l l
C\O
of
N C'_'R~
wherein R 1 is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed organic peroxyacid
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~- l -N R2 C -OOH R~ -N---C-R2- C-OOH
O R5 Ipl ~ 5 ~~
or R O p
wherein R 1 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-
O 170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and
diperbrassylic
acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach catalyst
The compositions optionally contain a transition metal containing bleach
catalyst. One
suitable type of bleach catalyst is a catalyst system comprising a heavy metal
canon of
CA 02261349 1999-O1-27
WO 98/04668 PCT/US97/12963
29
defined bleach catalytic activity, such as copper, iron or manganese canons,
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)
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 Iigand 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)2MnIVbipy2]-
(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
(fernc
complex catalyst), German Pat. specification 2,054,019 (cobalt chelant
catalyst)
CA 02261349 1999-O1-27
WO 98/04668 PCT/US97/12963
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).
5 Heavy 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
10 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%,
1 S 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-
20 hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine
tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid
and polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid,
ethylenediamine
diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts
thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-
CA 02261349 2001-12-20
31
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, aspariic acid-N-
monoacetic acid and irninodisuccinic acid sequestrants described in EP-A-
509,382 are
also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes
suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859
describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid
and 2-
phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-
disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
En~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, cellulases,
pectinases,
lactases and peroxidases conventionally incorporated imo 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, Dwazym, and Esperase by Novo
Industries
A/S (Denmark), those sold under the trademarks Maxatase, Maxacal and Maxapem
by
Gist-Brocades, those sold by Genencor International, and those sold under the
trademarks Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
incorporated into the compositions in accordance with the invention at a level
of from
0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-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 thetrademarksTermamyl and HAN
by Novo Industries A/S. Amylase enzyme may be incorporated into the
composition
CA 02261349 2001-12-20
3z
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., Thermomyce~ sp. or Pseudomonas sp.
including Pseudomonas pseudoalcali enes or Pseudomas fluorescens. Lipase from
chemically or genetically modified mutants of these strains are also useful
herein. A
preferred lipase is derived from Pseudomonas pseudoalcaliRenes, which is
described
in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanueinosa and expressing the gene in Asner ~g'llus orvza, as host, as
described in
European Patent Application, EP-A-0258 068, which is commercially available
from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade mark Lipolase. This
lipase
is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7,
1989.
Organic polymeric compound
Organic polymeric compounds are preferred additional components of the
detergent
compositions in accord with the invention, and are preferably present as
components
of any particulate components where they may act such as to bind the
particulate
component together. By organic polymeric compound it is meant herein
essentially
any polymeric organic compound commonly used as dispersants, and anti-
redeposition and soil suspension agents in detergent compositions, including
any of
the high molecular weight organic polymeric compounds described as clay
flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent
compositions
of the invention at a leve) of from 0.1 % to 30%, preferably from 0.5% to 15%,
most
preferably from 1 % to 10% by weight of the compositions.
CA 02261349 1999-O1-27
WO 98/04668 PCT/US97/12963
33
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.
Terpoiymers 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:
~ H3 ~ H3
X-f-OCH2CH2)n- i +-CH2-CH2-~CH2)a b ~ + CH2CH20 )n X
(CH2CH20 -j~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C 1-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
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WO 98/04668 PCT/US97/12963
34
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 compositions of the invention, when formulated for use in
machine
washing compositions, preferably comprise a suds suppressing system present at
a
level of from 0.01 % to 15%, preferably from 0.05% to 10%, most preferably
from
0.1% to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifoam compounds and 2-
alkyl
alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a
detergent composition, particularly in the presence of agitation of that
solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component. Such silicone antifoam compounds also typically contain a silica
component. The term "silicone" as used herein, and in general throughout the
industry, encompasses a variety of relatively high molecular weight polymers
containing siloxane units and hydrocarbyl 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
CA 02261349 2001-12-20
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
5 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-
10 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
15 a silicone antifoam compound comprising in combination
(i) polydimethyl silvxane, at a level of from 50% to 99%, preferably 75%
to 95% by weight of the silicone antifoam compound; and
20 (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 10%,
preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake
TM
copolymer of this type is DC0544, commercially available from DOW
Corning under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C 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;
CA 02261349 1999-O1-27
WO 98/04668 PCT/US97J12963
36
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.
Cla~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 inhibiting agents
The detergent compositions herein may also comprise from 0.01 % to 10 %,
preferably
from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
al Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula
T .._.. ... _. w _
CA 02261349 1999-O1-27
WO 98/04668 PCT/US97/12963
37
(~) Ax
R
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyciic 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
0
(R1) x _ ~ -(R2)Y
(Rg)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 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
CA 02261349 2001-12-20
38
such as pyrridine, 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 pyridine, 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~ Cot~olvmers of N-vinvlpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone
having
an average molecular weight range of from 5,000 to 50,000. The preferred
copolymers
have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
Polyvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrroiidone
("PVP")
having an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are commercially available 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
polyvinylpyrroMidones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone
CA 02261349 2001-12-20
39
The detergent compositions herein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average
molecular weight of from 2,500 to 400,000.
e) Polvvinxlimidazole
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 bri~htener
The detergent compositions herein also optionally contain from about 0.005% to
5%
by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural
formula:
Ri R2
N H H N
N 0>--N O C_C O Ij -~O N
~N H H N
R2 S03M S03M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino, chloro and amino; and M is a salt-forming canon such as sodium or
potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
canon such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-
s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the trademark Tinopal-UNPA-
GX
by Ciba-Geigy Corporation. Tinopal-CTNPA-GX is the preferred hydrophilic
optical
brightener useful in the detergent compositions herein.
CA 02261349 2001-12-20
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-
hydroxyethyl-N-methylamino)-s-triazine-2-yl)aminoJ2,2'-stilbenedisulfonic acid
disodium salt. This particular brightener species is commercially marketed
under the
S trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
10 commercially marketed under the trademark Tinopal AMS-GX by Ciba Geigy
Corporation.
Cationic fabric softening agents
15 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-1 514 276 and EP-B-0 011 340.
20 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
25 Other optional ingredients suitable for inclusion in the compositions of
the invention
include perfumes, colours and filler salts, wish 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
Form of the compositions
CA 02261349 1999-O1-27
WO 98/04668 PCT/ITS97/12963
41
The detergent composition of the invention can be made via a variety of
methods,
including dry-mixing and agglomerating of the various compounds comprised in
the
detergent composition. The acidic source of the invention is preferably dry-
added.
S The compositions in accordance with the invention can take a variety of
physical
forms including granular, tablet, bar and liquid forms. The compositions are
particularly the so-called concentrated granular detergent compositions
adapted to be
added to a washing machine by means of a dispensing device placed in the
machine
drum with the soiled fabric load.
The mean particle size of the base composition of granular compositions in
accordance with the invention can be from 0.1 mm to S.0 mm, but it should
preferably
be such that no more that 5% of particles are greater than 1.7mm in diameter
and not
more than S% of particles are less than 0.1 Smm in diameter.
1S
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 SO%
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 S00 g/litre, more
preferably from
6S0 g/litre to 1200, more preferably to 8S0 g/litre. Bulk density is measured
by means
2S 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
3S 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
CA 02261349 2001-12-20
42
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 aeQlomerate pa,ticles
The surfactant system herein is preferably present in granular compositions in
the
form of surfactant agglomerate particles, which may take the form of flakes,
prills,
marumes, 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 site 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).
A high active surfactant paste comprising from 50% by weight to 95% by weight,
preferably 70% by weight to 85% by weight of surfactant is typically used. The
paste
may be pumped into the agglomerator at a temperature high enough to maintain a
pumpable viscosity, but low enough to avoid degradation of the anionic
surfactants
used. An operating temperature of the paste of 50°C to 80°C is
typical.
In an especially preferred embodiment of the present invention, the detergent
composition is in the form of powder or a granulate containing more than about
5%
by weight of of the alkali, preferably (bi-)carbonate or percarbonate. The
carbonate
material is either dry-added or delivered via agglomerates. The addition of
the acid,
preferably citric acid, (up to 10%) may be introduced into the product as a
dry-add, or
via a separate particle.
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WO 98/04668 PCT/US97/12963
43
Laundry washing method
Machine laundry methods herein typically comprise treating soiled laundry with
an
aqueous wash solution in a washing machine having dissolved or dispensed
therein an
effective amount of a machine laundry detergent composition in accord with the
invention. By an effective amount of the detergent composition it is meant
from 40g
to 300g of product dissolved or dispersed in a wash solution of volume from 5
to 65
litres, 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,
CA 02261349 2001-12-20
44
EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published
in Manufacturing Chemist, November 1989, pages 4l -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 arrangemnt 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, 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.
Packaeine 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.
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Abbreviations used in following Examples
5 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
10 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 C 14_ 15 Predominantly linear primary
alcohol
condensed with an average of 7 moles of
ethylene oxide
15 C25E3 . A C 12-I S branched primary alcohol ondensed
with an
average of 3 moles of ethylene oxide
C25E5 . A C12-15 branched primary alcohol condensed
with an
average of 5 moles of ethylene oxide
CEQ : R 1 COOCH2CH2.N+(CH3 )3 with R 1 = C
11-C 13
20 QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14
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
25 STPP . Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated Sodium Aiuminosilicate of formula
Nal2(A102Si02)12~ 2~H20 having a primary
particle
size in the range from 0.1 to 10 micrometers
NaSKS-6 : Crystalline layered silicate of formula
30 8 -Na2Si205
Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a particle
size
between 200 p,m and 900pm
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size
35 distribution between 400p,m and 1200pm
Silicate : Amorphous Sodium Silicate (Si02:Na20;
2.0 ratio)
CA 02261349 2001-12-20
' 46
Sodium sulfate : Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a
particle size distribution between 425pm and 850pm
MAIAA . Copolymer of 1:4 maleic/acrylic acid, average
molecular
weight about 70,000.
CMC : Sodium carboxymethyl ceilulose '
Protease : Proteolytic enzyme of activity 4KNPU/g sold by
NOVO
Industries A/S under the trademark Savinase
Alcalase . Proteolytic enzyme of activity 3AU/g sold by NOVO
Industries A/S
Cellulase . Cellulytic enzyme of activity 1000 CEVU/g sold by
NOVO Industries A/S under the trademarkCarezyme
~Yl~e : Amylolytic enzyme of activity 60KNU/g sold by NOVO
Industries A/S under the trademark Termamyl 60T
Lipase : Lipolytic enzyme of activity 1 OOkLU/g sold by
NOVO Industries A/S under the trademark Lipolase
Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold
by
NOVO Industries A/S
PB4 : Sodium perborate tetrahydsate 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
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
Hrightener 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
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47
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
SRP 1 : Sulfobenzoyl end capped esters with
oxyethylene oxy
and terephtaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephthalate)
short
block polymer
Silicone antifoam : Polydimethylsiloxane foam controller
with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller
to said
dispersing agent of 10:1 to 100:1.
Alkalinity : % weight equivalent of NaOI-I, as obtained
using the
alkalinity release test method described
herein.
In the following Examples all levels are quoted as % by weight of the
composition:
20
Example 1
The following granular laundry detergent compositions A , B, C and D of bulk
density
650 g/litre were prepared in accord with the invention:
A B C D
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 - -
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48
QAS - _ - 1.0
STPP - _ _ _
Zeolite A 19.5 19.5 19.5 16.5
NaSKS-6/citric acid 10.6 10.6 10.6 I 0.6
(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 - -
PBI 13.7 15.0 14.0 17.5
TAED 3.1 - 4.2 -
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 I .6 1.6 I .6 I .6
CMC 0.4 0.4 0.4 0.4
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49
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%
Example 2
The following detergent formulations, according to the present invention were
prepared.
E F G
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 1.0 1.0
CEQ 1.5 3.0 -
Silicate 7.0 8.0 8.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
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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
PB 1 18.0 I 8.0 13.5
PB4 - 4.0 -
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
Citric acid 2.5 7.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
Example 3
The following detergent formulations according to the present invention were
5 prepared:
H I
Blown Powder
Zeolite A 15.0 -
Sodium sulfate 5.0 -
LAS 3.0 -
QAS 0.5 1.0
DTPMP 0.4
CMC 0.4 -
MA/AA 4.0 -
Agglomerates
C45AS - 11.0
LAS 6.0 -
_.__ _ _ __._,~ ___. __ ___
r
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$1
TAS 3.0 -
Silicate 4.0
Zeolite A 10.0 13.0
CMC - 0.5
M~~ - 2.0
Carbonate 9.0 7.0
PB 1 18.5 -
PB4 - 20.0
TAED 4.5 5.5
Spray On
Perfume 0.3 0.5
C45E7 4.0 4.0
C25E3 2.0 2.0
Dry additives
MA/AA - 3.0
NaSKS-6 - 12.0
Citric acid 5.0 3.0
Citrate 10.0 8.0
Bicarbonate 7.0 5.0
Carbonate 8.0 7.0
PVPVI/PVNO 0.5 0.5
Alcalase 0.5 0.9
Lipase 0.4 0.4
Amylase 0.6 0.6
Cellulase 0.6 0.6
Silicone antifoam 5.0 5.0
Dry additives
Sodium sulfate 0.0 0.0
Balance (Moisture and Miscellaneous)100.0 100.0
Density (g/litre) 700 700
Example 4
The following detergent formulations, according to the present invention were
prepared:
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52
J K L M
LAS 12.0 12.0 12.0 10.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5 - -
CEQ - - 1.0 1.0
STPP 30.0 18.0 15.0 -
Silicate 9.0 7.0 10.0 -
Carbonate 15.0 10.5 15.0 25.0
Bicarbonate - 10.5
DTPMP 0.7 1.0 - -
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.25
Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 - -
Photoactivated 70ppm 45ppm - lOppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB 1 8.0 17.0 - -
NOBS 2.0 1.0 - -
TAED - - 4.0 5.2
PB4 10.0 - 15.5 7.5
Citric acid 3.5 5.0 3.0 7.0
Balance (Moisture100 100 100 100
and Miscellaneous)
Example 5
The following high density and bleach-containing detergent formulations,
according
to the present invention were prepared:
T..__..__.____ . . __..._. _.~ _.. ...._.~..._ _...._.._... ___..~~~.. _...
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53
N O P
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
QAS 0.5 1.0 -
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
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 l 17.0 15.0 16.0
Sodium sulfate - 6.0 -
Citric acid 2.5 3.5 4.5
Balance (Moisture 100 100 100
and
Miscellaneous)
Example 6
The following detergent formulations, according to the present invention were
prepared:
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Q R
Blown Powder
Zeolite A 15.0 15.0
Sodim sulfate 0.0 0.0
LAS 3.0 3.0
QAS - 1.5
QAS 0.5 -
DTPMP 0.4 0.4
CMC 0.4 0.4
MA/AA 4.0 2.0
Agglomerates
LAS 4.0 4.0
TAS 2.0 1.0
Silicate 3.0 4.0
Zeolite A 8.0 8.0
Carbonate 8.0 6.0
Spray On
Perfume 0.3 0.3
C45E7 2.0 2.0
C25E3 2.0 -
Dry additives
Citric acid 2.0 5.5
Citrate 5.0 2.0
Bicarbonate - -
Carbonate 8.0 10.0
TAED 6.0 5.0
PB4 - 9.0
PB 1 15.5 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
_ _ .___ _____
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Silicone antifoam 5.0 5.0
Dry additives
Sodium sulfate 10.0 0,0
Balance (Moisture and 100.0 100.0
Miscellaneous)
Example 7
The following detergent formulations, according to the present invention were
5 prepared:
S T
Agglomerate
C45AS 11.0 14.0
ZeoIite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
Citric acid 4.5 3.0
HEDP 0.5 0.3
Carbonate i 0.0 -
SKS 6 10.0 13.0
Citrate 3.0 1.0
TAED 5.0 7.0
PB 1 20.0 20.0
SRP I 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
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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)
